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1.
We have determined Cr diffusion coefficients (D) in orthopyroxene parallel to the a-, b-, and c-axial directions as a function temperature at f(O2) corresponding to those of the wüstite-iron (WI) buffer. Diffusion is found to be significantly anisotropic with D(//c) > D(//b) > D(//a), conforming to an earlier theoretical prediction. Increase of f(O2) from WI buffer conditions to 4.5 log unit above the buffer at 950 and 1050 °C leads to decrease of D(Cr) by a factor of two to three, possibly suggesting significant contribution from an interstitial diffusion mechanism. We have used the diffusion data to calculate the closure temperatures (Tc) of the Mn-Cr decay system in orthopyroxene as a function of initial temperature (T0), grain size (a) and cooling rate for spherical and plane sheet geometries. We also present graphical relations that permit retrieval of cooling rates from knowledge of the resetting of Mn-Cr ages in orthopyroxene during cooling, T0 and a. Application of these relations to the Mn-Cr age data of the cumulate eucrite Serra de Magé yields a Tc of 830-980 °C, and cooling rates of 2-27 °C/Myr at Tc and ∼1-13 °C/Myr at 500 °C. It is shown that the cooling of Serra de Magé to the closure temperature of the Mn-Cr system took place at its original site in the parent body, and thus implies a thickness for the eucrite crust in the commonly accepted HED parent body, Vesta, of greater than 30 km. This thickness of the eucrite crust is compatible only with a model of relatively olivine-poor bulk mineralogy in which olivine constitutes 19.7% of the total asteroidal mass.  相似文献   

2.
The Emery mesosiderite contains large Ni-rich grains of the phosphide schreibersite, which have exsolved from kamacite. Computer simulation of diffusion-controlled growth of this schreibersite indicates that exsolution occurred during cooling at the rate of 0.1°C/Myr. This determination supports the cooling rate estimated for mesosiderites by Powell (Geochim. Cosmochim. Acta33, 789–810), using taenite-kamacite data.  相似文献   

3.
The solubility of neodymium (III) fluoride was investigated at temperatures of 150, 200 and 250 °C, saturated water vapor pressure, and a total fluoride concentration (HF°aq + F−) ranging from 2.0 × 10−3 to 0.23 mol/l. The results of the experiments show that Nd3+ and NdF2+ are the dominant species in solution at the temperatures investigated and were used to derive formation constants for NdF2+ and a solubility product for NdF3. The solubility product of NdF3(logKsp=logaNd3++3logaF-) is −24.4 ± 0.2, −22.8 ± 0.1, and −21.5 ± 0.2 at 250, 200 and 150 °C, respectively, and the formation constant of NdF2+(logβ=logaNdF2+-logaNd3+-logaF-) is 6.8 ± 0.1, 6.2 ± 0.1, and 5.5 ± 0.2 at 250, 200 and 150 °C, respectively. The results of this study show that published theoretical predictions significantly overestimate the stability of NdF2+ and the solubility of NdF3.The potential impact of the results on natural systems was evaluated for a hypothetical fluid with a composition similar to that responsible for REE mineralization in the Capitan pluton, New Mexico. In contrast to results obtained using the theoretical predictions of Haas [Haas J. R., Shock E. L., and Sassani D. C. (1995) Rare earth elements in hydrothermal systems: estimates of standard partial molal thermodynamic properties of aqueous complexes of the rare earth elements at high pressures and temperatures. Geochim. Cosmochim. Acta59, 4329-4350.], which indicate that NdF2+ is the dominant species in solution, calculations employing the data presented in this paper and previously published experimental data for chloride and sulfate species [Migdisov A. A., and Williams-Jones A. E. (2002) A spectrophotometric study of neodymium(III) complexation in chloride solutions. Geochim. Cosmochim. Acta66, 4311-4323; Migdisov A. A., Reukov V. V., and Williams-Jones A. E. (2006) A spectrophotometric study of neodymium(III) complexation in sulfate solutions at elevated temperatures. Geochim. Cosmochim. Acta70, 983-992.] show that neodymium chloride species predominate and that neodymium fluoride species are relatively unimportant. This suggests that accepted models for REE deposits that invoke fluoride complexation as the method of hydrothermal REE transport may need to be re-evaluated.  相似文献   

4.
The apparent equilibrium constant for the exchange of Fe and Ni between coexisting olivine and sulfide liquid (KD = (XNiS/XFeS)liquid/(XNiSi12O2/XFeSi12O2)olivine; Xi = mole fraction) has been measured at controlled oxygen and sulfur fugacities (fO2 = 10−8.1 to 10−10 and fS2 = 10−0.9 to 10−1.7) over the temperature range 1200 to 1385°C, with 5 to 37 wt% Ni and 7 to 18 wt% Cu in the sulfide liquid. At log fO2 of −8.7 ± 0.1, and log fS2 of −0.9 to −1.7, KD is relatively insensitive to sulfur fugacity, but comparison with previous results shows that KD increases at very low sulfur fugacities. KD values show an increase with the nickel content of the sulfide liquid, but this effect is more complex than found previously, and is greatest at log fO2 of −8.1, lessens with decreasing fO2, and KD becomes independent of melt Ni content at log fO2 ≤ −9.5. The origin of this variation in KD with fO2 and fS2 is most likely the result of nonideal mixing of Fe and Ni species in the sulfide liquid. Such behavior causes activity coefficients to change with either melt oxygen content or metal/sulfur ratio, effects that are well documented for metal-rich sulfide melts.Application of these experimental results to natural samples shows that the relatively large dispersion that exists in KD values from different olivine + sulfide-saturated rock suites can be interpreted as arising from variations in fO2, fS2, and the nickel content of the sulfide liquid. Estimates of fO2 based on KD and sulfide melt composition in natural samples yields a range from fayalite-magnetite-quartz (FMQ)-1 to FMQ-2 or lower, which is in good agreement with previous values determined for oceanic basalts that use glass ferric/ferrous ratios. Anomalously high KD values recorded in some suites, such as Disko Island, probably reflect low fS2 during sulfide saturation, which is consistent with indications of low fO2 for those samples. It is concluded that the variation in KD values from natural samples reflects olivine-sulfide melt equilibrium at conditions within the T-fO2-fS2 range of terrestrial mafic magmas.  相似文献   

5.
Mössbauer spectroscopy has been used widely to characterize the ferric (Fe3+) and ferrous (Fe2+) proportions and coordination of solid materials. To obtain these accurately, the recoilless fraction is indispensible. The recoilless fractions (f) of iron-bearing minerals, including oxides, oxyhydroxides, silicates, carbonates, phosphates and dichalcogenides, and silicate glasses were evaluated from the temperature dependence of their center shifts or absorption area with the Debye model approximation. Generally, the resolved Debye temperature (θD) of ferric iron in minerals, except dichalcogenides, through their center shifts ranging from 400 to 550 K, is significantly larger than ferrous iron ranging from 300 to 400 K, which is consistent with the conclusion from previous work. The resolved f (Fe3+)RT with the center shift model (CSM) ranges from 0.825 to 0.925, which is larger than that obtained for f(Fe2+)RT, which ranges from 0.675 to 0.750. Meanwhile, the θD and f resolved from temperature-dependence of absorption are generally lower than from center shifts, especially for ferric iron. The significant difference between f(Fe3+) and f(Fe2+) indicates the necessity of recoilless fraction correction on the Fe3+/(Fe3++Fe2+) resolved from Mössbauer spectra.  相似文献   

6.
Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO2) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg2+, Mn2+, Co2+, Ni2+, Zn2+) and Cu2+/Cu+ with increasing fO2 between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO2 implies a reciprocal relationship between a(Fe2+O) and a(Fe3+O1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO2 in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO2 in silicic, but less so in mafic bulk systems.  相似文献   

7.
Geospeedometry allows to estimate the cooling rate (sinit) of metamorphic rocks at the beginning of the cooling history using diffusion data. But the choice of a diffusion activation energy (E) and a preexponential factor (D0) from experimental results can be difficult. We propose a method to obtain E directly from the rock itself by studying the variation of the average concentration of elements or isotopes (〈C〉) as a function of mineral grain size (d). An appropriate value of D0 can then be estimated using an existing compensation rule, a linear relationship between log D0 and E. Consequently, uncertainties on sinit are markedly reduced. All parameters of this analytical model and their sensitivity on sinit can be estimated from 〈C〉 of the mineral grains under study. As a test we apply our model to a study by Edwards and Valley (1998)**** on 18O/16O fractionation between diopside and calcite in Adirondacks marbles, and find a cooling rate in agreement with previous works, without choosing experimental values for E and D0.  相似文献   

8.
Zoning patterns of light lithophile elements (the LLE: Li, Be, and B) in pyroxenes of some Martian basaltic meteorites have been used to suggest that the parent basalts were saturated in water and exsolved an aqueous fluid phase. Here, we examine LLE zoning in the augites of a quickly cooled Martian basalt that was not water-saturated—the Northwest Africa (NWA) 817 nakhlite. Analyses for LLE were by secondary ion mass spectrometry (SIMS), supported by EMP analyses of major and minor elements. In NWA 817, zoning of Be and B is consistent with igneous fractionations while Li abundances are effectively constant across wide ranges in abundance of other incompatible elements (Be, B, Ti, and Fe*). The lack of strong zoning in Li can be ascribed to intracrystalline diffusion, despite the rapid cooling of NWA 817. Most other nakhlites, notably Nakhla and Lafayette, cooled more slowly than did NWA 817 [Treiman, A.H., 2005. The nakhlite Martian meteorites: augite-rich igneous rock from Mars. Chem. Erde65, 203-270]. In them Li abundances are constant across augite, as are abundances of other elements. In Nakhla pyroxenes, all the LLE have effectively constant abundances across significant ranges in Fe* and Ti abundance. Lafayette is more equilibrated still, and shows constant abundances of LLE and nearly constant Fe*. A pyroxene in the NWA480 shergottite has constant Li abundances, and was interpreted to represent mineral fractionation coupled with exsolution of aqueous fluid. A simple quantitative model of this process requires that the partitioning of Li between basalt and aqueous fluid, LiDaq/bas, be 15 times larger than its experimentally determined value. Thus, its seems unlikely that the Li zoning pattern in NWA480 augite represents exsolution of aqueous fluid. Late igneous or sub-solidus diffusion seems more likely as is suggested by Li isotopic studies [Beck, P., Chaussidon, M., Barrat, J.-A., Gillet, Ph., Bohn, M., 2005. An ion-microprobe study of lithium isotopes behavior in nakhlites. Meteorit. Planet. Sci.40, Abstract #5118; Beck, P., Chaussidon, M., Barrat, J.-A., Gillet, Ph., Bohn, M., 2006. Diffusion induced Li isotopic fractionation during the cooling of magmatic rocks: the case of pyroxene phenocrysts from nakhlite meteorites. Geochim. Cosmochim. Acta70, in press]. Pyroxenes of the Shergotty and Zagami meteorites have nearly constant abundances of B, and Li that decreases core-to-rim. Applying the quantitative model to the constant B in these pyroxenes requires that BDaq/bas be 25 times larger than experimentally constrained values. Li abundances in pigeonite can be fit by the model of crystal fractionation and fluid loss, but only if LiDaq/bas is 30 times the experimentally constrained value. The Li abundance pattern in augite cannot be modeled by simple fractionation, suggesting some strong crystal-composition effects. Thus, Li and B distributions in Shergotty and Zagami pyroxenes cannot be explained by igneous fractionation and exsolution of aqueous vapor. Intracrystalline diffusion, complete for B and incomplete for Li, seems more consistent with the observed zoning patterns.  相似文献   

9.
Current methods for evaluating Sm-Nd isochron data determine initial ?Nd (?Ndi) values by extrapolation to 147Sm144Nd = 0, resulting in unnecessarily large uncertainties. It is shown that values of ?Ndi can be optimised by determining the present 143Nd144Nd composition of a hypothetical sample having chrondritic SmNd. This method of determination requires only a simple data translation for its implementation using standard line-fitting techniques, and is particularly advantageous in providing precise ?Ndi values for sample suites of limited compositional range close to chondritic SmNd.A method of constructing error (uncertainty) polygons appropriate to the optimised (?Ndi, T) values is discussed, and optimum?Ndi values are tabulated for all published Precambrian Sm-Nd isochrons.  相似文献   

10.
The isopiestic method has been used to determine the osmotic coefficients of the binary solutions NaBr-H2O (from 0.745 to 5.953 mol kg−1) and KBr-H2O (from 0.741 to 5.683 mol kg−1) at the temperature t = 50 °C. Sodium chloride solutions have been used as isopiestic reference standards. The isopiestic results obtained have been combined with all other experimental thermodynamic quantities available in literature (osmotic coefficients, water activities, bromide mineral’s solubilities) to construct a chemical model that calculates solute and solvent activities and solid-liquid equilibria in the NaBr-H2O, KBr-H2O and Na-K-Br-H2O systems from dilute to high solution concentration within the 0-300 °C temperature range. The Harvie and Weare [Harvie C., and Weare J. (1980) The prediction of mineral solubilities in naturalwaters: the Na-K-Mg-Ca-Cl-SO4-H2O system from zero to high concentration at 25 °C. Geochim. Cosmochim. Acta44, 981-997] solubility modeling approach, incorporating their implementation of the concentration-dependent specific interaction equations of Pitzer [Pitzer K. (1973) Thermodynamics of electrolytes. I. Theoretical basis and general equations. J. Phys. Chem.77, 268-277] is employed. The model for binary systems is validated by comparing activity coefficient predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solutions model due to data insufficiencies are discussed. This model expands the variable temperature sodium-potassium model of Greenberg and Moller [Greenberg J., and Moller N. (1989) The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Cl-SO4-H2O system to high concentration from 0 to 250 °C. Geochim. Cosmochim. Acta53, 2503-2518] by evaluating Br− pure electrolyte and mixing solution parameters and the chemical potentials of three bromide solid phases: NaBr-2H2O (cr), NaBr (cr) and KBr (cr).  相似文献   

11.
It is shown mathematically that if the activity coefficient of water in ternary water-magma (aluminosilicate) systems is constant or varies only with the mole fraction of water, it is not necessary that the binary magmas form ideal solutions contrary to the claims by Burnham et al. (1978, Geochim. Cosmochim. Acta42, 275–276). A molecular viewpoint is presented to support this argument. The properties of analytical equations capable of representing the activity coefficients of usual and unusual systems are discussed. The correct form of the Gibbs-Dunhem equation for dissociative dissolution processes is presented to disprove the claims by Burnham (1975, Fortschr. Mineral.52, 101–118; 1975, Geochim. Cosmochim. Acta39, 1077–1084), and by Burnhamet al. (1978, Geochim. Cosmochim. Acta42, 275–276).  相似文献   

12.
Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) 18O/16O datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233–262, 1997; Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010), these authors find variations in δ18Ool (~4.6–6.0 ‰) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231–241, 1994) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) speculate that δ18Ool values for La Palma olivine grains measured by LF (Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in δ18Ool values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that δ18Ool is weakly correlated (R 2 = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514–524, 2009) to describe the estimated weight fraction of pyroxenite-derived melt (Xpx). With this relationship, end-member δ18O values for HIMU-peridotite (δ18O = 5.3 ± 0.3 ‰) and depleted pyroxenite (δ18O = 5.9 ± 0.3 ‰) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) and Day and Hilton (Earth Planet Sci Lett 305:226–234, 2011), there are significant differences in the predicted δ18O values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565–6589, 2010) proposed a mantle source for La Palma lavas with low-δ18O (<5 ‰), rather than higher-δ18O (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349–363, 2011). Here we question the approach of using weakly correlated variations in δ18Ool and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques.  相似文献   

13.
Diffusion couple experiments were carried out with San Carlos olivine (Fo90) and NiFe alloys (Ni100, Ni97Fe3, Ni90Fe10) or other olivine compositions (Fo100, Fo25) in order to determine the dependence on temperature, oxygen fugacity, composition and crystallographic orientation of Ni diffusion coefficient (DNi) in olivine. Experiments at 1 atmosphere total pressure cover a temperature range of 900-1445°C with run durations from 48 to 2155 h at different oxygen fugacities. In an Arrhenius plot the best fit for all data for Fo90 yields an activation energy (ED) of 220 ± 14 kJ/mol and an fO2 dependence of (1/4.25)·Δ log fO2 = Δ log DNi. The relationship between diffusion coefficients along different crystallographic axes at 1200°C is given by D[001] ≈ 6·D[100] ≈ 6·D[010]. DNi depends strongly on the major element (i.e. Fe/Mg) composition of olivine and decreases by about 1 order of magnitude as the olivine composition changes from Fo35 to Fo90. Thus, experimental investigations in Fe-free systems cannot be applied to natural samples. For calculation of residence times or cooling rates the present Ni data yield shorter timescales compared to those obtained using diffusion data published until now.In addition to Ni diffusion coefficients, Fe-Mg, Mn and Ca diffusion data were obtained from some of the same diffusion couples (Fo90-Fo100). It is found that the activation energies, ED[Ni] ≅ ED[Fe-Mg] ≅ ED[Mn] ≤ ED[Ca]. All diffusion coefficients are strongly dependent on the major element composition of olivine.  相似文献   

14.
To determine evaporation coefficients for the major gaseous species that evaporate from silicate melts, the Hertz-Knudsen equation was used to model the compositions of residues of chondrule analogs produced by evaporation in vacuum by Hashimoto [Hashimoto A. (1983) Evaporation metamorphism in the early solar nebula-evaporation experiments on the melt FeO-MgO-SiO2-CaO-Al2O3 and chemical fractionations of primitive materials. Geochem. J. 17, 111-145] and Wang et al. [Wang J., Davis A. M., Clayton R. N., Mayeda T. K., Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO-MgO-SiO2-CaO-Al2O3-TiO2 rare earth element melt system. Geochim. Cosmochim. Acta 65, 479-494], in vacuum and in H2 by Yu et al. [Yu Y., Hewins R. H., Alexander C. M. O’D., Wang J. (2003) Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts. Geochim. Cosmochim. Acta 67, 773-786], and in H2 by Cohen et al. [Cohen B. A., Hewins R. H., Alexander C. M. O’D. (2004) The formation of chondrules by open-system melting of nebular condensates. Geochim. Cosmochim. Acta 68, 1661-1675]. Vapor pressures were calculated using the thermodynamic model of Ghiorso and Sack [Ghiorso M. S., Sack R. O. (1995) Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures. Contrib. Mineral. Petrol. 119, 197-212], except for the late, FeO-free stages of the Wang et al. (2001) and Cohen et al. (2004) experiments, where the CMAS activity model of Berman [Berman R. G. (1983) A thermodynamic model for multicomponent melts, with application to the system CaO-MgO-Al2O3-SiO2. Ph.D. thesis, University of British Columbia] was used. From these vapor pressures, evaporation coefficients (α) were obtained that give the best fits to the time variation of the residue compositions. Evaporation coefficients derived for Fe(g), Mg(g), and SiO(g) from the Hashimoto (1983) experiments are similar to those found by Alexander [Alexander C. M. O’D. (2004) Erratum. Meteoritics Planet. Sci. 39, 163] in his EQR treatment of the same data and also adequately describe the FeO-bearing stages of the Wang et al. (2001) experiments. From the Yu et al. (2003) experiments at 1723 K, αNa = 0.26 ± 0.05, and αK = 0.13 ± 0.02 in vacuum, and αNa = 0.042 ± 0.020, andαK = 0.017 ± 0.002 in 9 × 10−5 bar H2. In the FeO-free stages of the Wang et al. (2001) experiments, αMg and αSiO are significantly different from their respective values in the FeO-bearing portions of the same experiments and from the vacuum values obtained at the same temperature by Richter [Richter F. M., Davis A. M., Ebel D. S., Hashimoto A. (2002) Elemental and isotopic fractionation of Type B calcium-, aluminum-rich inclusions: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta 66, 521-540] for CMAS compositions much lower in MgO. When corrected for temperature, the values of αMg and αSiO that best describe the FeO-free stages of the Wang et al. (2001) experiments also adequately describe the FeO-free stage of the Cohen et al. (2004) H2 experiments, but αFe that best describes the FeO-bearing stage of the latter experiment differs significantly from the temperature-corrected value derived from the Hashimoto (1983) vacuum data.  相似文献   

15.
The standard thermodynamic properties at 25°C, 1 bar (ΔG fo, ΔH fo, S o, C Po, V o, ω) and the coefficients of the revised Helgeson–Kirkham–Flowers equations of state were evaluated for several aqueous complexes formed by dissolved metals and either arsenate or arsenite ions. The guidelines of Shock and Helgeson (Geochim Cosmochim Acta 52:2009–2036, 1988) and Sverjensky et al. (Geochim Cosmochim Acta 61:1359–1412, 1997) were followed and corroborated with alternative approaches, whenever possible. The SUPCRT92 computer code was used to generate the log K of the destruction reactions of these metal–arsenate and metal–arsenite aqueous complexes at pressures and temperatures required by the EQ3/6 software package, version 7.2b. Apart from the AlAsO4o and FeAsO4o complexes, our log K at 25°C, 1 bar are in fair agreement with those of Whiting (MS Thesis, Colorado School of Mines, Golden, CO, 1992). Moreover, the equilibrium constants evaluated in this study are in good to fair agreement with those determined experimentally for the Ca–dihydroarsenate and Ca–hydroarsenate complexes at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) and for Fe(III)–hydroarsenate complex at 25°C (Raposo et al., J Sol Chem 35:79–94, 2006), whereas the disagreement with the log K measured for the Ca–arsenate complex at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) might be due to uncertainties in this measured value. The implications of aqueous complexing between dissolved metals and arsenate/arsenite ions were investigated for seawater, high-temperature geothermal liquids and acid mine drainage and aqueous solutions deriving from mixing of acid mine waters and surface waters. Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users.  相似文献   

16.
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17.
Fault-creep events measured on the San Andreas and related faults near Hollister, California, can be described by a rheological model consisting of a spring, power-law dashpotand sliding block connected in series. An empirical creep-event law, derived from many creep-event records analyzed within the constraints of the model, provides a remarkably simple and accurate representation of creep-event behavior. The empirical creep law is expressed by the equation: D(t)= Df [1?1/{ct(n?1)Dfn?1+1}/(n?1)] where D is the value of displacement at time t following the onset of an event, Df is the final equilibrium value of the event displacementand C is a proportionality constant. This discovery should help determine whether the time—displacement character of creep events is controlled by the material properties of fault gouge, or by other parameters.  相似文献   

18.
An internal isochron determined for a gabbro from the Stillwater complex by the Sm-Nd method yields a precise age of 2701 ± 8 Myr and initial 143Nd/144Nd = 0.508248 ± 12. The initial is close to the CHUR evolution curve but clearly displaced below it by ?Nd = ?2.8 ± 0.2. A spectrum of total rocks in the Stillwater complex ranging from anorthosite to pyroxenite were found to lie on the same isochron to within experimental error indicating the same age and initial. These data demonstrate that some ancient mantle-derived rocks have initial 143Nd/144Nd which deviate substantially from the CHUR evolution curve at the time of their formation. This implies that there was early layering in the mantle with substantial REE fractionation (~6–12% Nd/Sm enrichment) or that the Stillwater complex was highly contaminated with REE from much older continental crust during emplacement. The results show the necessity of high-precision ages and initial 143Nd/144Nd values in order to properly describe REE fractionation in the mantle. While the Sm-Nd age results show no indication of any irregularities, we have confirmed that the Rb-Sr data for the Stillwater are highly disturbed. This comparison indicates that the Sm-Nd parent-daughter system may be much less susceptible to element redistribution during metamorphism, therefore permitting wide application of this technique to rocks of complex histories.  相似文献   

19.
The mechanism and rate of hydration of rhyolitic glass during weathering were studied. Doubly polished thin sections of two rhyolites with different duration of weathering (Ohsawa lava: 26,000 yr, Awanomikoto lava: 52,000 yr) were prepared. Optical microscope observation showed that altered layers had developed along the glass surfaces. IR spectral line profile analysis was conducted on the glass sections from the surface to the interior for a length of 250 μm and the contents of molecular H2O (H2Om), OH species (OH) and total water (H2Ot) were determined. The diffusion profile of H2Om in Ohsawa lava extends beyond the layer observed by optical microscope. The content of H2Om in the hydrated region is much higher than that of OH species. Thus, the reaction from H2Om to OH appears to be little and H2Om is the dominant water species moving into the glass during weathering. Based on the concentration profiles, the diffusion coefficients of H2Om(DH2Om) and H2Ot(DH2Ot) were determined to be 2.8 × 10−10 and 3.4 × 10−10 μm2 s−1 for Ohsawa lava, and 5.2 × 10−11 and 4.1 × 10−11 μm2 s−1 for Awanomikoto lava, respectively. The obtained DH2Om during weathering are more than 2-3 orders of magnitude larger than the diffusion coefficient at ∼20 °C that is extrapolated from the diffusivity data for >400 °C. This might suggest that the mechanism of water transport is different at weathering conditions and >400 °C.  相似文献   

20.
The kinetics of the dissolution of a (Na. K) sanidine in CO2-charged water, were studied experimentally at 200°C as a function of the surface area s and of the time t. The molalities of Na+ and K+ have been plotted against the product st. As for albite and adularia (Lagache, Bull. Soc. Fr. Minéral. Cristallogr. 88, 223–253, 1965), the rates of dissolution of Na2 and K+ are smooth continuous functions of st, which implies that they are controlled by the composition of the solution.The comparison between the dissolution of pure sodic or potassic feldspars and that of an intermediate feldspar shows that the sanidine dissolves as if it were composed of albite and K-feldspar grains in the proportions corresponding to its composition.Theoretical considerations presented by Helgeson (Geochim. Cosmochim. Acta35, 421–169, 1971; The Feldspars, pp. 184–217, 1972) and Pa?es (Geochim. Cosmochim. Acta37, 2641–2663, 1973) are reviewed: both had suggested, arguing from my first experimental results, that the dissolution could be described by a process of diffusional mass transfer through a surface layer of reaction products.The present experiments do not agree with such an interpretation of the mechanism of dissolution.  相似文献   

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