Low-temperature thermodynamic properties of disordered zeolites of the natrolite group

 The heat capacity of paranatrolite and tetranatrolite with a disordered distribution of Al and Si atoms has been measured in the temperature range of 6–309 K using the adiabatic calorimetry technique. The composition of the samples is represented with the formula (Na_1.90K_0.22Ca_0.06)[Al_2.24Si_2.76O₁₀]·nH₂O, where n=3.10 for paranatrolite and n=2.31 for tetranatrolite. For both zeolites, thermodynamic functions (vibrational entropy, enthalpy, and free energy function) have been calculated. At T=298.15 K, the values of the heat capacity and entropy are 425.1 ± 0.8 and 419.1 ±0.8 J K⁻¹ mol⁻¹ for paranatrolite and 381.0 ± 0.7 and 383.2 ± 0.7 J K⁻¹ mol⁻¹ for tetranatrolite. Thermodynamic functions for tetranatrolite and paranatrolite with compositions corrected for the amount of extraframework cations and water molecules have also been calculated. The calculation for tetranatrolite with two water molecules and two extraframework cations per formula yields: C _p (298.15)=359.1 J K⁻¹ mol⁻¹, S(298.15) −S(0)=362.8 J K⁻¹ mol⁻¹. Comparing these values with the literature data for the (Al,Si)-ordered natrolite, we can conclude that the order in tetrahedral atoms does not affect the heat capacity. The analysis of derivatives dC/dT for natrolite, paranatrolite, and tetranatrolite has indicated that the water- cations subsystem within the highly hydrated zeolite may become unstable at temperatures above 200 K. Received: 30 July 2001 / Accepted: 15 November 2001     

Electrons in feldspar II: a consideration of the influence of conduction band-tail states on luminescence processes

 Most natural feldspars contain many charged impurities, and display a range of bond angles, distributed about the ideal. These effects can lead to complications in the structure of the conduction band, giving rise to a tail of energy states (below the high-mobility conduction band) through which electrons can travel, but with reduced mobility: transport through these states is expected to be thermally activated. The purpose of this article is twofold. Firstly, we consider what kind of lattice perturbations could give rise to both localized and extended conduction band-tail states. Secondly, we consider what influence the band tails have on the luminescence properties of feldspar, where electrons travel through the sample prior to recombination. The work highlights the dominant role that 0.04–0.05-eV phonons play in both the luminescence excitation and emission processes of these materials. It also has relevance in the dating of feldspar sediments at elevated temperatures. Received: 11 May 2001 / Accepted: 6 September 2001     

Fluid-bearing alkaline carbonate melts as the medium for the formation of diamonds in the Earth''s mantle: an experimental study

We have experimentally studied the formation of diamonds in alkaline carbonate–carbon and carbonate–fluid–carbon systems at 5.7–7.0 GPa and 1150–1700 °C, using a split-sphere multi-anvil apparatus (BARS). The starting carbonate and fluid-generating materials were placed into Pt and Au ampoules. The main specific feature of the studied systems is a long period of induction, which precedes the nucleation and growth of diamonds. The period of induction considerably increases with decreasing P and T, but decreases when adding a C–O–H fluid to the system. In the range of P and T corresponding to the formation of diamonds in nature, this period lasts for tens of hours. The reactivity of the studied systems with respect to the diamond nucleation and growth decreases in this sequence: Na₂CO₃–H₂C₂O₄·2H₂O–C>K₂CO₃–H₂C₂O₄·2H₂O–C>>Na₂CO₃–C>K₂CO₃–C. The diamond morphology is independent of P and T, and is mainly governed by the composition of the crystallization medium. The stable growth form is a cubo-octahedron in the Na₂CO₃ melt, and an octahedron in the K₂CO₃ melt. Regardless of the composition of the carbonate melt, only octahedral diamond crystals formed in the presence of the C–O–H fluid. The growth rates of diamond varied in the range from 1.7 μm/h at 1420 °C to 0.1–0.01 μm/h at 1150 °C, and were used to estimate, for the first time, the possible duration of the crystallization of natural diamonds. From the analysis of the experimental results and the petrological evidence for the formation of diamonds in nature, we suggest that fluid-bearing alkaline carbonate melts are, most likely, the medium for the nucleation and growth of diamonds in the Earth's upper mantle.     

Rare gas isotopes and parent trace elements in ultrabasic-alkaline-carbonatite complexes, Kola Peninsula: identification of lower mantle plume component

During the Devonian magmatism (370 Ma ago) ∼20 ultrabasic-alkaline-carbonatite complexes (UACC) were formed in the Kola Peninsula (north-east of the Baltic Shield). In order to understand mantle and crust sources and processes having set these complexes, rare gases were studied in ∼300 rocks and mineral separates from 9 UACC, and concentrations of parent Li, K, U, and Th were measured in ∼70 samples. ⁴He/³He ratios in He released by fusion vary from pure radiogenic values ∼10⁸ down to 6 × 10⁴. The cosmogenic and extraterrestrial sources as well as the radiogenic production are unable to account for the extremely high abundances of ³He, up to 4 × 10⁻⁹ cc/g, indicating a mantle-derived fluid in the Kola rocks. In some samples helium extracted by crushing shows quite low ⁴He/³He = 3 × 10⁴, well below the mean ratio in mid ocean ridge basalts (MORB), (8.9 ± 1.0) × 10⁴, indicating the contribution of ³He-rich plume component. Magnetites are principal carriers of this component. Trapped ³He is extracted from these minerals at high temperatures 1100°C to 1600°C which may correspond to decrepitation or annealing primary fluid inclusions, whereas radiogenic ⁴He is manly released at a temperature range of 500°C to 1200°C, probably corresponding to activation of ⁴He sites degraded by U, Th decay.Similar ⁴He/³He ratios were observed in Oligocene flood basalts from the Ethiopian plume. According to a paleo-plate-tectonic reconstruction, 450 Ma ago the Baltica (including the Kola Peninsula) continent drifted not far from the present-day site of that plume. It appears that both magmatic provinces could relate to one and the same deep-seated mantle source.The neon isotopic compositions confirm the occurrence of a plume component since, within a conventional ²⁰Ne/²²Ne versus ²¹Ne/²²Ne diagram, the regression line for Kola samples is indistinguishable from those typical of plumes, such as Loihi (Hawaii). ²⁰Ne/²²Ne ratios (up to 12.1) correlate well with ⁴⁰Ar/³⁶Ar ones, allowing to infer a source ⁴⁰Ar/³⁶Ar ratio of about 4000 for the mantle end-member, which is 10 times lower than that of the MORB source end-member. In (³He/²²Ne)_PRIM versus (⁴He/²¹Ne)_RAD plot the Kola samples are within array established for plume and MORB samples; almost constant production ratio of (⁴He/²¹Ne)_RAD ≅ 2 × 10⁷ is translated via this array into (³He/²²Ne)_PRIM ∼ 10. The latter value approaches the solar ratio implying the non-fractionated solar-like rare gas pattern in a plume source.The Kola UACC show systematic variations in the respective contributions of in situ-produced radiogenic isotopes and mantle-derived isotopes. Since these complexes were essentially plutonic, we propose that the depth of emplacement exerted a primary control on the retention of both trapped and radiogenic species, which is consistent with geological observations. The available data allow to infer the following sequence of processes for the emplacement and evolution of Kola Devonian UACC: 1) Ascent of the plume from the lower mantle to the subcontinental lithosphere; the plume triggered mantle metasomatism not later than ∼700 to 400 Ma ago. 2) Metasomatism of the lithosphere (beneath the central part of the Kola Peninsula), including enrichment in volatile (e.g., He, Ne) and in incompatible (e.g., U, Th) elements. 3) Multistage intrusions of parental melts, their degassing, and crystallisation differentiation ∼370 Ma ago. 4) Postcrystallisation migration of fluids, including loss of radiogenic and of trapped helium. Based on model compositions of the principle terrestrial reservoirs we estimate the contributions (by mass) of the plume material, the upper mantle material, and the atmosphere (air-saturated groundwater), into the source of parent melt at ∼2%, 97.95%, and ∼0.05%, respectively.     

Comparative Re-Os systematics of chondrites: Implications regarding early solar system processes

A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average ¹⁸⁷Re/¹⁸⁸Os for carbonaceous chondrites is 0.392 ± 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ± 0.025 and 0.421 ± 0.013 for ordinary and enstatite chondrites (1σ standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ± 0.0031, 0.0876 ± 0.0052 and 0.0874 ± 0.0027, respectively. Correspondingly, the ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites average 0.1262 ± 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ± 0.0017 and 0.1281 ± 0.0004, respectively (1σ standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history.A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga.The ¹⁸⁷Os/¹⁸⁸Os ratio of Earth’s primitive upper mantle has been estimated to be 0.1296 ± 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites.     

A Comparison of Two-Phase Dynamic Upscaling Methods Based on Fluid Potentials

Although a number of methods for calculating dynamic pseudo-functions have been developed over the years, there is still a lack of understanding as to why a certain method will succeed in some cases but fail in others. In this paper, we describe the results of an assessment of several upscaling methods, namely the Kyte and Berry (KB) method, the Stone method, the Hewett and Archer (HA) method and the Transmissibility-Weighted (TW) method. We have analyzed the equations for deriving the methods and investigated the results of numerical simulations of gas displacing oil, in a variety of models to enable us to gain new insights into these, and related, upscaling methods. In particular, some novel observations on methods based on fluid potential are presented and the issue of using predicted fluid mobilities as a criterion of accuracy of an upscaling method is clarified.     

Numerical Homogenization of the Rigidity Tensor in Hooke's Law Using the Node-Based Finite Element Method

Combining a geological model with a geomechanical model, it generally turns out that the geomechanical model is built from units that are at least a 100 times larger in volume than the units of the geological model. To counter this mismatch in scales, the geological data model's heterogeneous fine-scale Young's moduli and Poisson's ratios have to be “upscaled” to one “equivalent homogeneous” coarse-scale rigidity. This coarse-scale rigidity relates the volume-averaged displacement, strain, stress, and energy to each other, in such a way that the equilibrium equation, Hooke's law, and the energy equation preserve their fine-scale form on the coarse scale. Under the simplifying assumption of spatial periodicity of the heterogeneous fine-scale rigidity, homogenization theory can be applied. However, even then the spatial variability is generally so complex that exact solutions cannot be found. Therefore, numerical approximation methods have to be applied. Here the node-based finite element method for the displacement as primary variable has been used. Three numerical examples showing the upper bound character of this finite element method are presented.