Standard states for the activities of mineral surface sites and species

A standard state commonly used for the activities of surface sites and surface species is the hypothetical 1.0 Molar standard state, which is implied by the use of molarity-based equilibrium constants. An undesirable practical consequence is that the magnitudes of such equilibrium constants are directly dependent on properties of the solid sorbent such as the site density and surface area. For reactions forming binuclear complexes, the magnitudes of the equilibrium constants even depend on the amount of solid. Although widely used, such equilibrium constants cannot be directly compared with each other without correction for differences in the properties or the amount of the solid. In the present study, new more general and useful standard states are proposed, leading to equilibrium constants independent of the surface area, site density, and the amount of the solid sorbent. Analytical relationships between the old and the new standard states enable conversion of equilibrium constants from one standard state to the other. These results have implications for several different types of surface complexation studies, including studies that correlate and compare equilibrium adsorption constants for different solids, sensitivity-analysis studies of the fitting of surface charge data as functions of pH and ionic strength, and studies employing correlations involving aqueous equilibrium constants for the purpose of predicting equilibrium constants for surface reactions.     

Diagenetic origin of Basal Anhydrite in the Cretaceous Maha Sarakham salt: Khorat Plateau, NE Thailand

Development of a diagenetic anhydrite bed at the base of the Cretaceous Maha Sarakham Saline Formation (the `Basal Anhydrite' member) of the Khorat Plateau in north-eastern Thailand took place due to leaching and/or pressure dissolution of salt at the contact between an underlying active sandstone aquifer system and an overlying massive halite-dominated evaporite sequence. Basal evaporites composed of halite with intercalated anhydrite of the latter sequence are undergoing dissolution as a result of subsurface flushing, with anhydrite produced as the insoluble residue. The result is a 1·1 m thick interval of nodular anhydrite displaying unique, basin-wide continuity. Observed textures, petrographic features and chemical data from the anhydrite and associated authigenic minerals support the origin of the Basal Anhydrite Member as an accumulation residue from the dissolution of the Maha Sarakham salts. Petrographically, the anhydrite in this unit is made up of crystals that are blocky and recrystallized, sheared, generally elongated and broken, and is bounded at the bottom by organic-rich stylolite surfaces. Authigenic and euhedral dolomite and calcite crystals are associated with the anhydrite. Traces of pyrite, galena and chalcopyrite are present along the stylolite surfaces suggesting supply of fresh water from the underlying sandstone at highly reducing conditions of burial. The δ<sup>34</sup>S of sulphate in the Basal Anhydrite averages 15 ‰ (CDT) and falls within the isotopic composition of the anhydrite in the Cretaceous Maha Sarakham Formation proper and the Cretaceous values of marine evaporites. Measured δ<sup>18</sup>O in dolomite range from ?4·37 to ?14·26‰ (PDB) suggesting a re-equilibration of dolomite with basinal water depleted in <sup>18</sup>O and possible recrystallization of dolomite under relatively elevated temperatures. The δ<sup>13</sup>C, however, varies from +1·57 to ?2·53‰ (PDB) suggesting a contribution of carbon from oxidation of organic matter. This basal anhydrite bed, similar to basinwide beds found at the bottom of many giant evaporite sequences, has always been considered to be depositional. Here, at the base of the Maha Sarakham Formation, we demonstrate that the anhydrite is diagenetic in origin and was formed by accumulation of original anhydrite by dissolution of interbedded halite from waters circulating though the underlying aquifer: it represents an `upside-down' caprock.     

The redox state of cerium in basaltic magmas: an experimental study of iron-cerium interactions in silicate melts

Ce(IV)-Ce(III) and Fe(III)-Fe(II) redox equilibria in Ca-Mg-Al-silicate melts have been individually measured with respect to the base composition, melt temperature, imposed oxygen fugacity, and multivalent element concentration (up to about 1.5 wt%). The mutual interaction of these two redox couples has been studied in analogous glasses which simultaneously contained iron and cerium. Analyses of Fe(III) concentrations in iron-cerium glasses by electron paramagnetic resonance and optical absorption spectroscopy indicate that Ce(IV) is stoichiometrically reduced by Fe(II) in the melt to produce Fe(III) and Ce(III) and that Ce(III)-O-Fe(III) complexes are formed in the melt. Consequently, it is concluded that cerium exists only as Ce(III) in basaltic magmas; cerium anomalies cannot be ascribed to the stabilization of Ce(IV) in magmas.     

Geological control of shallow gas and pockmarks in the Norwegian Channel; high resolution shallow subbottom profiling of small scale features

High resolution bathymetric and fine-scale parametric subbottom profiling along a line to the SW of Stavanger, Norway near the NE flank of the Norwegian Channel, show pockmarks clustered over neotectonic shallow fold structures in Quaternary sediments. Detailed profiles of the pockmarks indicate that they are collapsed gas seeps, rather than being collapse structures that followed doming and breaching with a more dramatic gas burst. The gentle folding and weak structures along the margin of a Mesozoic through Cenozoic sedimentary basin are probably due to differential uplift generating light compressional strain.     

The age and palæoenvironmental significance of the Kalahari Sands in western Zimbabwe: a thermoluminescence reconnaissance study

Thermoluminescence (TL) dating, has been applied to 10 samples from the æolian Kalahari Sands of western Zimbabwe using the total bleach (additive dose) and regeneration techniques on coarse-grain quartz separates. The results suggest that the main phases of sand accumulation occurred between 10 and 96 ka. This Upper Pleistocene age is consistent with current opinions and argues against an important period of Holocene æolian activity. The oldest sands were found in the Victoria Falls area where they overlie a ferricrete horizon. Based on our age determinations, we were able to constrain the age of this horizon to between 96±8 and 160±23 ka, which approximately coincides with the Last Integlaciation in the high latitudes. The youngest ages were obtained for sands from the southeastern part of the Hwange dune field but our limited sampling permits assigning only a minimum age of ca 20 ka to the ferricrete horizon observed in this area. Thus, we cannot ascertain if this ferricrete horizon is isochronous with the one at Victoria Falls or if it developed during a younger humid phase.Dune building activity most probably occurred in recurrent cycles of aridity interspersed with periods during which æolian activity was limited or non-existent. Unfortunately, besides the ferricrete horizons, no other stratigraphical evidence of climatic fluctuation has been observed in the study area. However, it is possible that palæosols have been entirely eroded before the subsequent deposition of new sediment, resulting in an incomplete stratigraphical record. The possibilities and limitations of luminescence dating for elucidating phases of climatic fluctuation in such situations are discussed briefly. In addition, we noticed serious discrepancies between the results yielded by the different techniques that were used for determining the dose rate. Hence, further work is needed to validate the accuracy of our dose rate measurements that may cause our TL ages to be about 30% too young.     

The growth of supermassive black holes in pseudo-bulges, classical bulges and elliptical galaxies

Using results from structural analysis of a sample of nearly 1000 local galaxies from the Sloan Digital Sky Survey, we estimate how the mass in central black holes is distributed amongst elliptical galaxies, classical bulges and pseudo-bulges, and investigate the relation between their stellar masses and central stellar velocity dispersion σ. Assuming a single relation between elliptical galaxy/bulge mass, M _Bulge, and central black hole mass, M _BH, we find that  55⁺⁸₋₄  per cent of the mass in black holes in the local universe is in the centres of elliptical galaxies,  41⁺⁴₋₂  per cent in classical bulges and  4^+0.9_−0.4  per cent in pseudo-bulges. We find that ellipticals, classical bulges and pseudo-bulges follow different relations between their stellar masses and σ, and the most significant offset occurs for pseudo-bulges in barred galaxies. This structural dissimilarity leads to discrepant black hole masses if single   M _BH– M _Bulge  and   M _BH–σ  relations are used. Adopting relations from the literature, we find that the   M _BH–σ  relation yields an estimate of the total mass density in black holes that is roughly 55 per cent larger than if the   M _BH– M _Bulge  relation is used.