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1.
Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H2O speciation and diffusion by dehydrating haploandesitic melts containing ?2.5 wt.% water at 743-873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H2O (H2Om) and hydroxyl group (OH)] and total H2O (H2Ot) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H2O speciation reaction H2Om+O?2OH, K = (XOH)2/(XH2OmXO) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547-2453/T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H2O concentration, contrary to previous H2O diffusion data in an andesitic melt at 1608-1848 K. The diffusion profiles are consistent with the model that molecular H2O is the diffusion species. Based on the above speciation model, H2Om and H2Ot diffusivity (in m2/s) in haploandesite at 743-873 K, 100 MPa, and H2Ot ? 2.5 wt.% can be formulated as
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3.
Bjorn O. Mysen 《Geochimica et cosmochimica acta》2007,71(22):5500-5513
The influence on olivine/melt transition metal (Mn, Co, Ni) partitioning of substitution in the tetrahedral network of silicate melt structure has been examined at ambient pressure in the 1450-1550 °C temperature range. Experiments were conducted in the systems NaAlSiO4-Mg2SiO4- SiO2 and CaAl2Si2O8-Mg2SiO4-SiO2 with about 1 wt% each of MnO, CoO, and NiO added. These compositions were used to evaluate how, in silicate melts, substitution and ionization potential of charge-balancing cations affect activity-composition relations in silicate melts and mineral/melt partitioning.The exchange equilibrium coefficient, , is a positive and linear function of melt Al/(Al + Si) at constant degree of melt polymerization, NBO/T. The is negatively correlated with the ionic radius, r, of the M-cation and also with the ionization potential (Z/r2, Z = electrical charge) of the cation that serves to charge-balance Al3+ in tetrahedral coordination in the melts. The activity coefficient ratio, (γM/γMg)melt, is therefore similarly correlated.These melt composition relationships are governed by the distribution of Al3+ among coexisting Q-species in the peralkaline (depolymerized) melts coexisting with olivine. This distribution controls Q-speciation abundance, which, in turn, controls (γM/γMg)melt and . The relations between melt structure and olivine/melt partitioning behavior lead to the suggestion that in natural magmatic systems mineral/melt partition coefficients are more dependent on melt composition and, therefore, melt structure the more alkali-rich and the more felsic the melt. Moreover, mineral/melt partition coefficients are more sensitive to melt composition the more highly charged or the smaller the ionic radius of the cation of interest. 相似文献
4.
H2O diffusion in dacitic melt was investigated at 0.48-0.95 GPa and 786-893 K in a piston-cylinder apparatus. The diffusion couple design was used, in which a nominally dry dacitic glass makes one half and is juxtaposed with a hydrous dacitic glass containing up to ∼8 wt.% total water (H2Ot). H2O concentration profiles were measured on quenched glasses with infrared microspectroscopy. The H2O diffusivity in dacite increases rapidly with water content under experimental conditions, similar to previous measurements at the same temperature but at pressure <0.15 GPa. However, compared with the low-pressure data, H2O diffusion at high pressure is systematically slower. H2O diffusion profiles in dacite can be modeled by assuming molecular H2O (H2Om) is the diffusing species. Total H2O diffusivity DH2Ot within 786-1798 K, 0-1 GPa, and 0-8 wt.% H2Ot can be expressed as: where DH2Ot is in m2/s, T is temperature in K, P is pressure in GPa, K = exp(1.49 − 2634/T) is the equilibrium constant of speciation reaction (H2Om+O?2OH) in the melt, X = C/18.015/[C/18.015 + (100 − C)/33.82], C is wt.% of H2Ot, and 18.015 and 33.82 g/mol correspond to the molar masses of H2O and anhydrous dacite on a single oxygen basis. Compared to H2O diffusion in rhyolite, diffusivity in dacite is lower at intermediate temperatures but higher at superliquidus temperatures. This general H2O diffusivity expression can be applied to a broad range of geological conditions, including both magma chamber processes and volcanic eruption dynamics from conduit to the surface. 相似文献
5.
Solubility and solution mechanism of H2O in alkali silicate melts and glasses at high pressure and temperature 总被引:2,自引:0,他引:2
The solubility behavior of H2O in melts in the system Na2O-SiO2-H2O was determined by locating the univariant phase boundary, melt = melt + vapor in the 0.8-2 GPa and 1000°-1300°C pressure and temperature range, respectively. The NBO/Si-range of the melts (0.25-1) was chosen to cover that of most natural magmatic liquids. The H2O solubility in melts in the system Na2O-SiO2-H2O (XH2O) ranges between 18 and 45 mol% (O = 1) with (∂XH2O/∂P)T∼14-18 mol% H2O/GPa. The (∂XH2O/∂P)T is negatively correlated with NBO/Si (= Na/Si) of the melt. The (∂XH2O/∂T)P is in the −0.03 to +0.05 mol% H2O/°C range, and is negatively correlated with NBO/Si. The [∂XH2O/∂(NBO/Si)]P,T is in the −3 to −8 mol% H2O/(NBO/Si) range. Melts with NBO/Si similar to basaltic liquids (∼0.6-∼1.0) show (∂XH2O/∂T)P<0, whereas more polymerized melts exhibit (∂XH2O/∂T)P>0. Complete miscibility between hydrous melt and aqueous fluid occurs in the 0.8-2 GPa pressure range for melts with NBO/Si ≤0.5 at T >1100°C. Miscibility occurs at lower pressure the more polymerized the melt. 相似文献
6.
Robert C. Newton 《Geochimica et cosmochimica acta》2006,70(22):5571-5582
Solubilities of corundum (Al2O3) and wollastonite (CaSiO3) were measured in H2O-NaCl solutions at 800 °C and 10 kbar and NaCl concentrations up to halite saturation by weight-loss methods. Additional data on quartz solubility at a single NaCl concentration were obtained as a supplement to previous work. Single crystals of synthetic corundum, natural wollastonite or natural quartz were equilibrated with H2O and NaCl at pressure (P) and temperature (T) in a piston-cylinder apparatus with NaCl pressure medium and graphite heater sleeves. The three minerals show fundamentally different dissolution behavior. Corundum solubility undergoes large enhancement with NaCl concentration, rising rapidly from Al2O3 molality (mAl2O3) of 0.0013(1) (1σ error) in pure H2O and then leveling off to a maximum of ∼0.015 at halite saturation (XNaCl ≈ 0.58, where X is mole fraction). Solubility enhancement relative to that in pure H2O, , passes through a maximum at XNaCl ≈ 0.15 and then declines towards halite saturation. Quenched fluids have neutral pH at 25 °C. Wollastonite has low solubility in pure H2O at this P and T(mCaSiO3=0.0167(6)). It undergoes great enhancement, with a maximum solubility relative to that in H2O at XNaCl ≈ 0.33, and solubility >0.5 molal at halite saturation. Solute silica is 2.5 times higher than at quartz saturation in the system H2O-NaCl-SiO2, and quenched fluids are very basic (pH 11). Quartz shows monotonically decreasing solubility from mSiO2=1.248 in pure H2O to 0.202 at halite saturation. Quenched fluids are pH neutral. A simple ideal-mixing model for quartz-saturated solutions that requires as input only the solubility and speciation of silica in pure H2O reproduces the data and indicates that hydrogen bonding of molecular H2O to dissolved silica species is thermodynamically negligible. The maxima in for corundum and wollastonite indicate that the solute products include hydrates and Na+ and/or Cl− species produced by molar ratios of reactant H2O to NaCl of 6:1 and 2:1, respectively. Our results imply that quite simple mechanisms may exist in the dissolution of common rock-forming minerals in saline fluids at high P and T and allow assessment of the interaction of simple, congruently soluble rock-forming minerals with brines associated with deep-crustal metamorphism. 相似文献
7.
Reports of the high ion content of steam and low-density supercritical fluids date back to the work of Carlon [Carlon H. R. (1980) Ion content of air humidified by boiling water.J. Appl.Phys.51, 171-173], who invoked ion and neutral-water clustering as mechanism to explain why ions partition into the low-density aqueous phase. Mass spectrometric, vibrational spectroscopic measurements and quantum chemical calculations have refined this concept by proposing strongly bound ion-solvent aggregates and water clusters such as Eigen- and Zundel-type proton clusters H3O+·(H2O)m and the more weakly bound water oligomers (H2O)m. The extent to which these clusters affect fluid chemistry is determined by their abundance, however, little is known regarding the stability of such moieties in natural low-density high-temperature fluids. Here we report results from quantum chemical calculations using chemical-accuracy multi-level G3 (Curtiss-Pople) and CBS-Q theory (Peterson) to address this question. In particular, we have investigated the cluster structures and clustering equilibria for the ions and H3S+·(H2O)m(H2S)n, where m ? 6 and n ? 4, at 300-1000 K and 1 bar as well as under vapor-liquid equilibrium conditions between 300 and 646 K. We find that incremental hydration enthalpies and entropies derived from van’t Hoff analyses for the attachment of H2O and H2S onto H3O+, and H3S+ are in excellent agreement with experimental values and that the addition of water to all three ions is energetically more favorable than solvation by H2S. As clusters grow in size, the energetic trends of cluster hydration begin to reflect those for bulk H2O liquids, i.e. calculated hydration enthalpies and entropies approach values characteristic of the condensation of bulk water (ΔHo = −44.0 kJ mol−1, ΔSo = −118.8 J K mol−1). Water and hydrogen sulfide cluster calculations at higher temperatures indicate that a significant fraction of H3O+, and H3S+ ions exists as solvated moieties. 相似文献
8.
Longitudinal acoustic velocities were measured at 1 bar in 10 Na2O-TiO2-SiO2 (NTS) liquids for which previous density and thermal expansion data are reported in the literature. Data were collected with a frequency-sweep acoustic interferometer at centered frequencies of 4.5, 5, and 6 MHz between 1233 and 1896 K; in all cases, the sound speeds decrease with increasing temperature. Six of the liquids have a similar TiO2 concentration (∼25 mol %), so that the effect of varying Na/Si ratio on the partial molar compressibility of the TiO2 component can be evaluated. Theoretically based models for βT and (∂V/∂P)T as a function of composition and temperature are presented. As found previously for the partial molar volume of TiO2 in sodium silicate melts, values of (13.7-18.8 × 10−2/GPa) vary systematically with the Na/Si and Na/(Si + Ti) ratio in the liquid. In contrast values of for the SiO2 and Na2O components (6.6 and 8.0 × 10−2/GPa, respectively, at 1573 K) are independent of composition. Na2O is the only component that contributes to the temperature dependence of the compressibility of NTS liquids (1.13 ± 0.04 × 10−4/GPa K). The results further indicate that the TiO2 component is twice as compressible as the Na2O and SiO2 components. The enhanced compressibility of TiO2 appears to be related to the abundance of five-coordinated Ti ([5]Ti) in these liquids, but not with a change in Ti coordination. Instead, it is proposed that the asymmetric geometry of [5]Ti in a square pyramidal site promotes different topological rearrangements in alkali titanosilicate liquids, which lead to the enhanced compressibility of TiO2. 相似文献
9.
Bjorn O. Mysen Kathryn Kumamoto Marilyn L. Fogel 《Geochimica et cosmochimica acta》2011,75(20):6183-6199
Solubility and solution mechanisms in silicate melts of oxidized and reduced C-bearing species in the C-O-H system have been determined experimentally at 1.5 GPa and 1400 °C with mass spectrometric, NMR, and Raman spectroscopic methods. The hydrogen fugacity, fH2, was controlled in the range between that of the iron-wüstite-H2O (IW) and the magnetite-hematite-H2O (MH) buffers. The melt polymerization varied between those typical of tholeiitic and andesitic melts.The solubility of oxidized (on the order of 1-2 wt% as C) and reduced carbon (on the order of 0.15-0.35 wt% as C) is positively correlated with the NBO/Si (nonbridging oxygen per silicon) of the melt. At given NBO/Si-value, the solubility of oxidized carbon is 2-4 times greater than under reducing conditions. Oxidized carbon dioxide is dissolved as complexes, whereas the dominant reduced species in melts are CH3-groups forming bonds with Si4+ together with molecular CH4. Formation of complexes results in silicate melt polymerization (decreasing NBO/Si), whereas solution of reduced carbon results in depolymerization of melts (increasing NBO/Si).Redox melting in the Earth’s interior has been explained with the aid of the different solution mechanisms of oxidized and reduced carbon in silicate melts. Further, effects of oxidized and reduced carbon on melt viscosity and on element partitioning between melts and minerals have been evaluated from relationships between melt polymerization and dissolved carbon combined with existing experimental data that link melt properties and melt polymerization. With total carbon contents in the melts on the order of several mol%, mineral/melt element partition coefficients and melt viscosity can change by several tens to several hundred percent with variable redox conditions in the range of the Earth’s deep crust and upper mantle. 相似文献
10.
Bjorn O. Mysen 《Geochimica et cosmochimica acta》2006,70(12):3121-3138
Olivine/melt partitioning of ΣFe, Fe2+, Mg2+, Ca2+, Mn2+, Co2+, and Ni2+ has been determined in the systems CaO-MgO-FeO-Fe2O3-SiO2 (FD) and CaO-MgO-FeO-Fe2O3-Al2O3-SiO2 (FDA3) as a function of oxygen fugacity (fO2) at 0.1 MPa pressure. Total iron oxide content of the starting materials was ∼20 wt%. The fO2 was to used to control the Fe3+/ΣFe (ΣFe: total iron) of the melts. The Fe3+/ΣFe and structural roles of Fe2+ and Fe3+ were determined with 57Fe resonant absorption Mössbauer spectroscopy. Changes in melt polymerization, NBO/T, as a function of fO2 was estimated from the Mössbauer data and existing melt structure information. It varies by ∼100% in melts coexisting with olivine in the FDA3 system and by about 300% in the FD system in the Fe3+/ΣFe range of the experiments (0.805-0.092). The partition coefficients ( in olivine/wt% in melt) are systematic functions of fO2 and, therefore, NBO/T of the melt. There is a -minimum in the FDA3 system at NBO/T-values corresponding to intermediate Fe3+/ΣFe (0.34-0.44). In the Al-free system, FD, where the NBO/T values of melts range between ∼1 and ∼2.9, the partition coefficients are positively correlated with NBO/T (decreasing Fe3+/ΣFe). These relationships are explained by consideration of solution behavior in the melts governed by Qn-unit distribution and structural changes of the divalent cations in the melts (coordination number, complexing with Fe3+, and distortion of the polyhedra). 相似文献
11.
Water diffusion in silicate melts is important for understanding bubble growth in magma, magma degassing and eruption dynamics of volcanos. Previous studies have made significant progress on water diffusion in silicate melts, especially rhyolitic melt. However, the pressure dependence of H2O diffusion is not constrained satisfactorily. We investigated H2O diffusion in rhyolitic melt at 0.95–1.9 GPa and 407–1629 °C, and 0.2–5.2 wt.% total water (H2Ot) content with the diffusion-couple method in a piston-cylinder apparatus. Compared to previous data at 0.1–500 MPa, H2O diffusivity is smaller at higher pressures, indicating a negative pressure effect. This pressure effect is more pronounced at low temperatures. Assuming H2O diffusion in rhyolitic melt is controlled by the mobility of molecular H2O (H2Om), the diffusivity of H2Om (DH2Om) at H2Ot ≤ 7.7 wt.%, 403–1629 °C, and ≤ 1.9 GPa is given by
DH2Om=D0exp(aX),