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 31 毫秒
1.
Experiments were conducted to determine the water solubility of alkali basalts from Etna, Stromboli and Vesuvius volcanoes, Italy. The basaltic melts were equilibrated at 1,200°C with pure water, under oxidized conditions, and at pressures ranging from 163 to 3,842 bars. Our results show that at pressures above 1 kbar, alkali basalts dissolve more water than typical mid-ocean ridge basalts (MORB). Combination of our data with those from previous studies allows the following simple empirical model for the water solubility of basalts of varying alkalinity and fO2 to be derived: \textH 2 \textO( \textwt% ) = \text H 2 \textO\textMORB ( \textwt% ) + ( 5.84 ×10 - 5 *\textP - 2.29 ×10 - 2 ) ×( \textNa2 \textO + \textK2 \textO )( \textwt% ) + 4.67 ×10 - 2 ×\Updelta \textNNO - 2.29 ×10 - 1 {\text{H}}_{ 2} {\text{O}}\left( {{\text{wt}}\% } \right) = {\text{ H}}_{ 2} {\text{O}}_{\text{MORB}} \left( {{\text{wt}}\% } \right) + \left( {5.84 \times 10^{ - 5} *{\text{P}} - 2.29 \times 10^{ - 2} } \right) \times \left( {{\text{Na}}_{2} {\text{O}} + {\text{K}}_{2} {\text{O}}} \right)\left( {{\text{wt}}\% } \right) + 4.67 \times 10^{ - 2} \times \Updelta {\text{NNO}} - 2.29 \times 10^{ - 1} where H2OMORB is the water solubility at the calculated P, using the model of Dixon et al. (1995). This equation reproduces the existing database on water solubilities in basaltic melts to within 5%. Interpretation of the speciation data in the context of the glass transition theory shows that water speciation in basalt melts is severely modified during quench. At magmatic temperatures, more than 90% of dissolved water forms hydroxyl groups at all water contents, whilst in natural or synthetic glasses, the amount of molecular water is much larger. A regular solution model with an explicit temperature dependence reproduces well-observed water species. Derivation of the partial molar volume of molecular water using standard thermodynamic considerations yields values close to previous findings if room temperature water species are used. When high temperature species proportions are used, a negative partial molar volume is obtained for molecular water. Calculation of the partial molar volume of total water using H2O solubility data on basaltic melts at pressures above 1 kbar yields a value of 19 cm3/mol in reasonable agreement with estimates obtained from density measurements.  相似文献   

2.
The onset of hydrous partial melting in the mantle above the transition zone is dictated by the H2O storage capacity of peridotite, which is defined as the maximum concentration that the solid assemblage can store at P and T without stabilizing a hydrous fluid or melt. H2O storage capacities of minerals in simple systems do not adequately constrain the peridotite water storage capacity because simpler systems do not account for enhanced hydrous melt stability and reduced H2O activity facilitated by the additional components of multiply saturated peridotite. In this study, we determine peridotite-saturated olivine and pyroxene water storage capacities at 10–13 GPa and 1,350–1,450°C by employing layered experiments, in which the bottom ~2/3 of the capsule consists of hydrated KLB-1 oxide analog peridotite and the top ~1/3 of the capsule is a nearly monomineralic layer of hydrated Mg# 89.6 olivine. This method facilitates the growth of ~200-μm olivine crystals, as well as accessory low-Ca pyroxenes up to ~50 μm in diameter. The presence of small amounts of hydrous melt ensures that crystalline phases have maximal H2O contents possible, while in equilibrium with the full peridotite assemblage (melt + ol + pyx + gt). At 12 GPa, olivine and pyroxene water storage capacities decrease from ~1,000 to 650 ppm, and ~1,400 to 1,100 ppm, respectively, as temperature increases from 1,350 to 1,450°C. Combining our results with those from a companion study at 5–8 GPa (Ardia et al., in prep.) at 1,450°C, the olivine water storage capacity increases linearly with increasing pressure and is defined by the relation C\textH2 \textO\textolivine ( \textppm ) = 57.6( ±16 ) ×P( \textGPa ) - 169( ±18 ). C_{{{\text{H}}_{2} {\text{O}}}}^{\text{olivine}} \left( {\text{ppm}} \right) = 57.6\left( { \pm 16} \right) \times P\left( {\text{GPa}} \right) - 169\left( { \pm 18} \right). Adjustment of this trend for small increases in temperature along the mantle geotherm, combined with experimental determinations of D\textH2 \textO\textpyx/olivine D_{{{\text{H}}_{2} {\text{O}}}}^{\text{pyx/olivine}} from this study and estimates of D\textH2 \textO\textgt/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{gt}}/{\text{olivine}}}} , allows for estimation of peridotite H2O storage capacity, which is 440 ± 200 ppm at 400 km. This suggests that MORB source upper mantle, which contains 50–200 ppm bulk H2O, is not wet enough to incite a global melt layer above the 410-km discontinuity. However, OIB source mantle and residues of subducted slabs, which contain 300–1,000 ppm bulk H2O, can exceed the peridotite H2O storage capacity and incite localized hydrous partial melting in the deep upper mantle. Experimentally determined values of D\textH2 \textO\textpyx/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{pyx}}/{\text{olivine}}}} at 10–13 GPa have a narrow range of 1.35 ± 0.13, meaning that olivine is probably the most important host of H2O in the deep upper mantle. The increase in hydration of olivine with depth in the upper mantle may have significant influence on viscosity and other transport properties.  相似文献   

3.
The in situ electrical conductivity of hydrous garnet samples (Py20Alm76Grs4–Py73Alm14Grs13) was determined at pressures of 1.0–4.0 GPa and temperatures of 873–1273 K in the YJ-3000t apparatus using a Solartron-1260 impedance/gain-phase analyzer for various chemical compositions and oxygen fugacities. The oxygen fugacity was controlled by five solid-state oxygen buffers (Fe2O3 + Fe3O4, Ni + NiO, Fe + Fe3O4, Fe + FeO, and Mo + MoO2). Experimental results indicate that within a frequency range from 10−2 to 106 Hz, electrical conductivity is strongly dependent on signal frequency. Electrical conductivity shows an Arrhenius increase with temperature. At 2.0 GPa, the electrical conductivity of anhydrous garnet single crystals with various chemical compositions (Py20Alm76Grs4, Py30Alm67Grs3, Py56Alm43Grs1, and Py73Alm14Grs13) decreases with increasing pyrope component (Py). With increasing oxygen fugacity, the electrical conductivity of dry Py73Alm14Grs13 garnet single crystal shows an increase, whereas that of a hydrous sample with 465 ppm water shows a decrease, both following a power law (exponents of 0.061 and −0.071, respectively). With increasing pressure, the electrical conductivity of this hydrous garnet increases, along with the pre-exponential factors, and the activation energy and activation volume of hydrous samples are 0.7731 ± 0.0041 eV and −1.4 ± 0.15 cm3/mol, respectively. The results show that small hopping polarons ( \textFe\textMg · ) \left( {{\text{Fe}}_{\text{Mg}}^{ \cdot } } \right) and protons ( \textH · {\text{H}}^{ \cdot } ) are the dominant conduction mechanisms for dry and wet garnet single crystals, respectively. Based on these results and the effective medium theory, we established the electrical conductivity of an eclogite model with different mineral contents at high temperatures and high pressures, thereby providing constraints on the inversion of field magnetotelluric sounding results in future studies.  相似文献   

4.
Sekaninaite (XFe > 0.5)-bearing paralava and clinker are the products of ancient combustion metamorphism in the western part of the Kuznetsk coal basin, Siberia. The combustion metamorphic rocks typically occur as clinker beds and breccias consisting of vitrified sandstone–siltstone clinker fragments cemented by paralava, resulting from hanging-wall collapse above burning coal seams and quenching. Sekaninaite–Fe-cordierite (XFe = 95–45) is associated with tridymite, fayalite, magnetite, ± clinoferrosilite and ±mullite in paralava and with tridymite and mullite in clinker. Unmelted grains of detrital quartz occur in both rocks (<3 vol% in paralavas and up to 30 vol% in some clinkers). Compositionally variable siliceous, K-rich peraluminous glass is <30% in paralavas and up to 85% in clinkers. The paralavas resulted from extensive fusion of sandstone–siltstone (clinker), and sideritic/Fe-hydroxide material contained within them, with the proportion of clastic sediments ≫ ferruginous component. Calculated dry liquidus temperatures of the paralavas are 1,120–1,050°C and 920–1,050°C for clinkers, with calculated viscosities at liquidus temperatures of 101.6–7.0 and 107.0–9.8 Pa s, respectively. Dry liquidus temperatures of glass compositions range between 920 and 1,120°C (paralava) and 920–960°C (clinker), and viscosities at these temperatures are 109.7–5.5 and 108.8–9.7 Pa s, respectively. Compared with worldwide occurrences of cordierite–sekaninaite in pyrometamorphic rocks, sekaninaite occurs in rocks with XFe (mol% FeO/(FeO + MgO)) > 0.8; sekaninaite and Fe-cordierite occur in rocks with XFe 0.6–0.8, and cordierite (XFe < 0.5) is restricted to rocks with XFe < 0.6. The crystal-chemical formula of an anhydrous sekaninaite based on the refined structure is | \textK0.02 |(\textFe1.542 + \textMg0.40 \textMn0.06 )\Upsigma 2.00M [(\textAl1.98 \textFe0.022 + \textSi1.00 )\Upsigma 3.00T1 (\textSi3.94 \textAl2.04 \textFe0.022 + )\Upsigma 6.00T2 \textO18 ]. \left| {{\text{K}}_{0.02} } \right|({\text{Fe}}_{1.54}^{2 + } {\text{Mg}}_{0.40} {\text{Mn}}_{0.06} )_{\Upsigma 2.00}^{M} [({\text{Al}}_{1.98} {\text{Fe}}_{0.02}^{2 + } {\text{Si}}_{1.00} )_{\Upsigma 3.00}^{T1} ({\text{Si}}_{3.94} {\text{Al}}_{2.04} {\text{Fe}}_{0.02}^{2 + } )_{\Upsigma 6.00}^{T2} {\text{O}}_{18} ].  相似文献   

5.
The addition of Fe and Cr to the simple system MgO-SiO2-Al2O3 markedly affects the activities of phases involved in the equilibrium
\textMg\text2 \textSiO\text4 \text + MgAl\text2 \textSiO\text6 \text = MgAl\text2 \textO\text4 \text + Mg\text2 \textSi\text2 \textO\text6 \textOlivine + Opx\textsolid solution \text = Spinel + Opx\textsolid solution \begin{gathered} {\text{Mg}}_{\text{2}} {\text{SiO}}_{\text{4}} {\text{ + MgAl}}_{\text{2}} {\text{SiO}}_{\text{6}} {\text{ = MgAl}}_{\text{2}} {\text{O}}_{\text{4}} {\text{ + Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} \hfill \\ {\text{Olivine + Opx}}_{{\text{solid solution}}} {\text{ = Spinel + Opx}}_{{\text{solid solution}}} \hfill \\ \end{gathered}  相似文献   

6.
Sogdianite, a double-ring silicate of composition ( \textZr0. 7 6 \textTi0. 3 84 + \textFe0. 7 33 + \textAl0.13 )\Upsigma = 2 ( \square 1. 1 5 \textNa0. 8 5 )\Upsigma = 2 \textK[\textLi 3 \textSi 1 2 \textO 30 ] ( {\text{Zr}}_{0. 7 6} {\text{Ti}}_{0. 3 8}^{4 + } {\text{Fe}}_{0. 7 3}^{3 + } {\text{Al}}_{0.13} )_{\Upsigma = 2} \left( {\square_{ 1. 1 5} {\text{Na}}_{0. 8 5} } \right)_{\Upsigma = 2} {\text{K}}[{\text{Li}}_{ 3} {\text{Si}}_{ 1 2} {\text{O}}_{ 30} ] from Dara-i-Pioz, Tadjikistan, was studied by the combined application of 57Fe M?ssbauer spectroscopy and electronic structure calculations. The M?ssbauer spectrum confirms published microprobe and X-ray single-crystal diffraction results that indicate that Fe3+ is located at the octahedral A-site and that no Fe2+ is present. Both the measured and calculated quadrupole splitting, ΔE Q, for Fe3+ are virtually 0 mm s−1. Such a value is unusually small for a silicate and it is the same as the ΔE Q value for Fe3+ in structurally related sugilite. This result is traced back to the nearly regular octahedral coordination geometry corresponding to a very symmetric electric field gradient around Fe3+. A crystal chemical interpretation for the regular octahedral geometry and the resulting low ΔE Q value for Fe3+ in the M?ssbauer spectrum of sogdianite is that structural strain is largely “taken up” by weak Li–O bonds permitting highly distorted LiO4 tetrahedra. Weak Li–O bonding allows the edge-shared more strongly bonded Fe3+O6 octahedra to remain regular in geometry. This may be a typical property for all double-ring silicates with tetrahedrally coordinated Li.  相似文献   

7.
The present work aims in discussing a principle that distinguishes between elastic parameters sets, $ \{ \Upphi \} \equiv \{ K_{0} , \, K^{\prime}, \, V_{0} ,\ldots\} The present work aims in discussing a principle that distinguishes between elastic parameters sets, { \Upphi } o { K0 ,  K,  V0 ,?} \{ \Upphi \} \equiv \{ K_{0} , \, K^{\prime}, \, V_{0} ,\ldots\} , on the basis of an energetic criterion: once a reference set, { \UpphiR } \{ \Upphi_{R} \} , is given, another one can be fixed, { \Upphi min } \left\{ {\Upphi_{ \min } } \right\} , so that they are as close as possible to each other, but yield non-equivalent deformation energy curves \Updelta G({ \Upphi } )\textdeform \Updelta G(\{ \Upphi \} )_{\text{deform}} , i.e. they give \Updelta G({ \UpphiR } )\textdeform \Updelta G(\{ \Upphi_{R} \} )_{\text{deform}} and \Updelta G({ \Upphi min } )\textdeform \Updelta G(\{ \Upphi_{ \min } \} )_{\text{deform}} such that | \Updelta G({ \Upphi min } )\textdeform - \Updelta G({ \UpphiR } )\textdeform | 3 1×s[\Updelta G\textdeform ]. \left| {\Updelta G(\{ \Upphi_{ \min } \} )_{\text{deform}} - \Updelta G(\{ \Upphi_{R} \} )_{\text{deform}} } \right| \ge 1\times \sigma [\Updelta G_{\text{deform}} ]. ΔG deform, calculated using the equation of state (EoS), and its uncertainty σ[ΔG deform], obtained by a propagation of the errors affecting { \Upphi } \{ \Upphi \} are crucial to fix which mineral assemblage forms at PT conditions and allow one to assess the reliability of such a prediction. We explore some properties related to the principle introduced, using the average values of the elastic parameters found in literature and related uncertainties for di-octahedral mica, olivine, garnet and clinopyroxene. Two elementary applications are briefly discussed: the effect of refining V 0 in fitting EoSs to P–V experimental data, in the case of garnet and omphacite, and the phengite 3T–2M 1 relative stability, controlled by pressure.  相似文献   

8.
In order to investigate directly the structure and properties of grain boundaries in silicate materials undergoing pressure solution, in situ measurements of these properties are required. We report electrical impedance spectroscopy measurements, performed, under hydrothermal conditions, on individual glass–glass and glass-quartz contacts undergoing pressure solution. Resulting estimates of the average grain boundary diffusivity product ( Z = Dd\textav C* Z = D\delta_{\text{av}} C^{*} ) for silica transport and of the average grain boundary fluid film thickness ( d\textav \delta_{\text{av}} ) fall in the ranges 6.3 ± 1.4 × 10−18 ms−1 and 350 ± 210 nm, respectively. However, the average values for Z and d\textav \delta_{\text{av}} obtained were likely influenced by cracking and irregular dissolution of the dissolving contact surfaces, rather than representing uniformly wetted grain boundary properties. Post-mortem SEM observations indicate that the contact surfaces were internally rough. Taken together, our data support the notion that during pressure solution of quartz, grain boundary diffusion is rapid, and interface processes (dissolution and precipitation) are more likely to be rate-limiting than diffusion.  相似文献   

9.
Monticellite is a common magmatic mineral in the groundmass of kimberlites. A new oxygen barometer for kimberlite magmas is calibrated based on the Fe content of monticellite, CaMgSiO4, in equilibrium with kimberlite liquids in experiments at 100 kPa from 1,230 to 1,350°C and at logfO2 from NNO-4.1 to NNO+5.3 (where NNO is the nickel–nickel oxide buffer). The XFeMtc/XFeliq was found to decrease with increasing fO2, consistent with only Fe2+ entering the monticellite structure. Although the XFe-in-monticellite varies with temperature and composition, these dependencies are small compared to that with fO2. The experimental data were fitted by weighted least square regression to the following relationship: \Updelta \textNNO = \frac{ log[ 0.858( ±0.021)\fracX\textFe\textLiq X\textFe\textMtc ] - 0.139( ±0.022) }0.193( ±0.004) \Updelta {\text{NNO}} = \frac{{\left\{ {\log \left[ {0.858( \pm 0.021)\frac{{X_{\text{Fe}}^{\text{Liq}} }}{{X_{\text{Fe}}^{\text{Mtc}} }}} \right] - 0.139( \pm 0.022)} \right\}}}{0.193( \pm 0.004)} where ΔNNO is the fO2 relative to that of the Nickel-bunsenite (NNO) buffer and XFeliq/XFeMtc is the ratio of mole fraction of Fe in liquid and Fe-in-monticellite (uncertainties at 2σ). The application of this oxygen barometer to natural kimberlites from both the literature and our own investigations, assuming the bulk rock FeO is that of their liquid FeO, revealed a range in fO2 from NNO-3.5 to NNO+1.7. A range of Mg/(Mg + Fe2+) (Mg#) for kimberlite melts of 0.46–0.88 was derived from the application of the experimentally determined monticellite-liquid Kd Fe2+–Mg to natural monticellites. The range in Mg# is broader and less ultramafic than previous estimates of kimberlites, suggesting an evolution under a wide range of petrologic conditions.  相似文献   

10.
Quantifying strain birefringence halos around inclusions in diamond   总被引:1,自引:0,他引:1  
The pressure and temperature conditions of formation of natural diamond can be estimated by measuring the residual stress that an inclusion remains under within a diamond. Raman spectroscopy has been the most commonly used technique for determining this stress by utilising pressure-sensitive peak shifts in the Raman spectrum of both the inclusion and the diamond host. Here, we present a new approach to measure the residual stress using quantitative analysis of the birefringence induced in the diamond. As the analysis of stress-induced birefringence is very different from that of normal birefringence, an analytical model is developed that relates the spherical inclusion size, R i, host diamond thickness, L, and measured value of birefringence at the edge of the inclusion, \Updelta n(R\texti )\textav \Updelta n(R_{\text{i}} )_{\text{av}} , to the peak value of birefringence that has been encountered; to first order \Updelta n\textpk = (3/4)(L/R\texti )  \Updelta n(R\texti )\textav \Updelta n_{\text{pk}} = (3/4)(L/R_{\text{i}} ) \, \Updelta n(R_{\text{i}} )_{\text{av}} . From this birefringence, the remnant pressure (P i) can be calculated using the photoelastic relationship \Updelta n\textpk = - (3/4)n3 q\textiso P\texti \Updelta n_{\text{pk}} = - (3/4)n^{3} q_{\text{iso}} P_{\text{i}} , where q iso is a piezo-optical coefficient, which can be assumed to be independent of crystallographic orientation, and n is the refractive index of the diamond. This model has been used in combination with quantitative birefringence analysis with a MetriPol system and compared to the results from both Raman point and 2D mapping analysis for a garnet inclusion in a diamond from the Udachnaya mine (Russia) and coesite inclusions in a diamond from the Finsch mine (South Africa). The birefringence model and analysis gave a remnant pressure of 0.53 ± 0.01 GPa for the garnet inclusion, from which a source pressure was calculated as 5.7 GPa at 1,175°C (temperature obtained from IR analysis of the diamond host). The Raman techniques could not be applied quantitatively to this sample to support the birefringence model; they were, however, applied to the largest coesite inclusion in the Finsch sample. The remnant pressure values obtained were 2.5 ± 0.1 GPa (birefringence), 2.5 ± 0.3 GPa (2D Raman map), and 2.5–2.6 GPa (Raman point analysis from all four inclusions). However, although the remnant pressures from the three methods were self-consistent, they led to anomalously low source pressure of 2.9 GPa at 1,150°C (temperature obtained from IR analysis) raising serious concerns about the use of the coesite-in-diamond geobarometer.  相似文献   

11.
Quartz and rutile were synthesized from silica-saturated aqueous fluids between 5 and 20 kbar and from 700 to 940°C in a piston-cylinder apparatus to explore the potential pressure effect on Ti solubility in quartz. A systematic decrease in Ti-in-quartz solubility occurs between 5 and 20 kbar. Titanium K-edge X-ray absorption near-edge structure (XANES) measurements demonstrate that Ti4+ substitutes for Si4+ on fourfold tetrahedral sites in quartz at all conditions studied. Molecular dynamic simulations support XANES measurements and demonstrate that Ti incorporation onto fourfold sites is favored over interstitial solubility mechanisms. To account for the PT dependence of Ti-in-quartz solubility, a least-squares method was used to fit Ti concentrations in quartz from all experiments to the simple expression
RTlnX\textTiO 2 \textquartz = - 60952 + 1.520 ·T(K) - 1741 ·P(kbar) + RTlna\textTiO 2 RT\ln X_{{{\text{TiO}}_{ 2} }}^{\text{quartz}} = - 60952 + 1.520 \cdot T(K) - 1741 \cdot P(kbar) + RT\ln a_{{{\text{TiO}}_{ 2} }}  相似文献   

12.
Li diffusion in zircon   总被引:2,自引:2,他引:0  
Diffusion of Li under anhydrous conditions at 1 atm and under fluid-present elevated pressure (1.0–1.2 GPa) conditions has been measured in natural zircon. The source of diffusant for 1-atm experiments was ground natural spodumene, which was sealed under vacuum in silica glass capsules with polished slabs of zircon. An experiment using a Dy-bearing source was also conducted to evaluate possible rate-limiting effects on Li diffusion of slow-diffusing REE+3 that might provide charge balance. Diffusion experiments performed in the presence of H2O–CO2 fluid were run in a piston–cylinder apparatus, using a source consisting of a powdered mixture of spodumene, quartz and zircon with oxalic acid added to produce H2O–CO2 fluid. Nuclear reaction analysis (NRA) with the resonant nuclear reaction 7Li(p,γ)8Be was used to measure diffusion profiles for the experiments. The following Arrhenius parameters were obtained for Li diffusion normal to the c-axis over the temperature range 703–1.151°C at 1 atm for experiments run with the spodumene source:
D\textLi = 7.17 ×10 - 7 exp( - 275 ±11 \textkJmol - 1 /\textRT)\textm2 \texts - 1. D_{\text{Li}} = 7.17 \times 10^{ - 7} { \exp }( - 275 \pm 11\,{\text{kJmol}}^{ - 1} /{\text{RT}}){\text{m}}^{2} {\text{s}}^{ - 1}.  相似文献   

13.
Great Salt Lake (GSL) is one of the largest and most saline lakes in the world. In order to accurately model limnological processes in GSL, hydrodynamic calculations require the precise estimation of water density (ρ) under a variety of environmental conditions. An equation of state was developed with water samples collected from GSL to estimate density as a function of salinity and water temperature. The ρ of water samples from the south arm of GSL was measured as a function of temperature ranging from 278 to 323 degrees Kelvin (oK) and conductivity salinities ranging from 23 to 182 g L−1 using an Anton Paar density meter. These results have been used to develop the following equation of state for GSL (σ = ± 0.32 kg m−3):
r- r0 = 184.0 10 6 2 + 1.0 4 70 8*\textS - 1. 2 10 6 1*\textT + 3. 1 4 7 2 1 \textE - 4*\textS 2 +  0.00 1 9 9 \textT 2 - 0.00 1 1 2*\textS*\textT, \rho - \rho^{0} = { 184}.0 10 6 2 { } + { 1}.0 4 70 8*{\text{S}} - 1. 2 10 6 1*{\text{T }} + { 3}. 1 4 7 2 1 {\text{E}} - 4*{\text{S}}^{ 2} + \, 0.00 1 9 9 {\text{T}}^{ 2} - 0.00 1 1 2*{\text{S}}*{\text{T}},  相似文献   

14.
To get deeper insight into the phase relations in the end-member system Fe2SiO4 and in the system (Fe, Mg)2SiO4 experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity. The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission electron microscopy. At fO2 corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe2SiO4 + O2 = 6 FeSiO3 + 5 Fe2.40Si0.60O4. Refinement of site occupancies in combination with stoichiometric Fe3+ calculations show that 32% of the total Fe is incorporated as Fe3+ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to accept higher Fe3+ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite with considerable Fe3+ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K D independent on composition and a bulk composition of x Fe = 0.44 this fractionation would stabilize spl with x Fe = 0.72. Thus, spl could be a potential Fe3+ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.
M. Koch-MüllerEmail:
  相似文献   

15.
Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al2O3–SiO2 and subsystem CaO–MgO–SiO2. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al2O3–SiO2 and subsystem CaO–MgO–SiO2. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 to $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 , D values for highly charged elements vary from $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 through $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 and $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 to $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 , and are all virtually independent of temperature. Cr and Co are the only compatible trace elements at the studied conditions. To elucidate charge-balancing mechanisms for incorporation of REE into Opx and to assess the possible influence of Fe on Opx-melt partitioning, we compare our experimental results with computer simulations. In these simulations, we examine major and minor trace element incorporation into the end-members enstatite (Mg2Si2O6) and ferrosilite (Fe2Si2O6). Calculated solution energies show that R2+ cations are more soluble in Opx than R3+ cations of similar size, consistent with experimental partitioning data. In addition, simulations show charge balancing of R3+ cations by coupled substitution with Li+ on the M1 site that is energetically favoured over coupled substitution involving Al–Si exchange on the tetrahedrally coordinated site. We derived best-fit values for ideal ionic radii r 0, maximum partition coefficients D 0, and apparent Young’s moduli E for substitutions onto the Opx M1 and M2 sites. Experimental r 0 values for R3+ substitutions are 0.66–0.67 ? for M1 and 0.82–0.87 ? for M2. Simulations for enstatite result in r 0 = 0.71–0.73 ? for M1 and ~0.79–0.87 ? for M2. Ferrosilite r 0 values are systematically larger by ~0.05 ? for both M1 and M2. The latter is opposite to experimental literature data, which appear to show a slight decrease in $ r_{0}^{{{\text{M}}2}} $ r_{0}^{{{\text{M}}2}} in the presence of Fe. Additional systematic studies in Fe-bearing systems are required to resolve this inconsistency and to develop predictive Opx-melt partitioning models for use in terrestrial and lunar magmatic differentiation models.  相似文献   

16.
By applying the Griffith stress criterion of brittle failure, one can find that the uniaxial compressive strength (σc) of rocks is eight times the value of the uniaxial tensile strength (σt). The Griffith strength ratio is smaller than what is normally measured for rocks, even with the consideration of crack closure. The reason is that Griffith’s theories address only the initiation of failure. Under tensile conditions, the crack propagation is unstable so that the tensile crack propagation stress (σcd)t and the peak tensile strength σt are almost identical to the tensile crack initiation stress (σci)t. On the other hand, the crack growth after crack initiation is stable under a predominantly compressive condition. Additional loading is required in compression to bring the stress from the crack initiation stress σci to the peak strength σc. It is proposed to estimate the tensile strength of strong brittle rocks from the strength ratio of R = \fracs\textc | s\textt | = 8\fracs\textc s\textci . R = {\frac{{\sigma_{\text{c}} }}{{\left| {\sigma_{\text{t}} } \right|}}} = 8{\frac{{\sigma_{\text{c}} }}{{\sigma_{\text{ci}} }}}. The term \fracs\textc s\textci {\frac{{\sigma_{\text{c}} }}{{\sigma_{\text{ci}} }}} accounts for the difference of crack growth or propagation in tension and compression in uniaxial compression tests. \fracsc sci {\frac{{\sigma_{c} }}{{\sigma_{ci} }}} depends on rock heterogeneity and is larger for coarse grained rocks than for fine grained rocks. σci can be obtained from volumetric strain measurement or acoustic emission (AE) monitoring. With the strength ratio R determined, the tensile strength can be indirectly obtained from | s\textt | = \fracs\textc R = \fracs\textci 8. \left| {\sigma_{\text{t}} } \right| = {\frac{{\sigma_{\text{c}} }}{R}} = {\frac{{\sigma_{\text{ci}} }}{8}}. It is found that the predicted tensile strengths using this method are in good agreement with test data. Finally, a practical estimate of the Hoek–Brown strength parameter m i is presented and a bi-segmental or multi-segmental representation of the Hoek–Brown strength envelope is suggested for some brittle rocks. In this fashion, the rock strength parameters like σt and m i, which require specialty tests such as direct tensile (or Brazilian) and triaxial compression tests for their determination, can be reasonably estimated from uniaxial compression tests.  相似文献   

17.
Comparison of polarized optical absorption spectra of natural Ca-rich diopsides and synthetic NaCrSi2O6 and LiCrSi2O6 clinopyroxenes, evidences as vivid similarities, as noticeable differences. The similarities reflect the fact that in all cases Cr3+ enters the small octahedral M1-site of the clinopyroxene structure. The differences are due to some iron content in the natural samples causing broad intense near infrared bands of electronic spin-allowed dd transitions of Fe2+(M1, M2) and intervalence Fe2+/Fe3+ charge-transfer transition, and by different symmetry and different local crystal fields strength of Cr3+ in the crystal structures. The positions of the spin-allowed bands of Cr3+, especially of the low energy one caused by the electronic 4 A 2g → 2 T 1g transition, are found to be in accordance with mean M1–O distances. The local relaxation parameter ε calculated for limCr 3+ → 0 from the spectra and interatomic á Cr - O ñ \left\langle {Cr - O} \right\rangle and á Mg - O ñ \left\langle {Mg - O} \right\rangle distances yields a very high value, 0.96, indicating that in the clinopyroxene structure the local lattice relaxation around the “guest” ion, Cr3+, deviates greatly from the “diffraction” value, ε = 0, than in any other known Cr3+-bearing systems studied so far. Under pressure the spin-allowed bands of Cr3+ shift to higher energies and decrease in intensity quite in accordance with the crystal field theoretical expectations, while the spin-forbidden absorption lines remain practically unshifted, but also undergo a strong weakening. There is no evident dependence of the Racah parameter B of Cr3+ reflecting the covalence of the oxygen-chromium bond under pressure: within the uncertainty of determination it may be regarded as practically constant. The values of CrO6 octahedral modulus, k\textpoly\textloc k_{\text{poly}}^{\text{loc}} , derived from high-pressure spectra of natural chromium diopside and synthetic NaCrSi2O6 kosmochlor are very close, ~203 and ~196 GPa, respectively, being, however, nearly twice higher than that of MgO6 octahedron in diopside, 105(4) GPa, obtained by Thompson and Downs (2008). Such a strong stiffening of the structural octahedron, i.e. twice higher value of k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} comparing with that of k\textMg2 + \textloc k_{{{\text{Mg}}^{2 + } }}^{\text{loc}} , may be caused by simultaneous substitution of Ca2+ by larger Na+ in the neighboring M2 sites at so-called jadeite-coupled substitution Mg2+ + Ca2+ → Cr3+ + Na+. It is also remarkable that the values of CrO6 octahedral modulus of NaCrSi2O6 kosmochlor obtained here are nearly twice larger than that of 90(16) GPa, evaluated by high-pressure X-ray structural refinement by Origlieri et al. (2003). Taking into account that the overall compressibility of the clinopyroxene structure should mainly be due to the compressibility of M1- and M2-sites, our k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} -value, ~196 GPa, looks much more consistent with the bulk modulus value, 134(1) GPa.  相似文献   

18.
Mineral-specific IR absorption coefficients were calculated for natural and synthetic olivine, SiO2 polymorphs, and GeO2 with specific isolated OH point defects using quantitative data from independent techniques such as proton–proton scattering, confocal Raman spectroscopy, and secondary ion mass spectrometry. Moreover, we present a routine to detect OH traces in anisotropic minerals using Raman spectroscopy combined with the “Comparator Technique”. In case of olivine and the SiO2 system, it turns out that the magnitude of ε for one structure is independent of the type of OH point defect and therewith the peak position (quartz ε = 89,000 ± 15,000  \textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}), but it varies as a function of structure (coesite ε = 214,000 ± 14,000  \textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}; stishovite ε = 485,000 ± 109,000  \textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}). Evaluation of data from this study confirms that not using mineral-specific IR calibrations for the OH quantification in nominally anhydrous minerals leads to inaccurate estimations of OH concentrations, which constitute the basis for modeling the Earth’s deep water cycle.  相似文献   

19.
20.
Relative humidity ( P\textH 2 \textO P_{{{\text{H}}_{ 2} {\text{O}}}} , partial pressure of water)-dependent dehydration and accompanying phase transitions in NAT-topology zeolites (natrolite, scolecite, and mesolite) were studied under controlled temperature and known P\textH 2 \textO P_{{{\text{H}}_{ 2} {\text{O}}}} conditions by in situ diffuse-reflectance infrared Fourier transform spectroscopy and parallel X-ray powder diffraction. Dehydration was characterized by the disappearance of internal H2O vibrational modes. The loss of H2O molecules caused a sequence of structural transitions in which the host framework transformation path was coupled primarily via the thermal motion of guest Na+/Ca2+ cations and H2O molecules. The observation of different interactions of H2O molecules and Na+/Ca2+ cations with host aluminosilicate frameworks under high- and low- P\textH 2 \textO P_{{{\text{H}}_{ 2} {\text{O}}}} conditions indicated the development of different local strain fields, arising from cation–H2O interactions in NAT-type channels. These strain fields influence the Si–O/Al–O bond strength and tilting angles within and between tetrahedra as the dehydration temperature is approached. The newly observed infrared bands (at 2,139 cm−1 in natrolite, 2,276 cm−1 in scolecite, and 2,176 and 2,259 cm−1 in mesolite) result from strong cation–H2O–Al–Si framework interactions in NAT-type channels, and these bands can be used to evaluate the energetic evolution of Na+/Ca2+ cations before and after phase transitions, especially for scolecite and mesolite. The 2,176 and 2,259 cm−1 absorption bands in mesolite also appear to be related to Na+/Ca2+ order–disorder that occur when mesolite loses its Ow4 H2O molecules.  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