Compression and coordination changes in pyroxenoids: an EXAFS study of MgGeO3 enstatite and CaGeO3 wollastonite

The evolution of the distortion of MgGeO₃ enstatite and CaGeO₃ wollastonite with increasing pressure, has been investigated using X-ray absorption spectroscopy (XAS) in a diamond anvil cell. At room temperature and low pressure (P<7 GPa), the compressibility of the GeO₄ tetrahedron is higher in MgGeO₃ enstatite (K _[GeO4]∼135 GPa) than in CaGeO₃ wollastonite (K _[GeO4]≥ 280 GPa). The compression mechanisms of the two compounds are different: the whole mineral compressibility of Ge-enstatite appears to be very homogeneous, in contrast to that of Ge-wollastonite which exhibits an inhomogeneous tretrahedral compressibility. This result is consistent with the variation of the Debye-Waller factors of the two compounds with increasing pressure. At higher pressures, the coordination of germanium atoms in the two compounds gradually changes from fourfold to sixfold. For CaGeO₃ the coordination change starts at 7 GPa and is complete a 12 GPa, whereas it starts at about 8.5 GPa for MgGeO₃ and is not complete at 31 GPa. The progressive evolution of the measured Ge-O distances as well as the modification in the X-ray absorption near-edge structure indicate two coexisting different sites rather than a progressive site modification. The transformation is found to be partially reversible in CaGeO₃ wollastonite, whereas it is totally reversible in MgGeO₃ enstatite.     

Polymorphism of wollastonite

Different superstructures of wollastonite from the regional metamorphic Lepontine zone (Southern Alps) and other localities (e.g., Sierra Nevada, California) have been found. Besides well ordered normal 1T, 2M (2T ?), 4T-wollastonite, all disordered intermediate states exist. The various polymorphs were studied with the precession method. The superstructure is observed in reflections hkl k=odd. 4T-wollastonite is described with a ₀=31.659 Å and is shown to be a common polymorph. The superstructure seems to be independent of metamorphic grade (in the well-zoned Lepontine area it does not follow any mineralogical isograds) and occurs only in strained rocks with well developed lineation and strong preferred orientation. Thus the formation of the superstructure is explained as a deformation effect. Contrary to temperature and pressure, both stress and strain show large local variations and inhomogeneities. Experimental deformation of a 2T-wollastonite at 4 kb and 700° C produced complete disorder. It is suggested that consecutive annealing of strained disordered wollastonite causes periodic stacking sequences of [SiO₃]-chains along the a^*-axis. It appears from these studies that superstructures in chainsilicates are more common than presently known and that they might be useful petrogenetic indicators for the deformation and cooling history of a rock.     

The unequilibrated enstatite chondrites

The enstatite chondrites formed under highly reducing (and/or sulfidizing) conditions as indicated by their mineral assemblages and compositions, which are sharply different from those of other chondrite groups. Enstatite is the major silicate mineral. Kamacite is Si-bearing and the enstatite chondrites contain a wide variety of monosulfide minerals that are not present in other chondrite groups. The unequilibrated enstatite chondrites are comprised of two groups (EH3 and EL3) and one anomalous member (LEW 87223), which can be distinguished by differences in their mineral assemblages and compositions. EH3 chondrites have >1.8 wt.% Si in their kamacite and contain the monosulfide niningerite (MgS), whereas EL3 chondrites have less than 1.4 wt.% Si in their kamacite and contain the monosulfide alabandite (MnS). The distinct mineralogies, compositions and textures of E3 chondrites make comparisons with ordinary chondrites (OCs) and carbonaceous chondrites (CCs) difficult, however, a range of recrystallization features in the E3s are observed, and some may be as primitive as type 3.1 OCs and CCs. Others, especially the EL3 chondrites, may have been considerably modified by impact processes and their primary textures disturbed. The chondrules in E3 chondrites, although texturally similar to type I pyroxene-rich chondrules, are sharply different from chondrules in other chondrite groups in containing Si-bearing metal, Ca- and Mg–Mn-rich sulfides and silica. This indicates formation in a reduced nebular environment separate from chondrules in other chondrites and possibly different precursor materials. Additionally the oxygen isotope compositions of E3 chondrules indicate formation from a unique oxygen reservoir. Although the abundance, size distribution, and secondary alteration minerals are not always identical, CAIs in E3 chondrites generally have textures, mineral assemblages and compositions similar to those in other groups. These observations indicates that CAIs in O, C and E chondrites all formed in the reservoir under similar conditions, and were redistributed to the different chondrite accretion zones, where the secondary alteration took place. Thus, chondrule formation was a local process for each particular chondrite group, but all CAIs may have formed in the similar nebular environment. Lack of evidence of water (hydrous minerals), and oxygen isotope compositions similar to Earth and Moon suggest formation of the E chondrites in the inner solar system and make them prime candidates as building blocks for the inner planets.     

Equilibration temperatures in enstatite chondrites

Equilibration temperatures for enstatite chondrites are calculated using a method suggested by Larimer (1968). The temperatures range from 640° to 840°C. The method yields temperatures which, in principle, are correct on a relative scale but the absolute error may be a large as 150°. There is a good correlation between the calculated temperatures and petrologic type as well as other mineralogic characteristics and bulk composition. Partial pressures of sulfur and oxygen at the time of equilibration were: pS₂ ~ 10^?8?10^?12 atm and pO₂ ~ 10^?28?10^?37.     

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.     

High-temperature flow of wet polycrystalline enstatite

Previous experiments by Raleigh et al. (1971) have shown that at strain rates of 10⁻².sec⁻¹ to 10⁻⁷.sec⁻¹ only slip occurs in dry enstatite at temperatures above 1300°C and 1000°C, respectively.The present experiments have been conducted on polycrystalline enstatite under wet conditions in this regime where enstatite only slips, polygonizes and recrystallizes. Slip occurs throughout the whole regime on the system (100)[001] and at strains greater than 40% the system (010)[001] is observed. Polygonization and intragranular recrystallization begin at about 1300°C and 10⁻⁴.sec⁻¹ and the orientation of these neoblasts is host-controlled. At lower strain rates intergranular neoblasts develop and their fabric is one of [100] maximum parallel with σ₁ and [010] and [001] girdles in the σ₂ = σ₃ plane, similar to those in natural enstatite tectonites.Dislocation substructures of experimentally deformed enstatite have been examined by transmission electron microscopy. The samples were deformed within the field in which slip polygonization and recrystallization are the dominant deformation mechanisms. Samples within this regime have microstructures that are characterized by stacking faults and partial dislocations. Under the conditions of steady-state flow in olivine, these microstructures inhibit the operation of recovery mechanisms in enstatite.Other samples deformed within the polygonization and recrystallization field have microstructures that confirm the optical observations of intragranular and intergranular growth of neoblasts. It is suggested that the former result from strain-induced tilt of subrains, whereas the latter may result from bulge nucleation into adjacent subgrains.Mechanical data from constant strain-rate experiments at steady state, stress relaxation and temperature-differential creep tests are best fit to a power-law creep equation with the stress exponent, n~3 and the apparent activation energy for creep, Q~65 kcal/mole. Extrapolation of this equation to a representative natural geologic strain rate of 10⁻⁴. sec⁻¹, over the temperature interval 1000–2000°C, gives an effective viscosity range of 10²⁰–10¹⁸ poise and stresses in the range of 7-0.1 bar, respectively. Comparison with corrected wet-olivine mechanical data (Carter, 1976) over the same environment indicates that olivine is consistently the weaker of the two minerals and will recrystallize whilst enstatite will only slip and kink, thus accounting for the different habits of olivine and enstatite in ultramafic tectonites.     

Theoretical study of OH-defects in pure enstatite

The infrared spectroscopic properties of selected defects in orthoenstatite are investigated by first-principles calculations. The considered defects include doubly protonated Mg vacancies at M1 and M2 sites, fully protonated SiA and SiB vacancies (hydrogarnet defects), and doubly protonated SiA and SiB vacancies associated with interstitial Mg²⁺ cations. The bands observed at 3,070 and 3,360 cm^?1 in the spectrum of synthetic enstatite samples are ascribed to O2A–H and O2B–H groups, respectively, associated with M2 vacancies. The theoretical models suggest that bands observed at 3,590 and 3,690 cm^?1 in the spectrum of enstatite samples synthesized under low silica-activity conditions correspond to O2H and O1H groups associated with SiB vacancies partially compensated by interstitial Mg²⁺ cations in fivefold coordination. The theoretical relation between the integrated absorption coefficient of OH-defects and vibrational frequencies is consistent with previous observations indicating that the absorption coefficients of OH-defects are comparatively stronger in enstatite than in the olivine polymorphs.     

High-precision osmium isotopes in enstatite and Rumuruti chondrites

Isotopic heterogeneity within the solar nebula has been a long-standing issue. Studies on primitive chondrites and chondrite components for Ba, Sm, Nd, Mo, Ru, Hf, Ti, and Os yielded conflicting results, with some studies suggesting large-scale heterogeneity. Low-grade enstatite and Rumuruti chondrites represent the most extreme ends of the chondrite meteorites in terms of oxidation state, and might thus also present extremes if there is significant isotopic heterogeneity across the region of chondrite formation. Osmium is an ideal tracer because of its multiple isotopes generated by a combination of p-, r-, and s-process and, as a refractory element; it records the earliest stages of condensation.Some grade 3-4 enstatite and Rumuruti chondrites show similar deficits of s-process components as revealed by high-precision Os isotope studies in some low-grade carbonaceous and ordinary chondrites. Enstatite chondrites of grades 5-6 have Os isotopic composition identical within error to terrestrial and solar composition. This supports the view of digestion-resistant presolar grains, most likely SiC, as the major carrier of these anomalies. Destruction of presolar grains during parent body processing, which all high-grade enstatite chondrites, but also some low-grade chondrites seemingly underwent, makes the isotopically anomalous Os accessible for analysis. The magnitude of the anomalies is consistent with the presence of a few ppm of presolar SiC with a highly unusual isotopic composition, produced in a different stellar environment like asymptotic giant branch stars (AGB) and injected into the solar nebula. The presence of similar Os isotopic anomalies throughout all major chondrite groups implies that carriers of Os isotopic anomalies were homogeneously distributed in the solar nebula, at least across the formation region of chondrites.     

Actinide microdistributions in the enstatite meteorites

Oldhamite is a major Th and U bearing phase in the enstatite meteorites. Oldhamite from E-6 chondrites has mean Th and U abundances of 1550 ± 80 ppb Th and 410 ± 20 ppb U, with $\text{Th}\text{U}\text{= 3.8 ± .2}$. With the exception of ferroan alabandite which contains 25 ± 1 ppb U, no other Th or U enriched phases were located in the E-6 chondrites, and nearly all of the total rock Th and U can be accounted for by oldhamite. In Khairpur (E6), excess fossil fission tracks were observed in enstatite grains in contact with oldhamite which indicates the presence of ²⁴⁴Pu in oldhamite. Oldhamite from St. Mark's (E5) and Abee (E4) also shows actinide enrichments but at levels about half the E-6 results. Niningerite in Abee contains 45 ± 5 ppb U and due to its high reported modal abundance is an important U reservoir in Abee. The U content of oldhamite from the aubrite Peña Blanca Spring is 1920 ± 100 ppb. All $\text{Th}\text{U}$ values measured in this study cluster tightly around a value of 4 which indicates a lack of ThU fractionation in both oldhamite and in the enstatite meteorites, themselves. This lack of fractionation, along with the presence of ²⁴⁴Pu in oldhamite and reported rare earth enrichments also in oldhamite, suggests that the enstatite chondrites may be well-suited for PuU chronology and for providing the initial PuU value in the early solar system.     

顽火辉石中Li同位素扩散与分馏

顽火辉石作为斜方辉石晶系的重要Mg端元矿物,是地球上地幔主要组成矿物之一。Li同位素作为重要的地幔地球化学示踪剂,在主要地幔矿物中(如橄榄石,辉石等)的扩散分馏相关性质的研究显得尤为重要。我们通过经典力学的方法,计算模拟了原子尺度下Li同位素在顽火辉石晶格以2种不同的迁移机制(填隙机制和取代空位机制)迁移的活化能和其在不同晶格位上不同温度条件下的分馏作用程度。计算结果表明,Li同位素易以填隙位机制在顽火辉石中迁移。重同位素~7Li会更多的进入晶格填隙位中,而6Li相对更多进入Mg位。温度是影响这种分馏作用的1个关键因素,相应的结果可用来解释地幔Li同位素组成特征及冷却条件下的同位素分馏等科学问题。     

The E asteroids and the origin of the enstatite achondrites

Color, polarization and albedo data are summarized for the three known minor planets of optical type E— 44 Nysa, 64 Angelina and 434 Hungaria. The inventory of E asteroids with dimensions > 50 km is shown to be essentially complete.The surfaces of the E objects evidently consist of colorless, translucent, iron-free silicates such as plagioclase, forstefite, or enstatite. Their possible identification as the source of enstatite achondrites is consistent with new laboratory polarimetry of the Norton County aubrite. Both Nysa and Hungaria seem to be rather favorably situated for the production of meteorites.Nysa has a highly non-spherical shape, and is dynamically associated with the metal-rich asteroid 135 Hertha and several small objects also apparently of the metal-depleted E type. The configuration is suggestive of the fragments of a differentiated parent body, in which Hertha originated as the iron core and Nysa as the largest surviving mantle fragment. The relative volumes, however, are not consistent with simple igneous differentiation from a chondritic composition.     

Two-dimensional lattice images of stacking disorder in wollastonite

Two-dimensional lattice images of low-temperature triclinic wollastonite (-CaSiO₃) indicate that two types of stacking disorder occur: (1) simple stacking faults and (2) twinning which also involves displacement in the composition plane. Both types of defect produce very similar structures with monoclinic symmetry (parawollastonite). Dislocations are involved at the termination of lamellae of parawollastonite in a triclinic matrix and a model for the dislocation core is proposed.Now at the Edward Davies Chemical Laboratories, Aberystwyth, SY23 1NE, U.K.     

R-mode factor analysis on enstatite chondrite analyses

R-mode factor analysis on 11 specimens of 9 enstatite chondrites, analysed for Ga, Se, Te, Zn, Cd, Bi, Tl, In, Sb, As, Co, showed three factors (rotated) to account for 92 per cent of the elemental variations (variance).Factor 1 dominates the first 8 elements listed, all volatile and mostly chalcophile: factors 2 and 3 express Sb and As variations, respectively, probably dependent on siderophile and less volatile behaviour; factors 1 and 2 contribute to Co.Factor-scores for individual meteorites indicate compositional differences (for these elements) between the E4 as against E5 and E6 stones (which are indistinguishable).Factor analysis of a second suite of 10 specimens analysed for Zn, Cd, Bi, Tl, In, Ag, Rb, Cs showed one factor to account for 93 per cent of the elemental variance. This expresses the association of Ag, Rb, Cs with the volatile-chalcophile factor.     

The temperature dependence of water solubility in enstatite

The solubility of water in pure enstatite was measured on samples synthesized under water-saturated conditions at 15 kbar and temperatures ranging from 700 to 1,100°C. Polarized FTIR measurements on millimetre-sized, clear crystals showed that water solubility increases strongly with temperature, from 101 ppm by weight at 700°C to 269 ppm by weight at 1,100°C. The position and shape of the infrared bands hardly changes with temperature, with one notable exception: a band close to 3,380 cm^–1 is present in samples synthesized between 700 and 1,000°C, while this band is absent from samples synthesized at 1,100°C. This effect appears to be very reproducible and points towards a slight change in the crystal structure of enstatite between 1,000 and 1,100°C at 15 kbar. The water solubility data of this study as well as those of Rauch and Keppler (Contrib Mineral Petrol 143:525–536, 2002) can be reproduced by the equation where K is water solubility, is water fugacity, A is 0.01354 ppm/bar, V^solid=12.1 cm³/mol is the volume change of enstatite during incorporation of water, and H^{1 bar}=-4,563 J/mol is the reaction enthalpy at 1 bar. This equation predicts the following behaviour of water solubility in enstatite as a function of pressure and temperature: (1) water solubility increases with pressure up to a maximum around 80 kbar; (2) water solubility decreases with temperature at 1 bar; and (3) water solubility increases with temperature between 10 and 100 kbar. If the observed temperature dependence for enstatite were representative for other upper mantle minerals as well, it would have the following implications: (1) Lateral temperature gradients in the upper mantle could cause major variations in water contents at the same depth; in particular, hot mantle plumes may scavenge water from the surrounding shallow upper mantle. (2) The scavenging of water by hot plumes could be a major factor in increasing the mobility of plumes. (3) The predicted temperature dependence of water solubility at the base of the upper mantle may allow plumes to bypass the transition zone water filter postulated by Bercovici and Karato (Nature 425:39–44, 2003).     

Phase transformations of enstatite in spherical shock waves

The analysis of available theoretical evaluations and experimental data reveals discrepancies and makes it possible to formulate the goals for the comprehensive study of the behavior of enstatite MgSiO₃ in shock isentropic waves of various scale and intensity. The paper presents the layout and results of an explosion experiment on the compression of an enstatite sphere with spherical shock waves and the subsequent recovery of the experimental material and its examination in discrete zones (along the sphere radius) that were produced by shock waves in the material. The latter were examined with the application of scanning electron microscopy, Raman spectroscopy, and X-ray diffraction analysis. The comparison of the systematic variations in the texture, chemistry, and phase composition of enstatite along the sphere radius with calculated pressure P(R, t) and temperature T(R, t) values led us to the following conclusions: enstatite starts melting on an isentrope upon pressure relief after shock wave compression at ?? _xx ?? 80 GPa and melts on the front of the spherically converging shock wave at ?? _xx ?? 160 GPa and T ?? 6300 K. Our laboratory experiments with shock waves were the world??s first in which enstatite was loaded with spherical converging shock isentropic waves and which provided evidence that shock wave-loaded MgSiO₃ shows certain morphological and mineralogical features never before detected in this mineral loaded with plane shock wave of smaller amplitude and duration. Goals are formulated for the further studying of shock wave-loaded materials, and the necessity is discussed for conducting an explosion experiment with a five to seven times greater spherical system in order to increase the duration of the shock wave loading impulse.     

Petrography,mineral chemistry and origin of Type I enstatite chondrites

Optical and cathodoluminescence petrography were coupled with electron microprobe analysis to relate the textures and chemical compositions of minerals in the chondrules and matrix of the Indarch, Kota-Kota, Adhi-Kot and Abee Type I enstatite chondrites. Clinoenstatites fall into two distinct chemical groups with characteristic red or blue luminescence; red crystals are higher in Ti, Al, Cr, Mn and Ca, and lower in Na, than blue ones. Rare forsterites in Indarch and Kota-Kota show distinct compositions associated with orange or blue luminescence. The chemical ranges are indistinguishable for each color type in chondrules of all textural types, and the presence of both color types in a single chondrule or a metal fragment requires mechanical aggregation of both crystals and liquids of both color types. Porphyritic chondrules are ascribed mainly to aggregation of existing crystals because both types of pyroxene and olivine occur in the same chondrule. Large crystals of one color type are surrounded by fine-grained crystals of another type in some barred and radiating chondrules. All types of chondrules are surrounded by fine-grained rims rich in sulfide. The matrix contains many broken chondrules and individual silicate grains but is rich in sulfide and metal. Analyses are given of albite (minor elements and luminescence color vary between chondrites), kamacite, schreibersite, oldhamite and niningerite.Although the mineral assemblages do not fit theoretical condensation sequences in detail, the red pyroxene and orange olivine might result ultimately from near-equilibrium crystallization in which early reduced condensates reacted with a gas, while the blue crystals might result from fractional condensation in which early condensates were removed mechanically from a gas. Subsequent episodes involving mixing, melting, crystallization, condensation, fracturing, and mechanical aggregation would be needed to produce the complex textures.     

Rare earth element diffusion in natural enstatite

Chemical diffusion coefficients of La, Nd, Eu, Gd, and Yb in natural enstatite have been measured at 850-1250 °C and 1 atm. Anhydrous diffusion experiments were run in Pt capsules in air, or in sealed silica glass capsules under an iron-wüstite (IW) solid buffer. The sources of diffusant were pre-reacted mixtures of synthetic enstatite powder and microcrystalline rare-earth aluminate garnet. Rutherford Backscattering Spectrometry (RBS) was used to measure diffusion profiles. For Gd diffusion in air over the temperature range 1000-1250 °C, the following Arrhenius relation is found for diffusion normal to (210):

     

The stable carbon isotopes in enstatite chondrites and Cumberland Falls

The carbon isotopic composition of the total carbon in the enstatite chondrites Indarch, Abee, St. Marks, Pillistfer, Hvittis and Daniel's Kuil and the enstatite achondrite Cumberland Falls has been measured. The empirical relationhip between carbon isotopic composition and total carbon content is distinct from that of carbonaceous and ordinary chondrites. Within the enstatite chondrite group the average ¹³C content increases with petrographic type: E4 < E5 < E6. Daniel's Kuil shows the largest ¹³C enrichment in the bulk carbon of any meteorite. The carbon isotopic composition is most clearly correlated with the abundance of the elements Zn, Cd and In. Insofar as these elements may hold the key to the understanding of enstatite chondrites, more detailed combined carbon isotope and trace element studies of these meteorites will play an important role in the deciphering of their history.     

Rates of grain boundary diffusion through enstatite and forsterite reaction rims

 The growth rates of enstatite rims produced by reaction of Fo₉₂ and SiO₂ were determined at 250–1500 MPa and 900–1100°C for a wide range of water contents. Growth rates were also determined for forsterite rims between MgO and Mg₂Si₂O₆ and between MgO and SiO₂. Rim growth rates are parabolic indicating diffusion-controlled growth of the polycrystalline rims which are composed of ˜ 2 μm diameter grains. Rim growth rates were used to calculate the product of the grain boundary diffusion coefficient (D'_A) times the effective grain boundary thickness (δ) assuming in turn that MgO, SiO₂, and Mg₂Si₋₁ are the diffusing components (coupled diffusion of a cation and oxygen or interdiffusion of Mg and Si). The values for D'_MgOδ, D', and D' for enstatite at 1000°C and 700 MPa confining pressure with about 0.1 wt %  water are about five times larger than the corresponding D'_Aδ values for samples initially vacuum dried at 250°C. Most of the increase in D'_Aδ occurs with the first 0.1 wt %  water. The activation energy for diffusion through the enstatite rims (1100–950°C) is 162 ± 30 kJ/mole. The diffusion rate through enstatite rims is essentially unchanged for confining pressures from 210–1400 MPa, but the nucleation rate is greatly reduced at low confining pressure (for  ≤ 1.0 wt % water present) and limits the conditions at which rim growth can be measured. The corresponding values for D'_Aδ through forsterite rims are essentially identical for the two forsterite-producing reactions when 0.1 wt % water is added and similar to the D'_Aδ values for enstatite at the same conditions. The D'_Aδ values for forsterite are ˜ 28 times larger for samples starting with 0.1 wt %  water compared to samples that were first vacuum dried. Thus water enhances these grain boundary diffusion rates by a factor of 5–30 depending on the mineralogy, but the total range in D'_Aδ is only slightly more than an order of magnitude for as wide a range of water contents as expected for most crustal conditions. Received: 1 July 1995 / Accepted: 1 August 1996