Ultrathin oxides: bulk-oxide-like model surfaces or unique films?

To better understand the electronic and chemical properties of wide-gap oxide surfaces at the atomic scale, experimental work has focused on epitaxial films on metal substrates. Recent findings show that these films are considerably thinner than previously thought. This raises doubts about the transferability of the results to surface properties of thicker films and bulk crystals. By means of density-functional theory and approximate GW corrections for the electronic spectra we demonstrate for three characteristic wide-gap oxides (silica, alumina, and hafnia) the influence of the substrate and highlight critical differences between the ultrathin films and surfaces of bulk materials. Our results imply that monolayer-thin oxide films have rather unique properties.Comment: 5 pages, 3 figures, accepted by PR

Models of the water retention curve for soils with a fractal pore size distribution

The relationship between water content and water potential for a soil is termed its water retention curve. This basic hydraulic property is closely related to the soil pore size distribution, for which it serves as a conventional method of measurement. In this paper a general model of the water retention curve is derived for soil whose pore size distribution is fractal in the sense of the Mandelbrot number-size distribution. This model, which contains two adjustable parameters (the fractal dimension and the upper limiting value of the fractal porosity) is shown to include other fractal approaches to the water retention curve as special cases. Application of the general model to a number of published data sets covering a broad range of soil texture indicated that unique, independent values of the two adjustable parameters may be difficult to obtain by statistical analysis of water retention data for a given soil. Discrimination among different fractal approaches thus will require water retention data of high density and precision. (Résumé d'auteur

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Hydrologic Transport of Dissolved Inorganic Carbon and Its Control on Chemical Weathering

Chemical weathering is one of the major processes interacting with climate and tectonics to form clays, supply nutrients to soil microorganisms and plants, and sequester atmospheric CO2. Hydrology and dissolution kinetics have been emphasized as factors controlling chemical weathering rates. However, the interaction between hydrology and transport of dissolved inorganic carbon (DIC) in controlling weathering has received less attention. In this paper, we present an analytical model that couples subsurface water and chemical molar balance equations to analyze the roles of hydrology and DIC transport on chemical weathering. The balance equations form a dynamical system that fully determines the dynamics of the weathering zone chemistry as forced by the transport of DIC. The model is formulated specifically for the silicate mineral albite, but it can be extended to other minerals, and is studied as a function of percolation rate and water transit time. Three weathering regimes are elucidated. For very small or large values of transit time, the weathering is limited by reaction kinetics or transport, respectively. For intermediate values, the system is transport controlled and is sensitive to transit time. We apply the model to a series of watersheds for which we estimate transit times and identify the type of weathering regime. The results suggest that hydrologic transport of DIC may be as important as reaction kinetics and dilution in determining chemical weathering rates

Cations extraction of sandy-clay soils from Cavado valley, Portugal, using sodium salts solutions

Cases of contamination by metals in the water wells of the Cavado Valley in north-west Portugal can be attributed to the heavy leaching of clay soils due to an excess of nitrogen resulting from the intensive use of fertilisers in agricultural areas. This work focuses on the natural weathering characteristics of soils, particularly the clay material, through the study of samples collected near the River Cavado. Samples taken from various sites, after physico-chemical characterisation, were subjected to clay dissolution tests, using sodium salts of different ionic forces, to detect the relationship between certain physico-chemical parameters of water, such as pH, nitrate, chloride and sulphate content, in the dissolution of clay and the subsequent extraction of such cations as Al, Fe and K. In acidic sandy clay soils, the mineralogical composition of which was characterised by a predominance of quartz, micas, kaolinite and K-feldspars, decreases of the clay material/water pH ratio increases dissolution of the micaceous and K-feldspars phases. The presence of nitrates in the aqueous solution apparently advanced the extraction of all three cations Al, Fe and K. The specific surface area of the clay material showed a significant correlation with the main kinetic parameters of cation extraction.Têm ocorrido casos de contaminações de águas de poços, por metais, no vale do Rio Cávado, região noroeste de Portugal. A princípio, poderiam ser explicáveis pela elevada lixiviação dos solos arenoargilosos da região, quando da prática de adubações intensivas de nitrogênio em áreas agrícolas. Assim, estudaram-se as características do intemperismo natural dos solos, particularmente da fração argila, característica da margem norte do rio Cávado. Coletaram-se amostras de vários locais, que foram submetidas, após caracterização físico-química, a ensaios de dissolução a partir de soluções de sais de sódio com diferentes forças iônicas. O objetivo foi observar as relações de determinados parâmetros físico-químicos da água, tais como: pH, nitratos, cloretos e sulfatos na dissolução das argilas e a conseqüente extração de espécies químicas tais como Al, K e Fe. Para solos areno-argilosos, ácidos, cuja composição mineralógica se caracteriza por um predomínio de quartzo, micas, caulinita e feldspato-K, o abaixamento do pH da suspensão solo/água promove a solubilização das fases micáceas e feldspáticas. A presença do nitrato nas soluções aquosas promoveu aparentemente a extração de todos os três cátions: Al, K e Fe. O efeito da área superfícial específica das partículas dos solos condicionou fortemente vários dos parâmetros cinéticos estudados relativos à extração dos cátions.(undefined

Arsenite sorption and co-precipitation with calcite

Sorption of As(III) by calcite was investigated as a function of As(III) concentration, time and pH. The sorption isotherm, i.e. the log As(III) vs. log [As(OH)3 degrees / Assat] plot is S-shaped and has been modelled on an extended version of the surface precipitation model. At low concentrations, As(OH)3 degrees is adsorbed by complexation to surface Ca surface sites, as previously described by the X-ray standing wave technique. The inflexion point of the isotherm, where As(OH)3 degrees is limited by the amount of surface sites (ST), yields 6 sites nm-2 in good agreement with crystallographic data. Beyond this value, the amount of sorbed arsenic increases linearly with solution concentration, up to the saturation of arsenic with respect to the precipitation of CaHAsO3(s). The solid solutions formed in this concentration range were examined by X-ray and neutron diffraction. The doped calcite lattice parameters increase with arsenic content while c/a ratio remains constant. Our results made on bulk calcite on the atomic displacement of As atoms along [0001] direction extend those published by Cheng et al., (1999) on calcite surface. This study provides a molecular-level explanation for why As(III) is trapped by calcite in industrial treatments.Comment: 9 page

Mechanisms of goethite dissolution in the presence of desferrioxamine B and Suwannee River fulvic acid at pH 6.5

Siderophores are Fe3+ specific low MW chelating ligands secreted by microorganisms in response to Fe stress. Low MW organic acids such as oxalate have been shown to enhance siderophore mediated dissolution of Fe3+ oxides. However, the effect of fulvic acid presence on siderophore function remains unknown. We used batch dissolution experiments to investigate Fe release from goethite in the goethite-fulvic acid desferrioxamine B (goethite-SRFA-DFOB) ternary system. Experiments were conducted at pH 6.5 while varying reagent addition sequence. FTIR and UV-Vis spectroscopy were employed to characterise the Fe-DFOB, Fe-SRFA and DFOB–SRFA complexes. Iron released from goethite in the presence of SRFA alone was below detection limit. In the presence of both SRFA and DFOB, dissolved Fe increased with reaction time, presence of the DFOB-SRFA complex, and where SRFA was introduced prior to DFOB. FTIR data show that in the ternary system, Fe3+ is complexed primarily to oxygen of the DFOB hydroxamate group, whilst the carboxylate C=O of SRFA forms an electrostatic association with the terminal NH3+ of DFOB. We propose that SRFA sorbed to goethite lowers the net positive charge of the oxide surface, thus facilitating adsorption of cationic DFOB and subsequent Fe3+ chelation and release. Furthermore, the sorbed SRFA weakens Fe-O bonds at the goethite surface, increasing the population of kinetically labile Fe. This work demonstrates the positive, though indirect role of SRFA in increasing the bioavailability of Fe3+

A Comparison of Computerized Chemical Models for Equilibrium Calculations in Aqueous Systems

A survey of computer programs which are currently being used to calculate the distribution of species in aqueous solutions, especially natural waters, has been made in order to 1) provide an inventory of available programs with a short description of their uses, 2) compare the consistency of their output for two given test solutions and 3) identify major weaknesses or problems encountered from their use. More than a dozen active programs which can be used for distribution of species and activity calculations for homogeneos equilibria among the major anions and cations of natural waters have been inventoried. Half of these programs can also accept several trace elements including Fe, Al, Mn, Cu, Ni, Zn, Cd, Pb, Ag, Hg, As, Ba, Sr, and B. Consistency between programs was evaluated by comparing the log of the molal concentrations of free ions and complexes for two test solutions: a hypothetical seawater analysis and a hypothetical river water analysis. Comparison of the free major ion concentrations in the river water test case shows excellent agreement for the major species. In the seawater test case there is less agreement and for both test cases the minor species commonly show orders of magnitude differences in concentrations. These differences primarily reflect differences in the thermodynamic data base of each chemical model although other factors such as activity coefficient calculations, redox assumptions, temperature corrections, alkalinity corrections and the number of complexes used all have an affect on the output

Bioavailability in soils

The consumption of locally-produced vegetables by humans may be an important exposure pathway for soil contaminants in many urban settings and for agricultural land use. Hence, prediction of metal and metalloid uptake by vegetables from contaminated soils is an important part of the Human Health Risk Assessment procedure. The behaviour of metals (cadmium, chromium, cobalt, copper, mercury, molybdenum, nickel, lead and zinc) and metalloids (arsenic, boron and selenium) in contaminated soils depends to a large extent on the intrinsic charge, valence and speciation of the contaminant ion, and soil properties such as pH, redox status and contents of clay and/or organic matter. However, chemistry and behaviour of the contaminant in soil alone cannot predict soil-to-plant transfer. Root uptake, root selectivity, ion interactions, rhizosphere processes, leaf uptake from the atmosphere, and plant partitioning are important processes that ultimately govern the accumulation ofmetals and metalloids in edible vegetable tissues. Mechanistic models to accurately describe all these processes have not yet been developed, let alone validated under field conditions. Hence, to estimate risks by vegetable consumption, empirical models have been used to correlate concentrations of metals and metalloids in contaminated soils, soil physico-chemical characteristics, and concentrations of elements in vegetable tissues. These models should only be used within the bounds of their calibration, and often need to be re-calibrated or validated using local soil and environmental conditions on a regional or site-specific basis.Mike J. McLaughlin, Erik Smolders, Fien Degryse, and Rene Rietr