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1.
Oxygen diffusion in albite has been determined by the integrating (bulk 18O) method between 750° and 450° C, for a P H2O of 2 kb. The original material has a low dislocation density (<106 cm?2), and its lattice diffusion coefficient (D 1), given below, agrees well with previous determinations. A sample was deformed at high temperature and pressure to produce a uniform dislocation density of 5 × 109 cm?2. The diffusion coefficient (D a) for this deformed material, given below, is about 0.5 and 0.7 orders of magnitude larger than D 1 at 700° and 450° C, respectively. This enhancement is believed due to faster diffusion along the cores of dislocations. Assuming a dislocation core radius of 4 Å, the calculated pipe diffusion coefficient (D p), given below, is about 5 orders of magnitude larger than D 1. These results suggest that volume diffusion at metamorphic conditions may be only slightly enhanced by the presence of dislocations. $$\begin{gathered} D_1 = 9.8 \pm 6.9 \times 10^{ - 6} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 33.4 \pm 0.6(kcal/mole)/RT] \hfill \\ \end{gathered} $$ $$\begin{gathered} D_a = 7.6 \pm 4.0 \times 10^{ - 6} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 30.9 \pm 1.1(kcal/mole)/RT] \hfill \\ \end{gathered} $$ $$\begin{gathered} D_p \approx 1.2 \times 10^{ - 1} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 29.8(kcal/mole)/RT]. \hfill \\ \end{gathered} $$   相似文献   

2.
Chemical diffusion coefficients for oxygen in melts of Columbia River basalt (Ice Harbor Dam flow) and Mt. Hood andesite have been determined at 1 atm. The diffusion model is that of sorption or desorption of oxygen into a sphere of uniform initial concentration from a constant and semi-infinite atmosphere. The experimental design utilizes a thermogravimetric balance to monitor the rate of weight change arising from the response of the sample redox state to an imposed fO2. Oxygen diffusion coefficients are approximately an order-ofmagnitude greater for basaltic melt than for andesitic melt. At 1260° C, the oxygen diffusion coefficients are: D=1.65×10–6cm2/s and D=1.43×10–7cm2/s for the basalt and andesite melts, respectively. The high oxygen diffusivity in basaltic melt correlates with a high ratio of nonbridging oxygen/tetrahedrally coordinated cations, low melt viscosity, and high contents of network-modifying cations. The dependence of the oxygen diffusion coefficient on temperature is: D=36.4exp(–51,600±3200/RT)cm2/s for the basalt and D=52.5exp(–60,060±4900/RT)cm2/s for the andesite (R in cal/deg-mol; T in Kelvin). Diffusion coefficients are independent of the direction of oxygen diffusion (equilibrium can be approached from extremely oxidizing or reducing conditions) and thus, melt redox state. Characteristic diffusion distances for oxygen at 1260° C vary from 10-2 to 102 m over the time interval of 1 to 106 years. A compensation diagram shows two distinct trends for oxygen chemical diffusion and oxygen tracer diffusion. These different linear relationships are interpreted as supporting distinct oxygen transport mechanisms. Because oxygen chemical diffusivities are generally greater than tracer diffusivities and their Arrhenius activation energies are less, transport mechanisms involving either molecular oxygen or vacancy diffusion are favored.  相似文献   

3.
Multipath diffusion in geochronology   总被引：5，自引：0，他引：5  
Recent developments in microanalytical tools such as the ion and laser microprobe have revealed spatial distributions of radiogenic isotopes in minerals which cannot be explained by a simple volume diffusion mechanism. Although it is known that diffusion of a substance along extended defects (such as dislocations, exsolution lamellae, micropores, microfractures, fission tracks, etc.), which may serve as high-diffusivity pathways in a crystal, can significantly influence the bulk diffusivity of a mineral, this has largely been ignored in the field of geochronology. A general numerical model has been developed, which solves coupled multipath diffusion equations that describe the simultaneous diffusion of a solute species through both the crystal lattice (via volume diffusion) and high-diffusivity pathways (via short-circuit diffusion) under non-steady state conditions. Addition of a radioactive source term to the appropriate equations further allows for the modelling of integrated cooling ages and closure temperatures, and has direct pertinence to geochronological and thermochronologial studies. Three key criteria can be used to distinguish multipath diffusion mechanisms from volume diffusion mechanisms: (a) non-Fickian concentration profiles, (b) enhanced solute diffusivity with increasing mineral grain size, and (c) a lack of any correlation between closure temperatures (and cooling ages) and larger grain sizes. With multipath diffusion, the effective diffusion dimension a for certain minerals appears to remain on the order of the grain size, and the model can adequately explain observed increases in the bulk diffusion coefficient D b with a in the hydrothermal bomb data of previous Ar diffusion studies. Arrhenius diagrams of a multipath diffusion D b vs 1/T will consist of curves that have a kink in them, reflecting a continuous change in the relative importance of the different diffusion mechanisms with temperature. The most important consequence of multipath diffusion is that the overall bulk diffusion coefficient D b of a diffusing species can be enhanced significantly above its volume diffusion coefficient D v . As a result, integrated ages and effective closure temperatures (T c ) can be much lower than those predicted assuming only a volume diffusion mechanism, to the extent that minerals normally characterized by low volume-diffusion T c may potentially have older integrated ages that minerals normally associated with higher volume-diffusion T c .  相似文献   

4.
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   

5.
In the estimation of momentum fluxes over land surfaces by the bulk aerodynamic method, no unique value of the drag coefficient (C D) is found in the literature. The drag coefficient is generally estimated from special observations at different parts of the world. In this study an attempt is made to estimate drag coefficient over the western desert sector of India using data sets of Monsoon Trough Boundary Layer Experiment (MONTBLEX) during the summer monsoon season of 1990. For this purpose, the fast and slow response data sets obtained simultaneously from a 30 m high micro-meteorological tower at Jodhpur are used. All the observations used in this study are confined to a wind speed regime of 2.5–9.0 ms−1. A comparison of momentum fluxes computed by eddy correlation (direct estimation) with profile and bulk aerodynamic (C D = 3.9 × 10−3, Garratt, 1977) methods revealed that though the nature of variation of the fluxes by all these methods is almost similar, both the indirect methods give an under-estimated value of the fluxes. The drag coefficient is estimated as a function of wind speed and surface stability by a multiple regression approach. An average value of the estimated drag coefficient is found to be of the order of 5.43 × 10−3. The estimated value ofC D is validated with a set of independent observations and found to be quite satisfactory. The recomputed momentum fluxes by bulk aerodynamic method using the estimated drag coefficient are in close agreement with the directly estimated fluxes.  相似文献   

6.
A novel experimental cell was developed for in situ measurements of transport phenomena in porous media using Fourier-Transform Infrared (FTIR) Spectroscopy. The technique was employed at ambient pressure in the temperatures range of 11–44 °C to study the H2O → D2O exchange between water-saturated weathered feldspars (bulk porosity of 5–19 vol% for feldspar) from granitic saprolites and a surrounding aqueous liquid. Such measurements are an important step for understanding internal weathering reactions of feldspars in soils and aquifers. Effective diffusion coefficients Deff for water in water-saturated porous feldspars were determined assuming one-dimensional diffusion in a quasi-homogeneous medium. The values of Deff vary from 7.2 × 10−10 to 1.9 × 10−11 m2/s and are 1–2 orders of magnitude lower than the diffusion coefficients (D) of protons and molecular H2O in liquid water. The activation energy for the H2O → D2O exchange process in porous feldspars ranges from 7.8 to 18.8 kJ/mol.The results imply that the effective diffusivity of water is mainly controlled by physical properties of the feldspars like porosity, pore connectivity, pore geometry and distribution. Perthitic feldspars with homogeneous pore distribution in the albitic lamellas have diffusional tortuosity factors X = D/Deff between 3 and 10 while alkali feldspars with inhomogeneously distributed and disconnected pores have much higher X values up to 129. Diffusion anisotropy has been verified for a vein perthite with diffusion perpendicular to the lamellas being faster by 0.3–0.5 log units than within the lamellas. It has to be emphasized that the study is based only on few selected feldspars, including perthitic feldspar, and additional work on samples with different weathering stages is needed to test the importance of the different parameters controlling diffusive transport in the pore system.  相似文献   

7.
Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for experiments was a mixture of ZrO2 and 30Si-enriched SiO2 in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. 30Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant nuclear reaction 30Si(p,γ)31P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol−1/RT) m2 s−1 for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements [62 exp(−738 ± 61 kJ mol−1/RT) m2 s−1]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we can rank the diffusivities of the major constituents in zircon as follows: D Zr < D Si << D O, dry < D O, ‘wet’.  相似文献   

8.
Diffusion profiles in minerals are increasingly used to determine the duration of geological events. For this purpose, the distinction between growth and diffusion zoning is critical; it requires the understanding of complex features associated with multicomponent diffusion. Seed-overgrowth interdiffusion experiments carried out in the range 1,050–1,250°C at 1.3 GPa have been designed to quantify and better understand Fe–Mg–Ca interdiffusion in garnet. Some of the diffusion profiles measured by analytical transmission electron microscope show characteristic features of multicomponent diffusion such as uphill diffusion, chemical solitary waves, zero-flux planes and complex diffusion paths. We implemented three different methods to calculate the interdiffusion coefficients of the D matrix from the experimental penetration curves and determined that with Ca as the dependent component, the crossed coefficients of the D matrix are negative. Experiments and numerical simulations indicate that: (1) uphill diffusion in garnet can be observed indifferently on the three components Fe, Mg and Ca, (2) it takes the form of complementary depletion/repletion waves and (3) chemical waves occur preferentially on initially flat concentration profiles. Derived D matrices are used to simulate the fate of chemical waves in time, in finite crystals. These examples show that the flow of atoms in multicomponent systems is not necessarily unidirectional for all components; it can change both in space along the diffusion profile and in time. Moving zero-flux planes in finite crystals are transitory features that allow flux reversals of atoms in the diffusion zone. Interdiffusion coefficients of the D matrices are also analyzed in terms of eigenvalues and eigenvectors. This analysis and the experimental results show that depending on the composition of the diffusion couple, (1) the shape of chemical waves and diffusion paths changes; (2) the width of the diffusion zone for each component may or may not be identical; and (3) the width of diffusion calculated at a given D and duration may greatly vary. D matrices were retrieved from thirteen sets of diffusion profiles. Data were cast in Arrhenius relations. Linear regressions of the data yield activation energies equal to 368, 148, 394, 152 kJ mol−1 at 1 bar and frequency factors Do equal to 2.37 × 10−6, −4.46 × 10−16, −1.31 × 10−5, 9.85 × 10−15 m2 s−1 for [(D)\tilde]FeFeCa \tilde{D}_{FeFe}^{Ca} , [(D)\tilde]FeMgCa \tilde{D}_{FeMg}^{Ca} , [(D)\tilde]MgFeCa \tilde{D}_{MgFe}^{Ca} , [(D)\tilde]MgMgCa \tilde{D}_{MgMg}^{Ca} , respectively. These values can be used to calculate interdiffusion coefficients in Fe–Mg–Ca garnets and determine the duration of geological events in high temperature metamorphic or magmatic garnets.  相似文献   

9.
The intracrystalline diffusion rate of oxygen in diopside was constrained based on natural isotopic variations from a granulite facies marble from Cascade Slide, Adirondacks (New York, USA). The oxygen isotope compositions of the diopsides, measured as a function of grain size, are nearly constant (20.9 ± 0.3‰ vs. SMOW) over the entire measured size range (0.3–3.2 mm diameter). The δ18O values of the cores of calcite grains are 23.0‰. Temperature estimates based on the Δ18O(calcite-diopside) are 800d?C, in agreement with the highest previous thermometric estimates for these rocks. The lack of isotopic variation in the diopsides as a function of grain size requires that the oxygen intracrystalline diffusion rate in diopside from the Adirondack samples was very slow. The maximum diffusion rates (D800d?C parallel to the c-axis) were calculated with an infinite reservoir model (IRM) and a finite reservoir model (FRM) that incorporates mineral modal abundances and initial isotopic variations. For an assumed activation energy (Q) = 100 kJ/mol, the IRM diffusion rate estimate of 1.6 times 10-20cm2/s is two orders of magnitude faster than from the FRM; at Q=500kJ/mol, the D800d?C estimate for both methods is c. 5.6 times 10-20 cm2/s. The present results require that a hydrothermal fluid significantly enhances the diffusion rate of oxygen in diopside if previous data are correct. The δ18O(SMOW) and δ13C(PDB) values of the calcite, measured in situ with a CO2 laser, are 22.9 ± 0.3, 0.1±0.3‰ in the grain cores, 22.1 ±0.3, 0.2 ±0.1‰ at the grain boundaries and 21.7 ±0.4, -0.6±0.1‰ abutting diopside grains. The δ18O and δ13δC values measured conventionally are: crystal cores, 22.96, -0.95‰; abutting diopside grains, 22.38, -0.93‰; bulk, 22.79, -0.95%. Use of the bulk δ18O(calcite) values for thermometry yields unreasonably high temperatures. The lower δ18O values at the calcite grain boundaries are not due to retrograde diffusional exchange with the diopside, they are thought to be a result of a late retrograde fluid infiltration.  相似文献   

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

11.
Diffusion couples made from homogeneous gem quality natural pyrope and almandine garnets were annealed within graphite capsules under anhydrous conditions at 22–40 kbar, 1057–1400 °C in a piston-cylinder apparatus. The concentration profiles that developed in each couple were modeled to retrieve the self diffusion coefficients [D(I)] of the divalent cations Fe, Mg, Mn and Ca. Because of their usually low concentrations and lack of sufficient compositional change across the interface of the diffusion couples, only a few reliable data can be obtained for D(Ca) and D(Mn) from these experiments. However, nine sets of D(Fe) and D(Mg) data were retrieved in the above P-T range, and cast in the form of Arrhenian relation, D=D 0exp{−[Q(1 bar)+PΔV +]/RT}. The values of the activation energy (Q) and activation volume (ΔV +) depend on whether f O2 is constrained by graphite in the system C-O or held constant. For the first case, we have for Fe:Q(1 bar)=65,532±10,111 cal/mol, D 0=3.50 (±2.30)×10−5 cm2/s, ΔV +=5.6(±2.9) cm3/mol, and for Mg:Q(1 bar)=60,760±8,257 cal/mol, D 0=4.66 (±2.48)×10−5 cm2/s, ΔV +=5.3(±3.0) cm3/mol. Here the ΔV + values have been taken from Chakraborty and Ganguly (1992). For the condition of constant f O2, the Q values are ∼9 kcal lower and ΔV + values are ∼4.9 cm3/mol larger than the above values. Lower temperature extrapolation of the Arrhenian relation for D(Mg) is in good agreement with the Mg tracer diffusion data (D * Mg) of Chakraborty and Rubie (1996) and Cygan and Lasaga (1985) at 1 bar, 750–900 °C, when all data are normalized to the same pressure and to f O2 defined by graphite in the system C-O. The D * Mg data of Schwandt et al. (1995), on the other hand, are lower by more than an order of magnitude than the low temperature extrapolation of the present data, when all data are normalized to the same pressure and to f O2 defined by the graphite buffer. Comparison of the D(Fe), D(Mg) and D(Mn) data in the pyrope-almandine diffusion couple with those in the spessartine-almandine diffusion couple of Chakraborty and Ganguly (1992) shows that the self diffusion of Fe and Mn are significantly enhanced with the increase in Mn/Mg ratio; the enhancement effect on D(Mg) is, however, relatively small. Proper application of the self diffusion data to calculate interdiffusion coefficient or D matrix elements for the purpose of modeling of diffusion processes in natural garnets must take into account these compositional effects on D(I) along with the effects of thermodynamic nonideality, f O2, and pressure. Received: 8 May 1997 / Accepted: 2 October 1997  相似文献   

12.
Fe–Mg partitioning between post-perovskite and ferropericlase has been studied using a laser-heated diamond anvil cell at pressures up to 154 GPa and 2,010 K which corresponds to the conditions in the lowermost mantle. The composition of the phases in the recovered samples was determined using analytical transmission electron microscopy. Our results reveal that the Fe–Mg partition coefficient between post-perovskite and ferropericlase (K DPPv/Fp) increases with decreasing bulk iron content. The compositional dependence of K DPPv/Fp on the bulk iron content explains the inconsistency in previous studies, and the effect of the bulk iron content is the most dominant factor compared to other factors, such as temperature and aluminum content. Iron prefers ferropericlase compared to post-perovskite over a wide compositional range, whereas the iron content of post-perovskite (X FePPv, the mole fraction) does not exceed a value of 0.10. The iron-rich ferropericlase phase may have significant influence on the physical properties, such as the seismic velocity and electrical conductivity at the core–mantle boundary region.  相似文献   

13.
We have measured diffusion coefficients for P, Cr, Co, Ni, Cu, Ga, Ge, Ru, Pd, Ir, and Au in Fe metal from 1150 to 1400°C and at 1 bar and 10 kbar. Diffusion couples were prepared from high-purity Fe metal and metal from the IIA iron meteorite Coahuila (single crystal kamacite) or the pallasite Springwater (polycrystalline kamacite) and held at run conditions for 3.5 to 123 h. Diffusion profiles were measured using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) or the electron microprobe. Many elements were measured from the same experimental runs so interelemental comparisons are improved over other data sets in which data for different elements come from different experiments. Some literature diffusion coefficients (D) for Ni and Co in taenite can be up to a factor of 3 higher for Ni than Co, yet our results show no difference (e.g., DNi and DCo ∼ 2.2 × 10-15 m2/s at 1150°C). Thus, diffusion of Ni and Co in single crystal taenite will not measurably fractionate the Ni/Co ratio. On the other hand, the large difference in DNi and DIr (DIr is ∼5 times lower) and the similarity of DNi and DRu at all temperatures investigated indicates that Ni/Ir and Ni/Ru ratios in zoned metal grains will be useful discriminators of processes controlled by diffusion vs. volatility. In zoned metal grains in primitive chondrites, deviations of the Ni/Ru and Ni/Ir ratios from a condensation curve are opposite to a diffusion-controlled process, but consistent with a volatility-controlled process. The new multielement diffusion coefficients will also be useful in evaluating a variety of other processes in planetary science.  相似文献   

14.
Fast diffusion along mobile grain boundaries in calcite   总被引：1，自引：0，他引：1  
Experimental measurements of grain boundary diffusion are usually conducted on static boundaries, despite the fact that grain boundaries deep in the Earth are frequently mobile. In order to explore the possible effect of boundary mobility on grain boundary diffusion rates we have measured the uptake of 44Ca from a layer of 44Ca-enriched calcite powder during the static recrystallization of a single crystal of calcite at 900°C. A region about 500 μm wide adjacent to the powder layer is heterogeneously enriched in 44Ca, and complex zoning patterns, including sharp steps in composition and continuous increases and decreases in 44Ca content, are developed. In metamorphic rocks, these would normally be interpreted in terms of changes in pressure or temperature, Rayleigh fractionation, or episodic fluid infiltration. These explanations cannot apply to our experiments, and instead the zoning patterns are interpreted as being due to variations in grain boundary migration rate. We have applied an analytical model which allows the product of grain boundary diffusion coefficient and grain boundary width (D GB δ) to be calculated from the grain boundary migration rate and the compositional gradient away from the powder layer. The value of D GB δ in the mobile grain boundaries is at least five orders of magnitude greater than the published value for static boundaries under the same conditions. In order to allow the scale of chemical equilibrium (and hence textural evolution) to be predicted under both experimental and geological conditions, we present quantitative diffusion-regime maps for static and mobile boundaries in calcite, using both published values and our new values for grain boundary diffusion in mobile boundaries. Enhanced diffusion in mobile boundaries has wide implications for the high temperature rheology of Earth materials, for geochronology, and for interpretations of the length- and time-scales of chemical mass-transport. Moreover, zones of anomalously high electrical conductivity in the crust and mantle could be regions undergoing recrystallization such as active shear zones, rather than regions of anomalous mineralogy, water- or melt-content as is generally suggested.  相似文献   

15.
Data from experimentally-induced diffusion profiles at approximately 40 Kbar, 1,300–1,500° C in spessartine-almandine couples and a pyrope-almandine couple at 40 Kbar, 1,440° C, described in Part I, were used to derive tracer diffusion coefficients (D *) of Fe, Mn and Mg in garnet. The experimental data were fitted by numerical simulations that model multicomponent, compositionally-dependent difussion, including the effects of nonideal thermodynamic mixing. The simulations use the formalism of irreversible thermodynamics and an eigenvector technique of solution. We were able to fit the asymmetrical spessartine-almandine profiles using constant D * and either the Darken/Hartley-Crank or Manning-Lasaga models relating D * and interdiffusion coefficients, and both models yielded D Mg * consistent with the direct measurement of D Mg * in by Cygan and Lasaga (1985) at lower temperatures (750–900° C). The results (equations 4.1–4.3 and Table 1) indicate that D Fe * D Mg * <D Mn * and Q FeQ Mg>Q Mn, where Q is the activation energy. In contrast, the asymmetry of pyrope-almandine profiles is too great to fit with either tracer model assuming constant D * and indicates that D Mg * is similar to its value in spessartine-almandine couples but D Fe * is an order of magnitude less. The fit also suggests that D Ca * < D Fe * Mg * in pyrope-almandine couples. Synthesis of data from the two types of diffusion couples suggests that D Mg * is insensitive to compositional changes, whereas D Fe * is affected by Mn/Mg and Fe/Mg ratios and probably by other factors. These compositional effects on tracer coefficients are compatible with those documented by Morioka (1983) for cation diffusion in olivine.  相似文献   

16.
The partitioning of samarium and thulium between garnets and melts in the systems Mg3Al2-Si3O12-H2O and Ca3Al2Si3O12-H2O has been studied as a function of REE concentration in the garnets at 30 kbar pressure. Synthesis experiments of variable time under constant P, T conditions indicate that garnet initially crystallizes rapidly to produce apparent values of D Sm (D Sm=concentration of Sm in garnet/concentration of Sm in liquid) which are too large in the case of pyrope and too small in the case of grossular. As the experiment proceeds, Sm diffuses out of or into the garnet and the equilibrium value of D Sm is approached. Approximate values of diffusion coefficients for Sm in pyrope garnet obtained by this method are 6 × 10–13 cm2 s–1 at 1,300 ° C and 2 × 10–12 cm2 s–1 at 1,500 ° C, and for grossular, 8.3 × 10–12 cm2 s–1 at 1,200 ° C and 4.6 × 10–11 cm2 s–1 at 1,300 ° C. The equilibrium values of D Sm have been reversed by experiments with Sm-free pyrope and Sm-bearing glass, and with Sm-bearing grossular and Sm-free glass.Between 12 ppm and 1,000 ppm Sm in pyrope at 1,300 ° C and between 80 ppm and >2 wt.% Tm in pyrope at 1,500 ° C, partition coefficients are constant and independent of REE concentration. Above 100 ppm of Sm in garnet at 1,500 ° C, partition coefficients are independent of Sm concentration. At lower concentrations, however, D Sm is dependent upon the Sm content of the garnet. The two regions may be interpreted in terms of charge-balanced substitution of Sm3Al5O12 in the garnet at high Sm concentrations and defect equilibria involving cation vacancies at low concentrations. At very low REE concentrations (< 1 ppm Tm in grossular at 1,300 ° C) DREE garnet/liquid again becomes constant with an apparent Henry's Law value greater than that at high concentrations. This may be interpreted in terms of a large abundance of cation vacancies relative to the number of REE ions.The importance of defects in the low concentration region has been confirmed by adding other REE (at 80 ppm level) to the system Mg3Al2Si3O12-H2O at low Sm concentrations. These change D Sm in the defect region, demonstrating their role in the production of vacancies.Experiments on a natural pyropic garnet indicate that defect equilibria are of importance to REE partitioning within the concentration ranges found in nature.  相似文献   

17.
Preferential water loss from synthetic fluid inclusions   总被引：4，自引：0，他引：4  
A fundamental question in most fluid inclusion studies is whether inclusions behave as compositionally closed systems after trapping, and, thus, represent samples of the fluid phase(s) present in the system at the time of their formation. This question was addressed in high-temperature laboratory experiments with synthetic fluid inclusions in quartz and it was found that at 825°C the inclusions exhibited open-system behavior with respect to water. Synthetic salt-water fluid inclusions in quartz were reequilibrated for 12 hours to 35 days at 825° C in a dry argon atmosphere under 1.5 kbar confining pressure. These conditions created initial internal overpressures (P int> P conf) of 1.5–4 kbar in the inclusions and differential water fugacities in the same sense i.e., fH2OfH2O. After 108 hours of reequilibration, preferential water loss had resulted in salinity increases as large as 22 wt% salt (e.g., from 57 to 79 wt% NaCl, as determined from measured temperatures of salt dissolution). Also, following reequilibration, a strong inverse correlation between salinity and inclusion volume was observed, and this trend became more pronounced with increasing reequilibration time. These observations, together with a lack of evidence for selective H2O removal via hydration reactions, suggest that water loss occurred by a diffusion-related mechanism. Fluxes of 4x10-11 g/cm2-s and diffusion coefficients on the order of 10-9 cm2/s are calculated for water loss from the inclusions. The calculated H2O diffusion coefficient is consistent with the determination of Blacic (1981) derived from hydrolytic weakening experiments, but is much larger than the value obtained by Giletti and Yund (1984) for volume diffusion of oxygen in isotope exchange experiments. These observations suggest that the mechanism of water loss from our synthetic fluid inclusions may have been pipe diffusion along dislocations, subgrain boundaries or other structural defects rather than bulk volume diffusion.The results of this study are relevant to the interpretation of fluid inclusions in quartz from several natural high-temperature environments where water fugacities of included and ambient fluids are known to have evolved along separate paths over geologic time.  相似文献   

18.
Sediments contained in the river bed do not necessarily contribute to morphological change. The finest part of the sediment mixture often fills the pores between the larger grains and can be removed without causing a drop in bed level. The discrimination between pore‐filling load and bed‐structure load, therefore, is of practical importance for morphological predictions. In this study, a new method is proposed to estimate the cut‐off grain size that forms the boundary between pore‐filling load and bed‐structure load. The method evaluates the pore structure of the river bed geometrically. Only detailed grain‐size distributions of the river bed are required as input to the method. A preliminary validation shows that the calculated porosity and cut‐off size values agree well with experimental data. Application of the new cut‐off size method to the river Rhine demonstrates that the estimated cut‐off size decreases in a downstream direction from about 2 to 0·05 mm, covariant with the downstream fining of bed sediments. Grain size fractions that are pore‐filling load in the upstream part of the river thus gradually become bed‐structure load in the downstream part. The estimated (mass) percentage of pore‐filling load in the river bed ranges from 0% in areas with a unimodal river bed, to about 22% in reaches with a bimodal sand‐gravel bed. The estimated bed porosity varies between 0·15 and 0·35, which is considerably less than the often‐used standard value of 0·40. The predicted cut‐off size between pore‐filling load and bed‐structure load (Dc,p) is fundamentally different from the cut‐off size between wash‐load and bed‐material load (Dc,w), irrespective of the method used to determine Dc,p or Dc,w. Dc,w values are in the order of 10?1 mm and mainly dependent on the flow characteristics, whereas Dc,p values are generally much larger (about 100 mm in gravel‐bed rivers) and dependent on the bed composition. Knowledge of Dc,w is important for the prediction of the total sediment transport in a river (including suspended fines that do not interact with the bed), whereas knowledge of Dc,p helps to improve morphological predictions, especially if spatial variations in Dc,p are taken into account. An alternative to using a spatially variable value of Dc,p in morphological models is to use a spatially variable bed porosity, which can also be predicted with the new method. In addition to the morphological benefits, the new method also has sedimentological applications. The possibility to determine quickly whether a sediment mixture is clast‐supported or matrix‐supported may help to better understand downstream fining trends, sediment entrainment thresholds and variations in hydraulic conductivity.  相似文献   

19.
Diffusivities for calcium, iron, magnesium, manganese and aluminum have been measured for St. John's olivine undergoing cation exchange with synthetic basaltic melts. The variety of temperature, pressure and fO2 conditions under which the diffusivities were measured complement the equilibrium-partitioning study of calcium in olivine-bearing basalts by Jurewicz and Watson, 1988. Olivine was found to be anisotropic with respect to the diffusion of calcium, iron, magnesium and manganese. This anisotropy is a weak function of temperature, but strongly dependent upon oxygen fugacity.Because diffusion is independent of olivine composition over the small range of compositions used in this study, it could be shown that the absolute values of the diffusion coefficients were also functions of temperature and fO2. At near-atmospheric total pressure and an oxygen fugacity of 10–8atm, D Fe>D Mn>D Ca and D MgD Mn for a range of geologically reasonable temperatures. These relative diffusivities were shown to change with oxygen fugacity. The power-law dependence of diffusion on oxygen partial-pressure was determined for each cation and the results are consistent with the range of values given by Stocker (1978) and by other workers.For Ca and Fe, the effect of hydrostatic pressure on diffusion appears to be weak, at least for transport parallel to the c crystallographic direction. Unfortunately, no true activation volumes (or other pressure-related parameters) could be computed because the oxygen fugacity was not held constant over changes in pressure, and because accurate post-experiment reconstruction of sample orientation was not possible. Al was found to enter high-pressure olivines at concentrations of up to 0.14 weight percent, thus allowing aluminum diffusion to be characterized. The diffusivity of aluminum is, within error, the same as iron at 20 kb at 1430° C at the ambient fO2 of our piston-cylinder cells. This correspondence suggests that diffusion of Al may depend on transport of either Fe or of Fe +3 defects. While the results of these experiments are generally consistent with results published elsewhere, there are important inconsistencies. Tracer diffusion and interdiffusion in pure, ordered, olivine endmembers (e.g., tephroite and forsterite) showed significantly higher activation energies. This discrepancy could reflect the role of Fe+3 defects in diffusion; however, it may also suggest that order-disorder phenomena may be significant factors influencing diffusion in analog systems.The results of this study are applied to four petrologic problems: (1) calculation of rates of equilibration for olivine xenocrysts; (2) calculation of closure temperatures for the CaO/MgO olivine/basalt geothermometer (Jurewicz and Watson 1988); (3) delineation of an intrinsic-/O2 geobarometer; and (4) investigation of the dependence of olivine dissolution upon crystallographic orientation. In addition, it is demonstrated that diffusion-exchange experiments are useful for studying the dominant point-defect mechanisms for cation diffusion.Currently, a visiting scientist with Air Force Wright Aeronautical Laboratories Materials Laboratory (MLLM), Wright-Patterson AFB, OH 45433  相似文献   

20.
The self-diffusion of oxygen has been measured for three silicate melts along the join diopsideanorthite. The experiments were done by isotope exchange between an “infinite” reservoir of oxygen gas and spheres of melt. The oxygen self-diffusion coefficients for the three melts are given as: C-1(diopside): D = 1.64 × 101 exp(?(63.2 ± 20)(kcal/mole)/RT) cm2/sec C-2(Di58An42): D = 1.35 × 10?1 exp(?(46.8 ± 9)(kcal/mole)/RT) cm2/sec C-3(Di40An60): D = 1.29 × 10?2 exp(?(44.2 ± 6)(kcal/mole)/RT) cm2/secThe self-diffusion coefficients do not agree with the Eyring equation unless mean ionic jump distances (λ) considerably larger than the diameter of oxygen anion are assumed. However, the sense of variation of the actual diffusivities is as the Eyring equation predicts.Consideration of the results of this study and the bulk of previous work shows that oxygen appears to conform to the compensation law for cationic diffusion in silicate melts and glasses. The range of oxygen diffusivities was also found to encompass the field of divalent cation diffusivities in silicate melts.Those results imply that the diffusion of oxygen in silicate melts may involve a contribution from a cation-like diffusion mechanism (discrete O2? anions) as well as contributions from the diffusion of larger structural units.  相似文献   

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