High-temperature infrared properties of forsterite

Polarized emittance measurements were acquired for synthetic forsterite, the pure magnesium end member of the olivines group, on the whole infrared spectral range and up to the melting point by using CO₂ laser heating. The experimental data, fitted with a semi-quantum dielectric function model, allowed the retrieval of the temperature dependence of the absorption coefficient of forsterite both in the opaque and semi-transparent regions. The analysis of the phonon parameters indicates that the lattice dynamics evolve drastically with increasing temperature. The normal modes involving motions of the magnesium cations located in site 1 are the more impacted, and some of them vanish around 1,200 K. The results confirm that the enhancement of the lattice anharmonicity and the increasing mobility of the magnesium cations are closely linked and are at the origin of the anomalies observed in the evolution of the thermophysical properties. This complete set of spectroscopic data may be a step toward a more precise evaluation of the impact of thermal radiation heat transfer inside systems involving forsterite and quantification of their heat budget.     

Thermoelastic and structural properties of forsterite as a function of P and T: a computer simulation study, by semi-classical potentials

A theoretical study of some thermoelastic and structural properties of forsterite, at non-ambient conditions, is presented in this work. A site-dependent potential (NP) has been developed, and successfully used to carry out theoretical investigations on the lattice parameters, specific heat and tensorial elastic properties of forsterite, at P and T conditions representative of the actual thermobaric environment of the upper mantle of the Earth. Calculations have been performed in the framework of lattice dynamics and of quasi-harmonic approximation. The results, from high temperature or high pressure simulations, have been compared with experimental data. Calculations at high pressure and high temperature have provided unprecedented data, which are not easy to achieve experimentally. Received: October 10 1997 / Revised, accepted: January 26 1998     

Thermodynamics, structure, dynamics, and freezing of Mg2SiO4 liquid at high pressure

We perform first principles molecular dynamics simulations of Mg₂SiO₄ liquid and crystalline forsterite. On compression by a factor of two, we find that the Grüneisen parameter of the liquid increases linearly from 0.6 to 1.2. Comparison of liquid and forsterite equations of state reveals a temperature-dependent density crossover at pressures of ∼12-17 GPa. Along the melting curve, which we calculate by integration of the Clapeyron equation, the density crossover occurs within the forsterite stability field at P = 13 GPa and T = 2550 K. The melting curve obtained from the root mean-square atomic displacement in forsterite using the Lindemann law fails to match experimental or calculated melting curves. We attribute this failure to the liquid structure that differs significantly from that of forsterite, and which changes markedly upon compression, with increases in the degree of polymerization and coordination. The mean Si coordination increases from 4 in the uncompressed system to 6 upon twofold compression. The self-diffusion coefficients increase with temperature and decrease monotonically with pressure, and are well described by the Arrhenian relation. We compare our equation of state to the available highpressure shock wave data for forsterite and wadsleyite. Our theoretical liquid Hugoniot is consistent with partial melting along the forsterite Hugoniot at pressures 150-170 GPa, and complete melting at 170 GPa. The wadsleyite Hugoniot is likely sub-liquidus at the highest experimental pressure to date (200 GPa).     

Quantum-thermodynamic treatment of intrinsic anharmonicity; Wallace’s theorem revisited

Wallace (in Thermodynamics of crystals, 1972) developed a theorem, rooted in rigid lattice dynamics, which incorporates intrinsic anharmonic effects in solids. The practical application of this theorem in mineral physics is computationally involved and this is the main reason for the theorem not getting the attention it deserves. Because intrinsic anharmonicity is an important issue at the extreme conditions in planetary mantles, we derived a method which removes the computational obstacles in applying this theorem. We extended the theorem to incorporate details of the phonon spectrum and tested our algorithm on forsterite (Mg₂SiO₄). Using a least squares inversion technique applied to all available experimental data, we show that it results in an accurate representation of thermodynamic properties and sound wave velocities of Mg₂SiO₄ in its complete pressure–temperature stability range. We also show that the accuracy of our results is not significantly affected by the use of a different equation of state.     

The lattice dynamics and thermodynamics of the Mg2SiO4 polymorphs

We use an approach based upon the Born model of solids, in which potential functions represent the interactions between atoms in a structure, to calculate the phonon dispersion of forsterite and the lattice dynamical behaviour of the beta-phase and spinel polymorphs of Mg₂SiO₄. The potential used (THB1) was derived largely empirically using data from simple binary oxides, and has previously been successfully used to model the infrared and Raman behaviour of forsterite. It includes ‘bond bending’ terms, that model the directionality of the Si-O bond, in addition to the pair-wise additive Coulombic and short range terms. The phonon dispersion relationships of the Mg₂SiO₄ polymorphs predicted by THB1 were used to calculate the heat capacities, entropies, thermal expansion coefficients and Gruneisen parameters of these phases. The predicted heat capacities and entropies are in outstandingly good agreement with those determined experimentally. The predicted thermodynamic data of these phases were used to construct a phase diagram for this system, which has Clausius-Clapeyron slopes in very close agreement with those found by experiment, but which has predicted transformation pressures that show less close agreement with those inferred from experiment. The overall success, however, that we have in predicting the lattice dynamical and thermodynamic properties of the Mg₂SiO₄ polymorphs shows that our potential THB1 represents a significant step towards finding the elusive quantitative link between the microscopic or atomistic behaviour of minerals and their macroscopic properties.     

Effect of Water on the Composition of Magmas Formed at High Pressures

Portions of the system MgO-CaO-Na₂O-Al₂O₃-SiO₂-H₂O have beenstudied in the pressure range 13–35 kb at near-liquidustemperatures. The liquidus field of forsterite relative to thatof orthopyroxene is considerably wider under anhydrous thanunder anhydrous conditions and it covers part of the plane ofsilica-saturation in a wide pressure range. Partial meltingof simple garnet lherzolite (= forsterite+orthopyroxene+clinopyroxene+garnet)with water produces quartz-normative liquids at pressures upto at least 25 kb regardless of water content. Hydrous mineralsare not encountered at or near the solidus temperatures exceptin a Na-rich part of the system. Microprobe analysis of therun products in this synthetic system shows that the liquid(glass) in equilibrium with the lherzolite mineral assemblageis silica and alumina-rich at 20 kb under vapor-present conditions.With increasing degree of partial melting, the liquid changesits composition, passing into a ‘vapour-absent region’and becoming less silicic. Fractional crystallization of olivinetholeiitic magma under hydrous conditions also produces silica-richmagmas at high pressures. If the system is open to water, andwater pressure is less than total pressure, the compositionof the liquid varies from quartz-normative to olivine (±nepheline)-normativedepending on water pressure. It is suggested that in the presenceof water, silica-rich magmas such as those of calc-alkalic andesiteor dacite may be formed by direct partial melting of the peridotiticupper mantle at depths down to about 80 km. A large degree ofpartial melting of lherzolite under hydrous conditions wouldproduce SiO2 and MgO-rich magmas. The clinoenstatite rock fromCape Vogel, Papua, may have been formed by such a process. Peridotiteswith low CaAl2SiO5/jadeite ratios in the clinopyroxene couldproduce nepheline-normative magma by small degree of partialmelting and tholeiitic magma by large degree of partial meltingunder hydrous conditions.     

Lattice dynamics and Raman spectroscopy of protoenstatite Mg2Si2O6

Enstatites (Mg₂Si₂O₆) are important rock forming silicates of the pyroxene group whose structures are characterised by double MgO₆ octahedral bands and single silicate chains. Orthoenstatite transforms to protoenstatite above 1273 K with a doubling of the a axis and a rearrangement of the silicate chains with respect to the Mg₂₊ ions. Lattice dynamical calculations based on a rigid-ion model in the quasi-harmonic approximation provide theoretical estimates of elastic constants, long wavelength phonon modes, phonon dispersion relations, total and partial density of states and inelastic neutron scattering cross-sections of protoenstatite. The computed elastic constants are in good agreement with experimental data. The computed density of states of a chain silicate such as protoenstatite is distinct from that of olivines (forsterite, Mg₂SiO₄ and fayalite, Fe₂-SiO₄) with isolated silicate tetrahedra. The band gaps in the density of states in forsterite are largely due to the separation in the frequency ranges of the external and internal vibrations of the isolated silicate group, whereas in protoenstatite these gaps are filled by the vibrations of the bridging oxygens of the silicate chain. The computed density of states is used to calculate the specific heat, the mean square atomic displacements and temperature factors. Validity of these calculations are supported by Raman scattering measurements. Polarised and unpolarised Raman spectra are obtained from small single crystals of protoenstatite (Li,Sc)_0.6Mg_1.4Si₂O₆ stable at room temperature using the 488 nm or 514.5 nm lines of an Ar⁺ ion laser and a micro-Raman spectrometer with backscattering geometry. The Raman spectra were analysed and interpreted based on the lattice dynamical model. The experimental Raman frequencies and mode assignments (based on polarised single crystal spectra) are in good agreement with those obtained from lattice dynamical calculations.     

An experimental study of partitioning of fluorine between K-richterite,apatite, phlogopite,and melt at 20 kbar

Phase relations have been determined at 20 kbar and primarily under suprasolidus conditions in the Fe−Ti-free F-bearing K-richterite—phlogopite and K-richterite—apatite systems in order to assess the partitioning of F among phlogopite, K-richterite, apatite, and melt under upper-mantle conditions. Both systems are pseudoternary because they contain forsterite, enstatite and a diopside-rich clinopyroxene from the breakdown of the mica and K-richterite. The F-bearing K-richterite systems have lower minimum melting temperatures than the F-bearing phlogopite —apatite system at the same pressure. However in the systems studied, F in phlogopite appears the most effective component in altering minimum liquid compositions whereas comparison between the present study and previous systems suggests that the presence of P₂O₅ during melting may result in more K-enriched melts. Variations in the compositions of the F-bearing phases are primarily controlled by the bulk compositions of the end-member minerals and by temperature, although buffering by non-F bearing minerals (e.g. clinopyroxene) may be effective. Distribution coefficients (as wt% ratios) between F-bearing minerals and coexisting liquids have been determined as functions of bulk composition and temperature for products of experiments. Distribution coefficients between K-richterite—liquid, apatite—liquid, and phlogopite—liquid are ≥1 to slightly <1 for most bulk compositions, indicating thatF is generally a compatible element. This conclusion is in agreement with the sequence ofF distribution for similar phases in ultrapotassic rocks. These results preclude F-bearing mineral reservoirs in the mantle, at depths corresponding to 20 kbar, being capable of producing F-enrichment in ultrapotassic magmas, or being effective in redox melting processes. Editorial responsibility: K. Hodges     

Reaction of forsterite with hydrogen molecules at high pressure and temperature

High pressure and temperature reactions of a mixture of forsterite and hydrogen molecules have been carried out using a laser heated diamond anvil cell at 9.8–13.2 GPa and ~1,000 K. In situ X-ray diffraction measurements showed no sign of decomposition or phase transitions of the forsterite under these experimental conditions, indicating that the olivine structure was maintained throughout all runs. However, a substantial expansion of the unit cell volume of the forsterite was observed for samples down to ~3 GPa upon quenching to ambient pressure at room temperature. The Raman spectroscopy measurements under pressure showed significant shifts of the Raman peaks of the Si–O vibration modes for forsterite and of the intramolecular vibration mode for H₂ molecules toward a lower frequency after heating. Additionally, no OH vibration modes were observed by Raman and FT-IR spectroscopic measurements. These lines of evidence show that the observed volume expansion in forsterite is not explained by the incorporation of hydrogen atoms as hydroxyl, but suggest the presence of hydrogen as molecules in the forsterite structure under these high pressure and temperature conditions.     

Phase equilibria in the silica-undersaturated part of the KAlSiO4– Mg2SiO4– Ca2SiO4– SiO2– F system at 1 atm and the larnite-normative trend of melt evolution

The evolution of nephelinitic melts in equilibrium with mica-bearing liquidus assemblages and melting relations have been studied on two silica-undersaturated joins of the KAlSiO₄– Mg₂SiO₄– Ca₂SiO₄– SiO₂– F system at atmospheric pressure by quench runs in sealed platinum capsules. Fluorine has been added to the batch compositions by the direct exchange of fluorine for oxygen (2F⁻ = O²⁻). The first join is the pseudo-ternary Forsterite – Diopside – KAlSiO₃F₂ system. Forsterite, diopside, F-phlogopite and leucite crystallisation fields and a fluoride-silicate liquid immiscibility solvus are present on the liquidus surface of the join. Sub-liquidus and sub-solidus phases include akermanite, cuspidine, spinel, fluorite and some other minor fluorine phases. The second system is the pseudo-binary Akermanite – F-phlogopite join that intersects the Forsterite – Diopside – KAlSiO₃F₂ join. Akermanite, forsterite, diopside, F-phlogopite, leucite and cuspidine are found to crystallise on the join. Forsterite (fo) and leucite (lc) are related to F-phlogopite (phl) by a reaction with the fluorine-bearing liquid: fo + lc + l = phl, and the reaction proceeds until forsterite or leucite are completely consumed. The reaction temperature and resulting phase association depend on batch composition. Thus, leucite is not stable in the sub-solidus of the Akermanite – F-phlogopite join, but is preserved in a part of the Forsterite – Diopside – KAlSiO₃F₂ system where forsterite reacts out, or does not crystallise at all. The phlogopite-in reaction has an important effect on the composition of the coexisting liquid. The liquids initially saturated in forsterite evolve to extremely Ca rich, larnite-normative residuals. The experimental data show that larnite-normative melilitolites can crystallise from evolved melilititic melts generated from “normal” melanephelinitic parental magmas with no normative larnite. The evolution towards melilitites requires fractionation of phlogopite-bearing assemblages under volatile pressure. Received: 3 June 1997 / Accepted: 5 January 1998     

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.     

Lattice dynamics and inelastic neutron scattering from forsterite,Mg2SiO4: Phonon dispersion relation,density of states and specific heat

Magnesium-rich olivine (Mg_0.9Fe_0.1)₂SiO₄ is considered to be a major constituent of the Earth's upper mantle. Because of its major geophysical importance, the temperature and pressure dependence of its crystal structure, elastic and dielectric constants, long-wavelength phonon modes and specific heat have been measured using a variety of experimental techniques. Theoretical study of lattice dynamics provides a means of analyzing and understanding a host of such experimental data in a unified manner. A detailed study of the lattice dynamics of forsterite, Mg₂SiO₄, has been made using a crystal potential function consisting of Coulombic and short-range terms. Quasiharmonic lattice dynamical calculations based on a rigid molecular-ion model have provided theoretical estimates of elastic constants, long-wavelength modes, phonon dispersion relation for external modes along the three high symmetry directions in the Brillouin zone, total and partial density of states and inelastic neutron scattering cross-sections. The neutron cross-sections were used as guides for the coherent inelastic neutron scattering experiment on a large single crystal using a triple axis spectrometer in the constant Q mode. The observed and predicted phonon dispersion relation show excellent agreement. The inelastically scattered neutron spectra from a powder sample have been analyzed on the basis of a phonon density of states calculated from a rigid-ion model, which includes both external and internal modes. The experimental data from a powder sample show good agreement with the calculated spectra, which include a multiphonon contribution in the incoherent approximation. The computed phonon densities of states are used to calculate the specific heat as a function of temperature using both the rigid molecular-ion and rigid ion models. These results are in very good agreement with the calorimetric measurement of the specific heat. The interatomic potential developed here can be used with some confidence to study physical properties of forsterite as a function of pressure and temperature.     

Computer simulations of the structural and physical properties of the olivine and spinel polymorphs of Mg2SiO4

The aim of the work presented is to develop a computer simulation technique which will predict the structure and physical properties of forsterite and ringwoodite, the major mantle-forming polymorphs of Mg₂SiO₄. The technique is based upon energy minimization, in which all structural parameters are varied until the configuration with the lowest energy is achieved. The lattice energy and physical properties (e.g. elasticity and dielectric constants) are calculated from interatomic potentials, which generally include electrostatic and short-range terms. We investigate several types of traditional potential models, and present a new type of model which includes partial ionic charges and a Morse potential to describe the effect of covalency on the Si-O bond. This new form of potential model is highly successful, and not only reproduces the zero-pressure structural, elastic and dielectric properties of forsterite and ringwoodite, but also accurately describes their pressure dependence.     

Compressibility of nanocrystalline forsterite

We established an equation of state for nanocrystalline forsterite using multi-anvil press and diamond anvil cell. Comparative high-pressure and high-temperature experiments have been performed up to 9.6 GPa and 1,300°C. We found that nanocrystalline forsterite is more compressible than macro-powder forsterite. The bulk modulus of nanocrystalline forsterite is equal to 123.3 (±3.4) GPa whereas the bulk modulus of macro-powder forsterite is equal to 129.6 (±3.2) GPa. This difference is attributed to a weakening of the elastic properties of grain boundary and triple junction and their significant contribution in nanocrystalline sample compare to the bulk counterpart. The bulk modulus at zero pressure of forsterite grain boundary was determined to be 83.5 GPa.     

Modelling the effect of water on the surface structure and stability of forsterite

 We describe the application of atomistic simulation techniques to investigate the effect of associative and dissociative adsorption of water on the structures and stabilities of the low-index surfaces of forsterite. All surfaces are amenable to associative adsorption of water, while dissociative adsorption is energetically favourable on all but the non-dipolar {1 0 0} surface. Often, otherwise unstable (dipolar) surfaces are stabilised to a large extent by hydration, e.g. the dipolar {0 1 0} surface. However, on thermodynamic grounds we do not expect associatively adsorbed water to dissociate on all surfaces, as the energies released for dissociative adsorption of water on the non-dipolar {0 1 0} and {1 0 0} surfaces are less than those released for associative adsorption. As such, there is no energetic incentive for the associatively adsorbed water molecules to dissociate. The stabilities of the two terminations of the {0 1 0} surface, the main cleavage plane of forsterite, are reversed when hydroxylated, indicating that some dissolution of the magnesium ions may occur upon hydration, which is shown to be an exothermic process for both surface terminations. The equilibrium morphology was calculated as a way of assessing the change in surface energies. The experimental morphology of forsterite is adequately reproduced, suggesting that the relative stabilities of the surfaces, both unhydrated and hydroxylated, are calculated correctly. Received: 4 August 1999 / Revised, accepted: 11 October 1999     

Condensation of major elements during chondrule formation and its implication to the origin of chondrules

Two glassy refractory Al-rich chondrules in Semarkona (LL3.0), the most primitive unequilibrated ordinary chondrite, provide direct evidence for condensation of Si and Mg on melt droplets during cooling. The chondrules are completely rounded, rich in Ca and Al, and poor in Fe and alkalis. They have extraordinarily abundant glass (70-80 vol%) with a subordinate amount of forsterite as the only crystalline phase that occurs mostly rimming the chondrule edge. The groundmass glass is concentrically zoned in terms of Si with an outward increase, which is overlapped with local heterogeneity of Mg and Al induced by crystallization of forsterite. The outward increase of Si, mostly compensated by Al, cannot be formed solely by crystallization of forsterite from a homogeneous melt in a closed system. Combined with skeletal or dendritic morphology and sector zoning of forsterite, it is suggested that Si condensed onto totally molten droplets (“initial melts”) accompanied by nucleation and rapid growth of forsterite with lowering temperature. The “initial melts”, the compositions of which were estimated from the Ca contents of the first crystallized forsterite, are very similar to Type C CAI but are notably poorer in Mg and Si than the bulk chondrules, indicating condensation of Mg in addition to Si with an atomic ratio of Mg:Si ∼ 3:2. The condensation after the nucleation of forsterite took place below ∼1300 °C under cooling at ∼70 °C/h and amounted to 30 wt% of the current chondrule. This study suggests a model that a short-time and local shock heating event induced melting of Type C CAI and concomitant evaporation of dusts, ferromagnesian chondrules of earlier generation, and their fragments to generate Mg and Si-rich gas, which condensed onto the melt droplets upon cooling accompanying condensation of Type I chondrules.     

Effect of KCl on melting in the Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>–MgSiO<Subscript>3</Subscript>–H<Subscript>2</Subscript>O system at 5 GPa

To examine the effect of KCl-bearing fluids on the melting behavior of the Earth’s mantle, we conducted experiments in the Mg₂SiO₄–MgSiO₃–H₂O and Mg₂SiO₄–MgSiO₃–KCl–H₂O systems at 5 GPa. In the Mg₂SiO₄–MgSiO₃–H₂O system, the temperature of the fluid-saturated solidus is bracketed between 1,200–1,250°C, and both forsterite and enstatite coexist with the liquid under supersolidus conditions. In the Mg₂SiO₄–MgSiO₃–KCl–H₂O systems with molar Cl/(Cl + H₂O) ratios of 0.2, 0.4, and 0.6, the temperatures of the fluid-saturated solidus are bracketed between 1,400–1,450°C, 1,550–1,600°C, and 1,600–1,650°C, respectively, and only forsterite coexists with liquid under supersolidus conditions. This increase in the temperature of the solidus demonstrates the significant effect of KCl on reducing the activity of H₂O in the fluid in the Mg₂SiO₄–MgSiO₃–H₂O system. The change in the melting residues indicates that the incongruent melting of enstatite (enstatite = forsterite + silica-rich melt) could extend to pressures above 5 GPa in KCl-bearing systems, in contrast to the behavior in the KCl-free system.     

The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite

Density functional theory calculations have been used to study the pressure-induced changes of the hydrogen bond of Fe-free orthozoisite and clinozoisite and the concomitant shifts of the OH-stretching frequencies. Two independent parameter-free lattice dynamical calculations have been employed. One was based on a plane-wave basis set in conjunction with norm-conserving pseudopotentials and a density functional perturbation theory approach, while the other used a localised basis set and a finite displacement algorithm for the lattice dynamical calculations. Both models confirm the unusually large pressure-induced red-shift found experimentally (−33.89 cm⁻¹/GPa) in orthozoisite, while the pressure-induced shifts in clinozoisite are much smaller (−5 to −9 cm⁻¹/GPa). The atomistic model calculations show that in orthozoisite the nearly linear O–H⋯O arrangement is compressed by about 8% on a pressure increase to 10 GPa, while concomitantly the O–H distance is significantly elongated (by 2.5% at 10 GPa). In clinozoisite, the O–H⋯O arrangement is kinked at ambient conditions and remains kinked at high pressures, while the O-H distance is elongated by only 0.5% at 10 GPa. The current calculations confirm that correlations between the distances and dynamics of hydrogen bonds, which have been established at ambient conditions, cannot be used to infer hydrogen positions at high pressures.     

Pressure–volume–temperature equations of state: a comparative study based on numerical simulations

 The P–V–T equation of state (EoS) models of Birch–Murnaghan, Vinet and Poirier–Tarantola have been compared with one another and discussed in the light of their ability to reproduce thermoelastic functions and parameters by means of fitting to pressure–volume–temperature data artificially generated for spinel, corundum and forsterite. Numerical simulations relying upon semi-empirical potentials, lattice dynamics and the quasiharmonic approximation have been used to generate P–V–T data. The results obtained indicate that all the P–V–T EoSs tested predict bulk modulus at ambient conditions with errors confined, at worst, within a few percent, and reproduce correctly its dependence on temperature. The derivatives of the bulk modulus versus P and PT are less satisfactorily modelled. The bulk thermal expansion is determined by EoSs within a few percent error, but the deviations increase significantly if the approximation of linear dependence of EoS on temperature is used (linearised thermal pressure model). Received: 30 January 2001 / Accepted: 16 June 2001     

Growth of multilayered polycrystalline reaction rims in the MgO–SiO<Subscript>2</Subscript> system,part I: experiments

Growth of transport-controlled reaction layers between single crystals of periclase and quartz, and forsterite and quartz was investigated experimentally at 1.5 GPa, 1100°C to 1400°C, 5 min to 72 h under dry and melt-free conditions using a piston-cylinder apparatus. Starting assemblies consisting of Per | Qtz | Fo sandwiches produced polycrystalline double layers of forsterite and enstatite between periclase and quartz, and enstatite single layers between forsterite and quartz. The position of inert Pt-markers initially deposited at the interface of the reactants and inspection of mass balance confirmed that both layer-producing reactions are controlled by MgO diffusion, while SiO₂ is relatively immobile. BSE and TEM imaging revealed thicknesses from 0.6 μm to 14 μm for double layers and from 0 to 6.8 μm for single layers. Both single and double layers displayed non-parabolic growth together with pronounced grain coarsening. Textural evolution and growth rates for each reaction are directly comparable. Forsterite–enstatite double layers are always wider than enstatite single layers, and the growth of enstatite in the double layer is slower than that in the single layer. In double layers, the enstatite/forsterite layer thickness ratio significantly increases with temperature, reflecting different MgO mobilities as temperature varies. Thus, thickness ratios in multilayered reaction zones may contain a record of temperature, but also that of any physico-chemical parameter that modifies the mobilities of the chemical components between the various layers. This potential is largely unexplored in geologically relevant systems, which calls for further experimental studies of multilayered reaction zones.