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1.
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:
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2.
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   

3.
Reaction between dissolved water and sulphide was experimentally investigated in soda-lime-silicate (NCS) and sodium trisilicate (NS3) melts at temperatures from 1000 to 1200 °C and pressures of 100 or 200 MPa in internally heated gas pressure vessels. Diffusion couple experiments were conducted at water-undersaturated conditions with one half of the couple being doped with sulphide (added as FeS or Na2S; 1500-2000 ppm S by weight) and the other with H2O (∼3.0 wt.%). Additionally, two experiments were performed using a dry NCS glass cylinder and a free H2O fluid. Here, the melt was water-saturated at least at the melt/fluid interface. Profiling by electron microprobe (sulphur) and infrared microscopy (H2O) demonstrate that H2O diffusion in the melts is faster by 1.5-2.3 orders of magnitude than sulphur diffusion and, hence, H2O can be considered as a rapidly diffusing oxidant while sulphur is quasi immobile in these experiments.In Raman spectra a band at 2576 cm−1 appears in the sulphide - H2O transition zone which is attributed to fundamental S-H stretching vibrations. Formation of new IR absorption bands at 5025 cm−1 (on expense of the combination band of molecular H2O at 5225 cm−1) and at 3400 cm−1 was observed at the front of the in-diffusing water in the sulphide bearing melt. The appearance and intensity of these two IR bands is correlated with systematic changes in S K-edge XANES spectra. A pre-edge excitation at 2466.5 eV grows with increasing H2O concentration while the sulphide peak at 2474.0 eV decreases in intensity relative to the peak at 2477.0 eV and the feature at 2472.3 eV becomes more pronounced (all energies are relative to the sulphate excitation, calibrated to 2482.5 eV). The observations by Raman, IR and XANES spectroscopy indicate a well coordinated S2− - H2O complex which was probably formed in the glasses during cooling at the glass transition. No oxidation of sulphide was observed in any of the diffusion couple experiments. On the contrary, XANES spectra from experiments conducted with a free H2O fluid show complete transformation of sulphide to sulphate near the melt surface and coexistence of sulphate and sulphide in the center of the melt. This can be explained by a lower H2O activity in the diffusion couple experiments or by the need of a sink for hydrogen (e.g., a fluid which can dissolve high concentration of hydrogen) to promote oxidation of sulphide by H2O via the reaction S2− + 4H2O = SO42− + 4H2. Sulphite could not be detected in any of the XANES spectra implying that this species, if it exists in the melt, it is a subordinate or transient species only.  相似文献   

4.
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   

5.
Raman spectroscopy is a powerful method for the determination of CO2 densities in fluid inclusions, especially for those with small size and/or low fluid density. The relationship between CO2 Fermi diad split (Δ, cm−1) and CO2 density (ρ, g/cm3) has been documented by several previous studies. However, significant discrepancies exist among these studies mainly because of inconsistent calibration procedures and lack of measurements for CO2 fluids having densities between 0.21 and 0.75 g/cm3, where liquid and vapor phases coexist near room temperature.In this study, a high-pressure optical cell and fused silica capillary capsules were used to prepare pure CO2 samples with densities between 0.0472 and 1.0060 g/cm3. The measured CO2 Fermi diad splits were calibrated with two well established Raman bands of benzonitrile at 1192.6 and 1598.9 cm−1. The relationship between the CO2 Fermi diad split and density can be represented by: ρ = 47513.64243 − 1374.824414 × Δ + 13.25586152 × Δ2 − 0.04258891551 × Δ3 (r2 = 0.99835, σ = 0.0253 g/cm3), and this relationship was tested by synthetic fluid inclusions and natural CO2-rich fluid inclusions. The effects of temperature and the presence of H2O and CH4 on this relationship were also examined.  相似文献   

6.
Chlorine-35 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were collected at 14.1 and 18.8 Tesla fields to determine the atomic scale structural environments of the chloride ions in anhydrous and hydrous silicate and aluminosilicate glasses containing 0.2 to 0.7 wt% Cl. NMR peaks are broad and featureless, but are much narrower than the total chemical shift range for the nuclide in inorganic chlorides. Peak widths are primarily due to quadrupole interactions and to a lesser extent to chemical shift distributions. Peak positions are quite different for the Na- and Ca-containing glasses, suggesting that most Cl− coordination environments contain network modifier cations. Comparison of peak positions and shapes for silicate and aluminosilicate glasses containing either Na or Ca suggests that there is no obvious contribution from Cl− bonded to Al, and relative quantitation of peak areas indicates that there is no systematic undercounting of 35Cl spins in the aluminous vs. the Al-free samples. In Ca-Na silicate glasses with varying Ca/(Ca + Na), the mixed-cation glasses have intermediate chemical shifts between those of the end members, implying that there is not a strong preference of either Ca2+ or of Na+ around Cl−. Hydrous Na-aluminosilicate glasses with H2O contents up to 5.9 wt% show a shift to higher frequency NMR signal with increasing H2O content, while the quadrupole coupling constant (CQ) remains constant at ∼3.3 MHz. However, the change in frequency is much smaller than that expected if H2O systematically replaced Na+ in the first-neighbor coordination shell around Cl−. A series of hydrous Ca-aluminosilicate glasses with H2O contents up to 5.5 wt% show no shift in NMR signal with increasing H2O content. The CQ remains constant at ∼4.4 MHz, again suggesting no direct interaction between Cl− and H2O in these samples.  相似文献   

7.
Information about the state of sulfur in silicate melts and glasses is important in both earth sciences and materials sciences. Because of its variety of valence states from S2− (sulfide) to S6+ (sulfate), the speciation of sulfur dissolved in silicate melts and glasses is expected to be highly dependent on the oxygen fugacity. To place new constraint on this issue, we have synthesized sulfur-bearing sodium silicate glasses (quenched melts) from starting materials containing sulfur of different valence states (Na2SO4, Na2SO3, Na2S2O3 and native S) using an internally heated gas pressure vessel, and have applied electron-induced SKα X-ray fluorescence, micro-Raman and NMR spectroscopic techniques to probe their structure. The wavelength shift of SKα X-rays revealed that the differences in the valence state of sulfur in the starting compounds are largely retained in the synthesized sulfur-bearing glasses, with a small reduction for more oxidized samples. The 29Si MAS NMR spectra of all the glasses contain no peaks attributable to the SiO4-nSn (with n > 0) linkages. The Raman spectra are consistent with the coexistence of sodium sulfate (Na2SO4) species and one or more types of more reduced sulfur species containing S-S linkages in all the sulfur-bearing silicate glasses, with the former dominant in glasses produced from Na2SO4-doped starting materials, and the latter more abundant in more reduced glasses. The 29Si MAS NMR and Raman spectra also revealed changes in the silicate network structure of the sulfur-bearing glasses, which can be interpreted in terms of changes in the chemical composition and sulfur speciation.  相似文献   

8.
The structure of H2O-saturated silicate melts and of silicate-saturated aqueous solutions, as well as that of supercritical silicate-rich aqueous liquids, has been characterized in-situ while the sample was at high temperature (to 800 °C) and pressure (up to 796 MPa). Structural information was obtained with confocal microRaman and with FTIR spectroscopy. Two Al-bearing glasses compositionally along the join Na2O•4SiO2-Na2O•4(NaAl)O2-H2O (5 and 10 mol% Al2O3, denoted NA5 and NA10) were used as starting materials. Fluids and melts were examined along pressure-temperature trajectories of isochores of H2O at nominal densities (from PVT properties of pure H2O) of 0.85 g/cm3 (NA10 experiments) and 0.86 g/cm3 (NA5 experiments) with the aluminosilicate + H2O sample contained in an externally-heated, Ir-gasketed hydrothermal diamond anvil cell.Molecular H2O (H2O°) and OH groups that form bonds with cations exist in all three phases. The OH/H2O° ratio is positively correlated with temperature and pressure (and, therefore, fugacity of H2O, fH2O) with (OH/H2O°)melt > (OH/H2O°)fluid at all pressures and temperatures. Structural units of Q3, Q2, Q1, and Q0 type occur together in fluids, in melts, and, when outside the two-phase melt + fluid boundary, in single-phase liquids. The abundance of Q0 and Q1 increases and Q2 and Q3 decrease with fH2O. Therefore, the NBO/T (nonbridging oxygen per tetrahedrally coordination cations), of melt is a positive function of fH2O. The NBO/T of silicate in coexisting aqueous fluid, although greater than in melt, is less sensitive to fH2O.The melt structural data are used to describe relationships between activity of H2O and melting phase relations of silicate systems at high pressure and temperature. The data were also combined with available partial molar configurational heat capacity of Qn-species in melts to illustrate how these quantities can be employed to estimate relationships between heat capacity of melts and their H2O content.  相似文献   

9.
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   

10.
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   

11.
Silicic acid (H4SiO4) can have significant effects on the properties of iron oxide surfaces in both natural and engineered aquatic systems. Understanding the reactions of H4SiO4 on these surfaces is therefore necessary to describe the aquatic chemistry of iron oxides and the elements that associate with them. This investigation uses attenuated total reflectance infrared spectroscopy (ATR-IR) to study silicic acid in aqueous solution and the products formed when silicic acid adsorbs onto the surface of a ferrihydrite film in 0.01 M NaCl at pH 4. A spectrum of 1.66 mM H4SiO4 at pH 4 (0.01 M NaCl) has an asymmetric Si-O stretch at 939 cm−1 and a weak Si-O-H deformation at 1090 cm−1. ATR-IR spectra were measured over time (for up to 7 days) for a ferrihydrite film (≈1 mg) approaching equilibrium with H4SiO4 at concentrations between 0.044 and 0.91 mM. Adsorbed H4SiO4 had a broad spectral feature between 750 and 1200 cm−1 but the shape of the spectra changed as the amount of H4SiO4 adsorbed on the ferrihydrite increased. When the solid phase Si/Fe mole ratio was less than ≈0.01 the ATR-IR spectra had a maximum intensity at 943 cm−1 and the spectral shape suggests that a monomeric silicate species was formed via a bidentate linkage. As the solid phase Si/Fe mole ratio increased to higher values a discrete oligomeric silicate species was formed which had maximum intensity in the ATR-IR spectra at 1001 cm−1. The spectrum of this species suggests that it is larger than a dimer and it was tentatively identified as a cyclic tetramer. A small amount of a polymeric silica phase with a broad spectral feature centered at ≈1110 cm−1 was also observed at high surface coverage. The surface composition was estimated from the relative contribution of each species to the area of the ATR-IR spectra using multivariate curve resolution with alternating least squares. For a ferrihydrite film approaching equilibrium with 0.044, 0.14, 0.40 and 0.91 mM H4SiO4 the area of the spectra accounted for by monomeric species were 92%, 49%, 23% and 6%, respectively. The remainder was oligomer apart from a small amount (<5%) of polymerized silica at the two higher H4SiO4 concentrations. The solid phase Si/Fe mole ratios for these samples were 0.020, 0.037, 0.071 and 0.138, respectively.  相似文献   

12.
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   

13.
The Raman spectra of albite glasses with 4.5 and 6.6 weight percent water have been obtained, and are compared with that of a dry sample. The hydrous glasses show bands near 3600 cm?1 due to O-H stretching, and a previously unreported weak band near 1600 cm?1 due to bending of molecular H2O. Other weak spectral features are discussed, and the effect of dissolved water on the aluminosilicate framework vibrations is considered.  相似文献   

14.
To understand possible volcanogenic fluxes of CO2 to the Martian atmosphere, we investigated experimentally carbonate solubility in a synthetic melt based on the Adirondack-class Humphrey basalt at 1-2.5 GPa and 1400-1625 °C. Starting materials included both oxidized and reduced compositions, allowing a test of the effect of iron oxidation state on CO2 solubility. CO2 contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and Fe3+/FeT was measured by Mössbauer spectroscopy. The CO2 contents of glasses show no dependence on Fe3+/FeT and range from 0.34 to 2.12 wt.%. For Humphrey basalt, analysis of glasses with gravimetrically-determined CO2 contents allowed calibration of an integrated molar absorptivity of 81,500 ± 1500 L mol−1 cm−2 for the integrated area under the carbonate doublet at 1430 and 1520 cm−1. The experimentally determined CO2 solubilities allow calibration of the thermodynamic parameters governing dissolution of CO2 vapor as carbonate in silicate melt, KII, (Stolper and Holloway, 1988) as follows: , ΔV0 = 20.85 ± 0.91 cm3 mol−1, and ΔH0 = −17.96 ± 10.2 kJ mol−1. This relation, combined with the known thermodynamics of graphite oxidation, facilitates calculation of the CO2 dissolved in magmas derived from graphite-saturated Martian basalt source regions as a function of P, T, and fO2. For the source region for Humphrey, constrained by phase equilibria to be near 1350 °C and 1.2 GPa, the resulting CO2 contents are 51 ppm at the iron-wüstite buffer (IW), and 510 ppm at one order of magnitude above IW (IW + 1). However, solubilities are expected to be greater for depolymerized partial melts similar to primitive shergottite Yamato 980459 (Y 980459). This, combined with hotter source temperatures (1540 °C and 1.2 GPa) could allow hot plume-like magmas similar to Y 980459 to dissolve 240 ppm CO2 at IW and 0.24 wt.% of CO2 at IW + 1. For expected magmatic fluxes over the last 4.5 Ga of Martian history, magmas similar to Humphrey would only produce 0.03 and 0.26 bars from sources at IW and IW + 1, respectively. On the other hand, more primitive magmas like Y 980459 could plausibly produce 0.12 and 1.2 bars at IW and IW + 1, respectively. Thus, if typical Martian volcanic activity was reduced and the melting conditions cool, then degassing of CO2 to the atmosphere may not be sufficient to create greenhouse conditions required by observations of liquid surface water. However, if a significant fraction of Martian magmas derive from hot and primitive sources, as may have been true during the formation of Tharsis in the late Noachian, that are also slightly oxidized (IW + 1.2), then significant contribution of volcanogenic CO2 to an early Martian greenhouse is plausible.  相似文献   

15.
Aragonite and calcite single crystals can be readily transformed into polycrystalline hydroxyapatite pseudomorphs by hydrothermal treatment in a (NH4)2HPO4 solution. Scanning electron microscopy of the reaction products showed that the transformation of aragonite to apatite is characterised by the formation of a sharp interface between the two phases and by the development of intracrystalline porosity in the hydroxyapatite phase. In addition, electron backscattered diffraction (EBSD) imaging showed that the c-axis of apatite is predominantly oriented perpendicular to the reaction front with no crystallographic relationship to the aragonite lattice. However, the Ca isotopic composition of the parent aragonite, measured by thermal ionization mass spectrometry was inherited by the apatite product.Hydrothermal experiments conducted with use of phosphate solutions prepared with water enriched in 18O (97%) further revealed that the 18O from the solution is incorporated in the product apatite, as measured by micro-Raman spectroscopy. Monitoring the distribution of 18O with Raman spectroscopy was possible because the incorporation of 18O in the PO4 group of apatite generates four new Raman bands at 945.8, 932, 919.7 and 908.8 cm−1, in addition to the ν1(PO4) symmetric stretching band of apatite located at 962 cm−1, which can be assigned to four 18O-bearing PO4 species. The relative intensities of these bands reflect the 18O content in the PO4 group of the apatite product. By using equilibrated and non-equilibrated solutions, with respect to the 18O distribution between aqueous phosphate and water, we could show that the concentration of 18O in the apatite product is linked to the degree of 18O equilibration in the solution. The textural and chemical observations are indicative of a coupled mechanism of aragonite dissolution and apatite precipitation taking place at a moving reaction interface.  相似文献   

16.
The dissolution rates of natural, well crystallized variscite (AlPO4·2H2O) were determined from the evolution of aqueous Al and P concentrations in closed and open-system mixed-flow reactors at 25 °C and pH from 1.5 to 9.0. Measured dissolution rates decrease with increasing pH, from 6 × 10−16 mol/cm2/s at pH 1.5 to 5 × 10−17 mol/cm2/s at pH 5.89, and then increase with increasing pH to 4 × 10−16 mol/cm2/s at pH 9.0. Geochemical modeling calculations, performed using measured dissolution rates, indicate that it would take no more than a few weeks or months to equilibrate a mildly acidic, Al and P-free solution with variscite. Hence, variscite can buffer aqueous phosphate concentrations in mildly acidic near surface environments. This conclusion is confirmed by consideration of the compositions of natural waters.  相似文献   

17.
Diffusion coefficients for oxygen and hydrogen were determined from a series of natural uraninite-H2O experiments between 50 and 700 °C. Under hydrous conditions there are two diffusion mechanisms: (1) an initial extremely fast-path diffusion mechanism that overprinted the oxygen isotopic composition of the entire crystals regardless of temperature and (2) a slower volume-diffusive mechanism dominated by defect clusters that displace or eject nearest neighbor oxygen atoms to form two interstitial sites and two partial vacancies, and by vacancy migration. Using the volume diffusion coefficients in the temperature range of 400-600 °C, diffusion coefficients for oxygen can be represented by D = 1.90e−5 exp (−123,382 J/RT) cm2/s and for temperatures between 100 and 300 °C the diffusion coefficients can be represented by D = 1.95e−10 exp (−62484 J/RT) cm2/s, where the activation energies for uraninite are 123.4 and 62.5 kJ/mol, respectively. Hydrogen diffusion in uraninite appears to be controlled by similar mechanisms as oxygen. Using the volume diffusion coefficients for temperatures between 50 and 700 °C, diffusion coefficients for hydrogen can be represented by D = 9.28e−6 exp (−156,528 J/RT) cm2/s for temperatures between 450 and 700 °C and D = 1.39e−14 exp (−34518 J/RT) cm2/s for temperatures between 50 and 400 °C, where the activation energies for uraninite are 156.5 and 34.5 kJ/mol, respectively.Results from these new experiments have implications for isotopic exchange during natural UO2-water interactions. The exceptionally low δ18O values of natural uraninites (i.e. −32‰ to −19.5‰) from unconformity-type uranium deposits in Saskatchewan, in conjunction with theoretical and experimental uraninite-water and UO3-water fractionation factors, suggest that primary uranium mineralization is not in oxygen isotopic equilibrium with coeval clay and silicate minerals. The low δ18O values have been interpreted as resulting from the low temperature overprinting of primary uranium mineralization in the presence of relatively modern meteoric fluids having δ18O values of ca. −18‰, despite petrographic and U-Pb isotope data that indicate limited alteration. Our data show that the anomalously low oxygen isotopic composition of the uraninite from the Athabasca Basin can be due to meteoric water overprinting under reducing conditions, and meteoric water or groundwater can significantly affect the oxygen isotopic composition of spent nuclear fuel in a geologic repository, with minimal change to the chemical composition or texture. Moreover, the rather fast oxygen and hydrogen diffusion coefficients for uraninite, especially at low temperatures, suggest that oxygen and hydrogen diffusion may impart characteristic isotopic signals that can be used to track the route of fissile material.  相似文献   

18.
Infrared spectroscopy has been used to study the speciation of CO2 in glasses near the NaAlO2-SiO2 join quenched from melts held at high temperatures and pressures. Absorption bands resulting from the antisymmetric stretches of both molecular CO2 (2,352 cm–1) and CO 3 2– (1,610 cm–1 and 1,375 cm–1) are observed in these glasses. The latter are attributed to distorted Na-carbonate ionic-complexes. Molar absorptivities of 945 liters/mole-cm for the molecular CO2 band, 200 liters/mole-cm for the 1,610 cm–1 band, and 235 liters/mole-cm for the 1,375 cm–1 band have been determined. These molar absorptivities allow the quantitative determination of species concentrations in the glasses with a precision on the order of several percent of the amount present. The accuracy of the method is estimated to be ±15–20% at present.The ratio of molecular CO2 to CO 3 2– in sodium aluminosilicate glasses varies little for each silicate composition over the range of total dissolved CO2 content (0–2%), pressure (15–33 kbar) and temperature (1,400–1,560° C) that we have studied. This ratio is, however, a strong function of silicate composition, increasing both with decreasing Na2O content along the NaAlO2-SiO2 join and with decreasing Na2O content in peraluminous compositions off the join.Infrared spectroscopic measurements of species concentrations in glasses provide insights into the molecular level processes accompanying CO2 solution in melts and can be used to test and constrain thermodynamic models of CO2-bearing melts. CO2 speciation in silicate melts can be modelled by equilibria between molecular CO2, CO 3 2– , and oxygen species in the melts. Consideration of the thermodynamics of such equilibria can account for the observed linear relationship between molecular CO2 and carbonate concentrations in glasses, the proposed linear relationship between total dissolved CO2 content and the activity of CO2 in melts, and observed variations in CO2 solubility in melts.  相似文献   

19.
Solubility and solution mechanisms of H2O in depolymerized melts in the system Na2O-Al2O3-SiO2 were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na2Si4O9-Na2(NaAl)4O9] with Al/(Al+Si) = 0.00-0.25. The H2O solubility was fitted to the expression, XH2O=0.20+0.0020fH2O-0.7XAl+0.9(XAl)2, where XH2O is the mole fraction of H2O (calculated with O = 1), fH2O the fugacity of H2O, and XAl = Al/(Al+Si). Partial molar volume of H2O in the melts, , calculated from the H2O-solulbility data assuming ideal mixing of melt-H2O solutions, is 12.5 cm3/mol for Al-free melts and decreases linearly to 8.9 cm3/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H2O, , increases with Al/(Al+Si).Solution mechanisms of H2O were obtained by combining Raman and 29Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H2O content. The rate of NBO/T-change with H2O is negatively correlated with H2O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q4-species to form Q2 species. Steric hindrance appears to restrict bonding of H+ with nonbridging oxygen in Q3 species. The presence of Al3+ does not affect the water solution mechanisms significantly.  相似文献   

20.
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   

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