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1.
 The partitioning of Fe and Mg between the M1 and M2 octahedral sites of olivine has been investigated by in situ time-of-flight neutron powder diffraction. The degree of M-cation order was determined from direct measurements of site occupancies in a synthetic sample of Fo50Fa50 heated to 1250 °C at the Fe-FeO oxygen buffer. Fe shows slight preference for M1 at temperatures below about 600 °C, progressively disordering on heating to this temperature. Above 630 °C, the temperature at which site preferences cross over (T cr), Fe preferentially occupies M2, becoming progressively more ordered into M2 on increasing temperature. The cation-ordering behaviour is discussed in relation to the temperature dependence of the M1 and M2 site geometries, and it is suggested that vibrational entropy, crystal field effects and changes in bond characteristics play a part in the cross-over of partitioning behaviour. The temperature dependence of site ordering is modelled using a Landau expansion of the free energy of ordering of the type ΔG = −hQ + gTQ +  (T − T c)Q 2 +  Q 4, with a/h = 0.00406 K−1, b/h = 2.3, T c = 572 K and g/h = 0.00106 K−1. These results suggest that the high-temperature ordering behaviour across the forsterite-fayalite join will have a bearing on the activity-composition relations of this important rock-forming mineral, and indicate that Fe-Mg olivine solid solutions become less ideal as temperature increases. Received: 12 August 1999 / Accepted: 25 April 2000  相似文献   

2.
Crystallographic determinations on natural olivine single crystals of mantle composition and origin, carried out by in situ neutron diffraction at high temperature, show that the octahedrally co-ordinated Fe2+ and Mg cations undergo two successive trends of cation ordering with increasing temperature. An initial slight preference of Fe2+ for site M1, up to a temperature of about 850?°C, is followed by a reverse-ordering reaction with a site preference exchange between the two cations. The cross-over between the two regimes of ordering, corresponding to a situation of complete disorder, occurs at about 900?°C. Above this temperature Fe2+ progressively and strongly segregates into site M2 up to 1300?°C, the practical limit of the experimental setup utilized in the experiments. Care was taken to ensure that no chemical changes occurred in the crystals (i.e. oxidation), as testified by Mössbauer spectroscopy determinations carried out before and after the heat treatment. The cation-ordering behaviour is reflected in temperature-dependent changes of geometrical and atomic displacement parameters occurring in the octahedral sites M1 and M2. A thermodynamical explanation of this behaviour is proposed in terms of a prevailing vibrational contribution to entropy.  相似文献   

3.
The crystal structure and site preference of Co2+ in a synthetic Co1.10Mg0.90SiO4 olivine have been determined from single crystal X-ray diffraction data collected on an automatic diffractometer. The R factor is 0.044 for 612 reflections. The site occupancies are: Ml site: Co 0.730±0.006; Mg 0.270; M2 site: Co 0.370, Mg 0.630. The Gibbs free energy change, ΔG° for the ion-exchange reaction between M1 and M2 sites is ?4.06 kcals/mole, assuming ideal mixing at each set of sites. This energy may be called ‘site preference energy’ of Co2+ in olivine. The strong preference of Co2+ for the M1 site can be quantitatively explained by two competing forces: preference of ions larger than Mg2+ for the M2 site and stronger covalent bonding of transition metal ions at the M1 site. For Fe2+, Mg2+, these two effects nearly neutralize each other, explaining the lack of considerable cation-ordering in Fe-Mg olivines.  相似文献   

4.
In the olivine crystal structure, cations are distributed over two inequivalent octahedral sites, M1 and M2. Kinetics of cation exchange between the two octahedral sites in (Co0.1Mg0.9)2SiO4 single crystal have been studied in the temperature range from 600 to 800°C by monitoring the time evolution of the absorbance of Co2+ ions in M1 or M2 sites using optical spectroscopy after rapid temperature jumps. It was found from such temperature-jump induced relaxation experiments that with increasing temperature the absorbance of Co2+ ions in the M1 site decreases while that in the M2 site increases. This indicates a tendency of Co2+ cations to populate the M2 site with increasing temperatures and vice versa. The experimental relaxation data can be modeled using a triple exponential equation based on theoretical analysis. Activation energies of 221 ± 4 and 213 ± 10 kJ/mol were derived from relaxation experiments on the M2 site and M1 site, respectively, for the cation exchange processes in (Co0.1Mg0.9)2SiO4 olivine. Implications for cation diffusion at low temperatures are discussed.  相似文献   

5.
Ten spinel-lherzolite inclusions and one olivine-websterite inclusion, which were collected from Fujian, Jiangsu, Hebei and Yunnan Provinces, consist of olivine (FΦ87.7–91.2), enstatite (En87.3–89.7), Cr-diopside and spinel. According to the Mg/(Mg+Fe2+) ratios in the rocks and their mineralogies, they are designated to the Cr-diopside type. The websterite is composed of bronzite (En71.9) and augite, while the gabbro-norite consists of hypersthene (En68.9) and augite, belonging to the Al-augite type. The geothermos of spinel-lherzolites were calculated with four geothermometric methods, giving a temperature range of 925°–1,072°C. However, according to P. R. A. Wells' method, temperatures range from 845δ to 1,014°C, and by D. H. Lindsly's approach, from 716°–974°C. Pressures range from 15.1 to 19.8 kb. Genetically, Spinel-lherzolites and olivine-websterite are thought to have been derived from residual mantle material by partial melting at approximately 1,000°C and at a depth of about 50–70 km. Websterite and gabbro-norite may be products of the crystallization-differentiation of alkali basaltic magma.  相似文献   

6.
The interdiffusion coefficient of Mg–Fe in olivine (D Mg–Fe) was obtained at 1,400–1,600 °C at the atmospheric pressure with the oxygen fugacity of 10?3.5–10?2 Pa using a diffusion couple technique. The D Mg–Fe shows the anisotropy (largest along the [001] direction and smallest along the [100] direction), and its activation energy (280–320 kJ/mol) is ~80–120 kJ/mol higher than that estimated at lower temperatures. The D Mg–Fe at temperatures of >1,400 °C can be explained by the cation-vacancy chemistry determined both by the Fe3+/Fe2+ equilibrium and by the intrinsic point defect formation with the formation enthalpy of 220–270 kJ/mol depending on the thermodynamical model for the Fe3+/Fe2+ equilibrium in olivine. The formation enthalpy of 220–270 kJ/mol for the point defect (cation vacancy) in olivine is consistent with that estimated from the Mg self-diffusion in Fe-free forsterite. The increase in the activation energy of D Mg–Fe at >1,400 °C is thus interpreted as the result of the transition of diffusion mechanism from the transition metal extrinsic domain to the intrinsic domain at the atmospheric pressure.  相似文献   

7.
The exsolutious of diopside and magnetite occur as intergrowth and orient within olivine from the mantle dunite, Luobusa ophiolite, Tibet. The dunite is very fresh with a mineral assemblage of olivine （〉95%） ＋ chromite （1%-4%） ＋ diopside （〈1%）. Two types of olivine are found in thin sections： one （Fo = 94） is coarse-grained, elongated with development of kink bands, wavy extinction and irregular margins; and the other （Fo = 96） is fine-grained and poly-angied. Some of the olivine grains contain minor Ca, Cr and Ni. Besides the exsolutions in olivine, three micron-size inclusions are also discovered. Analyzed through energy dispersive system （EDS） with unitary analytical method, the average compositions of the inclusions are： Na20, 3.12%-3.84%; MgO, 19.51%-23.79%; Al2O3, 9.33%-11.31%; SiO2, 44.89%-46.29%; CaO, 11.46%-12.90%; Cr2O3, 0.74%-2.29%; FeO, 4.26%- 5.27%, which is quite similar to those of amphibole. Diopside is anhedral f＇dling between olivines, or as micro-inclusions oriented in olivines. Chromite appears euhedral distributed between olivines, sometimes with apparent compositional zone. From core to rim of the chromite, Fe content increases and Cr decreases; and A! and Mg drop greatly on the rim. There is always incomplete magnetite zone around the chromite. Compared with the nodular chromite in the same section, the euhedral chromite has higher Fe3O4 and lower MgCr2O4 and MgAI2O4 end member contents, which means it formed under higher oxygen fugacity environment. With a geothermometer estimation, the equilibrium crystalline temperature is 820℃-960℃ for olivine and nodular chromite, 630℃-770℃ for olivine and euhedral chromite, and 350℃-550℃ for olivine and exsoluted magnetite, showing that the exsolutions occurred late at low temperature. Thus we propose that previously depleted mantle harzburgite reacted with the melt containing Na, Al and Ca, and produced an olivine solid solution added with Na^＋, Al^3＋, Ca^2＋, Fe^3＋, Cr^3＋. With temperature d  相似文献   

8.
Mutual relationships among temperatures estimated with the most widely used geothermometers for garnet peridotites and pyroxenites demonstrate that the methods are not internally consistent and may diverge by over 200°C even in well-equilibrated mantle xenoliths. The Taylor (N Jb Min Abh 172:381–408, 1998) two-pyroxene (TA98) and the Nimis and Taylor (Contrib Mineral Petrol 139:541–554, 2000) single-clinopyroxene thermometers are shown to provide the most reliable estimates, as they reproduce the temperatures of experiments in a variety of simple and natural peridotitic systems. Discrepancies between these two thermometers are negligible in applications to a wide variety of natural samples (≤30°C). The Brey and Köhler (J Petrol 31:1353–1378, 1990) Ca-in-Opx thermometer shows good agreement with TA98 in the range 1,000–1,400°C and a positive bias at lower T (up to +90°C, on average, at T TA98 = 700°C). The popular Brey and Köhler (J Petrol 31:1353–1378, 1990) two-pyroxene thermometer performs well on clinopyroxene with Na contents of ~0.05 atoms per 6-oxygen formula, but shows a systematic positive bias with increasing NaCpx (+150°C at NaCpx = 0.25). Among Fe–Mg exchange thermometers, the Harley (Contrib Mineral Petrol 86:359–373, 1984) orthopyroxene–garnet and the recent Wu and Zhao (J Metamorphic Geol 25:497–505, 2007) olivine–garnet formulations show the highest precision, but systematically diverge (up to ca. 150°C, on average) from TA98 estimates at T far from 1,100°C and at T < 1,200°C, respectively; these systematic errors are also evident by comparison with experimental data for natural peridotite systems. The older O’Neill and Wood (Contrib Mineral Petrol 70:59–70, 1979) version of the olivine–garnet Fe–Mg thermometer and all popular versions of the clinopyroxene–garnet Fe–Mg thermometer show unacceptably low precision, with discrepancies exceeding 200°C when compared to TA98 results for well-equilibrated xenoliths. Empirical correction to the Brey and Köhler (J Petrol 31:1353–1378, 1990) Ca-in-Opx thermometer and recalibration of the orthopyroxene–garnet thermometer, using well-equilibrated mantle xenoliths and TA98 temperatures as calibrants, are provided in this study to ensure consistency with TA98 estimates in the range 700–1,400°C. Observed discrepancies between the new orthopyroxene–garnet thermometer and TA98 for some localities can be interpreted in the light of orthopyroxene–garnet Fe3+ partitioning systematics and suggest localized and lateral variations in mantle redox conditions, in broad agreement with existing oxybarometric data. Kinetic decoupling of Ca–Mg and Fe–Mg exchange equilibria caused by transient heating appears to be common, but not ubiquitous, near the base of the lithosphere.  相似文献   

9.
Melt inclusions in olivine and pyroxene phenocrysts in kersantite and camptonite at Chhaktalao in Madhya Pradesh, India are mainly of the evolved type forming daughter minerals of olivine, pyroxene, plagioclase, spinel, mica, titanomagnetite and sulphides. Heating studies exhibit a temperature range from 1215° to 1245°C for the melt inclusions in olivine in camptonite and 1220–1245°C for olivine in kersantite. The temperature for melt inclusions in pyroxene ranged from 1000° to 1150°C in camptonite and 850–1100°C for pyroxene in kersantite. The bubble inside these melt inclusions is mainly CO2. The Th°C of CO2 into liquid phase occurred between 26° and 31°C in olivine and 25–30°C in pyroxene from kersantite and camptonite. The maximum density estimated is 0.72 g/cm3 and the minimum is 0.45 g/cm3. The depth of entrapment of the melt inclusion is estimated between 10–15 km. The pressure of entrapment of melt inclusion in olvine is 4.6 kbar where as that in pyroxene is 3.7 kbar. The lamprophyres in the Chhaktalao area are considered to be derived from low depth and low pressure region, possibly within spinel lherzolite zone.  相似文献   

10.
The temperature induced structural evolution and thermoelastic behaviour of a natural (Pbca) orthopyroxene (Opx), with chemical formula M2(Mg0.856Ca0.025Fe2+ 0.119) M1(Mg0.957Fe2+ 0.011Fe3+ 0.016Cr0.011Al0.005)Al0.032Si1.968O6, from a suite of high pressure ultramafic nodules of mantle origin, have been investigated by in-situ neutron powder diffraction at several temperatures starting from 1,200°C down to 150°C. Unit-cell parameter variations as a function of T show no phase transition within this temperature range. The volume thermal expansion coefficient, α = V −1(∂V/∂T) P0, varies linearly with T. The axial thermal expansion coefficients, αj = l j−1(∂l j/∂T)P0, increase non-linearly with T. The principal Lagrangian unit-strain coefficients (ɛ//a, ɛ//b, ɛ//c), increase continuously with T. However, the orientation of the unit-strain ellipsoid appears to change with T. With decreasing T, the values of the unit-strain coefficients along the b and c axes tend to converge. The orientation at ΔT = 1,080°C is maintained down to the lowest temperature (150°C). The two non-equivalent tetrahedral chains, TA n OA3n and TB n OB3n , are kinked differently. At room-T, the TB n OB3n chain is more strongly kinked by about 23° than the TA n OA3n chain. With increasing T, the difference decreases by 3° for the TB n OB3n chain. The intersite cation exchange reaction between M1 and M2 (Mg2+ and Fe2+) shows a slight residual order at 1,200°C followed by reordering with decreasing temperature although seemingly not with a definite progressive trend. At the lowest temperature reached (150°C), reordering has occurred with the same value of partitioning coefficient K D as that before heating. The absence of the expected phase transition is most likely due to the presence of minor amounts of Fe3+, Al, Ca and Cr which must play a crucial role on the thermoelastic behaviour and phase stability fields in natural Opx, with consequent important petrologic and geological implications.  相似文献   

11.
Polarized optical absorption spectra of natural olivine, Fa10Fo90, were measured before and after annealing/quenching experiments performed at 650, 800, 1,000 and 1,200°C under controlled oxygen fugacity. It was found that the annealing induces weak but definite changes in the olivine spectra. The intensity of the spin-allowed Z > X-polarized band at 9,560 cm?1 and shoulder at ～8,300 cm?1 attributed to Fe2+(M2), continuously decreases with annealing temperature, whereas a weaker band at ～11,600 cm?1 assigned to electronic spin-allowed transitions of Fe2+(M1), increases. This evidently shows that annealing treatments cause a redistribution of Fe2+ from M2 to M1. The fractionation increases with increasing temperature. This observation is in good correspondence with many diffraction structural studies of natural and synthetic olivines, as well as with recent Raman and Mössbauer investigations by Kolesov and Geiger (Mitt Österr Mineral Ges 149:48, 2004) and Morozov et al. (Eur J Mineral 17:495–500, 2005) evidencing a weak tendency of Fe to order into the M1 site with increasing temperature. However, this deduction is incompatible with the results of the in situ neutron power diffraction study of synthetic FeMgSiO4 by Redfern et al. (Phys Chem Minerals 27:630–637, 2000). Polarization properties of the UV absorption edge, attributed to ligand-to-metal charge-transfer transitions in Fe3+, changes from Y > X ? Z in natural samples to a weak Y ≥ X ≥ Z-pleochroism in annealed ones. This may be due to redistribution of a small content of Fe3+ among M1 and M2 structural sites.  相似文献   

12.
The distribution of rare earth elements (REE) between clinopyroxene (cpx) and basaltic melt is important in deciphering the processes of mantle melting. REE and Y partition coefficients from a given cpx-melt partitioning experiment can be quantitatively described by the lattice strain model. We analyzed published REE and Y partitioning data between cpx and basaltic melts using the nonlinear regression method and parameterized key partitioning parameters in the lattice strain model (D 0, r 0 and E) as functions of pressure, temperature, and compositions of cpx and melt. D 0 is found to positively correlate with Al in tetrahedral site (Al T ) and Mg in the M2 site (MgM2) of cpx and negatively correlate with temperature and water content in the melt. r 0 is negatively correlated with Al in M1 site (AlM1) and MgM2 in cpx. And E is positively correlated with r 0. During adiabatic melting of spinel lherzolite, temperature, Al T , and MgM2 in cpx all decrease systematically as a function of pressure or degree of melting. The competing effects between temperature and cpx composition result in very small variations in REE partition coefficients along a mantle adiabat. A higher potential temperature (1,400°C) gives rise to REE partition coefficients slightly lower than those at a lower potential temperature (1,300°C) because the temperature effect overwhelms the compositional effect. A set of constant REE partition coefficients therefore may be used to accurately model REE fractionation during partial melting of spinel lherzolite along a mantle adiabat. As cpx has low Al and Mg abundances at high temperature during melting in the garnet stability field, REE are more incompatible in cpx. Heavy REE depletion in the melt may imply deep melting of a hydrous garnet lherzolite. Water-dependent cpx partition coefficients need to be considered for modeling low-degree hydrous melting.  相似文献   

13.
We have measured the mixing properties of Mn-Mg olivine and Mn-Mg garnet at 1300° C from a combination of interphase partitioning experiments involving these phases, Pt-Mn alloys and Mn-Mg oxide solid solutions. Activity coefficients of Mn dilute in Pt-Mn alloys at 1300° C/1 atm were measured by equilibrating the alloy with MnO at known f O 2. Assuming that the log f O 2 of the Mn-MnO equilibrium under these conditions is-17.80 (Robie et al. 1978), we obtain for Mn: logMn = –5.25 + 3.67 XMn + 11.41X2 Mn Mixing properties of (Mn,Mg)O were determined by reversing the Mn contents of the alloys in equilibrium with oxide at known f O 2. Additional constraints were obtained by measuring the maximum extent of immiscibility in (Mn,Mg)O at 800 and 750° C. The data are adequately described by an asymmetric (Mn,Mg)O solution with the following upper and lower limits on nonideality: (a) WMn = 19.9kj/Mol; WMg = 13.7kj/Mol; (b) WMn = 19.9kj/Mol; WMg = 8.2kj/Mol; Olivine-oxide partitioning was tightly bracketed at 1300° C and oxide properties used to obtain activity-composition relations for Mn-Mg olivine. Despite strong M2 ordering of Mn in olivine, the macroscopic properties are adequately described by a symmetric model with: Wol = 5.5 ± 2.5 kj/mol (1-site basis) Using these values for olivine, garnet-olivine partitioning at 27 kbar/1300° C leads to an Mn-Mg interaction parameter in garnet given by: Wgt = 1.5 ± 2.5kJ/mol (1-site basis) Garnet-olivine partitioning at 9 kbar/1000° C is consistent with the same extent of garnet nonideality and the apparent absence of excess volume on the pyrope-spessartine join indicates that any pressure-dependence of WGt must be small. If olivine and garnet properties are both treated as unknown and the garnet-olivine partitioning data alone used to derive WOl and WGt, by multiple linear regression, best-fit values of 6.16 and 1.44 kJ/mol. are obtained. These are in excellent agreement with the values derived from metal-oxide, oxide-olivine and olivine-garnet equilibria.  相似文献   

14.
We present H2O analyses of MgSiO3 pyroxene crystals quenched from hydrous conditions in the presence of olivine or wadsleyite at 8–13.4 GPa and 1,100–1,400°C. Raman spectroscopy shows that all pyroxenes have low clinoenstatite structure, which we infer to indicate that the crystals were high clinoenstatite (C2/c) during conditions of synthesis. H2O analyses were performed by secondary ion mass spectrometry and confirmed by unpolarized Fourier transform infrared spectroscopy on randomly oriented crystals. Measured H2O concentrations increase with pressure and range from 0.08 wt.% H2O at 8 GPa and 1,300°C up to 0.67 wt.% at 13.4 GPa and 1,300°C. At fixed pressure, H2O storage capacity diminishes with increasing temperature and the magnitude of this effect increases with pressure. This trend, which we attribute to diminishing activity of H2O in coexisting fluids as the proportion of dissolved silicate increases, is opposite to that observed previously at low pressure. We observe clinoenstatite 1.4 GPa below the pressure stability of clinoenstatite under nominally dry conditions. This stabilization of clinoenstatite relative to orthoenstatite under hydrous conditions is likely owing to preferential substitution of H2O into the high clinoenstatite polymorph. At 8–11 GPa and 1,200–1,400°C, observed H2O partitioning between olivine and clinoenstatite gives values of D ol/CEn between 0.65 and 0.87. At 13 GPa and 1,300°C, partitioning between wadsleyite and clinoenstatite, D wd/CEn, gives a value of 2.8 ± 0.4.  相似文献   

15.
Experiments have been performed on the system MgO-SiO2-Cr-O at 0-2.88 GPa and 1100-1450℃,focusing on the stability of Cr^2 in olivine(O1),orthopyroxene(Opx) and spinel(Sp) and its partitioning between these phases.Analytical reagent grade chemicals,MgO,SiO2,Cr2O3.and Cr were used to make starting mixtures.Excess Cr(50%) was then added in these mixtures to ensure that the resultant phases were in equilibrium with the metal Cr.Flux of BaO B2O3(%) was added for facilitating experimental equilibrium and crystal growth.Cr was used as capsule material.All phases in the product were identified by X-ray and analyzed by electron microprobe,The contents of CrO in the different phases(O1,Opx and Sp)were calculated according to stoichiometry.The obtained results of calculation indicate that Cr^3 in Ol and Opx is negligible.The experimental results show;(a) with increasing temperature and decreasing pressure,Cr^2 solubility in Ol,Opx and Sp increases;(b) with in creasing temperature,the partitioning coefficient of Mg and Cr^2 between Ol and Opx decreases,that between Opx and Sp increases,and that between Ol and Sp remains almost unchanged;(c) the effect of pressure on all partitioning coefficients is negligible.  相似文献   

16.
A thermodynamic solution model is developed for minerals whose compositions lie in the two binary systems Mg2SiO4-Fe2SiO4 and Mg2Si2O6-Fe2Si2O6. The formulation makes explicit provision for nonconvergent ordering of Fe2+ and Mg2+ between M1 and M2 sites in orthopyroxenes and non-zero Gibbs energies of reciprocal ordering reactions in both olivine and orthopyroxene. The calibration is consistent with (1) constraints provided by available experimental and natural data on the Fe-Mg exchange reaction between olivine and orthopyroxene ± quartz, (2) site occupancy data on orthopyroxenes including both crystallographic refinements and Mössbauer spectroscopy, (3) enthalpy of solution data on olivines and orthopyroxenes and enthalpy of disordering data on orthopyroxene, (4) available data on the temperature and ordering dependence of the excess volume of orthopyroxene solid solutions, and (5) direct activity-composition determinations of orthopyroxene and olivine solid solutions at elevated temperatures. Our analysis suggests that the entropies of the exchange [Mg(M2)Fe(M1)Fe(M2)Mg(M1)] and reciprocal ordering reactions [Mg(M2)Mg(M1)+ Fe(M2)Fe(M1)Fe(M2)Mg(M1)+Mg(M2)Fe(M1)] cannot differ significantly (± 1 cal/K) from zero over the temperature range of calibration (400°–1300° C). Consideration of the mixing properties of olivine-orthopyroxene solid solutions places tight constraints on the standard state thermodynamic quantities describing Fe-Mg exchange reactions involving olivine, orthopyroxene, pyralspite garnets, aluminate spinels, ferrite spinels and biotite. These constraints are entirely consistent with the standard state properties for the phases-quartz,-quartz, orthoenstatite, clinoenstatite, protoenstatite, fayalite, ferrosilite and forsterite which were deduced by Berman (1988) from an independent analysis of phase equilibria and calorimetric data. In conjunction with these standard state properties, the solution model presented in this paper provides a means of evaluating an internally consistent set of Gibbs energies of mineral solid solutions in the system Mg2SiO4-Fe2SiO4-SiO2 over the temperature range 0–1300° C and pressure interval 0.001–50 kbars. As a consequence of our analysis, we find that the excess Gibbs energies associated with mixing of Fe and Mg in (Fe, Mg)2SiO4 olivines, (Fe, Mg)3Al2Si3O12 garnets, (Fe, Mg)Al2O4 and (Fe, Mg)Fe2O4 spinels, and K(Mg, Fe)3AlSi3O10(OH)2 biotites may be satisfactory described, on a macroscopic basis, with symmetric regular solution type parameters having values of 4.86±0.12 (olivine), 3.85±0.09 (garnet), 1.96±0.13 (spinel), and 3.21±0.29 kcals/gfw (biotite). Applications of the proposed solution model demonstrate the sensitivity of petrologic modeling to activity-composition relations of olivine-orthopyroxene solutions. We explore the consequences of estimating the activity of silica in melts forming in the mantle and we develop a graphical geothermometer/geobarometer for metamorphic assemblages of olivine+orthopyroxene+quartz. Quantitative evaluation of these results suggests that accurate and realistic estimates of silica activity in melts derived from mantle source regions,P-T paths of metamorphism and other intensive variables of petrologic interest await further refinements involving the addition of trace elements (Al3+ and Fe3+) to the thermodynamic formulation for orthopyroxenes.  相似文献   

17.
The validity of the thermodynamic cBΩ model is tested in terms of the experimentally determined diffusion coefficients of He in a natural Fe-bearing olivine (Fo90) and a synthetic end-member forsterite (Mg2SiO4) over a broad temperature range (250–950 °C), as reported recently by Cherniak and Watson (Geochem Cosmochim Acta 84:269–279, 2012). The calculated activation enthalpies for each of the three crystallographic axes were found to be (134 ± 5), (137 ± 13) and (158 ± 4) kJ mol?1 for the [100], [010] and [001] directions in forsterite, and (141 ± 9) kJ mol?1 for the [010] direction in olivine, exhibiting a deviation of <1 % with the corresponding reported experimental values. Additional point defect parameters such as activation volume, activation entropy and activation Gibbs free energy were calculated as a function of temperature. The estimated activation volumes (3.2–3.9 ± 0.3 cm3 mol?1) of He diffusion in olivine are comparable with other reported results for hydrogen and tracer diffusion of Mg cations in olivine. The pressure dependence of He diffusion coefficients was also determined, based on single experimental diffusion measurements at 2.6 and 2.7 GPa along the [001] direction in forsterite at 400 and 650 °C.  相似文献   

18.
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   

19.
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   

20.
Two examples of mineral reactions accompanying intragranular fracturing of silicates are described from amphibolites at the Grenville front, Coniston, Ontario, and a granodiorite within the Miéville shear zone, Switzerland. At these localities coarse grained (> 1 mm) hornblende and biotite respectively have undergone initial deformation by intense transgranular fracturing. The ambient temperature of deformation is estimated at 400–500°C for the amphibolites, and 250–300°C for the granodiorite.Fracture intensity within hornblende increases with progressive deformation until fractures coalesce and grains lose cohesion. Fractures are occupied by hornblende in close optical continuity with the parent grain, and typically contain median sutures decorated by arrays of solid inclusions. Relative to the parent grain, hornblende in fractures is depleted in Ti, Al, plus K, and enriched in Mg. Given the preferential partitioning of Mg, AlVI and Ti into the M2 site of calcic amphiboles, the decrease of Ti and AlVI in the host-to-crack transition is consistent with the corresponding increase of the Mg/(Mg + Fe2+) ratio.Fractures within biotite are bounded by an envelope of paler brown biotite which corresponds to a decrease of Ti and increase of Fe + Mg relative to regions unaffected by cracking. Fractures are occupied by secondary ilmenite, low-Ti biotite and high-Ti muscovite. Ti and Al do not vary significantly as a function of Mg/(Fe + Mg) in the host-to-crack transition, as anticipated from the approximately equal partitioning of these two cations into the M1 and M2 octahedral cation sites. The direct relationship of the mineral reactions to the fractures is taken as evidence for the participation of the reactions in crack propagation. These features may thus represent examples of natural stress corrosion cracking.  相似文献   

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