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1.
A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe3O4–FeCr2O4 spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe1-x2+ Fex3+)[Fex2+Fe2-2y-x3+Cr2y]O4, and their thermodynamic properties depend strongly on Fe2+–Cr3+ cation mixing. Mixing of Fe2+–Fe3+ and Fe3+–Cr3+ can be accepted as ideal. If Fe2+, Fe3+ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x2/((1–x)(2–2y–x)))= G13* + (1–2x)W13+y(W14–W13–W34) where G13* is the difference between the Gibbs energy of inverse and normal magnetite, Wij is a Margules parameter of cation mixing and G13*, J/mol =–23,000+13.4 T, W14=36 kJ/mol, W13=W34=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe3O4–FeCr2O4 spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.  相似文献   

2.
Three natural Mg(Al2-yCry)O4 spinels (y 0.07–0.16), highly ordered in terms of Mg–Al, and one Mg(Al2–yFe3+y)O4 spinel (y0.08), highly ordered also in terms of Fe3+, were studied by means of X-ray single-crystal diffraction. All samples were heated in situ from 25 to 1000 °C in order to follow both thermal expansion and evolution of the structural state of spinel with temperature. Thermal expansion was monitored by means of the variation of cell edge a with temperature, and found to be well represented throughout the temperature range by a regression line a = a0 (1+T), slightly different at lower and higher temperatures. Thermal expansion coefficient 1, referring to the lower temperature range (i.e. during pure thermal expansion), was slightly lower than 2, calculated only over the highest temperatures. The trend showed different slopes for individual crystals. Structural evolution with temperature was studied by means of the variation of oxygen positional parameter u, which is strongly influenced by intersite cation exchange and thus closely correlated with inversion parameter x. In particular, in the three Cr samples, in which Cr resides only in the octahedral site, u parameter variations and hence the order–disorder process, started at about 700 °C. Instead, in the Fe3+ sample, this process was triggered at lower temperatures, starting at 550 °C with Fe3+–Mg exchange followed at higher temperatures by that of Mg–Al. Cr contents in the Cr samples affected the occupancy of Al in the tetrahedral site at the highest temperatures. In both Mg–Al–Cr and Mg–Al–Fe3+ compositions, if CrFe3+, parameter u reached the same value only when the Mg–Al exchange was dominant, i.e. at the highest temperatures, but not before. Cation distribution at each temperature was obtained by the bond-length model, applying thermal expansion to pure bond lengths. This method is applied here to complex compositions for the first time.  相似文献   

3.
Summary Phosphates of compositions (Na1–xLix)1.5Mn1.5Fe1.5(PO4)3 were synthesized by solid state reactions in air, and pure alluaudite-type compounds were obtained for x=0.00, 0.25, and 0.50. Rietveld refinements of X-ray powder diffraction data indicate the occurrence of Mn2+ in the M(1) site, and of Fe3+ and Mn2+ in the M(2) site. For x=0.25 and 0.50, A(1) is occupied by Li+ and Na+, whereas A(2) is occupied by Na+ and vacancies. A careful examination of the number of electrons occurring in the A sites of the alluaudite-type compounds (Na1–xLix)MnFe2(PO4)3 and (Na1–xLix) CdIn2(PO4)3 confirms that lithium occupies only the A(1) crystallographic site of the alluaudite structure.  相似文献   

4.
B. Py 《Mineralium Deposita》1994,29(1):281-285
One of the very few disadvantages of the mass-transfer transducer when compared with the hot-film sensor, is a slightly diminished frequency-response due to the higher Prandtl number encountered. Mass or thermal balance and transfer equations were solved first by Fortuna and Hanratty (1971) for small fluctuations of the wall shear. The solutions allow to make accurate corrections on the frequency spectra and the power of the fluctuations, but in different time. In this paper, the author deduces the frequency response of split rectangular electrodes and shows how a combination of signals improves the response at higher frequencies and makes it comparable to the thermal transducer with the same size, in the same fluid. Two experimental devices are described and compared. With these devices, the measurement of the wall shear fluctuations is improved in real time. Accurate determinations of turbulent power fluctuations and probability density spectra are feasible and illustrate the subject.List of Symbols A total area of the electrode - A j area of the partj of the electrode - a coefficient - C concentration - C bulk concentration - c fluctuation of concentration - D diffusion coefficient - F Faraday's constant - f(n +) transfer function - g gain of the differential electrode - I j electrolysis current on the partj of the electrode - K transfert coefficient - k fluctuation ofK - l electrode length - n frequency - P r Prandtl number - S wall shear - s fluctuation of the wall-shear - t time - x direction of the flow - y direction normal to the wall - phase delay - kinematic viscosity A version of this paper was presented at the 11th Symposium on Turbulence, University of Missouri-Rolla, 17–19 October 1988  相似文献   

5.
Subseabed disposal of radioactive waste applies a multiple-barrier concept with the sediment being the most important barrier for preventing a release of nuclides into the biosphere. While many investigations have been carried out to analyze the risk potential in this type of disposal, the effects of sediment consolidation and associated fluid flow have not fully been taken into consideration. Here, possible effects of consolidational fluid flow in the penetrator disposal option and possible consequences to the transport of nuclides in the sediment are analyzed. Results of numerical experiments demonstrate that consolidation contributes to the transport of radioactive nuclides released from containers buried in the sediment and to the release of nuclides at the sediment-water interface. Both depend on geological conditions and to a large extent on possible alterations of hydraulic conductivity i of the sediment in the vicinity of the entry path of a penetrator.Symbols c concentration ml m–3 - c a concentration of adsorbed solute mg kg–1 (relative to dry weight of sorbing substance) - c in solute concentration of source q mg m–3 - c 0 initial concentration mg m–3 - ID dispersion tensorm 2s–1 - ID * diffusion tensor m2s–1 - D coefficient of dispersion m2s–1 - d 0 coefficient of molecular diffusion m2s–1 - d coefficient of effective diffusion m2s–1 - g gravity m2s–1 - h piezometric pressure m - k hydraulic conductivity m2s–1 - m mass kg - p pressure Pa - q source/sink m3s–1 - S 0 specific surface m2m–3 - t time s - v velocity m s–1 - x, z cartesian coordinates m - compressibiliy of sediment m2N–1 - L longitudinal dispersivity m - effective porosity (decimal fraction) - density kg m–3 - s density of sediment kg m–3 - w density of water kg m–3 - decay constant per s - kinematic viscosity m2s–1  相似文献   

6.
A solution model is developed for rhombohedral oxide solid solutions having compositions within the ternary system ilmenite [(Fe 2+ s Ti 4+ 1–s ) A (Fe 2+ 1–s Ti 4+ s ) B O3]-geikielite [(Mg 2+ t Ti 4+ 1–t ) A (Mg 2+ 1–t Ti 4+ t ) B O3]-hematite [(Fe3+) A (Fe3+) B O3]. The model incorporates an expression for the configurational entropy of solution, which accounts for varying degrees of structural long-range order (0s, t1) and utilizes simple regular solution theory to characterize the excess Gibbs free energy of mixing within the five-dimensional composition-ordering space. The 13 model parameters are calibrated from available data on: (1) the degree of long-range order and the composition-temperature dependence of the transition along the ilmenite-hematite binary join; (2) the compositions of coexisting olivine and rhombohedral oxide solid solutions close to the Mg–Fe2+ join; (3) the shape of the miscibility gap along the ilmenite-hematite join; (4) the compositions of coexisting spinel and rhombohedral oxide solid solutions along the Fe2+–Fe3+ join. In the course of calibration, estimates are obtained for the reference state enthalpy of formation of ulvöspinel and stoichiometric hematite (–1488.5 and –822.0 kJ/mol at 298 K and 1 bar, respectively). The model involves no excess entropies of mixing nor does it incorporate ternary interaction parameters. The formulation fits the available data and represents an internally consistent energetic model when used in conjuction with the standard state thermodynamic data set of Berman (1988) and the solution theory for orthopyroxenes, olivines and Fe–Mg titanomagnetite-aluminate-chromate spinels developed by Sack and Ghiorso (1989, 1990a, b). Calculated activity-composition relations for the end-members of the series, demonstrate the substantial degree of nonideality associated with interactions between the ordered and disordered structures and the dominant influence of the miscibility gap across much of the ternary system. The predicted shape of the miscibility gap, and the orientation of tie-lines relating the compositions of coexisting phases, display the effects of coupling between the excess enthalpy of solution and the degree of long-range order. One limb of the miscibility gap follows the composititiontemperature surface corresponding to the ternary second-order transition.  相似文献   

7.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   

8.
Voluminous granitic intrusions are distributed in the West Junggar, NW China, and they can be classified as the dioritic rocks, charnockite and alkali-feldspar granite groups. The dioritic rocks (SiO2 = 50.4–63.8 wt.%) are calc-alkaline and Mg enriched (average MgO = 4.54 wt.%, Mg# = 0.39–0.64), with high Sr/Y ratios (average = 21.2), weak negative Eu (average Eu/Eu = 0.80) and pronounced negative Nb–Ta anomalies. Their Sr–Nd and zircon Hf isotopic compositions ((87Sr/86Sr)i = 0.7035–0.7042, εNd(t) = 4.5–7.9, εHf(t) = 14.1–14.5) show a depleted mantle-like signature. These features are compatible with adakites derived from partial melting of subducted oceanic crust that interacted with mantle materials. The charnockites (SiO2 = 60.0–65.3 wt.%) show transitional geochemical characteristics from calc-alkaline to alkaline, with weak negative Eu (average Eu/Eu = 0.75) but pronounced negative Nb–Ta anomalies. Sr–Nd and zircon Hf isotopic compositions ((87Sr/86Sr)i = 0.7037–0.7039, εNd(t) = 5.2–8.0, εHf(t) = 13.9–14.7) also indicate a depleted source, suggesting melts from a hot, juvenile lower crust. Alkali-feldspar granites (SiO2 = 70.0–78.4 wt.%) are alkali and Fe-enriched, and have distinct negative Eu and Nb–Ta anomalies (average Eu/Eu = 0.26), low Sr/Y ratios (average = 2.11), and depleted Sr–Nd and zircon Hf isotopic compositions ((87Sr/86Sr)i = 0.7024–0.7045, εNd(t) = 5.1–8.9, εHf(t) = 13.7–14.2). These characteristics are also comparable with those of rocks derived from juvenile lower crust. Despite of the differences in petrology, geochemistry and possibly different origins, zircon ages indicate that these three groups of rocks were coevally emplaced at ~ 305 Ma.A ridge subduction model can account for the geochemical characteristics of these granitoids and coeval mafic rocks. As the “slab window” opened, upwelling asthenosphere provided enhanced heat flux and triggered voluminous magmatisms: partial melting of the subducting slab formed the dioritic rocks; partial melting of the hot juvenile lower crust produced charnockite and alkali-feldspar granite, and partial melting in the mantle wedge generated mafic rocks in the region. These results suggest that subduction was ongoing in the Late Carboniferous and, thus support that the accretion and collision in the Central Asian Orogenic Belt took place in North Xinjiang after 305 Ma, and possibly in the Permian.  相似文献   

9.
A semi-empirical treatment of isothermal element partitioning caused by flow rate-dependent calcite growth from hydrothermal solutions yields element/Ca ratios that are qualitatively similar to those observed in calcite bands of the Pb-Zn banded ores from the Harz Mountains, Germany. The comparison of the calculations with the analytical results suggests that flow rates varied between episodes of calcite precipitation as well as during formation of individual bands. Based on a flow rate-dependent element partition coefficient, changing element/Ca ratios in precipitates from a hydrotherm are therefore not necessarily indicative of changing compositions of the fluid. The variations in element/Ca ratios to be envisaged could be as much as a factor of three.Notation A defined by Eq. 8 - a, b individual values of any element in Eq. 1 - c concentration in moles/m3 - C 0 initial concentration moles/m3 - i running parameter - F area of precipitation in m2 - k p rate constant of pth order reaction in s · m3/molesp - R linear (one-dimensional) growth rate in moles/m2 · s - p order of growth reaction - s distance from entry of solution in m - s 0 vertical extension of a vein in m - t time in s - v flow rate of hydrothermal solution in m/s - v0 standard flow rate in m/s - r relative flow rate in multiple of v0 - fraction of total precipitation - 0 fraction of precipitation under reference conditions when the hydrothermal solution leaves the vein - defining the sign in Eq. 1 for elements that are en riched (= +1) or impoverished (= -1) - logarithmic partition coefficient in Eq. 10 - (R) logarithmic partition coefficient as a function of variable growth rate - [ ], { } concentration ratios of fluids and solids, respectively - EL/Ca calculated ratio of El/Ca in the calcite surface zone after Eq. 11  相似文献   

10.
Electron paramagnetic resonance (EPR) spectra of CO 3 3– molecule-ions stabilized by Sc3+ in natural calcite were identified and studied at X-band frequencies and room temperature. The principal values of the g-tensor (g xx= 1.9997, g yy = 2.0030, g zz = 1.9972) and the direction cosines of the g and A tensors for CO 3 3– -Sc3+ center were found to be close to that for the well-known CO 3 3– -Y3+ center. A quantitative comparison of different impurity contents in calcite samples and analysis of the intensities of forbidden transitions were used to identify Sc3+. An estimation of the unpaired electron spin density on the nuclei of paramagnetic centers confirms that both centers, CO 3 3– -Sc3+ and CO 3 3– -Y3+, have the same nature.  相似文献   

11.
The unit-cell and atomic parameters of perdeuterated brushite have been extracted from Rietveld analysis of neutron powder diffraction data within the temperature range 4.2 to 470 K. The thermal expansion of brushite is anisotropic, with the largest expansion along the b axis due principally to the effect of the O(1)···D(4) and O(3)···D(2) hydrogen bonds. Expansion along the c axis, influenced by the Ow1···D(5) interwater hydrogen bond, is also large. The high temperature limits for the expansion coefficients for the unit-cell edges a, b and c are 9.7(5) × 10–6, 3.82(9) × 10–5 and 5.54(5) × 10–5 K–1, respectively, and for the cell volume it is 9.7(1) × 10–5 K–1. The angle displays oscillatory variation, and empirical data analysis results in = 1.28(3) × 10–6sin(0.0105 T) K–1, within this temperature range. The evolution of the thermal expansion tensor of brushite has been calculated between 50 T 400 K. At 300 K the magnitudes of the principal axes are 11 = 50(6) × 10–6 K–1, 22 = 26.7(7) × 10–6 K–1 and 33 = 7.0(5) × 10–6 K–1. The intermediate axis, 22, is parallel to b, and using IRE convention for the tensor orthonormal basis, the axes 11 and 33 have directions equal to (–0.228, 0, –0.974) and (–0.974, 0, 0.228) respectively. Under the conditions of these experiments, the onset of dehydration occurred at temperatures above 400 K. Bond valence analysis combined with assessments of the thermal evolution of the bonding within brushite suggests that dehydration is precipitated through instabilities in the chemical environment of the second water molecule.  相似文献   

12.
Summary The crystal structures of copper-substituted manganese-denningites, Mn(Mn1–x Cu x )(Te2O5)2 (0 x 1), were refined in space groupP42/nbc from single-crystal X-ray data. Single crystals with different degree of Cu-substitution suitable for X-ray investigation were synthesized under hydrothermal conditions, varying the Cu/Mn ratio and thepH-value. One main feature of the crystal structure is the distribution of Mn and Cu atoms among an eight and a six-coordinated site, respectively. Bond strength calculations support the site occupancies of the MnO8-polyhedra and MeO6-octahedra (Me = Cu., Mn1–x ). The decrease in length of the four Me[6]-O bonds clearly correlates with the increase of the Cu-substitution resulting in a distortion of the octahedra according to the Jahn-Teller effect of divalent copper. The stronger decrease of the lattice parameterc as compared toa is probably due to the variations of the bond lengths.
Kupfer-substituierte Mangan-Denningite, Mn(Mn1–x Cu x )(Te2O5)2 (0 x 1): Synthese und Kristallchemie
Zusammenfassung Die Kristallstrukturen von Kupfer-substituierten Mangan-Denningiten, Mn(Mn–x Cu x )(Te2O5)2 (0 x 1) wurden mittels Einkristall-Röntgenbeugungsdaten in der RaumgruppeP42/nbc verfeinert. Geeignete Einkristalle mit unterschiedlich starker Cu-Substitution wurden unter hydrothermalen Bedingungen durch Variieren des Cu/Mn-Verhältnisses bzw. despH-Wertes dargestellt. Ein wesentlicher struktureller Gesichtspunkt ist die Verteilung der Mn und Cu-Atome auf eine acht- bzw. sechskoordinierte Punktlage. Die Verringerung von vier Me[6]-O Bindungslängen ist klar korrelierbar mit zunehmender Cu-Substitution, und führt zu einer Verzerrung der Oktaeder gemäß dem für zweiwertiges Kupfer bekannten Jahn-Teller Effekt. Bindungsstärkenberechnungen belegen die Besetzung der MnO8-Polyeder und MeO6-Oktaeder (Me = Cu x Mn1–x ). Die bevorzugte Verkleinerung der Gitterkonstantec gegenübera kann auf die Variationen der Bindungslängen zurückgeführt werden.

Dedicated to Prof Dr. Josef Zemann on the occasion of his 70th birthday

With 10 Figures  相似文献   

13.
Résumé L'étude chimique comparée, à la microsonde électronique, d'owyheeite de treize gisements différents a révélé des fluctuations sensibles des teneurs en éléments majeurs, en liaison avec la nature des sulfosels associés, ainsi que la présence occasionnelle de différents éléments mineurs: Cu et As (très fréquents), Sn et Bi (moins fréquents), Tl et Se (exceptionnels). Compte tenu du mode de substitution de ces éléments mineurs, la projection des analyses dans le système Pb2S2–Ag2S–Sb2S3 délimite un champ restreint de solution solide dont l'allongement s'accorde avec la substitution 2 Pb2+Ag++Sb3+. Ce champ de solution solide englobe la composition de la variété téremkovite, mais exclue la formule donnée initialement parShannon. La formule Pb10–2x Sb11+x Ag3+x S28 (–0,13x+0,20) rend compte des termes à la résolution de la Ag/Sb maximal; l'obtention d'une formule plus générale reste subordonée à la résolution de la structure cristalline. Aucun élément mineur ne peut jouer à lui seul le rôle de stabilisateur de la structure, mais ce même rôle peut être joué complémentairement par différents éléments, tels que Cu et Sn. Les clichés de microdiffraction électronique montrent des phénomènes de sur-structure plus ou moins prononcés, en liaison avec la concentration en (Ag+Cu), ou avec le degré de finesse du maclage complexe spécifique de l'owyheeite.
Crystal chemistry of owyheeite: New data
Summary Comparative electron microprobe study of owyheeite from thirteen ore deposits shows significant variations in the concentration of major elements. These can be correlated with the chemical composition of the associated sulfosalts. Sometimes, some minor elements may be present: Cu and As (very frequent), Sn and Bi (less frequent), Tl and Se (exceptional). Considering certain substitution rules for minor elements, the analyses plotted in the Pb2S2–Ag2S–Sb2S3 system show a limited solid-solution field, the elongation of which follows the substitution 2 Pb2+Ag++Sb3+. This solid-solution field includes the composition of the variety teremkovite, but excludes the initial formula for owyheeite proposed byShannon. The formula Pb10–2x Sb11+x Ag3+x S28 (–0.13x+0.20) describes compositional variation of members with the highest Ag/Sb ratio; a more general formula would require the determination of the crystal structure. No individual minor element appears to be responsible for stabilizing owyheeite. The stabilization may be due to a combined effect of two elements, such as Cu and Sn. Electron diffraction patterns show superstructure reflections which are related to the (Ag+Cu) concentration, as well as to the scale of the complex twinning characteristic of owyheeite.

Avec 3 Figures  相似文献   

14.
The mineral paragonite, NaAl2[AlSi3O10 (OH)]2, has been synthesized on its own composition starting from a variety of different materials. Indexed powder data and refined cell parameters are given for both the 1M and 2M1 polymorphs obtained. The upper stability limit of paragonite is marked by its breakdown to albite + corundum + vapour. The univariant equilibria pertaining to this reaction have been established by reversing the reaction at six different pressures, the equilibrium curve running through the following intervals: 1 kb: 530°–550° C 2 kb: 555°–575° C 3 kb: 580°–600° C 5kb: 625°–640° C 6 kb: 620°–650° C 7 kb: 650°–670° C.Comparison with the upper stability limit of muscovite (Velde, 1966) shows that paragonite has a notably lower thermal stability thus explaining the field observation that paragonite is absent in many higher grade metamorphic rocks in which muscovite is still stable.The enthalpy and entropy of the paragonite breakdown reaction have been estimated. Since intermediate albites of varying structural states are in equilibrium with paragonite, corundum and H2O along the univariant equilibrium curve, two sets of data pertaining to the entropy of paragonite (S 298 0 ) as well as the enthalpy ( H f,298 0 ) and Gibbs free energy ( G f,298 0 ) of its formation were computed, assuming (1) high albite and (2) low albite as the equilibrium phase. The values are: (1) (2) S 298 0 67.8±3.9 cal deg–1 gfw–1 63.7±3.9 cal deg–1 gfw–1 H f,298 0 –1417.9±2.7 kcal gfw–1 –1420.2±2.6 kcal gfw–1 G f,298 0 –1327.4±4.0 kcal gfw–1 –1328.5±4.0 kcal gfw–1.Adapted from a part of the author's Habilitationsschrift accepted by the Ruhr University, Bochum (Chatterjee, 1968).  相似文献   

15.
Equations are developed describing migration of stable isotopes via a fluid phase infiltrating porous media. The formalism of continuum fluid mechanics is used to deal with the problem of microscopic inhomogeneity. Provision is made explicitly for local equilibrium exchange of isotopes between minerals and fluids as well as for kinetic control of isotopic exchange. Changing characteristic parameters of transport systems such as porosity, permeability, and changes in modal proportions of minerals due to precipitation or dissolution are taken into account.The kinetic continuum theory (KCIT) is used to show how to deduce the dominant mechanism of mass transport in metasomatic rocks. Determination of the transport mechanism requires data on the spatial distribution of the reaction progress of exchange reactions between minerals and fluids involving at least two stable isotope systems such as 13C-12C and 18O-16O, for example. It is concluded that a combination of field and laboratory measurements of two or more stable isotope systems can be used to place constraints not only on the mechanism of transport but also on the magnitude of fluid fluxes, the identity of fluid sources, and the molecular species composition of fluids.Variables used C number of chemical components - D i,j hydrodynamic dispersion tensor [m2/s] - D i j diffusion coefficient matrix [m2/s] - D * apparent diffusion coefficient, includes sorption, dispersion, porosity and tortuosity [m2/s] - F number of degrees of freedom (variance) - f i j mass or number of isotope j in fluid species i - g acceleration due to gravity [m/s2] - flow [m3/m2 s] - j isotope species - j chemical element - k coefficient defined in Eq. 17 - K permeability of porous media [m2], [darcy] - L ij phenomenological diffusion coefficient matrix [mol2/j m s] - m number of fluid species - n number of isotope exchange vectors - p number of phases - P pressure [Pa] - P * hydrological pressure potential [Pa] - R j ratio of concentration of rare to common isotope of element j - r number of restrictions imposed on system - s i j mass or number of isotope j in one mole of mineral phase i - t time [s] - V volume [m3] - X i number of moles of fluid species i in unit fluid volume - X l number of moles of mineral l in unit volume - X l j mole fraction of isotope j in one mole mineral l - X * mole fraction with respect to the whole system - z space coordinate [m] - z transformed space coordinate - z * location of an infiltration front [m] - x–y j fractionation factor between two phases, x, y, for isotope j - porosity - fluid viscosity [Ns/m2] - fraction of porosity accessible to a specific mass transport mechanism - chemical potential [j/mole] - stoichiometric reaction coefficient - normalized reaction progress variable - mass, specific mass [gr/cm] - tortuosity - fluid velocity [m/s] - c common isotope - init initial - j isotope species - r rare isotope - tot sum of common and rare isotope - dif diffusive - disp dispersive - eq mineral composition in equilibrium with initial infiltration concentration of the fluid - f fluid - inf infiltrative - r rock, without fluid phase - samp sample - std standard - sys system - tot fluid and rock  相似文献   

16.
Summary Synthesis of Mn-bearing ilvaites, CaFe 2–x 2+ MnxFe3+ [Si2O7/O/(OH)], with 0 x 0.19, have been performed under hydrothermal conditions at 2 and 3 kbars, T = 300 -400°C and at oxygen fugacities defined by the Fe2O3/Fe3O4 - and the Ni/NiO -buffer. As shown by X-ray diffraction, the substitution of Fe2+ by Mn2+ decreases the monoclinic angle and causes a phase transition from monoclinic to orthorhombic at x = 0.19. The Fe-distribution has been determined by Mössbauer spectroscopy.
Synthese und Charakterisierung von Mn-haltigem Ilvait CaFe 2–x 2+ MnxFe3+ [Si2O7/O/(OH)]
Zusammenfassung Mn-haltiger Ilvait CaFe 2–x 2+ Mnx Fe3+ [Si2O7/O/(OH)] wurde unter hydrothermalen Bedingungen bei Drucken von 2 und 3 kbar, Temperaturen zwischen 300 und 400°C und bei Sauerstoff Fugazitäten, die durch Festkörperpuffer (Fe2O3/Fe3O4 und Ni/NiO) kontrolliert wurden, hergestellt. Röntgenbeugungsuntersuchungen zeigen, daß mit steigendem Mn-Einbau der monokline Winkel kleiner wird, und daß bei x = 0.19 ein Phasenübergang von der monoklinen zur orthorhombischen Struktur erfolgt. Die Fe-Verteilung wurde mit Mössbauer-Spektroskopie bestimmt.

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17.
Divariant oxide plus metal assemblages potentially make useful redox sensors for use in hydrothermal and other high pressure experiments. Here we report the calibration of the (Ni, Mn)O/Ni redox sensor in which the Ni/NiO (NNO) oxygen buffer is displaced to lower oxygen chemical potentials (O2), by the solid solution of MnO in the oxide phase. This assemblage was chosen because: (1) it covers a useful range of O2; (2) the system can be calibrated very accurately. Values of O2 defined by the (Ni, Mn)O/Ni assemblage were determined electrochemically, from 900 to 1300 K, using calcia-stabilized zirconia solid electrolytes. The oxide compositions (8 in total, ranging from 0.1X NiO0.8) were analysed afterwards by electron microprobe, and were checked for internal consistency by measuring the lattice parameters (a0), using powder XRD. The accuracies of the measurements, both assessed theoretically and established empirically, are (1): ±80J/mol in O2, ±0.0002 Å in a0 and ±0.002 to 0.005 in X NiO. Activity-composition relations were fitted to the Redlich-Kister formalism. There is a slight asymmetry (corresponding to a subregular model) across the solution with A 0 G =9577(±45) J/mol, and A 1 G =–477(±80) J/mol. The experimental data were also used to derive the parameters Vex, Hex and Sex. There is no obvious relationship between excess volumes and enthalpies of mixing, nor between excess volumes and excess entropies. The experimental data from this study have been used to formulate the (Ni, Mn)O/Ni redox sensor expression: O2 = 2(NNO) + 2RTlnX NiO + 2(1 – X NiO)2[11483 – 1.697T] – 477(4X NiO – 1)(900 < T(K) < 1300) where O2(NNO)=–478967+248.514T–9.7961 T In T, from O'Neill and Pownceby(1993a).  相似文献   

18.
Coupled substitutions in the tourmaline group   总被引：2，自引：0，他引：2  
Statistical analysis of 136 natural tourmaline compositions from the literature reveals the presence and extent of coupled substitutions involving several cations and structural sites. In schorls and dravites these are a dehydroxylation type substitution (1) (OH)–+R2+ = R3++O2– and an alkali-defect type substitution (2) R++R2+ = R3++, Al3+ being the predominant R3+ action. Substitution (1) which represents solid solution towards a proton-deficient end-member, R+ R 3 3+ R 6 3+ (BO3)3 Si6O18O3(OH), accounts for three times as much of the observed compositional variability as does (2) which represents substitution toward a hypothetical alkali-free end-member, (R 2 2+ R3+) R 6 3+ (BO3)3Si6O18(OH)4. The occurrence of both of these substituions produces intermediates between end-member schorl/ dravite, R+ R 3 2+ R 6 3+ (BO3)3Si6O18(OH)4, and a new series within the tourmaline group, R 1–x + R 3 3+ R 6 3+ (BO3)3Si6O18O3–x (OH)1+x.In addition to dehydroxylation type, 2(OH)–+Li+ = R3++202–, and possibly alkali-defect type, 2R++Li+ = R3++2, substitutions, a third type Li++O2– = (OH)–+, occurs in the elbaites giving rise to Li-poor, proton-rich species. All three substitutions serve to reduce the Li-content of natural elbaite which, as a result, does not attain the composition of the ideal end-member, Na(Li1.5Al1.5)Al6(BO3)3Si6O18(OH)4. Substitution from elbaite and schorl/dravite toward R 1–x + R 3 3+ R 6 3+ (BO3)3Si6O18O3–x(OH)1+x is very extensive and may be complete.Substitution toward R 1–x + R 3 3+ R 6 3+ (BO3)3Si6O18O3–x(OH)1+x results in improved local charge balance. The mean deviation from oxygen charge saturation is at a maximum in end-member schorl, dravite and elbaite. Substitutions (1) and (2) progressively decrease but substitution (1) does so more effectively, which may explain its predominance in nature. However, alkali-defective end-members appear to be unstable regardless of . Substitution (3) in the elbaites cannot be discussed on the basis of charge balance considerations at present due to the lack of structural information on proton-rich species.  相似文献   

19.
Dispersive mass transport processes in naturally heterogeneous geological formations (porous media) are investigated based on a particle approach to mass transport and on its numerical implementation using LPT3D, a Lagrangian Particle Tracking 3D code. We are currently using this approach for studying microscale and macroscale space–time behavior (advection, diffusion, dispersion) of tracer plumes, solutes, or miscible fluids, in 1,2,3-dimensional heterogeneous and anisotropic subsurface formations (aquifers, petroleum reservoirs). Our analyses are based on a general advection-diffusion model and numerical scheme where concentrations and fluxes are discretized in terms of particles. The advection-diffusion theory is presented in a probabilistic framework, and in particular, a numerical analysis is developed for the case of advective transport and rotational flows (numerical stability of the explicit Euler scheme). The remainder of the paper is devoted to the behavior of concentration, mass flux density, and statistical moments of the transported tracer plume in the case of heterogeneous steady flow fields, where macroscale dispersion occurs due to geologic heterogeneity and stratification. We focus on the case of perfectly stratified or multilayered media, obtained by generating many horizontal layers with a purely random transverse distribution of permeability and horizontal velocity. In this case, we calculate explicitly the exact mass concentration field C(x, t), mass flux density field f(x, t), and moments. This includes spatial moments and dispersion variance 2 x (t) on a finite domain L, and temporal moments on a finite time scale T, e.g., the mass variance of arrival times 2 T (x). The moments are related to flux concentrations in a way that takes explicitly into account finite space–time scales of analysis (time-dependent tracer mass; spatially variable flow through mass). The multilayered model problem is then used in numerical experiments for testing different ways of recovering information on tracer plume migration, dispersion, concentration and flux fields. Our analyses rely on a probabilistic interpretation that emerges naturally from the particle approach; it is based on spatial moments (particle positions), temporal moments (mass weighted arrival times), and probability densities (both concentrations and fluxes). Finally, as an alternative to direct estimations of the flux and concentration fields, we formulate and study the Moment Inverse Problem. Solving the MIP yields an indirect method for estimating the space–time distribution of flux concentrations based on observed or estimated moments of the plume. The moments may be estimated from field measurements, or numerically computed by particle tracking as we do here.  相似文献   

20.
Summary The crystal structure of curite, of which until now only the arrangement of the U and Pb atoms was known, has been redetermined with a synthetic crystal using three-dimensional X-ray techniques.R=0.043 for 1270 observed reflections. Curite is orthorhombic, space groupPnam-D 2h 16 ,a=12.513,b=13.002,c=8.373 ,Z=6.56 PbO·16UO3·9.44H2O. The structure consists of a novel type of washboard like puckered layers 2 [(UO2)8O8 (OH)6]6– formed by tetragonal bipyramidal [(UO2)O3(OH)] and pentagonal bipyramidal [(UO2)O3 (OH)2] polyhedra. The layers are parallel to {100} and are directly connected by hydrogen bonds. Lead atoms and oxygen atoms (H2O+OH) are located in folds between the layers, helping to connect them. The interlayer atomic positions are slightly disordered and one of them is partially occupied. The variable concentrations of the interlayer atoms are responsible for the changes in chemical composition.The structural formula [Pb8–x (OH)4–2x (H2O)2x ] [(UO2)8(OH)6]2 is suggested for curite;x=1.44 for the investigated synthetic curite. Within the three different U–O polyhedra the axial U–O distances are 1.81–1.88 , the equatorial 2.14–2.57 . The two different Pb atoms have ionic coordinations, each by ten oxygens with Pb–O distances of 2.46–3.32 , on the average 2.82 .
Die Kristallstruktur von Curit, [Pb 6,56 (H 2 O, OH) 4 ] [(UO 2)8 O 8(OH)6]2
Zusammenfassung Die Kristallstruktur von Curit, von der bisher nur die Lagen der Uran- und Bleiatome bekannt waren, wurde anhand eines künstlichen Kristalls mit dreidimensionalen Röntgendaten neu bearbeitet und für 1270 Reflexe aufR=0,043 verfeinert. Curit kristallisiert rhombisch, RaumgruppePnam-D 2h 16 ,a=12,513,b=13,002,c=8,373 ,Z=6,56 PbO·16 UO3·9,44 H2O. Die Struktur enthält gewellte Schichten eines neuen Typs, 2 [(UO2)8O8(OH)6]6–, die sich aus tetragonal bipyramidalen [(UO2)O3(OH)]- und pentagonal-bipyramidalen [(UO2)O3(OH)2]-Polyedern zusammensetzen. Die Schichten verlaufen parallel {100} und sind über Wasserstoffbrücken miteinander unmittelbar verknüpft. Zwischen den Schichten befinden sich Bleiatome und zusätzliche Sauerstoffatome (H2O+OH). Diese Atome weisen zum Teil Fehlordnung auf; eine der beiden Pb-Lagen ist nur partiell besetzt. Für Schwankungen in der chemischen Zusammensetzung von Curit ist der unterschiedliche Gehalt an Zwischenschichtatomen verantwortlich. Aufgrund dieser Untersuchung wird die Strukturformel [Pb8–x (OH)4–2x (H2O)2x ] [(UO2)8O8(OH)6]2 vorgeschlagen; für den untersuchten Curit istx=1,44. Die drei verschiedenen U–O-Polyeder der Struktur besitzen axiale bzw. äquatoriale U–O-Abstände von 1,81–1,88 bzw. 2,14–2,57 . Die zwei Arten von Bleiatomen besitzen eine ionische Koordination; beide sind von 10 Sauerstoffatomen in Abständen von 2,46–3,32 (Mittelwert 2,82 ) umgeben.

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