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1.
A kinetic model for the rate of iron-hydrogen redox exchange in silicate glasses and melts has been derived from time-series experiments performed on natural rhyolitic obsidians. Cylinders of the starting glasses were exposed to reducing mixtures composed of H2-Ar-CO2-CO in 1-atm furnaces and H2-Ar in a cold seal pressure vessel. Overall, runs covered the temperature range 300 to 1000°C. The progression of a front of ferric iron reduction within the quenched melt was observed optically through a change of color. For all run conditions, the advancement of the front (ξ) was proportional to the square root of time, revealing the reaction as a diffusion-limited process. Iso-fO2 runs performed in CO2-CO, H2-Ar, and H2-CO2 gases have shown that fH2 rather than fO2 is the dominant parameter controlling the reaction rate. The fH2 dependence of the rate constant was characterized in the range 0.02 to 70 bar. The growth of the reduced layer, which is accompanied by an increase in reaction-derived OH-group content, was fitted considering that the reaction rate is controlled by the migration of a free mobile species (H2) immobilized in the form of OH subsequent to reaction with ferric iron. The reaction rate is thus a function of both solubility and diffusivity of H2 weighted by the concentration of its sink (ferric iron). We extracted a single law for both solubility and diffusivity of H2 in amorphous silicates that applies over a range of temperatures below and above the glass transition temperature. Melt/glass structure (degree of polymerization) does not seem to significantly affect both solubility and diffusivity of H2. We therefore provide a model that allows the prediction of oxidation-reduction rates in the presence of hydrogen for a wide range of compositions of amorphous glasses and melts. Comparisons with previous work elucidating rate of redox exchange in dry systems allow us to anticipate the fH2-T domains where different redox mechanisms may apply. We conclude that equilibration of redox potential in nature should be dominated by H2 transfer at a rate controlled by both H2 solubility and diffusion. Numerical applications of the model illustrate redox exchanges in natural magmas and in glasses exposed to weathering under near surface conditions. We show that crustal events such as magmas mixing should not modify the iron redox state of magmas. In the case of nuclear-waste-bearing glasses, the fH2 conditions in the host terrain are clearly a parameter that must be taken into account to predict glass durability.  相似文献   

2.
The possibility of shock wave-induced interaction between meteoritic iron was estimated based on the results of experiments on the shock wave loading of mixtures of kamacite from the Sikhote Alin iron meteorite with quartz, albite, oligoclase, enstatite, olivine, and serpentine. The experimental samples were then examined with the application of optical microscopy, microprobe analysis, and M?ssbauer spectroscopy. As a result of shock wave load, the metal was proved to become enriched in Si, while the quartz, albite, and oligoclase melted glasses acquired bivalent Fe ions. The products of our experiments with quartz and feldspar mixtures with kamacite were determined to contain paramagnetic metallic iron, and the surroundings of iron atoms in the silicate constituent of the olivine and enstatite mixtures with kamacite become locally more heterogeneous. Our results indicate that shock waves induce redox reactions between Fe and silicates according to the scheme 2Fe+2 + Si+4 = 2Fe+2 + Si0, where Fe0 and Si0 are iron and silicon in metal and Fe+2 and Si+4 are iron and silicon in the sillimanite matrix.  相似文献   

3.
We have analysed the kinetics of Argon and CO2 diffusion in simplified iron free rhyolitic to hawaiitic melts using the diffusion couple technique. The concentration distance profiles of Ar and CO2 were measured with electron microprobe analysis and Fourier Transform Infrared Spectroscopy, respectively. Error functions were fitted to the symmetrical concentration distance profiles to extract the diffusion coefficients.In the temperature range 1373 to 1773 K the activation energies for Ar diffusion range from 169 ± 20 to 257 ± 62 kJ mol−1. Ar diffusivity increases exponentially with the degree of depolymerisation. In contrast, the mobility of total CO2, that is identical to Ar mobility in rhyolitic melt, keeps constant with changing bulk composition from rhyolite to hawaiite. CO2 speciation at 1623 K and 500 MPa was modeled for the range of compositions studied using the diffusion data of Ar and total CO2 in combination with network former diffusion calculated from viscosity data. Within error this model is in excellent agreement with CO2 speciation data extrapolated from temperatures near the glass transition temperature for dacitic melt composition. This model shows that even in highly depolymerised hawaiitic and tholeiitic melts molecular CO2 is a stable species and contributes 70 to 80% to the total CO2 diffusion, respectively.  相似文献   

4.
A series of powdered and oriented single crystals of riebeckite-arfvedsonite have been examined with the Mössbauer technique above and below the magnetic ordering temperatures. Using fitted spectra that result in essentially similar quadrupole pairs, site occupancies were determined for 5 samples. Fitted spectra of oriented single crystals are associated with inequal pairs. The quadrupole splitting and isomer shifts are indistinguishable from those of the powdered samples. For the purpose of determining site occupancy paramagnetic spectra at L.N. temperatures appear to have little advantage over those obtained at room temperatures. The use of cryogenics to obtain magnetic hyperfine splitting increases experimental times several fold; however we conclude that in most cases the additional information and greater accuracy of Fe+2/Fe+3 warrants the additional effort. Magnetic order detected at cryogenic temperatures has an overall antiferromagnetic character. The orientation of the magnetic moment for Fe+3 is not parallel to a principal crystallographic axis, and its orientation near 〈316〉 suggests that there is magnetic coupling between the cation ribbons containing the octahedrally coordinated iron. The magnetic behavior can be interpreted satisfactorily using the Ising model developed for two dimensional lattices and extended to loosely coupled chains.  相似文献   

5.
The glass transition temperatures and the thermal expansions both below and above the glass transition temperature region of synthetic glasses of compositions close to those of plagioclases have been determined. The linear thermal expansion coefficient of the rigid glasses decreases on average from 7.4×10–6/dgC for albite glass to 4.9×10–6/dgC for glass close to anorthite composition. The glass transition temperature of the glasses initially decreases from 763° C for albite glass to 752°C for An9.7 glass and then increases nearly linearly with further increasing anorthite content to 813° C for glass close to anorthite composition.—Measurements made for comparison on a glass prepared from Madagascar orthoclase yielded a linear thermal expansion coefficient of 6.1×10–6/dgC and a glass transition temperature of 905° C.The variations in thermal expansion and glass transition temperature of the feldspar glasses with composition are discussed in terms of structural changes which are assumed to be associated with cation replacement.  相似文献   

6.
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   

7.
Isothermal solid state experiments on the diffusion of Cu, Fe, Zn and In and related effects have been carried out in sphalerite single crystals. The driving force for the diffusion and corresponding reactions are chemical potential gradients which are established by differences in sulfur fugacity, oxygen fugacity and the chemical activity between sulfide powders as metal sources and receptor crystals.Studies in the system ZnS-CuInS2 show replacement rims in sphalerite produced by the formation of solid solutions between ZnS and CuInS2. These differences reflect the extent of mutual solid solution. The composition profiles of these rims at different temperatures and sulfur fugacities are calculated to diffusion coefficients for the coupled substitution of Cu+ + In3+ versus 2 Zn2+. The interdiffusion coefficients of (Cu + In) in Fe-free sphalerite at the Fe/FeS sulfur fugacity of the sources obey to the relation:  相似文献   

8.
Iron isotopic compositions measured in chondrules from various chondrites vary between δ57Fe/54Fe = +0.9‰ and −2.0‰, a larger range than for igneous rocks. Whether these compositions were inherited from chondrule precursors, resulted from the chondrule-forming process itself or were produced by later parent body alteration is as yet unclear. Since iron metal is a common phase in some chondrules, it is important to explore a possible link between the metal formation process and the observed iron isotope mass fractionation. In this experimental study we have heated a fayalite-rich composition under reducing conditions for heating times ranging from 2 min to 6 h. We performed chemical and iron isotope analyses of the product phases, iron metal and silicate glass. We demonstrated a lack of evaporation of Fe from the silicate melt in similar isothermal experiments performed under non-reducing conditions. Therefore, the measured isotopic mass fractionation in the glass, ranging between −0.32‰ and +3.0‰, is attributed to the reduction process. It is explained by the faster transport of lighter iron isotopes to the surface where reduction occurs, and is analogous to kinetic isotope fractionation observed in diffusion couples [Richter, F.M., Davis, A.M., Depaolo, D.J., Watson, E.B., 2003. Isotope fractionation by chemical diffusion between molten basalt and rhyolite. Geochim. Cosmochim. Acta67, 3905-3923]. The metal phase contains 90-99.8% of the Fe in the system and lacks significant isotopic mass fractionation, with values remaining similar to that of the starting material throughout. The maximum iron isotope mass fractionation in the glass was achieved within 1 h and was followed by an isotopic exchange and re-equilibration with the metal phase (incomplete at ∼6 h). This study demonstrates that reduction of silicates at high temperatures can trigger iron isotopic fractionation comparable in its bulk range to that observed in chondrules. Furthermore, if metal in Type I chondrules was formed by reduction of Fe silicate, our observed isotopic fractionations constrain chondrule formation times to approximately 60 min, consistent with previous work.  相似文献   

9.
Hydrogen defect saturation in natural pyroxene   总被引：1，自引：0，他引：1  
Dehydration via the redox reaction: OH? + Fe2+ ? O2? + Fe3+ + ½H2 is believed to be a commonly occurring process in pyroxenes and other nominally anhydrous minerals (NAMs) from the upper mantle and appears to be fast enough to allow significant dehydration during magma ascent. Nevertheless, the mobility of hydrogen incorporating defects is controlled by cation diffusion with approximately two orders of magnitude slower reaction kinetics than the iron redox reaction, and host defects have a much higher likelihood to be preserved than the hydrogen itself. Therefore, restoring hydrogen into the structure would be possible by driving the redox reaction backwards, as long as temperature and time are limited so as not to change the defect state of the crystal structure. Here we investigate the re-hydration capacity of megacryst and xenocryst ortho- and clinopyroxene by stepwise thermal annealing of crystallographically oriented samples in 1 atm H2. H concentration was measured by FTIR spectroscopy after each annealing step. Most samples show only a small increase in water content up to a presumed saturation level, after which further heat treatments in H2 resulted in a slight decrease in water contents. However, two of the studied samples, both fairly Fe rich megacrysts, are significantly rehydrated. Some samples or crystal sections exhibit a practically inert behavior, with minor fluctuations around initial water concentrations. Present results indicate that most mantle pyroxenes have not been substantially dehydrated during late stage magma processes, and that restoring water is possible in samples which have lost considerable amounts of water.  相似文献   

10.
The kinetics of calcite dissolution in aqueous KCl-solutions far from equilibrium, between 1 and 62°C in the pH-range 2.7 to 8.4 have been investigated using a rotating disc apparatus. At neutral and alkaline pH in the mixed kinetic regime the empirical apparent activation energy (EAAE) for the surface chemical reaction rate constant is 54 ± 4 kJ mole?1 for Carrara marble and 46 ± 4 kJ mole?1 for Iceland spar. Under similar conditions the EAAE of the transport rate constant increases with decreasing temperature, but has a mean value of 27 ± 2 kJ mole?1. The corresponding diffusion coefficient has a mean EAAE of 37 ± 3 kJ mole?1 and this high EAAE is consistent with transport dependence on product diffusion in this H+-independent regime.In contrast, in acid solutions, where the rate approaches end-member transport control, the EAAE of the diffusion coefficient is 16 kJ mole?1, also decreasing with increasing temperature. This is compatible with H+-diffusion to the surface being rate-controlling.In inhibitor-free natural systems, calcite dissolution kinetics far from equilibrium can be described in terms of three regimes: an H+-dependent regime (pH < 4 at 25°C), a transition regime (4 < pH < 5.5 at 25°C) and an H+-independent regime (pH > 5.5 at 25°C). At lower temperatures these boundaries move to higher pH values. The presence of inhibitors in natural systems may enhance surface controlled kinetics.  相似文献   

11.
Four major processes are observed to take place in the coastal aquifer of Israel, detectable even in the short times of water contact with the carbonate-containing host rocks. Three are chemical reactions, Ca2+-Mg2+ exchange, Na+-Ca2+ or Na+-Mg2+ base exchange, SO2?4 reduction and the fourth is dilution by freshwater. These reactions and their effects on the chemical composition of the waters were demonstrated experimentally. The range of chemical changes observed in the laboratory experiments overlap the range of the studied natural waters. This indicates that simulation of geologically long-term rock-water interaction could be achieved in laboratory experiments even at low temperatures.  相似文献   

12.
 Iron tracer diffusion experiments in diopside have been performed using natural and synthetic single crystals of diopside, and stable iron tracers enriched in 54Fe, at temperatures in the range 950–1100 °C, total pressure 1 atm, for times up to 29 days. Iron isotope diffusion profiles were determined with an ion microprobe. For experiments performed at log pO2 = −13, in directions parallel to the c axis and the b axis of two natural, low iron (Fe ∼ 1.8 at %) diopsides, the data obey a single Arrhenius relationship of the form D = 6.22−5.9 +49.6×10−15 exp(−161.5 ± 35.0 kJ mol−1/RT) m2 s−1. A single datum for iron diffusion in iron-free, single-crystal diopside at 1050 °C, is approximately 1 order of magnitude slower than in the natural crystals. The pO2 dependence of iron diffusion in natural crystals at 1050 °C (power exponent = 0.229 ± 0.036) indicates a vacancy mechanism; this is consistent with the results of unpublished atomistic simulation studies. There is no evidence of anisotropy for iron diffusion in diopside. Received: 16 March 1999 / Accepted: 10 April 2000  相似文献   

13.
The nuclear magnetic relaxation of 23Na and 29Si in albite glass and liquid has been studied from 800 K to 1400 K. The dominant spin-lattice relaxation mechanism for 23Na is found to be nuclear quadrupole interaction arising from the Na+ diffusion. The activation energy of the Na diffusion is found to be 71±3 kJ/mol, in close agreement with the results on electrical conductivity and on Na self-diffusion from radio-tracer experiments. The correlation time of the Na motion is estimated to be about 8.5×10?11 s near the melting point (～1390 K). Both nuclear dipole-dipole interaction and chemical shift anisotropy interaction are large enough to contribute to the 29Si relaxation. However, calculations based on a simplified model which employ single correlation time and exponential correlation function, with interactions typical of crystalline silicates, cannot completely account for the experimental data. NMR relaxation data also reveal that the Si motion is correlated to the Na motion and that the Si is relatively immobile. Several possible motions of SiO4 tetrahedra that can cause 29Si relaxation are suggested. The motion responsible for 29Si relaxation differs from that which is responsible for viscosity: the apparent activation energy for the former is much lower. Measurements of spin-spin relaxation times and linewidths are also presented and the significance of their temperature dependence is discussed.  相似文献   

14.
Orthopyroxene porphyroblasts zoned to interiors abnormally low in Al and Cr and containing numerous inclusions of olivine occur in some spinel peridotite xenoliths from the Colorado Plateau. Rims of these orthopyroxene grains contain 2.5–3.0 wt% Al2O3, consistent with equilibration in spinel peridotite at temperatures near 850 °C, but interiors contain as little as 0.20 wt% Al2O3 and 0.04 wt% Cr2O3. The Al-poor compositions are inferred to have equilibrated in chlorite peridotite, before porphyroblast growth during heating and consequent reactions that eliminated talc, tremolite, and chlorite. The distinctive orthopyroxene textures are inferred to have formed during reaction of talc and olivine. Rare intergrowths of orthopyroxene plus diopside are attributed to olivine-tremolite reaction. Al and Cr have gradients at grain rims that appear little modified by diffusion, but divalent elements are almost homogeneous throughout the porphyroblasts. Judging from the relative gradients, diffusion of Ca was at least 100 times faster than that of Al and Cr at the temperatures near and below 850 °C. Diffusion of Al and Cr was most effective along subgrain boundaries, and along these boundaries it appears to have been at least ten times faster than within the lattice: diffusion along such boundaries may be a dominant mechanism for re-equilibration of orthopyroxene at low mantle temperatures. Orthopyroxene with similar low Al and Cr occurs in chlorite peridotite xenoliths from the Navajo field, 300 km east of the Grand Canyon localities, and in spinel peridotite xenoliths from the Sierra Nevada, 500 km west across the extended Basin and Range province. Chlorite peridotite may therefore have been a significant minor component in much of the mantle lithosphere of western North America, although evidence for it would be erased at the higher temperatures recorded by xenoliths from the Basin and Range. Chemical changes during hydration may have been important in the evolution of these mantle volumes, and the case for addition of Sr is particularly strong. Dehydration reactions during heating could have influenced patterns of extension and crustal magmatism. Received: 1 July 1996 / Accepted: 2 December 1996  相似文献   

15.
A computational study of oxygen diffusion in olivine   总被引：1，自引：1，他引：0  
Atomistic modelling techniques are used to study the rate-determining steps that limit diffusion of oxygen in forsterite. The activation energies for diffusion parallel to all three crystallographic axes by the vacancy and interstitial mechanisms are calculated. The activation energy for extrinsic vacancy diffusion is predicted to be isotropic with a barrier height of 119 kJ mol–1. Conversely, in the interstitial case it is found to be anisotropic, with extrinsic activation energies that range between 94 and 178 kJ mol–1. The effect of intrinsic defects and two typical impurities, iron and hydrogen, upon diffusion is also considered. We find that the migration energy is slightly higher in iron-rich fayalite compared with forsterite and that the presence of hydrogen defects will not affect the diffusion mechanism. These observations lead us to reinterpret existing experimental results on oxygen diffusion in natural olivine. We suggest that at low oxygen partial pressure the mechanism observed is a vacancy mechanism, while at high oxygen partial pressure the mechanism is interstitial. We believe that this change in mechanism is mediated by iron redox reactions. Taking this process into account, we derive activation energies in excellent agreement with those found experimentally in natural samples of olivine. The anisotropy of activation barriers and hence the change in diffusion rates with temperature could be used to distinguish between the two mechanisms in future experimental work.  相似文献   

16.
Assessing the ferric-ferrous ratio in magmas prior to eruption remains a challenging task. X-ray absorption near-edge structure (μXANES) spectra were collected at the iron K-edge in water-rich peralkaline silicic melt/glass inclusions trapped in quartz. These experiments were carried out between 800 and 20 °C. The chemical environment of iron was also determined in the naturally quenched samples (glass inclusions and matrix glass) and in the peralkaline rhyolitic reference glasses, with variable [Fe3+ / ∑Fe] ratios.In the reference glasses, both the intensity of the pre-peaks (Fe2+, Fe3+) and site geometry of iron change as the oxidation state increases. Fourfold-coordinated Fe3+ prevails in highly oxidised peralkaline silicic glasses, using alkalis for charge balance. The position of the pre-edge centroid of the 1s-3d transition correlates with the Fe3+ / ΣFe ratios that allowed calibration of the redox state of iron of our natural samples.At high temperatures, Fe2+ dominates in the pre-edge structure of melt inclusions. Upon cooling down to 20 °C, the intensity of the Fe3+ peak increases, the centroid position of the pre-edge features shifts by nearly 0.5 eV and the main edge moves slightly towards higher energies. The slower the cooling rate, the higher the ferric iron contribution. Iterative μXANES experiments performed on the same samples show that the process is reversible. However, this apparent oxidation of iron upon cooling is an artefact of changes in Fe coordination. It implies that the [Fe3+ / ΣFe] ratio of glassy samples, measured at 20 °C, may be overestimated by a factor > 1.7, and that this ratio cannot be reliably retrieved by probing naturally cooled glass inclusions, and most silicate glasses. High temperature μXANES experiments led first to an assessment of the ferric-ferrous ratio in the water-rich peralkaline melt in pre-eruptive magmatic conditions and second to the determination of the corresponding oxygen fugacity at 740 °C.  相似文献   

17.
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   

18.
Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.  相似文献   

19.
Molecular dynamics simulations based on ab initio interatomic potentials have been performed to study the kinetics and mechanisms of interdiffusion in MgSiO3 and Mg2SiO4 melts. Diffusion coefficients in the presence of a concentration gradient are lower than self-diffusion coefficients due to the requirements of local charge-balance within the system. Extrapolations of Mg2+ diffusion coefficients obtained at high temperatures (5000 to 3000 K) into geologically relevant temperatures (1500 to 2500 K) are reasonably accurate compared to experimental Mg2+ diffusion coefficients in a compositionally similar system. A significant system-size effect is also observed on the rates of diffusion obtained from the molecular dynamics simulations. Diffusion mechanisms involve movement of individual Mg2+ and O2- ions and anionic [SiOn](4–2n) complexes for both self-diffusion and interdiffusion.  相似文献   

20.
Transition metal stable isotope signatures can be useful for tracing both natural and anthropogenic signals in the environment, but only if the mechanisms responsible for fractionation are understood. To investigate isotope fractionations due to electrochemistry (or redox processes), we examine the stable isotope behavior of iron and zinc during the reduction reaction  + 2e− = Mmetal as a function of electrochemical driving force, temperature, and time. In all cases light isotopes are preferentially electroplated, following a mass-dependent law. Generally, the extent of fractionation is larger for higher temperatures and lower driving forces, and is roughly insensitive to amount of charge delivered. The maximum fractionations are δ56/54Fe = −4.0‰ and δ66/64Zn = −5.5‰, larger than observed fractionations in the natural environment and larger than those predicted due to changes in speciation. All the observed fractionation trends are interpreted in terms of three distinct processes that occur during an electrochemical reaction: mass transport to the electrode, chemical speciation changes adjacent to the electrode, and electron transfer at the electrode. We show that a large isotope effect adjacent the electrode surface arises from the charge-transfer kinetics, but this effect is attenuated in cases where diffusion of ions to the electrode surface becomes the rate-limiting step. Thus while a general increase in fractionation is observed with increasing temperature, this appears to be a result of thermally enhanced mass transport to the reacting interface rather than an isotope effect associated with the charge-transfer kinetics. This study demonstrates that laboratory experiments can successfully distinguish isotopic signatures arising from mass transport, chemical speciation, and electron transfer. Understanding how these processes fractionate metal isotopes under laboratory conditions is the first step towards discovering what role these processes play in fractionating metal isotopes in natural systems.  相似文献   

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