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1.
Elastic constants of single crystal MgO have been measured by the rectangular parallelepiped resonance (RPR) method at temperatures between 80 and 1,300 K. Elastic constants C ij (Mbar=103 kbar) and their temperature coefficients (kbar/K) are: $$\begin{gathered} {\text{ }}C_{{\text{11}}} {\text{ }}C_{{\text{12}}} {\text{ }}C_{{\text{44}}} {\text{ }}K_s {\text{ }}C_s \hfill \\ C_{ij} {\text{ 300 K 2}}{\text{.966 0}}{\text{.959 1}}{\text{.562 1}}{\text{.628 1}}{\text{.004}} \hfill \\ \partial C_{ij} {\text{/}}\partial T{\text{100 K }} - {\text{0}}{\text{.259 0}}{\text{.013 }} - {\text{0}}{\text{.072 }} - {\text{0}}{\text{.078 }} - {\text{0}}{\text{.136}} \hfill \\ {\text{ 300K }} - {\text{0}}{\text{.596 0}}{\text{.068 }} - {\text{0}}{\text{.122 }} - {\text{0}}{\text{.153 }} - {\text{0}}{\text{.332}} \hfill \\ {\text{ 800 K }} - {\text{0}}{\text{.619 0}}{\text{.009 }} - {\text{0}}{\text{.152 }} - {\text{0}}{\text{.200 }} - {\text{0}}{\text{.314}} \hfill \\ {\text{ 1,300 K }} - {\text{0}}{\text{.598 0}}{\text{.036 }} - {\text{0}}{\text{.130 }} - {\text{0}}{\text{.223 }} - {\text{0}}{\text{.218}} \hfill \\ \end{gathered} $$ By combining the present results with the previous data on the thermal expansivity and specific heat, the thermodynamic properties of magnesium oxide are presented and discussed. The elastic parameters of MgO at very high temperatures in the earth's lower mantle are also clarified.  相似文献   

2.
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   

3.
4.
Mössbauer and polarized optical absorption spectra of the kyanite-related mineral yoderite were recorded. Mössbauer spectra of the purple (PY) and green yoderite (GY) from Mautia Hill, Tanzania, show that the bulk of the iron is Fe3+ in both varieties, with Fe2+/(Fe2++Fe3+) ratios near 0.05. Combining this result with new microprobe data for PY and with literature data for GY gives the crystallochemical formulae: $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.95}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{0}}{\text{.01}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.34}}}^{{\text{3 + }}} {\text{Mn}}_{{\text{0}}{\text{.07}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.57}}} )_{5.97}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.98}}} {\text{P}}_{{\text{0}}{\text{.03}}} ){\text{O}}_{{\text{18}}{\text{.02}}} ({\text{OH)}}_{{\text{1}}{\text{.98}}} ] \hfill \\ \end{gathered}$$ and PY and $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.98}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{< 0}}{\text{.001}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.45}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.56}}} )_{6.02}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.91}}} {\text{O}}_{{\text{17}}{\text{.73}}} {\text{(OH)}}_{{\text{2}}{\text{.27}}} ] \hfill \\ \end{gathered}$$ for GY. The Mössbauer spectra at room temperature contain one main doublet with isomer shifts and quadrupole splittings of 0.36 (PY), 0.38 (GY) and 1.00 (PY), 0.92 (GY) mm s?1, respectively. These values correspond to Fe3+ in six or five-fold coordination. The doublet components have anomalously large half widths indicating either accomodation of Fe3+ in more than one position (e.g., octahedraA1 and five coordinatedA2) or the yet unresolved superstructure. Besides strong absorption in the ultraviolet (UV) starting from about 25,000 cm?1, the polarized optical absorption spectra are dominated by strong bands around 16,500 and 21,000 cm?1 (PY) and a medium strong band at around 13,800 cm?1 (GY). Position and polarization of these bands, in combination with the UV absorption, explain the colour and pleochroism of the two varieties. The bands in question are assigned to homonuclear metal-to-metal charge transfer transitions: Mn2+(A1) Mn3+(A1′) ? Mn3+(A1) Mn2+(A1′) and Mn2+(A1) Mn3+(A2 ? Mn3+(A1) Mn2+(A2) in PY and Fe2+(A1) Fe3+(A1′) ? Fe3+(A1) Fe2+(A1′) in GY. The evidence for homonuclear Mn2+ Mn3+ charge transfer (CTF) is not quite clear and needs further study. Heteronuclear FeTi CTF does not contribute to the spectra. In PY, additional weak bands were resolved at energies around 17,700, 18,700, 21,000, and 21,900 cm?1 and assigned to Mn3+ in two positions. Weak bands around 10,000 cm?1 in both varieties are assigned to Fe2+ spin-alloweddd-transitions. Very weak and sharp bands, around 15,400, 16,400, 21,300, 22,100, 23,800, and 25,000 cm?1 are identified in GY and assigned to Fe3+ spin-forbiddendd-transitions.  相似文献   

5.
Kanonaite forms rare porphyroblasts up to 12mm long in a gahnite— Mg-chlorite — coronadite — quartz schist occurring near Kanona, Zambia. The composition is (microprobe analysis): SiO2 32.2, Al2O3 33.9, Mn as Mn2O3 32.2, Fe2O3 0.66, ZnO 0.13, MgO 0.04, BaO 0.04, TiO2 0.01, CaO 0.01, PbO 0.01, CuO 0.01, total 99.21, corresponding to $$\left( {{\text{Mn}}_{{\text{0}}{\text{.76}}}^{{\text{3 + }}} {\text{Al}}_{{\text{0}}{\text{.23}}} {\text{Fe}}_{{\text{0}}{\text{.015}}}^{{\text{3 + }}} } \right)_{1.005}^{\left[ 6 \right]} {\text{AL}}_{1.00}^{\left[ 5 \right]} \left[ {{\text{O}}_{{\text{1}}{\text{.00}}} |{\text{Si}}_{{\text{0}}{\text{.99}}} {\text{O}}_{{\text{4}}{\text{.00}}} } \right]$$ The mineral is greenish black, strongly pleochroic with X(∥a) yellow green, Y(∥b) bluish green, Z(∥c) deep golden yellow, biaxial positive, with 2V = 53°(3°), α = 1.702, β = 1.730, γ = 1.823. Vickers microhardness (100 gram load) ranges between 906 and 1017kp/mm2. The structure is orthorhombic, isotypic with andalusite, space group Pnnm, a = 0.7953(2), b = 0.8038(2), c = 0.5619(2) nm, V = 0.3592(1) nm3, a/b = 0.9895(3), c/b = 0.6990(3), S.G.(x) = 3.395 g/cm3, Z = 4. The strongest X-ray powder lines are (d in nm, I, hkl):0.5669, 100, 110; 0.4590, 75, 011 and 101; 0.3577, 90, 120 and 210; 0.2827, 94, 220; 0.2517, 90, 310 and 112; 0.2212, 83, 320, 122 and 212. Comparison of the intensities of 373 observed X-ray reflections with those calculated for several models of Mn3+-distribution indicates octahedral coordination of all or most of the manganese present. Interpretation of magnetic measurements (μeff = 3.15B.M. per Mn atom at 25 ° C) indirectly supports octahedral coordination of Mn3+. The name of the mineral is for Kanona, a town near the type locality. The name is proposed for the end member Mn3+ [6]Al[5][O¦SiO4] and for members of the solid-solution series towards andalusite with octahedral Mn3+>Al. The presently described mineral may be referred to as aluminian kanonaite.  相似文献   

6.
Three independent Pb isotope homogenizing processes operating on large volumes of rock material during limited intervals in the Phanerozoic have been used to define a unique evolutionary curve for rock and ore lead isotopic compositions of the southern Massif Central, France. The model is
  相似文献   

7.
Multiple linear regression analysis has been applied to the geometric and chemical variables in sodic plagioclases in order to determine their relative effects on individual T-O bond lengths in the Al1+xSi3?xO8 tetrahedral framework. Using data from crystal structure analyses of low and high albite, An16 and An28, and assuming that low albite is completely ordered, 1 $$\begin{gathered} {\text{T}} - {\text{O = 1}}{\text{.568}} + {\text{[(0}}{\text{.122) x (Al content of the T site)]}} \hfill \\ {\text{ }} - {\text{[(0}}{\text{.037) x (}}\Delta {\text{{\rm A}l}}_{{\text{br}}} )] + [0.063){\text{ x }}(\Sigma {\text{[}}q{\text{/(Na,Ca}} - {\text{O)}}^{\text{2}} ])] \hfill \\ {\text{ }} + {\text{[(0}}{\text{.029) x (}} - {\text{1/cosT}} - {\text{O}} - {\text{T)]}} \hfill \\ \end{gathered}$$ where the Al content of a particular tetrahedral (T) site can be estimated from empirically-derived determinative curves, where Δ Albr is a linkage factor to account for the Al content of adjacent tetrahedral sites, where the formal charge on the (Na1?xCax) atom is q=1+x, and where T-O-T is the inter-tetrahedral angle involving the T-O bond. For sodic plagioclases it is essential to know only the anorthite content and the 2Θ131-2Θ1¯31 spacing (CuK α radiation) in order to determine the independent variables in this equation and thus to evaluate the individual T-O distances. The 64 individual T-O distances predicted for the four sodic plagioclases by this equation agree well with the observed T-O bond lengths (σ=0.004 Å; r=0.994), and the method has been used by way of example to rationalize the T-O bond lengths in analcime (cf. Ferraris, Jones and Yerkess, 1972).  相似文献   

8.
The existing experimental data [Ferry and Spear 1978; Perchuk and Lavrent'eva 1983] on Mg?Fe partitioning between garnet and biotite are disparate. The underlying assumption of ideal Mg?Fe exchange between the minerals has been examined on the basis of recently available thermochemical data. Using the updated mixing parameters for the pyrope-almandine asymmetric regular solution as inputs [Ganguly and Saxena 1984; Hackler and Wood 1984], thermodynamic analysis points to non-ideal mixing in the phlogopite-annite binary in the temperature range of 550°C–950°C. The non-ideality can be approximated by a temperature-independent, one constant Margules parameter. The retrieved values for enthalpy of mixing for Mg?Fe biotites and the standard state enthalpy and entropy changes of the exchange reaction were combined with existing thermochemical data on grossular-pyrope and grossular-almandine binaries to obtain geothermometric expressions for Mg?Fe fractionation between biotite and garnet. [T in K] $$\begin{gathered} {\text{T(HW) = [20286 + 0}}{\text{.0193P - \{ 2080(X}}_{{\text{Mg}}}^{{\text{Gt}}} {\text{)}}^{\text{2}} {\text{ - 6350(X}}_{{\text{Fe}}}^{{\text{Gt}}} {\text{)}}^{\text{2}} \hfill \\ {\text{ - 13807(X}}_{{\text{Ca}}}^{{\text{Gt}}} {\text{)(1 - X}}_{{\text{Mn}}}^{{\text{Gt}}} {\text{) + 8540(X}}_{{\text{Fe}}}^{{\text{Gt}}} {\text{)(X}}_{{\text{Mg}}}^{{\text{Gt}}} {\text{)(1 - X}}_{{\text{Mn}}}^{{\text{Gt}}} {\text{)}} \hfill \\ {\text{ + 4215(X}}_{{\text{Ca}}}^{{\text{Gt}}} {\text{)(X}}_{{\text{Mg}}}^{{\text{Gt}}} {\text{ - X}}_{{\text{Fe}}}^{{\text{Gt}}} {\text{)\} + 4441}}{{{\text{(2X}}_{{\text{Mg}}}^{{\text{Bt}}} {\text{ - 1)]}}} \mathord{\left/ {\vphantom {{{\text{(2X}}_{{\text{Mg}}}^{{\text{Bt}}} {\text{ - 1)]}}} {{\text{[13}}{\text{.138}}}}} \right. \kern-\nulldelimiterspace} {{\text{[13}}{\text{.138}}}} \hfill \\ {\text{ + 8}}{\text{.3143 InK}}_{\text{D}} {\text{ + 6}}{\text{.276(X}}_{{\text{Ca}}}^{{\text{Gt}}} ){\text{(1 - X}}_{{\text{Mn}}}^{{\text{Gt}}} )] \hfill \\ {\text{T(GS) = [13538 + 0}}{\text{.0193P - \{ 837(X}}_{{\text{Mg}}}^{{\text{Gt}}} )^{\text{2}} {\text{ - 10460(X}}_{{\text{Fe}}}^{{\text{Gt}}} )^2 \hfill \\ {\text{ - 13807(X}}_{{\text{Ca}}}^{{\text{Gt}}} )(1{\text{ - X}}_{{\text{Mn}}}^{{\text{Gt}}} {\text{) + 19246(X}}_{{\text{Fe}}}^{{\text{Gt}}} ){\text{(X}}_{{\text{Mg}}}^{{\text{Gt}}} ){\text{(1 - X}}_{{\text{Mn}}}^{{\text{Gt}}} ) \hfill \\ {\text{ }}{{{\text{ + 5649(X}}_{{\text{Ca}}}^{{\text{Gt}}} ){\text{(X}}_{{\text{Mg}}}^{{\text{Gt}}} {\text{ - X}}_{{\text{Fe}}}^{{\text{Gt}}} ){\text{\} + 7972(2X}}_{{\text{Mg}}}^{{\text{Bt}}} {\text{ - 1)]}}} \mathord{\left/ {\vphantom {{{\text{ + 5649(X}}_{{\text{Ca}}}^{{\text{Gt}}} ){\text{(X}}_{{\text{Mg}}}^{{\text{Gt}}} {\text{ - X}}_{{\text{Fe}}}^{{\text{Gt}}} ){\text{\} + 7972(2X}}_{{\text{Mg}}}^{{\text{Bt}}} {\text{ - 1)]}}} {{\text{[6}}{\text{.778}}}}} \right. \kern-\nulldelimiterspace} {{\text{[6}}{\text{.778}}}} \hfill \\ {\text{ + 8}}{\text{.3143InK}}_{\text{D}} {\text{ + 6}}{\text{.276(X}}_{{\text{Ca}}}^{{\text{Gt}}} )(1{\text{ - X}}_{{\text{Mn}}}^{{\text{Gt}}} )] \hfill \\ \end{gathered} $$ The reformulated geothermometer is an improvement over existing biotite-garnet geothermometers because it reconciles the experimental data sets on Fe?Mg partitioning between the two phases and is based on updated activity-composition relationship in Fe?Mg?Ca garnet solid solutions.  相似文献   

9.
A unique clinopyroxene (En19Fs78Wo3), clinoeulite, space group P21/c, $${\text{(Fe}}_{{\text{1}}{\text{.48}}} {\text{Mg}}_{{\text{0}}{\text{.37}}} {\text{Mn}}_{{\text{0}}{\text{.08}}}^{{\text{2 + }}} {\text{Ca}}_{{\text{0}}{\text{.05}}} {\text{Al}}_{{\text{0}}{\text{.01}}} {\text{)}}_{{\text{1}}{\text{.99}}} {\text{ [Si}}_{{\text{2}}{\text{.01}}} {\text{O6],}}$$ contains sharp exsolution lamellae of ferroaugite (En17Fs43Wo40) from which the former presence of a ferropigeonite near En17Fs70Wo13 can be calculated. This two-pyroxene intergrowth is the main component of a eulysite containing also magnetite, olivine (Fo9Fa86Te5), quartz, oligoclase-K feldspar inter-growth, and retrograde cummingtonite with about 76 % grunerite end member. The occurrence of this most unusual rock type in the center of the Vredefort structure is attributed to a period of high-temperature metamorphism (at least 800 °–850 °C) which was followed by hot deformation of the rock during the Vredefort event thus probably preventing the common formation of orthopyroxene through pigeonite exsolution and inversion upon cooling. After this tectonic deformation, the rock recrystallized within the low-temperature stability range of clinoeulite to yield fine annealing textures. Late-stage equilibria at temperatures well below 500 °C include the complete unmixing of a former high-temperature anorthoclase, a Mg/Fe redistribution in the clinoeulite and olivine and, with the introduction of water, the partial formation of cummingtonite through reaction of clinoeulite, olivine, and quartz. During weathering the olivine was transformed to a nearly opaque, anhydrous ferrisilicate which, except for the change of Fe2+ to Fe3+ and the oxygen introduction, largely retained its original chemistry.  相似文献   

10.
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   

11.
A mineralogic geobarometer based on the reaction garnet+clinopyroxene+quartz=2 orthopyroxene+anorthite is proposed. The geobarometric formulations for the Fe- and Mg- end member equilibria are $$\begin{gathered} P_{({\text{Fe}})} {\text{ }}({\text{bars}}){\text{ = 32}}{\text{.097 }}T{\text{ }} - {\text{ 26385 }} - {\text{ 22}}{\text{.79 (}}T - 848 - T1{\text{n(}}T/848{\text{))}} \hfill \\ {\text{ }} - (3.655 + 0.0138T){\text{ }}\left( {\frac{{{\text{(}}T - 848{\text{)}}^{\text{2}} }}{T}} \right) \hfill \\ {\text{ }} - {\text{(3}}{\text{.123) }}T1{\text{n }}\frac{{(a_{a{\text{n}}}^{{\text{Plag}}} )(a_{{\text{fs}}}^{{\text{P}}\ddot u{\text{x}}} )^2 }}{{(a_{{\text{alm}}}^{{\text{Gt}}} )(a_{{\text{hed}}}^{{\text{Opx}}} )}} \hfill \\ P_{({\text{Mg}})} {\text{ (bars) = 9}}{\text{.270 }}T + 4006 - 0.9305{\text{ }}(T - 848 - T1{\text{n (}}T/848{\text{)}}) \hfill \\ {\text{ }} - (1.1963{\text{ }} - {\text{ }}6.0128{\text{ x 10}}^{ - {\text{3}}} T)\left( {\frac{{(T - 848)^2 }}{T}} \right) \hfill \\ {\text{ }} - 3.489{\text{ }}T1{\text{n }}\frac{{(a_{an}^{{\text{Plag}}} ){\text{ }}(a_{{\text{ens}}}^{{\text{Opx}}} )}}{{{\text{(}}a_{{\text{pyr}}}^{{\text{Gt}}} {\text{) (}}a_{{\text{diop}}}^{{\text{Cpx}}} {\text{)}}}}. \hfill \\ \end{gathered}$$ The end member thermodynamic data have been taken from the data base of Helgeson et al. (1978) and Saxena and Erikson (1983). The activities of pyroxene components and anorthite in plagioclase have been modelled after Wood and Banno (1973) and Newton (1983) respectively. The activities of pyrope and almandine are calculated from the binary interaction parameters for garnet solid solutions proposed by Saxena and Erikson (1983). Pressures computed from these equations for fifty sets of published mineral data from several granulite areas are comparable with those obtained from dependable geobarometers. The pressure values determined from the Fe-end member equilibrium appear to be more reasonable than those from the Mg-end member reaction. It is likely that the difference in pressures computed from the Fe- and Mg-end members, ΔP *, have been caused by non-ideal mixing in the phases, especially in garnets.  相似文献   

12.
The response of magnesiochloritoid to pressure has been studied by single crystal X-ray diffraction in a diamond anvil cell, using crystals with composition Mg1.3Fe0.7Al4Si2O10(OH)4. The unit cell parameters decrease from a = 9.434 (3), b = 5.452 (2), c = 18.136 (5) Å, β = 101.42° (2) (1 bar pressure) to a = 9.370 (7), b = 5.419 (5), c = 17.88 (1) Å, β = 101.5° (1) (42 kbar pressure), following a slightly anisotropic compression pattern (linear compressibilities parallel to unit cell edges: β a = 1.85, β b = 1.74, βc = 3.05 × 10?4 kbar?1) with a bulk modulus of 1480 kbar. Perpendicular to c, the most compressible direction, the crystal structure (space group C2/c) consists of two kinds of alternating octahedral layers connected via isolated SiO4 tetrahedra. With increasing pressure the slightly wavy layer [Mg1.3Fe0.7AlO2(OH)4] tends to flatten. Furthermore, the octahedra in this layer, with all cations underbonded, are more compressible than the octahedra in the (A13O8) layer with slightly overbonded aluminum. Comparison between high-pressure and high-temperature data yields the following equations: $$\begin{gathered} a_{P,T} = 9.434{\text{ }}{\AA} - 174 \cdot 10^{ - 5} {\text{ }}{\AA}{\text{kb}}^{{\text{ - 1}}} \cdot P \hfill \\ {\text{ }} + 9 \cdot 10^{ - 5} {\text{ }}{\AA}^\circ C^{ - 1} \cdot (T - 25^\circ C) \hfill \\ b_{P,T} = 5.452{\text{ }}{\AA} - 95 \cdot 10^{ - 5} {\text{ }}{\AA}{\text{kb}}^{{\text{ - 1}}} \cdot P \hfill \\ {\text{ }} + 5 \cdot 65 \cdot 10^{ - 5} {\text{ }}{\AA}^\circ C^{ - 1} \cdot (T - 25^\circ C) \hfill \\ c_{P,T} = 18.136{\text{ }}{\AA} - 549 \cdot 10^{ - 5} {\text{ }}{\AA}{\text{kb}}^{{\text{ - 1}}} \cdot P \hfill \\ {\text{ }} + 16 \cdot 2^{ - 5} {\text{ }}{\AA}^\circ C^{ - 1} \cdot (T - 25^\circ C) \hfill \\ \end{gathered} $$ with P in kbar and T in °C. These equations indicate that the unit cell and bond geometry of magnesiochloritoid at formation conditions do not differ greatly from those at the outcrop conditions, e.g. the calculated unitcell volume is 917.3 Å3 at P = 16 kbar and T=500 °C, whereas the observed volume at room conditions is 914.4 Å3. In addition, they show that the specific gravity increases from formation at depth to outcrop at surface conditions.  相似文献   

13.
River, rain and spring water samples from a region covered in “Shirasu” ignimbrite were collected on Kyushu Island, Japan. The analytical results were subjected to multivariate statistical analysis and stoichiometric calculation to understand the geographical distribution of chemical components in water and to extract geochemical underlying factors. The multivariate statistical analysis showed that the river-water chemistry is only slightly influenced by hot springs or polluted waters, but is highly controlled by weathering of ignimbrite. On the basis of the stoichiometric calculation based on water–rock interaction, the water chemistry was successfully estimated by a simple equation:\({\left[ {{\text{Si}}} \right]}{\text{ = 2}}{\left[ {{\text{Na}}^{{\text{ + }}} } \right]}{\text{ + }}{\left[ {{\text{Mg}}^{{{\text{2 + }}}} } \right]}\) in the upstream area, complemented by \({\left[ {{\text{Si}}} \right]}{\text{ = }}{\left[ {{\text{Na}}^{{\text{ + }}} } \right]}{\text{ - 3}}{\left[ {{\text{K}}^{{\text{ + }}} } \right]}{\text{ + }}{\left[ {{\text{Mg}}^{{{\text{2 + }}}} } \right]}{\text{ - 2}}{\left[ {{\text{Ca}}^{{{\text{2 + }}}} } \right]}\) in the downstream area.  相似文献   

14.
The exchage equilibrium has been used to measure activity-composition relations along the olivine join FeSi0.5O2−MgSi0.5O2 at 1400 K and 1 atm pressure. Equilibrium Fe−Mg partitioning between the two phases was determined by reversing the compositions of olivine coexisting with oxide and matallic iron over the composition range Fo23 to Fo92. A detailed study of the thermodynamic properties of the oxide phase has recently been made by Srečec et al. and we have confirmed their results in the composition range of interest. Application of the oxide data to the exchange equilibrium enables the properties of olivine to be determined. Within experimental uncertainly (Fe, Mg)Si0.5O2 olivine can, at 1400 K, be treated as a symmetric solution with W Fe-Mg o1 of 3.7±0.8 kJ/mol. The data permit the presence of only very slight asymmetry in the series. The data do not support recent assertions that olivine is highly non-ideal (W≈10 kJ/mol) under these conditions.  相似文献   

15.
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   

16.
Equilibrium alumina contents of orthopyroxene coexisting with spinel and forsterite in the system MgO-Al2O3-SiO2 have been reversed at 15 different P-T conditions, in the range 1,030–1,600° C and 10–28 kbar. The present data and three reversals of Danckwerth and Newton (1978) have been modeled assuming an ideal pyroxene solid solution with components Mg2Si2O6 (En) and MgAl2SiO6 (MgTs), to yield the following equilibrium condition (J, bar, K): $$\begin{gathered} RT{\text{ln(}}X_{{\text{MgTs}}} {\text{/}}X_{{\text{En}}} {\text{) + 29,190}} - {\text{13}}{\text{.42 }}T + 0.18{\text{ }}T + 0.18{\text{ }}T^{1.5} \hfill \\ + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP = 0,} \hfill \\ \end{gathered} $$ where $$\begin{gathered} + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP} \hfill \\ = [0.013 + 3.34 \times 10^{ - 5} (T - 298) - 6.6 \times 10^{ - 7} P]P. \hfill \\ \end{gathered} $$ The data of Perkins et al. (1981) for the equilibrium of orthopyroxene with pyrope have been similarly fitted with the result: $$\begin{gathered} - RT{\text{ln(}}X_{{\text{MgTs}}} \cdot X_{{\text{En}}} {\text{) + 5,510}} - 88.91{\text{ }}T + 19{\text{ }}T^{1.2} \hfill \\ + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP = 0,} \hfill \\ \end{gathered} $$ where $$\begin{gathered} + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP} \hfill \\ = [ - 0.832 - 8.78{\text{ }} \times {\text{ 10}}^{ - {\text{5}}} (T - 298) + 16.6{\text{ }} \times {\text{ 10}}^{ - 7} P]{\text{ }}P. \hfill \\ \end{gathered} $$ The new parameters are in excellent agreement with measured thermochemical data and give the following properties of the Mg-Tschermak endmember: $$H_{f,970}^0 = - 4.77{\text{ kJ/mol, }}S_{298}^0 = 129.44{\text{ J/mol}} \cdot {\text{K,}}$$ and $$V_{298,1}^0 = 58.88{\text{ cm}}^{\text{3}} .$$ The assemblage orthopyroxene+spinel+olivine can be used as a geothermometer for spinel lherzolites, subject to a choice of thermodynamic mixing models for multicomponent orthopyroxene and spinel. An ideal two-site mixing model for pyroxene and Sack's (1982) expressions for spinel activities provide, with the present experimental calibration, a geothermometer which yields temperatures of 800° C to 1,350° C for various alpine peridotites and 850° C to 1,130° C for various volcanic inclusions of upper mantle origin.  相似文献   

17.
The chemical composition of 2188 terrestrial igneous rocks ranging from ultrabasic to granitic composition was analyzed statistically using the method of factor analysis (principal components). The resultant first and second factors were: $$\begin{gathered} {\text{ }}F_1 = 0.933{\text{ Na}}_{\text{2}} {\text{O + 0}}{\text{.143 SiO}}_{\text{2}} + 0.206{\text{ K}}_{\text{2}} {\text{O}} - 0.346{\text{ CaO}} - 0.263{\text{ MgO}} - \hfill \\ .203{\text{ FeO}} \pm \cdot \cdot \cdot \hfill \\ {\text{ }}F_2 = 0.979{\text{ Al}}_{\text{2}} {\text{O}}_{\text{3}} - 0.269{\text{ MgO}} - 0.151{\text{ SiO}}_{\text{2}} - 0.112{\text{ FeO}} \pm \cdot \cdot \cdot \hfill \\ \end{gathered} $$ where oxides are in weight percent. A plot of the first factor against the second results in a useful igneous variation diagram. When the compositions of the 2188 terrestrial rocks and 604 lunar rocks are plotted on this diagram, the two groups of rocks are clearly separated within an albite-anorthite-forsterite-fayalite-quartz polygon. None of the terrestrial differentiation trends are significant for lunar rocks. The major difference in the chemistry of lunar and terrestrial rocks lies in the former being albite poor. Removal of most of the albite from the compositions of terrestrial layered intrusives such as the Skaergaard results in an excellent match between the compositions of the two groups of rocks. Albite subtracted compositions of Skaergaard rocks in particular cover the entire range of chemical variation in the lunar rocks. The statistical results prompt us to speculate further on the similarity of the moon and Skaergaard. We note that the average composition of the moon (Wanke et al., 1974) is similar to the albite subtracted composition of the Skaergaard magma. The lunar crust and a significant part of the lunar interior may match the albite subtracted and somewhat Mg enriched Skaergaard magma.  相似文献   

18.
Photon correlation spectroscopy has been applied to the study of longitudinal strain relaxation of vitreous Jadeite (NaAlSi2O6) in the temperature range 811–1014° C. The correlation function $\left| {g^{\left( 1 \right)} \left. {\left( t \right)} \right|^2 \propto \exp \left( {\left( { - 2t/\tau _\beta } \right)^\beta } \right)} \right.$ obeys a Kohlrausch type function with β=0.64±0.01. Individual correlation functions fit altogether a master relaxation curve, thus demonstrating thermorheological simplicity (TRS). The temperature dependence of the measured relaxation times shows Arrhenian behaviour with $\log \left( \tau \right) = - 21.4 \pm 0.3{\text{s}} {\text{ + }} {\text{471}}{\text{.6}} \pm {\text{22}} {\text{kJmol}}^{{\text{ - 1}}} /RT$ . The time scale of longitudinal strain relaxation is consistent with the existing data on shear relaxation derived from shear viscosity and structural relaxation calculated from calorimetric C pmeasurements. Comparison with oxygen diffusion indicates that network forming elements relax at about the same time scale as viscoelastic properties. On the other hand, Na+ relaxation times derived from impedance spectroscopy are short compared to viscoelastic relaxation times at low temperatures. This difference is decreasing with increasing temperature and possibly disappearing at approximately 1100° C.  相似文献   

19.
Raman sprectra of a gypsum crystal were made at pressures between 0.001 and 7 kbar using He gas as the pressure medium. \(\frac{{{\text{d}}v}}{{dP}}\) values for bands in the range 3,600–100 cm?1 were obtained. Comparison of results with \(\frac{{{\text{d}}v}}{{{\text{d}}T}}\) from the literature for temperatures of 77 and 300° K. shows that the internal modes of the SO4 units are more sensitive to pressure than to temperature. The effect is small. Coupled H2O-SO4 translational modes are greatly affected by both pressure and temperature while coupled Ca-SO4 mode are less so. It was found that stretching vibrations of water molecules were affected differently under pressure. The band at 3,500 cm?1 is more greatly displaced by pressure \(\left( {\frac{{{\text{d}}v}}{{{\text{d}}P}} = {\text{2}}{\text{.11cm}}^{{\text{ - 1}}} /{\text{kbar}}} \right)\) than the band at 3,400 cm?1 \(\left( {\frac{{{\text{d}}v}}{{{\text{d}}P}} \simeq {\text{2}}{\text{.11cm}}^{{\text{ - 1}}} /{\text{kbar}}} \right)\) . Assuming two different hydrogen bond intensities for the water molecules, one can attribute this difference in behavior of stretching modes to and increase in hydrogen bonding of one of the hydrogens which is exterior to the double H2O planes in the gypsum structure. The great variety of pressure derivatives for the different types of vibrational modes observed indicates that each molecular unit readjusts internally to pressure induced volume changes and the some of the chemical bonds between the units are significantly affected.  相似文献   

20.
Five geobarometers involving cordierite have been formulated for quantitative pressure sensing in high grade metapelites. The relevant reactions in the FeO-Al2O3-SiO2 (±H2O) system are based on the assemblages (A) cordierite-garnet-sillimanite-quartz, (B) cordierite-spinel-quartz, (C) cordierite-garnet-spinel-sillimanite, (D) cordierite-garnet-orthopyroxene-quartz and (E) cordierite-orthopyroxene-sillimanite-quartz. Application of the barometric formulations to a large number of granulite grade rocks indicates that the cordierite-garnet-sillimanite-quartz equilibrium is widely applicable and registers pressures which are in good agreement with the “consensus” pressure estimates. The dispersion in the computed P values, expressed as one standard deviation, is within ±1.2 kbar. The geobarometers (B) and (C) also yield pressures which are reasonable and compare well with those computed from equilibrium (A). The estimated pressures from (D) and (E), both involving orthopyroxene, are at variance with these estimates. It has been argued that the discrepancy in pressures obtained from these geobarometers stems from an inadequate knowledge of activity-composition relations and/or errors in input thermodynamic data of aluminous orthopyroxene. The convergence of pressure values estimated from the barometric formulations, especially (A), (B) and (C), implies that the present formulations are more dependable than the existing formulations and are also capable of setting limits on P values in response to varying $$\begin{gathered} {\text{1/2Fe}}_{\text{2}} {\text{Al}}_{\text{4}} {\text{Si}}_{\text{5}} {\text{O}}_{{\text{18}}} \hfill \\ {\text{ = 1/3Fe}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} {\text{ + 2/3Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + 5/6SiO}}_{\text{2}} {\text{. (A)}} \hfill \\ {\text{1/2Fe}}_{\text{2}} {\text{Al}}_{\text{4}} {\text{Si}}_{\text{5}} {\text{O}}_{{\text{18}}} {\text{ = FeAl}}_{\text{2}} {\text{O}}_{\text{4}} {\text{ + 5/2SiO}}_{\text{2}} {\text{. (B)}} \hfill \\ {\text{Fe}}_{\text{2}} {\text{Al}}_{\text{4}} {\text{Si}}_{\text{5}} {\text{O}}_{{\text{18}}} {\text{ + FeAl}}_{\text{2}} {\text{O}}_{\text{4}} \hfill \\ = {\text{Fe}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} {\text{ + 2Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{. (C)}} \hfill \\ {\text{1/2Fe}}_{\text{2}} {\text{Al}}_{\text{4}} {\text{Si}}_{\text{5}} {\text{O}}_{{\text{18}}} {\text{ + Fe}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} \hfill \\ = {\text{Fe}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} {\text{ + 3/2SiO}}_{\text{2}} .{\text{ (D)}} \hfill \\ {\text{1/2Fe}}_{\text{2}} {\text{Al}}{}_{\text{4}}{\text{Si}}_{\text{5}} {\text{O}}_{{\text{18}}} \hfill \\ = 1/2{\text{Fe}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} {\text{ + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + 1/2SiO}}_{\text{2}} .{\text{ (E)}} \hfill \\ \end{gathered}$$ . The present communication addresses the calibration, applicability and reliability of these barometers with reference to granulite facies metapelites.  相似文献   

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