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1.
Analysis of existing data and models on point defects in pure (Fe,Mg)-olivine (Phys Chem Miner 10:27–37,1983; Phys Chem Miner 29:680–694, 2002) shows that it is necessary to consider thermodynamic non-ideality of mixing to adequately describe the concentration of
point defects over the range of measurement. In spite of different sources of uncertainties, the concentrations of vacancies
in octahedral sites in (Fe,Mg)-olivine are on the order of 10−4 per atomic formula unit at 1,000–1,200 °C according to both the studies. We provide the first explicit plots of vacancy concentrations
in olivine as a function of temperature and oxygen fugacity according to the two models. It is found that in contrast to absolute
concentrations at ∼1,100 °C and dependence on fO2, there is considerable uncertainty in our knowledge of temperature dependence of vacancy concentrations. This needs to be
considered in discussing the transport properties such as diffusion coefficients. Moreover, these defect models in pure (Fe,Mg)-olivine
need to be extended by considering aliovalent impurities such as Al, Cr to describe the behavior of natural olivine. We have
developed such a formulation, and used it to analyze the considerable database of diffusion coefficients in olivine from Dohmen
et al. (Phys Chem Miner this volume, 2007) (Part - I) and older data in the literature. The analysis documents unequivocally for the first time a change of diffusion
mechanism in a silicate mineral—from the transition metal extrinsic (TaMED) to the purely extrinsic (PED) domain, at fO2 below 10−10 Pa, and consequently, temperatures below 900 °C. The change of diffusion mechanism manifests itself in a change in fO2 dependence of diffusivity and a slight change in activation energy of diffusion—the activation energy increases at lower temperatures. These are consistent with the predictions of Chakraborty (J Geophys Res 102(B6):12317–12331, 1997). Defect formation enthalpies in the TaMED regime (distinct from intrinsic defect formation) lie between −66 and + 15 kJ/mol
and migration energies of octahedral cations in olivine are most likely ∼ 260 kJ/mol, consistent with previous inferences
(Phys Chem 207:147–162, 1998). Plots are shown for diffusion at various constant fO2 as well as along fO2 buffers, to highlight the difference in behavior between the two. Considering all the diffusion data and constraints from
the point defect models, (Fe–Mg) diffusion in olivine along [001] is best described by the Master equations: (1) At oxygen
fugacities greater than 10−10 Pa:
where T is in Kelvin, P and fO2 is in Pascals, X
Fe is the mole fraction of the fayalite component and R is the gas constant in J/mol/K. (2) At oxygen fugacities less than 10−10 Pa:
These equations reproduce all of the 113 experimental data points within half an order of magnitude. (3) Alternately, a global
equation averaging out the change of mechanism may be used, with somewhat larger errors in reproducing the measured diffusion
data. It underestimates data at higher temperatures, and overestimates them at lower temperatures on the average. Note that
fO2 is not explicitly considered here, leading to additional sources of error:
To obtain diffusion coefficients along [100] and [010], log 6 needs to be subtracted from each of the above equations.
An erratum to this article can be found at 相似文献
2.
S. B. Dwivedi 《Journal of Earth System Science》1996,105(4):365-377
The non-ideal regular Mg-Fe binary in cordierite has been derived through multivariate linear regression of the expressionRT InKD +(P- 1)ΔVK 1 0 , 298 along with updated subfegular mixing parameter of almandine-pyrope solution (Hackler and Wood 1989; Berman 1990). The data base used for multivariate analyses consists of published experimental data (n = 177) on Mg-Fe partitioning between garnet and cordierite in theP-T range 650–1050°C and 4–12 K bar. The non-ideality can be approximated by temperature-dependent Margules parameters. The retrieved values of ΔH<T> o and ΔH<T> o of exchange reaction between garnet and cordierite and enthalpy and entropy of mixing of Mg-Fe cordierite were combined with recent quaternary (Fe-Mg-Ca-Mn) mixing data in garnet to obtain the geothermometric expressions to determine temperature (T Kelvin): $$\begin{gathered} T(WH) = 6832 + 0.031(P - 1) - \{ 166(X_{Mg}^{Gt} )^2 - 506(X_{Fe}^{Gt} )^2 + 680X_{Fe}^{Gt} X_{Mg}^{Gt} + 336(X_{Ca} + X_{Mn} ) \hfill \\ (X_{Mg} - X_{Fe} )^{Gt} - 3300X_{Ca}^{Gt} - 358X_{Mn}^{Gt} \} + 954(X_{Fe} - X_{Mg} )^{Crd} /1.987\ln K_D + 3.41 + 1.5X_{Ca}^{Gt} \hfill \\ + 1.23(X_{Fe} - X_{Mg} )^{Crd} \hfill \\ \end{gathered} $$ $$\begin{gathered} T(Br) = 6920 + 0.031(p - 1) - \{ 18(X_{Mg}^{Gt} )^2 - 296(X_{Fe}^{Gt} )^2 + 556X_{Fe}^{Gt} X_{Mg}^{Gt} - 6339X_{Ca}^{Gt} X_{Mg}^{Gt} \hfill \\ - 99(X_{Ca}^{Gt} )^2 + 4687X_{Ca}^{Gt} (X_{Mg} - X_{Fe}^{Gt} ) - 4269X_{Ca}^{Gt} X_{Fe}^{Gt} - 358X_{Mn}^{Gt} \} + 640(X_{Fe} - X_{Mg} )^{Crd} \hfill \\ + 1.90X_{Ca}^{Gt} (X_{Mg} - X_{Ca} )^{Gt} . \hfill \\ \end{gathered} $$ 相似文献
3.
Experimental tests of garnet peridotite oxygen barometry 总被引：1，自引：0，他引：1
We have performed experiments aimed at testing the calibration of oxygen barometers for the garnet peridotite [garnet (Gt)-olivine (Ol)-orthopyroxene (Opx)] phase assemblage. These involved equilibrating a thin layer of garnet sandwiched between layers of olivine and orthopyroxene at 1300°C and 23–35 kbar for 1–7 days. Oxygen fugacity was controlled (but not buffered) by using inner capsules of Fe?Pt alloy or graphitc or molybdenum sealed in welded Pt outer capsules. Post-experiment measurement of fO2 was made by determining the compositions of Pt-Fe alloy sensors at the interface between garnet and olivine + orthopyroxene layers. The composition of alloy in equilibrium with olivine + orthopyroxene was approached from Fe-oversaturated and Fe-undersaturated conditions in the same experiment with, in general, excellent convergence. Product phase compositions were determined by electron microprobe and a piece of the garnet layer saved for 57Fe Mössbauer spectroscopy. The latter gave the Fe3+ content of the garnet at the measured P-T-fO2 conditions. Approach to equilibrium was checked by observed shifts in Fe3+ content and by the approach of garnet-olivine Fe?Mg partitioning to the expected value. The compositions of the phases were combined with mixing properties and thermodynamic data to calculate an apparent fO2 from two possible garnet oxybarometers:- (1) $\begin{gathered} 2Ca_3 Fe_2 Si_3 O_{12} + 2Mg_3 Al_2 Si_3 O_{12} + 4FeSiO_3 = 2Ca_3 Al_2 Si_3 O_{12} \hfill \\ Gt Gt Opx Gt \hfill \\ + 8FeSi_{0.5} O_2 + 6MgSiO_3 + O \hfill \\ Ol Opx \hfill \\ \end{gathered} $ and (2) $\begin{gathered} 2Fe_3 Fe_2 Si_3 O_{12} = 8FeSi_{0.5} O_2 + 2FeSi_3 O_2 \hfill \\ Gt Ol Opx \hfill \\ \end{gathered} $ Comparison of calculated fO2s with those measured by the Pt-Fe sensors demonstrated that either barometer gives the correct answer within the expected uncertainty. Data from the first (Luth et al. 1990) has an uncertainty of about 1.6 logfO2 units, however, while that from equilibrium (2) (Woodland and O'Neill 1993) has an error of +/- 0.6 log units, comparable to that of the spinel peridotite oxybarometer. We therefore conclude that equilibrium (2) may be used to calculate the fO2 recorded by garnet peridotites with an uncertainty of about +/- 0.6 log units, providing the potential to probe the oxidation environment of the deep continental lithosphere. Preliminary application based on data from Luth et al. (1990) indicates that garnet peridotite xenoliths from Southern Africa record oxygen fugacities about 3.0 log units below the FMQ (fayalite-magnetite-quartz) buffer. These are substantially more reducing conditions than those recorded by continental spinel lherzolites which typically give oxygen fugacities close to FMQ (Wood et al. 1990). 相似文献
4.
The solubility of pentatungstate of sodium (PTS) Na2W5O16 · H2O and sodium tungsten bronzes (STB) Na0.16WO3 in acid chloride solutions containing 0.026, 0.26, and 3.02m NaCl have been studied at 500°C, 1000 bar, given fO2 (Co-CoO, Ni-NiO, PTS-STB buffers), and constant NaCl/HCl ratio (Ta2O5-Na2Ta4O11 buffer). Depending on experimental conditions, the tungsten content in the solutions after experiments varied from 10−3 to 2 × 10−2 mol/kg H2O. Obtained data were used to calculate the formation constants of predominant tungsten complexes (VI, V): H3W3VIO123−, W3VO93−, [WVW4VIO16]3−, for reactions
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$
\begin{gathered}
3H_2 WO_4^0 \leftrightarrow H_3 W_3 O_{12}^{3 - } + 3H^ + \log K_p = - 7.5 \pm 0.1, \hfill \\
3H_2 WO_4^0 \leftrightarrow W_3 O_9^{3 - } + 1.5H_2 O + 3H^ + + 0.75O_2 \log K_p = - 25.7 \pm 0.2, \hfill \\
5H_2 WO_4^0 \leftrightarrow \left[ {W^V W_4^{VI} O_{16} } \right]^{3 - } + 3H^ + + 3.5H_2 O + 0.25O_2 \log K_p = - 4.6 \pm 0.1 \hfill \\
\end{gathered}
$
\begin{gathered}
3H_2 WO_4^0 \leftrightarrow H_3 W_3 O_{12}^{3 - } + 3H^ + \log K_p = - 7.5 \pm 0.1, \hfill \\
3H_2 WO_4^0 \leftrightarrow W_3 O_9^{3 - } + 1.5H_2 O + 3H^ + + 0.75O_2 \log K_p = - 25.7 \pm 0.2, \hfill \\
5H_2 WO_4^0 \leftrightarrow \left[ {W^V W_4^{VI} O_{16} } \right]^{3 - } + 3H^ + + 3.5H_2 O + 0.25O_2 \log K_p = - 4.6 \pm 0.1 \hfill \\
\end{gathered}
相似文献
5.
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
6.
Breakdown of hydrous ringwoodite to pyroxene and spinelloid at high P and T and oxidizing conditions
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.
7.
The enthalpy of formation of andradite (Ca3Fe2Si3O12) has been estimated as-5,769.700 (±5) kJ/mol from a consideration of the calorimetric data on entropy (316.4 J/mol K) and of the experimental phaseequilibrium data on the reactions:
8.
A series of liquidus determinations is reported for a primitive arc basalt (15.4 wt % MgO, 45.5 wt % SiO2) from Grenada, Lesser Antilles, at anhydrous, H2O-undersaturated and H2O-saturated conditions in the pressure range 1 atm to 1.7 GPa. \(\hbox{Fe}^{3+}/\Upsigma\hbox{Fe}\) of high-pressure experimental glasses as measured by μXANES ranges from 0.44 to 0.86, corresponding to oxygen fugacities (fO2) between 3.2 and 7.8 log units above the nickel–nickel oxide redox buffer (NNO). 1-atm experiments conducted from NNO ? 2.5 to + 3.8 show that increasing fO2 mainly increases the forsterite content (Fo) of olivine and has little effect on phase relations. The crystallisation sequence at lower crustal pressures for all water contents is forsteritic olivine + Cr-rich spinel followed by clinopyroxene. The anhydrous liquidus is depressed by 100 and 120 °C in the presence of 2.9 and 3.8 wt % H2O, respectively. H2O-undersaturated experiments at NNO + 3.2 to + 4.5 produce olivine of equivalent composition to the most primitive olivine phenocrysts in Grenadan picrites (Fo91.4). We conclude that direct mantle melts originating beneath Grenada could be as oxidised as ~NNO + 3, consistent with the uppermost estimates from olivine–spinel oxybarometry of high Mg basalts. μXANES analyses of olivine-bearing experimental glasses are used to develop a semi-empirical oxybarometer based on the value of \({{K}_{D}}_{\rm ol-melt}^{\rm Fe-Mg}\) when all Fe is assumed to be in the Fe2+ state (\({K}_{D}^{{\rm Fe}_T}\)). The oxybarometer is tested on an independent data set and is able to reproduce experimental fO2 to ≤1.2 log units. Experiments also show that the geochemically and petrographically distinct M- and C-series lavas on the island can be produced from hydrous melting of a common picritic source. Low pressures expand the olivine stability field at the expense of clinopyroxene, enriching an evolving melt in CaO and forcing differentiation to take place along a C-series liquid line of descent. Higher pressure conditions allow early and abundant clinopyroxene crystallisation, rapidly depleting the melt in both CaO and MgO, and thus creating the M-series. 相似文献
9.
The chemical potential of oxygen (µO2) in equilibrium with magnesiowüstite solid solution (Mg, Fe)O and metallic Fe has been determined by gas-mixing experiments at 1,473 K supplemented by solid-cell EMF experiments at lower temperatures. The results give:
10.
S. K. Saxena 《Contributions to Mineralogy and Petrology》1979,70(3):229-235
A garnet-clinopyroxene geothermometer based on the available experimental data on compositions of coexisting phases in the system MgO-FeO-MnO-Al2O3-Na2O-SiO2 is as follows: $$T({\text{}}K) = \frac{{8288 + 0.0276 P {\text{(bar)}} + Q1 - Q2}}{{1.987 \ln K_{\text{D}} + 2.4083}}$$ where P is pressure, and Q1, Q2, and K D are given by the following equations $$Q1 = 2,710{\text{(}}X_{{\text{Fe}}} - X_{{\text{Mg}}} {\text{)}} + 3,150{\text{ }}X_{{\text{Ca}}} + 2,600{\text{ }}X_{{\text{Mn}}} $$ (mole fractions in garnet) $$\begin{gathered}Q2 = - 6,594[X_{{\text{Fe}}} {\text{(}}X_{{\text{Fe}}} - 2X_{{\text{Mg}}} {\text{)]}} \hfill \\{\text{ }} - 12762{\text{ [}}X_{{\text{Fe}}} - X_{{\text{Mg}}} (1 - X_{{\text{Fe}}} {\text{)]}} \hfill \\{\text{ }} - 11,281[X_{{\text{Ca}}} (1 - X_{{\text{Al}}} ) - 2X_{{\text{Mg}}} 2X_{{\text{Ca}}} ] \hfill \\{\text{ + 6137[}}X_{{\text{Ca}}} (2X_{{\text{Mg}}} + X_{{\text{Al}}} )] \hfill \\{\text{ + 35,791[}}X_{{\text{Al}}} (1 - 2X_{{\text{Mg}}} )] \hfill \\{\text{ + 25,409[(}}X_{{\text{Ca}}} )^2 ] - 55,137[X_{{\text{Ca}}} (X_{{\text{Mg}}} - X_{{\text{Fe}}} )] \hfill \\{\text{ }} - 11,338[X_{{\text{Al}}} (X_{{\text{Fe}}} - X_{{\text{Mg}}} )] \hfill \\\end{gathered} $$ [mole fractions in clinopyroxene Mg = MgSiO3, Fe = FeSiO3, Ca = CaSiO3, Al = (Al2O3-Na2O)] K D = (Fe/Mg) in garnet/(Fe/Mg) in clinopyroxene. Mn and Cr in clinopyroxene, when present in small concentrations are added to Fe and Al respectively. Fe is total Fe2++Fe3+. 相似文献
11.
A redox profile of the Slave mantle and oxygen fugacity control in the cratonic mantle 总被引：6，自引：2，他引：4
The authors report a redox profile based on Mössbauer data of spinel and garnet to a depth of 210 km from mantle xenoliths of the northern (N) and southeastern (SE) Slave craton (northern Canada). The profile transects three depth facies of peridotites that form segments of different bulk composition, represented by spinel peridotite, spinel–garnet peridotite, low-temperature garnet peridotite, high-temperature garnet peridotite, and pyroxenite. The shallow, more depleted N Slave spinel peridotite records lower oxygen fugacities compared to the deeper, less depleted N Slave spinel–garnet peridotite, consistent with their different spinel Fe3+ concentrations. Garnet peridotites show a general reduction in log fO2 (FMQ)s with depth, where values for garnet peridotites are lower than those for spinel–garnet peridotites. There is a strong correlation between depletion and oxygen fugacity in the spinel peridotite facies, but little correlation in the garnet peridotite facies. The strong decrease in log fO2 (FMQ) with depth that arises from the smaller partial molar volume of Fe3+ in garnet, and the observation of distinct slopes of log fO2 (FMQ) with depth for spinel peridotite compared to spinel–garnet peridotite strongly suggest that oxygen fugacity in the cratonic peridotitic mantle is intrinsically controlled by iron equilibria involving garnet and spinel.
12.
13.
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
14.
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
15.
The interdependence of the Fe(Mg)–1 (e.g., FeO-MgO in silicate melt; CaFeSi2O6-CaMgSi2O6 in pyroxene) and TiAl2(MgSi2)–1 exchange reactions between silicate melts and coexisting Ca-pyroxene has been examined. High-calcium clinopyroxenes were grown in 1 atmosphere melting and crystallization experiments on rock powders spanning the composition range tholeiite to melilitite (1,092
16.
Solubility of Ca and Al in orthopyroxene from spinel peridotite: an improved version of an empirical geothermometer 总被引：1，自引：1，他引：0
Geothermometric equations for spinel peridotites by Fujii (1976), Gasparik and Newton (1984), and Chatterjee, and Terhart (1985) based on the reaction enstatite (en)+spinel (sp)Mg–Tschermaks (mats)+forsterite (fo) were tested using a nearly isothermal suite of mantle xenoliths from the Eifel, West Germany. In spite of using activities of MgAl2O4, en, and mats to allow for the non-ideal solution behaviour of the constituent phases, temperatures calculated from these equations systematically change as a function of Cr/(Cr+AL+Fe3+) in spinel. We propose an improved version of the empirical geothermometer for spinel peridotites of Sachtleben and Seck (1981) derived from the evaluation of the solubilities of Ca and Al in orthopyroxene from more than 100 spinel peridotites from the Rhenish Volcanic Province. A least squares regression yielded a smooth correlation between
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