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1.
The growth rates of albite and pyroxene (enstatite + diopside + spinel) reaction rims were measured at 1000°C and ˜700 MPa and found to be parabolic indicating diffusion-controlled growth. The parabolic rate constants for the pyroxene (+ spinel) rims in samples with 0.5 wt% H2O added or initially vacuum dried at 25°C and 250°C are 1.68 ± 0.09, 0.54 ± 0.05 and 0.25 ± 0.06 μm2/h, respectively. The values for albite rim growth in samples initially dried at 60°C and with 0.1 wt% H2O added are 0.25 ± 0.04 and 0.33 ± 0.03 μm2/h, respectively. The latter values were used to derive the product of the grain boundary diffusion coefficient D′A, where A = SiO2, NaAlO2, or NaAlSi−1, and the grain boundary thickness δ in albite. The calculated D′SIO2δ in the albite aggregate for the situations of two different water contents are about 9.9 × 10−23 and 1.4 × 10−22 m3 s−1, respectively. Both the rate constants and the calculated D′Aδ demonstrate that the effect of water content on the grain boundary diffusion rate in monomineralic albite and polymineralic pyroxene (+ spinel) aggregates is small, consistent with recent studies of monomineralic enstatite and forsterite rims. Received: 1 July 1995 / Accepted: 1 August 1996  相似文献   

2.
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.  相似文献   

3.
  The diffusivity of water has been investigated for a haplogranitic melt of anhydrous composition Qz28Ab38Or34 (in wt %) at temperatures of 800–1200°C and at pressures of 0.5–5.0 kbar using the diffusion couple technique. Water contents of the starting glass pairs varied between 0 and 9 wt %. Concentration-distance profiles for the different water species (molecular water and hydroxyl groups) were determined by near-infrared microspectroscopy. Because the water speciation of the melt is not quenchable (Nowak 1995; Nowak and Behrens 1995; Shen and Keppler 1995), the diffusivities of the individual species can not be evaluated directly from these profiles. Therefore, apparent chemical diffusion coefficients of water (D water) were determined from the total water profiles using a modified Boltzmann-Matano analysis. The diffusivity of water increases linearly with water content <3 wt % but exponentially at higher water contents. The activation energy decreases from 64 ± 10 kJ/mole for 0.5 wt % water to 46 ± 5 kJ/mole for 4 wt % water but remains constant at higher water contents. A small but systematic decrease of D water with pressure indicates an average activation volume of about 9 cm3/mole. The diffusivity (in cm2/s) can be calculated for given water content (in wt %), T (in K) and P (in kbar) by
in the ranges 1073 K ≤ T ≤ 1473 K; 0.5 kbar ≤ P≤ 5␣kbar; 0.5 wt % ≤ C water ≤ 6 wt %. The absence of alkali concentration gradients in the glasses after the experiments shows that interdiffusion of alkali and H+ or H3O+ gives no contribution to the transport of water in aluminosilicate melts. The H/D interdiffusion coefficients obtained at 800°C and 5 kbar using glass pieces with almost the same molar content of either water or deuterium oxide are almost identical to the chemical diffusivities of water. This indicates that protons are transported by the neutral component H2O under these conditions. Received: 26 March 1996 / Accepted: 23 August 1996  相似文献   

4.
 A practical and reliable method for the preparation of fine-grained forsterite and forsterite–enstatite polycrystals, in the system MgO–SiO2, is described. The method employs state-of-the-art techniques from materials science, namely sol-gel synthesis, powder processing and sintering. The resulting dense polycrystalline materials are homogeneously fine-grained (1–2 μm) and uniformly foam-textured. Moreover, they are highly reproducible in composition and microstructure. The enstatite content can be controlled to within ∼1%, in the range 0–50%, and densities up to 98% of theoretical density can be achieved. The method thus yields polycrystalline forsterite–enstatite material suitable for a range of geochemical, petrological and geophysical studies. Received: 19 October 1999 / Accepted: 18 June 2001  相似文献   

5.
Water-saturated and water-undersaturated experiments (a H2 O = 1.0 and 0.5) were performed in the temperature range 780–1040°C at 2 and 5 kbar in order to determine the upper thermal stability of phlogopite in granitic melts. Starting compositions were: (A) subaluminous mixtures of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous haplogranitic glass; (B) peraluminous mixtures (normative corundum  = 4 %) of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous peraluminous haplogranitic glass. The molar quartz: albite: orthoclase ratio of the glasses of the 2␣kbar runs was 35:39:26 and that of the 5 kbar runs 30:42:28. In the subaluminous system, phlogopite is stable up to 820°C at a H2 O = 1.0 and up to 780°C at a H2 O = 0.5. At higher temperatures, it is replaced by enstatite. In the peraluminous system phlogopite has a remarkably higher thermal stability (up to 1000°C at 5 kbar and a H2 O = 1.0) and there is a temperature interval of 80°C at a H2 O = 1.0, and 90–100°C at a H2 O = 0.5 between the first appearance of enstatite and the disappearance of phlogopite. In the peraluminous system, phlogopite is a solid solution (ss) of phlogopite, muscovite, talc and eastonite components. The crystalline product of the phlogopitess breakdown reaction is an aluminous enstatite. The MgO-content of the melt depends on the normative corundum content of the starting material and the run temperature. It is independent of pressure. In the subaluminous system, the MgO-content ranges between 0.05 and 0.3 wt % in the temperature interval 780–880°C at both investigated water activities. The MgO-content of the peraluminous melts at a H2 O = 1.0 ranges between 0.4 and 1.7 wt % and at a H2 O = 0.5 between 0.2 and 1.4 wt % in the temperature range 780–980°C. Received: 28 August 1995 / Accepted: 6 August 1996  相似文献   

6.
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7.
The Jervois region of the Arunta Inlier, central Australia, contains para- and orthogneisses that underwent low-pressure amphibolite facies metamorphism (P = 200–300 MPa, T = 520–600 °C). Marble layers cut by metre-wide quartz + garnet ± epidote veins comprise calcite, quartz, epidote, clinopyroxene, grandite garnet, and locally wollastonite. The marbles also contain locally discordant decimetre-thick garnet and epidote skarn layers. The mineral assemblages imply that the rocks were infiltrated by water-rich fluids (XCO2 = 0.1–0.3) at ∼600 °C. The fluids were probably derived from the quartz-garnet vein systems that represent conduits for fluids exsolved from crystallizing pegmatites emplaced close to the metamorphic peak. At one locality, the marble has calcite (Cc) δ18O values of 9–18‰ and garnet (Gnt) δ18O values of 10–14‰. The δ18O(Gnt) values are only poorly correlated with δ18O(Cc), and the δ18O values of some garnet cores are higher than the rims. The isotopic disequilibrium indicates that garnet grew before the δ18O values of the rock were reset. The marbles contain  ≤15% garnet and, for water-rich fluids, garnet-forming reactions are predicted to propagate faster than O-isotopes are reset. The Sm-Nd and Pb-Pb ages of garnets imply that fluid flow occurred at 1750–1720 Ma. There are no significant age differences between garnet cores and rims, suggesting that fluid flow was relatively rapid. Texturally late epidote has δ18O values of 1.5–6.2‰ implying δ18O(H2O) values of 2–7‰. Waters with such low-δ18O values are probably at least partly meteoric in origin, and the epidote may be recording the late influx of meteoric water into a cooling hydrothermal system. Received: 29 April 1996 / Accepted: 12 March 1997  相似文献   

8.
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.  相似文献   

9.
The evolution of nephelinitic melts in equilibrium with mica-bearing liquidus assemblages and melting relations have been studied on two silica-undersaturated joins of the KAlSiO4– Mg2SiO4– Ca2SiO4– SiO2– F system at atmospheric pressure by quench runs in sealed platinum capsules. Fluorine has been added to the batch compositions by the direct exchange of fluorine for oxygen (2F− = O2−). The first join is the pseudo-ternary Forsterite – Diopside – KAlSiO3F2 system. Forsterite, diopside, F-phlogopite and leucite crystallisation fields and a fluoride-silicate liquid immiscibility solvus are present on the liquidus surface of the join. Sub-liquidus and sub-solidus phases include akermanite, cuspidine, spinel, fluorite and some other minor fluorine phases. The second system is the pseudo-binary Akermanite – F-phlogopite join that intersects the Forsterite – Diopside – KAlSiO3F2 join. Akermanite, forsterite, diopside, F-phlogopite, leucite and cuspidine are found to crystallise on the join. Forsterite (fo) and leucite (lc) are related to F-phlogopite (phl) by a reaction with the fluorine-bearing liquid: fo + lc + l = phl, and the reaction proceeds until forsterite or leucite are completely consumed. The reaction temperature and resulting phase association depend on batch composition. Thus, leucite is not stable in the sub-solidus of the Akermanite – F-phlogopite join, but is preserved in a part of the Forsterite – Diopside – KAlSiO3F2 system where forsterite reacts out, or does not crystallise at all. The phlogopite-in reaction has an important effect on the composition of the coexisting liquid. The liquids initially saturated in forsterite evolve to extremely Ca rich, larnite-normative residuals. The experimental data show that larnite-normative melilitolites can crystallise from evolved melilititic melts generated from “normal” melanephelinitic parental magmas with no normative larnite. The evolution towards melilitites requires fractionation of phlogopite-bearing assemblages under volatile pressure. Received: 3 June 1997 / Accepted: 5 January 1998  相似文献   

10.
To examine the effect of KCl-bearing fluids on the melting behavior of the Earth’s mantle, we conducted experiments in the Mg2SiO4–MgSiO3–H2O and Mg2SiO4–MgSiO3–KCl–H2O systems at 5 GPa. In the Mg2SiO4–MgSiO3–H2O system, the temperature of the fluid-saturated solidus is bracketed between 1,200–1,250°C, and both forsterite and enstatite coexist with the liquid under supersolidus conditions. In the Mg2SiO4–MgSiO3–KCl–H2O systems with molar Cl/(Cl + H2O) ratios of 0.2, 0.4, and 0.6, the temperatures of the fluid-saturated solidus are bracketed between 1,400–1,450°C, 1,550–1,600°C, and 1,600–1,650°C, respectively, and only forsterite coexists with liquid under supersolidus conditions. This increase in the temperature of the solidus demonstrates the significant effect of KCl on reducing the activity of H2O in the fluid in the Mg2SiO4–MgSiO3–H2O system. The change in the melting residues indicates that the incongruent melting of enstatite (enstatite = forsterite + silica-rich melt) could extend to pressures above 5 GPa in KCl-bearing systems, in contrast to the behavior in the KCl-free system.  相似文献   

11.
 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  相似文献   

12.
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.  相似文献   

13.
Diffusion of water was experimentally investigated for melts of albitic (Ab) and quartz-orthoclasic (Qz29Or71, in wt %) compositions with water contents in the range of 0 to 8.5 wt % at temperatures of 1100 to 1200 °C and at pressures of 1.0 and 5.0 kbar. Apparent chemical diffusion coefficients of water (D water) were determined from concentration-distance profiles measured by FTIR microspectroscopy. Under the same P-T condition and water content the diffusivity of water in albitic, quartz-orthoclasic and haplogranitic (Qz28Ab38 Or34, Nowak and Behrens, this issue) melts is identical within experimental error. Comparison to data published in literature indicates that anhydrous composition only has little influence on the mobility of water in polymerized melts but that the degree of polymerization has a large effect. For instance, Dwater is almost identical for haplogranitic and rhyolitic melts with 0.5–3.5 wt % water at 850 °C but it is two orders of magnitude higher in basaltic than in haplogranitic melts with 0.2–0.5 wt % water at 1300 °C. Based on the new water diffusivity data, recently published in situ near-infrared spectroscopic data (Nowak 1995; Nowak and Behrens 1995), and viscosity data (Schulze et al. 1996) for hydrous haplogranitic melts current models for water diffusion in silicate melts are critically reviewed. The NIR spectroscopy has indicated isolated OH groups, pairs of OH groups and H2O molecules as hydrous species in polymerized silicate melts. A significant contribution of isolated OH groups to the transport of water is excluded for water contents above 10 ppm by comparison of viscosity and water diffusion data and by inspection of concentration profiles from trace water diffusion. Spectroscopic measurements have indicated that the interconversion of H2O molecules and OH pairs is relatively fast in silicate glasses and melts even at low temperature and it is inferred that this reaction is an active step for migration of water. However, direct jumps of H2O molecules from one cavity within the silicate network to another one can not be excluded. Thus, we favour a model in which water migrates by the interconversion reaction and, possibly, small sequences of direct jumps of H2O molecules. In this model, immobilization of water results from dissociation of the OH pairs. Assuming that the frequency of the interconversion reaction is faster than that of diffusive jumps, OH pairs and water molecules can be treated as a single diffusing species having an effective diffusion coefficient . The shape of curves of Dwater versus water content implies that increases with water content. The change from linear to exponential dependence of Dwater between 2 and 3 wt % water is attributed to the influence of the dissociation reaction at low water content and to the modification of the melt structure by incorporation of OH groups. Received: 26 March 1996 / Accepted: 23 August 1996  相似文献   

14.
 Spectroscopic measurements of water in glass inclusions in pyroxene from boninite samples from the Bonin Islands conclusively document the high (2.8–3.2 wt %) primary water contents of boninite magmas. Associated quenched glass from pillow lava rims have slightly lower (2.2–2.4 wt %) water contents, suggesting that minor amounts of degassing occurred between the time of melt entrapment in the orthopyroxenes and subsequent eruption on the sea floor. Some zonation of molecular water contents in pillow rim glasses was observed. OH contents of the host orthopyroxene phenocrysts were also measured, allowing for the calculation of partition coefficients for water between boninite melt and orthopyroxene. These values (0.003–0.004) for water partitioning between orthopyroxene and mafic melts may help constrain petrogenetic models of mantle-derived magmas. Received: 20 September 1993 / Accepted: 26 June 1994  相似文献   

15.
 Calcium self-diffusion rates in natural calcite single crystals were experimentally determined at 700 to 900° C and 0.1 MPa in a stream of CO2. Diffusion coefficients (D) were determined from 42Ca concentration profiles measured with an ion microprobe. The Arrhenius parameters yield an activation energy (Q)=382±37 kJ/mol and pre-exponential factor (D0)=0.13 m2/s, and there is no measurable anisotropy. Calcium grain boundary diffusion rates were experimentally determined in natural (Solnhofen) limestone and hot-pressed calcite aggregates at 650° to 850° C and 0.1 to 100 MPa pressure. The Solnhofen limestone was first pre-annealed for 24 h at 700° C and 100 MPa confining pressure under anhydrous conditions to produce an equilibrium microstructure for the diffusion experiments. Values for the product of the grain boundary diffusion coefficient (D′) and the effective grain boundary diffusion width (δ) were determined from 42Ca concentration profiles measured with an ion microprobe. The results show that there is no measurable difference between D′δ values obtained for pre-annealed Solnhofen samples at 0.1 and 100 MPa or between hot-pressed calcite aggregates and pre-annealed Solnhofen samples. The temperature dependence for calcium grain boundary diffusion in Solnhofen samples annealed at 0.1 MPa is described by the Arrhenius parameters D′ 0δ=1.5×10−9 m3/s and Q=267±47 kJ/mol. Comparison of the results of this study with previously published data show that calcium is the slowest volume diffusing species in calcite. The calcium diffusivities measured in this study place constraints on several geological processes that involve diffusive mass transfer including diffusion-accommodated mechanisms in the deformation of calcite rocks. Received: 19 December 1994/Accepted: 30 June 1995  相似文献   

16.
A unique sapphirine + orthopyroxene + quartz granulite from Mt. Riiser-Larsen in the Tula Mountains of Enderby Land, East Antarctica, preserves two generations of coarse and texturally equilibrated orthopyroxene and sapphirine coexisting with quartz. Initial subhedral orthopyroxene porphyroblasts retain core compositions enriched in Al2O3 (12.2 ± 0.5 wt%) compared with their rims and finer orthopyroxene (9.6 ± 0.5 wt% Al2O3) that forms granoblastic textures with sapphirine. Sapphirine and quartz also form symplectites on and along cleavage planes within orthopyroxene. These compositional and textural features are consistent with the reaction [2MgAl2SiO6=Mg2Al4 SiO10 + SiO2] leading to the formation of sapphirine + quartz at the expense of aluminous orthopyroxene. Calculations in the MAS and FMAS systems and theoretical considerations involving the phases enstatite, sapphirine, sillimanite, quartz and cordierite indicate that the reaction above progresses from left to right with decreasing temperature in the orthopyroxene + sapphirine + quartz field, at pressures of ca. 8–10 kbar. The temperature difference required to account for the ca. 2.5–3 wt% decrease in Al2O3 in orthopyroxene is at least 60–80 °C, and implies peak temperatures for the initial assemblage of at least 1120 °C if the second granoblastic assemblage equilibrated at 1040 °C, the P–T conditions required by the sapphirine + quartz association and other P–T-sensitive assemblage indicators in the Napier Complex. It is not possible to distinguish whether the two assemblages are simply related by cooling and re-equilibration or reflect a polyphase evolution involving the superposition of a second UHT event on an earlier, even higher temperature, UHT metamorphism. Preliminary thermodynamic modelling of the reaction above incorporating the observed range in orthopyroxene Al2O3 zoning indicates that present estimates for the entropy of high-temperature sapphirine are potentially too high by 15–18% compared with sapphirine entropy estimates that are consistent with MAS system experiments. The Mt. Riiser-Larsen sapphirine–quartz rocks preserve the first definitive record of regional metamorphic temperatures in excess of 1120 °C in the Napier Complex, or indeed any UHT granulite terrain worldwide. Similarly high peak temperatures may be retrieved from detailed studies of sapphirine–quartz granulites from other regions, further expanding the thermal realm of crustal metamorphism, but progress will critically depend on the experimental acquisition of new entropy data for sapphirine. Received: 3 September 1998 / Accepted: 8 November 1999  相似文献   

17.
 Grain boundary diffusion rates of oxygen, potassium and calcium in fine-grained feldspar aggregates were determined experimentally. The starting materials were a natural albite rock from the Tanco pegmatite and aggregates hot-pressed from fragments of Amelia albite or Ab, Or and An composition glasses. The technique employed isotopic tracers (18O, 41K, 42Ca) either evaporated onto the surface or in an aqueous solution surrounding the sample, and depth profiling using an ion microprobe (SIMS). From the depth profiles, the product of the grain boundary diffusion coefficient (D′) and effective boundary width (δ) was calculated using numerical solutions to the appropriate diffusion equation. The experimental reproducibility of D′δ is a factor of 3. A separate determination of D′ independent of δ yields an effective grain boundary width of ∼3 nm, consistent with high resolution TEM observations of a physical grain boundary width <5 nm. Oxygen (as molecular water) grain boundary diffusion rates were determined in the Ab and Or aggregates at 450°–800° C and 100 MPa (hydrothermal), potassium rates in Or aggregates at 450°–700° C both at 0.1 MPa (in air) and at 100 MPa (hydrothermal), and calcium rates in An aggregates at 700°–1100° C and 0.1 MPa (in air). Oxygen grain boundary diffusion rates are similar in all three of the Ab aggregates and in the Or aggregate. Potassium and oxygen depth profiles measured in the same samples yield different D′δ values, confirming a diffusional transport mechanism. Potassium diffusion in the Or aggregate has a greater activation energy (216 vs 78 kJ/mol) than oxygen, and the Arrhenius relations cross at ∼625° C. Potassium D′δ values in Or aggregates are about a factor of five greater in hydrothermal experiments at 100 MPa than in experiments at 0.1 MPa in air. Calcium grain boundary diffusion rates in An aggregates are 4 to 5 orders of magnitude slower than potassium in Or and have a greater (291 kJ/mol) activation energy. This suggests that differences in formal charge and/or size of diffusing species may play an important role in their relative grain boundary diffusion rates. Received: 24 December 1993 / Accepted: 16 June 1994  相似文献   

18.
Part I of this contribution (Gardés et al. in Contrib Mineral Petrol, 2010) reported time- and temperature-dependent experimental growth of polycrystalline forsterite-enstatite double layers between single crystals of periclase and quartz, and enstatite single layers between forsterite and quartz. Both double and single layers displayed growth rates decreasing with time and pronounced grain coarsening. Here, a model is presented for the growth of the layers that couples grain boundary diffusion and grain coarsening to interpret the drop of the growth rates. It results that the growth of the layers is such that (Δx)2 ∝ t 1−1/n , where Δx is the layer thickness and n the grain coarsening exponent, as experimentally observed. It is shown that component transport occurs mainly by grain boundary diffusion and that the contribution of volume diffusion is negligible. Assuming a value of 1 nm for the effective grain boundary width, the following Arrhenius laws for MgO grain boundary diffusion are derived: log D gb,0Fo (m2/s) = −2.71 ± 1.03 and E gbFo = 329 ± 30 kJ/mol in forsterite and log D gb,0En (m2/s) = 0.13 ± 1.31 and E gbEn = 417 ± 38 kJ/mol in enstatite. The different activation energies are responsible for the changes in the enstatite/forsterite thickness ratio with varying temperature. We show that significant biases are introduced if grain boundary diffusion-controlled rim growth is modelled assuming constant bulk diffusivities so that differences in activation energies of more than 100 kJ/mol may arise. It is thus important to consider grain coarsening when modelling layered reaction zones because they are usually polycrystalline and controlled by grain boundary transport.  相似文献   

19.
The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H2O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al2O3 in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.  相似文献   

20.
Summary The investigated mantle section of the Leka ophiolite complex extends 1.4 km from and 1.1 km along the exposed Moho. The foliated peridotite contains numerous tabular and elongated dunite bodies, orthopyroxenite dikes, websterite veins, and dikes. The foliation of the peridotite is inclined by about 45° to the Moho. The dunite bodies and the dikes cut the foliation at low angles. The dunite bodies vary in width from 0.1 to 50 m and in length from 10 m to more than 1 km. Wider dunite bodies are commonly surrounded by 0 to 1.0 m wide margins of dunitized peridotite. Websterite veins may be present outside these margins. Apart from sporadic chromite layers the dunite is very homogenous. The dunite bodies are considered to have formed by deposition of olivine along the walls of dikes originally containing tholeiitic melt. The tholeiitic melt at first heated the peridotitic sidewalls so that they became partially molten and dunitized. The ascending magma then eroded the sidewalls and removed olivine as xenocrysts. When the ascent rate decreased, the temperature of the sidewalls decreased, so that olivine (Fo89–92) began to crystallize along the dike walls. There is also evidence for percolative melt migration along foliation planes, however, the largest proportion of the melts intruded along dikes. The websterite dikes are mostly 1 to 4 cm wide and 3 to 20 m long and dispersed with mutual distances of 20–50 m. The websterite veins and dikes probably originated from melts that were generated along the heated sidewalls of the dunite bodies. The 0.02 to 10 m wide orthopyroxenite dikes have exceptionally high MgO contents for their SiO2 contents; about 36 wt.% MgO and 50 wt.% SiO2. They may have formed as segregates from a SiO2-rich magma, although the parent magma does not appear to have been boninitic. The parent magma may instead have formed by second stage partial melting of depleted lherzolite.  相似文献   

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