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1.
Tracer diffusion coefficients of 153Gd and 152Eu in olivine tholeiite have been determined at temperatures between 1150 and 1440°C. The results are identical for both tracers within experimental error. Between 1440 and 1320°C the diffusion coefficients are given by D(Eu, Gd) = 0.058 exp(?40,600/ RT). Between 1320 and 1210°C, the diffusion coefficients are constant at D = (1.4 ± 0.4) × 10?7 cm2s?1 and between 1210 and 1150°C, the D values drop irregularly to 4 × 10?9 cm2s?1. The liquidus temperature (1270°C) lies within the region of constant D. Such anomalous behavior has not been encountered in previous studies of Ca, Sr, Ba and Co diffusion in basalt. To explain the constant D value near the liquidus, we speculate that the structure of the melt changes as a function of temperature in such a way that the normal temperature dependence of the diffusivity is compensated. For example, the rare earth ions may be displaced from their (high temperature) octahedral coordination sites to other sites where they are more readily dissociated and therefore become progressively more mobile. The behavior below 1210°C may be the result of relatively stable complexes or molecules in the melt or of the formation of a REE bearing crystalline phase that has so far escaped detection. Preliminary results for Eu diffusion in obsidian are D (Eu, 800°C) = 5 × 10?13 cm2 s?1 and D (Eu, 950°C) = 1.5 × 10?11 cm2 s?1. These data are consistent with an activation energy of 59 Kcal mole?1. These low diffusivities indicate that the partitioning of REE in crystallizing intermediate and acidic melts may be controlled by diffusion in the melt rather than equilibrium between the crystal surface and the bulk melt.The diffusion data are applied to partial melting in the mantle, in an attempt to explain how LREE enriched tholeiites may be derived from a LREE depleted mantle source. In this model LREE diffuse from garnet bearing regions that have small melt fractions into garnet free regions that have relatively large melt fractions. REE diffusion is so slow that this process is quantitatively significant only in small partially molten bodies (diameter ~1 km or less) or in larger, but strongly flattened bodies. Internal convective motion during diapiric rise would also increase the efficiency of the process.  相似文献   

2.
A workflow is described to estimate specific storage (S s) and hydraulic conductivity (K) from a profile of vibrating wire piezometers embedded into a regional aquitard in Australia. The loading efficiency, compressibility and S s were estimated from pore pressure response to atmospheric pressure changes, and K was estimated from the earliest part of the measurement record following grouting. Results indicate that S s and K were, respectively, 8.8?×?10?6 to 1.2?×?10?5 m?1 and 2?×?10?12 m s?1 for a claystone/siltstone, and 4.3?×?10?6 to 9.6?×?10?6 m?1 and 1?×?10?12 to 5?×?10?12 m s?1 for a thick mudstone. K estimates from the pore pressure response are within one order of magnitude when compared to direct measurement in a laboratory and inverse modelled flux rates determined from natural tracer profiles. Further analysis of the evolution and longevity of the properties of borehole grout (e.g. thermal and chemical effects) may help refine the estimation of formation hydraulic properties using this workflow. However, the convergence of K values illustrates the benefit of multiple lines of evidence to support aquitard characterization. An additional benefit of in situ pore pressure measurement is the generation of long-term data to constrain groundwater flow models, which provides a link between laboratory scale data and the formation scale.  相似文献   

3.
In order to test the chronometer qualities of speculante for the (U + Th)/He dating method, 4He release experiments by stepwise heating of two specularites from the Rimbach mineralization locality in the southern Vosgues (France) have been carried out. The diffusion coefficients define linear Arrhenius plots within a temperature interval of 250 to 830 °C, which is suggestive of volume diffusion. Extrapolation of the diffusion behavior to 20° C yields diffusion coefficients (D20 values) smaller than 10?26 [cm2 s?1] for both hematites with activation energies at 116 [kJ/mole]. The results of our study suggest that specularite is a very helium retentive hematite variety which is capable of quantitatively retaining radiogenic helium over geologic periods of time.  相似文献   

4.
The weathering rates and mechanisms of three types of glassy rocks were investigated experimentally at 25 °C, pH 1.0 to 6.2, and reaction times as much as to 3 months. Changes in major element chemistry were monitored concurrently as a function of time in the aqueous solution and within the near surface region of the glass. Leach profiles, obtained by a HF leaching technique, displayed near-surface zones depleted in major cations. These zones increased in depth with increasing time and decreasing pH of reactions. Release rates into the aqueous solution were parabolic for Na and K and linear for Si and Al. A coupled weathering model, involving surface dissolution with concurrent diffusion of Na, K, and Al, produced a mass balance between the aqueous and glass phases. Steady state conditions are reached at pH 1.0 after approximately 3 weeks of reaction. Steady-state is not reached even after 3 months at pH 6.2.An interdiffusion model describes observed changes in Na diffusion profiles for perlite at pH 1.0. The calculated Na self-diffusion coefficient of 5 × 10?19 cm2·s?1 at 25°C approximates coefficients extrapolated from previously reported high temperature data for obsidian. The self-diffusion coefficient for H3O+, 1.2 × 10?20 cm2·s?1, is similar to measured rates of water diffusion during hydration of obsidian to form perlite.  相似文献   

5.
Interdiffusion coefficients of Al + Al vs. Mg + Si in the gehlenite–åkermanite system of melilite were determined by coupled annealing of synthesized end-member single crystals. The observed diffusion coefficients for a couple-annealed sample vary for about 2 orders of magnitude, showing strong dependence on the gehlenite–åkermanite composition: diffusion coefficient observed at 1350 °C, for example, is 3 × 10?13 cm2 s?1 at 5 mol% åkermanite composition (Ak5), increases to 2 × 10?11 cm2 s?1 at Ak80, and then decreases to 1 × 10?12 cm2 s?1 at Ak95. The diffusion coefficient–temperature relation indicates high activation energy of diffusion of about 420 kJ mol?1 for gehlenite-rich melilite. The observed diffusion coefficient–composition relation may be explained by a combination of (1) the diffusion coefficient–melting temperature relation (Flynn's rule) and (2) the feasibility of local charge compensation, which can possibly be maintained more easily in the intermediate chemical composition. The high activation energy value for gehlenitic melilite appears to correspond to the complex diffusion mechanism. The observed highly variable diffusion coefficients suggest that gehlenite–åkermanite zoning in the melilite crystals in Ca, Al-rich inclusions in the carbonaceous meteorites may provide a sensitive indicator for the thermal history of the inclusions.  相似文献   

6.
The dissolution of chrysotile is studied in regard to the surfaces analysis by photoelectron spectrometry. After leaching of chrysotile (Provenance: Thetford; about 200 mg of fibers of 1 cm length) in nonstirred 0.1 N oxalic conditions, the composition of the mineral surfaces is determined by XPS; kinetic curves of dissolution are given in the range 22–80°C. Two conditions for the rate-limiting step are involved for the explanation of the dissolution: diffusion of Mg2+ through the fibrous gel or dissociation of chrysotile. By the former, some values of the diffusion coefficient are proposed: D varies from 5·10?19 cm2s?1 to 5·10?16 cm2s?1, in the range 22–80°C. By the second model, the leaching rate is estimated from 3 Å (22°C) per h to 250 Å (80°C) per h. For the 2 models, the activation heat energy is in the range 15–20 Kcal.  相似文献   

7.
《Applied Geochemistry》1998,13(6):707-714
The properties of fluorapatite, both a useful radiochronometer and a potential storage matrix specific for minor actinides produced by the reprocessing of spent nuclear fuel, have been investigated with emphasis to its response to alpha decay. Exfoliation, which occurs after implantation of high doses of 1.6-MeV He-ions (>1.4×1017 ions cm−2, corresponding to 5% atomic proportion), could set an upper limit to the concentration of imbedded actinides (about 2 atoms % corresponding to 20 wt. %) or storage age unless significant diffusion of radiogenic He intervenes. This process has been studied by combining He implantation, thermal treatments in the temperature range 124–250°C and measurement of the resulting He profile by an ion beam technique (ERDA) using 8.5-MeV C ions. The diffusion coefficient follows an Arrhenius' law with an activation energy of 120 (±2) KJ/mole and a frequency factor of 14.5 (±7)×10−3 cm2 sec−1 in agreement with literature data. The inferred closure temperature which validates the U,Th–He radiochronological method also fits previous values: 97 (±10)°C for grain size 165 μm. With respect to radwaste disposal. He volume diffusion is too small to exclude the occurrence of exfoliation unless diffusion at grain boundary is much higher and a fine-grain matrix is deliberately chosen.  相似文献   

8.
Electron transport properties of single crystal and polycrystalline natural mineral galena (PbS) samples from the Trep?a mine, Yugoslavia, were determined using the photoacoustic frequency transmission technique. Their thermal diffusivity (D T≈0.16 × 10?5 m2 s?1), the coefficient of diffusion (D between 0.15×10?2 0.16×10?2 m2 s?1) and lifetime of the excess carrier (τ≈35 μs and the front and rear recombination velocity (s g≈65.5 m s?1 and s b≈66.4 m s?1, respectively), were calculated by comparing the experimental results and the theoretical photoacoustic amplitude and phase signals. The lattice parameter obtained by X-ray work was a?=5.936?Å. The free carrier concentration of these single-crystal samples was measured using the Hall method (N?=?3×1018 cm?3). Measurements of the optical reflectivity of the same samples, as a function of wavelength, in the infrared and far infrared ranges, were performed. In the far infrared range a free electron plasma frequency was observed and numerically analyzed, using the least-squares fitting procedure. The values of optical parameters were calculated and the value of the free carrier concentration obtained by the Hall method was confirmed.  相似文献   

9.
Ground waters in a Precambrian granitic batholith at the Whiteshell Nuclear Research Establishment (WNRE) in Pinawa, Manitoba contain between 5 × 10?5 and 10?1 cc STP/gH2O of radiogenic helium-4 but have relatively uniform 3He/4He ratios of between 0.6 × 10?8 and 2.3 × 103. The highest helium samples also contain radiogenic 21,22Ne produced by (α,n) or (n,α) reactions with other isotopes. As much as 1.8 × 10?9ccSTP/gH2O of excess 21Ne and 3.8 × 10?9ccSTP/gH2O of excess 22Ne have been measured. Helium and 21Ne ages of these ground waters, calculated on the basis of known crustal production rates of 4He and 21Ne, are unreasonably high (up to 2 × 105 years) and incompatible with the 14C ages and other isotopic and hydrogeologic data. Uranium enrichment in the flow porosity of the granite may dominate 4He and 21,22Ne production in this granite and mask the contributions from more typical U and Th concentrations in the rock matrix.At the Chalk River Nuclear Laboratories in Ontario helium concentrations in ground waters in a Precambrian monzonitic gneiss range from 1.5 × 10?7 to 8.7 × 10?4ccSTP/gH2O with the 3He/4He ratios ranging from 2.0 × 10?3 to 1.5 × 10?7. The highest helium concentrations may be attributable to the presence of a thick uraniferous pegmatite vein and yield helium ages more than two orders of magnitude higher than the 14C ages. Application of He age dating equations to ground waters from Precambrian granitic rocks requires knowledge of the nature of uranium and thorium enrichment in the subsurface in order to select appropriate values for porosity and uranium and thorium concentration in the rock.  相似文献   

10.
The kinetics of zoned garnet porphyroblast growth is exemplified in a sample of garnet-staurolite-biotite schist from the northern Ladoga region. The diffusion-controlled porphyroblast growth was accompanied by a decrease in the kinetic coefficient during phase reactions. Even at insignificant (1–2°C) thermal overstepping, the leading role of diffusion as a factor that controls kinetics of porphyroblast growth in medium-grade metapelites is consistent with the parameters of metamorphic crystallization: T = 500–650°C, t = 1 Ma; D A1 app = 10?14 cm2/s, L = 0.2–0.6 cm, r = 1–3 mm, ΔC Al = 1.5 × 10?4–1.5 × 10?3 mol/cm3.  相似文献   

11.
Helium‐3 is a stable cosmogenic isotope that can be used to determine the time interval during which a rock sample has been at or close to the Earth’s surface. As a result of the high production rate of ‘cosmogenic’3He (≈ 130 at g?1 year?1) and the low detection limit of modern mass spectrometers, it is possible to date exceptionally young surfaces (≈ 1000 years). The precision and accuracy of cosmogenic 3He measurements depend critically on the passive helium blank (produced by the metalwork of the extraction furnace) which can be significant relative to the sample signals. We have developed and constructed, at the CRPG (Nancy, France), a new high temperature furnace (< 1500 °C) to extract helium in minerals such as apatite, pyroxene and olivine at 1050, 1350 and 1450 °C, respectively. The furnace demonstrated an excellent helium extraction yield (> 99% for olivine and pyroxene for heating times of 20–30 min and temperatures in the range 1050–1450 °C) and low residual helium contributions (the blank, obtained under the same analytical conditions as for sample extraction: 1 × 10?15 mole 4He and < 4 × 10?21 mole 3He). This is approximately an order of magnitude lower than those reported by other laboratories using conventional furnaces.  相似文献   

12.
The validity of the thermodynamic cBΩ model is tested in terms of the experimentally determined diffusion coefficients of He in a natural Fe-bearing olivine (Fo90) and a synthetic end-member forsterite (Mg2SiO4) over a broad temperature range (250–950 °C), as reported recently by Cherniak and Watson (Geochem Cosmochim Acta 84:269–279, 2012). The calculated activation enthalpies for each of the three crystallographic axes were found to be (134 ± 5), (137 ± 13) and (158 ± 4) kJ mol?1 for the [100], [010] and [001] directions in forsterite, and (141 ± 9) kJ mol?1 for the [010] direction in olivine, exhibiting a deviation of <1 % with the corresponding reported experimental values. Additional point defect parameters such as activation volume, activation entropy and activation Gibbs free energy were calculated as a function of temperature. The estimated activation volumes (3.2–3.9 ± 0.3 cm3 mol?1) of He diffusion in olivine are comparable with other reported results for hydrogen and tracer diffusion of Mg cations in olivine. The pressure dependence of He diffusion coefficients was also determined, based on single experimental diffusion measurements at 2.6 and 2.7 GPa along the [001] direction in forsterite at 400 and 650 °C.  相似文献   

13.
The infinite dilution diffusion coefficient for Al(OH)4? necessary to calculate fluxes of dissolved Al between sediments and overlying waters, was determined at 25°C. Measurements were made using the diaphragm-cell method by diffusing Al(OH)4? spiked KBr solutions against KCL over a range of ionic strengths. The mean of 9 separate measurements gives 1.04 ± .02 × 10?5cm2/s as the infinite dilution diffusion coefficient for Al(OH)4? at 25°C.  相似文献   

14.
The solubility of quartz in water from 25° to 900°C at specific volume of the solvent ranging from about 1 to 10 and from 300° to 600°C at specific volume of the solvent ranging from about 10 to 100 is given by an empirically derived equation of the form: log m = A + B(log V) + C(log V)2 where m is the molal silica concentration, V is the specific volume of pure water, and A = ?4.66206 + 0.0034063T + 2179.7T?1 ? 1.1292 × 106T?2 + 1.3543 × 108T?3B = ?0.0014180T— 806.97T?1C = 3.9465 × 10?4T T is temperature in kelvins. The experimental data used in formulating the empirical relation ranged in pressure from 1 bar at 25°C to about 10,000 bars at 900°C, and the lowest pressure in the low-density steam region was about 30 bars. According to the above equation, the average difference in molality between 518 measured and calculated solubilities is ?0.016 m with a standard deviation of 0.089.  相似文献   

15.
About possibility of isotope dating of native gold by the (U-Th)/He method   总被引:2,自引:0,他引:2  
For investigation of helium in native gold, a new measuring complex was created and used: the high sensitivity mass spectrometer MSU-G (ZAO SKB “SPECTRON”). The sensitivity of measuring 4He was 5.3 × 10?13 cm3/g per impulse. Experiments in stepwise heating of samples have been carried out, and the kinetics of radiogenic 4He emanation from native gold was investigated. Migration parameters (activation energy and frequency factor) were determined. Model calculations of stability (closure temperature) of radiogenic 4He in the native gold structure with a given time and temperature of thermal influences were made using the data received. The concentration of 4He in native gold from the original deposit Nesterovskoe is (4.7 ± 0.1) × 10?5 cm3/g in the sample from the placer; from Chudnoe deposit, it is (3.8 ± 0.1) × 10?5 cm3/g; from sulfide deposits of Kitoiskii knot of Eastern Sayani, it is (1.9 ± 0.1) × 10?5 cm3/g; and from the South Muiskii ore region it is (8.7 ± 0.5) × 10?7 cm3/g. The received curve lines of kinetics of 4He emanation from native gold show that radiogenic helium is well bonded in the native gold structure: in all the examined samples, most 4He emanates only by reaching the temperature of 950–1000°C. A specific feature of the kinetics of radiogenic 4He emanation in all examined samples is an outburstlike emanation in the form of a peak of large amplitude in the area of temperatures near the melting temperature point of gold. This is stipulated by the existence of helium bubbles released by metals only while they melt. The spectrum of helium thermal desorption from native gold has a complicated form and is a result of superposition of several peaks. This proves the migration of groups of atoms located in the gold structure in different energy states. Very large values of the activation energy of helium migration from native gold were received: up to 161–176 kcal/mol. Extremely large values of the frequency factor, from 2 × 1018 to 3 × 1032, correspond to such values of activation energies. This is caused probably by helium migration in the form of gas bubbles. The received data indicate the very high stability of the (U-Th)/He isotope system in native gold. Using the (U-Th)/He method of isotope geochronology seems to be very promising for isotope dating of these strategic raw materials.  相似文献   

16.
We have investigated the effect of undercooling and deformation on the evolution of the texture and the crystallization kinetics of remelted basaltic material from Stromboli (pumice from the March 15, 2007 paroxysmal eruption) and Etna (1992 lava flow). Isothermal crystallization experiments were conducted at different degrees of undercooling and different applied strain rate (T = 1,157–1,187 °C and $ \dot{\gamma }_{i} $ γ · i  = 4.26 s?1 for Stromboli; T = 1,131–1,182 °C and $ \dot{\gamma }_{i} $ γ · i  = 0.53 s?1 for Etna). Melt viscosity increased due to the decrease in temperature and the increase in crystal content. The mineralogical assemblage comprises Sp + Plg (dominant) ± Cpx with an overall crystal fraction (?) between 0.06 and 0.27, increasing with undercooling and flow conditions. Both degree of undercooling and deformation rate deeply affect the kinetics of the crystallization process. Plagioclase nucleation incubation time strongly decreases with increasing ΔT and flow, while slow diffusion-limited growth characterizes low ΔT—low deformation rate experiments. Both Stromboli (high strain rate) and Etna (low strain rate) plagioclase growth rates (G) display relative small variations with Stromboli showing higher values (4.8 ± 1.9 × 10?9 m s?1) compared to Etna (2.1 ± 1.6 × 10?9 m s?1). Plagioclase average nucleation rates J continuously increase with undercooling from 1.4 × 106 to 6.7 × 106 m?3 s?1 for Stromboli and from 3.6 × 104 to 4.0 × 106 m?3 s?1 for Etna. The extremely low value of 3.6 × 104 m?3 s?1 recorded at the lowest undercooling experiment for Etna (ΔT = 20 °C) indicates that the crystallization process is growth-dominated and that possible effects of textural coarsening occur. G values obtained in this paper are generally one or two orders of magnitude higher compared to those obtained in the literature for equivalent undercooling conditions. Stirring of the melt, simulating magma flow or convective conditions, facilitates nucleation and growth of crystals via mechanical transportation of matter, resulting in the higher J and G observed. Any modeling pertaining to magma dynamics in the conduit (e.g., ascent rate) and lava flow emplacement (e.g., flow rate, pāhoehoe–‘a‘ā transition) should therefore take the effects of dynamic crystallization into account.  相似文献   

17.
Sized aggregates of glasses (47–84 wt% SiO2) were fused from igneous-derived cohesive fault rock and igneous rock, and step-heated from ~400 to >1,200 °C to obtain their 39Ar diffusion properties (average E=33,400 cal mol?1; D o=4.63×10?3 cm2 s?1). At T<~1,000 °C, glasses containing <~69 wt% SiO2 and abundant network-forming cations (Ca, Fe, Mg) reveal moderate to strong non-linear increases in D and E, reflecting structural modifications as the solid transitions to melt. Extrapolation of these Arrhenius properties down to typical geologic T-t conditions could result in a 1.5 log10 unit underestimation in the diffusion rate of Ar in similar materials. Numerical simulations based upon the diffusion results caution that some common geologic glasses will likely yield 40Ar/39Ar cooling ages rather than formation ages. However, if cooling rates are sufficiently high, ambient temperatures are sufficiently low (e.g., <65–175 °C), and coarse particles (e.g., radius (r) >~1 mm) are analyzed, glasses with compositions similar to ours may preserve their formation ages.  相似文献   

18.
The solubility and dissolution kinetics of apatite in felsic melts at 850°–1500°C have been examined experimentally by allowing apatite crystals to partially dissolve into apatite-undersaturated melts containing 0–10 wt% water. Analysis of P and Ca gradients in the crystal/melt interfacial region enables determination of both the diffusivities and the saturation levels of these components in the melt. Phosphorus diffusion was identified as the rate-limiting factor in apatite dissolution. Results of four experiments at 8 kbar run in the virtual absence of water yield an activation energy (E) for P diffusion of 143.6 ± 2.8 kcal-mol?1 and frequency factor (D0) of 2.23+2.88?1.26 × 109cm2-sec?1. The addition of water causes dramatic and systematic reduction of both E and D0 such that at 6 wt% H2O the values are ~25 kcal-mol?1 and 10?5 cm2-sec?1, respectively. At 1300°C, the diffusivity of P increases by a factor of 50 over the first 2% of water added to the melt, but rises by a factor of only two between 2 and 6%, perhaps reflecting the effect of a concentration-dependent mechanism of H2O solution. Calcium diffusion gradients do not conform well to simple diffusion theory because the release of calcium at the dissolving crystal surface is linked to the transport rate of phosphorus in the melt, which is typically two orders of magnitude slower than Ca. Calcium chemical diffusion rates calculated from the observed gradients are about 50 times slower than calcium tracer diffusion.Apatite solubilities obtained from these experiments, together with previous results, can be described as a function of absolute temperature (T) and melt composition by the expression: In Dapatite/meltP = [(8400 + ((SiO2 ? 0.5)2.64 × 104))/T] ? [3.1 + (12.4(SiO2 ? 0.5))] where SiO2 is the weight fraction of silica in the melt. This model appears to be valid between 45% and 75% SiO2, 0 and 10% water, and for the range of pressures expected in the crust.The diffusivity information extracted from the experiments can be directly applied to several problems of geochemical interest, including I) dissolution times for apatite during crustal anatexis, and 2) pileup of P, and consequent local saturation in apatite, at the surfaces of growing major-mineral phases.  相似文献   

19.
Cobalt and magnesium interdiffusion coefficients in synthetic crystals of olivine have been determined by a method of couple annealing. These coefficients increase with temperature and Co concentration. The coefficients in forsterite along the c crystallographic axis range from 1.13 × 10?12 to 6.85 × 10?11 cm2sec?1 at temperatures ranging from 1150 to 1400°C. The calculated activation energies for Co-Mg interdiffusion in forsterite are 526 kJmol?1 above approximately 1300°C and 196 kJmol?1 at lower temperatures. These results indicate that the Co-Mg mobility in olivine is relatively low compared to published results for Fe-Mg interdiffusion.  相似文献   

20.
Metasomatic reactions between quartz and incompatible oxides or hydroxides were experimentally studied at 550°C and 1000 bars water pressure. Two porous pellets of the initial reagents pressed one against the other were used. Reaction rims in the millimeter range develop at the initial boundary in the oxide pellet. All the experiments show that an important transfer of silica occurs by diffusion in the stationary intergranular solution.The chemical transfer of silica through the intergranular fluid is quantitatively determined by studying the kinetics of growth of the forsterite rim in the system quartz-brucite. The kinetics limiting stage being silica transfer, the experiments allow the determination of the diffusion coefficient of silica through the solution. At 550°C and 1000 bars, a value of 2.4 × 10?1cm2 s1 is found.This high value shows the importance of chemical diffusion in the intergranular fluid of rocks during metamorphic processes.  相似文献   

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