A Precambrian fayalite granite from the south coast of Western Australia

A Precambrian fayalite granite outcropping at Lower King, near Albany, Western Australia, is interpreted as a high-Fe²⁺/(Fe²⁺ + Mg) analogue of charnockite. Calculation of the original titanomagnetite composition from analytical data on ilmenomagnetite ‘exsolution’ intergrowths suggests initial crystallisation of opaque oxides at about 940°C and 10^?12 bars f_o2. This result indicates a magmatic origin for the rock. Other determinable points on the T-f_o2 cooling curve of the fayalite granite pluton include crystallisation of biotite at roughly 800–820°C and 10^?14.5 bars f_o2, and final equilibration of opaque oxides below 550°C and 10^?23 bars f_o2. Mineralogical data on nearby granulite facies country rocks suggest a regional total pressure of roughly 5 kb, and hence the depth of pluton emplacement was probably around 18–19 km. Thus the Lower King fayalite granite is believed to have crystallised from water-deficient, high-T melt or partial melt generated, possibly from metasedimentary rocks, deep in the crust under granulite facies conditions.     

Kinetics of diffusion-controlled growth of fayalite

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 $\bar D$ _O ^gb (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.     

A reassessment of the human dimension of desertification

So far, the human dimension of desertification has been confined to some peripheral aspects of desertification. Man is either set at the beginning of the process as a triggerer or at the end as a victim. This paper tries to show the high degree of involvement of human communities in the process of desertification itself and that they undergo degradation just like the vegetation associations and the wildlife communities. A new, more human-orientated definition of desertification is discussed here.     

Reinvestigation of fayalite+anorthite=garnet

The reaction fayalite+anorthite=garnet (GAF) has been investigated in a piston-cylinder apparatus and in an internally heated gas apparatus. Piston-cylinder reversals were obtained at 900 °C (6.0–6.4 kbar), 950 °C (6.3–6.8 kbar), 1000 °C (6.6–7.1 kbar), and 1050 °C (7.0–7.3 kbar). Gas-apparatus experiments yielded a reversal at 7 kbar (993–1049 °C). Results are consistent with earlier experimental studies. Unless garnet Ca–Fe mixing is attended by an excess entropy of at least 2–3 J/K-atom, discrepancies remain between calculated and experimentally determined slopes for GAF. The discrepancy is greater if there is no Al–Si disorder in anorthite. High temperature thermodynamic data for almandine and grossular are needed to help resolve this problem.     

Impedance spectroscopy and defect chemistry of fayalite

Impedance spectra of polycrystalline synthetic fayalite were measured at 900°C and 1 atm pressure in a CO/CO₂ gas mixing furnace at oxygen fugacities f _{O 2}=10^-13 to 10^-17 atm. The frequency range applied to the samples was 20 Hz–1 MHz. The spectra show two semicircular arcs, which are attributed to polarization processes within the bulk material and at the sample-electrode interface. Two different types of behaviour of the bulk resistance as a function of oxygen fugacity were observed. The first is proportional to the -1/4.5 to -1/6 power of f_{I 2}, which is consistent with the existing defect model. The second shows a lesser dependence on f_{O 2}, often lowered by a factor of about two, relative to the expected value, resulting in a resistance proportional to the -1/10 to -1/12 power of f_{O 2}. It is assumed, that the lesser f _{O 2}-dependence is caused by aliovalent impurities, producing an f_{O 2}-independent amount of charge carriers. The electrode arcs show a resistance proportional to the-1/2 to -1/4 power of oxygen fugacity, implying that a reaction with the gas phase is involved in the polarization process at the sample-electrode interface.     

Electron density and polarized absorption spectra of fayalite

The maxima of the electron difference densities of Fe²⁺ atM(1) andM(2) positions of fayalite, Fe₂SiO₄, determined by x-ray diffraction are considered to correspond to atomic dipoles. Provided the selection rules of dipole radiation are satisfied and the energy of the incident radiation lies within the appropriate range, the interaction of incident radiation with these atomic dipoles should lead to three absorption bands of which two originate from Fe²⁺ atM(1), one from Fe²⁺ atM(2). The relative intensities of the three bands, dependent on the polarization direction, are estimated. The result ist in excellent agreement with the interpretation of olivine spectra given by Burns (1970).     

A temperature-dependent single-crystal Raman spectroscopic study of fayalite: evidence for phonon-magnetic excitation coupling

The polarized single-crystal Raman spectrum of synthetic fayalite, Fe₂SiO₄, was recorded between 5 and 773 K in order to investigate its lattice dynamic behavior. A broad absorption envelope is observed at wavenumbers between 800 and 960 cm^–1 and it contains two intense bands at 816 and 840 cm^–1 at 293 K in the (cc) spectrum. The integral area of the envelope decreases upon cooling from 293 K and reaches a minimum around 55 K. It then increases again with a further decrease in temperature down to 5 K. It is proposed that the envelope in the (cc) spectra consists of seven different modes, some of which are symmetry-forbidden, that arise from combination scattering of nonsymmetric internal SiO₄-stretching modes of B_ig symmetry (i = 1, 2, 3) and low-energy excitations. The individual modes can be observed under different polarizations and agree in number and wavenumber with those obtained by fitting the broad envelope with Lorentzians. An analysis of the Raman spectrum as a function of temperature, using the known magnetic properties of fayalite, allows the assignment of the low-energy excitations to short-range magnetic interactions. Modulation of the Fe²⁺(1)–Fe²⁺(2) exchange energy leads to phonon-magnetic excitation coupling and the main role in the Fe²⁺(1)–Fe²⁺(2) magnetic interaction occurs via superexchange through the oxygens. The magnetic excitations are not magnons in the usual sense, that is as quasiparticles having a long wavelength in an ordered system. The degree of observed broadening of the SiO₄-stretching modes is consonant with a Fe²⁺(1)–Fe²⁺(2) exchange energy of 4.7 cm^–1 presented by Schmidt et al. (1992). At temperatures above 300 K the line width of the mode at 840 cm^–1 decreases slightly, whereas those of low energy lattice modes increase. This suggests that a decrease in mode broadening due to weakened magnetic interactions compensates any thermally related broadening. Complete Fe²⁺ spin disorder may not be reached until at least 530 K. Results from this study show that estimates of third-law entropies for silicates using simple crystal-chemical considerations that do not account for magnetic properties cannot give accurate values for many transition-metal-containing phases.     

Thermal expansion of fayalite,Fe2SiO4

Thermal expansion of single-crystal fayalite has been measured by a dilatometric method at temperatures between 25 °C and 850 °C. The results show the presence of anomalous expansion in the b axis, which is correlated to the anomalous variation of elastic moduli with temperature. Grüneisen's parameter is 1.10 and the thermal Debye temperature is 565 K, which is close to the acoustic Debye temperature of 511 K.     

A reassessment of the status of the benthic macrofauna of the Raritan estuary

The benthic macrofauna of the Raritan estuary, at the mouth of New York Harbor, has been reported to be severely impacted by pollution, with a significant change occurring between surveys in the late 1950’s and the early 1970’s. We review this assessment using five-fold more macrofaunal data (including biomass), not reported or used before, from a 1973–1974 survey. These data are compared to previous and similar studies in the area. This reassessment suggests benthic community structure is not as degraded as previously reported and is, in many ways, similar to other relatively unpolluted middle Atlanic estuaries.     

A reassessment of the role of tidal dispersion in estuaries and bays

The role of tidal dispersion is reassessed, based on a consideration of the relevant physical mechanisms, particularly those elucidated by numerical simulations of tide-induced dispersion. It appears that the principal influence of tidal currents on dispersion occurs at length scales of the tidal excursion and smaller; thus the effectiveness of tidal dispersion depends on the relative scale of the tidal excursion to the spacing between major bathymetric and shoreline features. In estuaries where the typical spacing of topographic features is less than the tidal excursion, tidal dispersion may contribute significantly to the overall flushing. In estuaries and embayments in which the typical spacing between major features is larger than the tidal excursion, the influence of tidal dispersion will be localized, and it will not markedly contribute to overall flushing. Tidal dispersion is most pronounced in regions of abrupt topographic changes such as headlands and inlets, where flow separation occurs. The strong strain rate in the region of flow separation tends to stretch patches of fluid into long filaments, which are subsequently rolled up and distorted by the transient eddy field. The dispersion process accomplished by the tides varies strongly as a function of position and tidal phase and thus does not lend itself to parameterization by an eddy diffusion coefficient.     

Timing of regional deformation of the hill end trough: A reassessment

Layered and differentiated mafic/ultramafic sills are an important component of greenstones in the Eastern Goldfields Province and can be grouped into tholeiitic and high‐Mg associations. These associations can be further subdivided according to geochemical parameters and order of crystallization of the main mineral phases. The distribution of sills is consistent with models that envisage the Kalgoorlie Terrane (abundant komatiitic and MORB‐like tholeiitic volcanics and intrusive equivalents) as an ancient continental margin basin. Although mafic volcanic rocks and sills encompass a similar range of compositions, chemostratigraphic trends for sills in the Ora Banda domain oppose those of the enclosing volcanic rocks. Plagioclase‐rich (leucodolerite) sills in the Melita area (Gindalbie Terrane) have alumina‐rich, TiO₂‐poor compositions comparable to island‐arc tholeiites and were derived by partial melting of an enriched mantle source. The geochemistry and distribution of sills is not compatible with a simple, craton‐scale plume model for the formation of the greenstone belts.     

Dielectric constants of tephroite,fayalite and olivine and the oxide additivity rule

The dielectric constants and dissipation factors of synthetic tephroite (Mn₂SiO₄), fayalite (Fe₃SiO₄) and a forsteritic olivine (Mg_1.80Fe_0.22SiO₄) were measured at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: tephroite, κ′_a= 8.79 tan δ_a = 0.0006 κ′_b = 10.20 tan δ_b = 0.0006 κ′_c= 8.94 tan δ_c= 0.0008 fayalite, gk′_a = 8.80 tan δ_a = 0.0004 gk′_b= 8.92 tan δ_b = 0.0018 gk′_c = 8.58 tan δ_c = 0.0010 olivine, gk′_a = 7.16 tan δ_a = 0.0006 gk′_b = 7.61 tan δ_b = 0.0008 gk′_c = 7.03 tan δ_c = 0.0006 The low dielectric constant and loss of the fayalite indicate an exceptionally low Fe³⁺ content. An FeO polarizability of 4.18 ų, determined from α_D(FeO) = [α_D (Fe₂SiO₄)-α_D(SiO₂)]/2, is probably a more reliable value for stoichiometric FeO than could be obtained from Fe_xO where x = 0.90–0.95. The agreement between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to α_D(M₂M′X₂) = 2α_D(MX) + α_D(M′X₂) is ～+2.8% for tephroite and +0.2% for olivine. The deviation from additivity in tephroite is discussed.     

Oxidation kinetics of fayalite (Fe2SiO4)

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.     

Single-crystal absorption and reflection infrared spectroscopy of forsterite and fayalite

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 B_3u 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 capacityC _v 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.S _magnetic 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.     

Surface destabilization and laboratory-induced non-stoichiometry in San Carlos olivine

Annealing experiments on natural olivine (Mg_1-x Fe _x )₂SiO₄ (with x≈0.11) crystals (San Carlos, Arizona, spinel-lherzolite context) have been performed between T=1,100° C and 1,500° C for oxygen partial pressures pO₂=10^?3 to 10^?13 bar and times of 1 to 140 h in CO/CO₂ or H₂/H₂O gas mixtures. Even specimens annealed within the T-pO₂ theoretical stability field (TSF) calculated for stoichiometric olivine (Nitsan 1974) show systematic alterations developed within the first few microns of the surface of the crystals. Pyroxene crystals or melt form on the original olivine surface even at T=1,100° C, with preference of pyroxene when T<1,350° C and SiO₂-rich glass if T>1,350° C. This glass (rhyolite-like) can concentrate calcium from the starting olivine, and aluminum when Cr-Al spinels are present as inclusions. These observations are in contradiction with the TSF. They are obviously due to the presence of platinum used as a container of our samples, even if the contact between olivine and platinum is very weak. Rapid surficial diffusion of iron toward platinum (or via the gas phase) induces a Fe-depleted surface. According to the TSF, this more forsteritic surface should have a wider pO₂ range of stability. This is not the case, just because this situation is largely out of equilibrium. This iron loss induces a departure from cationic stoichiometry: (Mg, Fe)_2(1?δ), SiO₄ with δ small and positive. We extended the model that Nakamura and Schmalzried (1983) (N.S.) developed for fayalite (x=1) to our natural olivine composition, under the assumption that the majority defects are magnesium vacancies, Fe³⁺ occupying octahedral and tetrahedral sites, and the more complex neutral defect corresponding to Coulombic attraction between neighboring Fe³⁺ ions. We have recalculated the olivine stability field in pO₂ vs. δ space at T=1,300° C using this model for x≈0.1 (its extreme limit of validity) and conclude that olivine is stable only in a very narrow range in pO₂ which depends on δ. The calculation shows also that when olivine has nearly cationic stoichiometry (δ=0) as we believe for our starting material, the pO₂ range of stability is narrower than indicated by the TSF. In particular, it explains why Fe precipitates from the olivine (δ=0) (in absence of any other precipitation of SiO₂-rich phases) between 10^?11 and 10^?13 bar at 1,300° C; this was not predicted by the TSF. Magnetite or iron precipitates also coexist with SiO₂-rich exsolutions or pyroxene when pO₂ is close to the upper or lower boundaries of the TSF, respectively. The N.S. model may have important implications for the interpretation of the existence of partial melting and/or the low-viscosity/low velocity zone in the upper mantle.     

铁橄榄石高温高压流变性的实验研究

通过高温高压实验研究了铁橄榄石集合体的流变性.首先,利用高精度的Paterson气体介质变形装置对铁橄榄石集合体Fe2SiO4进行了高温三轴压缩蠕变试验.变形试验条件为温度1273～1423K,围压300MPa,差应力10～250MPa,应变率10-7～10-4s-1,试件的最大变形量不超过20%.利用三维非线性拟合方法对蠕变试验数据进行分析,得到铁橄榄石集合体的微观变形机制为扩散域和位错域,扩散域的应力指数为1左右.位错蠕变域中,干燥铁橄榄石集合体的应力指数为5.4.活化能为781kJ/mol;含水铁橄榄石集合体的应力指数为3.4,活化能为516kJ/mol.实验结果表明,含水时铁橄榄石的流变强度比干燥时小一个数量级.将实验结果与铁橄榄石单晶的强度进行对比,发现铁橄榄石集合体的流变强度比铁橄榄石单晶的强度高.从而得到了铁橄榄石集合体高温高压流变性(强度)的初步试验结果.     

Temperature dependence of the polarized electronic absorption spectra of olivines. Part I – fayalite

 Polarized electronic absorption spectra of orthorhombic fayalite, Fe₂SiO₄, [E || a(|| Z),E || b(|| X), E || c(|| Y)], space group Pbnm, have been studied in the temperature range 293 ≤T/K ≤ 1273. The spectra were analysed into component bands originating from spin-allowed dd transitions of iron(II) at the different sites, M1 and M2, in the structure. The assignments of bands, made on the basis of the polarization dependence of the spectra and considerations of transition energies, were confirmed by the analysis of the temperature-dependent spectra. The temperature dependencies of integral intensities, half band widths and energy positions of absorptions bands caused by Fe²⁺ on the different octahedral sites, M1 and M2, were evaluated for the individual transitions. Independent of the site symmetry, absorption bands shift to lower energies and half band widths increase on rising temperature. The temperature dependence of band intensities depends on site symmetry. The integral intensities are found to increase with temperature for the transition metal ion on a centrosymmetric site, or remain constant when the site is missing an inversion centre. This is consistent with the general conclusion of Taran et al. (1994). Received: 11 October 2001 / Accepted: 17 January 2002