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1.
Analysis of existing data and models on point defects in pure (Fe,Mg)-olivine (Phys Chem Miner 10:27–37,1983; Phys Chem Miner 29:680–694, 2002) shows that it is necessary to consider thermodynamic non-ideality of mixing to adequately describe the concentration of point defects over the range of measurement. In spite of different sources of uncertainties, the concentrations of vacancies in octahedral sites in (Fe,Mg)-olivine are on the order of 10−4 per atomic formula unit at 1,000–1,200 °C according to both the studies. We provide the first explicit plots of vacancy concentrations in olivine as a function of temperature and oxygen fugacity according to the two models. It is found that in contrast to absolute concentrations at ∼1,100 °C and dependence on fO2, there is considerable uncertainty in our knowledge of temperature dependence of vacancy concentrations. This needs to be considered in discussing the transport properties such as diffusion coefficients. Moreover, these defect models in pure (Fe,Mg)-olivine need to be extended by considering aliovalent impurities such as Al, Cr to describe the behavior of natural olivine. We have developed such a formulation, and used it to analyze the considerable database of diffusion coefficients in olivine from Dohmen et al. (Phys Chem Miner this volume, 2007) (Part - I) and older data in the literature. The analysis documents unequivocally for the first time a change of diffusion mechanism in a silicate mineral—from the transition metal extrinsic (TaMED) to the purely extrinsic (PED) domain, at fO2 below 10−10  Pa, and consequently, temperatures below 900 °C. The change of diffusion mechanism manifests itself in a change in fO2 dependence of diffusivity and a slight change in activation energy of diffusion—the activation energy increases at lower temperatures. These are consistent with the predictions of Chakraborty (J Geophys Res 102(B6):12317–12331, 1997). Defect formation enthalpies in the TaMED regime (distinct from intrinsic defect formation) lie between −66 and + 15 kJ/mol and migration energies of octahedral cations in olivine are most likely ∼ 260 kJ/mol, consistent with previous inferences (Phys Chem 207:147–162, 1998). Plots are shown for diffusion at various constant fO2 as well as along fO2 buffers, to highlight the difference in behavior between the two. Considering all the diffusion data and constraints from the point defect models, (Fe–Mg) diffusion in olivine along [001] is best described by the Master equations: (1) At oxygen fugacities greater than 10−10 Pa:
where T is in Kelvin, P and fO2 is in Pascals, X Fe is the mole fraction of the fayalite component and R is the gas constant in J/mol/K. (2) At oxygen fugacities less than 10−10  Pa:
These equations reproduce all of the 113 experimental data points within half an order of magnitude. (3) Alternately, a global equation averaging out the change of mechanism may be used, with somewhat larger errors in reproducing the measured diffusion data. It underestimates data at higher temperatures, and overestimates them at lower temperatures on the average. Note that fO2 is not explicitly considered here, leading to additional sources of error:
To obtain diffusion coefficients along [100] and [010], log 6 needs to be subtracted from each of the above equations. An erratum to this article can be found at  相似文献   

2.
The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H2O t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H2O t ) and water-rich (~2 wt% H2O t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H2O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al2O3 with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:
where is the water diffusivity at 1 wt% H2O t in m2/s, T is the temperature in K and P is the pressure in MPa. The above equation reproduces the experimental data (14 runs in total) with a standard fit error of 0.15 log units. It can be employed to model degassing of peralkaline melts at water contents up to 2 wt%.  相似文献   

3.
Interdiffusion of Fe and Mg in (Mg,Fe)O has been investigated experimentally under hydrous conditions. Single crystals of MgO in contact with (Mg0.73Fe0.27)O were annealed hydrothermally at 300 MPa between 1,000 and 1,250°C and using a Ni–NiO buffer. After electron microprobe analyses, the dependence of the interdiffusivity on Fe concentration was determined using a Boltzmann–Matano analysis. For a water fugacity of ∼300 MPa, the Fe–Mg interdiffusion coefficient in Fe x Mg1−x O with 0.01 ≤ x ≤ 0.25 can be described by with and C = −80 ± 10 kJ mol−1. For x = 0.1 and at 1,000°C, Fe–Mg interdiffusion is a factor of ∼4 faster under hydrous than under anhydrous conditions. This enhanced rate of interdiffusion is attributed to an increased concentration of metal vacancies resulting from the incorporation of hydrogen. Such water-induced enhancement of kinetics may have important implications for the rheological properties of the lower mantle.
Sylvie DemouchyEmail:
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4.
Commonly used thermometer and barometer calibrations are sensitive to mineral assemblage and, thus, bulk-rock composition. Calculated mineral stabilities for an average pelitic rock over a pressure–temperature (PT) range appropriate for normal, thickened, heated and shallowly subducted continental crust (400–900°C at 0.1–3.0 GPa) reveal more than one hundred possible assemblages. Individual phase compositions are dependent on the assemblage in which they belong and combining isopleth sets to represent and reveals several PT-ranges where commonly used mineral thermobarometers are less effective. For example, the garnet-biotite thermometer becomes increasingly P dependent in the absence of muscovite in high T melt-bearing assemblages, and biotite and plagioclase are not stable at pressures appropriate for lower thickened continental crust. Compositional thermobarometers involving equilibration between alternative phases (namely garnet, phengite and omphacite) are presented. Although the equilibrium compositions of phases at any P and T may change significantly as a function of bulk-rock composition, compositional-ratio thermobarometers are typically insensitive to this, unless a pseudo-univariant reaction is crossed and the buffering assemblage is altered. Quantification of the limits of efficacy of various thermobarometers allows the mineralogy of metapelites to be used to precisely determine segments of PT paths and infer their likely tectonic controls. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.
Mark J. CaddickEmail:
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5.
In the course of a thorough study of the influences of the second coordination sphere on the crystal field parameters of the 3d N -ions and the character of 3d N –O bonds in oxygen based minerals, 19 natural Cr3+-bearing (Mg,Ca)-garnets from upper mantle rocks were analysed and studied by electronic absorption spectroscopy, EAS. The garnets had compositions with populations of the [8] X-sites by 0.881 ± 0.053 (Ca + Mg) and changing Ca-fractions in the range 0.020 ≤ w Ca[8] ≤ 0.745, while the [6] Y-site fraction was constant with x Cr3+ [6] = 0.335 ± 0.023. The garnets had colours from deeply violet-red for low Ca-contents (up to x Ca = 0.28), grey with 0.28 ≤ x Ca ≤ 0.4 and green with 0.4 ≤ x Ca. The crystal field parameter of octahedral Cr3+ 10Dq decreases strongly on increasing Ca-fraction from 17,850 cm−1 at x Ca[8] = 0.020 to 16,580 cm−1 at x Ca[8] = 0.745. The data could be fit with two model which do statistically not differ: (1) two linear functions with a discontinuity close to x Ca[8] ≈ 0.3,
(2) one continuous second order function,
The behaviour of the crystal field parameter 10Dq and band widths on changing Ca-contents favour the first model, which is interpreted tentatively by different influences of Ca in the structure above and below x Ca[8] ≈ 0.3. The covalency of the Cr–O bond as reflected in the behaviour of the nephelauxetic ratio decreases on increasing Ca-contents.  相似文献   

6.
Opening and resetting temperatures in heating geochronological systems   总被引：2，自引：0，他引：2  
We present a theoretical model for diffusive daughter isotope loss in radiochronological systems with increasing temperature. It complements previous thermochronological models, which focused on cooling, and allows for testing opening and resetting of radiochronometers during heating. The opening and resetting temperatures are, respectively,
where R is the gas constant, E and D 0 are the activation energy and the pre-exponential factor of the Arrhenius law for diffusion of the daughter isotope, a the half-size of the system (radius for sphere and cylinder and half-thickness for plane sheet) and τ the heating time constant, related to the heating rate by
For opening and resetting thresholds corresponding to 1 and 99% loss of daughter isotope, respectively, the retention parameters for sphere, cylinder and plane sheet geometries are A op = 1.14 × 105, 5.07 × 104 and 1.27 × 104 and A rs = 2.40, 1.37 and 0.561. According to this model, the opening and resetting temperatures are significantly different for most radiochronometers and are, respectively, lower and higher than the closure temperature. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

7.
Olivine crystals were grown in the presence of a hydrous silicate fluid during multi-anvil experiments at 8 GPa and 1,000–1,600°C. Experiments were conducted both in a simple system (FeO–MgO–SiO2–H2O) and in a more complex system containing additional elements (CaO–Na2O–Al2O3–Cr2O3–TiO2–FeO–MgO–SiO2–H2O). Silica activity was buffered by the presence of either pyroxene (high a SiO2) or ferropericlase (low a SiO2), and was buffered by the presence of Ni + NiO or Fe + FeO, or constrained by the presence of Fe2O3. Raman spectroscopy was used to identify pyroxene polymorphs in the run products. Clinoenstatite was present in the 1,000°C experiment, and enstatite in experiments at 1,400–1,520°C. The H2O content of olivine was measured using secondary ion mass spectroscopy, and infrared spectroscopy was used to investigate the nature of hydrous defects. The H2O storage capacity of olivine decreases with increasing temperature at 8 GPa. In contrast to previous experimental results at ≤2 GPa, no significant effect of varying oxygen fugacity is evident, but H2O storage capacity is enhanced under conditions of low silica activity. No significant growth of low wavenumber (<3,400 cm−1) peaks, generally associated with high at low pressure, was observed in the FTIR spectra of olivine from the high experiments. Our experiments show that previous high pressure H2O storage capacity measurements for olivine synthesized under more oxidizing conditions than the Earth’s mantle are not likely to be compromised by the of the experiments. However, the considerable effect of temperature on H2O storage capacity in olivine must be taken into account to avoid overestimation of the bulk upper mantle H2O storage capacity.  相似文献   

8.
The density ρ of Caspian Sea waters was measured as a function of temperature (273.15–343.15) K at conductivity salinities of 7.8 and 11.3 using the Anton-Paar Densitometer. Measurements were also made on one of the samples (S = 11.38) diluted with water as a function of temperature (T = 273.15–338.15 K) and salinity (2.5–11.3). These latter results have been used to develop an equation of state for the Caspian Sea (σ = ±0.007 kg m−3)
where ρ0 is the density of water and the parameters A, B and C are given by
Measurements of the density of artificial Caspian Sea water at 298.15 K agree to ± 0.012 kg m−3 with the real samples. These results indicate that the composition of Caspian Sea waters must be close to earlier measurements of the major components. Model calculations based on this composition yield densities that agree with the measured values to ± 0.012 kg m−3. The new density measurements are higher than earlier measurements. This may be related to a higher concentration of dissolved organic carbon found in the present samples (500 μM) which is much higher than the values in ocean waters (~65 μM).  相似文献   

9.
We determined the forward rate constant (K+) for the Fe2+–Mg order–disorder between the M2 and M1 sites of orthopyroxene (OPx), which is described by the homogeneous reaction Fe2+ (M2) + Mg(M1) ↔ Mg(M2) + Fe2+ (M1), by both ordering and disordering experiments at isothermal condition and also by continuous cooling experiments. The rate constant was determined as a function of temperature in the range of 550–750°C, oxygen fugacity between quartz–fayalite–iron and Ni–NiO buffers, and at compositions of 16 and 50 mol% ferrosilite component. The K+ value derived from disordering experiment was found to be larger than that derived from ordering experiment at 550°C, while at T>580°C, these two values are essentially the same. The fO2 dependence of the rate constant can be described by the relation K+ α (fO2) n with n=5.5–6.5, which is compatible with the theoretically expected relation. The Arrhenius relation at the WI buffer condition is given by
where C o represents the total number of M2 + M1 sites occupied by Fe2+ and Mg per unit volume of the crystal. The above relation can be used to calculate the cooling rates of natural OPx crystals around the closure temperature (T c) of Fe–Mg ordering, which are usually below 300°C for slowly cooled rocks. We determined the Fe–Mg ordering states of several OPx crystals (∼ Fs50) from the Central Gneissic Complex (Khtada Lake), British Columbia, which yields T c ∼290°C. Numerical simulation of the change of Fe2+-Mg ordering in OPx as a function of temperature using the above expression of rate constant and a non-linear cooling model yields quenched values of ordering states that are in agreement with the observed values for cooling rates of 11–17°C/Myr below 300°C. The inferred cooling rate is in agreement with the available geochronological constraints.  相似文献   

10.
Dissolution Kinetics of Dolomite in Water at Elevated Temperatures   总被引：1，自引：0，他引：1  
Kinetic experiments of dolomite dissolution in water over a temperature range from 25 to 250°C were performed using a flow through packed bed reactor. Authors chose three different size fractions of dolomite samples: 18–35 mesh, 35–60 mesh, and 60–80 mesh. The dissolution rates of the three particle size samples of dolomite were measured. The dissolution rate values are changed with the variation of grain size of the sample. For the sample through 20–40 mesh, both the release rate of Ca and the release rate of Mg increase with increasing temperature until 200°C, then decrease with continued increasing temperature. Its maximum dissolution rate occurs at 200°C. The maximum dissolution rates for the sample through 40–60 mesh and 60–80 mesh happen at 100°C. Experimental results indicate that the dissolution of dolomite is incongruent in most cases. Dissolution of fresh dolomite was non-stoichiometric, the Ca/Mg ratio released to solution was greater than in the bulk solid, and the ratio increases with rising temperatures from 25 to 250°C. Observations on dolomite dissolution in water are presented as three parallel reactions, and each reaction occurs in consecutive steps as
where the second part is a slow reaction, and also the reaction could occur as follows:
The following rate equation was used to describe dolomite dissolution kinetics
where refers to one of each reaction among the above reactions; k ij is the rate constant for ith species in the jth reaction, a i stands for activity of ith aqueous species, n is the stoichimetric coefficience of ith species in the jth reaction, and define . The experiments prove that dissolved Ca is a strong inhibitor for dolomite dissolution (release of Ca) in most cases. Dissolved Mg was found to be an inhibitor for dolomite dissolution at low temperatures. But dissolution rates of dolomite increase with increasing the concentration of dissolved Mg in the temperature range of 200–250°C for 20–40 mesh sample, and in the temperature range of 100–250°C for 40–80 mesh sample, whereas the Mg2+ ion adsorption on dolomite surface becomes progressively the step controlling reaction. The following rate equation is suitable to dolomite dissolutions at high temperatures from 200 to 250°C.
where refers to dissolution rate (release of Ca), and are molar concentrations of dissolved Ca and Mg, k ad stands for adsorption reaction rate constant, K Mg refers to adsorption equilibrium constant. At 200°C for 40–60 mesh sample, the release rate of Ca can be described as:
  相似文献   

11.
We present the results of a series of density experiments in the system O–S–Fe–Ni–Cu. These experiments were designed to extend our understanding of the physical properties of sulfide liquids, and to extend one-bar thermochemical models for sulfide liquids to apply to low to moderate pressures. Density measurements indicate both positive and negative deviations from linear mixing of partial molar volumes across this five-dimensional composition space. In terms of the homogeneous speciation model of Kress (in Contrib Mineral Petrol 154:191–204, 2007), the best fit to experimental data can be achieved by starting with a model where the volume of formation reaction for associated species initially is set to zero. Further refinement of this first-order fit yields a volume mixing model which reproduces experimental data to within nearly the estimated experimental uncertainty. Experimental ultrasonic and X-ray absorption data from the literature, along with the bulk modulus–volume relation of Anderson and Nafe (J Geophys Res 16:3951–3963, 1965), allow the estimation of the pressure dependence of partial molar volumes for sulfide liquid species. The resulting combined thermochemical model should be valid to about 2,000 K and 3 GPa. Application of this thermochemical model in a simple adiabatic magma ascent scenario confirms earlier work suggesting that the pressure dependence of sulfur solubility in sulfide-saturated magma will decrease with increasing pressure along geologically reasonable paths in P–T–– space.  相似文献   

12.
Mechanisms of hydrogen incorporation and diffusion in iron-bearing olivine   总被引：1，自引：1，他引：0  
The incorporation and diffusion of hydrogen in San Carlos olivine (Fo90) single crystals were studied by performing experiments under hydrothermal conditions. The experiments were carried out either at 1.5 GPa, 1,000°C for 1.5 h in a piston cylinder apparatus or at 0.2 GPa, 900°C for 1 or 20 h in a cold-seal vessel. The oxygen fugacity was buffered using Ni–NiO, and the silica activity was buffered by adding San Carlos orthopyroxene powders. Polarized Fourier transform infrared (FTIR) spectroscopy was utilized to quantify the hydroxyl distributions in the samples after the experiments. The resulting infrared spectra reproduce the features of FTIR spectra that are observed in olivine from common mantle peridotite xenoliths. The hydrogen concentration at the edges of the hydrogenated olivine crystals corresponds to concentration levels calculated from published water solubility laws. Hydrogen diffusivities were determined for the three crystallographic axes from profiles of water content as a function of position. The chemical diffusion coefficients are comparable to those previously reported for natural iron-bearing olivine. At high temperature, hydrogenation is dominated by coupled diffusion of protons and octahedrally coordinated metal vacancies where the vacancy diffusion rate limits the process. From the experimental data, we determined the following diffusion laws (diffusivity in m2 s−1, activation energies in kJ mol−1): for diffusion along [100] and [010]; for diffusion along [001]. These diffusion rates are fast enough to modify significantly water contents within olivine grains in xenoliths ascending from the mantle.  相似文献   

13.
Solubility experiments were conducted for the dissolution reaction of brucite, Mg(OH)2 (cr): Experiments were conducted from undersaturation in deionized (DI) water and 0.010–4.4 m NaCl solutions at 22.5°C. In addition, brucite solubility was measured from supersaturation in an experiment in which brucite was precipitated via dropwise addition of 0.10 m NaOH into a 0.10 m MgCl2 solution also at 22.5°C. The attainment of the reversal in equilibrium was demonstrated in this study. The solubility constant at 22.5°C at infinite dilution calculated from the experimental results from the direction of supersaturation by using the specific interaction theory (SIT) is: with a corresponding value of 17.0 ± 0.2 (2σ) when extrapolated to 25°C. The dimensionless standard chemical potential (μ°/RT) of brucite derived from the solubility data in 0.010 m to 4.4 m NaCl solutions from undersaturation extrapolated to 25°C is −335.76 ± 0.45 (2σ), with the corresponding Gibbs free energy of formation of brucite, , being −832.3 ± 1.1 (2σ) kJ mol−1. In combination with the auxiliary thermodynamic data, the is calculated to be 17.1 ± 0.2 (2σ), based on the above Gibbs free energy of formation for brucite. This study recommends an average value of 17.05 ± 0.2 in logarithmic unit as solubility constant of brucite at 25°C, according to the values from both supersaturation and undersaturation. Sandia National Laboratories is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under Contract DE-AC04-94AL85000.  相似文献   

14.
To get deeper insight into the phase relations in the end-member system Fe2SiO4 and in the system (Fe, Mg)2SiO4 experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity. The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission electron microscopy. At fO2 corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe2SiO4 + O2 = 6 FeSiO3 + 5 Fe2.40Si0.60O4. Refinement of site occupancies in combination with stoichiometric Fe3+ calculations show that 32% of the total Fe is incorporated as Fe3+ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to accept higher Fe3+ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite with considerable Fe3+ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K D independent on composition and a bulk composition of x Fe = 0.44 this fractionation would stabilize spl with x Fe = 0.72. Thus, spl could be a potential Fe3+ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.
M. Koch-MüllerEmail:
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15.
The impact of land-use change on the quality of groundwater in the Xiaotjiang watershed, China was assessed for the period 1982–2004. Groundwater samples were collected from 30 monitoring points across the watershed, and were representative of the various changes, determined by remote sensing and geographical information systems. The results indicate that 610 km2 (60% of the total watershed area) were subject to land-use change during the period. The most important changes were the conversion of 135 km2 of forested land to cultivated land, and 211 km2 of unused land to cultivated land. The main impact was ascribed to diffuse pollution from fertilizers applied to newly cultivated land, and from building development. Overall the groundwater pH value was significantly increased, as were the concentrations of ions , , , , and Cl− in groundwater whilst the concentrations of Ca2+ and declined. More precisely, in the regions where forested land and unused land were converted into cultivated land, the pH value and the concentrations of Mg2+, , , , , Cl− increased whilst the concentrations of Ca2+ and declined. However in the region where cultivated land was converted into construction land, the pH value and the concentrations of Ca2+, Mg2+, , , , , , Cl− increased.
Résumé  L’impact des changements de l’utilisation du territoire sur la qualité de l’eau souterraine dans le bassin versant de Xiaojiang, en Chine, a été évalué de 1982 à 2004. Des échantillons d’eau souterraine ont été récoltés à partir de 30 points d’observation éparpillés sur le bassin, représentant les divers changements déterminés par télédétection et système d’information géographique. Les résultats indiquent que 610 km2 (soit 60% de la surface du bassin) ont été sujets à des modifications de l’utilisation du territoire sur cette période. Les changements les plus importants furent la conversion de 135 km2 de forêt et 211 km2 de terres inutilisées en terres cultivées. Le principal impact est attribué à la pollution diffuse des engrais utilisés en agriculture et pour les batiments. De manière générale le pH de l’eau souterraine a augmenté significativement, ainsi que les concentrations des ions , , , , et Cl−, tandis que les concentration en Ca2+ et ont diminué. Plus précisément dans les régions transformées en terres cultivées, la valeur du pH et les concentrations en Mg2+, , , , , Cl− ont augmenté tandis que les concentrations en Ca2+ et ont diminué. Toutefois dans les régions cultivées converties en zones de construction, le pH et les concentrations en Ca2+, Mg2+, , , , , , Cl− ont augmenté.
Resumen  El impacto del cambio en uso de la tierra en la calidad del agua en la cuenca Xiaojiang, China fue evaluado para el periodo 1982–2004. Muestras de agua subterránea fueron tomadas de 30 puntos de monitoreo a través de la cuenca, y fueron representativas de los múltiples cambios, determinados por sensores remotos y sistemas de información geográfica. Los resultados indican que 610 km2 (60% del área total de la cuenca) estaban sujetos a cambios de uso de la tierra durante el periodo estudiado. Los cambios más importantes fueron la conversión de 135 km2 de bosques a tierra cultivada, y 211 km2 de tierra sin uso (ociosa) a tierra cultivada. El impacto principal fue causado por contaminación difusa de fertilizantes aplicados a la tierra recientemente cultivada, y a desarrollo de construcciones. En general el pH en agua subterránea creció significantemente, al igual que las concentraciones de los iones , , , , y Cl− en agua subterránea mientras que las concentraciones de Ca2+ y decrecieron. Mas precisamente, en las regiones donde bosque y tierra ociosa fueron convertidas en tierra cultivada, el valor de pH y las concentraciones de Mg2+, , , , , Cl− crecieron mientras las concentraciones de Ca2+ y decrecieron. Sin embargo en la región donde tierra cultivada fue convertida en construcciones, el valor de pH y las concentraciones de Ca2+, Mg2+, , , , , , Cl− crecieron.
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16.
We performed decompression experiments to simulate the ascent of a phenocryst-bearing rhyolitic magma in a volcanic conduit. The starting materials were bubble-free rhyolites water-saturated at 200 MPa–800°C under oxidizing conditions: they contained 6.0 wt% dissolved H2O and a dense population of hematite crystals (8.7 ± 2 × 105 mm−3). Pressure was decreased from the saturation value to a final value ranging from 99 to 20 MPa, at constant temperature (800°C); the rate of decompression was either 1,000 or 27.8 kPa/s. In all experiments, we observed a single event of heterogeneous bubble nucleation beginning at a pressure P N equal to 63 ± 3 MPa in the 1,000 kPa/s series, and to 69 ± 1 MPa in the 27.8 kPa/s series. Below P N, the degree of water supersaturation in the liquid rapidly decreased to a few 0.1 wt%, the nucleation rate dropped, and the bubble number density (BND) stabilized to a value strongly sensitive to decompression rate: 80 mm−3 at 27.8 kPa/s vs. 5,900 mm−3 at 1,000 kPa/s. This behaviour is like the behavior formerly described in the case of homogeneous bubble nucleation in the rhyolite-H2O system and in numerical simulations of vesiculation in ascending magmas. Similar degrees of water supersaturation were measured at 27.8 and 1,000 kPa/s, implying that a faster decompression rate does not result in a larger departure from equilibrium. Our experimental results imply that BNDs in acid to intermediate magmas ascending in volcanic conduits will depend on both the decompression rate and the number density of phenocrysts, especially the number density of magnetite microphenocrysts (1–100 mm−3), which is the only mineral species able to reduce significantly the degree of water supersaturation required for bubble nucleation. Very low BNDs (≈1 mm−3) are predicted in the case of effusive eruptions ( ≈ 0.1 kPa/s). High BNDs (up to 107 mm−3) and bimodal bubble size distributions are expected in the case of explosive eruptions: (1) a relatively small number density of bubbles (1–100 mm−3) will first nucleate in the lower part of the conduit ( ≈ 10 kPa/s), either at high pressure on magnetite or at lower pressure on quartz and feldspar (or by homogeneous nucleation in the liquid) and (2) then, extreme decompression rates near the fragmentation level ( ≈ 103 kPa/s) will trigger a major nucleation event leading to the multitude of small bubbles, typically a few micrometers to a few tens of micrometers in diameter, which characterizes most silicic pumices.  相似文献   

17.
Garnet in silicic liquids and its possible use as a P-T indicator   总被引：1，自引：0，他引：1  
Melting experiments on a model pelitic composition yield low-spessartine garnet as an important residual phase at pressures above 7 kb. The K D values for distribution of iron and magnesium between coexisting garnet and liquid in the pelitic composition are mainly sensitive to temperature, but also have a small pressure dependence. At temperatures above 950 ° C garnet has a higher value than coexisting liquid, but below 950 ° C the garnet value is lower than that of the coexisting liquid. Thus at temperatures below 950 ° C silicic magmas may fractionate garnet and produce more magnesian derivative liquids.Reconnaissance experiments with added MnO content in the model pelite demonstrate that spessartine-rich garnets are stable in silicic liquids to pressures as low as 3 kb. The MnO and CaO contents of the experimentally crystallized garnets show an antipathetic relation. Also, the grossular content of near-liquidus garnets crystallizing from a range of compositions increases with increasing pressure. The spessartine and grossular contents of most natural garnets in eastern Australian granitic rocks suggest that these garnets formed at pressures greater than 5 kb. Increased spessartine content allows crystallization of garnet in equilibrium with a silicic magma well within the pressure limit of stability of cordierite, provided the garnet contains 10 mol.% spessartine. Thus the depth range over which garnet and cordierite may coexist in a silicic melt is broadened, subject to the availability of MnO. The effect of increased Mn content on the low-pressure stability limit of garnet may also explain the lack of resorption of some garnets in granitic magmas, as these magmas rise to shallower levels. These euhedral garnets characteristically show zoning from an Mn-poor core (typically <4 % MnO) to an Mn-richer rim (typically >4 % MnO) and may reflect continued growth of the garnet in a low pressure regime, stabilized by Mn concentrated in the residual liquid fractions of the crystallizing magma.  相似文献   

18.
Concentration gradients in calcium are common in metamorphic or magmatic garnets and can be used to determine the timescales of geological processes. However, the kinetics of Ca diffusion in garnet is poorly constrained and experimental studies have to date yielded widely varying diffusion coefficients. In this paper, we describe a new method for generating diffusion profiles in garnet. We incorporated polished and compositionally homogeneous garnet seeds in a finely ground powder of clinopyroxene and garnet. During the experiments (1.3 GPa, 1,050–1,250°C, and ƒO2 ≤ the graphite-O2 buffer), the mineral powder partially melted, recrystallized, and formed a 10–50 μm wide overgrowth zone of compositionally distinct garnet around the seeds. Long duration experiments generated measurable relaxation profiles at these seed/overgrowth interfaces. We performed analytical transmission electron microscope traverses across the interfaces in each experiment. Thirteen usable compositional profiles were obtained with characteristic distances of diffusion ranging from 300 to 1,000 nm. From these profiles, Ca–(Fe, Mg) interdiffusion coefficients were retrieved using an analytical solution for the diffusion equation and the data were cast in an Arrhenius relation. Linear regression of the data yields an activation energy Q Ca–(Fe, Mg) equal to 188 ± 48 kJ mol−1 and a frequency factor D 0 equal to 6.6 × 10−14 m2 s−1. Within the compositional range studied, the composition of garnet has no major effect on the Ca–(Fe, Mg) interdiffusion coefficient. The very slow diffusion rate of Ca is in agreement with natural observations indicating that Ca diffuses more slowly than Fe and Mg. The Ca diffusion coefficients derived from this study are not model-dependent and can be used to determine the durations of geological events from Ca relaxation profiles in natural garnets.
D. VielzeufEmail:
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19.
The Chemical Speciation of Fe(III) in Freshwaters   总被引：1，自引：0，他引：1  
Dialysis and chemical speciation modelling have been used to calculate activities of Fe3+ for a range of UK surface waters of varying chemistry (pH 4.3–8.0; dissolved organic carbon 1.7–40.3 mg l−1) at 283 K. The resulting activities were regressed against pH to give the empirical model: . Predicted Fe3+ activities are consistent with a solid–solution equilibrium with hydrous ferric oxide, consistent with some previous studies on Fe(III) solubility in the laboratory. However, as has also sometimes been observed in the laboratory, the slope of the solubility equation is lower than the theoretical value of 3. The empirical model was used to predict concentrations of Fe in dialysates and ultrafiltrates of globally distributed surface and soil/groundwaters. The predictions were improved greatly by the incorporation of a temperature correction for , consistent with the temperature dependence of previously reported hydrous ferric oxide solubility. The empirical model, incorporating temperature effects, may be used to make generic predictions of the ratio of free and complexed Fe(III) to dissolved organic matter in freshwaters. Comparison of such ratios with observed Fe:dissolved organic matter ratios allows an assessment to be made of the amounts of Fe present as Fe(II) or colloidal Fe(III), where no separate measurements have been made. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

20.
Five Cu–Au epidote skarns are associated with the Mt. Shea intrusive complex, located in the 2.7–2.6 Ga Eastern Goldfields Province of the Archean Yilgarn craton, in greenstones bounded by the Boulder Lefroy and Golden Mile strike-slip faults, which control the Golden Mile (1,435 t Au) at Kalgoorlie and smaller “orogenic” gold deposits at Kambalda. The Cu–Au deposits studied are oxidized endoskarns replacing faulted and fractured quartz monzodiorite–granodiorite. The orebodies are up to 140 m long and 40 m thick. Typical grades are 0.5% Cu and 0.3 g/t Au although parts are richer in gold (1.5–4.5 g/t). At the Hannan South mine, the skarns consist of epidote, calcite, chlorite, magnetite (5–15%), and minor quartz, muscovite, and microcline. Gangue and magnetite are in equilibrium contact with pyrite and chalcopyrite. The As–Co–Ni-bearing pyrite contains inclusions of hematite, gold, and electrum and is intergrown with cobaltite and Cu–Pb–Bi sulfides. At the Shea prospect, massive, net-textured, and breccia skarns are composed of multistage epidote, actinolite, albite, magnetite (5%), and minor biotite, calcite, and quartz. Gangue and magnetite are in equilibrium with Co–Ni pyrite and chalcopyrite. Mineral-pair thermometry, mass-balance calculations, and stable-isotope data (pyrite δ34SCDT = 2.5‰, calcite δ13CPDB = −5.3‰, and δ18OSMOW = 12.9‰) indicate that the Cu–Au skarns formed at 500 ± 50°C by intense Ca–Fe–CO2–S metasomatism from fluids marked by an igneous isotope signature. The Mt. Shea stock–dike–sill complex postdates the regional D1 folding and metamorphism and the main phase of D2 strike-slip faulting. The suite is calc-akaline and comprises hornblende–plagioclase monzodiorite, quartz monzodiorite, granodiorite, and quartz–plagioclase tonalite porphyry. The intrusions display a wide range in silica content (53–73 wt% SiO2), in ratio (0.37–0.89), and in ratio (0.02–0.31). Chromium (62–345 ppm), Ni (23–158), Sr (311–1361 ppm), and Ba (250–2,581 ppm) contents are high, Sr/Y ratios are high (24–278, mostly >50), and the rare earth element patterns are fractionated . These features and a negative niobium anomaly relative to the normal mid-ocean ridge basalt indicate that the suite formed by hornblende fractionation from a subduction-related monzodiorite magma sourced from metasomatized peridotite in the upper mantle. The magnesian composition of many intrusions was enhanced due to hornblende crystallization under oxidizing hydrous conditions and during the subsequent destruction of igneous magnetite by subsolidus actinolite–albite alteration. At the Shea prospect, main-stage Cu–Au epidote skarn is cut by biotite–albite–dolomite schist and by red biotite–albite replacement bands. Post-skarn alteration includes 20-m-thick zones of sericite–chlorite–ankerite schist confined to two D3 reverse faults. The schists are mineralized with magnetite + pyrite + chalcopyrite (up to 0.62% Cu, 1.6 g/t Au) and are linked to skarn formation by shared Ca–Fe–CO2 metasomatism. Red sericitic alteration, marked by magnetite + hematite + pyrite, occurs in fractured porphyry. The biotite/sericite alteration and oxidized ore assemblages at the Shea prospect are mineralogically identical to magnetite–hematite-bearing gold lodes at Kambalda and in the Golden Mile. Published fluid inclusion data suggest that a “high-pressure”, oxidized magmatic fluid (2–9 wt% NaCl equivalent, , 200–400 MPa) was responsible for gold mineralization in structural sites of the Boulder Lefroy and Golden Mile faults. The sericite–alkerite lodes in the Golden Mile share the assemblages pyrite + tennantite + chalcopyrite and bornite + pyrite, and accessory high-sulfidation enargite with late-stage sericitic alteration zones developed above porphyry copper deposits.  相似文献   

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