Single-crystal X-ray structure refinement of natural olivines equilibrated at high temperature under controlled oxygen fugacity (fO2) conditions, coupled with a structure-energy model were used to establish the influence of T, fO2 and bulk chemistry on intracrystalline disorder.The results are: 1) The kD (kD = [(Fe M1·Mg M2)/(Fe M2·Mg M1)]) factor describing site population on M1, M2 polyhedra increases from values lower than 1 at T below 400–600° C (depending on composition) to values higher than 1 at higher temperature. 2) The increase of kD with T is quite regular. 3) At constant temperature and pressure, kD increases with increasing fayalite content in the mixture; 4) Contrary to previous observations (Will and Nover 1979; Nover and Will 1981) varying fO2, within the stability range of the substance, has a negligible influence on intracrystalline disorder. 5) As ancillary results, the model confirms the defect scheme of Nakamura and Schmalzried (1983) for the investigated solids. Moreover, it shows that cationic vacancies are always created on M 1 site at the expense of Mg ions, while trivalent iron is always stabilized on M2 site. This explains the marked anisotropies observed in Fe-Mg interdiffusion (Buening and Busek 1973; Misener 1974; Schock et al. 1989). 相似文献
The rate of growth of fayalite (Fe2SiO4) has been measured at one atmosphere total pressure, temperatures from 1000° to 1120° C, and oxygen fugacities controlled by CO/CO2 gas-mixing from 10-9.9 to 10-13.0atm, chosen to span the fayalite stability field. The fine-grained polycrystalline fayalite layer was formed by reacting the oxides FeO or Fe3O4 with a thin slice of single-crystal quartz. The rate of growth of the fayalite increases with increasing temperature and decreasing oxygen fugacity, and is consistent with a parabolic rate law, indicating that the growth rate is controlled by diffusion through the fayalite. Microstructural observations and platinum marker experiments suggest that the reaction phase is formed at the quartz-fayalite interface, and is therefore controlled by the diffusion of iron and oxygen. The parabolic rate constant was analyzed in terms of the oxide activity gradient to yield mean chemical diffusivities for the rate-limiting ionic species, assuming bulk transport through the fayalite layer. Given that iron diffusion in olivine polycrystals occurs either by lattice diffusion, which shows a positive dependence on oxygen activity, or by grain boundary diffusion, which would result in growth rates significantly faster than we observe, we conclude that the diffusivities derived in this study represent oxygen diffusion. However, since oxygen lattice diffusion in fayalite has been established to be much slower than our measurements, it is likely that the transport path for oxygen is along the grain boundaries. Thus, the mean grain boundary diffusivity of oxygen in fayalite $\bar D$ Ogb(m2 s-1), using the measured grain size of 0.25 μm, is then given by $$\bar D_O^{gb} {\mathbf{ }}\delta = 1.28 \times 10^{ - 3} f_{O_2 }^{ - 0.17} {\mathbf{ }}e^{ - 540/RT} $$ , where δ is the grain boundary width (in m), and the activation energy is in kJ/mol. Assuming δ=10-9 m (Ricoult and Kohlstedt 1983), the oxygen grain boundary diffusivities are about a factor of 30 × slower than those reported by Watson (1986) for Fo90 olivine. 相似文献
Acidithiobacillus ferrooxidans are commonly present in acid mine drainage (AMD). A. ferrooxidans derive metabolic energy from oxidation of Fe2+ present in natural acid solutions and also may be able to utilize Fe2+ released by dissolution of silicate minerals during acid neutralization reactions. Natural and synthetic fayalites were reacted in solutions with initial pH values of 2.0, 3.0 and 4.0 in the presence of A. ferrooxidans and in abiotic solutions in order to determine whether these chemolithotrophic bacteria can be sustained by acid-promoted fayalite dissolution and to measure the impact of their metabolism on acid neutralization rates. The production of almost the maximum Fe3+ from the available Fe in solution in microbial experiments (compared to no production of Fe3+ in abiotic controls) confirms A. ferrooxidans metabolism. Furthermore, cell division was detected and the total cell numbers increased over the duration of experiments. Thus, over the pH range 2–4, fayalite dissolution can sustain growth of A. ferrooxidans. However, ferric iron released by A. ferrooxidans metabolism dramatically inhibited dissolution rates by 50–98% compared to the abiotic controls.
Two sets of abiotic experiments were conducted to determine why microbial iron oxidation suppressed fayalite dissolution. Firstly, fayalite was dissolved at pH 2 in fully oxygenated and anoxic solutions. No significant difference was observed between rates in these experiments, as expected, due to extremely slow inorganic ferrous iron oxidation rates at pH 2. Experiments were also carried out to determine the effects of the concentrations of Fe2+, Mg2+ and Fe3+ on fayalite dissolution. Neither Fe2+ nor Mg2+ had an effect on the dissolution reaction. However, Fe3+, in the solution, inhibited both silica and iron release in the control, very similar to the biologically mediated fayalite dissolution reaction. Because ferric iron produced in microbial experiments was partitioned into nanocrystalline goethite (with very low Si) that was loosely associated with fayalite surfaces or coated the A. ferrooxidans cells, the decreased rates of accumulation of Fe and Si in solution cannot be attributed to diffusion inhibition by goethite or to precipitation of Fe–Si-rich minerals. The magnitude of the effect of Fe3+ addition (or enzymatic iron oxidation) on fayalite dissolution rates, especially at low extents of fayalite reaction, is most consistent with suppression of dissolution by interaction between Fe3+ and surface sites. These results suggest that microorganisms can significantly reduce the rate at which silicate hydrolysis reactions can neutralize acidic solutions in the environment. 相似文献
The iron-rich olivine end-member, fayalite, occurs in the matrix, chondrules, Ca-Al-rich inclusions (CAIs), silicate aggregates, and dark inclusions in the Kaba and Mokoia oxidized CV3 chondrites. In most occurrences, fayalite is associated with magnetite and troilite. To help constrain the origin of the fayalite (Fa98-100), we measured oxygen and silicon isotopic compositions and Mn-Cr systematics in fayalite from two petrographic settings of the Kaba meteorite. One setting consists of big fayalite laths embedded in the matrix and radiating from a core of fine-grained magnetite and sulfide, while the other setting consists of small fayalite-magnetite-sulfide assemblages within or at the surface of Type I barred or porphyritic olivine chondrules. Oxygen in the big fayalite laths and small chondrule fayalites falls on the terrestrial fractionation line, and is distinct from that in chondrule forsterites, which are enriched in 16O (Δ17O = ∼−4‰). Oxygen in the big fayalite laths may be isotopically heavier than that in chondrule fayalites. Silicon isotopes suggest that forsterite is ∼1‰/amu heavier than adjacent fayalite within Kaba chondrules. However, we were unable to confirm large silicon isotopic differences among fayalites reported previously. The Mn-Cr data for big Kaba fayalites give an initial 53Mn/55Mn ratio of (2.07 ± 0.17) × 10−6, consistent with literature results on Mokoia chondrule fayalites. The combined data suggest that fayalites in both petrographic settings formed at about the same time, ∼9.7 Ma after the formation of CAIs. Our data indicate that those fayalite-magnetite-troilite assemblages replacing metal inside and around chondrules formed by aqueous alteration on the meteorite parent body. The formation site and mechanism for the big fayalite laths is less clear, but the petrographic setting indicates that they did not form in situ. None of the models that have been suggested for formation of these fayalites is entirely satisfactory. 相似文献
Experiments were conducted to study Mg diffusion in quartz grain boundaries. A detector particle method was used to study grain-boundary diffusion because Mg was confined exclusively to the grain boundaries. Diffusion couples were assembled by placing a MgF2 disk against a disk of quartzite, which was placed against a disk of quartzite that contained fayalite (Fe2SiO4) ‘detector particles.’ During diffusion experiments, Mg diffused along the grain boundaries of the central quartzite toward the fayalite quartzite where it was incorporated into fayalite detector particles. The only pathway for transport from the diffusant source to fayalite detector particles was through the grain boundaries in the central quartzite. The cross-sectional area of the grain boundaries that delivered Mg to the fayalite detector particles was determined from scanning electron microscope images. The Mg contents of the fayalite detector particles were used to calculate the mass of Mg that fluxed through the grain boundaries. During the diffusion experiments, pyroxene crystallites nucleated and grew in the central quartzites from Mg and Fe that was transported along quartz grain boundaries. The Mg contents of the crystallites vary linearly throughout the quartzites, suggesting that steady-state transport conditions were rapidly established in the quartz grain boundaries. Magnesium concentrations in the pyroxene crystallites are proportional to concentration gradients in the grain boundaries of the central quartzite. Grain-boundary fluxes and linear concentration gradients were used to calculate diffusion of Mg in grain boundaries of the central quartzite component in the diffusion couples. 相似文献
We calculated the forsterite Mg K-edge and the fayalite Fe K-edge X-ray absorption spectra both for the M 1 and M 2 sites and for the overall edge by using the one-electron multiple-scattering theory. The validity of the theoretical model is well illustrated by comparison of calculations with experimental data at the Mg K-edge of MgO (periclase) and at the Mg and Fe K-edges spectra of forsterite and fayalite. Starting from these results at room conditions, we calculated the Mg and Fe K-edges X-ray absorption spectra of forsterite and fayalite at low and high temperatures and at high pressures as well. Variations of fine structures occur mostly in the intermediate multiple scattering (IMS) regions and as a result of the applied pressure. In order to demonstrate the capability of XAS to lead to deeper knowledge of structure relevant to Earth's upper mantle we also attempted calcuating the high-P edge for Fe2+ in low-spin using a different occupation of valence electrons. If a change in spin state really occurs in fayalite, our simple model shows that XAS would evidence it easily even with low resolution. 相似文献
The paper reports data on the inner structure and composition of fine-grained fayalite-hedenbergite hydrothermal-metasomatic veinlet in unusual quartzite (so-called kluchevite) in the Black Shale Formation in the Southern Urals. The fayalite and hedenbergite are the most ferrous among these minerals ever found worldwide, and their compositions extend to the ferrous end members. The minerals are devoid of Mg but contain variable Zn concentrations. The groundmass of the rock is very fine-grained and bears fayalite-hedenbergite symplectites with a minor amount of barite. The composition of fayalite in the minute phenocrysts is close to the composition of the mineral in the symplectites. Both fayalite varieties contain variable but always high ZnO concentrations (0.40–3.70 wt %). The hedenbergite exhibits analogous compositional features. Zn-bearing magnetite grains were found near these minerals, along with a number of varieties of pyrrhotite, covellite, and other Cu sulfides. Judging by its morphological features and texture, the rock is of hydrothermal genesis. 相似文献
Polarized single-crystal absorption and reflection spectra of fundamental modes in both the mid- and far-infrared are presented for microscopic crystals of forsterite and fayalite. All modes predicted by symmetry were observed for forsterite, but two B3u modes were not observed for fayalite. Consideration of previously determined frequency shifts for isotopically and chemically substituted olivines, along with symmetry analysis, produced a complete set of band assignments satisfying all constraints for forsterite. A plausible assingment was derived for fayalite by analogy. The frequency shifts from forsterite to fayalite are consistently small for bands assigned to SiO4 stretching and bending, moderate for rotations, and large for translations of M-site ions, suggesting that in olivine, SiO4 groups vibrate separately from the lattice. Allocating the bending and external modes among multiple continua in Kieffer's (1979c) model considerably improves prediction of quasiharmonic heat capacityCv and entropy for forsterite (～1% discrepancy from 200–1000 K). The experimental entropy of fayalite is closely accounted for (1.8 to 0.1%) by summing lattice, electronic (from Burns' (1985) optical band assignment), and constant magnetic contributions above 200 K.Smagnetic determined from the difference of the experimental and model lattice entropies shows inflection points at the two magnetic transition temperatures (23 and 66 K) and indicates that complete spin disorder is not achieved below 680 K. 相似文献
The nine adiabatic elastic stiffness constants of synthetic single-crystal fayalite, Fe2SiO4, were measured as functions of pressure (range, 0 to 1.0 GPa) and temperature (range, 0 to 40° C) using the pulse superposition ultrasonic method. Summary calculated results for a dense fayalite polycrystalline aggregate, based on the HS average of our single-crystal data, are as follows: Vp = 6.67 km/s; Vs = 3.39km/s; K= 127.9 GPa; μ = 50.3 GPa; (?K/?P)T = 5.2; (?μ/?P)T=1.5;(?K/?T)P= ?0.030 GPa/K;and,(?/?T)P =-0.013 GPa/K (the pressure and temperature data are referred to 25° C and 1 atm, respectively). Accuracy of the single-crystal results was maintained by numerous cross and redundancy checks. Compared to the single-crystal elastic properties of forsterite, Mg2SiO4, the fayalite stiffness constants, as well as their pressure derivatives, are lower for each of the on-diagonal (Cij for which i=j) values, and generally higher for the off-diagonal (Cij for which i≠j) data. As a result, the bulk moduli (K) and dK/dP for forsterite and fayalite are very similar, but the rigidity modulus (μ) and dμ/dP for polycrystalline fayalite are much lower than their forsterite counterparts. The bulk compression properties derived from this study are very consistent with the static-compression x-ray results of Yagi et al. (1975). The temperature dependence of the bulk modulus of fayalite is somewhat greater (in a negative sense) than that of forsterite. The rigidity dependencies are almost equivalent. Over the temperature range relevant to this study, the elastic property results are generally consistent with the data of Sumino (1978), which were obtained using the RPR technique. However, some of the compressional modes are clearly discrepant. The elastic constants of fayalite appear to be less consistent with a theoretical HCP model (Leibfried 1955) than forsterite, reflecting the more covalent character of the Fe-O bonding in the former. 相似文献
Fayalite is a common mineral of Fe-rich paralavas related to spontaneous combustion of coal seams. Fayalite has also been
found in parabasalts from burned coal waste piles of the Chelyabinsk coal basin. Among paralavas from different combustion
metamorphic (CM) complexes of the world, fayalite is the most widespread in the fused rocks of the Kuznetsk coal basin (Kuzbass)
and the Ravat area in Tajikistan. The optimal conditions for fayalite formation as products of coal fires in the Kuzbass and
Ravat resulted from a favorable combination of the composition of fused protolith (parental rocks) composed of pelitic and
Fe-rich sediments and the redox conditions of the deep subsurface ($
f_{O_2 }
$
f_{O_2 }
is lower than the QFM buffer). In the Kuzbass, fayalite is commonly hosted in high-silica aluminous Fe-rich paralavas composed
of Fe-cordierite (sekaninaite), tridymite, hercynite-magnetite, cristobalite, aluminous clinoferrosilite, and Al-K silicic
glass. The composition of all Kuzbass fayalites is close to the Fe2SiO4 end member. Kuzbass fayalites are characterized by a negligibly low CaO content and higher MnO and P2O5 contents like fayalites from burned rocks of other CM complexes. In Kuzbass paralavas, Fe-olivine is the late phase that
crystallized after sekaninaite and tridymite, immediately before melt quenching. 相似文献
Single crystals of fayalite (Fe2SiO4) have been oxidized either in the hematite or the magnetite stability field to investigate the kinetics and mechanisms of oxidation. For samples heated in air at 770° C, a two-phase region composed of fine-grained iron oxide and silica phases formed as the reaction front moved into the sample, and an iron oxide layer formed external to this two-phase region. The presence of the single-phase oxide layer coating the specimens indicates that oxidation occurs by the migration of iron from the fayalite to the gas-solid interface rather than by the movement of oxygen in the opposite direction. For oxidation in air, the kinetics followed a parabolic growth law, with the rate of oxidation limited by the diffusion of iron from the internal reaction front to the gas-solid interface through the iron oxide. When fayalite was oxidized in the magnetite stability field, using a CO/CO2 gas mixture at 1030° C, oxidation was controlled by the reaction at the gas-solid interface, yielding an oxidation rate considerably slower than that predicted for diffusion-controlled growth of the oxide layer. 相似文献
A high-temperature solution calorimetric method suitable for thermochemical studies of anhydrous minerals containing Fe2+ ions has been developed. The method is based on an oxide melt solvent with 52 wt% LiBO2 and 48 wt% NaBO2 maintained at a temperature of 750°C. In a first application of this method the enthalpies of solution of synthetic almandine, fayalite, a mixture of fayalite plus quartz on FeSiO3 composition, and natural quartz were measured. For the reaction: the enthalpy change at 1023 K is ?3.82 ± 0.87 kcal, based on fayalite, quartz, corundum and almandine, and ?5.96 ± 0.90 kcal based on the fayalite plus quartz mixture, corundum, and almandine. These values lead to standard molar enthalpies of formation of almandine from the oxides at 1023 K of ?14.10 ± 1.22 kcal and ?16.24 ± 1.74 kcal, respectively. The measured enthalpy of formation of almandine is less negative by several kilocalories than values derived from analysis of the phase equilibrium work of Hsu (1968), but in closer agreement with the phase equilibrium study of O'Neill and Wood (1979) and similar to the phase equilibrium deduction of Froese (1973).The agreement of the present almandine enthalpy of formation with O'Neill and Wood (1979) and Froese (1973) suggests that almandine entropies at 298 K to be obtained from their studies, in the range 79–81 cal/K, are more nearly correct than the several estimates based on oxide sum and volume-entropy systematics, most of which are much lower. 相似文献
The activity of a given mineral component in a silicate melt can be calculated from the compositions of coexisting melt and crystals, provided that 1) the component is an independently variable component of the crystal, and 2) appropriate thermodynamic data for the component are known. This approach is used to calibrate the compositional dependence of the activities of forsterite, fayalite, anorthite, and albite from experimental data on natural mafic-to-intermediate melts. The natural logarithms of the activities of forsterite and anorthite can be closely approximated as second-degree polynomial functions of the melt composition (r2=0.99 and 0.97, respectively); corresponding fits for fayalite and albite are significantly poorer (r2=0.81 and 0.87, respectively). The shapes of the fitted activity surfaces yield information about speciation in silicate melts. The activity models for forsterite and anorthite provide excellent geothermometers with standard deviations of temperature residuals of approximately 10° C. These geothermometers, when combined with the activity models for fayalite and albite, can be used to predict the temperature at which olivine or plagioclase will crystallize from a melt, along with the composition of the crystals. 相似文献
Two mineralogic geobarometers based on the assemblages olivine-plagioclase-garnet and orthopyroxeneplagioclase-garnet-quartz have been calibrated from the reaction (1) fayalite+anorthite?garnet (Gr1Alm2). The reaction boundary has been determined to within 0.2 kbar using piston-cylinder apparatus. It is located at 4.7, 5.1, 5.5, 5.8, 6.2, 6.6, and 7.0 kbar at 750, 800, 850, 900, 950, 1,000, and 1,050° C, respectively. Summation of ΔG for reaction (1) and fayalite +quartz?ferrosilite locates to within 0.3 kbar the following model garnet-forming reaction for quartz-saturated granulites: (2) ferrosilite+ anorthite?garnet(Gr1 Alm2) + quartz. Geobarometers based on (1) and (2) are widely applicable in granulite terranes and yield precise pressures that are in agreement with other well-calibrated barometers. Pressures of 7–10 kbar are inferred for many granulite terranes requiring the widespread development of 60–70 km thick continental crust by mid-Proterozoic. 相似文献
Summary A spectacular occurrence of harrisitic textures has been observed near the upper margin of the Centre Hill complex, a cyclically layered mafic intrusion emplaced within komatiitic and tholeiitic volcanic rocks of the Archean Abitibi Subprovince in the Canadian Shield. The harrisitic textures, interpreted as pseudomorphs after fayalite, reach up to 50 cm in length and consistently extend away from the upper sill margin. They poikilitically enclose crystals of the surrounding matrix, indicating that they originally formed within a crystal-liquid mush. The harrisitic fayalite crystals are interpreted to have grown in situ under far from equilibrium conditions, where growth was limited by the supply of nutrients to the crystal boundaries. Mineral growth conditions were simulated using a diffusion limited aggregation (DLA) algorithm to produce branching clusters qualitatively similar to the observed textures. Based on this model, it is proposed that the original fayalite crystals formed in the late stages of differentiation cycles, where diffusivity was low due to increasing viscosity and Fe-Si enrichment of the interstitial melt. Mineral growth was initiated by an imposed thermal gradient established through the injection of primitive magma into the chamber.
Textures harrisitiques dans le complexe de Centre Hill, canton de Munro, Ontario: produit de croissance limitée par la diffusion
Résumé De spectaculaires textures harrisitiques furent observées près de la marge supérieure du complexe de Centre Hill, une intrusion mafique à stratification cyclique mise en place à l'intérieur de roches volcaniques komatiitiques et tholéiitiques de la Sous-province de l'Abitibi du bouclier canadien. Les textures harrisitiques, interprétées comme étant des pseudomorphes après la fayalite, atteignent 50 cm de hauteur et s'étendent invariablement vers le centre du filon-couche. Ils englobent des cristaux de la matrice environnante, indiquant qu'ils se sont formés à l'origine dans un mélange de cristaux et de fondu silicaté. Les cristaux de fayalite semblent s'être développés en place dans des conditions éloignées de l'équilibre, où leur croissance était limitée par l'approvisionnement de substances nutritives á la bordure des cristaux. Les conditions de croissance furent simulées à l'aide d'un algorithme d'agrégation limitée par la diffusion (DLA), produisant des agrégats en forme de branches qualitativement similaire aux textures observées. A partir de ce modèle, il est interprété que les cristaux de fayalite se sont formes durant les stages tardifs de cycles de différentiation, où la diffusion était réduite dû à une augmentation de la viscosité et à un enrichissement en Fe et Si du liquide interstitiel. La croissance des cristaux fut initiée suite à l'établissement d'un gradient thermique relié à l'injection de magma primitif dans la chambre magmatique.
We studied ferrous paralava, a high-temperature rock, produced by complete fusion of the sedimentary protolith in the Ravat natural coal fire which has been on for over two thousand years. The paralava was sampled from the Fan-Yagnob coal deposit at the Kukhi-Malik site in the vicinity of former Ravat Village in central Tajikistan. This rock contains fayalite, sekaninaite, hercynite, Ti-magnetite, tridymite, and siliceous glass. Low-Ca pyroxene (clinoferrosilite), globules of sulfides (mainly pyrrhotite) and Fe-Ti oxides, secondary greenalite (after fayalite) and hematite are minor. Paralava includes xenoliths of partially molten clinkers (up to 20 vol.%) composed of mullite, cordierite, tridymite, and relict detrital quartz. We found relatively high Fe contents (100?Fe/(Fe+Mg) > 60) in mafic minerals, high K2O enrichment (up to 1.4 wt.%) in sekaninaite, and an unusually low CaO content (0.5 wt.%) in the rock. The Ravat paralava appears to be derived from a mixture of pelitic rocks (50–70%) and iron-rich rocks (30–50%), but without participation of calcareous material, which explains the low CaO and the absence of plagioclase and Ca-bearing pyroxene. The primary melt was as hot as >1210 °C, and the coal-fired fayalite-sekaninaite paralava crystallized at 1200–1100 °C, at a relatively low oxygen fugacity (near the QFM buffer), outside the zone of active aeration. Large-scale crystallization of ferrospinels and fayalite led to increasing Al2O3 and SiO2 in the melt whence sekaninaite and tridymite crystallized as later phases. The residual melt progressively acquired a more silicic-aluminous composition, rich in K2O, CaO, and P2O5, and became quenched to glass at >1080–1090 °C, when temperature dropped abruptly, possibly, by roof collapse or opening of large cracks, as it usually happens in underground coal fires. 相似文献
