Assessment of alternative adsorption models and global sensitivity analysis to characterize hexavalent chromium loss from soil to surface runoff

We investigate our ability to assess transfer of hexavalent chromium, Cr(VI), from the soil to surface runoff by considering the effect of coupling diverse adsorption models with a two‐layer solute transfer model. Our analyses are grounded on a set of two experiments associated with soils characterized by diverse particle size distributions. Our study is motivated by the observation that Cr(VI) is receiving much attention for the assessment of environmental risks due to its high solubility, mobility, and toxicological significance. Adsorption of Cr(VI) is considered to be at equilibrium in the mixing layer under our experimental conditions. Four adsorption models, that is, the Langmuir, Freundlich, Temkin, and linear models, constitute our set of alternative (competing) mathematical formulations. Experimental results reveal that the soil samples characterized by the finest grain sizes are associated with the highest release of Cr(VI) to runoff. We compare the relative abilities of the four models to interpret experimental results through maximum likelihood model calibration and four model identification criteria (i.e., the Akaike information criteria [AIC and AIC_C] and the Bayesian and Kashyap information criteria). Our study results enable us to rank the tested models on the basis of a set of posterior weights assigned to each of them. A classical variance‐based global sensitivity analysis is then performed to assess the relative importance of the uncertain parameters associated with each of the models considered, within subregions of the parameter space. In this context, the modelling strategy resulting from coupling the Langmuir isotherm with a two‐layer solute transfer model is then evaluated as the most skilful for the overall interpretation of both sets of experiments. Our results document that (a) the depth of the mixing layer is the most influential factor for all models tested, with the exception of the Freundlich isotherm, and (b) the total sensitivity of the adsorption parameters varies in time, with a trend to increase as time progresses for all of the models. These results suggest that adsorption has a significant effect on the uncertainty associated with the release of Cr(VI) from the soil to the surface runoff component.     

Opposition polarimetry and photometry of S- and E-type asteroids

The first results of the observational program devoted to simultaneous investigation of asteroid polarimetric and photometric opposition phenomena are presented. UBVRI polarimetric and V-band photometric observations of the S-type Asteroid 20 Massalia and the E-type Asteroids 214 Aschera and 620 Drakonia were carried out in 1996-1999 down to phase angles of 0.08°, 0.7°, and 1.2°, correspondingly. The S-type Asteroid 20 Massalia is characterized by the pronounced brightness opposition surge with an amplitude larger than that observed for the E-type asteroids. A sharp peak of negative polarization at small phase angles was not observed for this asteroid. The value of polarization degree at phase angle α<1° is less than 0.5% for both S and E types. The negative polarization branches of S and especially E-asteroids have an asymmetrical shape. The phase angle at which the polarization minimum occurs is close to the angle at which non-linear increase begins in the asteroid magnitude phase curves. A relation of the observed effects to the mechanism of coherent backscattering is discussed.     

Semi-Classical Cosmological Models with Scalar, Dirac and Electromagnetic Fields

Exact solutions of the semi-classical Einstein equations for conformally invariant free quantum fields in an homogeneous and isotropic space-time, with cosmological constant and containing a classical scalar field, dust matter, an unquantised Dirac field and electromagnetic radiation are found. The initial behaviour of the semiclassical models is investigated. Some of the solutions found avoid the singularity and do not have particle horizons. This revised version was published online in July 2006 with corrections to the Cover Date.     

The luminosity oscillation of X-ray bursters and recurrent novae

Thermo-mechanical oscillations of a radiating spherically-symmetric shell containing a fermion gas (i.e., oscillation where only mechanical, thermodynamical, and eventually radiation phenomena are taken into account) are studied. With a reasonable choice of the three relevant parameters all other observational data are similar to the ones of X-ray bursters and recurrent novae.Therefore, thermo-mechanical oscillations could play an important role in the oscillation spectrum of these astronomical objects.     

Geomorphological hazards related to deep dissolution phenomena in the Western Italian Alps: Distribution, assessment and interaction with human activities

Deep dissolution affects great part of soluble rocks (e.g. gypsum and anhydrite) of the Western Italian Alps. The related superficial phenomena (sinkholes, gravity-induced processes and a local worsening of geomechanical rock properties) are not limited to typical karsts landscape and cause slope instability also affecting populated sites and infrastructures. The paper aims to describe general characteristic of dissolution phenomena, to interpret their conditioning factors and evolutionary stages and to assess possible hazards due to their superficial effects.The search for evidences of deep dissolution leads to the selection of representative sites in the central part of the Western Italian Alps (Piemonte and Valle d'Aosta Region). Detailed geological and geomorphological studies have been used to classify the selected sites by type, size and variable state of activity. Very different evolutionary stages of dissolution phenomena have been interpreted by comparison of case-studies: some are early “embryonic”; others are more evolved, up to typical sinkholes, or even remodelled by other phenomena. Some cases show an extreme complexity in the interactions between corrosion phenomena and other geomorphic processes: slope deformations, from one side, and karst, fluvial and glacial phenomena, to the other. A wide range of movement rates on slope instabilities induced by deep dissolution have been estimated by topographic and geomorphic data. Geochemical data on removed rocks by dissolution indicate 0.4 mm/year values for local subsidence. Historical and technical data indicate low frequency of major dissolution-induced collapses, but highlight widespread damages to tunnels, roads and buildings, especially along slopes.     

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.     

The European vision for oceans and seas—Social and political dimensions of the Green Paper on Maritime Policy for the EU

The EU Green Paper on Maritime Policy is the European response to the new generation of ocean strategies based on science, technology and innovation aimed at new objectives, such as the strengthening of security and access to new resources. The European character of the proposal is found in the presence of social, cultural and historical elements, what is called the “European vision”. The viability of a European vision of the oceans and the idea of maritime empire as an extension of the current concept of empire within the general context of emerging ocean strategies are the elements offered up for debate on this European Union initiative.     

Southern elephant seal trajectories, fronts and eddies in the Brazil/Malvinas Confluence

This study describes the association between transient, mesoscale hydrographic features along the axis of the Brazil–Malvinas Confluence, in the SW Atlantic, and the foraging behavior of 2–3-year-old (focal) juvenile southern elephant seals, Mirounga leonina, from Península Valdés, Argentina. Departing from the dominant pattern of foraging on predictable bathymetric fronts on the Patagonian shelf and slope, three females out of 12 satellite-tracked juveniles remained at the edge of young warm-core eddies and near the outer core of cold-core eddies, coinciding with the most productive areas of these temperature fronts. Seal trajectories along high-temperature gradients were always consistent with the speed and direction of surface currents inferred from the temperature distribution and confirmed by surface drifters. Movements of foraging seals were compared with those of surface drifters, coinciding in time and space and yielding independent and consistent data on regional water circulation parameters. The diving pattern recorded for one focal seal yielded shallower dives and a loose diel pattern in the eddy, and a marked diurnal cycle compatible with foraging on vertically migrating prey in the cold waters of the Malvinas Current. Pre-reproductive females that use the mesoscale fronts of the Argentine Basin as an alternative foraging area would benefit from lower competition with more experienced seals and with other top predators that reproduce along the coast of Patagonia.     

Freezing as a method of sample preservation for the analysis of dissolved inorganic nutrients in seawater

It is often desirable or necessary to store collected seawater samples prior to analysis for dissolved inorganic nutrients. It is therefore important to establish preservation and storage techniques that will ensure sample integrity and will not alter the precision or accuracy of analysis. We have performed a series of experiments on the storage of nutrient samples collected at the oligotrophic North Pacific benchmark Station ALOHA, using both standard autoanalyses and low-level techniques. Our results reveal that for oligotrophic oceanic waters, the immediate freezing of an unfiltered water sample in a clean polyethylene bottle is a suitable preservation method. This procedure is simple, it avoids potentially contaminating sample manipulations and chemical additions, and it adequately preserves the concentrations of nitrate + nitrite, soluble reactive phosphate, and soluble reactive silicate within a single water sample.