Chemical alteration of tephra in the depositional environment: theoretical stability modelling

The study of the chemical stability of vitreous material in aqueous media is well‐established. There has to date been little consideration of the implications of variations in the chemical durability of tephra in Quaternary tephrochronology. Chemical alteration can take the form of cationic leaching from the matrix, or complete destruction of the silica network, either of which could constrain the ability to chemically identify distal tephra. Here we apply established models of vitreous durability to the published chemical analyses of a large number of Icelandic tephras in order to predict their relative durabilities under equivalent conditions. This suggests that some important tephras have relatively poor chemical stability, and that rhyolitic tephras are, in general, more stable than basaltic. We conclude that tephras should be expected to show predictable differential chemical stability in the post‐depositional environment. Copyright © 2003 John Wiley & Sons, Ltd.     

The structural role of Ti in aluminosilicate liquids in the glass transition range: insights from heat capacity and shear viscosity measurements

The shear viscosities and 1 bar heat capacities of glasses and melts along the 67mol% silica isopleth in the system SiO₂-Al₂O₃-Na₂O-TiO₂ have been determined in the temperature ranges 780-1140 K and 305-1090 K respectively. Anomalous behaviour of both these properties is observed for compositions rich in TiO₂ and/or Al₂O₃, an observation attributed to liquid-liquid phase separation followed by anatase crystallization. For samples which do not show anomalous behaviour, it is found that the partial molar heat capacity of the TiO₂ component previously determined in Al-free compositions reproduces our heat capacities to within 1.3%. Viscosity data show that addition of TiO₂ tends to increase viscosity and melt fragility at constant temperature. Furthermore, heat capacity and viscosity data may be combined within the framework of the Adam-Gibbs theory to extract values of the configurational entropy of the liquids and qualitative estimates of the variation of the average energy barrier to viscous flow. Configurational entropy at 900K is inferred to decrease upon addition of TiO₂, in contrast to previous results from Al-free systems. The compositional limit separating normal from anomalous behaviour, as well as the data for homogenous melts have been used to constrain the structural role of Ti in these samples. Our data are consistent with a majority of Ti in five-fold coordination associated with a titanyl bond, in agreement with previous spectroscopic studies. Furthermore, we find no evidence for a Ti-Al interaction in our samples, and we are led to the conclusion that Al and Ti are incompletely mixed, a hypothesis consistent with the observed reduction of configurational entropy upon addition of TiO₂, suggesting an important role of medium range order in controlling the variations in thermodynamic properties.     

Determining the maximum degree of harmonic coefficients in geopotential models by Monte Carlo methods

Random errors for the harmonic coefficients of a geopotential model are generated from the matrix of normal equations by a parallel computer applying the Gibbs sampler. This leads to random values for the harmonic coefficients. They are transformed by nonlinear, quadratic transformations to random values for the square roots of degree variances, of mean squares of geoid undulations and gravity anomalies. The expected values of these quantities are not equal to the values of these quantities computed by the estimated harmonic coefficients, due to correlations and errors in the estimation. By hypothesis tests estimated harmonic coefficients distorted by correlations and errors are detected. Applying the tests to the geopotential model ITG-CHAMP01 of the Institute of Theoretical Geodesy in Bonn it is concluded that above the degree 62 the harmonic coefficients cannot add any information to the geopotential model.     

Conditional Simulation of Random Fields with Bivariate Gamma Isofactorial Distributions

This work focuses on a random function model with gamma marginal and bivariate isofactorial distributions, which has been applied in mining geostatistics for estimating recoverable reserves by disjunctive kriging. The objective is to widen its use to conditional simulation and further its application to the modeling of continuous attributes in geosciences. First, the main properties of the bivariate gamma isofactorial distributions are analyzed, with emphasis in the destructuring of the extreme values, the presence of a proportional effect (higher variability in high-valued areas), and the asymmetry in the spatial correlation of the indicator variables with respect to the median threshold. Then, we provide examples of stationary random functions with such bivariate distributions, for which the shape parameter of the marginal distribution is half an integer. These are defined as the sum of squared independent Gaussian random fields. An iterative algorithm based on the Gibbs sampler is proposed to perform the simulation conditional to a set of existing data. Such ‘multivariate chi-square’ model generalizes the well-known multigaussian model and is more flexible, since it allows defining a shape parameter which controls the asymmetry of the marginal and bivariate distributions.     

确定沉积岩成岩作用顺序的定量方法

本文从热力学基本定律出发，将复杂的成岩作用过程归结为各种不同的化学反应，从而建立了一套利用反应自由能定量确定成岩作用顺序的方法。该方法将沉积岩成岩作用历史研究从定性引向定量，使其更具理论依据，结果更可靠。利用本方法对国内外两个不同碎屑岩定量研究结果表明，这种方法获得的结果与传统方法的顺序完全一致，从而说明了该方法的良好实用性。     

Heat capacity of γ-Fe2SiO4 between 5 and 303 K and derived thermodynamic properties

A multi-anvil device was used to synthesize 24 mg of pure γ-Fe₂SiO₄ crystals at 8.5 GPa and 1,273 K. The low-temperature heat capacity (C _p) of γ-Fe₂SiO₄ was measured between 5 and 303 K using the heat capacity option of a physical properties measurement system. The measured heat capacity data show a broad λ-transition at 11.8 K. The difference in the C _p between fayalite and γ-Fe₂SiO₄ is reduced as the temperature increases in the range of 50–300 K. The gap in C _p data between 300 and 350 K of γ-Fe₂SiO₄ is an impediment to calculation of a precise C _p equation above 298 K that can be used for phase equilibrium calculations at high temperatures and high pressures. The C _p and entropy of γ-Fe₂SiO₄ at standard temperature and pressure (S°₂₉₈) are 131.1 ± 0.6 and 140.2 ± 0.4 J mol⁻¹ K⁻¹, respectively. The Gibbs free energy at standard pressure and temperature (ΔG° _f,298) is calculated to be −1,369.3 ± 2.7 J mol⁻¹ based on the new entropy data. The phase boundary for the fayalite–γ-Fe₂SiO₄ transition at 298 K based on current thermodynamic data is located at 2.4 ± 0.6 GPa with a slope of 25.4 bars/K, consistent with extrapolated results of previous experimental studies.     

Gibbs sampler by sampling-importance-resampling

Among the Markov chain Monte Carlo methods, the Gibbs sampler has the advantage that it samples from the conditional distributions for each unknown parameter, thus decomposing the sample space. In the case the conditional distributions are not tractable, the Gibbs sampler by means of sampling-importance-resampling is presented here. It uses the prior density function of a Bayesian analysis as the importance sampling distribution. This leads to a fast convergence of the Gibbs sampler as demonstrated by the smoothing with preserving the edges of 3D images of emission tomography.     

长江水系水文地球化学特征及主要离子的化学成因

在分析长江流域76个位点的水化学数据的基础上,运用吉布斯(Gibbs)图、三角图、主成分分析方法研究岩性对长江水表河水中离子化学特征的影响和流域的主要风化过程.结果表明,长江水系的主要离子化学特征受岩石风化作用的影响,其中碳酸盐和蒸发岩矿物对干流水系溶质的贡献率分别为43.6%和37.9%,而对支流水系溶质的贡献率分别为33.1%和39.1%.干流流域内主要的风化反应以白云石和方解石的溶解为主,而支流流域内C1~-/(Na~++K~+)接近1:1,体现出蒸发岩风化的显著特性.Si/K比值较低,表明长江流域内的风化反应是在表生环境中进行的,且产物是富含阳离子的次生矿物.     

The Energy Relationship between Ions and Soil Particles based on Wien Effect and Its Application in Soil Science

The interaction between ions and soil particles plays an important role in the mobilization and bioavailability of ions in soils, which is one of the main research areas of soil chemistry. The new method based on suspension Wien effect has been developed recently to determine the binding energy and adsorption energy between ions and soil particles. Compared with other methods on the basis of adsorption isotherm or ions activity, Wien effect method has more advantages including convenience and direct measurement. The term suspension Wien effect refers to the increase of electrical conductivity of suspension with increasing applied electrical field. In this review paper, we introduced the fundamentals of suspension Wien effect, the apparatus about the Wien effect measurement, and along with demonstrating their application to quantifying the particles-ions interactions for several systems of soils. Our studies indicated that divalent cations have larger binding energies and adsorption energies on soil particles than monovalent because of the electrostatic interaction. However, few studies about the interaction between Cr³⁺ and La³⁺ on soil particles showed that the binding energy and adsorption energy of trivalent cations are lower than those of divalent cations because of hydrolysis. Soil properties such as soil organic matter, soil pH, and iron oxides significantly affected the binding energy and adsorption energy of ions. Our results deepened our understanding about the non specific adsorption of ions in soil chemistry, and enlarged the research area of soil chemistry in fundamental and methodology.