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1.
The elastic moduli of magnesioferrite spinel, MgFe2O4, and their temperature dependence have been determined for the first time by ultrasonic measurements on a polycrystalline specimen. The measurements were carried out at 300 MPa and to 700°C in a gas-medium high-pressure apparatus. On heating, both the elastic bulk (K S) and shear (G) moduli decrease linearly to 350°C. By combining with extant thermal-expansion data, the values for the room-temperature K S and G, and their temperature derivatives are as follows: K 0 = 176.3(7) GPa, G 0 = 80.1(2) GPa, (∂K S/∂T) P = −0.032(3) GPa K−1 and (∂G/∂T) P = −0.012(1) GPa K−1. Between 350 and 400°C, there are abrupt increases of 1.4% in both of the elastic moduli; these closely coincide with the magnetic Curie transition that was observed by thermal analyses at about 360°C.  相似文献   

2.
Isobaric volume measurements for MgO were carried out at 2.6, 5.4, and 8.2 GPa in the temperature range 300–1073 K using a DIA-type, large-volume apparatus in conjunction with synchrotron X-ray powder diffraction. Linear fit of the thermal expansion data over the experimental pressure range yields the pressure derivative, (∂α/∂P) T , of −1.04(8) × 10−6 GPa−1 K−1 and the mean zero-pressure thermal expansion α0, T  = 4.09(6) × 10−5 K−1. The α0, T value is in good agreement with results of Suzuki (1975) and Utsumi et al. (1998) over the same temperature range, whereas (∂α/∂P) T is determined for the first time on MgO by direct measurements. The cross-derivative (∂α2/∂P∂T) cannot be resolved because of large uncertainties associated with the temperature derivative of α at all pressures. The temperature derivative of the bulk modulus, (∂K T/∂T) P , of −0.025(3) GPa K−1, obtained from the measured (∂α/∂P) T value, is in accord with previous findings. Received: 2 April 1999 / Revised, accepted: 22 June 1999  相似文献   

3.
The ambient pressure elastic properties of single-crystal TiO2 rutile are reported from room temperature (RT) to 1800 K, extending by more than 1200 oK the maximum temperature for which rutile elasticity data are available. The magnitudes of the temperature derivatives decrease with increasing temperature for five of the six adiabatic elastic moduli (C ij ). At RT, we find (units, GPa): C 11=268(1); C 33=484(2); C 44=123.8(2); C 66=190.2(5); C 23=147(1); and C 12=175(1). The temperature derivatives (units, GPa K−1) at RT are: (∂C 11/∂T) P =−0.042(5); (∂C 33/∂T) P =−0.087(6); (∂C 44/∂T) P =−0.0187(2); (∂C 66/∂T) P =−0.067(2); (∂C 23/∂T) P =−0.025; and (∂C 12/∂T) P −0.048(5). The values for K S (adiabatic bulk modulus) and μ (isotropic shear modulus) and their temperature derivatives are K S =212(1) GPa; μ=113(1) GPa; (∂K S /∂T) P =−0.040(4) GPa K−1; and (∂μ/∂T) P =−0.018(1) GPa K−1. We calculate several dimensionless parameters over a large temperature range using our new data. The unusually high values for the Anderson-Gròneisen parameters at room temperature decrease with increasing temperature. At high T, however, these parameters are still well above those for most other oxides. We also find that for TiO2, anharmonicity, as evidenced by a non-zero value of [∂ln (K T )/∂lnV] T , is insignificant at high T, implying that for the TiO2 analogue of stishovite, thermal pressure is independent of volume (or pressure). Systematic relations indicate that ∂2 K S /∂T∂P is as high as 7×10−4 K−1 for rutile, whereas ∂2μ/∂T∂P is an order of magnitude less. Received: 19 September 1997 / Revised, accepted: 27 February 1998  相似文献   

4.
Elastic wave velocities for dense (99.8% of theoretical density) isotropic polycrystalline specimens of synthetic pyrope (Mg3Al2Si3O12) were measured to 1,000 K at 300 MPa by the phase comparison method of ultrasonic interferometry in an internally heated gas-medium apparatus. The temperature derivatives of the elastic moduli [(∂Ks/∂T) P = −19.3(4); (∂G/∂T) P = −10.4(2) MPa K−1] measured in this study are consistent with previous acoustic measurements on both synthetic polycrystalline pyrope in a DIA-type cubic anvil apparatus (Gwanmesia et al. in Phys Earth Planet Inter 155:179–190, 2006) and on a natural single crystal by the rectangular parallelepiped resonance (RPR; Suzuki and Anderson in J Phys Earth 31:125–138, 1983) method but |(∂Ks/∂T) P | is significantly larger than from a Brillouin spectroscopy study of single-crystal pyrope (Sinogeikin and Bass in Phys Earth Planet Inter 203:549–555, 2002). Alternative approaches to the retrieval of mixed derivatives of the elastic moduli from joint analysis of data from this study and from the solid-medium data of Gwanmesia et al. in Phys Earth Planet Inter 155:179–190 (2006) yield ∂2 G/∂P∂T = [0.07(12), 0.20(14)] × 10−3 K−1 and ∂2 K S /∂P∂T = [−0.20(24), 0.22(26)] × 10−3 K−1, both of order 10−4 K−1 and not significantly different from zero. More robust inference of the mixed derivatives will require solid-medium acoustic measurements of precision significantly better than 1%.  相似文献   

5.
We determined the forward rate constant (K+) for the Fe2+–Mg order–disorder between the M2 and M1 sites of orthopyroxene (OPx), which is described by the homogeneous reaction Fe2+ (M2) + Mg(M1) ↔ Mg(M2) + Fe2+ (M1), by both ordering and disordering experiments at isothermal condition and also by continuous cooling experiments. The rate constant was determined as a function of temperature in the range of 550–750°C, oxygen fugacity between quartz–fayalite–iron and Ni–NiO buffers, and at compositions of 16 and 50 mol% ferrosilite component. The K+ value derived from disordering experiment was found to be larger than that derived from ordering experiment at 550°C, while at T>580°C, these two values are essentially the same. The fO2 dependence of the rate constant can be described by the relation K+ α (fO2) n with n=5.5–6.5, which is compatible with the theoretically expected relation. The Arrhenius relation at the WI buffer condition is given by
where C o represents the total number of M2 + M1 sites occupied by Fe2+ and Mg per unit volume of the crystal. The above relation can be used to calculate the cooling rates of natural OPx crystals around the closure temperature (T c) of Fe–Mg ordering, which are usually below 300°C for slowly cooled rocks. We determined the Fe–Mg ordering states of several OPx crystals (∼ Fs50) from the Central Gneissic Complex (Khtada Lake), British Columbia, which yields T c ∼290°C. Numerical simulation of the change of Fe2+-Mg ordering in OPx as a function of temperature using the above expression of rate constant and a non-linear cooling model yields quenched values of ordering states that are in agreement with the observed values for cooling rates of 11–17°C/Myr below 300°C. The inferred cooling rate is in agreement with the available geochronological constraints.  相似文献   

6.
Using powder X-ray diffraction of heated solids to pressures reaching 68 GPa, the pressure-volume-temperature (PVT) data on corundum Al2O3 and ɛ-Fe were determined with the following results: *Corundum,*Iron, *Al2O3*ɛ-Fe Isothermal bulk*258 (2)*164 (3)  modulus K'300, 1 (GPa) Pressure derivative K300, 1*4.88 (4)*5.36 (16) Temperature derivative*–0.020 (2)*–0.043 (3)  (∂K T,1 /∂T) P (GPa/K) Molar volume V300,1*25.59 (2)*6.76 (2)  (cm3/mol) Isobaric thermal expansion at 1 atm (0.101 MPa) is given by (K–1): α T =2.6 (2) 10–5+1.81 (9) 10–9 T–0.67 (6)/T 2 for corundum, and α T =5.7 (4) 10–5+4.2 (4) 10–9 T–0.17 (7)/T 2 for iron ɛ-Fe. Received: 1 March 1997 / Revised, accepted: 21 August 1997  相似文献   

7.
In order to assess the geothermometric potential of the Na2(Mn2−2x Fe1+2x )(PO4)3 system (x = 0–1), which represents the compositions of natural weakly oxidized alluaudites, we performed hydrothermal experiments between 400 and 800°C, at 1 kbar, under an oxygen fugacity (f(O2)) controlled by the Ni–NiO (NNO), Fe2O3–Fe3O4 (HM), Cu2O–CuO (CT), and Fe–Fe3O4 (MI) buffers. When f(O2) is controlled by NNO, single-phase alluaudites crystallize at 400 and 500°C, whereas the association alluaudite + marićite appears between 500 and 700°C. The limit between these two fields corresponds to the maximum temperature that can be reached by alluaudites in granitic pegmatites, because marićite has never been observed in these geological environments. Because alluaudites are very sensitive to variations of oxygen fugacity, the field of hagendorfite, Na2MnFe2+Fe3+(PO4)3, has been positioned in the f(O2)–T diagram, and provides a tool that can be used to estimate the oxygen fugacity conditions that prevailed in granitic pegmatites during the crystallization of this phosphate.  相似文献   

8.
 Ferrian magnesian spodumene was synthesized in the MLFSH system at P=0.4 GPa, T=700 °C, fO2=NNO+2.3. The space group at room T is P21/c [a=9.638(3) ?, b=8.709(2) ?, c=5.258(2) ?, β=109.83(3)∘, V=415.2 ?3]. The structure is topologically equivalent to that of ferrian spodumene, LiFeSi2O6, and has two symmetrically independent tetrahedral chains, A and B, and two independent octahedral sites, M1 and M2. The crystal-chemical composition was determined combining EMP, SIMS and single-crystal XRD analysis, yielding M2(Li0.85Mg0.09Fe2+ 0.06) M1(Fe3+ 0.85Mg0.15)Si2O6. Li is ordered at the M2 site and Fe3+ is ordered at the M1 site, whereas Mg (and Fe2+) distribute over both octahedral sites. Structure refinements done at different temperatures (25, 70, 95, 125, 150 and 200 °C) allowed characterization of a reversible displacive P21/c→C2/c transition at 106 °C. Previous HT-XRD studies of Li-clinopyroxenes had shown that the transition temperature is inversely related to the size of the M1 cation. For the crystal of this work, the aggregate ionic radius at M1 is longer than that of ferrian spodumene, for which the transition temperature is −44 °C. The higher transition temperature observed can only be explained on the basis of the shorter aggregate radius at the M2 site (due to the presence of Mg substituting after Li), in keeping with the results obtained for ferromagnesian P21/c pyroxenes. The effects of all the chemical substitutions must be considered when modelling transition temperatures and thermodynamic behaviour in clinopyroxenes. Received: 7 May 2002 / Accepted: 23 October 2002  相似文献   

9.
Phase transformations in a natural sample of hedenbergite ((Ca0.93Fe0.61Mn0.34Mg0.08Na0.01Zn0.02Al0.003)Si2O6) have been studied by X-ray diffraction up to 40 GPa at ∼ 1200°C in a diamond anvil cell interfaced with a laser heating system. The starting hedenbergite phase decomposed into a garnet plus γ-spinel and stishovite at ∼ 14 GPa; then into garnet plus stishovite and wüstite at ∼ 18 GPa; and finally into perovskite plus stishovite and wüstite at pressures higher than ∼ 24 GPa. On decompression to 0.1 MPa, all the high pressure phases are retained except for the cubic perovskite, which reverts back into the ɛ-CaSiO3 phase, in accordance with previous reports. Energy-dispersive SEM analyses show that the garnet is present as a calcium-rich ABO 3-type phase. As no garnet phase has been previously observed either in pure CaSiO3 or in pure CaMgSi2O6, it appears that the observed calcium-rich garnet phase has been stabilized by the presence of other cations such as the Na+, Zn2+, Mn2+, Fe2+, Mn3+, Fe3+ and Al3+.  相似文献   

10.
 In Madagascar, hibonite occurs as a rather frequent mineral within thorianite-bearing skarns which are widespread in the Pan African granulitic formations constituting the S-E part of the Island (Tranomaro area). In these skarns, leucocratic segregations made up of CO3-scapolite to meionite (Anequivalent=89–95% which implies T≥850° C), spinel and corundum were formed at stage 1 of metasomatism in a titanite-bearing matrix consisting of scapolite (Aneq=77–88) and aluminous diopside. During stage 2 of metasomatism, scapolite from the lenses were altered to anorthite+calcite while the less calcic scapolite remained stable which indicates T≈800° C. Hibonite crystallized at the expense of corundum and spinel. Expressed as mol% of the CaAl12O19/Ca(Al10TiR2+)O19/REE(Al11R2+)O19 [+Th (Al10R2+ 2)O19] end-members (R 2+=Mg, Fe2+, Zn2+; Al=Al, Fe3+; Ti=Ti, Si), its composition varies from 26/72/2 to 50/23/27. The ideal activity of the CaAl12O19 component is about 0.25. Fluid inclusions in corundum, hibonite and anorthite are composed of nearly pure CO2. In corundum, the isochores for primary inclusions are in agreement with the P-T estimates for regional metamorphism and stage 1 metasomatism (T≈850° C, P≈5 kbar). Inclusions with the highest density in hibonite and anorthite constrain P to about 3–3.5 kbar for T=800° C. Thermodynamic calculations indicate that, in addition to a low activity of CaAl12O19, stability of hibonite in equilibrium with anorthite and calcite implies an extremely low activity of silica (below the zircon-baddeleyite buffer). By contrast the activity of CO2 may be high, in agreement with the observed fluid compositions. These results are corroborated by a short comparison with the other granulite occurrences of hibonite in Tanzania and South India. Received: 18 August 1994 / Accepted: 12 October 1995  相似文献   

11.
 P–V–T measurements on magnesite MgCO3 have been carried out at high pressure and high temperature up to 8.6 GPa and 1285 K, using a DIA-type, cubic-anvil apparatus (SAM-85) in conjunction with in situ synchrotron X-ray powder diffraction. Precise volumes are obtained by the use of data collected above 873 K on heating and in the entire cooling cycle to minimize non-hydrostatic stress. From these data, the equation-of-state parameters are derived from various approaches based on the Birch-Murnaghan equation of state and on the relevant thermodynamic relations. With K′0 fixed at 4, we obtain K0=103(1) GPa, α(K−1)=3.15(17)×10−5 +2.32(28)×10−8 T, (∂KT/∂T)P=−0.021(2) GPaK−1, (dα/∂P)T=−1.81×10−6 GPa−1K−1 and (∂KT/∂T)V= −0.007(1) GPaK−1; whereas the third-order Birch-Murnaghan equation of state with K′0 as an adjustable parameter yields the following values: K0=108(3) GPa, K′0=2.33(94), α(K−1)=3.08(16)×10−5+2.05(27) ×10−8 T, (∂KT/∂T)P=−0.017(1) GPaK−1, (dα/∂P)T= −1.41×10−6 GPa−1K−1 and (∂KT/∂T)V=−0.008(1) GPaK−1. Within the investigated P–T range, thermal pressure for magnesite increases linearly with temperature and is pressure (or volume) dependent. The present measurements of room-temperature bulk modulus, of its pressure derivative, and of the extrapolated zero-pressure volumes at high temperatures, are in agreement with previous single-crystal study and ultrasonic measurements, whereas (∂KT/∂T)P, (∂α/∂P)T and (∂KT/∂T)V are determined for the first time in this compound. Using this new equation of state, thermodynamic calculations for the reactions (1) magnesite=periclase+CO2 and (2) magnesite+enstatite=forsterite+CO2 are consistent with existing experimental phase equilibrium data. Received September 28, 1995/Revised, accepted May 22, 1996  相似文献   

12.
 Powder diffraction measurements at simultaneous high pressure and temperature on samples of 2M1 polytype of muscovite (Ms) and paragonite (Pg) were performed at the beamline ID30 of ESRF (Grenoble), using the Paris-Edinburgh cell. The bulk moduli of Ms, calculated from the least-squares fitting of V–P data on each isotherm using a second-order Birch–Murnaghan EoS, were: 57.0(6), 55.1(7), 51.1(7) and 48.9(5) GPa on the isotherms at 298, 573, 723 and 873 K, respectively. The value of (∂K T /∂T) was −0.0146(2) GPa K−1. The thermal expansion coefficient α varied from 35.7(3) × 10−6 K−1 at P ambient to 20.1(3) × 10−6 K−1 at P = 4 GPa [(∂α/∂P) T = −3.9(1) × 10−6 GPa−1 K−1]. The corresponding values for Pg on the isotherms at 298, 723 and 823 K were: bulk moduli 59.9(5), 55.7(6) and 53.8(7) GPa, (∂K T /∂T) −0.0109(1) GPa K−1. The thermal expansion coefficient α varied from 44.1(2) × 10−6 K−1 at P ambient to 32.5(2) × 10−6 K−1 at P = 4 GPa [(∂α/∂P) T = −2.9(1) × 10−6 GPa−1 K−1]. Thermoelastic coefficients showed that Pg is stiffer than Ms; Ms softens more rapidly than Pg upon heating; thermal expansion is greater and its variation with pressure is smaller in Pg than in Ms. Received: 28 January 2002 / Accepted: 5 April 2002  相似文献   

13.
Values of the complete adiabatic elastic tensor for single-crystal chrome-diopside (a monoclinic pyroxene mineral) are presented from 298 to 1,300 K. The data were obtained using resonant ultrasound spectroscopy (RUS). They are the first published results for the temperature T dependences of the 13 individual elastic constants C ij of any clinopyroxene mineral. Each C ij is appropriately described by a linear function in T throughout the range of T. Values for each (∂C ij /∂T) P in GPa K−1 are as follows: C 11, −0.0291; C 22, −0.0248; C 33, −0.0179; C 44, −0.0103; C 55, −0.0077; C 66, −0.0152; C 12, −0.0119; C 13, −0.0064; C 23, 0.0000; C 15, 0.0025; C 25, 0.0022; C 35, −0.0046; and C 46, 0.0026. Values of (∂M/∂T) P in GPa K−1, where M represents an isotropic bulk property calculated from the C ij data, are as follows: adiabatic bulk modulus K S , −0.0123; isothermal bulk modulus K T , −0.0178; and shear modulus G, −0.00998. Some diopside derivatives, notably (∂K S /∂T) P , (∂K T /∂T) P , and (∂V P /∂T) P , where V P is the compressional wave velocity, have smaller magnitudes than all other minerals of importance in Earth’s mantle, thus, confirming predictions from systematics studies. We find several dimensionless quantities for this monoclinic mineral have normal values compared to other mantle minerals. Further, αK T (α is the volume coefficient of thermal expansion) for diopside is approximately independent of both T and volume V at elevated temperature, so its equation of state is accurately expressed in simplified form.  相似文献   

14.
 In order to develop a model for simulating naturally occurring chromian spinel compositions, we have processed published experimental data on chromian spinel-melt equilibrium. Out of 259 co-existing spinel-melt experiments reported in the literature, we have selected 118 compositions on the basis of run time, melt composition and experimental technique. These data cover a range of temperatures 1150–1500° C, oxygen fugacities of −13<log f O2< −0.7, and bulk compositions ranging from basalt and norite, to komatiite. Six major spinel components with Cr3+, Al3+, Ti4+, Mg2+, Fe3+ and Fe2+-bearing end-members were considered for the purpose of describing chromite saturation as a function of melt composition, temperature and oxygen fugacity at 1 atmosphere pressure (0.101 MPa). The empirically calibrated mineral-melt expression based on multiple linear regressions is: K Sp i =A/T(K)+B log f O2+C ln (Fe3+/Fe2+)L+D ln R L +E, where K Sp i is an equilibrium constant and R L is a melt structure-chemical parameter (MSCP). Twenty-eight forms of equilibrium constants were considered, including single distribution coefficients, exchange equilibrium constants, formation constants for AB2O4 components, as well as simple “spinel cation ratios”. For each form of the equilibrium constants, a set of 16 combinations of the MSCPs have been investigated. The MSCP is present in the form of composite ratios [e.g., Si/O, NBO/T,(Al+Si)/Si, or (Na+K)/Al] or as simple cation ratios (e.g., Mg/Fe2+). For the calculation of Fe3+ and Fe2+ species in silicate melts, we used existing equations, whereas the Fe3+/Fe2+ ratio of spinels was calculated from the spinel stoichiometry. The regression parameters that best repoduce the experimental data were for the following constants: (Fe3+/Fe2+) Sp , (Mg/Fe2+) Sp /(Mg/Fe2+) L , (Cr/Al) Sp / (Cr/Al) L , K FeCr2O4, and Ti Sp /Ti L . These expressions have been combined into a single program called SPINMELT, which calculates chromite crystallization temperature and composition at a given f O2 with an average accuracy of ∼10° C and 1–2 mol%. An example of the use of SPINMELT is presented for a magma parental to the Bushveld Complex. Received: 30 May 1995/Accepted: 1 November 1995  相似文献   

15.
The Happo-O’ne peridotite complex is situated in the northeastern part of the Hida Marginal Tectonic Zone, central Japan, characterized by the high-P/T Renge metamorphism, and is considered as a serpentinite mélange of Paleozoic age. Peridotitic rocks, being massive or foliated, have been subjected to hydration and metamorphism. Their protoliths are mostly lherzolites to harzburgites with subordinate dunites. We found a characteristic mineral assemblage, olivine + orthopyroxene + tremolite + chlorite + chromian spinel, being stable at low-T, from 650 to 750°C, and high-P, from 16 to 20 kbar, tremolite–chlorite peridotites of the tremolite zone. Olivines are Fo88–Fo91, and orthopyroxenes (Mg# = 0.91) show low and homogenous distributions of Al2O3 (up to 0.25 wt%), Cr2O3 (up to 0.25 wt%), CaO (up to 0.36 wt%) and TiO2 (up to 0.06 wt%) due to the low equilibration temperature. Chromian spinels, which are euhedral and enclosed mainly in the orthopyroxenes, have high TiO2, 3.1 wt% (up to 5.7 wt%) on average, and high Cr# [=Cr/(Cr + Al) atomic ratio], 0.95 on average but low Fe3+ [=Fe3+/(Cr + Al + Fe3+) atomic ratio, <0.3]. The bulk-rock chemistry shows that the Happo-O’ne metaperidotites with this peculiar spinel are low in TiO2 (0.01–0.02 wt%), indicating no addition of TiO2 from the outside source during the metamorphism; the high TiO2 of the peculiar spinel has been accomplished by Ti release from Ti-bearing high-T pyroxenes during the formation of low-T, low-Ti silicates (<0.1 wt% TiO2) during cooling. Some dunites are intact from hydration: their olivine is Fo92 and spinel shows high Cr#, 0.72. The Happo-O’ne metaperidotites (tremolite–chlorite peridotites), being in the corner of the mantle wedge, are representative of a hydrous low-T, high-P mantle peridotite facies transitional from a higher T anhydrous peridotite facies (spinel peridotites) formed by in situ retrograde metamorphism influenced by fluids from the subducting slab. They have suffered from low-T (<600°C) retrogressive metamorphism to form antigorite and diopside during exhumation of the Renge metamorphic belt.  相似文献   

16.
A pressure-volume-temperature data set has been obtained for lawsonite [CaAl2Si2O7(OH)2.H2O], using synchrotron X-ray diffraction and an externally heated diamond anvil cell. Unit-cell volumes were measured to 9.4 GPa and 767 K by angle dispersive X-ray diffraction using imaging plates. Phase changes were not observed within this pressure-temperature range, and lawsonite compressed almost isotropically at constant temperature. The P-V-T data have been analyzed using a Birch- Murnaghan equation of state and a linear equation of state expressed as β=–1/V0 (∂V/∂P) T . At room temperature, the derived equation of state parameters are: K 0=124.1 (18) GPa K'0 set to 4) and β–1=142.0(24) GPa, respectively. Our results are intermediate between previously reported measurements. The high-temperature data show that the incompressibility of lawsonite decreases with increasing temperature to ∼500 K and then increases above. Hence, the second order temperature derivative of the bulk modulus is taken into account in the equation of state; a fit of the volume data yields K 0=123.9(18) GPa, (∂K/∂T)P=–0.111(3) GPa K–1, (∂2 K/∂T 2)P=0.28(6) 10–3 GPa K–2, α0=3.1(2) 10–5 K–1, assuming K'0=4. Received: 2 June 1998 / Revised, accepted: 12 Ocotber 1998  相似文献   

17.
The thermoelastic behavior of a natural clintonite-1M [with composition: Ca1.01(Mg2.29Al0.59Fe0.12)Σ3.00(Si1.20Al2.80)Σ4.00O10(OH)2] has been investigated up to 10 GPa (at room temperature) and up to 960°C (at room pressure) by means of in situ synchrotron single-crystal and powder diffraction, respectively. No evidence of phase transition has been observed within the pressure and temperature range investigated. P–V data fitted with an isothermal third-order Birch–Murnaghan equation of state (BM-EoS) give V 0 = 457.1(2) ?3, K T0 = 76(3)GPa, and K′ = 10.6(15). The evolution of the “Eulerian finite strain” versus “normalized stress” shows a linear positive trend. The linear regression yields Fe(0) = 76(3) GPa as intercept value, and the slope of the regression line leads to a K′ value of 10.6(8). The evolution of the lattice parameters with pressure is significantly anisotropic [β(a) = 1/3K T0(a) = 0.0023(1) GPa−1; β(b) = 1/3K T0(b) = 0.0018(1) GPa−1; β(c) = 1/K T0(c) = 0.0072(3) GPa−1]. The β-angle increases in response to the applied P, with: βP = β0 + 0.033(4)P (P in GPa). The structure refinements of clintonite up to 10.1 GPa show that, under hydrostatic pressure, the structure rearranges by compressing mainly isotropically the inter-layer Ca-polyhedron. The bulk modulus of the Ca-polyhedron, described using a second-order BM-EoS, is K T0(Ca-polyhedron) = 41(2) GPa. The compression of the bond distances between calcium and the basal oxygens of the tetrahedral sheet leads, in turn, to an increase in the ditrigonal distortion of the tetrahedral ring, with ∂α/∂P ≈ 0.1°/GPa within the P-range investigated. The Mg-rich octahedra appear to compress in response to the applied pressure, whereas the tetrahedron appears to behave as a rigid unit. The evolution of axial and volume thermal expansion coefficient α with temperature was described by the polynomial α(T) = α0 + α1 T −1/2. The refined parameters for clintonite are as follows: α0 = 2.78(4) 10−5°C−1 and α1 = −4.4(6) 10−5°C1/2 for the unit-cell volume; α0(a) = 1.01(2) 10−5°C−1 and α1(a) = −1.8(3) 10−5°C1/2 for the a-axis; α0(b) = 1.07(1) 10−5°C−1 and α1(b) = −2.3(2) 10−5°C1/2 for the b-axis; and α0(c) = 0.64(2) 10−5°C−1 and α1(c) = −7.3(30) 10−6°C1/2for the c-axis. The β-angle appears to be almost constant within the given T-range. No structure collapsing in response to the T-induced dehydroxylation was found up to 960°C. The HP- and HT-data of this study show that in clintonite, the most and the less expandable directions do not correspond to the most and the less compressible directions, respectively. A comparison between the thermoelastic parameters of clintonite and those of true micas was carried out.  相似文献   

18.
 Peridotites, dykes and gabbros from the 470–420 Ma Trinity Ophiolite Complex of northern California exhibit large geochemical rare earth element (REE) and Nd isotopic variations on the small scales which are indicative of a complex history. The Trinity Ophiolite, which covers an area of ≈1600 km2, consists of three distinct units: (1) a ∼2–4 km-thick sheet of plastically deformed peridotites, including various ultrabasic lithologies (plagioclase and spinel lherzolite, harzburgite, wherlite and dunite); the peridotite unit is a fragment of mantle lithosphere of oceanic affinity; (2) a series of small (∼1 km diameter) undeformed gabbroic massifs; (3) several generations of basic dykes. The peridotites display the largest geochemical and isotopic variations, with ɛNd(T) values ranging from +10 down to 0. In the gabbroic massifs and intrusive dykes, the variation in model ɛNd(T) values is reduced to 7 ɛNd units: 0 to +7. As a general rule, peridotites, gabbros and dykes with ɛNd(T) values around 0 or +3 give less depleted L(light)REE patterns than do those with ɛNd(T) values in the range +7 to +10. In the peridotites, the Nd isotopic variations take place over very short distances, with jumps as large as 7 ɛNd units occurring on scales of less than 20 m. Comparison with available age data indicates that the peridotites with ɛNd(T)≈+10 could be slightly older than the intrusive gabbro massifs and basic dykes (470 Ma vs. 420 Ma). Strontium isotopic data used in connection with Sm-Nd results demonstrate that the 10 ɛNd units variation displayed by the Trinity Peridotite is a primary feature and not an artefact due to REE mobility during seawater interaction. The variable Nd isotopic signatures and variable LREE patterns in the Trinity Peridotite cannot represent mantle source characteristics as there is evidence that this unit was partially melted when it rose as part of the upwelling convecting mantle. Field, petrographic, geochemical and isotopic data rather suggest that the observed heterogeneity is due to local reactions between a 470 Ma proto-peridotite with ɛNd(T)=+10 and younger (420 Ma) basaltic melts with lower ɛNd(T) values (i.e. the gabbroic massifs and the dykes). The gabbros and basic dykes of the Trinity Complex have geochemical and isotopic compositions similar to the arc basalts from the adjacent Copley Formation, so it is proposed that the younger melts are related to arc magmatism. Received: 13 January 1995/Accepted 5 May 1995  相似文献   

19.
A natural Ca-poor pigeonite (Wo6En76Fs18) from the ureilite meteorite sample PCA82506-3, free of exsolved augite, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P21/c, was annealed up to 1,093°C to induce a phase transition from P21/c to C2/c symmetry. The variation with increasing temperature of the lattice parameters and of the intensity of the b-type reflections (h + k = 2n + 1, present only in the P21/c phase) showed a displacive phase transition P21/c to C2/c at a transition temperature T Tr = 944°C, first order in character. The Fe–Mg exchange kinetics was studied by ex situ single-crystal X-ray diffraction in a range of temperatures between the closure temperature of the Fe–Mg exchange reaction and the transition temperature. Isothermal disordering annealing experiments, using the IW buffer, were performed on three crystals at 790, 840 and 865°C. Linear regression of ln k D versus 1/T yielded the following equation: ln k\textD = - 3717( ±416)/T(K) + 1.290( ±0.378);    (R2 = 0.988) \ln \,k_{\text{D}} = - 3717( \pm 416)/T(K) + 1.290( \pm 0.378);\quad (R^{2} = 0.988) . The closure temperature (T c) calculated using this equation was ∼740(±30)°C. Analysis of the kinetic data carried out taking into account the e.s.d.'s of the atomic fractions used to define the Fe–Mg degree of order, performed according to Mueller’s model, allowed us to retrieve the disordering rate constants C 0 K dis+ for all three temperatures yielding the following Arrhenius relation: ln( C0 K\textdis + ) = ln K0 - Q/(RT) = 20.99( ±3.74) - 26406( ±4165)/T(K);    (R2 = 0.988) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = \ln \,K_{0} - Q/(RT) = 20.99( \pm 3.74) - 26406( \pm 4165)/T(K);\quad (R^{2} = 0.988) . An activation energy of 52.5(±4) kcal/mol for the Fe–Mg exchange process was obtained. The above relation was used to calculate the following Arrhenius relation modified as a function of X Fe (in the range of X Fe = 0.20–0.50): ln( C0 K\textdis + ) = (21.185 - 1.47X\textFe ) - \frac(27267 - 4170X\textFe )T(K) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = (21.185 - 1.47X_{\text{Fe}} ) - {\frac{{(27267 - 4170X_{\text{Fe}} )}}{T(K)}} . The cooling time constant, η = 6 × 10−1 K−1 year−1 calculated on the PCA82506-3 sample, provided a cooling rate of the order of 1°C/min consistent with the extremely fast late cooling history of the ureilite parent body after impact excavation.  相似文献   

20.
 Complete chemical analyses, including ferric and ferrous iron, H2O contents and δD values for 16 phlogopite and biotite and 2 hornblende separates are presented. Samples were obtained from volcanic rocks from four localities: (1) phlogopite phenocrysts from minette lavas from the western Mexico continental arc, (2) biotite and hornblende phenocrysts from andesite lavas from Mono Basin, California, (3) phlogopite and biotite from clinopyroxenite nodules entrained in potassic lavas from the East African Rift, Uganda, and (4) phlogopite phenocrysts from a wyomingite lava in the Leucite Hills, Wyoming. The Fe2O3 contents in the micas range from 0.8 to 10.5 wt%, corresponding to 0.09 to 1.15 Fe3+ per formula unit (pfu). Water contents vary from 1.6 to 3.0 wt%, corresponding to 1.58 to 3.04 OH pfu, significantly less than would be expected for a site fully occupied by hydroxyl. Cation- and anion-based normalization procedures provide accurate mineral formulae with respect to most cations and anions, but are unable to generate accurate estimates of Fe3+/FeT, and overestimate OH at the expense of O on the hydroxyl site. These inaccuracies are present despite acceptable adjusted totals and stoichiometric calculated site occupancies. The phlogopite and biotite phenocrysts in arc-related lavas from western Mexico and eastern California have the highest Fe3+/FeT ratios (56–87%), reflecting high magmatic oxygen fugacities (ΔNNO = +2 to +5), in contrast to those from Uganda (25–40%) and the Leucite Hills (23%). There is no correlation between the OH content and the Fe3+/FeT ratio in the micas. Values of KMg/Fe2+D (± 2σ errors) were calculated for three phlogopite-olivine pairs (0.12 ± 0.12, 0.26 ± 0.14, 0.09 ± 0.12), two biotite-hornblende pairs (0.73 ± 0.08 and 1.22 ± 0.10) and a single phlogopite-augite pair (1.15 ± 0.12). Values of KF/OHD for two biotite and hornblende pairs could not be determined without significant error because of the extremely low F contents (< 0.2 wt%) of the four phases. The δD values obtained in this study encompass a large range (−137 to −43‰). The phlogopite and biotite separates from Uganda have δD values of −70 to −49‰, which overlap those believed to represent “primary” mantle. There is a larger range in δD values (−137 to −43‰) for phlogopite phenocrysts from western Mexico minette lavas, although their range in δ18O values (5.2–6.2‰) is consistent with “normal” mantle. It is unlikely, therefore, that the variable δD values reflect heterogeneity in the mantle source region of the minette magmas. Nor can the extremely low δD values reflect degassing of H2 or H2O since almost 100% loss of dissolved water in the magma is required, an unrealistic scenario given the stability of the hydrous phenocrysts. The very low δD values of the Mascota minette phlogopites require that the hydrogen be introduced from an external source (e.g., meteoric water). Whatever the process responsible for the observed hydrogen isotope composition, it had no effect on the δ18O value, f O 2, a H 2O or bulk composition of the host magmas. Received: 5 January 1995 / Accepted: 19 March 1996  相似文献   

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