Prediction of surface charge on oxides in salt solutions: Revisions for 1:1 (ML) electrolytes     

Dimitri A. Sverjensky 《Geochimica et cosmochimica acta》2005,69(2):225-257

Quantitative characterization of the development of proton surface charge on the surfaces of minerals is necessary for a fundamental understanding of reactions between minerals and aqueous electrolyte solutions. Despite many experimental studies of charge development, few attempts have been made to integrate the results of such studies with a theoretical framework that permits prediction. The present study builds on a theoretical framework to analyze a total of 55 sets of proton surface charge data referring to wide ranges of ionic strengths, and types of electrolyte and oxide. The resulting parameters were interpreted with the aid of crystal chemical, electrostatic, and thermodynamic theory, which enable a number of generalizations. Prediction of values of the pHZPC and ΔpKnθ reduces the number of triple-layer parameters to be estimated. New standard states for the equilibrium constants for electrolyte adsorption (KM+θ and KL−θ) permit direct comparison of samples with a range of surface areas or site densities. Predicted cation binding on high dielectric constant solids (e.g., rutile) shows KM+θ, increasing in the sequence Cs+, Rb+, K+, Na+, Li+. In contrast, on low dielectric constant solids (e.g., amorphous silica), the predicted sequence is Li+, Na+, K+, Rb+, Cs+. The opposite sequences are attributable to the large solvation energy contribution opposing adsorption on low-dielectric constant solids. Cation and anion binding constants are in general different, which enables direct prediction of the point-of-zero-salt effect (pHPZSE) relative to the pristine point-of-zero charge. The inner and outer capacitances in the triple-layer model (C1 and C2) are predictable parameters consistent with physically reasonable distances and interfacial dielectric constants for water. In summary, all the parameters in the triple-layer model can be estimated with the revised equations of this study, which enables prediction of proton surface charge for any oxide in 1:1 electrolyte solutions independent of experiments. Such predictions can serve as a complement to the experimental study of new oxide/electrolyte systems, or more complex systems, where additional mechanisms of charge development are likely.  相似文献   

Physical constraints in engineering seismic hazard analysis     

Dimitri Papastamatiou  Sarada K. Sarma 《地震工程与结构动力学》1988,16(7):967-984

In engineering seismic hazard probabilistic analysis, physical constraints are generally overlooked. We formulate such constraints for the general case of a site within an annular seismogenic zone. This configuration provides a first approximation of seismic hazard analysis within a broad zone undergoing crustal deformation; such zones are a common expression of continental tectonics. Applications are restricted to medium size earthquakes (M_s < 7). The formulation is applied to two cases reflecting the mid-plate (case I) and plate boundary (case II) seismotectonic environments. It is found that, for a given strain rate and for an upper bound magnitude of 6 3/4, the extreme hazard in both the environments is the same but of different character. In the plate boundary example, it is associated with widespread ground deformation while in the mid-plate example, it involves more intense ground motion. On the other hand, if the upper bound magnitude is 5 3/4, the extreme hazard is likely to be an order of magnitude less in case I than in case II. Moreover, when the extreme hazard is associated with singular conditions generated by a single fault, the assumption of a Poissonian process may not be safe for earthquake resistant design decisions.  相似文献   

Strengthening the Ties Between Tourism and Economic Geography: A Theoretical Agenda*     

Dimitri Ioannides 《The Professional geographer》1995,47(1):49-60

This paper stresses the importance of bridging the conceptual gap between tourism research and economic geography. It explains why the tourism production system has been unable to avoid its peripheral position in economic geography. The paper then focuses on the structure and organization of the principal agents comprising the tourism production system and identifies the state's pivotal role as coordinator of these agents. Lastly, it highlights two under-researched issues relating to entreprcneurship and labor pools and makes recommendations for further research.  相似文献   

Atmospheric lee waves in the Aegean Sea and their possible influence on the sea surface     

Lucien Wald  Dimitri Georgopoulos 《Boundary-Layer Meteorology》1984,28(3-4):309-315

Unusual satellite images of the Aegean Sea, in both the visible and infrared ranges, are discussed. Alternating bright and dark features downwind of islands suggest the presence of atmospheric lee waves. However, close examination of these features indicates that the observed signal is likely the signature of the influence of the lee waves on the sea surface rather than the signature of the lee waves themselves through atmospheric effects.  相似文献   

Prediction of Gibbs free energies of calcite-type carbonates and the equilibrium distribution of trace elements between carbonates and aqueous solutions     

Dimitri A Sverjensky 《Geochimica et cosmochimica acta》1984,48(5):1127-1134

A linear correlation exists between the standard Gibbs free energies of formation of calcite-type carbonates (MCO3) and the corresponding conventional standard Gibbs free energies of formation of the aqueous divalent cations (M2+) at 25 °C and 1 bar ΔGMCO30 = m(ΔGf,M2+0) ? 141,200 cal · mole?1 where m is equal to 0.9715. This relationship enables prediction of the standard free energies of formation of numerous hypothetical carbonates with the calcite structure. Associated uncertainties typically range from about ± 250 to 600 cal · mole?1. An important consequence of the above correlation is that the thermodynamic equilibrium constant for the distribution of two trace elements M and N between carbonate mineral and aqueous solution at 25 °C and 1 bar is proportional to the free energy difference between the corresponding two aqueous ions: In Combination of predicted standard free energies, entropies and volumes of carbonate minerals at 25°C and 1 bar with standard free energies of aqueous ions and the equation of state in Helgesonet al. (1981) enables prediction of the thermodynamic equilibrium constant for trace element distribution between carbonates and aqueous solutions at elevated temperatures and pressures. Interpretation of the thermodynamic equilibrium constant in terms of concentration ratios in the aqueous phase is considerably simplified if pairs of divalent trace elements are considered that have very similar ionic radii (e.g., $\text{Sr}{}^{\mathrm{2+}}\text{Pb}{}^{\mathrm{2+}}$, $\text{Mg}{}^{\mathrm{2+}}\text{Zn}{}^{\mathrm{2+}}$). In combination with data for the stabilities of complex ions in aqueous solutions, the above calculations enable useful limits to be placed on the concentrations of trace elements in hydrothermal solutions.  相似文献   

Changes of macrobenthos composition under different ENSO cycle conditions on the continental shelf off central Chile     

Javier Sellanes  Eduardo Quiroga  Carlos Neira  Dimitri Gutiérrez 《Continental Shelf Research》2007

The course of environmental conditions and shelf macrobenthic communities off Central Chile (∼36°S) during the strong 1997–98 El Niño (EN) event is compared with a subsequent and basically “normal” period (2002–2003). Changes in macrofaunal community, feeding mode structure, and biomass size spectra are contrasted over time with changes in oceanographic and sediment settings, in order to assess intra- and inter-annual changes in faunal composition during both ENSO periods.  相似文献   

Numerical quantification of sources and phase partitioning of chemical species in cloud: application to wintertime anthropogenic air masses at the Puy de Dôme station     

Maud Leriche  R. Lyana Curier  Laurent Deguillaume  Dimitri Caro  Karine Sellegri  Nadine Chaumerliac 《Journal of Atmospheric Chemistry》2007,57(3):281-297

The Model of Multiphase Cloud Chemistry M2C2 has recently been extended to account for nucleation scavenging of aerosol particles in the cloud water chemical composition. This extended version has been applied to multiphase measurements available at the Puy de Dôme station for typical wintertime anthropogenic air masses. The simulated ion concentrations in cloud water are in reasonable agreement with the experimental data. The analysis of the sources of the chemical species in cloud water shows an important contribution from nucleation scavenging of particles which prevails for nitrate, sulphate and ammonium. Moreover, the simulation shows that iron, which comes only from the dissolution of aerosol particles in cloud water, has a significant contribution in the hydroxyl radical production. Finally, the simulated phase partitioning of chemical species in cloud are compared with measurements. Numerical results show an underestimation of interstitial particulate phase fraction with respect to the measurements, which could be due to an overestimation of activated mass by the model. However, the simulated number scavenging efficiency of particles agrees well with the measured value of 40% of total number of aerosol particles activated in cloud droplets. Concerning the origin of chemical species in cloud water, the model reproduces quite well the contribution of gas and aerosol scavenging estimated from measurements. In addition, the simulation provides the contribution of in-cloud chemical reactivity to cloud water concentrations.  相似文献   

Determination of the poroelasticity of shale     

Ma  Shuqi  Gutierrez  Marte 《Acta Geotechnica》2021,16(2):581-594

Shales play important roles in various civil, energy and environmental engineering applications. Shales are categorized as poroelastic materials due to their tight and very stiff structure, and reliable poroelastic properties are required when dealing with shales. This paper presents simple procedures to determine the poroelastic properties of rocks using oedometer and triaxial consolidation tests. The procedures, which avoid the difficulty to perform determination of the unjacketed bulk modulus of the rock minerals, are demonstrated on a North Sea shale. The experimentally obtained Biot coefficient α and the drained bulk modulus K of the shale range from 0.95 to 0.99, and from 0.17 to 2.00 GPa, respectively. The Biot coefficient α and the drained bulk modulus K values determined from the oedometer and triaxial tests are compared and show good agreement and consistency between the two test procedures. The Skempton’s coefficient B-value of the triaxial samples was also experimentally measured prior to the triaxial consolidation tests. The theoretically predicted B-value varies from 0.81 to 0.96 which is, on the average, only about 10% higher than the experimentally obtained B-value which range from 0.80 to 0.85.

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Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite     

Carla?TiraboschiEmail authorView author&#;s OrcID profile  Simone?Tumiati  Dimitri?Sverjensky  Thomas?Pettke  Peter?Ulmer  Stefano?Poli 《Contributions to Mineralogy and Petrology》2018,173(1):2

We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 °C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni–NiO–H₂O (ΔFMQ = ??0.21 to ??1.01), employing a double-capsule setting. Fluids, binary H₂O–CO₂ mixtures at the P, T, and fO₂ conditions investigated, were generated from graphite, oxalic acid anhydrous (H₂C₂O₄) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO₂-bearing fluids. The experimental data show that forsterite?+?enstatite solubility in H₂O–CO₂ fluids is higher compared to pure water, both in terms of dissolved silica (mSiO₂?=?1.24 mol/kg_H2O versus mSiO₂?=?0.22 mol/kg_H2O at P?=?1 GPa, T?=?800 °C) and magnesia (mMgO?=?1.08 mol/kg_H2O versus mMgO?=?0.28 mol/kg_H2O) probably due to the formation of organic C–Mg–Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H₂O–CO₂ fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO₂ ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO₂ ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P–T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle.  相似文献   

Distribution of erosion across bedrock channels     

Jens M. Turowski  Niels Hovius  Hsieh Meng‐Long  Dimitri Lague  Chen Men‐Chiang 《地球表面变化过程与地形》2008,33(3):353-363

Lateral erosion in bedrock rivers is an important control on the shape of channel cross‐sections, and the coupling of channels and hillslopes. Recent observations link lateral erosion to the variability of flow. We propose two mechanisms to explain this. One is based on changing shear stress distributions within the channel with varying flood level, the other on the competition between cover and tool effects in fluvial bedrock erosion. We assess these processes for the Liwu River, Taiwan, and conclude that cover and tool effects dominate the partitioning of lateral and vertical erosion in this case. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献