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1.
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   

2.
We have explored first-principles molecular dynamics simulation data for hydrous MgSiO3 liquid (with 10 wt% water) to gain insight into its structural and dynamical behavior as a function of pressure (0–150 GPa) and temperature (2,000–6,000 K). By visualizing/analyzing a number of parameters associated with short- and mid-range orders, we have shown that the melt structure changes substantially on compression. The speciation of the water component at low pressures is dominated by the isolated structures (with over 90% hydrogen participated) consisting of hydroxyls, water molecules, O–H–O bridging and four-atom (O–H–O–H and H–O–H–O) groups, where every oxygen atom may be a part of polyhedron or free (i.e., bound to only magnesium atom). Hydroxyls favor polyhedral sites over magnesium sites whereas molecular water is almost entirely bound to magnesium sites, and also interpolyhedral bridging (Si–O–H–O–Si) dominates other types of bridging. Water content is shown to enhance and suppress, respectively, the proportions of hydroxyls and molecular water. As compression increases, these isolated structures increasingly combine with each other to form extended structures involving a total of five or more O and H atoms and also containing threefold coordination species, which together consume over 80% hydrogen at the highest compression studied. Our results show that water lowers the mean coordination numbers of different types including all cation–anion environments. The hydrous melt tends to be more tetrahedrally coordinated but with the Si–Si network being more disrupted compared to the anhydrous melt. Protons increase the content of non-bridging oxygen and decrease the contents of bridging oxygen as well as oxygen triclusters (present at pressures above 10 GPa). The calculated self-diffusion coefficients of all atomic species are enhanced in the presence of water compared to those of the anhydrous melt. This is consistent with the prediction that water depolymerizes the melt structure at all pressures. Our analysis also suggests that proton diffusion involves two processes—the transfer of H atoms (requiring the rupture and formation of O–H bonds) and the motion of hydroxyls as hydrogen carriers (requiring the rupture and formation of Si–O and/or Mg–O bonds). Both the processes are operative at low compression whereas only the first process is operative at high compression.  相似文献   

3.
The determination of total water content (H2OT: 0.1-10 wt%) and water speciation (H2Omolecular/OH) in volcanic products by confocal microRaman spectrometry are discussed for alkaline (phonolite) and calcalkaline (dacite and rhyolite) silicic glasses. Shape and spectral distribution of the total water band (H2OT) at ∼3550 cm−1 show systematic evolution with glass H2OT, water speciation and NBO/T. In the studied set of silicic samples, calibrations based on internal normalization of the H2OT band to a band related to vibration of aluminosilicate network (TOT) at ∼490 cm−1 vary with glass peraluminosity. An external calibration procedure using well-characterized glass standards is less composition-dependent and provides excellent linear correlation between total dissolved water content and height or area of the H2OT Raman band. Accuracy of deconvolution procedure of the H2OT band to quantify water speciation in water-rich and depolymerized glasses depends on the strength of OH hydrogen bonding. System confocal performance, scattering from embedding medium and glass microcrystallinity have a crucial influence on accuracy of Raman analyses of water content in glass-bearing rocks and melt inclusions in crystals.  相似文献   

4.
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   

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.
A review of published and newly measured densities for 40 hydrous silicate glasses indicates that the room-temperature partial molar volume of water is 12.0 ± 0.5 cm3/mol. This value holds for simple or mineral compositions as well as for complex natural glasses, from rhyolite to tephrite compositions, prepared up to 10–20 kbar pressures and containing up to 7 wt% H2O. This volume does not vary either with the molar volume of the water-free silicate phase, with its degree of polymerization or with water speciation. Over a wide range of compositions, this constant value implies that the volume change for the reaction between hydroxyl ions and molecular water is zero and that, at least in glasses, speciation does not depend on pressure. Consistent with data from Ochs and Lange (1997, 1999), systematics in volume expansion for SiO2–M2O systems (M=H, Li, Na, K) suggests that the partial molar thermal expansion coefficient of H2O is about 4 × 10−5 K−1 in silicate glasses. Received: 30 June 1999 / Accepted: 5 November 1999  相似文献   

7.
《Applied Geochemistry》2006,21(5):802-812
Development of Raman spectrometry for quantification of water content in natural glasses requires the assessment of the dependence of the technique on glass composition and thermal history. In the low frequency domain, Raman spectra topology varies due to glass depolymerization and substitution in the framework of (Si4+)IV by alkali-balanced (Al3+)IV and (Fe3+)IV in calcalkaline (rhyolite to basaltic andesite) and alkaline (trachyte, phonolite to alkali basalt) glasses. These processes result in strong dependence of previous analytical procedure (internal calibration) on glass composition. Here, we show that an analytical procedure based on calibration to an external standard is only faintly composition-dependent for Si-rich alkaline glasses (trachytes–phonolites). For a given glass composition, thermal history also plays a fundamental role in the choice of Raman procedure for water analysis. Repeated cycles of thermal annealing induce microcrystallization of hydrous trachyte glasses and modify cation distribution in the glass structure. Application of these concepts to analysis of banded obsidians suggests that small-scale heterogeneities in glasses are not simply related to magma degassing, but could depend on thermal history and consequent relaxation paths in the melt.  相似文献   

8.
Kerimasi calciocarbonatite consists principally of calcite together with lesser apatite, magnetite, and monticellite. Calcite hosts fluid and S-bearing Na–K–Ca-carbonate inclusions. Carbonatite melt and fluid inclusions occur in apatite and magnetite, and silicate melt inclusions in magnetite. This study presents statistically significant compositional data for quenched S- and P-bearing, Ca-alkali-rich carbonatite melt inclusions in magnetite and apatite. Magnetite-hosted silicate melts are peralkaline with normative sodium-metasilicate. On the basis of our microthermometric results on apatite-hosted melt inclusions and forsterite–monticellite phase relationships, temperatures of the early stage of magma evolution are estimated to be 900–1,000°C. At this time three immiscible liquid phases coexisted: (1) a Ca-rich, P-, S- and alkali-bearing carbonatite melt, (2) a Mg- and Fe-rich, peralkaline silicate melt, and (3) a C–O–H–S-alkali fluid. During the development of coexisting carbonatite and silicate melts, the Si/Al and Mg/Fe ratio of the silicate melt decreased with contemporaneous increase in alkalis due to olivine fractionation, whereas the alkali content of the carbonatite melt increased with concomitant decrease in CaO resulting from calcite fractionation. Overall the peralkalinity of the bulk composition of the immiscible melts increased, resulting in a decrease in the size of the miscibility gap in the pseudoquaternary system studied. Inclusion data indicate the formation of a carbonatite magma that is extremely enriched in alkalis with a composition similar to that of Oldoinyo Lengai natrocarbonatite. In contrast to the bulk compositions of calciocarbonatite rocks, the melt inclusions investigated contain significant amount of alkalis (Na2O + K2O) that is at least 5–10 wt%. The compositions of carbonatite melt inclusions are considered as being better representatives of parental magma composition than those of any bulk rock.  相似文献   

9.
Micro-Raman spectroscopy, even though a very promising technique, is not still routinely applied to analyse H2O in silicate glasses. The accuracy of Raman water determinations critically depends on the capability to predict and take into account both the matrix effects (bulk glass composition) and the analytical conditions on band intensities. On the other hand, micro-Fourier transform infrared spectroscopy is commonly used to measure the hydrous absorbing species (e.g., hydroxyl OH− and molecular H2O) in natural glasses, but requires critical assumptions for the study of crystal-hosted glasses. Here, we quantify for the first time the matrix effect of Raman external calibration procedures for the quantification of the total H2O content (H2OT = OH− + H2Om) in natural silicate glasses. The procedures are based on the calibration of either the absolute (external calibration) or scaled (parameterisation) intensity of the 3550 cm−1 band. A total of 67 mafic (basanite, basalt) and intermediate (andesite) glasses hosted in olivines, having between 0.2 and 4.8 wt% of H2O, was analysed. Our new dataset demonstrates, for given water content, the height (intensity) of Raman H2OT band depends on glass density, reflectance and water environment. Hence this matrix effect must be considered in the quantification of H2O by Raman spectroscopy irrespective of the procedure, whereas the parameterisation mainly helps to predict and verify the self-consistency of the Raman results. In addition, to validate the capability of the micro-Raman to accurately determine the H2O content of multicomponent aluminosilicate glasses, a subset of 23 glasses was analysed by both micro-Raman and micro-FTIR spectroscopy using the band at 3550 cm−1. We provide new FTIR absorptivity coefficients (ε3550) for basalt (62.80 ± 0.8 L mol−1 cm−1) and basanite (43.96 ± 0.6 L mol−1 cm−1). These values, together with an exhaustive review of literature data, confirm the non-linear decline of the FTIR absorptivity coefficient (ε3550) as the glass depolymerisation increases. We demonstrate the good agreement between micro-FTIR and micro-Raman determination of H2O in silicate glasses when the matrix effects are properly considered.  相似文献   

10.
 Interstitial glasses and glasses in small inclusions in Mg-rich phenocrysts of 14 boninites from New Caledonia, the Mariana Trench, Cape Vogel and Chichi-jima were analysed by electron microprobe and the water contents measured in situ by ion microprobe. The glasses are remarkably fresh and abundant (∼30–90 vol.%), and the phenocrysts are often skeletal with glass inclusions. Broad-beam analyses (∼1030) of interstitial glasses and ∼180 point analyses of glass inclusions were carried out, as well as ∼100 hydrogen analyses. Most glasses have low water-free totals, high water contents, very low MgO, and low total iron; they are almost entirely quartzofeldspathic and with few exceptions (Q+or+ab+ an+C) lies in the range 83–96. The interstitial glasses from New Caledonia, the Marianas and most of the glasses from Chichi-jima are dacitic, those from Cape Vogel straddle dacitic and andesitic compositions, whereas the glasses in a highly glassy sample from Chichi-jima are high-Mg andesitic or boninitic with up ∼9 wt% MgO, and are, with the exception of a few high-Ca boninites from Tonga, the most Mg-rich interstitial glasses so far described in boninites. Glasses included in orthopyroxene, olivine or clinoenstatite are boninitic or high-Mg andesitic in the highly glassy rock and dacitic to high-silica dacitic in the others. They are in general slightly more differentiated than the interstitial glasses, because of more-extensive crystallization on the host crystal in small inclusions. The interstitial glass compositions show a direct relationship between silica and Al2O3 and, for most glasses, alkalis, and inverse relationships between silica and CaO, FeO and MgO; alkalis and TiO2 show, however, a broad spread in values in glasses from the Marianas and New Caledonia. Included glasses show similar variations. Water contents in interstitial glasses are ∼2 wt% for the highly glassy high-Mg andesitic glasses from Chichi-jima, ∼5.4 wt% for the more differentiated andesitic to dacitic glasses from Cape Vogel, and ∼6.7–7.0 wt% in the most differentiated dacitic ones from the Marianas and New Caledonia. Water contents in glass inclusions in olivine, orthopyroxene and clinoenstatite are in the range ∼1.9–3.3 wt%. The interstitial glasses are black and not vesicular, showing that the liquids did not reach supersaturation after eruption on or intrusion near the sea floor, or were insufficiently so to allow nucleation of water vapour bubbles. The water is inferred to be primary and to increase strongly with crystallization in the residual liquid down to the glass-transition T. Received: 19 December 1994 / Accepted: 5 October 1995  相似文献   

11.
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   

12.
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   

13.
This paper is focused on the progress in the determination of water in glasses and melt inclusions with Raman spectroscopy.Using the presented"Comparator Technique"the water content of a sample is determined by simple comparison with a known standard.A calibration curve is not necessary.Furthermore,with this technique the water concentration in silicate melt inclusions can be determined without exposing the inclusions for measurements.This is very important for extremely water-rich melt inclusions,which would loose H_2O on exposure.  相似文献   

14.
The development of an accurate analytical procedure for determination of dissolved water in complex alumino-silicate glasses via micro-Raman analysis requires the assessment of the spectra topology dependence on glass composition. We report here a detailed study of the respective influence of bulk composition, iron oxidation state and total water content on the absolute and relative intensities of the main Raman bands related to glass network vibrations (LF: ∼490 cm−1; HF: ∼960 cm−1) and total water stretching (H2OT: ∼3550 cm−1) in natural glasses. The evolution of spectra topology was examined in (i) 33 anhydrous glasses produced by the re-melting of natural rock samples, which span a very large range of polymerisation degree (NBO/T from 0.00 to 1.16), (ii) 2 sets of synthetic anhydrous basaltic glasses with variable iron oxidation state (Fe3+/FeT from 0.05 to 0.87), and (iii) 6 sets of natural hydrous glasses (CH2OT from 0.4 to 7.0 wt%) with NBO/T varying from 0.01 to 0.76.In the explored domain of water concentration, external calibration procedure based on the H2OT band height is matrix-independent but its accuracy relies on precise control of the focusing depth and beam energy on the sample. Matrix-dependence strongly affects the internal calibrations based on H2OT height scaled to that of LF or HF bands but its effect decreases from acid (low NBO/T, SM) to basic (high NBO/T, SM) glasses. Structural parameters such as NBO/T (non-bridging oxygen per tetrahedron) and SM (sum of structural modifiers) describe the matrix-dependence better than simple compositional parameters (e.g. SiO2, Na2O + K2O). Iron oxidation state has only a minor influence on band topology in basalts and is thus not expected to significantly affect the Raman determinations of water in mafic (e.g. low SiO2, iron-rich) glasses. Modelling the evolution of the relative band height with polymerisation degree allows us to propose a general equation to predict the dissolved water content in natural glasses:
  相似文献   

15.
 We have investigated new samples from the Gees mantle xenolith suite (West Eifel), for which metasomatism by carbonatite melt has been suggested. The major metasomatic change is transformation of harzburgites into phlogopite-rich wehrlites. Silicate glasses are associated with all stages of transformation, and can be resolved into two major groups: a strongly undersaturated alkaline basanite similar to the host magma which infiltrated the xenoliths during ascent, and Si-Al-enriched, variably alkaline glass present exclusively within the xenoliths. Si-Al-rich glasses (up to 72 wt% SiO2 when associated with orthopyroxene (Opx) are usually interpreted in mantle xenoliths as products of decompressional breakdown of hydrous phases like amphibole. In the Gees suite, however, amphibole is not present, nor can the glass be related to phlogopite breakdown. The Si-Al-rich glass is compositionally similar to glasses occurring in many other xenolith suites including those related to carbonatite metasomatism. Petrographically the silicate glass is intimately associated with the metasomatic reactions in Gees, mainly conversion of harzburgite orthopyroxene to olivine + clinopyroxene. Both phases crystallize as microlites from the glass. The chemical composition of the Si-Al-enriched glass shows that it cannot be derived from decompressional melting of the Gees xenoliths, but must have been present prior to their entrainment in the host magma. Simple mass-balance calculations, based on modal analyses, yield a possible composition of the melt prior to ascent of the xenoliths, during which glass + microlite patches were modified by dissolution of olivine, orthopyroxene and spinel. This parental melt is a calc-alkaline andesite (55–60 wt% SiO2), characterized by high Al2O3 (ca. 18 wt%). The obtained composition is very similar to high-alumina, calc-alkaline melts that should form by AFC-type reactions between basalt and harzburgite wall rock according to the model of Kelemen (1990). Thus, we suggest that the Si-Al-enriched glasses of Gees, and possibly of other suites as well, are remnants of upper mantle hybrid melts, and that the Gees suite was metasomatized by silicate and not carbonatite melts. High-Mg, high-Ca composition of metasomatic olivine and clinopyroxene in mantle xenoliths have been explained by carbonatite metasomatism. As these features are also present in the Gees suite, we have calculated the equilibrium Ca contents of olivine and clinopyroxene using the QUI1F thermodynamical model, to show that they are a simple function of silica activity. High-Ca compositions are attained at low a SiO2 and can thus be produced during metasomatism by any melt that is Opx-undersaturated, irrespective of whether it is a carbonatite or a silicate melt. Such low a SiO2 is recorded by the microlites in the Gees Si-Al-rich glasses. Our results imply that xenolith suites cannot confidently be related to carbonatite metasomatism if the significance of silicate glasses, when present, is not investigated. Received: 2 March 1995 / Accepted: 12 June 1995  相似文献   

16.
 The viscosities of hydrous haplogranitic melts synthesized by hydrothermal fusion at 2 kbar pressure and 800 to 1040° C have been measured at temperatures just above the glass transition and at a pressure of 1 bar using micropenetration techniques. The micropenetration viscometry has been performed in the viscosity range of 109 Pa s to 1012 Pa s. The samples ranged in water content from 0.4 to 3.5 wt%. For samples with up to 2.5 wt% H2O, the water contents have been determined using infrared spectroscopy obtained before and after each viscometry experiment to be constant over the duration of the measurements. Above this water content a measurable loss of water occurs during the viscometry. The viscosity data illustrate an extremely nonlinear decrease in viscosity with added water. The viscosity drops drastically with the addition of 0.5 wt% of water and then shallows out at water contents of 2 wt%. An additional viscosity datum point obtained from the analysis of fluid inclusions in a water-saturated HPG8 confirms a near invariance of the viscosity with the addition of water between 2 and 6 wt%. These measurements may be compared directly with the data of Hess et al. (1995, in press) for the effects of excess alkali and alkaline earth oxides on the viscosity of HPG8 (also obtained at 1 bar). The viscosity of the melts, compared on an equivalent molar basis, increases in the order H2O<(Li2O<Na2O< K2O<Rb2O,Cs2O<BaO<SrO<CaO<MgO< BeO). The extraordinary decrease in melt viscosity with added water is poorly reproduced by the calculation scheme of Shaw (1972) for the range of water contents investigated here. The speciation of water in the quenched glasses can be used to quantify the dependence of the viscosity on hydroxyl content. Considering only the hydroxyl groups as active fluidizers in the hydrous melts the nonlinearity of the viscosity decrease and the difference with the effects of the alkali oxides becomes larger. Consequences for degassing calcalkaline rhyolite are discussed. Received: 17 August 1995/Accepted: 8 January 1996  相似文献   

17.
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   

18.
The structure of glasses and melts of Na2O· 0.5Fe2O3·3SiO2 and Na2O·FeO·3SiO2 compositions have been measured using high temperature Raman spectroscopy. For the oxidized sample it has been demonstrated that there is a close structural relationship between melt and glass. No coordination changes of Fe3+ with temperature and no new anionic species have been observed in the oxidized melt. The Raman spectra of the reduced sample clearly show a decrease in the degree of polymerization, as determined by the observation of the polarization character of the spectra and the details of the change of the Raman intensities during heating in hydrogen. Mössbauer spectra suggest that Fe3+ is tetrahedrally coordinated in the oxidized glass and part of the Fe2+ is tetrahedrally coordinated in the reduced glass.  相似文献   

19.
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   

20.
This study demonstrates that a hydrous, halide bearing silicate melt is a viable medium for diamond growth. Experiments were conducted in the MgO–SiO2–H2O–C ± KCl ± NaCl system, which was used as a model for harzburgitic mantle. In no case did we observe crystals that could be interpreted as spontaneously nucleated, but growth of diamond on seed crystals at 1,400–1,600°C and 7 GPa in experiments of 4 h duration was observed. The addition of KCl to the system produced crystallization of diamond at temperatures as low as 1,400°C. At higher temperatures, larger growth features were produced than those that seen in the KCl-free system at the same conditions. The NaCl-bearing system is different; in these experiments, the diamond seed crystals show evidence of possible dissolution and layer growth, albeit more subdued growth than in the KCl system. Therefore, NaCl may be an inhibitor of diamond growth in a hydrous silicate melt. Based on these results, hydrous silicate melts could play a role in formation of diamond in either deep subduction zones, or above slabs imbricated against a lithospheric ‘root’ in the sub-continental lithospheric mantle. The water and halide necessary for their formation could be transported into the mantle in hydrous phases such as serpentine in subducting lithospheric slabs. Dehydration of serpentine at >200 km depth would release hydrous, halide-bearing fluids into the overlying mantle wedge or lithospheric root, triggering melting at conditions similar to those of the formation of natural diamond.  相似文献   

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