Experimental studies of the distribution of rare earths as trace elements among silicate minerals and liquids and water

The distribution of the REE between synthetic diopside, forsterite, enstatite, and gaseous water and between natural plagioclase, 2 rhyolite obsidian melts and gaseous water have been measured. Values for distribution coefficients (D) for the REE between the minerals and aqueous fluid vary significantly over the temperature range of 550°C to 850°C, but little variation was found for the values of D between the silicate liquids and aqueous fluid over a temperature range of 100°C. By assuming that the values of D for the silicate liquids are independent of major element composition and temperature, it is possible to calculate values of D for REE between silicate minerals and silicate liquid. The values obtained for diopside, forsterite, enstatite and plagioclase compare favorably with those obtained for the natural materials clinopyroxene, olivine, orthopyroxene and plagioclase (except for Eu). The values of D for diopside were found to increase and those for forsterite and enstatite to decrease with increasing temperatuie. Values of temperature of equilibration for natural minerals obtained by extrapolation of graphs for experimental data of In D against 1/T for the systems diopside-silicate liquid, forsterite-silicate liquid, and forsterite-diopside fall within a reasonable range, suggesting the possibility of geothermometry using REE concentrations of minerals.     

Water solubility in nominally anhydrous minerals measured by FTIR and 1H MAS NMR: the effect of sample preparation

Samples of enstatite and forsterite were crystallized in the presence of a hydrous fluid at 15 kbar and 1100 °C. Water contents in quenched samples were measured by ¹H MAS NMR and by FTIR. If the samples were prepared in the same way, similar water concentrations were obtained by both methods. There is no evidence that one or the other method would severely over or underestimate water contents in nominally anhydrous minerals. However, measured water contents vary by orders of magnitude depending on sample preparation. The lowest water contents are measured by polarized FTIR spectroscopy on clear, inclusion-free single crystals. These water contents probably reflect the real point defect solubility in the crystals. Polycrystalline material shows much higher total water concentrations, presumably due to hydrous species on grain boundaries, growth defects, and in submicroscopic fluid inclusions. Grinding the sample in air further increases water concentration. This effect is even more pronounced if the sample is ground in water and subsequently dried at 150 °C. Polarized FTIR measurements on clear single crystals of enstatite saturated at 15 kbar and 1100 °C give 199 ± 25 ppm by weight of water. The spectra show sharp and strongly polarized bands. These bands are also present in spectra measured through turbid, polycrystalline aggregates of enstatite. However, in these spectra, they are superimposed on much broader, nearly isotropic bands resulting from hydrous species in grain boundaries, growth defects, and submicroscopic fluid or melt inclusions. Total water contents for these polycrystalline aggregates are between 2000 and 4000 ppm. Water contents measured by FTIR on enstatite powders are 5300 ppm after grinding in air and 12 600 ppm after grinding under water und subsequent drying at 150 °C. Received: 25 June 1999 / Revised, accepted: 4 October 1999     

Partitioning of halogens between mantle minerals and aqueous fluids: implications for the fluid flow regime in subduction zones

We have performed phase equilibrium experiments in the system forsterite–enstatite–pyrope-H₂O with MgCl₂ or MgF₂ at 1,100 °C and 2.6 GPa to constrain the solubility of halogens in the peridotite mineral assemblage and the fluid–mineral partition coefficients. The chlorine solubility in forsterite, enstatite and in pyrope is very low, 2.1–3.9 and 4.0–11.4 ppm, respectively, and it is independent of the fluid salinity (0.3–30 wt% Cl), suggesting that some intrinsic saturation limit in the crystal is reached already at very low chlorine concentrations. Chlorine is therefore exceedingly incompatible in upper-mantle minerals. The fluorine solubility is 170–336 ppm in enstatite and 510–1,110 ppm in pyrope, again independent of fluid salinity. Forsterite dissolves 1,750–1,900 ppm up to a fluid salinity of 1.6 wt% F. At higher fluorine contents in the system, forsterite is replaced by the minerals of the humite group. The lower solubility of chlorine by three orders of magnitude when compared to fluorine is consistent with increasing lattice strain. Fluid–mineral partition coefficients are 10⁰–10² for fluorine and 10³–10⁵ for chlorine. Since the latter values are orders of magnitude higher than those for hydroxyl partitioning, fluid flow from the subducting slab through the mantle wedge will lead to an efficient sequestration of H₂O into the nominally anhydrous minerals in the wedge, whereas chlorine becomes enriched in the residual fluid. Simple mass balance calculations reveal that rock–fluid ratios of up to >3,000 are required to produce the elevated Cl/H₂O ratios observed in some primitive arc magmas. Accordingly, fluid flow from the subducted slab into the zone of melting in the mantle wedge does not only occur rapidly in narrow channels, but at least in some subduction zones, fluid pervasively infiltrates the mantle peridotite and interacts with a large volume of the mantle wedge. Together with the Cl/H₂O ratios of primitive arc magmas, our data therefore constrain the fluid flow regime below volcanic arcs.     

The origin of chondrules: experimental investigation of metastable liquids in the system Mg2SiO4-SiO2

Laser-melted magnesium silicate droplets, supercooled 400–750°C below their equilibrium liquidus temperatures before crystallization, were examined to provide a comparison with meteoritic and lunar chondrules and to examine physicochemical parameters that may indicate the conditions of their formation. Internal textures of the spherules strikingly resemble textures observed in some chondrules. Definite trends in crystal morphology, crystal width and texture were established with respect to nucleation temperature and bulk composition. Such trends provide a framework for determining the nucleation temperature of chondrules. The only phase to nucleate from the supercooled forsterite-enstatite normative melts was forsterite, which was present in more-than-normative amounts. Highly siliceous glass (~65wt. % SiO₂) was identified interstitially to the forsterite crystals in seven of the spherules and is thought to be present in all. The presence of enstatite and the large proportion of crystals in some meteoritic chondrules implies that they were maintained at temperatures considerably in excess of 600°C at some point in their history.     

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.     

Preferential dissolution of SiO<Subscript>2</Subscript> from enstatite to H<Subscript>2</Subscript> fluid under high pressure and temperature

Stability and phase relations of coexisting enstatite and H₂ fluid were investigated in the pressure and temperature regions of 3.1–13.9 GPa and 1500–2000 K using laser-heated diamond-anvil cells. XRD measurements showed decomposition of enstatite upon heating to form forsterite, periclase, and coesite/stishovite. In the recovered samples, SiO₂ grains were found at the margin of the heating hot spot, suggesting that the SiO₂ component dissolved in the H₂ fluid during heating, then precipitated when its solubility decreased with decreasing temperature. Raman and infrared spectra of the coexisting fluid phase revealed that SiH₄ and H₂O molecules formed through the reaction between dissolved SiO₂ and H₂. In contrast, forsterite and periclase crystals were found within the hot spot, which were assumed to have replaced the initial orthoenstatite crystals without dissolution. Preferential dissolution of SiO₂ components of enstatite in H₂ fluid, as well as that observed in the forsterite H₂ system and the quartz H₂ system, implies that H₂-rich fluid enhances Mg/Si fractionation between the fluid and solid phases of mantle minerals.     

Experimentelle Bestimmung der P-T-Stabilitätsbereiche in der Mischkristallreihe Tremolit-Tschermakit

The join tremolite (Tr)—tschermakite (Ts) was studied at temperatures of 450 to 900° C under water vapour pressure of 2 kbar. Solid solution between the end members is restricted to composition range Tr₁₀₀-Tr₄₅. Reconnaissance runs at 800°C and 10 kbar indicated that no further substitution of Al in the tremolite structure is possible by an increase of pressure. In the composition range Ts₅₅-Ts₁₀₀ tremolite-tschermakite solid solution Tr₄₅Ts₅₅ is formed with anorthite, forsterite and enstatite above 700°C and with anorthite and chlorite below 700° C. No amphibole could be synthezised from a material of composition Ts₁₀₀. Materials of composition Ts₁₀₀ crystallized to anorthite, enstatite and frosterite above 700°C and to anorthite and chlorite below 700°C. The high temperature breakdown curve for tremolite-tschermakite solid solutions drops from 870°C for pure tremolite to 826°C for Tr₄₅Ts₅₅. Additional experiments at 1 and 3 kbar indicate that the pressure effect on breakdown temperatures amounts to about 35°C/kbar. The formation of natural amphiboles belonging to the tremolite-tschermakite series is discussed in the light of the experimental data.     

The low-pressure stability of phase A,Mg7Si2O8(OH)6

 Phase A, Mg₇Si₂O₈(OH)₆, is a dense hydrous magnesium silicate whose importance as a host of H₂O in the Earth’s mantle is a subject of debate. We have investigated the low-pressure stability of phase A in experiments on the reaction phase A=brucite+forsterite. Experiments were conducted in piston-cylinder and multi-anvil apparatus, using mixtures of synthetic phase A, brucite and forsterite. The reaction was bracketed between 2.60 and 2.75 GPa at 500° C, between 3.25 and 3.48 GPa at 600° C and between 3.75 and 3.95 GPa at 650^° C. These pressures are much lower than observed in the synthesis experiments of Yamamoto and Akimoto (1977). At 750^° C the stability field of brucite + chondrodite was entered. The enthalpy of formation and entropy of phase A at 1 bar (10⁵ Pa), 298 K, were derived from the experimental brackets on the reaction phase A=brucite+forsterite using a modified version of the thermodynamic dataset THERMOCALC of Holland and Powell (1990), which includes a new equation of state of H₂O derived from the molecular dynamics simulations of Brodholt and Wood (1993). The data for phase A are: ΔH ^o _f =−7126±8 kJ mol^-1, S ^o=351 J K^-1 mol^-1. Incorporating these data into THERMOCALC allows the positions of other reactions involving phase A to be calculated, for example the reaction phase A + enstatite=forsterite+vapour, which limits the stability of phase A in equilibrium with enstatite. The calculated position of this reaction (753° C at 7 GPa to 937° C at 10 GPa) is in excellent agreement with the experimental brackets of Luth (1995) between 7 and 10 GPa, supporting the choice of equation of state of H₂O used in THERMOCALC. Comparison of our results with calculated P-T paths of subducting slabs (Peacock et al. 1994) suggests that, in the system MgO–SiO₂–H₂O, phase A could crystallise in compositions with Mg/Si>2 at pressures as low as 3 GPa. In less Mg rich compositions phase A could crystallise at pressures above approximately 6 GPa. Received: 3 July 1995/Accepted: 14 December 1995     

Thermal decomposition of serpentine during coseismic faulting: Nanostructures and mineral reactions

This paper reports a detailed characterization of an antigorite-bearing serpentinite, deformed at seismic slip-rate (1.1 m/s) in a high-velocity friction apparatus. Micro/nanostructural investigation of the slip zone (200 μm thick) revealed a zonal arrangement, with a close juxtaposition of horizons with significantly different strength, respectively consisting of amorphous to poorly-crystalline phases (with bulk anhydrous composition close to starting antigorite) and of highly-crystalline assemblages of forsterite and disordered enstatite (200 nm in size and in polygonal-like nanotextures). The slip zone also hosts micro/nanometre sized Cr-magnetite grains, aligned at low angle with respect to the slipping surface and inherited from the host serpentinite.Overall observations suggest that frictional heating at asperities on the slipping surface induced a temperature increase up to 820–1200 °C (in agreement with flash temperature theory), responsible for serpentine complete dehydration and amorphization, followed by crystallization of forsterite and enstatite (under post-deformation, static conditions). The results of this study may provide important keys for the full comprehension of the mechanical behaviour and of the possible geodynamical role of serpentinite-hosted faults through the seismic cycle.     

Electrical conductivity measurements on olivines Mg2SiO4-Fe2SiO4 under defined thermodynamic conditions

The isobaric (P=10 kb) temperature dependence of the electrical conductivities of forsterite, fayalite and forsterite-fayalite mixed crystals was measured with special regard to the thermodynamics of point defects in these minerals. Measurements, taken at increasing and decreasing temperature, were performed on synthetic powders of the following compositions: Fo 100/Fa 0, Fo 90/Fa 10, Fo 80/Fa 20, Fo 60/Fa 40, and Fo 0/Fa100. Control of oxygen partial pressure was achieved with solid state buffers (Fa/Q/M, Fa/Q/I, and Fe/FeO). Activities of the binary components were controlled by equilibrating the sample with its neighbouring phases. All values for σ, obtained with controlled pO₂ and fixed activities of the binary components, agree well upon either heating or cooling. From the gradient of lg σ vs. 1/T plots, the following activation energies were estimated: 2,461 eV (970°–1075°C) and 0.984 eV (522°–970°C) for Fo 100/Fa 0 equilibrated with MgO; 0.777 eV and 0.683 eV for Fo 90/Fa 10 and Fo 80/Fa 20 equilibrated with enstatite and pO₂ controlled by Fe/FeO buffer; 0.622 eV, 0.528 eV, and 0.479 eV for Fo 90/Fa 10, Fo 80/Fa 20, and Fo 60/Fa 40 equilibrated with enstatite and pO₂ controlled by Fa/Q/M buffer; and 0.524 eV and 0.383 eV for Fo 0/Fa 100 equilibrated with Q/I and Q/M respectively.     

Hydrothermal serpentinization of peridotite within the oceanic crust: Experimental investigations of mineralogy and major element chemistry

Mantle derived ultramafic rocks form a significant portion of lithosphere created at slow-spreading mid-ocean ridges. These rocks are ubiquitously serpentinized, due at least in part to interaction with seawater, at temperatures below approximately 500°C. To evaluate reaction pathways, primary mineral reaction rates, major element exchange between rock and solution, and alteration mineral formation, interaction of equigranular peridotites with seawater and seawater derived solutions has been investigated experimentally at 200°C and 300°C, 500 bars.Seawater chemistry changed greatly during the experiments. Initially, the concentrations of Mg, Ca, and SO₄ decreased, as did pH. During Iherzolite experiments, however, the trend of dissolved Ca concentrations reversed with time, first decreasing, then increasing. pH also increased during the latter part of the experiments. Mg, Ca, SiO₂, Fe, Cl and ΣCO₂ decreased as pH increased Fe^II oxidation is shown to be affected by solution pH, being greatly enhanced under alkaline conditions. Resulting solution composition and reaction pathway are dependent on initial solution composition, particularly initial concentrations of Mg in solution. Consistent with changes in solution chemistry, the peridotites were significantly altered. Substantial amounts of olivine, relatively minor amounts of diopside and all the enstatite dissolved. Alteration products included serpentine + anhydrite ± magnesium hydroxide sulfate hydrate ± magnetite ± brucite ± tremolite-actinolite or truscottite.From the changes in solution chemistry and examination of the alteration products, the reaction rates (moles per unit time) of olivine to enstatite to diopside during 300°C Iherzolite-seawater experiments are estimated to be approximately 1.0/1.0/0.1. These rates correspond to constant surface area rates of 1.5:5:1 (moles per unit time per unit surface area), which are consistent with experimental data on the dissolution kinetics of these minerals and emphasize the importance of initial rock texture on reaction rates.     

Experimental study of incongruent evaporation kinetics of enstatite in vacuum and in hydrogen gas

Variations in bulk Mg/Si ratios in the various groups of chondritic meteorites indicate that Mg/Si fractionation occurred in the primitive solar nebula. Enstatite (MgSiO₃) evaporates incongruently forming forsterite (Mg₂SiO₄) as an evaporation residue; therefore, evaporation of enstatite produces Mg/Si variations in solid (Mg-rich) and gas (Si-rich) and must be considered as a probable process responsible for Mg/Si fractionation recorded in chondrites. To understand the evaporation kinetics of enstatite, incongruent evaporation experiments on enstatite single crystals have been carried out in vacuum and in hydrogen gas at temperatures of 1300 to 1500°C. A polycrystalline forsterite layer is formed on the surface of enstatite by preferential evaporation of the SiO₂ component, both in vacuum and in hydrogen gas. The thickness of the forsterite layer in vacuum increases with time in the early stage of evaporation and later the thickness of the forsterite layer remains constant (several microns). This is due to the change in the rate limiting process from surface reaction plus nucleation and growth to diffusion in the surface forsterite layer. The activation energy of the diffusion-controlled evaporation rate constant of enstatite is 457 (±58) kJ/mol. A thinner forsterite layer is formed on the surface of enstatite in hydrogen gas than in vacuum. Evaporation of enstatite in hydrogen gas is also considered to be controlled by diffusion of ions through the forsterite layer. The thin forsterite layer formed in hydrogen gas is ascribed to the enhanced evaporation rate of forsterite in the presence of hydrogen gas.The results are applied to incongruent evaporation under the solar nebular conditions. The steady thickness of the forsterite of nebular pressure-temperature conditions is estimated to be submicron because of the enhanced evaporation rate of forsterite under hydrogen-rich nebular conditions if evaporated gases are taken away immediately and no back reaction occurs (an open system). Because enstatite grains in the solar nebula would be comparable to the estimated steady thickness of forsterite, evaporation of such enstatite grains under kinetic conditions could play an important role in producing variations in Mg/Si ratios between solid and gas in the solar nebula.     

The high-pressure stability of Mg-sursassite in a model hydrous peridotite: a possible mechanism for the deep subduction of significant volumes of H<Subscript>2</Subscript>O

The stability of the high-pressure phase Mg-sursassite, previously MgMgAl-pumpellyite, in ultramafic compositions has been determined in experiments in the system MgO-Al₂O₃-SiO₂-H₂O (MASH). The breakdown of Mg-sursassite + forsterite + enstatite to pyrope + vapour with increasing temperature was bracketed at 6.0 and 7.0 GPa. Below 6.0 GPa, Mg-sursassite + forsterite + vapour reacts to chlorite + enstatite. This reaction provides a mechanism for transfer of water from chlorite- to Mg-sursassite-bearing assemblages. At pressures of 7.0 GPa and above, the assemblage Mg-sursassite + phase A + enstatite was found. Phase relations involving Mg-sursassite and phase A are considered. For bulk compositions with a low water content, the vapour-absent reaction Mg-sursassite + forsterite = pyrope + phase A + enstatite determines the upper-pressure stability of Mg-sursassite, and provides a mechanism for the complete transfer of water from Mg-sursassite to phase A-bearing assemblages. Mg-sursassite plays an important role in peridotite compositions in the subducting slab because, at temperatures below 700 °C, it can transfer water from hydrous phases such as antigorite and chlorite to high-pressure stable phases such as phase A.     

Composition of aqueous fluid coexisting with mantle minerals at high pressure and its bearing on the differentiation of the Earth’s mantle

In order to understand the role of aqueous fluid on the differentiation of the mantle, the compositions of aqueous fluids coexisting with mantle minerals were investigated in the system MgO-SiO₂-H₂O at pressures of 3 to 10 GPa and temperatures of 1000 to 1500°C with an MA8-type multianvil apparatus. Phase boundaries between the stability fields of forsterite + aqueous fluid, forsterite + enstatite + aqueous fluid, and enstatite + aqueous fluid were determined by varying the bulk composition at constant temperature and pressure. The composition of aqueous fluid coexisting with forsterite and enstatite can be defined by the intersection of these two phase boundaries. The solubility of silicate components in aqueous fluid coexisting with forsterite and enstatite increases with increasing pressure up to 8 GPa, from about 30 wt% at 3 GPa to about 70 wt% at 8 GPa. It becomes almost constant above 8 GPa. The Mg/Si weight ratio of these aqueous fluids is much higher than at low pressure (0.2 at 1.5 GPa) and almost constant (1.2) at pressures between 3 and 8 GPa. At 10 GPa, it becomes about 1.4. Aqueous fluid migrating upward through the mantle can therefore dissolve large amounts of silicates, leaving modified Mg/Si ratios of residual materials. It is suggested that the chemical stratification of Mg/Si in the Earth may have been formed as a result of aqueous fluid migration.     

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     

Silicate mineral dissolution at pH 4 and near standard temperature and pressure

The dissolution of labradorite, microcline, enstatite, augite and forsterite in acidified deionized water was investigated at near standard temperature and pressure and constant pH of 4.00 to determine the kinetics of the release of silica, and cations. Saturation indices and mass balance calculations suggest that after 700 hours, the release of silica from forsterite and augite was controlled by the precipitation of a solid silica phase, whereas silica mass transfer from the feldspars and enstatite was essentially as silicic acid. Iron release from the pyroxenes and olivine was probably controlled by the precipitation of iron oxyhydroxide phases. Linear-rate constants calculated after 700 hours for release of magnesium ranged from 10^?15.2 to 10^?14.4 M · cm^?2 s^?1 for augite and forsterite respectively. Linear-rate constants for the release of cations from feldspars ranged from 10^?15.8 to 10^?15.3 M · cm^?2 s^?1.     

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.     

Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite

We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 °C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni–NiO–H₂O (ΔFMQ = ??0.21 to ??1.01), employing a double-capsule setting. Fluids, binary H₂O–CO₂ mixtures at the P, T, and fO₂ conditions investigated, were generated from graphite, oxalic acid anhydrous (H₂C₂O₄) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO₂-bearing fluids. The experimental data show that forsterite?+?enstatite solubility in H₂O–CO₂ fluids is higher compared to pure water, both in terms of dissolved silica (mSiO₂?=?1.24 mol/kg_H2O versus mSiO₂?=?0.22 mol/kg_H2O at P?=?1 GPa, T?=?800 °C) and magnesia (mMgO?=?1.08 mol/kg_H2O versus mMgO?=?0.28 mol/kg_H2O) probably due to the formation of organic C–Mg–Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H₂O–CO₂ fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO₂ ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO₂ ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P–T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle.     

Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca²⁺, Mg²⁺, and Si(OH)₄ and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M₂ structural sites. Loss mainly from M₂ sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca²⁺ and/or Mg²⁺ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on a_H⁺ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.