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1.
The rates of grain growth of stoichiometric dolomite [CaMg(CO3)2] and magnesite (MgCO3) have been measured at temperatures T of 700–800°C at a confining pressure P c of 300 MPa, and compared with growth rates of calcite (CaCO3). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO3)2, MgCO3, and CaCO3, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO3)2, MgCO3, and CaCO3, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (≃5 × 10−5 μm3/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.  相似文献   

2.
 We investigated grain growth of calcite aggregates fabricated from crushed natural single crystals with different impurity content. The total trace-element concentration of the starting powders varied from about 170 ppm to more than 930 ppm with Mn as the major component. Samples were produced by hot-isostatic pressing of the different powders at 300 MPa confining pressure at 600 °C for 2 h. The starting material for the anneals was dry and had a uniform microstructure with an average grain size of about 5 μm and a porosity of <2.1%. Three disks with Mn concentrations of 10, 350, and 670 ppm, respectively, were annealed in the same run at a confining pressure of 300 MPa, and temperatures between 700 and 900 °C for up to 20 h. Grain growth was fastest in samples with the highest Mn concentrations. A multivariable fit to the data yields grain-growth exponents of 2.0 ± 0.3 for samples with 10 ppm Mn and 2.3 ± 0.2 for those with 670 ppm Mn. The activation energies for grain growth vary from 99 ± 12 kJ mol−1 to 147 ± 14 kJ mol−1 for the respective calcite compositions. Received: 22 August 2000 / Accepted: 12 March 2001  相似文献   

3.
Using a recently developed ion microprobe technique, a detailed oxygen isotope map of calcite grains in a coarse-grained marble has been constructed, supported by trace element (Mn, Sr, Fe) analysis and cathodoluminescence (CL) imaging, in order to constrain scales of oxygen isotope equilibrium, timescales and mechanisms of metamorphic fluid infiltration, and fluid sources and pathways. Results are compared with a previous study of this sample (Wada 1988) carried out using a cryo-microtome technique and conventional oxygen isotope analysis. The marble, from the high temperature/low pressure Hida metamorphic belt in north-central Japan, underwent granulite facies followed by amphibolite facies metamorphic events, the latter associated with regional granite intrusion. The CL imaging indicates two types of calcite, a yellow luminescing (YLC) and a purple luminescing (PLC) variety. The YLC, which occupies grain boundaries, fractures, replacement patches, and most of the abundant deformation twin lamellae, post-dates the dominant PLC calcite and maps out fluid pathways. Systematic relationships were established between oxygen isotope and trace element composition, calcite type and texture, based on 74 18O/16O and 17 trace element analyses with 20–30 μ m spatial resolution. The YLC is enriched in Mn and Fe, and depleted in 18O and Sr compared to PLC, and is much more 18O depleted than is indicated from conventional analyses. Results are interpreted to indicate infiltration of 18O-depleted (metamorphic or magmatic) fluid (initial δ18O = 9‰–10.5‰) along grain boundaries, fractures and deformation twin lamellae, depleting calcite grains in Sr and enriching them in Mn and Fe. The sample is characterised by gross isotopic and elemental disequilibrium, with important implications for the application of chromatographic theory to constrain fluid fluxes in metacarbonate rocks. Areas of PLC unaffected by “short-circuiting” fluid pathways contain oxygen diffusion profiles of ∼10‰/∼200 μm in grain boundary regions or adjacent to fractures/patches. When correction is made for estimated grain boundary/fracture and profile orientation in 3D, profiles are indistinguishable within error. Modelling of these profiles gives consistent estimates of Dt (where D is the diffusion coefficient and t is time) of ∼0.8 × 10−8 m2, from which, using experimental data for oxygen diffusion in calcite, timescales of fluid transport along grain boundaries at amphibolite facies temperatures of ∼103 to ∼104 years are obtained. These short timescales, which are much shorter than plausible durations of metamorphism, imply that rock permeabilities may be transiently much higher during fluid flow than those calculated from time integrated fluid fluxes or predicted from laboratory measurements. The preservation of 18O/16O profiles requires either rapid cooling rates (∼100–600 °C/million years), or, more plausibly, loss of grain boundary fluid such that a dry cooling history followed the transient passage of fluid. The δ18O/trace element correlations are also consistent with volume diffusion-controlled transport in the PLC. Fluid transport and element exchange occurred by two inter-related mechanisms on short timescales and on different lengthscales – long-distance flow along cracks, grain boundaries and twin lamellae coupled to ∼200 μm-scale volume diffusion of oxygen. Received: 8 December 1997 / Accepted: 18 May 1998  相似文献   

4.
We carried out an experimental study to characterize the kinetics of Ostwald ripening in the forsterite-basalt system and in the plagioclase (An65)-andesite system. Eight experiments were done in each system to monitor the evolution of mean grain size and crystal size distribution (CSD) with time t; the experiments were performed in a 1-atmosphere quench furnace, at 1,250°C for plagioclase and 1,300°C for olivine. Very contrasted coarsening kinetics were observed in the two series. In the plagioclase series, the mean grain size increased as log(t), from ≈3 μm to only 8.7 μm in 336 h. The kinetic law in log(t) means that Ostwald ripening was rate-limited by surface nucleation at plagioclase-liquid interfaces. In the olivine series, the mean grain size increased as t 1/3, from ≈3 μm to 23.2 μm in 496 h. A kinetic law in t 1/3 is expected when Ostwald ripening is rate-limited either by diffusion in the liquid or by grain growth/dissolution controlled by a screw dislocation mechanism. The shape of olivine CSDs, in particular their positive skewness, indicates that grain coarsening in the olivine experiments was controlled by a screw dislocation mechanism, not by diffusion. As the degrees of undercooling ΔT (or supersaturation) involved in Ostwald ripening are essentially <1°C, the mechanisms of crystal growth identified in our experiments are expected to be those prevailing during the slow crystallisation of large magma chambers. We extrapolated our experimental data to geological time scales to estimate the effect of Ostwald ripening on the size of crystals in magmas. In the case of plagioclase, Ostwald ripening is only efficient for mean grain sizes of a few microns to 20 μm, even for a time scale of 105 years. It can, however, result in a significant decrease of the number of small crystals per unit volume, and contribute to the development of convex upwards CSDs. For olivine, the mean grain size increases from 2–3 μm to ≈70 μm in 1 year and 700 μm in 103 years; a mean grain size of 3 mm is reached in 105 years. Accordingly, the rate of grain size-dependent processes, such as compaction of olivine-rich cumulates or melt extraction from partially molten peridotites, may significantly be enhanced by textural coarsening.  相似文献   

5.
Grain growth kinetics in CaTiO3-perovskite + FeO-wüstite aggregates were studied at the conditions of T = 1223–1623 K, P = 0.1 MPa and P = 200 MPa. Starting samples were fabricated by hot-pressing mechanically mixed powders of CaTiO3 + FeO with FeO = 0%, 1%, 3%, 6%, 10%, 20% and 100% by weight in a gas-medium apparatus at 1323 K and 300 MPa for 5 h. The increase of grain size (G) of CaTiO3 with time (t) follows a growth law: G n −G n 0 = κ·t(κ=κ0exp(−(Q/RT)). Two grain growth regimes are observed at T < 1523 K and T ≥ 1523 K. For T < 1523 K, the best fits of the data to the growth law yield growth exponents of n = 2.2 ± 0.2, 3.0 ± 0.3 and 3.5 ± 0.3 for samples with FeO = 0%, 3% and 10% respectively. Under these conditions the rate constants, κ, obey an Arrhenius relation with Q = 206 ± 35 kJ/mol and 385 ± 65 kJ/mol for samples with FeO = 3% and 10%. Grain growth of CaTiO3 becomes sluggish when FeO content exceeds 6%. For T ≥ 1523 K, the best fits of the data to the growth law yield n = 2.5 ± 0.2 for both samples with FeO = 3% and 10%. The activation energies (Q ) were determined as 71 ± 30 kJ/mol and 229 ± 45 kJ/mol for samples with FeO = 3% and 10%, respectively. The TEM observations show a remarkable difference in the distribution and geometry of FeO below and above 1523 K: nanometer-sized particles of FeO were observed along CaTiO3 grain boundaries in samples annealed at T < 1523 K. No FeO particles were detected along CaTiO3 grain boundaries in samples annealed at T ≥ 1523 K, but large clusters of FeO particles are observed locally indicating a fast separation of FeO from CaTiO3. Thus we conclude that the slow growth rate of CaTiO3 at T < 1523 K is due to the pinning by FeO particles at grain boundary, and that the change of grain growth kinetics in CaTiO3 at T ≥ 1523 K may relate to the separation of FeO from CaTiO3, which we interpret as due to the phase transformation of CaTiO3 at around 1523 K. Received: 19 June 1998 / Revised, accepted: 24 March 1999  相似文献   

6.
 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   

7.
Optical constituents as suspended particulate matter (SPM), chlorophyll (Chl-a), colored dissolved organic matter (CDOM), and grain sizes were obtained on a transect in the arctic fjord-type estuary Kangerlussuaq (66°) in August 2007 along with optical properties. These comprised diffuse attenuation coefficient of downwelling PAR (K d(PAR)), upwelling PAR (K u(PAR)), particle beam attenuation coefficient (c p), and irradiance reflectance R(−0, PAR). PAR is white light between 400 and 700 nm. The estuary receives melt water from the Greenland Inland Ice and stations covered a transect from the very high turbid melt water outlet to clear marine waters. Results showed a strong spatial variation with high values as for suspended matter concentrations, CDOM, diffuse attenuation coefficient K d(PAR), particle beam attenuation coefficients (c p), and reflectance R(−0, PAR) at the melt water outlet. Values of optical constituents and properties decreased with distance from the melt water outlet to a more or less constant level in central and outer part of the estuary. There was a strong correlation between inorganic suspended matter (SPMI) and diffuse attenuation coefficient K d(PAR) (r 2 = 0.92) and also for particle beam attenuation coefficient (c p; r 2 = 0.93). The obtained SPMI specific attenuation—K d*(PAR) = 0.13 m2 g−1 SPMI—and the SPMI specific particle beam attenuation—c p* = 0.72 m2 g−1—coefficients were about two times higher than average literature values. Irradiance reflectance R(−0, PAR) was comparatively high (0.09−0.20) and showed a high (r 2 = 0.80) correlation with K u(PAR). Scattering dominated relative to absorption—b(PAR)/a(PAR) = 12.3. Results strongly indicated that the high values in the optical properties were related to the very fine particle sizes (mean = 2–6 μm) of the suspended sediment. Data and results are discussed and compared to similar studies from both temperate and tropical estuaries.  相似文献   

8.
Normal grain growth of calcite was investigated by combining grain size analysis of calcite across the contact aureole of the Adamello pluton, and grain growth modeling based on a thermal model of the surroundings of the pluton. In an unbiased model system, i.e., location dependent variations in temperature-time path, 2/3 and 1/3 of grain growth occurs during pro- and retrograde metamorphism at all locations, respectively. In contrast to this idealized situation, in the field example three groups can be distinguished, which are characterized by variations in their grain size versus temperature relationships: Group I occurs at low temperatures and the grain size remains constant because nano-scale second phase particles of organic origin inhibit grain growth in the calcite aggregates under these conditions. In the presence of an aqueous fluid, these second phases decay at a temperature of about 350 °C enabling the onset of grain growth in calcite. In the following growth period, fluid-enhanced group II and slower group III growth occurs. For group II a continuous and intense grain size increase with T is typical while the grain growth decreases with T for group III. None of the observed trends correlate with experimentally based grain growth kinetics, probably due to differences between nature and experiment which have not yet been investigated (e.g., porosity, second phases). Therefore, grain growth modeling was used to iteratively improve the correlation between measured and modeled grain sizes by optimizing activation energy (Q), pre-exponential factor (k0) and grain size exponent (n). For n=2, Q of 350 kJ/mol, k0 of 1.7×1021 mns–1 and Q of 35 kJ/mol, k0 of 2.5×10-5 mns–1 were obtained for group II and III, respectively. With respect to future work, field-data based grain growth modeling might be a promising tool for investigating the influences of secondary effects like porosity and second phases on grain growth in nature, and to unravel differences between nature and experiment.Editorial responsibility: J. Hoefs  相似文献   

9.
Mineralogical and textural changes accompanying ageing of silica sinter   总被引：3，自引：0，他引：3  
Twenty nine samples of silica sinter, ranging in age from modern to Miocene, record temporal changes in both mineralogy and texture. When first deposited, sinters consist largely of noncrystalline spheres (<1–8 μm diameter) of opal-A exhibiting varying degrees of close-packing. Particle densities range from 1.5 to 2.1 g cm−3, total water 4–10 wt%, and porosities 35–60%. Changes over ∼10,000 years following deposition are slight although the spheres may be invested by an additional film of secondary silica. For the next 10,000 to ∼50,000 years, the silica incrementally crystallises to become poorly crystalline opal-CT and/or opal-C; spherical particles of thin-bladed crystals (lepispheres) replace opal-A particles and coalesce in microbotryoidal aggregates (∼10–30 μm diameter). Amygdaloidal fibrous clusters occur with lepispheres. As silica lattice ordering becomes enhanced, total water content drops to <7 wt%, particle density increases to ∼2.3 g cm−3, and porosity reduces to <30%. The change from opal-A to opal-C takes place over a briefer periods (∼50 years) in silica sinters that contain other materials (e.g. calcite, sulfur, alunite, plant remains). Sinters older than ∼50,000 years have recrystallised to microcrystalline quartz. With the onset of quartz crystallisation at ∼20,000 years, total water is <0.2 wt%, particle density approximates quartz (2.65 g cm−3), and porosity is <4%. The progressive changes in silica species and texture yield ageing profiles for sinters that may serve as guides to the paleohydrology of geothermal systems and/or epithermal ore deposits in areas where surface thermal activity has declined or ceased. Received: 18 November 1998 / Accepted: 6 July 1999  相似文献   

10.
Carbon and oxygen isotopic profiles around a low pressure metasomatic wollastonite reaction front in a marble of the Hida metamorphic terrain, central Japan, display typical metamorphic fluid-enhanced isotopic zonations. Isotopic profiles obtained from detailed microscale analyses perpendicular to the chemical reaction front in calcite marble show that diffusion-enhanced isotopic exchange may control these profiles. Carbon and oxygen isotopic behaviour in grain boundaries is remarkably different. Oxygen isotopic troughs (18O depleted rims) around the calcite-grain boundaries are widely observed in this contact aureole, demonstrating that diffusion of oxygen in calcite grain boundary dominates over lattice diffusion in calcite. In contrast, no difference is observed in carbon isotopic profiles obtained from grain cores and rims. There is thus no specific role of the grain boundary for diffusion of carbonic species in the metamorphic fluid during transportation. Carbon chemical species such as CO2 and CO3 ions in metamorphic fluid migrate mainly through lattice diffusion. The carbon and oxygen isotope profiles may be modelled by diffusion into a semi-infinite medium. Empirically lattice diffusion of oxygen isotopes is almost six times faster than that of carbon isotopes, and oxygen grain-boundary diffusion is ten times faster than oxygen lattice diffusion. Oxygen isotopic results around the wollastonite vein indicate that migration of the metamorphic fluid into calcite marble was small and was parallel to the aquifer. From the stability of wollastonite and the attainment of oxygen isotopic equilibrium, we suggest that diffusion of oxygen occurred through an aqueous fluid phase. The timescale of formation of the oxygen isotopic profile around the wollastonite vein is calculated to be about 0.76 × 106 years using the experimentally determined diffusion constant. Received: 14 January 1997 / Accepted: 23 April 1998  相似文献   

11.
 The southern Voltaian Sedimentary Basin underlies an area of about 5000 km2 in east-central Ghana. Groundwater in the basin occurs in fractures in highly consolidated siliciclastic aquifers overlain by a thin unsaturated zone. Aquifer parameters were evaluated from available aquifer-test data on 28 shallow wells in the basin. Hydraulic-conductivity values range from 0.04–3.6 m/d and are about two orders of magnitude greater than the hydraulic conductivity calculated using Darcy's Law and the average groundwater velocity estimated from carbon-14 dating. Linear-regression analysis of the transmissivity and specific-capacity data allowed the establishment of an empirical relationship between log transmissivity and log specific capacity for the underlying aquifers. Groundwater chemistry in the basin is controlled by the weathering of albitic plagioclase feldspar. The weathering rates of various minerals were estimated using 14C-derived average velocity in the basin. The weathering rate of albite was calculated to be 2.16 μmol L–1 yr–1 with the resulting formation of 3.3 μmol L–1 yr–1 of kaolinite and 0.047 μmol L–1 yr–1 of calcite. The low porosity and permeability of the aquifers in the basin are attributed to the precipitation of secondary minerals on fracture surfaces and interlayer pore spaces. Received, September 1997 Revised, July 1998, August 1998 Accepted, August 1998  相似文献   

12.
The Archean Shawmere anorthosite lies within the granulite facies portion of the Kapuskasing Structural Zone (KSZ), Ontario, and is crosscut by numerous linear alteration veins containing calcite + quartz ± dolomite ± zoisite ± clinozoisite ± margarite ±paragonite ± chlorite. These veins roughly parallel the trend of the Ivanhoe Lake Cataclastic Zone. Equilibria involving clinozoisite + margarite + quartz ± calcite ± plagioclase show that the vein minerals were stable at T < 600 °C, XCO2 < 0.4 at P ≈ 6 kbar. The stabilities of margarite and paragonite in equilibrium with quartz are also consistent with T < 600 °C and XCO2 < 0.4 at 6 kbar. Additional assemblages consisting of calcite + clinochlore + quartz + talc + margarite indicate T < 500 °C with XCO2 > 0.9. Thus, vein formation, while clearly retrograde, spanned a range of temperatures, and fluid compositions evolved from H2O-rich to CO2-rich. The calcite in the retrograde veins has δ18O values that range from 8.4 to 11.2‰ (average = +9.7 ± 0.9‰) and δ13C values that range from −3.9 to −1.6‰ (average = −3.1 ± 0.6‰). These values indicate that the fluids from which calcite precipitated underwent extensive exchange with the anorthosite and other crustal lithologies. The fluids may have been initially derived either from devolatilization of metamorphic rocks or crystallization of igneous rocks in the adjacent Abitibi subprovince. Vein quartz contains CO2-rich fluid inclusions (final melting T = −57.0 to −58.7 °C) that range in size from 5 to 17 μm. Measured homogenization temperatures (T h) range from −44.0 to 14.5 °C, however for most inclusions (46 of S1), T h = −44.0 to −21.1 °C (ρCO2 ≈ 1.13 to 1.05 g/cm3). At 400 to 600 °C, these densities correspond to pressures of 3.5 to 7 kbar, which is the best estimate of pressures of vein formation. It has been argued that some high density CO2-rich fluid inclusions found in the KSZ were formed during peak metamorphism and thus document the presence of a CO2-rich fluid during peak granulite facies metamorphism (Rudnick et al. 1984). The association of high density CO2-rich fluid inclusions with clearly retrograde veins documents the formation of similar composition and density inclusions after the peak of metamorphism. Thus, the coincidence of entrapment pressures calculated from fluid inclusion density measurements with peak metamorphic pressures alone should not be considered strong evidence for peak metamorphic inclusion entrapment. All fluid inclusion results are consistent with an initially semi-isobaric retrograde P–T path. Received: 2 April 1996 / Accepted: 15 November 1996  相似文献   

13.
 Infiltration of a metabasite sill from Islay, Scotland by an H2O-CO2 fluid caused (1) modification of δ18O and (2) carbonation at the sill margins. Maps of δ18O and reaction progress were constructed from a 20 × 47.7 metre sample grid across the sill. The grid consisted of 300 samples, spaced at m, dm and cm intervals, many of which were analysed for both δ18O and reaction progress. The δ18O was determined by laser fluorination of whole rock silicate powders and reaction progress was determined by rapid field-based measurement of % calcite (“fizz-o-meter”, Skelton et al. 1995). Reaction and isotope fronts outlined tube-like features that emanate from the sill margin and discrete nodes that, although detached from the sill margin in two dimensions, are thought to represent sections through similar tubes in three dimensions. We envisage that these protrusions are the fossil record of metamorphic “fluid pathways” whereby fluid permeated the sill. Isotope and reaction fronts are found to correlate spatially as predicted by a modified form of the chromatographic equation which describes this envisaged geometry, that is where isotopic and reactive transport in the fluid phase are facilitated by advection along specific fluid pathways and transverse diffusion in the surrounding rock. These fluid pathways consist of bundles of anastomosing grain boundary channels or micro-cracks, which are thought to propagate through transient cyclic infiltration, reaction, porosity enhancement and fracturing. This mechanism is self-perpetuating and accentuates random perturbations at the sill margin to form the observed tubes. We argue that this is the earliest stage of the infiltration process which has affected metabasites of the SW Scottish Highlands and that subsequent shear deformation of the reacted rims of these pathways, has caused their re-orientation and juxtaposition to form the reacted sill margins described by Skelton et al. (1995). Received: 17 February 1998 / Accepted: 6 December 1999  相似文献   

14.
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  相似文献   

15.
Synthesized mineral powders with particle size of <100 nm are vacuum sintered to obtain highly dense and fine-grained polycrystalline mantle composites: single phase aggregates of forsterite (iron-free), olivine (iron containing), enstatite and diopside; two-phase composites of forsterite + spinel and forsterite + periclase; and, three-phase composites of forsterite + enstatite + diopside. Nano-sized powders of colloidal SiO2 and highly dispersed Mg(OH)2 with particle size of ≤50 nm are used as chemical sources for MgO and SiO2, which are common components for all of the aggregates. These powders are mixed with powders of CaCO3, MgAl2O4, and Fe(CO2CH3)2 to introduce mineral phases of diopside, spinel, and olivine to the aggregates, respectively. To synthesize highly dense composites through pressureless sintering, we find that calcined powders should be composed of particles that have: (1) fully or partially reacted to the desired minerals, (2) a size of <100 nm and (3) less propensity to coalesce. Such calcined powders are cold isostatically pressed and then vacuum sintered. The temperature and duration of the sintering process are tuned to achieve a balance between high density and fine grain size. Highly dense (i.e., porosity ≤1 vol%) polycrystalline mantle mineral composites with grain size of 0.3–1.1 μm are successfully synthesized with this method.  相似文献   

16.
 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  相似文献   

17.
 High-temperature creep behavior in Ni2GeO4 spinel was investigated using synthetic polycrystalline aggregates with average grain sizes ranging from submicron to 7.4 microns. Cylindrical samples were deformed at constant load in a gas-medium apparatus at temperatures ranging from 1223 to 1523 K and stresses ranging from 40 to 320 MPa. Two deformation mechanisms were identified, characterized by the following flow laws: where σ is in MPa, d is in μm and T is in Kelvin. These flow laws suggest that deformation was accommodated by dislocation creep and grain-boundary diffusion (Coble) creep, respectively. A comparison with other spinels shows that an isomechanical group can be defined for spinels although some differences between normal and inverse spinels can be identified. When creep data for olivine and spinel are normalized and extrapolated to Earth-like conditions, spinel (ringwoodite) has a strength similar to olivine in the dislocation creep regime and is considerably stronger than olivine in the diffusion creep regime at coarse grain size. However, when grain-size reduction occurs, spinel can become weaker than olivine due to its high grain-size sensitivity (Coble creep behavior). Analysis of normalized diffusion creep data for olivine and spinel indicate that spinel is weaker than olivine at grain sizes less than 2 μm. Received: 18 June 2000 / Accepted: 3 April 2001  相似文献   

18.
The reaction kinetics and fluid expulsion during the decarbonation reaction of calcite+quartz=wollastonite+CO2 in water-absent conditions were experimentally investigated using a Paterson-type gas apparatus. Starting materials consisted of synthetic calcite/quartz rock powders with variable fractions of quartz (10, 20, and 30 wt%) and grain sizes of 10 µm (calcite) and 10 and 30 µm (quartz). Prior to reaction, samples were HIPed at 700 °C and 300 MPa confining pressure and varying pore pressures. Initial porosity was low at 2.7–6.3%, depending on pore pressure during HIP and the amount and grain size of quartz particles. Samples were annealed at reaction temperatures of 900 and 950 °C at 150 and 300 MPa confining pressures, well within the wollastonite stability field. Run durations were between 10 min and 20 h. SEM micrographs of quenched samples show growth of wollastonite rims on quartz grains and CO2-filled pores between rims and calcite grains and along calcite grain boundaries. Measured widths of wollastonite rims vs. time indicate a parabolic growth law. The reaction is diffusion-controlled and reaction progress and CO2 production are continuous. Porosity increases rapidly at initial stages of the reaction and attains about 10–12% after a few hours. Permeability at high reaction temperatures is below the detection limit of 10–21 m2 and not affected by increased porosity. This makes persistent pore connectivity improbable, in agreement with observed fluid inclusion trails in form of unconnected pores in SEM micrographs. Release of CO2 from the sample was measured in a downstream reservoir. The most striking observation is that fluid release is not continuous but occurs episodic and in pulses. Ongoing continuous reaction produces increase in pore pressure, which is, once having attained a critical value (Pcrit), spontaneously released. Connectivity of the pore space is short-lived and transient. The resulting cycle includes pore pressure build-up, formation of a local crack network, pore pressure release and crack closure. Using existing models for plastic stretching and decrepitation of pores along with critical stress intensity factors for the calcite matrix and measured pore widths, it results that Pcrit is about 20 MPa. Patterns of fluid flow based on mineralogical and stable isotope evidence are commonly predicted using the simplifying assumption of a continuous and constant porosity and permeability during decarbonation of the rock. However, simple flow models, which assume constant pore pressure, constant fluid filled porosity, and constant permeability may not commonly apply. Properties are often transient and it is most likely that fluid flow in a specific reacting rock volume is a short-lived episodic process.Editorial responsibility: J. Hoefs  相似文献   

19.
Calcite in former aragonite–dolomite-bearing calc-schists from the ultrahigh-pressure metamorphic (UHPM) oceanic complex at Lago di Cignana, Valtournanche, Italy, preserved different kinds of zoning patterns at calcite grain and phase boundaries. These patterns are interpreted in terms of lattice diffusion and interfacial mass transport linked with a heterogeneous distribution of fluid and its response to a changing state of stress. The succession of events that occurred during exhumation is as follows: As the rocks entered the calcite stability field at T=530–550 °C, P ca. 1.2 GPa, aragonite occurring in the matrix and as inclusions in poikilitic garnet was completely transformed to calcite. Combined evidence from microstructures and digital element distribution maps (Mn-, Mg-, Fe- and Ca–Kα radiation intensity patterns) indicates that transformation rates have been much higher than rates of compositional equilibration of calcite (involving resorption of dolomite and grain boundary transport of Mg, Fe and Ca). This rendered the phase transformation an isochemical process. During subsequent cooling to T ca. 490 °C (where lattice diffusion effectively closed), grains of matrix calcite have developed diffusion-zoned rims, a few hundred micrometres thick, with Mg and Fe increasing and Ca decreasing towards the phase boundary. Composition profiles across concentrically zoned, large grains in geometrically simple surroundings can be successfully modelled with an error function describing diffusion into a semi-infinite medium from a source of constant composition. The diffusion rims in matrix calcite are continuous with quartz, phengite, paragonite and dolomite in the matrix. This points to an effective mass transport on phase boundaries over a distance of several hundred micrometres, if matrix dolomite has supplied the Mg and Fe needed for incorporation in calcite. In contrast, diffusion rims are lacking at calcite–calcite and most calcite–garnet boundaries, implying that only very minor mass transport has occurred on these interfaces over the same T–t interval. From available grain boundary diffusion data and experimentally determined fluid–solid grain boundary structures, inferred large differences in transport rates can be best explained by the discontinuous distribution of aqueous fluid along grain/phase boundaries. Observed patterns of diffusion zoning indicate that fluid was distributed not only along grain-edge channels, but spread out along most calcite–white mica and calcite–quartz two-grain junctions. On the other hand, the inferred non-wetting of calcite grain boundaries in carbonate-rich domains is compatible with fluid–calcite–calcite dihedral angles >60° determined by Holness and Graham (1995) for a wide range of fluid compositions under the P–T conditions of interest. Whereas differential stress has been very low at the stage of diffusion zoning (T > 490 °C), it increased as the rocks were cooling below 440 °C (at 0.3–0.5 GPa). Dislocation creep and the concomitant increase of strain energy in matrix calcite induced migration recrystallisation of high-angle grain boundaries. For that stage, the compositional microstructure of recrystallised calcite grain boundary domains indicates significant mass transport along calcite two-grain junctions, which at the established low temperatures is likely to have been accomplished by ionic diffusion within a hydrous grain boundary fluid film (“dynamic wetting” of migrating grain boundaries). Received: 10 January 2000 / Accepted: 10 April 2000  相似文献   

20.
We extended a previous study on the influence of Mg solute impurity on diffusion creep in calcite to include deformation under a broader range of stress conditions and over a wider range of Mg contents. Synthetic marbles were produced by hot isostatic pressing (HIP) mixtures of calcite and dolomite powders for different intervals (2–30 h) at 850°C and 300 MPa confining pressure. The HIP treatment resulted in high-magnesian calcite aggregates with Mg content ranging from 0.5 to 17 mol%. Both back-scattered electron images and chemical analysis suggested that the dolomite phase was completely dissolved, and that Mg distribution was homogeneous throughout the samples at the scale of about two micrometers. The grain size after HIP varied from 8 to 31 μm, increased with time at temperature, and decreased with increasing Mg content (>3.0 mol%). Grain size and time were consistent with a normal grain growth equation, with exponents from 2.4 to 4.7, for samples containing 0.5–17.0 mol% Mg, respectively. We deformed samples after HIP at the same confining pressure with differential stresses between 20 and 200 MPa using either constant strain rate or stepping intervals of loading at constant stresses in a Paterson gas-medium deformation apparatus. The deformation tests took place at between 700 and 800°C and at strain rates between 10−6 and 10−3 s−1. After deformation to strains of about 25%, a bimodal distribution of large protoblasts and small recrystallized neoblasts coexisted in some samples loaded at higher stresses. The deformation data indicated a transition in mechanism from diffusion creep to dislocation creep. At stresses below 40 MPa, the strength was directly proportional to grain size and decreased with increasing Mg content due to the reductions in grain size. At about 40 MPa, the sensitivity of log strain rate to log stress, (n), became greater than 1 and eventually exceeded 3 for stresses above 80 MPa. At a given strain rate and temperature, the stress at which that transition occurred was larger for samples with higher Mg content and smaller grain size. At given strain rates, constant temperature, and fixed grain size, the strength of calcite in the dislocation creep regime increased with solute content, while the strength in the diffusion creep regime was independent of Mg content. The results suggest that chemical composition will be an important element to consider when solid substitution can occur during natural deformation.  相似文献   

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