Uranium (VI) sorption on colloidal magnetite under anoxic environment: experimental study and surface complexation modelling

Magnetite is one of the most important end member of iron corrosion products under a reducing environment; therefore, it may be one of the first products interacting with radionuclides in a radioactive waste disposal after the canister failure.Nanocrystalline magnetite was synthetised in the laboratory and its main physico-chemical properties (microstructure, surface area, surface charge) were analysed. The stability of the oxide was also investigated under the experimental conditions used in sorption studies. The sorption behaviour of U^VI onto magnetite was analysed under O₂- and CO₂-free conditions in a wide range of pH, ionic strengths and radionuclide concentrations.The uranyl binding to magnetite is characterised by a sorption edge between pH 4 and 5.5, and sorption was found to be independent on the electrolyte concentration, which indicates the formation of inner sphere complexes. The sorption isotherms showed a linear behaviour up to the saturation of the sorption sites with a Langmuir-type behaviour.One of the aims of this work was to find the simplest model capable to reproduce the experimental data. Sorption data were fitted using a classical approximation (diffuse double layer model), considering only one type of surface site and evaluating two different options: the first one involving two different monodentate complexes, and the second one a single binuclear bidentate complex. A highly satisfactory fit of the experimental data was obtained by both approaches in the range of the experimental conditions investigated.     

The high-pressure C2/c–P21/c phase transition along the LiAlSi2O6–LiGaSi2O6 solid solution

Two synthetic single-crystals with composition Li(Al_0.53Ga_0.47)Si₂O₆ and LiGaSi₂O₆ and space group C2/c at room conditions have been studied under pressure by means of X-ray diffraction using a diamond anvil cell. The unit-cell parameters were determined at 12 and 10 different pressures up to P = 8.849 and P = 7.320 GPa for Li(Al_0.53Ga_0.47)Si₂O₆ and LiGaSi₂O₆, respectively. The sample with mixed composition shows a C2/c to P2₁/c phase transformation between 1.814 and 2.156 GPa, first-order in character. The transition is characterised by a large and discontinuous decrease in the unit-cell volume and by the appearance of the b-type reflections (h + k = odd) typical of the primitive symmetry. The Ga end-member shows the same C2/c to P2₁/c transformation at a pressure between 0.0001 and 0.39 GPa. The low-pressure value at which the transition occurred did not allow collecting any data in the C2/c pressure stability field except that on room pressure. Our results compared with those relative to spodumene (LiAlSi₂O₆, Arlt and Angel 2000a) indicate that the substitution of Al for Ga at the M1 site of Li-clinopyroxenes strongly affects the transition pressure causing a decrease from 3.17 GPa (spodumene) to less than 0.39 GPa (LiGaSi₂O₆) and decreases the volume discontinuity at the transition. As already found for other compounds, the C2/c low-pressure phases are more rigid than the P2₁ /c high-pressure ones. Moreover, the increase of the M1 cation radius causes a decrease in the bulk modulus K _T0. The axial compressibility among the Li-bearing clinopyroxenes indicates that the c axis is the most rigid for the C2/c phases while it becomes the most compressible for the P2₁ /c phases.     

Debris-flow risk analysis in south Gargano watersheds (Southern-Italy)

This article describes a methodology to analyse debris-flow risk in the torrential watersheds of the southern hillside of Gargano (Puglia—Italy). The approach integrates a stability model that identifies the areas of potential shallow landslides in different meteorological conditions with a two-dimensional flood routing model that allows hazard mapping and GIS interface. The results were combined with a susceptibility map that was defined by analyzing the vulnerability conditions and the exposure of the alluvial fan. The models were calibrated on the 1972, July catastrophic event for which the distribution of rainstorm intensity was available. The geo-mechanical properties of the debris were studied by field surveys and laboratory tests while the sediment source areas and the shape of the alluvial cone were obtained using photo-aerial interpretation. The risk conditions of the areas under consideration were also investigated in order to plan and guide measures aimed at limiting the damage such hazards may cause.     

Effects of quasar feedback in galaxy groups

We study the effect of quasar feedback on distributions of baryons in galaxy groups using high-resolution numerical simulations. We use the entropy-conserving gadget code that includes gas cooling and star formation, modified to include a physically based model of quasar feedback. For a sample of 10 galaxy group-sized dark matter haloes with masses in the range of  1–5 × 10¹³ M_⊙  h ⁻¹  , star formation is suppressed by more than 50 per cent in the inner regions due to the additional pressure support by quasar feedback, while gas is driven from the inner region towards the outer region of the haloes. As a result, the average gas density is 50 per cent lower in the inner region and 10 per cent higher in the outer region in the simulation, compared to a similar simulation with no quasar feedback. Gas pressure is also higher in the outer region, while temperature and entropy are enhanced in the inner region. The total group gas fraction in the two simulations generally differs by less than 10 per cent. We also find a small change of the total thermal Sunyaev–Zeldovich distortion, leading to 10 per cent changes in the microwave angular power spectrum at angular scales below 2 arcmin.     

Seismic images and rock properties of the very shallow structure of Campi Flegrei caldera (southern Italy)

In September 2001, an extensive active-seismic investigation (Serapis experiment) was carried out in the Gulfs of Naples and Pozzuoli, with the aim of investigating and reconstructing the shallow crustal structure of the Campi Flegrei caldera, and possibly identifying its feeding system at depth. The present study provides a joint analysis of the very shallow seismic reflection data and tomographic images based on the Serapis dataset. This is achieved by reflection seismic sections obtained by the 3D data gathering and through refined P-velocity images of the shallowest layer of Pozzuoli Gulf (z < 1,000 m). From the refined Vp model, the overall picture of the velocity distribution confirms the presence of a complex arc-shaped anomaly that borders the bay offshore. The deeper part of the anomaly (beneath 700 m, with Vp > 3,500 m/s) correlates with units made up of agglomerate tuffs and interbedded lava, which form the southern edge of the caldera, which was probably formed following the two large ignimbritic eruptions that marked the evolutionary history of the area under study. The upper part of the anomaly that tends to split into two parallel arcs is correlated with dikes, volcanic mounds and hydrothermal alteration zones noted in previous shallow reflection seismic analyses. The depth of the transition between the upper and lower parts of the anomaly is characterized by an abrupt Vp increase on the one-dimensional (1D) profiles extracted from the 3D tomographic model and by the presence of a strong reflector located at about 0.6/0.7 s Two Way Time (TWT) on Common Mid Point gathers. The move-out velocity analysis and stack of the P–P and P–S reflections at the layer bottom allowed to estimate relatively high Vp/Vs values (3.7 ± 0.9). This hypothesis has been tested by a theoretical rock physical modeling of the Vp/Vs ratio as a function of porosity suggesting that the shallow layer is likely formed by incoherent, water saturated, volcanic and marine sediments that filled Pozzuoli Bay during the post-caldera activity.     

Behaviour of Fe<Subscript>4</Subscript>O<Subscript>5</Subscript>–Mg<Subscript>2</Subscript>Fe<Subscript>2</Subscript>O<Subscript>5</Subscript> solid solutions and their relation to coexisting Mg–Fe silicates and oxide phases

Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe₄O₅–Mg₂Fe₂O₅ solid solutions and (2) to explore the phase relations involving (Mg,Fe)₂Fe₂O₅ (denoted as O₅-phase) and Mg–Fe silicates. Multi-anvil experiments were performed at 11–20 GPa and 1100–1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O₅-phase coexists with Fe₂O₃, hp-(Mg,Fe)Fe₂O₄, (Mg,Fe)₃Fe₄O₉ or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O₅-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe³⁺-bearing phase B. However, (Mg,Fe)₂Fe₂O₅ does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe²⁺ and Fe³⁺ (at least ~?1.0 cations Fe per formula unit). Fe-L_2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe³⁺/Fe_tot?=?~?0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si⁴⁺?+?[6]Mg²⁺?=?2Fe³⁺. The ability to accommodate Fe²⁺ and Fe³⁺ makes this potential “water-storing” mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg₂Fe₂O₅ have been refined, yielding H°_1bar,298?=???1981.5 kJ mol^??1. Solid solution is complete across the Fe₄O₅–Mg₂Fe₂O₅ binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe²⁺ with silicates indicates that (Mg,Fe)₂Fe₂O₅ has a strong preference for Fe²⁺. Modelling of partitioning with olivine is consistent with the O₅-phase exhibiting ideal mixing behaviour. Mg–Fe²⁺ partitioning between (Mg,Fe)₂Fe₂O₅ and ringwoodite or wadsleyite is influenced by the presence of Fe³⁺ and OH incorporation in the silicate phases.     

Crystal structure of columbite under high pressure

The structural evolution of two columbites under pressure, one ferrocolumbite from Raode (Africa) and one manganocolumbite from Kragero (Norway), has been determined by single-crystal X-ray diffraction. Structural investigations at high pressure have been carried out on samples which were preliminarily annealed to attain the complete cation-ordered state. For each crystal, five complete datasets have been collected from room pressure up to ca. 7 GPa. Structure refinements converged to final discrepancy factors R ranging between 5.2 and 5.8% for both the crystals. Structure refinements of X-ray diffraction data at different pressures allowed characterisation of the mechanisms by which the columbite structure accommodates variations in pressure. A and B octahedral volumes in both samples decrease linearly as pressure increases, with a larger compression of the larger A site. The difference in polyhedral bulk moduli of the A sites for the two samples does not appear to relate directly to the octahedral sizes, the A site being more compressible in the Fe-rich sample than in the Mn-rich one. By far the most compressible direction in both the analysed samples is along b. The cations are in fact free to move along this direction, thus allowing the octahedral chains to slide over each other; this effect is particularly evident in the manganocolumbite sample which shows a steep shortening of interchain A–B distances along b.