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1.
Radiogenic Ar diffusion from phlogopite mica has been measured at 900° and 1080°C at 15 kbars pressure, using a Griggs-type hot creep tester operated at hydrostatic pressure, and followed by standard mass spectrometric analysis. The diffusion coefficients fall within the uncertainty of the diffusion results reported by Giletti (1974) at 1 kbar at 900° and on extrapolation of that Arrhenius plot to 1080°C. That linear plot is given by D0 = 0.75 and Q = 57.9kcal/g-atom Ar. In the observed temperature range, the effect of pressure up to 15 kbars is not significant. A second Ar diffusion, which employed Ca(OH)2-CaO as a water buffer, was run at 1 atm H2O pressure and 550°C for 781 days. The resulting diffusion coefficient agrees, within the uncertainty, with the extrapolation of the earlier curve. This result, and both earlier ones at 600°, are similar in that they fall below the curve. Consequently, despite the agreement within the uncertainty, it is possible that diffusion of Ar from phlogopite below 650°C is somewhat slower than given by the above equation parameters.  相似文献   

2.
Data for the diffusion of cations in pyroxenes are relevant to a variety of sub-solidus processes including order-disorder and exsolution. Similar data must also be available if the reliability of geobarometers and geothermometers involving pyroxenes is to be assessed. Two types of diffusion experiment have been performed to determine cation diffusion rates in pyroxenes: (1) interdiffusion between single crystals of diopside and polycrystalline sinters enriched in Al and Fe, and (2) interdiffusion between single crystals of diopside and a glass of the same composition which was isotopically enriched in26Mg and43Ca. Following high-temperature annealing for periods up to several hundred hours, analysis of the diffusion couples, using an electron microprobe and an ion microprobe respectively, failed to show any measurable diffusion profiles. From these “null result” experiments the diffusion coefficients (D) for Al and Fe in diopside are estimated to be less than4×10?14cm2s?1 at 1200°C, and values ofD for Ca and Mg in diopside are estimated to be less than7 × 10?14cm2s?1 at 1250°C. These rates are significantly slower than published tracer-type diffusion data for Ca and Al.A review of studies of order-disorder, microstructural coarsening, and diffusion in pyroxenes suggest that activation energies for cation exchange are typically in excess of 60 kcal mol?1. Transport rates will be assisted, and activation energies lowered by sample non-stoichiometry, inhomogeneities, high dislocation densities and the presence of water.The collective data for Al, Mg and Ca diffusion in diopside indicate diffusion coefficients? 10?15cm2s?1 at 1200°C. A comparison with data for diffusion in garnet, olivine and spinel suggests that pyroxenes may have the highest blocking temperatures.  相似文献   

3.
Spectra of internal friction between 2 and 8 Hz were studied in a single crystal of enstatite, in a polycrystal of synthetic forsterite and in several samples of natural peridotite. Measurements of Q?1 and μ were performed in vacuum (10?6 torr), from room temperature up to 1100°C. For these experimental conditions no peak was observed in the polycrystalline undeformed forsterite, but the background attenuation irregularly increased from 5 · 10?3 to 10?2.A peak Q?1 = 7 · 10?2 appears in a deformed peridotite at 930°C. It is reduced of 60% after 5 h of annealing at 1100°C. But the background attenuation persists. In the single crystal of enstatite, a peak is observed at 760°C (Q?1 = 6 · 10?2). A mechanism involving dislocations is suggested as a possible explanation for the peak obtained with the peridotite samples. If this hypothesis is right, the observed effect would be diffusion controlled so that one can expect pressure to translate it towards higher temperature. This mechanism could therefore appear in the upper mantle. Background attenuation could be the result of intergranular thermal losses.  相似文献   

4.
We have determined the concentrations and isotopic composition of helium in oceanic basaltic glass both by melting and by crushing in vacuo. A significant fraction of the helium is released by crushing, confirming that it resides within the vesicles. Comparison of volume percent vesicles to the fraction of helium contained in the vesicles gives qualitative agreement with experimental gas-melt partitioning studies. Measured concentrations are therefore, a function of original helium content, magmatic history, vesicle size and quantity, and grain size analyzed. Helium released by crushing is isotopically indistinguishable from that contained in the glass. Diffusion rates for helium in basaltic glass (in the temperature range 125–400°C) determined using the method of stepwise heating, yielded an activation energy of 19.9 ± 1 kcal/mole andlnD0 = ?2.7 ± 0.6 (cgs units). Extrapolation of these results to ocean floor temperatures (0°C) gives a diffusivity of 1.0 ± 0.6 × 10?17 cm2/s, indicating that diffusion is an insignificant mechanism for helium loss from fresh basaltic glasses. The3He/4He ratios are remarkably constant (at 1.10 ± 0.03 × 10?5) for samples from the Mid-Atlantic Ridge (FAMOUS area and 23°N), the Juan de Fuca Ridge, the Galapagos spreading center, the Mid-Cayman Rise, and the Central Indian Ocean Ridge. This result is interpreted in terms of similar geochemical histories within the source regions for these samples.  相似文献   

5.
In previous attempts to determine the40Ar36Ar ratio in the ancient atmosphere, the only direct measurement yielding a value below the atmospheric value of today is for argon released at low temperatures from a pre-Cambrian shungite, an amorphous carbon mineral [1]. The present work confirms a low value for40Ar36Ar in gas released from a type I shungite at low temperatures. But quantitative scrutiny of the accompanying38Ar36Ar ratios and the enhanced ratio of40Ar36Ar for the fractions released at high temperatures shows convincingly that the effect seen here is an artifact of the stepwise heating and the argon diffusion mobilized thereby. The low40Ar36Ar previously obtained is very likely from the same cause rather than reflecting the isotopic composition of the pre-Cambrian atmosphere. The vitreous character of and the sharp, conchoidal fractures seen in the specimens of type I shungite suggest that the substance may exhibit simple volume diffusion over macroscopic dimensions as glasses do. If so, the diffusion parameters (D∞ = 3 × 10?4cm2/s andE = 11kcal/mole) obtained from the data imply rapid exchange with the atmosphere for any argon initially trapped in centimeter-thick veins of the material.  相似文献   

6.
Relaxation experiments on vitreous SiO2, densified at 900°C, 20 kbar to a permanent density of 2.36 g cm?3 yield an activation energy of69 ± 5kcal mol?1 in the temperature range 700–800°C. The data can be used to estimate minimum cooling rates, maximum depositional temperatures or maximum thicknesses of shock-metamorphosed rocks containing diaplectic glasses, if relaxation of a glass densified under dynamic conditions is assumed to be similar to that of statically densified glass.  相似文献   

7.
An ion-microprobe-based technique has been used to measure lithium tracer-diffusion coefficients (DLi) in an alkali-basaltic melt at 1300, 1350 and 1400°C. The results can be expressed in the form:DLi=7.5 ×10?2exp(?27,600/RT)cm2S?1The results show significantly faster diffusion rates than those previously recorded for other monovalent, divalent and trivalent cations in a tholeiitic melt. Consequently, diffusive transport of ions acting over a given time in a basaltic melt can produce a wider range of transport distance values than hitherto supposed. Hence, it is concluded that great care should be exercised when applying diffusion data to petrological problems.  相似文献   

8.
Self-diffusion of potassium in biotite has been measured by inducing isotopic exchange between the potassium in the biotite and potassium enriched in 41K in a hydrothermal alkali chloride solution at 650°C and 2000 bars pressure, and then analyzing the resulting distribution of the K isotopes in the mica using an ion microprobe mass analyzer. The distribution of K isotopes in one mica flake was studied by three-dimensional mapping. The results show the diffusivity in the a or b directions to be greater than in the c direction by 2 to 4 orders of magnitude. In the c direction, the isotopic profile yields a diffusion coefficient of D = 1 × 10?17cm2sec?1 with an estimated error of a factor of ten. These results are in good agreement with bulk isotopic transport measurements on the same experiment reported by A.W. Hofmann and B.J. Giletti (1970). It is thus shown that diffusivities involving very slow net transport can be measured using an isotopic exchange technique and measuring the effect using an ion microprobe mass analyzer.  相似文献   

9.
A new technique has been developed for measuring the diffusion coefficient in ionic crystals. Based on Einstein's formula expressing the relation between diffusion coefficient and electric mobility, the electrical impedance of a diatomic ionic crystal is derived theoretically as a function of frequency of the applied electric field. In this method, the diffusion coefficients of both cations and anions are determined simultaneously by fitting the measured impedance to the theoretical relation. This method was applied to NaCl single crystals in the temperature range 370–780°C. The impedance was determined over the frequency range 0.01 Hz to 1 kHz, at constant temperature. The diffusion coefficients thus obtained for NaCl agree reasonably well with previous data by means of a radioactive isotope technique. The activation energies for Na+ and Cl? obtained are 1.97±0.03 eV and 2.08±0.06 eV, respectively, in the intrinsic region, and 0.92±0.02 eV and 1.06±0.02 eV in the extrinsic region. It was discovered that there are diffusion blocks of approximately 2 μm width, which obstruct free migration of ions in a single crystal.  相似文献   

10.
40Ar/39Ar age spectrum analyses of samples from Broken Hill, New South Wales, indicate that the region has experienced a complex thermal history following high-grade metamorphism, 1660 Ma ago. The terrain cooled slowly (～3°C Ma?1) until about 1570 Ma ago, when the temperature fell below about 500°C. Following granitoid emplacement ～1500 Ma ago, the region remained relatively cold until affected by a thermal pulse 520±40Ma ago, causing temperatures to rise to～350°C in some places. During this event, accumulated40Ar was released from minerals causing a significant Ar partial pressure to develop. Laboratory Ar solubility data combined with the40Ar/39Ar age spectra gives a local estimate of this partial pressure of ～10?4atm. The region finally cooled below 100°C about 280 Ma ago.40Ar/39Ar age spectrum analyses of hornblende, plagioclase and clinopyroxene containing excess40Ar are characterized by saddle-shaped age spectra. Detailed analysis of plagioclase samples reveals a complex diffusion behaviour, which is controlled by exsolution structures. This effect, in conjunction with the presumed different lattice occupancy of excess40Ar with respect to radiogenic40Ar, appears to be responsible for the saddle-shaped age spectra.  相似文献   

11.
An assessment of local and regional isotopic equilibrium in the mantle   总被引：2，自引：0，他引：2  
The assumption of local equilibrium during partial melting is fundamental to the interpretation of isotope and trace element data for mantle-derived rocks. If disequilibrium melting is significant, the scale of the chemical and isotopic heterogeneity in the mantle indicated by the data could be as small as the grain size of the mantle rock, and the isotope data themselves are then of doubtful value to the understanding of mantle processes. To assess the scale of isotopic heterogeneity in a partially molten asthenosphere we review the Sr isotopic data of volcanic rocks from oceanic regions and the available experimental data on diffusion kinetics in minerals and melts similar to those existing in the mantle. Although diffusion data are scarce and afflicted with uncertainties, most of the diffusion coefficients for cations in mantle minerals at temperatures of 1000–1200°C appear to be greater than 10?13 cm2 s?1. Sr diffusion in liquid basalt is more rapid, with diffusion coefficients of D = 10?7 to 10?6cm2s?1 near 1300°C. Simple model calculations show that, with these D values, a fluid-free mantle can maintain a state of disequilibrium on a centimeter scale for periods of 108 to 109 years. The state of disequilibrium found in many mantle-derived xenoliths is thus easily explained. A partially molten mantle, on the other hand, will tend to equilibrate locally in less than 105 to 106 years. The analytical data on natural rocks likewise indicate that the inhomogeneities are both old (>FX1.5 b.y.) and regional in character and that the consistent isotopic difference between ocean island and ocean floor volcanics cannot be explained by small-scale heterogeneity of the source rock.  相似文献   

12.
The temperature dependence of water diffusivity in rhyolite melts over the range 650–950°C and [PT(H2O] = 700 bars is evaluated from water concentration-distance profiles measured in glass with an ion microprobe. Diffusivities are exponentially dependent on concentration over this temperature range and vary from about 10?8 cm2/s at 650°C to about 10?7 cm2/s at 950°C at 2 wt.% water. Water solubility also varies with temperature at a rate of ?0.14 wt. per 100°C increase. The avtivation energy (Ea) appears to be constant at 19 ± 1kal/mole for 1, 2,and 3 wt.% H2O. Comparison of these data with results for cation diffusion indicates that this value is a minimum Ea for diffusion of any species in a rhyolite melt.Compensation plots of log10D0 (the frequency factor) versus Ea indicate that hydrous rhyolite melts follow the same trend as anhydrous basalts. D0 increases for H2O and Ca2+ [1] as Ea decreases. This suggests that these molecules may diffuse by different mechanisms than do monovalent cations, and that hydration of the melt affects diffusion of Ca2+ and H2O differently than it does monovalent cation diffusion. The results imply that dramatic increases in cation diffusivities by hydration [1] may occur with additions of less than 1 wt.% H2O.  相似文献   

13.
FAMOUS basalt 527-1-1 (a high-Mg oceanic pillow basalt) has three generations of spinel which can be distinguished petrographically and chemically. The first generation (Group I) have reaction coronas and are high in Al2O3. The second generation (Group II) have no reaction coronas and are high in Cr2O3 and the third generation (Group III) are small, late-stage spinels with intermediate Al2O3 and Cr2O3. Experimental synthesis of spinels from fused rock powder of this basalt was carried out at temperatures of 1175–1270°C and oxygen fugacities of 10?5.5 to 10?10 atm at 1 atm pressure. Spinel is the liquidus phase at oxygen fugacities of 10?8.5 atm and higher but it does not crystallize at any temperature at oxygen fugacities less than 10?9.5. The composition of our spinels synthesized at 1230–1250°C and 10?9 atmfO2 are most similar to the high-Cr spinels (Group II) found in the rock. Spinels synthesized at 1200°C and 10?8.5 atmO2 are chemically similar to the Group III spinels in 527-1-1. We did not synthesize spinel at any temperature or oxygen fugacity that are similar to the high-Al (Group I) spinel found in 527-1-1. These results indicate that the high-Cr (Group II) spinel is the liquidus phase in 527-1-1 at low pressure and Group III spinel crystallize below the liquidus (～1200°C) after eruption of the basalt on the sea floor. The high-Al spinel (Group I) could have crystallized at high pressure or from a magma enriched in Al and perhaps Mg compared to 527-1-1.  相似文献   

14.
The electrical conductivity of a single crystal of San Carlos olivine (Fo92, 0.16 wt.% Fe2O3) has been measured as a function of temperature and oxygen fugacity (fO2). After heating to 1338°C at fO2 = 10?12 atm., the conductivity at 950°C was 10?5 (ohm-m)?1, almost 3 orders of magnitude less than that measured in air. This decrease is due to the reduction of Fe3+ to Fe2+. Further heating to 1500°C at fO2 = 10?14 atm., decreased the electrical conductivity at 950°C to 10?6 (ohm-m)?1. When recovered at room temperature, the speciment had Fo96 composition and contained small, opaque blebs distributed throughout the crystal. Derivations of temperature profiles for the earth's mantle from conductivity-depth models must take account of the important role played by iron oxidation state in the electrical conductivity of olivine.  相似文献   

15.
Diffusion coefficients for Si, Ti, Al, Na, K, Ca, Mg and Fe between pairs of glasses of basaltic, rhyolitic or phonolitic compositions have been determinated experimentally. This method involves the heating of coaxial cylinders of paired glasses under atmospheric conditions, over a range of temperatures from 900 to 1300°C, followed by microprobe analysis determination of the concentration gradients across the interface.The measured diffusivities are similar for all cations and range from 10?13 cm2/s at 900°C to 5 × 10?9 cm2/s at 1300°C. Depending mainly on the composition contrast, the diffusion is characterized by asymmetrical concentration profiles. This peculiar feature increases with temperature and chemical gradients across the contact surface of the glasses and leads to higher diffusion coefficients (D) in the more “basic” glass of a given pair. In the case of the rhyolite-basalt couple, this variation increases by a factor of about 10 at 1300°C. Diffusion dependence on temperature follows an Arrhenius equation which gives activation energies ranging from 65 to 85 kcal/mole. Assuming a constant and overall D for the two glasses we have attempted to apply our results to some geological examples such as exchanges between molten enclaves and liquids of contrasting composition.  相似文献   

16.
The distribution of Ca and Mg among coexisting olivine, clinopyroxene and orthopyroxene has been studied in a piston-cylinder apparatus in the temperature range 1100–1300°C and pressure range 9–41 kbar. Ca in olivine decreases with increasing pressure and decreasing temperature. The pressure effect is the result of Ca going into the higher-coordination M2 site in clinopyroxene as pressure is increased. For the CaMg exchange reaction between olivine and clinopyroxene, ΔV°=0.249J bar?1 mole?1; this is sufficient for pressure estimates accurate to ±3kbar if temperatures of equilibration are independently known. CaMg exchange between olivine and orthopyroxene is not sufficiently pressure dependent to be used as a geobarometer.Application of the olivine-clinopyroxene geobarometer to coarse garnet lherzolites from southern Africa gives P-T results consistent with a continental geotherm. For spinel lherzolites from southwestern United States, the geotherm appears to be displaced to higher temperatures indicating oceanic affinities. Application of the geobarometer to natural systems requires assumptions about activity relationships in clinopyroxene which should be checked by experiment.  相似文献   

17.
The thermal expansion of stishovite has been determined by an X-ray camera technique in a temperature range of 18 – 600°C at an atmospheric pressure. The thermal-expansion coefficients along the crystallographic a- and c-axes at 300 K are αa = (6.0 ± 0.6) · 10?6K?1 and αc = (1.4 ± 0.5) · 10?6K?1, respectively. The volume coefficient at 300 K is αν = (13.5 ± 0.6) · 10?6K?1.  相似文献   

18.
An apparatus designed to determine the complex shear modulus of rock samples by forced torsion oscillations at high temperature and in the seismic frequency band 0.003–30 Hz is briefly described. Measurements were performed on natural dunite from Åheim (Norway) up to 1400°C and on polycrystalline forsterite up to 1500°C at 1 atm pressure. The two materials were chosen to study, by comparison, the effect of melt on the elasticity and anelasticity of mantle rocks.Between 1000 and 1200°C the absolute values of the shear modulus G are almost equal for both materials. Above 1200°C G for natural dunite decreases progressively with temperature and at 1400°C and 1 Hz reaches ～13 of its value at 1100°C. In contrast, G of pure forsterite depends little on temperature. For petrological reasons, supported by simultaneous measurements of the electric resistivity, there is strong evidence that the decrease of G in dunite above 1200°C is due to melt from the lower melting components of the dunite. Based on different models estimates of the melt fraction are made.At high temperature, in both materials Q?1 is characterized by a monotonic decrease with frequency according to ω?α, with α ≈ 0.25. An apparent activation energy of 38±5 kcal mol?1 for forsterite and 48±8 kcal mol?1 for dunite was found with no significant change in the regime of partial melting. From this it is concluded that Q?1, even at partial melting, is dominated by solid state high temperature background absorption. There is no indication from these experiments for a constant-Q-band at low seismic frequencies or an increase of Q proportional to frequency as suggested by some seismologists. The present results are in good qualitative agreement with those for Young's modulus obtained previously by strain retardation experiments.  相似文献   

19.
The diffusivity of18O in forsterite Mg2SiO4 has been measured in the temperature range 1150–1600°C. The activation energy of oxygen self-diffusion in this silicate is found to equal0.32 ± 0.04MJ/mol(77 ± 10kcal/mol), and there is no dependence of the diffusivity upon the oxygen partial pressure surrounding the samples. The diffusion profiles were analysed either with an ion probe or by means of the18O(p, α)15N nuclear reaction. The latter method made use of a resonance in the nuclear cross-section in the case of diffusion profiles shorter than 100 nm (1000Å); for diffusion profiles up to 4 μm the same reaction was used, but in a non-resonant mode. New data on creep in forsterite and natural olivine are also given, including the influence of the oxygen partial pressurepO2 which is zero for forsterite and proportional to(pO2)16 for natural olivine. From this set of data we infer the possible relationship between diffusion and creep for these materials. This relationship may be more complicated than that predicted by simple climb mechanism.  相似文献   

20.
Illite clay particles with adsorbed137Cs were added as a submillimeter layer to the surface of silt-clay sediments contained in rectangular Plexiglas cells stored in a temperature-regulated aquarium, in order to trace the effect of the oligochaete, Tubifex tubifex, and the amphipod, Pontoporeia hoyi, on mass redistribution near the sediment-water interface. A well-collimated NaI gamma detector scanned each sediment column (～10 cm deep) at daily or weekly intervals for six months, depicting the time evolution of radioactivity with and without added benthos. In a cell with tubificids (～5 × 104 m?2), which feed below 3 cm and defecate on surface sediments, the labeled layer was buried at a rate of 0.052 ± 0.007 cm/day (20°C). When labeled particles entered the feeding zone,137Cs reappeared in surface sediments creating a bimodal activity profile. In time, the activity tended toward a uniform distribution over the upper 6 cm, decreasing exponentially below to undetectable levels by 9 cm. In a cell with amphipods (～1.6 × 104 m?2) uniform activity developed rapidly (～17 days) down to a well-defined depth (1.5 cm). The mixing of sediments by Pontoporeia is described by a simple quantitative model of eddy diffusive mixing of sediment solids. The value of the diffusion coefficient, 4.4 cm2/yr (7°C) was computed from a least squares fit of theoretical to observed profile broadening over time. In a cell without benthos, small but measurable migration of137Cs indicated an effective molecular diffusion coefficient of 0.02 cm2/yr.  相似文献   

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