首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 78 毫秒
1.
Experiments reproducing the development of bimetasomatic zoning in the CaO-MgO-SiO2-H2O-CO2 system were conducted at elevated P-T parameters with the use of samples of naturally occurring quartzdolomite and calcite-serpentinite rocks. In order to maintain mass transfer exclusively via the diffusion-controlled mechanism, we used the method of the ensured compaction of the cylindrical sample surface with a thin-walled gold tube. In the course of the experiments, a single diopside zone ～2.5 × 10?5 m thick was obtained at the quartz-dolomite interface at T = 600°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.5 for 25–40 days and a succession of metasomatic zones at T = 750°C, $P_{H_2 O + CO_2 } $ = 300 MPa, and $X_{CO_2 } $ = 0.4 for 48 days. The metasomatic zones were as follows (listed in order from quartz to dolomite): wollastonite ‖ diopside ‖ tremolite ‖ calcite + forsterite; with the average width of the diopside zone equal to ～1.3 × 10?5 m and the analogous part of the wollastonite zone equal to ～2.6 × 10?5 m. Two zones (listed in order from calcite to serpentine) diopside and diopside-forsterite (the average widths of these zones were ～6 × 10?4 and ～8 × 10?4 m, respectively) were determined to develop at contact between serpentine and calcite during experiments that lasted 124 days at T = 500°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.2–0.4. In the former and latter situations, the growth rate of the zoning ranged between 3.1 × 10?12 and 1.2 × 10?11 m/s and between 5.6 × 10?11 and 7.5 × 10?11 m/s, respectively. The higher growth rate in the latter case can be explained by the higher water mole fraction in the fluid, with this water released during serpentinite decomposition in the experiments. The development of the only diopside zone in the experiments modeling the interaction of quartz and dolomite at T = 600–650°C and $P_{H_2 O + CO_2 } $ = 200 MPa is in conflict with theoretical considerations underlain by the Korzhinskii-Fisher-Joesten model. The interaction of quartz and dolomite in the CaO-MgO-SiO2-CO2-H2O system at the P-T- $X_{CO_2 } $ parameters specified above should be attended by the origin of a number of reaction zones consisting of various proportions of talc, forsterite, tremolite, diopside, and calcite. The saturation of the fluid with respect to these minerals was likely not reached, and this resulted in the degeneration of the respective stability fields in the succession of zones. Conceivably, this was related to the insufficient rates of quartz and dolomite dissolution and the relatively low diffusion rates of the dissolved species in the low-permeable medium. In the experiments with interacting calcite and serpentine, the zoning calcite ‖ diopside ‖ diopside + forsterite ‖ serpentine developed in its complete form, in agreement with the theory. Equilibrium was likely achieved in these experiments due to the higher diffusion coefficients.  相似文献   

2.
The nucleation of H2O bubbles in magmas has been proposed as a trigger for volcanic eruptions. To determine how bubbles nucleate heterogeneously in silicate melts, experiments were carried out in which high-silica rhyolitic melts were hydrated at 740-800°C and 50-175 MPa, decompressed by 20-70 MPa, and held at the lower pressures for ≥10 s before being quenched. The hydration conditions were subliquidus, and all samples contain blocky magnetite + needle-shaped hematite ± plagioclase. Magnetite is abundant at 800°C and high pressures, whereas hematite becomes more abundant at lower temperatures and pressures. Bubbles nucleated in a single event in all samples, with the number density (NT) of bubbles varying between 2 × 107 and 1 × 109 cm−3. At low degrees of supersaturation, one to a few bubbles nucleate on faces of magnetite, but at medium to high degrees of supersaturation, multiple bubbles nucleate on single magnetite grains. On hematite, one to a few bubbles nucleated at the ends of the needle-shaped crystals at medium supersaturations, but formed along their entire lengths at high supersaturations. NT increases as water diffusivity decreases, indicating that the number of bubbles nucleated is influenced by their growth, which depletes the melt with respect to H2O and lowers supersaturation. If volcanic eruptions are triggered by bubble formation in magmas stored in shallow-level magma chambers, then the supersaturations needed for heterogeneous nucleation suggest that only small amounts of crystallization are needed, whereas homogeneous nucleation is unlikely to trigger eruptions.  相似文献   

3.
The mechanism of the reaction 1 tremolite +3 calcite+2 quartz=5 diopside+3 CO2+1 H2O was investigated at 2 and 5 kb, , using powder experiments lasting from 14 to 170 days. Because experiments were at high ratios of fluid to solids, the study identified the mechanism under surface-control conditions and thus establishes which reactant surface determines the kinetics. To achieve a diopside nucleation rate high enough to gain detectable reaction in the time of experimentation, the equilibrium boundary had to be overstepped by 30°–60° C at 5 kb. Experiments in which diopside successfully nucleated show that the reaction proceeds by a dissolution-crystallization mechanism. Experimentally-produced textures are presented in a series of SEM images and demonstrate that diopside nucleates and grows topotactically exclusively on tremolite. The mechanism of the forward reaction is modeled by a simplified scheme consisting of three processes, each comprising formation, transport and incorporation of 1) the Ca-, 2) the Mg-, and 3) the Si-bearing species in the fluid in response to dissolution of the reactants and crystallization of diopside. Using the dependence of the overall-reaction rate on the surface area of the reactants, it was experimentally determined that process 2) (dissolution of tremolite, transport of the Mg-bearing species in the fluid and crystallization of diopside) will be rate-limiting in most cases where metamorphism occurs in an internally controlled system. Due to the experimental design chosen, the dissolution of tremolite at the beginning of process 2) is rate-limiting in the experiments. The magnitude of the probable temperature-overstep necessary to achieve a significant nucleation rate during metamorphism is discussed on the basis of the experimental evidence and a simple nucleation rate model.  相似文献   

4.
The cation exchange equilibrium has been investigated by hydrothermal experiments at 700 and 800°C at 200 MPa. To avoid equilibration problems of conventional exchange experiments, we synthesized amphiboles with an excess fluid allowing exchange between solid and fluid during the experiment. The exchangeable cations Na and K were provided as excess 1 to 2n chloridic solution. These exchange syntheses can be described by the reaction equation with (aq) for hydroxides and chlorides in aqueous solutions and ( s ) and ( p )?=?start and product fluid. The amphiboles grew in presence of the exchange fluid and adjusted their stoichiometry in equilibrium with the fluid phase. The solid products consist of more than 99% amphibole (Na,K-richteritess) with traces of diopside and quartz. The amphiboles are up to 1?mm long and often ≈ 40 μm thick. Detailed EMP- and HRTEM-observations show that they are chemically homogeneous and structurally wellordered. The experimental results give consistent phase relations in the reciprocal ternary system Na-richterite–K-richterite–NaCl–KCl. We analysed the product fluid with AAS- and ICP-methods. The Na-K distribution coefficients between fluid and amphiboles of the richterite–K-richterite join are close to unity at 700°C and 800°C at 200 MPa. Small systematic deviations are explained by a symmetric solution model for the A-position of the amphiboles. Using ideal mixing for H2O-NaCl-KCl fluids, a mixing model for the system richterite–K-richterite is presented. We suggest that the composition of richterite solid solutions can be used as a sensor for NaCl/KCl-ratios in metamorphic fluids.  相似文献   

5.
Dissolution experiments were conducted on {101?4} cleavage faces of calcite at various under-saturations to determine how the saturation state controls etch pit formation. Experimental observations were made by using in situ fluid cell Atomic Force Microscopy. Three dissolution modes were observed. When the saturation index Ω > 0.541, no etch pit formation was seen and dissolution primarily occurred at existing steps. When Ω decreased to Ωc = 0.541-0.410, the first visible pits appeared and continuous reduction in saturation state slowly increased the pit density on terraces while dissolution simultaneously proceeded at step edges. Finally, when the saturation state fell below Ωmax = ∼0.007, a precipitous increase in pit density took place that sharply contrasted to the ordered fashion of pit formation observed at saturation conditions above this level. These observations are interpreted to be two-dimensional and unassisted pit formation at Ω < ∼0.007, defect- and step-assisted dissolution in between Ω = 0.541 and 0.007, and existing step-induced dissolution for Ω > 0.541.The values of Ωc are in good agreement with the dislocation theory's predicted critical under-saturations for pit formation at line dislocations. The occurrence of Ωmax is not directly predicted but is a logical consequence of dissolution thermodynamics. These findings suggest that (1) dissolution near and far from equilibrium (i.e., Ω > Ωc, Ω < Ωmax) is not controlled by dislocations, therefore (2) dislocation density should significantly impact dissolution rate only in the saturation range of Ωmax < Ω < Ωc; (3) dissolution kinetics and chemical affinity of dissolution reactions should have a non-linear relationship: at sufficiently close to equilibrium, when dislocations cannot open up to form etch pits, the dissolution kinetics will be limited by the number of existing steps; at far from equilibrium, when pits are able to form in defect-free regions, the dissolution rate will be capped by the maximum number of achievable steps.These findings may provide explanations for several well-observed geochemical relationships, including the weak dependence of dissolution rate upon dislocation density in distilled water and the ‘plateau’ behavior of dissolution kinetics both near and far from equilibrium. The explosive occurrence of unassisted pit nucleation at Ω ∼ Ωmax is not predicted by the current dissolution rate equations. This suggests that an accurate ‘general’ rate law describing universal dissolution processes has yet to be developed.  相似文献   

6.
The dissolution behavior of two biogenic Mg-calcites, the echinoid, Tripneustes (12 mol% MgCO3), and the red alga, Neogoniolithon (18 mol% MgCO3 plus brucite), was studied using free-drift methods in distilled water and phosphate-spiked solutions at 25°C and PCO2 = 1 atm. Small concentrations of phosphate strongly inhibit dissolution rates. Inhibition increases with increased phosphate levels and with approach toward saturation. Near saturation, dissolution rates are reduced by 103 by the presence of 0.6 μmol adsorbed-P/m2. The magnitude of phosphate inhibition is similar to that observed for low-Mg calcite, and like calcite, the mechanism of inhibition is probably by adsorption of P at surface kink sites. Phosphate appears to inhibit removal of Mg and Ca equally during Mg-calcite dissolution. Rates of brucite dissolution are unaffected by phosphate.Mg-calcites containing >8.5 mol% MgCO3 should be thermodynamically unstable relative to aragonite in most natural waters. Recent work, however, shows that in contrast to its effect on the behavior of Mg-calcites. phosphate does not inhibit aragonite dissolution. The presence of phosphate might thus reverse the relative stability of these two minerals during diagenesis of shallow marine carbonate sediments.  相似文献   

7.
We have used a direct imaging technique, in situ atomic force microscopy (AFM), to observe the dissolution of the basal biotite surface by oxalic acid over a range of temperatures close to ambient conditions, using a specially designed AFM liquid cell and non-invasive intermittent contact mode of operation. From the 3-dimensional nanometre-resolution data sets, we observe a process characterised by the slow formation of shallow etch pits in the (0 0 1) surface and fast growth of etch pits from the resulting steps, which represent proxies for the {h k 0} surface. Measurements of dissolution rates as a function of temperature allow a determination of an apparent activation energy (Ea,app) for the process, via mass-loss calculations from image analysis. We obtain a value of Ea,app = 49 ± 2 kJ mol−1, which is consistent with separate calculations based on planar area etch pit growth, and measurements of etch pit perimeters, indicating that this value of Ea,app is representative of {h k 0} surface dissolution. The measurement of etch pit perimeters also enables an estimation of apparent activation energy as a function of step density indicating substantially higher apparent activation energy, up to Ea,app = 140 kJ mol−1, on extrapolation towards a pristine surface with no defects. We suggest that this higher value of Ea,app represents the slow formation of etch pits into the (0 0 1) surface.  相似文献   

8.
The dissolution kinetics of shallow water marine carbonates (low-Mg calcite, aragonite and Mg-calcites) were investigated in seawater (S = 35) at 25°C and a PCO2 of 10?2.5 atm. using the pH-stat method. Carbonate dissoluton rates (μmoles g?1 hr?1) fit the empirical kinetic expression, R = k(1 - Ω)n, where R = dissolution rate, k = rate constant, Ω = saturation state, and n = order of reaction. Reaction orders were near 2.9 for low-Mg calcites, 2.5 for aragonites and 3.4 for Mg-calcites.The rate constant, k, expressed as μmoles g?1 hr?1, varied by nearly a factor of ten for the different samples, reflecting differences in amount of reactive surface area. Reactive surface area of the biogenic phases ranged from 0.3% to 66% of the total surface area determined by the BET gas adsorption method. The discrepancy between reactive and total surface area was greatest for samples with high BET surface areas (> 1 m2 g?1) and delicate microstructures.Relative dissolution rates of the various biogenic carbonates as a function of seawater calcium carbonate ion molal product (IMP) were related to both mineral stability and grain microstructure. In seawater undersaturated with respect to aragonite, finely crystalline aragonites dissolved more rapidly than thermodynamically less stable high Mg-calcites (15–18 mole% MgCO3) with lower reactive surface areas. Therefore, under certain conditions, differences in grain microstructural complexity can override thermodynamic constraints and lead to selective dissolution of a thermodynamically more stable mineral phase.  相似文献   

9.
The solubility and dissolution kinetics of apatite in felsic melts at 850°–1500°C have been examined experimentally by allowing apatite crystals to partially dissolve into apatite-undersaturated melts containing 0–10 wt% water. Analysis of P and Ca gradients in the crystal/melt interfacial region enables determination of both the diffusivities and the saturation levels of these components in the melt. Phosphorus diffusion was identified as the rate-limiting factor in apatite dissolution. Results of four experiments at 8 kbar run in the virtual absence of water yield an activation energy (E) for P diffusion of 143.6 ± 2.8 kcal-mol?1 and frequency factor (D0) of 2.23+2.88?1.26 × 109cm2-sec?1. The addition of water causes dramatic and systematic reduction of both E and D0 such that at 6 wt% H2O the values are ~25 kcal-mol?1 and 10?5 cm2-sec?1, respectively. At 1300°C, the diffusivity of P increases by a factor of 50 over the first 2% of water added to the melt, but rises by a factor of only two between 2 and 6%, perhaps reflecting the effect of a concentration-dependent mechanism of H2O solution. Calcium diffusion gradients do not conform well to simple diffusion theory because the release of calcium at the dissolving crystal surface is linked to the transport rate of phosphorus in the melt, which is typically two orders of magnitude slower than Ca. Calcium chemical diffusion rates calculated from the observed gradients are about 50 times slower than calcium tracer diffusion.Apatite solubilities obtained from these experiments, together with previous results, can be described as a function of absolute temperature (T) and melt composition by the expression: In Dapatite/meltP = [(8400 + ((SiO2 ? 0.5)2.64 × 104))/T] ? [3.1 + (12.4(SiO2 ? 0.5))] where SiO2 is the weight fraction of silica in the melt. This model appears to be valid between 45% and 75% SiO2, 0 and 10% water, and for the range of pressures expected in the crust.The diffusivity information extracted from the experiments can be directly applied to several problems of geochemical interest, including I) dissolution times for apatite during crustal anatexis, and 2) pileup of P, and consequent local saturation in apatite, at the surfaces of growing major-mineral phases.  相似文献   

10.
Aragonite was converted to calcite in dilute CaCl2 fluid at temperatures ranging from 50 to 100°C. Surface areas of aragonite and calcite seed crystals were varied by over an order of magnitude to permit independent assessment of calcite nucleation and growth processes. Aragonite conversion rates were measured using isotopic attenuation of dissolved 44Ca, which was added to the fluid at the beginning of each experiment. Measured conversion rates were found to be constant with respect to time and proportional to the initial surface area of aragonite. Rates were independent of the surface area of calcite seed crystals owing to heterogeneous nucleation of calcite on aragonite during experiments. The data imply that calcite nucleates on aragonite surfaces until the level of saturation with respect to calcite reaches a critical threshold value where further nucleation is precluded. Thereafter, conversion to calcite occurs at a steady state rate consistent with aragonite dissolution at a fixed level of saturation. Aragonite converts to calcite under these conditions and in dilute fluids at rates of approximately 10 and 100 microns/yr at 25 and 100°C, respectively.  相似文献   

11.
  相似文献   

12.
Perovskite-type compounds in the series tausonite-loparite, (Sr1?2 x Na x La x )TiO3, were synthesized by solid-state reaction (final heating at 1200–1300?°C), and studied using “conventional” and synchrotron X-ray powder diffractometry. The structures of intermediate compositions were determined using the Rietveld profile refinement method. In the compositional range 0?≤x?≤ 0.1, the series comprises perovskites characterized by an undistorted cubic structure (space group Pm3¯m, a?≈ 3.905–3.902?Å, Z?=?1). Intermediate compounds in the range 0.15?≤?x?≤?0.35 crystallize with tetragonal symmetry (I4/mcm, a?≈? , c?≈? , Z?=?4) derived from the cubic aristotype by antiphase rotation of the TiO6 octahedra about a fourfold axis. The angle of rotation estimated from the positional parameters of oxygen atoms ranges from 2.5(7)° to 5.5(4)°. The cubic-to-tetragonal transition arises from substitution of Sr2+ by the comparatively smaller Na1+ and La3+ cations. A further transition from the tetragonal to rhombohedral symmetry (R3¯c, a?≈? , c?≈?2 , Z?=?6) occurs between x?=?0.35 and 0.40, and apparently does not involve formation of perovskite with an intermediate two-tilt structure (Imma). The rhombohedral structure is characterized by a multicomponent octahedral tilt about a threefold axis ranging in magnitude from 6.5(2)° to 7.7(2)°. In the series (Sr1?2 x Na x La x )TiO3, the unit-cell dimensions decrease, and the degree of structural distortion increases with x.  相似文献   

13.
The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca2+, Mg2+, and Si(OH)4 and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M2 structural sites. Loss mainly from M2 sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca2+ and/or Mg2+ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on aH+ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.  相似文献   

14.
The temperature dependence of diffusion is usually found to follow the Arrhenius law: D = D0e?E/RT Winchell (1969) showed that there is commonly an inter-dependence between D0 and E (for diffusion in silicate glasses), such that diffusion of different species show a positive correlation on a log D0 vs E plot. A similar effect was noted by Hofmann (1980) for cation diffusion in basalt. This implies that diffusion rates of different species tend to converge at a particular temperature; this effect is known as the ‘compensation effect’. I will show that this effect is also present for diffusion in feldspars and olivines. The equations for the compensation lines (with E given in kcal/mol) are: basalt—E = 50 + 7.5 log D0 feldspar—E = 50.7 + 3.4 log D0 olivine—E = 78.0 + 7.5 log D0 The convergence, or crossover, temperatures for diffusion in various materials are: obsidian—3400°C basalt—1370°C olivine—1360°C feldspar—460°C Compensation plots are useful for evaluating and comparing experimental diffusion data (though of limited usefulness in a predictive sense) and for understanding ‘closure temperatures’ for diffusion in petrogenetic processes (since closure temperature, the temperature at which natural diffusion processes are frozen in, is dependent on E, log d0, and cooling rate). I show that most diffusing species in feldspar have a closure-temperature close to the crossover or convergence temperature, implying that all species in feldspars can be expected to ‘freeze-in’ simultaneously at temperatures in the range 400–600°C (for cooling rates in the range 101–105°C/myr). Closure temperatures of various species in olivine, on the other hand, span a much larger range (800°C) for a similar range in cooling rates, implying that different elements in olivine will record different time-temperature stages in petrogenetic processes.  相似文献   

15.
The intracrystalline diffusion rate of oxygen in diopside was constrained based on natural isotopic variations from a granulite facies marble from Cascade Slide, Adirondacks (New York, USA). The oxygen isotope compositions of the diopsides, measured as a function of grain size, are nearly constant (20.9 ± 0.3‰ vs. SMOW) over the entire measured size range (0.3–3.2 mm diameter). The δ18O values of the cores of calcite grains are 23.0‰. Temperature estimates based on the Δ18O(calcite-diopside) are 800d?C, in agreement with the highest previous thermometric estimates for these rocks. The lack of isotopic variation in the diopsides as a function of grain size requires that the oxygen intracrystalline diffusion rate in diopside from the Adirondack samples was very slow. The maximum diffusion rates (D800d?C parallel to the c-axis) were calculated with an infinite reservoir model (IRM) and a finite reservoir model (FRM) that incorporates mineral modal abundances and initial isotopic variations. For an assumed activation energy (Q) = 100 kJ/mol, the IRM diffusion rate estimate of 1.6 times 10-20cm2/s is two orders of magnitude faster than from the FRM; at Q=500kJ/mol, the D800d?C estimate for both methods is c. 5.6 times 10-20 cm2/s. The present results require that a hydrothermal fluid significantly enhances the diffusion rate of oxygen in diopside if previous data are correct. The δ18O(SMOW) and δ13C(PDB) values of the calcite, measured in situ with a CO2 laser, are 22.9 ± 0.3, 0.1±0.3‰ in the grain cores, 22.1 ±0.3, 0.2 ±0.1‰ at the grain boundaries and 21.7 ±0.4, -0.6±0.1‰ abutting diopside grains. The δ18O and δ13δC values measured conventionally are: crystal cores, 22.96, -0.95‰; abutting diopside grains, 22.38, -0.93‰; bulk, 22.79, -0.95%. Use of the bulk δ18O(calcite) values for thermometry yields unreasonably high temperatures. The lower δ18O values at the calcite grain boundaries are not due to retrograde diffusional exchange with the diopside, they are thought to be a result of a late retrograde fluid infiltration.  相似文献   

16.
The molar volumes of 19 hydrous albitic liquids (1.9 to 6.1 wt% H2Ototal) were determined at one bar and 505–765 K. These volume data were derived from density measurements on hydrous glasses at 298 K, followed by measurements of the thermal expansion of each glass from 298 K to its respective glass transition temperature. The technique exploits the fact that the volume of a glass is equal to that of the corresponding liquid at the limiting fictive temperature (T f′), and that T f′ can be approximated as the temperature near the onset of the rapid increase in thermal expansion that occurs in the glass transition interval. The volume data of this study were combined with available volume data for anhydrous, Na2O-Al2O3-SiO2 liquids to derive the partial molar volume (±1) of the H2O component in an albitic melt at ∼565 K and one bar. To extend the determination of to higher temperatures and pressures, the molar volumes of the hydrous albitic liquids determined in this study were combined with those measured by previous authors at 1023–1223 K and 480–840 MPa, leading to the following fitted values (±1) at 1673 K and one bar: (±0.46)×10−3 cm−3/mol-K, and dVˉ H 2 O total /dP=−3.82 (±0.36)×10−4 cm3/mol-bar. The measured molar volumes of this study and those of previous authors can be recovered with a standard deviation of 0.5%, which is within the respective experimental errors. There is a significant difference between the values for derived in this study as a function of temperature and pressure and those obtained from an existing polynomial, primarily caused by the previous absence of accurate density measurements on anhydrous silicate liquids. The coefficients of thermal expansion (=4.72×10−4/K) and isothermal compressibility ( T =1.66×10−5/bar) for the H2O component at 1273 K and 100 MPa, indicate that H2Ototal is the single most expansive and compressible component in silicate liquids. For example, at 1473 K and 70 MPa (conditions of a mid-ocean ridge crustal magma chamber), the presence of just 0.4 wt% H2O will decrease the density of a basaltic liquid by more than one percent. An equivalent decrease in melt density could be achieved by increasing the temperature by 175 degrees or the decreasing pressure by 230 MPa. Therefore, even minor quantities of dissolved water will have a marked effect on the dynamic properties of silicate liquids in the crustal environment. Received: 20 August 1996 / Accepted: 15 March 1997  相似文献   

17.
The concentrations and behavior of oxygen and oxide ion were studied in silicate melts of composition CaO · MgO · xSiO2 (1.25 ≤ x ≤ 3) in the temperature range 1425 to 1575°C by cyclic voltammetry and chronopotentiometry. Electroreduction of oxygen is a reversible, 2 electron process involving dissociated oxygen atoms. The Henry's Law constant for O2 in molten diopside (CaO · MgO · 2SiO2) is 0.023 ± 0.004 mole/l atm at 1450°C. The diffusion coefficient for molecular oxygen in diopside melt is 4.5 ± .5 × 10?6 cm2/sec at 1450°C and the activation energy of diffusion is 80 ± 2 kcal/mole. Oxide ions produced by electroreduction of oxygen, rapidly dissociate silicate polymers, causing the concentration of free oxide ions in diopside melt to be buffered at a low level (4.7 ± .8 × 10?5 mole/l). The concentration of free oxide ion increases at higher proportions of metal oxides but remains at this value in more silicic melts. The rate of formation of oxide ions by polymerization in diopside melt is 0.021 ± .007 mole/l sec. Thermodynamic parameters (the standard free energy, enthalpy and entropy) for the oxidation of Ni, Co, and Zn in diopside melt in equilibrium with gaseous oxygen agree with those for solid oxide systems. The platinum reference electrode in molten diopside is a reversible, oxygen electrode.  相似文献   

18.
The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K1.38Na0.05)(Al2.87Mg0.46Fe3+0.39Fe2+0.28Ti0.07)[Si7.02Al0.98]O20(OH)4 was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H2SO4) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K+ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na+ from the solution and K+ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower RAl (dissolution rate calculated from steady state Al release) than RSi (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.  相似文献   

19.
Synthetic, flux-grown uvarovite, Ca3Cr2 [SiO4]3, was investigated by optical methods, electron microprobe analysis, UV-VIS-IR microspectrometry, and luminescence spectroscopy. The crystal structure was refined using single-crystal X-ray CCD diffraction data. Synthetic uvarovite is optically isotropic and crystallizes in the “usual” cubic garnet space group Ia3¯d [a=11.9973 Å, Z=8; 21524 reflections, R1=2.31% for 454 unique data and 18 variables; Cr–O=1.9942(6), Si–O=1.6447(6), Ca–Oa=2.3504(6), Ca–Ob= 2.4971(6) Å]. The structure of Ca3Cr2[SiO4]3 complies with crystal-chemical expectations for ugrandite group garnets in general as well as with predictions drawn from “cubically averaged” data of non-cubic uvarovite–grossular solid solutions (Wildner and Andrut 2001). The electronic absorption spectra of Cr3+ in trigonally distorted octahedra of synthetic uvarovite were analyzed in terms of the superposition model (SM) of crystal fields. The resulting SM and interelectronic repulsion parameters are =9532 cm?1, =4650 cm?1, power law exponent t 4=6.7, Racah B35=703 cm?1 at 290 K (reference distance R 0=1.995 Å; fixed power law exponent t 2=3 and spin-orbit parameter ζ=135 cm?1). The interelectronic repulsion parameters Racah B 55=714 cm?1 and C=3165 cm?1 were extracted from spin-forbidden transitions. This set of SM parameters was subsequently applied to previously well-characterized natural uvarovite–grossular solid solutions (Andrut and Wildner 2001a; Wildner and Andrut 2001) using their extrapolated Cr–O bond lengths to calculate the energies of the spin-allowed bands. These results are in very good agreement with the experimentally determined band positions and indicate the applicability of the superposition model to natural 3d N prevailing systems in geosciences. Single-crystal IR absorption spectra of synthetic uvarovite in the region of the OH-stretching vibration exhibit one isotropic absorption band at 3508 cm?1 at ambient conditions, which shifts to 3510 cm?1 at 77 K. This band is caused by structurally incorporated hydroxyl groups via the (O4H4)-hydrogarnet substitution. The water content, calculated using an integral extinction coefficient ?=60417 cm?2 l mol?1, is c H2O=33 ppm.  相似文献   

20.
Calcite dissolution rates were measured as a function of saturation state in NaCl–CaCl2–MgCl2 solutions at 1 bar (0.1 MPa) pCO2 and 25 °C. Rates measured in phosphate- and sulfate-free pseudo-seawater (Ca2+:Mg2+= 0.2, I= 0.7) were compared with those in synthetic brines. The brines were prepared by co-varying calcium and magnesium (Ca2+:Mg2+= 0.9; 2.0; 2.8; 3.1; 4.8; 5.8) along with ionic strength (I= 0.9; 1.1; 1.6; 2.1; 3.0; 3.7; 4.4 m) to yield solutions approximating those of subsurface formation waters. The rate data were modeled using the equation, R = k(1 ? Omega;) n , where k is the empirical rate constant, n describes the order of the reaction and ω is saturation state. For rates measured in the pseudo-seawater, n= 1.5 and k= 4.7 × 10?2 mol m?2 hr?1. In general, rates were not significantly faster in the synthetic brines (n= 1.4 ± 0.2 and k= 5.0 ± 7 × 10?2 mol m?2 hr?1). The rate coefficients agree within experimental error indicating that they are independent of ionic strength and Ca2+:Mg2+ over a broad range of brine compositions. These findings have important application to reaction-transport modeling because carbonate bearing saline reservoirs have been identified as potential repositories for CO2 sequestration.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号