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1.
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
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.
James M. Stroh 《Contributions to Mineralogy and Petrology》1976,54(3):173-188
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
4.
The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K
and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing
about 2 wt% H2O
t
in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H2O
t
) and water-rich (~2 wt% H2O
t
) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles
of hydrous species (OH groups and H2O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity
() was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The
water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess
of Al2O3 with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor
of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the
peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:
5.
The system Fe-Si-O: Oxygen buffer calibrations to 1,500K 总被引:1,自引:0,他引:1
The five solid-phase oxygen buffers of the system Fe-Si-O, iron-wuestite (IW), wuestite-magnetite (WM), magnetite-hematite (MH), quartz-iron-fayalite (QIF) and fayalite-magnetite-quartz (FMQ) have been recalibrated at 1 atm pressure and temperatures from 800°–1,300° C, using a thermogravimetric gas mixing furnace. The oxygen fugacity, \(f_{{\text{O}}_{\text{2}} }\) was measured with a CaO-doped ZrO2 electrode. Measurements were made also for wuestite solid solutions in order to determine the redox behavior of wuestites with O/Fe ratios varying from 1.05 to 1.17. For FMQ, additional determinations were carried out at 1 kb over a temperature range of 600° to 800° C, using a modified Shaw membrane. Results agree reasonably well with published data and extrapolations. The reaction parameters K, ΔG r o , ΔH r o , and ΔS r o were calculated from the following log \(f_{{\text{O}}_{\text{2}} }\) /T relations (T in K): $$\begin{gathered} {\text{IW }}\log f_{{\text{O}}_{\text{2}} } = - 26,834.7/T + 6.471\left( { \pm 0.058} \right) \hfill \\ {\text{ }}\left( {{\text{800}} - 1,260{\text{ C}}} \right), \hfill \\ {\text{WM }}\log f_{{\text{O}}_{\text{2}} } = - 36,951.3/T + 16.092\left( { \pm 0.045} \right) \hfill \\ {\text{ }}\left( {{\text{1,000}} - 1,300{\text{ C}}} \right), \hfill \\ {\text{MH }}\log f_{{\text{O}}_{\text{2}} } = - 23,847.6/T + 13.480\left( { \pm 0.055} \right) \hfill \\ {\text{ }}\left( {{\text{1,040}} - 1,270{\text{ C}}} \right), \hfill \\ {\text{QIF }}\log f_{{\text{O}}_{\text{2}} } = - 27,517.5/T + 6.396\left( { \pm 0.049} \right) \hfill \\ {\text{ }}\left( {{\text{960}} - 1,140{\text{ C}}} \right), \hfill \\ {\text{FMQ }}\log f_{{\text{O}}_{\text{2}} } = - 24,441.9/T + 8.290\left( { \pm 0.167} \right) \hfill \\ {\text{ }}\left( {{\text{600}} - 1,140{\text{ C}}} \right). \hfill \\ \end{gathered}$$ These experimentally determined reaction parameters were combined with published 298 K data to determine the parameters Gf, Hf, and Sf for the phases wuestite, magnetite, hematite, and fayalite from 298 K to the temperatures of the experiments. The T? \(f_{{\text{O}}_{\text{2}} }\) data for wuestite solid solutions were used to obtain activities, excess free energies and Margules mixing parameters. The new data provide a more reliable, consistent and complete reference set for the interpretation of redox reactions at elevated temperatures in experiments and field settings encompassing the crust, mantle and core as well as extraterrestrial environments. 相似文献
6.
Yastami Oka Petra Steinke Niranjan D. Chatterjee 《Contributions to Mineralogy and Petrology》1984,87(2):196-204
Three Al-Cr exchange isotherms at 1,250°, 1,050°, and 796° between Mg(Al, Cr)2O4 spinel and (Al, Cr)2O3 corundum crystalline solutions have been studied experimentally at 25 kbar pressure. Starting from gels of suitable bulk
compositions, close approach to equilibrium has been demonstrated in each case by time studies.
Using the equation of state for (Al, Cr)2O3 crystalline solution (Chatterjee et al. 1982a) and assuming that the Mg(Al, Cr)2O4 can be treated in terms of the asymmetric Margules relation, the exchange isotherms were solved for Δ G
*,
and
. The best constrained data set from the 1,250° C isotherm clearly shows that the latter two quantities do not overlap within
three standard deviations, justifying the choice of asymmetric Margules relation for describing the excess mixing properties
of Mg(Al, Cr)2O4 spinels. Based on these experiments, the following polybaric-polythermal equation of state can be formulated:
, P expressed in bars, T in K, G
m
ex
and W
G,i
Sp
in joules/mol.
Temperature-dependence of G
m
ex
is best constrained in the range 796–1,250° C; extrapolation beyond that range would have to be done with caution. Such extrapolation
to lower temperature shows tentatively that at 1 bar pressure the critical temperature, T
c, of the spinel solvus is 427° C, with dTc/dP≈1.3 K/kbar. The critical composition, X
c, is 0.42
, and changes barely with pressure.
Substantial error in calculated phase diagrams will result if the significant positive deviation from ideality is ignored
for Al-Cr mixing in such spinels. 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\}
8.
Rodney Grapes Sophia Korzhova Ella Sokol Yurii Seryotkin 《Contributions to Mineralogy and Petrology》2011,162(2):253-273
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
9.
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
10.
Paula M. Davidson John Grover Donald H. Lindsley 《Contributions to Mineralogy and Petrology》1982,80(1):88-102
Experiments at high pressure and temperature indicate that excess Ca may be dissolved in diopside. If the (Ca, Mg)2Si2O6 clinopyroxene solution extends to more Ca-rich compositions than CaMgSi2O6, macroscopic regular solution models cannot strictly be applied to this system. A nonconvergent site-disorder model, such as that proposed by Thompson (1969, 1970), may be more appropriate. We have modified Thompson's model to include asymmetric excess parameters and have used a linear least-squares technique to fit the available experimental data for Ca-Mg orthopyroxene-clinopyroxene equilibria and Fe-free pigeonite stability to this model. The model expressions for equilibrium conditions \(\mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction A) and \(\mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction B) are given by:
11.
J. William Carey 《Contributions to Mineralogy and Petrology》1995,119(2-3):155-165
A thermodynamic formulation of hydrous Mg-cordierite (Mg2Al4Si5O18·nH2O) has been obtained by application of calorimetric and X-ray diffraction data for hydrous cordierite to the results of hydrothermal syntheses. The data include measurements of the molar heat capacity and enthalpy of hydration and the molar volume. The synthesis data are consistent with a thermodynamic formulation in which H2O mixes ideally on a single crystallographic site in hydrous cordierite. The standard molar Gibbs free energy of hydration is-9.5±1.0 kJ/mol (an average of 61 syntheses). The standard molar entropy of hydration derived from this value is-108±3 J/mol-K. An equation providing the H2O content of cordierite as a function of temperature and fugacity of H2O is as follows (n moles of H2O per formula unit, n<1): $$\begin{gathered}n = {{f_{{\text{ H}}_{\text{2}} O}^{\text{V}} } \mathord{\left/{\vphantom {{f_{{\text{ H}}_{\text{2}} O}^{\text{V}} } {\left( {f_{{\text{ H}}_{\text{2}} O}^{\text{V}} + {\text{exp}}\left[ { - {\text{3}}{\text{.8389}} - 5025.2\left( {\frac{1}{T} - \frac{1}{{298.15}}} \right)} \right.} \right.}}} \right.\kern-\nulldelimiterspace} {\left( {f_{{\text{ H}}_{\text{2}} O}^{\text{V}} + {\text{exp}}\left[ { - {\text{3}}{\text{.8389}} - 5025.2\left( {\frac{1}{T} - \frac{1}{{298.15}}} \right)} \right.} \right.}} \hfill \\{\text{ }}\left. {\left. { - {\text{ln}}\left( {\frac{T}{{{\text{298}}{\text{.15}}}}} \right) - \left( {\frac{{298.15}}{T} - 1} \right)} \right]} \right) \hfill \\\end{gathered}$$ Application of this formulation to the breakdown reaction of Mg-cordierite to an assemblage of pyrope-sillimanite-quartz±H2O shows that cordierite is stabilized by 3 to 3.5 kbar under H2O-saturated conditions. The thermodynamic properties of H2O in cordierite are similar to those of liquid water, with a standard molar enthalpy and Gibbs free energy of hydration that are the same (within experimental uncertainty) as the enthalpy and Gibbs free energy of vaporization. By contrast, most zeolites have Gibbs free energies of hydration two to four times more negative than the corresponding value for the vaporization of water. 相似文献
12.
The effect of H<Subscript>2</Subscript>O on the olivine liquidus of basaltic melts: experiments and thermodynamic models 总被引:2,自引:2,他引:0
We designed and carried out experiments to investigate the effect of H2O on the liquidus temperature of olivine-saturated primitive melts. The effect of H2O was isolated from other influences by experimentally determining the liquidus temperatures of the same melt composition
with various amounts of H2O added. Experimental data indicate that the effect of H2O does not depend on pressure or melt composition in the basaltic compositional range. The influence of H2O on melting point lowering can be described as a polynomial function
This expression can be used to account for the effect of H2O on olivine-melt thermometers, and can be incorporated into fractionation models for primitive basalts. The non-linear effect
of H2O indicates that incorporation of H2O in silicate melts is non-ideal, and involves interaction between H2O and other melt components. The simple speciation approach that seems to account for the influence of H2O in simple systems (albite-H2O, diopside-H2O) fails to describe the mixing behavior of H2O in multi-component silicate melts. However, a non-ideal solution model that treats the effect of H2O addition as a positive excess free energy can be fitted to describe the effect of melting point lowering. 相似文献
13.
The effective binary diffusion coefficient (EBDC) of silicon has been measured during the interdiffusion of peralkaline, fluorine-bearing (1.3 wt% F), hydrous (3.3 and 6 wt% H2O), dacitic and rhyolitic melts at 1.0 GPa and temperatures between 1100°C and 1400°C. From Boltzmann-Matano analysis of diffusion profiles the diffusivity of silicon at 68 wt% SiO2 can be described by the following Arrhenius equations (with standard errors): $$\begin{gathered} {\text{with 1}}{\text{.3 wt\% F and 3}}{\text{.3\% H}}_{\text{2}} {\text{O:}} \hfill \\ {\text{D}}_{{\text{Si}}} = \begin{array}{*{20}c} { + {\text{3}}{\text{.59}}} \\ {{\text{3}}{\text{.66}} \times {\text{10}}^{ - {\text{9}}} } \\ { - {\text{1}}{\text{.86}}} \\ \end{array} {\text{exp}}\left( {{{ - {\text{86}}{\text{.1}} \pm {\text{8}}{\text{.9}}} \mathord{\left/ {\vphantom {{ - {\text{86}}{\text{.1}} \pm {\text{8}}{\text{.9}}} {{\text{RT}}}}} \right. \kern-\nulldelimiterspace} {{\text{RT}}}}} \right) \hfill \\ {\text{with 1}}{\text{.3 wt\% F and 6}}{\text{.0\% H}}_{\text{2}} {\text{O:}} \hfill \\ {\text{D}}_{{\text{Si}}} = \begin{array}{*{20}c} { + {\text{3}}{\text{.59}}} \\ {{\text{3}}{\text{.51}} \times {\text{10}}^{ - {\text{8}}} } \\ { - {\text{1}}{\text{.77}}} \\ \end{array} {\text{exp}}\left( {{{ - {\text{109}}{\text{.5}} \pm {\text{8}}{\text{.9}}} \mathord{\left/ {\vphantom {{ - {\text{109}}{\text{.5}} \pm {\text{8}}{\text{.9}}} {{\text{RT}}}}} \right. \kern-\nulldelimiterspace} {{\text{RT}}}}} \right) \hfill \\ \end{gathered} $$ where D is in m2s?1 and activation energies are in kJ/mol. Diffusivities measured at 64 and 72 wt% SiO2 are only slightly different from those at 68 wt% SiO2 and frequently all measurements are within error of each other. Silicon, aluminum, iron, magnesium, and calcium EBDCs were also calculated from diffusion profiles by error function inversion techniques assuming constant diffusivity. With one exception, silicon EBDCs calculated by error function techniques are within error of Boltzmann-Matano EBDCs. Average diffusivities of Fe, Mg, and Ca were within a factor of 2.5 of silicon diffusivities whereas Al diffusivities were approximately half those of silicon. Alkalies diffused much more rapidly than silicon and non-alkalies, however their diffusivities were not quantitatively determined. Low activation energies for silicon EBDCs result in rapid diffusion at magmatic temperatures. Assuming that water and fluorine exert similar effects on melt viscosity at high temperatures, the viscosity can be calculated and used in the Eyring equation used to determine diffusivities, typically to within a factor of three of those measured in this study. This correlation between viscosity and diffusivity can be inverted to calculate viscosities of fluorine- and water-bearing granitic melts at magmatic temperatures; these viscosities are orders of magnitude below those of hydrous granitic melts and result in more rapid and effective separation of granitic magmas from partially molten source rocks. Comparison of Arrhenius parameters for diffusion measured in this study with Arrhenius parameters determined for diffusion in similar compositions at the same pressure demonstrates simple relationships between Arrhenius parameters, activation energy-Ea, kJ/mol, pre-exponential factor-Do, m2s?1, and the volatile, X=F or OH?, to oxygen, O, ratio of the melt {(X/X+O)}: $$\begin{gathered} {\text{E}}a = - {\text{1533\{ }}{{\text{X}} \mathord{\left/ {\vphantom {{\text{X}} {\left( {{\text{X}} + {\text{O}}} \right)}}} \right. \kern-\nulldelimiterspace} {\left( {{\text{X}} + {\text{O}}} \right)}}{\text{\} }} + {\text{213}}{\text{.3}} \hfill \\ {\text{D}}_{\text{O}} = {\text{2}}{\text{.13}} \times {\text{10}}^{ - {\text{6}}} {\text{exp}}\left[ { - {\text{6}}{\text{.5\{ }}{{\text{X}} \mathord{\left/ {\vphantom {{\text{X}} {\left( {{\text{X}} + {\text{O}}} \right)}}} \right. \kern-\nulldelimiterspace} {\left( {{\text{X}} + {\text{O}}} \right)}}{\text{\} }}} \right] \hfill \\ \end{gathered} $$ These relationships can be used to estimate diffusion in various melts of dacitic to rhyolitic composition containing both fluorine and water. Calculations for the contamination of rhyolitic melts by dacitic enclaves at 800°C and 700°C provide evidence for the virtual inevitability of diffusive contamination in hydrous and fluorine-bearing magmas if they undergo magma mixing of any form. 相似文献
14.
M. Cai 《Rock Mechanics and Rock Engineering》2010,43(2):167-184
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
15.
Equilibrium Zn isotope fractionation was investigated using first-principles quantum chemistry methods at the B3LYP/6-311G* level. The volume variable cluster model method was used to calculate isotope fractionation factors of sphalerite, smithsonite, calcite, anorthite, forsterite, and enstatite. The water-droplet method was used to calculate Zn isotope fractionation factors of Zn2+-bearing aqueous species; their reduced partition function ratio factors decreased in the order \(\left[ {{\text{Zn}}\left( {{\text{H}}_{2} {\text{O}}} \right)_{6} } \right]^{2 + } > \left[ {{\text{ZnCl}}\left( {{\text{H}}_{2} {\text{O}}} \right)_{5} } \right]^{ + } > \left[ {{\text{ZnCl}}_{2} \left( {{\text{H}}_{2} {\text{O}}} \right)_{4} } \right] > \left[ {{\text{ZnCl}}_{3} \left( {{\text{H}}_{2} {\text{O}}} \right)_{2} } \right]^{ - } > {\text{ZnCl}}_{4} ]^{2 - }\). Gaseous ZnCl2 was also calculated for vaporization processes. Kinetic isotope fractionation of diffusional processes in a vacuum was directly calculated using formulas provided by Richter and co-workers. Our calculations show that in addition to the kinetic isotope effect of diffusional processes, equilibrium isotope fractionation also contributed nontrivially to observed Zn isotope fractionation of vaporization processes. The calculated net Zn isotope fractionation of vaporization processes was 7–7.5‰, with ZnCl2 as the gaseous species. This matches experimental observations of the range of Zn isotope distribution of lunar samples. Therefore, vaporization processes may be the cause of the large distribution of Zn isotope signals found on the Moon. However, we cannot further distinguish the origin of such vaporization processes; it might be due either to igneous rock melting in meteorite bombardments or to a giant impact event. Furthermore, isotope fractionation between Zn-bearing aqueous species and minerals that we have provided helps explain Zn isotope data in the fields of ore deposits and petrology. 相似文献
16.
Trace element analyses of 1-atm and high-pressure experiments show that in komatiite and peridotite, the olivine (OL)/liquid (L) distribution coefficient for Al2O3 (
) increases with pressure and temperature. Olivine in equilibrium with liquid accepts as much as 0.2 wt% Al2O3 in solution at 6 GPa. Convergence to equilibrium compositions at this high level is shown by cation diffusion of Al into synthetic forsterite crystals of low-Al contents in the presence of melt. Convergence to low-Al equilibrium compositions at lower P and T is shown by diffusion of Al out of synthetic forsterite with high initial Al content. Isobaric and isothermal experimental data subsets reveal that temperature and pressure variations both have real effects on
. Variation in silicate melt composition has no detectable effect on
within the limited range of experimentally investigated mixtures. Least-squares regression for 24 experiments, using komatiite and peridotite, performed at 1 atm to 6 GPa and 1300 to 1960°C, gives the best fit equation:
Increase in
with increasingly higher-pressure melting is consistent with incorporation of a spinel-like component of low molar volume into olivine, although other substitutions possibly involving more complex coupling cannot be ruled out. High P-T ultrabasic melting residues, if pristine, may be recognized by the high
calculated from microprobe analyses of Al2O3 concentrations in residual olivines and estimated Al2O3 concentration in the last liquid removed. In general the low levels of Al in natural olivine from mantle xenoliths suggest that pristine residues are rarely recovered. 相似文献
17.
David L. Naftz Frank J. Millero Blair F. Jones W. Reed Green 《Aquatic Geochemistry》2011,17(6):809-820
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):
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