Matrix rheology effects on reaction rim growth I: evidence from orthopyroxene rim growth experiments

The rim-forming reaction quartz + olivine = orthopyroxene is used to investigate the effect of matrix rheology on rim growth rates. Orthopyroxene rim growth around olivine grains in quartz matrix is compared to rim growth around quartz grains in an olivine matrix. At constant P–T , within one single capsule, orthopyroxene rims grow faster around quartz clasts in olivine matrix than around olivine clasts in quartz matrix. Fourier transform infra-red spectra indicate that the entire samples are water saturated because of water adsorption on the reactant grain surfaces. The increased orthopyroxene growth rates in olivine matrix as opposed to quartz matrix are interpreted in terms of matrix rheology, where in the two different matrix-inclusion arrangements the olivine matrix behaves 'softer' and the quartz matrix 'more rigid'. The strain energy associated with accommodation of the negative reaction volume is higher for the quartz than the olivine matrix and reduces the free energy that drives orthopyroxene rim growth. Growth textures in both kinds of orthopyroxene rims indicate that the diffusivity of MgO slightly exceeds the diffusivity of SiO₂. The relative mobility of MgO and SiO₂ at given P , T , f H₂O seems to be controlled by energy minimization during orthopyroxene growth at the compressive Ol/Opx interface. Our experiments provide evidence for two previously overlooked effects relevant to rim growth reactions in metamorphic rocks: (i) diffusivity along chemical potential gradients to reaction sites is a function of rheology and (ii) the relative diffusivity of components during reaction rim or corona growth is a function of local volume changes at the rim's interfaces.     

Grain boundary diffusion in enstatite

We have investigated grain boundary diffusion rates in enstatite by heating single crystals of quartz packed in powdered San Carlos olivine (Mg_0.90Fe_0.10)₂SiO₄ at controlled oxygen fugacities in the range 10^?5.7 to 10^?8.7?atm and temperatures from 1350° to 1450?°C for times from 5 to 100?h at 1?atm total pressure. Following the experiments, the thickness of the coherent polycrystalline reaction rim of pyroxene that had formed between the quartz and olivine was measured using backscatter scanning imaging in the electron microprobe. Quantitative microprobe analysis indicated that the composition of this reaction phase is (Mg_0.92Fe_0.08)₂Si₂O₆. The rate of growth of the pyroxene increases with increasing temperature, is independent of the oxygen fugacity, and is consistent with a parabolic rate law, indicating that the growth rate is controlled by ionic diffusion through the pyroxene rim. Microstructural observations and platinum marker experiments suggest that the reaction phase is formed at the olivine-pyroxene interface, and is therefore controlled by the diffusion of silicon and oxygen. The parabolic rate constants determined from the experiments were analyzed in terms of the oxide activity gradient across the rim to yield mean effective diffusivities for the rate-limiting ionic species, assuming bulk transport through the pyroxene layer. These effective diffusivities are faster than the lattice diffusivities for the slowest species (silicon) calculated from creep experiments, but slower than measured lattice diffusivities for oxygen in enstatite. Thus, silicon grain boundary diffusion is most likely to be the rate-limiting process in the growth of the pyroxene rims. Also, as oxygen transport through the pyroxene rims must be faster than silicon transport, diffusion of oxygen along the grain boundaries must be faster than through the lattice. The grain boundary diffusivity for silicon in orthopyroxenite is then given by D¯gbSiδ=(3.3±3.0)×10^?9f0.0O₂e^?400±65/RT?m³s^?1, where the activation energy for diffusion is in kJ/mol, and δ is the grain boundary width in m. Calculated growth rates for enstatite under these conditions are significantly slower than predicted by an extrapolation from similar experiments performed at 1000?°C under high pressure (hydrous) conditions by Yund and Tullis (1992), perhaps due to water-enhancement of diffusion in their experiments.     

The formation of columnar fiber texture in wollastonite rims by induced stress and implications for diffusion-controlled corona growth

 The evolution of columnar fiber texture was studied in wollastonite reaction rims synthesized by the reaction calcite + quartz=wollastonite + CO₂. Experiments were performed at 850 to 950 °C at 100 MPa in dry CO₂ and were evaluated by scanning and transmission electron microscopy. Rim growth rates are interpreted as controlled by the diffusion of the SiO₂ component through the rims from the quartz–wollastonite to the wollastonite–calcite interface. The temperature dependence of rim growth rates yields an apparent activation energy of 314 ± 53 kJ mol⁻¹. The columnar fibrous wollastonite crystallizes at the quartz–wollastonite interface and comprises the largest parts of the rims. Ultimately, at the growth front strain contrast centers are present in the quartz. The strained volume extends about 200 nm into the quartz grains. We suggest that this might signify deformation of the quartz lattice due to wollastonite crystallization. Wollastonite fiber thickness was measured from TEM images along traverses that represent intermediate positions of the growth front during the experiments. The average thickness is in the 100–200 nm range. Fiber thickness increases with increasing growth temperature. At a given temperature, the thickness of the fibers at the growth front slightly decreases with time, i.e., the number of fiber tips per unit area in the growth front increases. The decrease of the fiber thickness is well fitted by a parabolic rate law. The generation of the columnar fiber texture is interpreted as an effect of induced stresses at the growth front, resulting from the volume increase due to the local reaction. This volume increase forces SiO₂ to diffuse along the growth front to the grain boundaries between the wollastonite fibers. These serve as fast diffusion pathways through the rims. The fiber thickness monitors the diffusion distances in the growth front and thus the height of the induced stress gradients. Since interface reactions are usually associated with volume changes, growth rates of reaction rims and zones in coronas are not only controlled by the diffusive mobility of the components but also by the volume restraints on the interface reactions. Received: 19 July 2002 / Accepted: 14 February 2003     

Diffusion-controlled growth of wollastonite rims between quartz and calcite: comparison between nature and experiment

Growth rates of wollastonite reaction rims between quartz and calcite were experimentally determined at 0.1 and 1 GPa and temperatures from 850 to 1200 °C. Rim growth follows a parabolic rate law indicating that this reaction is diffusion‐controlled. From the rate constants, the D′δ‐values of the rate‐limiting species were derived, i.e. the product of grain boundary diffusion coefficient D′ and the effective grain boundary width, δ. In dry runs at 0.1 GPa, wollastonite grew exclusively on quartz surfaces. From volume considerations it is inferred that (D′_CaOδ)/(D′_SiO2δ)≥1.33, and that SiO₂ diffusion controls rim growth. D′_SiO2δ increases from about 10^?25 to 10^?23 m³ s^?1 as temperature increases from 850 to 1000 °C, yielding an apparent activation energy of 330±36 kJ mol^?1. In runs at 1 GPa, performed in a piston‐cylinder apparatus, there were always small amounts of water present. Here, wollastonite rims always overgrew calcite. Rims around calcite grains in quartz matrix are porous and their growth rates are controlled by a complex diffusion‐advection mechanism. Rim growth on matrix calcite around quartz grains is controlled by grain boundary diffusion, but it is not clear whether CaO or SiO₂ diffusion is rate‐limiting. D′δ increases from about 10^?21 to 10^?20 m³ s^?1 as temperature increases from 1100 to 1200 °C. D′_SiO2δ or D′_CaOδ in rims on calcite is c. 10 times larger than D′_SiO2δ in dry rims at the same temperature. Growth structures of the experimentally produced rims are very similar to contact‐metamorphic wollastonite rims between metachert bands and limestone in the Bufa del Diente aureole, Mexico, whereby noninfiltrated metacherts correspond to dry and brine‐infiltrated metacherts to water‐bearing experiments. However, the observed diffusivities were 4 to 5 orders of magnitude larger during contact‐metamorphism as compared to our experimental results.     

The behavior of Mg, Fe, and Ni during the replacement of olivine by orthopyroxene: experiments relevant to mantle metasomatism

Replacement of olivine by orthopyroxene is a frequently observed phenomenon in mantle metasomatism. In order to study element redistribution in SiO₂ metasomatism we synthesised orthopyroxene reaction rims at the contacts between forsterite-rich olivine and quartz. The orthopyroxene rims grew from the original quartz-olivine interface into both directions implying counterdiffusion of iron/magnesium and silicon. Following local equilibrium partitioning the X_Fe is lower in the orthopyroxene than in the reactant olivine at the olivine-orthopyroxene replacement front. The resulting local iron excess is compensated by formation of orthopyroxene with a higher X_Fe at the quartz-orthopyroxene interface, which is out of equilibrium with the reactant olivine. This is facilitated through short circuit diffusion along grain boundaries within the orthopyroxene rim. Due to the low capacity of orthopyroxene to accommodate Ni, this component is forced to diffuse back into the olivine producing a Ni enriched zone ahead of the replacement front. This leads to Ni contents in the orthopyroxene rim, which are higher than what is expected in equilibrium with the unaltered olivine. Taking quartz as a proxy for a silica rich fluid or liquid metasomatising agent, we conclude that the overall element fractionation between olivine and the silica rich phase may deviate from equilibrium partitioning so that the Fe and Ni concentrations in the orthopyroxene which is in contact with quartz are higher than in equilibrium with the reactant olivine. This indicates that kinetic fractionation is important for the chemical evolution of both the mantle rocks and the metasomatising agents.     

Reaction rim growth in the system MgO-Al2O3-SiO2 under uniaxial stress

We synthesize reaction rims between thermodynamically incompatible phases in the system MgO-Al₂O₃-SiO₂ applying uniaxial load using a creep apparatus. Synthesis experiments are done in the MgO-SiO₂ and in the MgO-Al₂O₃ subsystems at temperatures ranging from 1150 to 1350 °C imposing vertical stresses of 1.2 to 29 MPa at ambient pressure and under a constant flow of dry argon. Single crystals of synthetic and natural quartz and forsterite, synthetic periclase and synthetic corundum polycrystals are used as starting materials. We produce enstatite rims at forsterite-quartz contacts, enstatite-forsterite double rims at periclase-quartz contacts and spinel rims at periclase-corundum contacts. We find that rim growth under the “dry” conditions of our experiments is sluggish compared to what has been found previously in nominally “dry” piston cylinder experiments. We further observe that the nature of starting material, synthetic or natural, has a major influence on rim growth rates, where natural samples are more reactive than synthetic ones. At a given temperature the effect of stress variation is larger than what is anticipated from the modification of the thermodynamic driving force for reaction due to the storage of elastic strain energy in the reactant phases. We speculate that this may be due to modification of the physical properties of the polycrystals that constitute the reaction rims or by deformation under the imposed load. In our experiments rim growth is very sluggish at forsterite-quartz interfaces. Rim growth is more rapid at periclase-quartz contacts. The spinel rims that are produced at periclase-corundum interfaces show parabolic growth indicating that reaction rim growth is essentially diffusion controlled. From the analysis of time series done in the MgO-Al₂O₃ subsystem we derive effective diffusivities for the Al₂O₃ and the MgO components in a spinel polycrystal as ${\rm D}_{MgO} = 1.4 \pm 0.2 \cdot 10^{-15}$  m²/s and ${\rm D}_{Al_2O_3} = 3.7 \pm 0.6 \cdot 10^{-16}$  m²/s for T?=?1350 °C and a vertical stress of 2.9 MPa.     

Deformation-enhanced reaction in experimentally deformed plagioclase-olivine aggregates

The effects of deformation on the kinetics of the net-transfer reaction anorthite + forsterite → cpx + opx + spinel ± gt were studied using static and shear deformation experiments. Experiments were performed on dry anorthite-olivine (An₉₂–Fo₉₃) samples at 900°C and pressures between 1,000 and 1,600 MPa in a Griggs apparatus. Deformed (‘non-hydrostatic’) and undeformed (‘static’) samples are compared in terms of phase petrology, reaction rate and reaction mechanisms. Anorthite + olivine reactions are diffusion-controlled as seen from reaction rim structures. In undeformed samples, delayed reaction onset and low reaction rates demonstrate sluggish nucleation of reaction products and slow rates of diffusion at dry conditions, even at 700–900 MPa confining pressure overstepping. The reaction rate is enhanced in deformed An–Fo samples. The higher rate is mainly attributed to a combination of high stresses and viscous deformation processes of the reactants and products, which cause an increase in the nucleation rate of products. The results imply that viscous deformation processes alone can be responsible for the initiation and localisation of metamorphic reactions in dry rocks in the absence of fluid infiltration. A. A. de Ronde was supported by the Swiss National Fond grants 2100-057092.99 and 2000-065041.01.     

Asymmetrically zoned reaction rims: assessment of grain boundary diffusivities and growth rates related to natural diffusion-controlled mineral reactions

This study explores garnet coronas around hedenbergite, which were formed by the reaction plagioclase + hedenbergite→garnet + quartz, to derive information about diffusion paths that allowed for material redistribution during reaction progress. Whereas quartz forms disconnected single grains along the garnet/hedenbergite boundaries, garnet forms ～20‐μm‐wide continuous polycrystalline rims along former plagioclase/hedenbergite phase boundaries. Individual garnet crystals are separated by low‐angle grain boundaries, which commonly form a direct link between the reaction interfaces of the plagioclase|garnet|hedenbergite succession. Compositional variations in garnet involve: (i) an overall asymmetric compositional zoning in Ca, Fe²⁺, Fe³⁺ and Al across the garnet layer; and (ii) micron‐scale compositional variations in the near‐grain boundary regions and along plagioclase/garnet phase boundaries. These compositional variations formed during garnet rim growth. Thereby, transfer of the chemical components occurred by a combination of fast‐path diffusion along grain boundaries within the garnet rim, slow diffusion through the interior of the garnet grains, and by fast diffusion along the garnet/plagioclase and the garnet/hedenbergite phase boundaries. Numerical simulation indicates that diffusion of Ca, Al and Fe²⁺ occurred about three to four, four and six to seven orders of magnitude faster along the grain boundaries than through the interior of the garnet grains. Fast‐path diffusion along grain boundaries contributed substantially to the bulk material transfer across the growing garnet rim. Despite the contribution of fast‐path diffusion, bulk diffusion through the garnet rim was too slow to allow for chemical equilibration of the phases involved in garnet rim formation even on a micrometre scale. Based on published garnet volume diffusion data the growth interval of a 20‐μm‐wide garnet rim is estimated at ～10³–10⁴ years at the inferred reaction conditions of 760 ± 50 °C at 7.6 kbar. Using the same parameterization of the growth law, 100‐μm‐ and 1‐mm‐thick garnet rims would grow within 10⁵–10⁶ and 10⁶–10⁷ years respectively.     

Coronitic textures in the ferrogabbroids of the Elet’ozero intrusive complex (northern Karelia,Russia) as evidence for the existence of Fe-rich melt. 1. Types of coronas

Fe–Ti oxides (magnetite, Ti-magnetite, ilmenite, and associated high-Al spinel) in the ferrogabbroids of the Middle Paleoproterozoic Elet’ozero syenite–gabbro intrusion are intercumulus minerals usually surrounded by coronitic rims of two types. The first type usually represents multilayer amphibole–biotite ± olivine coronas along contacts of Fe–Ti oxides with cumulus moderate-Ca plagioclase and more rarely, clinopyroxene. Two-layer rim is developed in contact with high-Ca plagioclase; the inner rim consists of pargasite and spinel, while the outer rim is made up of sadanagaite and spinel. The second type is represented by two-stage coronitic textures developed along boundaries of olivine and Fe–Ti oxide clusters with plagioclase. Initially, the olivine was surrounded by orthopyroxene rim, while Fe–Ti oxides were rimmed by pargasite with thin ingrowths of high-Al spinel (hercynite). At the next stage, the entire cluster was fringed by a common symplectite reaction rim, the composition of which also depended on the composition of plagioclase matrix: the spinel–sadanagaite rim was formed in contact with high-Ca plagioclase, while pargasite–muscovite–scapolite rim was formed in contact with moderate-Ca plagioclase. The formation of the outer rims occurred after hydration of the inner parts of coronas around olivine and oxides within the clusters. It is suggested that the Fe–Ti oxides and surrounding coronitic rims were microsystems formed by crystallization of drops of residual hydrous Fe-rich liquid.     

Kinetics of a garnet granulite reaction

It is necessary to understand the mechanisms of disequilibrium reactions in metamorphic rocks in order to (1) model the rate of reaction in response to changing state variables during tectonic process, and (2) interpret the assemblages of natural disequilibrium samples in terms of tectonic history. A sample was selected from an area of known tectonic history to examine in detail and document the kinetics of reaction. The sample preserves evidence of the garnet granulite to gabbro transition.Orthopyroxene and anorthite coronas around garnet and orthopyroxene rims around clinopyroxene are textural observations suggesting the overall reaction: garnet+clinopyroxene+quartz+plagioclase(matrix) orthopyroxene+ anorthite (corona). The disequilibrium nature of reaction is evident from compositional zoning of garnet, some zoning of clinopyroxene, and difference between corona anorthite (An₉₀) and matrix plagioclase (An₃₅).Several texturally-distinguished microenvironments in a single thin section were investigated to determine how components were redistributed during reaction; T and P are assumed to have been the same throughout. The compositional data are best explained by a partial equilibrium model in which orthopyroxene, garnet rims, Fe-rich clinopyroxene, and a hypothetical intergranular fluid approach equilibrium and are not in equilibrium with reactant garnet cores and matrix plagioclase. Corona texture suggests that intergranular diffusion had some effect but the composition data indicate that it was not rate-limiting. The fact that garnet rim compositions are nearly in equilibrium with product phases (with respect to Mg-Fe partitioning) suggests that diffusion in garnet can be considered a rate-limiting reaction step. Combining the differential equation of zoning for this system with mass and volume balance equations of reaction enables one to predict the density change with time by numerical integration.I conclude that comparison of core compositions of zoned minerals in high-grade rocks is meaningful only if a compositional plateau is preserved that can be proven not to be altered by diffusion. Diffusion in pyroxene is apparently too fast at high grade to make relict pyroxenes useful tracers of metamorphic conditions. The rim composition of zoned phases depends on the relative rate of reaction and internal diffusion; the approach of the rim of a reactant phase to equilibrium with products is a measure of the degree to which intragranular diffusion is rate-limiting. In general, this work supports reaction models that assume that intergranular diffusion is rapid and that interface kinetics or intragranular diffusion are usually rate-limiting factors.Reactions controlled by diffusion in garnet are slow geologically. Tectonic hysteresis can be produced because garnet can form in granulite assemblages more rapidly than it is consumed with changing heat flow. The rate of gabbro-garnet granulite transition depends on whether plagioclase reacts by zoning or separate product grains nucleate.     

Complex chemical zoning in eclogite facies garnet reaction rims: the role of grain boundary diffusion

In metapelites of the Saualpe complex (Eastern Alps) continuous 10 µm to 20 µm wide garnet reaction rims formed along biotite-plagioclase and biotite-perthite interfaces. The pre-existing mineral assemblages are remnants of low pressure high temperature metamorphism of Permian age. The garnet reaction rims grew during the Cretaceous eclogite facies overprint. Reaction rim growth involved transfer of Fe and Mg components from the garnet-biotite interface to the garnet-feldspar interface and transfer of the Ca component in the opposite direction. The garnets show complex, asymmetrical chemical zoning, which reflects the relative contributions of short circuit diffusion along grain boundaries within the polycrystalline garnet reaction rims and volume diffusion through the grain interiors on bulk mass transfer. It is demonstrated by numerical modelling that the spacing of the grain boundaries, i.e. the grain size of the garnet in the reaction rim is a first order control on its internal chemical zoning.     

Orthopyroxene rim growth between olivine and quartz at low temperatures (750–950°C) and low water concentration

Orthopyroxene reaction rims were synthesized between polished plates of natural olivine or synthetic forsterite and quartz at 1.9 GPa and temperatures of 750–950°C. The experiments were performed in a piston-cylinder apparatus after drying the samples at 600°C. Each experiment comprised 4 or 7 quartz-olivine contacts that were positioned along a temperature gradient. As a monitor for water content in the samples, the water concentration in the two olivines was determined by FTIR before and after the experiments. The orthopyroxene layers show two different structural variants. Type one (normal layers) has very constant thickness at each contact and formed with equal growth rates at both interfaces. Type two (bulging layers) comprises more irregular areas with 3–5 times thicker rims where porosity provides evidence for the local presence of a fluid. In the bulging layers the growth rate at the olivine-orthopyroxene interface exceeds that at the quartz-orthopyroxene interface. The relative growth rates at the interfaces are in accordance with SiO₂-immobile growth of the normal layers and SiO₂-mobile growth of the bulging layers. The natural olivine contains about 60 wt-ppm intracrystalline water before and after experiment and took up about 20 wt-ppm water molecular adsorbed to micro- and nanocracks and -pores during the runs. The synthetic forsterite contains about 7 wt-ppm internally adsorbed molecular water before and after experiment, and during the runs took up hydrogen equivalent to 3 wt-ppm adsorbed water. The IR spectra indicate that large parts of the point defects (possibly tetrahedral) were frozen-in at the conditions of the experiments. In both olivines a new band appeared at 3,355 or 3,357 cm^?1, respectively, equivalent to about 3 wt-ppm water that at the high pressure of the experiments and opx-buffered aSiO₂ of the experiments might already mean water saturation of the olivines. Despite the effective drying before experiment and the absence of porosity, the bulk diffusivity derived from the rim growth rates is perfectly in line with data from water-bearing piston-cylinder experiments at higher temperatures. The bulk diffusivity during rim growth is 4 to 7 orders of magnitude higher than an extrapolation of really dry experiments to the temperature range of this study.     

Textural evolution and metamorphism of pillow basalts from the Franciscan Complex,western Marin County,California

Petrogenesis of Franciscan pillow basalts from the Franciscan Complex of western Marin County California entails both dynamic crystallization of tholeiitic magma and subsequent low-temperature metamorphism. Brittle deformation during tectonic emplacement of pillow basalts into a chert greywacke terrain is manifested by the shearing of interpillow matrix and polishing of pillow rims, but the igneous textures within pillows are well preserved.The cooling history of pillow basalts can be understood through analysis of morphologic variations of primary olivine and plagioclase from rim to core of the pillow. Crystal sizes and plagioclase dendrite spacings are consisted with a cooling rate which generally decreases inward. Some pillows show a marked asymmetry in plagioclase and olivine morphology suggesting lower cooling rates caused by asymmetric cooling of the pillows. Olivine morphologies, primarily hopper and chain forms, are consistent with cooling rates of 2–10 °C/h for pillow cores and 50–75 °C/h for pillow rims.Low temperature hydrothermal alteration has produced secondary minerals indicative of zeolite facies conditions. Pillow matrix is either chloritic or zeolitic (in part laumontized). Pillow rims display incomplete replacement of calcic palagonite by pumpellyite (Fe₂O₃=9–21 wt%), prehnite (Fe₂O₃=5–7 wt%), sphene and quartz. Metamorphism of pillow interiors, manifested by: (1) veins of quartz, pumpellyite, calcite, or harmotome (BaO=15 wt%); (2) amygdules containing analcime, chlorite or quartz; and (3) replacement of olivine by pumpellyite or smectite/illite, of plagioclase by albite (An3)+sericite, and of glassy groundmass by fine-grained chlorite. Primary augite (Wo3₃₉En₁₃Fs₄₈) was not altered. The described paragenesis may be attributed to oceanfloor and/or Franciscan-type metamorphism.     

大同新生代火山岩浆的快速喷发——来自橄榄石地幔捕掳晶的证据

量化研究幔源岩浆从源区运移至喷发或者侵位的时间尺度，对理解基性岩浆作用具有重要意义。然而，对于岩浆的喷发和就位的时间尺度研究仍缺乏有效的约束，位于我国华北克拉通北部山西大同新生代火山岩群是理想的研究地区。本文以该火山群～0.2 Ma喷发的神泉寺碱性玄武岩为研究对象，重点研究其中携带的地幔橄榄石捕掳晶来约束喷发前的时间尺度。通过对其开展详细的矿物化学研究，发现地幔捕掳晶核部的Fo值高达97.7,为极富镁橄榄石，结合其极低的Ca、Mn和Ni含量特征，认为它们捕获自被交代的地幔橄榄岩。另外，地幔橄榄石捕掳晶发育明显的CaO成分环带，表明其在地壳岩浆系统内经历了复杂的岩浆演化过程。地幔橄榄石捕掳晶反应边宽度变化很大，说明它们在源区被捕获时及在运移过程中经过了多次破碎过程。橄榄石捕掳晶最边缘的Fo值为70左右，平衡计算表明它们在边部已与主岩浆(碱性玄武岩)达到平衡。Fe-Mg元素扩散计时结果显示，橄榄石地幔捕掳晶仅在岩浆中滞留了几个月的时间。对于40～70 km的岩石圈地幔厚度来说，岩浆平均上升速率最快可能超过500 m/d。     

Silicon and oxygen self diffusion in enstatite polycrystals: the Milke et al. (2001) rim growth experiments revisited

Milke et al. (Contrib Mineral Petrol 142:15–26, 2001) studied the diffusion of Si, Mg and O in synthetic polycrystalline enstatite reaction rims. The reaction rims were grown at 1,000°C and 1 GPa at the contacts between forsterite grains with normal isotopic compositions and a quartz matrix extremely enriched in ¹⁸O and ²⁹Si. The enstatite reaction rim grew from the original quartz-forsterite interface in both directions producing an inner portion, which replaced forsterite and an outer portion, which replaced quartz. Here we present new support for this statement, as the two portions of the rim are clearly distinguished based on crystal orientation mapping using electron backscatter diffraction (EBSD). Milke et al. (Contrib Mineral Petrol 142:15–26, 2001) used the formalism of LeClaire (J Appl Phys 14:351–356, 1963) to derive the coefficient of silicon grain boundary diffusion from stable isotope profiles across the reaction rims. LeClaires formalism is designed for grain boundary tracer diffusion into an infinite half space with fixed geometry. A fixed geometry is an undesired limitation in the context of rim growth. We suggest an alternative model, which accounts for simultaneous layer growth and superimposed silicon and oxygen self diffusion. The effective silicon bulk diffusivity obtained from our model is approximately equal within both portions of the enstatite reaction rim: D _Si,En ^eff =1.0–4.3×10^–16 m² s^–1. The effective oxygen diffusion is relatively slow in the inner portion of the reaction rim, D _O,En ^eff =0.8–1.4×10^–16 m² s^–1, and comparatively fast, D _O,En ^eff =5.9–11.6×10^–16 m² s^–1, in its outer portion. Microstructural evidence suggests that transient porosity and small amounts of fluid were concentrated at the quartz-enstatite interface during rim growth. This leads us to suspect that the presence of an aqueous fluid accelerated oxygen diffusion in the outer portion of the reaction rim. In contrast, silica diffusion does not appear to have been affected by the spatial variation in the availability of an aqueous fluid.

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Growth kinetics of enstatite reaction rims studied on nano-scale,Part I: Methodology,microscopic observations and the role of water

The kinetics of (Mg, Fe)SiO₃ pyroxene layer growth within silicate thin films with total thickness <1 μm was studied experimentally at 0.1 MPa total pressure, controlled fO₂ and temperatures from 1,000 to 1,300°C. The starting samples were produced by pulsed laser deposition. Layer thickness before and after the experiments and layer composition as well as microstructures, grain size and shape of the interfaces were determined by Rutherford back scattering and transmission electron microscopy assisted by focused ion beam milling. Due to the miniaturization of the starting samples and the use of high resolution analytical methods the experimentally accessible temperature range for rim growth experiments was extended by about 300°C towards lower temperatures. The thickness of the layers at a given temperature increases proprotional to the square root of time, indicating a diffusion-controlled growth mechanism. The temperature dependence of rim growth yields an apparent activation energy of 426 ± 34 kJ/mol. The small grain size in the orthopyroxene rims implies a significant contribution of grain boundary diffusion to the bulk diffusion properties of the polycrystalline rims. Based on microstructural observations diffusion scenarios are discussed for which the SiO₂ component behaves immobile relative to the MgO component. Volume diffusion data for Mg in orthopyroxene from the literature indicate that the measured diffusivity is probably controlled by the mobility of oxygen. The observed reaction rates are consistent with earlier results from dry high-temperature experiments on orthopyroxene rim growth. Compared to high pressure experiments at 1,000°C and low water fugacities, reaction rates are 3–4 orders of magnitude smaller. This observation is taken as direct evidence for a strong effect of small amounts of water on diffusion in silicate polycrystals. In particular SiO₂ changes from an immobile component at dry conditions to an extremely mobile component even at very low water fugacities.     

Indicators of parent-body processes: Hydrated chondrules and fine-grained rims in the Mokoia CV3 carbonaceous chondrite

A petrographic and electron microscopic study of the Mokoia CV3 carbonaceous chondrite shows that all of the chondrules and inclusions (>400 μm in diameter) and most of their fine-grained rims studied (referred to as chondrules/rims) contain various amounts of hydrous phyllosilicates (mostly saponite) formed by aqueous alteration of anhydrous silicates. The rims mainly consist of fine-grained olivine and saponite in varying proportions and contain crosscutting veins of Fe-rich olivine. The boundaries between the chondrules and their rims are irregular and show abundant evidence of aqueous alteration interactions between them. In contrast, the host matrix contains very minor amounts of saponite and shows no evidence of such extensive aqueous alteration. The boundaries between the chondrules/rims and the matrix are sharp and show no traces of the matrix having been involved in the alteration of the chondrules/rims. These observations indicate that the aqueous alteration in the chondrules/rims did not occur in the present setting.We suggest that the chondrules/rims are actually clasts transported from a location on the meteorite parent body different from where the Mokoia meteorite was from. The aqueous alteration of the chondrules/rims probably occurred there. The veins in the rims were originally fractures produced in an interchondrule matrix by impacts; these were later filled by Fe-rich olivine during aqueous activity. This location was then involved in impact brecciation, and individual chondrules were ejected as clasts with remnants of the matrix surrounding them. During the continuing brecciation, those chondrule/rim clasts were transported, mixed with anhydrous matrix grains, and finally lithified to the present meteorite. Therefore, the rims are fragmented remnants of a former matrix.Textures characterized by fine-grained rims surrounding chondrules in chondrites have been widely thought to have formed in the solar nebula before they accreted into their parent bodies. However, our results suggest that some textures may not be explained by such an accretionary model; instead, the multi-stage parent-body process modeled for the Mokoia rim formation may be a more plausible explanation.     

Experimental reactions between olivine and orthopyroxene with phonolite melt: implications for the origins of hydrous amphibole + phlogopite + diopside bearing metasomatic veins

Amphibole + phlogopite + diopside bearing veins are observed in a large number of upper mantle xenoliths, but the composition of the melt that forms them is poorly constrained. Recent data from the Heldburg Phonolite, Central Germany, has shown that phonolite melt will react with olivine and orthopyroxene xenocrysts to form reaction rims of amphibole + phlogopite + diopside at mid-lower crustal pressures. This is the first example of where a melt has reacted with peridotite to form the mineralogy of the metasomatic veins. It is therefore necessary to explore whether a phonolite melt could be the parent melt that forms amphibole + phlogopite + diopside metasomatic veins. Experimental reactions between single crystals of olivine and orthopyroxene with phonolite melt were conducted at upper mantle conditions of 1.0–1.5 GPa and 900–1,000 °C. Melt water contents were varied from anhydrous to >12 wt. H₂O. Olivine reacts to form phlogopite reaction rims with overgrowths of diopside <1,000 °C or rims of secondary olivine >1,000 °C. Orthopyroxene reacts to form amphibole with epitaxial diopside overgrowths <1,000 °C. No reaction rims form when the bulk melt H₂O is lower than ~3.8 wt%. Pressure has little effect over the small range tested. These experiments reproduce reaction rims on olivine and orthopyroxene observed in the Heldburg Phonolite, Central Germany, and suggest that a relatively narrow range of temperatures and melt water contents is required for rim formation. The compositions of rim amphibole, phlogopite and diopside from the experiments have very similar compositions to those from Heldburg but do not match those from metasomatic veins. Phenocrysts from Heldburg are similar to the metasomatic veins, suggesting that a phonolite could potentially form the veins if vein formation is dominated by crystallization rather than reaction and replacement of wall rock phases.     

Cathodoluminescence imaging and titanium thermometry in metamorphic quartz

Cathodoluminescence (CL) of quartz from metamorphic rocks representing a range of conditions from the garnet grade to the migmatite grade reveals a variety of textures, that is, a function of metamorphic grade and deformation history. Ti concentrations, determined by electron microprobe and ion microprobe, generally correlate with CL intensity (blue wavelengths), and application of the Ti‐in‐quartz thermometer (TitaniQ) reflects the temperature of quartz growth or recrystallization, and, in some settings, modification by diffusion. Quartz from garnet grade samples is not visibly zoned, records temperatures of 425–475 °C, and is interpreted to have recrystallized during fabric formation. Quartz grains from staurolite grade samples are zoned in CL with markedly darker cores and brighter rims, some of which are interpreted to have been produced by the dominant staurolite‐producing reaction, whereas others are interpreted as having formed by diffusion of Ti into quartz rims. Quartz from the matrix of kyanite and sillimanite grade samples are generally unzoned, although locally displays slightly brighter rims (higher Ti); quartz inclusions within garnet and staurolite have distinctly brighter rims, which are interpreted as having been produced by diffusive exchange with the host mineral. Quartz from migmatite grade samples displays highly variable CL intensity, which is dependent on the location of the grain. Matrix grains in melanosomes are largely unzoned or rarely zoned with darker cores. Leucosome quartz is strongly zoned with bright cores and dark rims and is interpreted as having formed during crystallization of the melt. Locally within the leucosome is observed oscillatory‐zoned quartz, which is interpreted as a subsolidus recrystallization to achieve strain relaxation. Quartz inclusions within garnet or plagioclase crystals often show bright domains separated by zones of dark CL. These enigmatic textures possibly reflect local melting fluxed by fluid inclusions. Temperatures calculated from the Ti–in–quartz thermometer are a function of the metamorphic grade of the sample, the textural setting of the quartz, the reaction history and the deformation history of the rock. The TitaniQ temperatures can be used to constrain the conditions at which various metamorphic processes have occurred.     

Experimental study of silica diffusion during metasomatic reactions in the presence of water at 550°C and 1000 bars

Metasomatic reactions between quartz and incompatible oxides or hydroxides were experimentally studied at 550°C and 1000 bars water pressure. Two porous pellets of the initial reagents pressed one against the other were used. Reaction rims in the millimeter range develop at the initial boundary in the oxide pellet. All the experiments show that an important transfer of silica occurs by diffusion in the stationary intergranular solution.The chemical transfer of silica through the intergranular fluid is quantitatively determined by studying the kinetics of growth of the forsterite rim in the system quartz-brucite. The kinetics limiting stage being silica transfer, the experiments allow the determination of the diffusion coefficient of silica through the solution. At 550°C and 1000 bars, a value of 2.4 × 10^?1cm² s¹ is found.This high value shows the importance of chemical diffusion in the intergranular fluid of rocks during metamorphic processes.