Arsenite sorption at the magnetite-water interface during aqueous precipitation of magnetite: EXAFS evidence for a new arsenite surface complex

The interaction of aqueous As(III) with magnetite during its precipitation from aqueous solution at neutral pH has been studied as a function of initial As/Fe ratio. Arsenite is sequestered via surface adsorption and surface precipitation reactions, which in turn influence the crystal growth of magnetite. Sorption samples were characterized using EXAFS spectroscopy at the As K-edge in combination with HRTEM observations, energy dispersive X-ray analysis at the nanoscale, electron energy loss spectroscopy at the Fe L₃-edge, and XRD-Rietveld analyses of reaction products. Our results show that As(III) forms predominantly tridentate hexanuclear As(III)O₃ complexes (³C), where the As(III)O₃ pyramids occupy vacant tetrahedral sites on {1 1 1} surfaces of magnetite particles. This is the first time such a tridentate surface complex has been observed for arsenic. This complex, with a dominant As-Fe distance of 3.53 ± 0.02 Å, occurs in all samples examined except the one with the highest As/Fe ratio (0.33). In addition, at the two highest As/Fe ratios (0.133 and 0.333) arsenite tends to form mononuclear edge-sharing As(III)O₃ species (²E) within a highly soluble amorphous As(III)-Fe(III,II)-containing precipitate. At the two lowest As/Fe ratios (0.007 and 0.033), our results indicate the presence of additional As(III) species with a dominant As-Fe distance of 3.30 ± 0.02 Å, for which a possible structural model is proposed. The tridentate ³C As(III)O₃ complexes on the {1 1 1} magnetite surface, together with this additional As(III) species, dramatically lower the solubility of arsenite in the anoxic model systems studied. They may thus play an important role in lowering arsenite solubility in putative magnetite-based water treatment processes, as well as in natural iron-rich anoxic media, especially during the reductive dissolution-precipitation of iron minerals in anoxic environments.     

A model for decoding the life cycle of granular avalanches in a rotating drum

Granular materials can behave as harmless sand dunes or as devastating landslides. A granular avalanche marks the transition between these distinct solid-like and fluid-like states. The solid-like state is typically described using plasticity models from critical state theory. In the fluid regime, granular flow is commonly captured using a visco-plastic model. However, due to our limited understanding of the mechanism governing the solid–fluid-like transition, characterizing the material behavior throughout the life cycle of an avalanche remains an open challenge. Here, we employ laboratory experiments of transient avalanches spontaneously generated by a rotating drum. We report measurements of dilatancy and grain kinematics before, during, and after each avalanche. Those measurements are directly incorporated into a rate-dependent plasticity model that quantitatively predicts the granular flow measured in experiments. Furthermore, we find that dilatancy in the solid-like state controls the triggering of granular avalanches and therefore plays a key role in the solid–fluid-like transition. With the proposed approach, we demonstrate that the life cycle of a laboratory avalanche, from triggering to run out, can be fully explained. Our results represent an important step toward a unified understanding of the physical phenomena associated with transitional behavior in granular media.     

Experimental study of the atmospheric marine boundary layer from in-situ aircraft measurements (TOSCANE-T Campaign): Variability of boundary conditions and eddy flux parameterization

The need for a thorough knowledge of boundary conditions over the vast oceanic surfaces makes remote sensing appear as the most suitable tool for future development. Remote sensing techniques require calibration data and consequently in-situ experiments to yield those data. Over the sea, aircraft seem to be the most convenient means of conducting validation experiments because they allow exploration of a large range of scales (from local measurements to measurements of pixel scale). This paper reports on some in-situ atmospheric aircraft measurements that were conducted as part of the TOSCANE-T experiment organized by the European Space Agency to calibrate the scatterometer for launch on ERS-1 in the early 1990's for global ocean wind measurement.The data analysed are the thermodynamic and turbulent variables measured by an instrumented aircraft, the Hurel Dubois, flying at a constant level of 50 m over the sea surface. Special attention was drawn to the variability of the boundary conditions within areas of 25 × 30 km. In fact, the two-dimensional fields of fluxes and thermodynamic parameters were inhomogeneous with some rather strong wind distortion.The eddy fluxes were parameterized with the aid of bulk aerodynamic formulations at a basic scale of 30 km samples, which corresponds to the aircraft flux computation legs. The bulk aerodynamic coefficients for momentum and heat were found to remain independent of windspeed (for wind velocities less than 12 m/s). Fluxes and thermodynamic parameters were also investigated at two other scales: the integration scale was either reduced to small areas of which size always remains larger than several characteristic lengths of turbulent transfer, or extended to a large area of 25 × 30km. The results of the bulk aerodynamic relationships appeared to be scale invariant, which would therefore justify the application of average values, within the range of scales under study.     

Integrating variations in the soil chloride profile and evaporativity for in-situ estimation of evaporation in arid zones: an application in south-eastern Morocco

In arid regions, knowledge of the evaporation rate from the water table is essential for appropriate management of scarce resources and to prevent land degradation. Soil chloride profiles in the unsaturated zone of a bare soil in an arid area of south-eastern Morocco were used to assess the evaporation flux, using chloride inventories in conjunction with evaporative demand. Moisture fluxes were calculated from measured chloride concentrations on the basis of a steady-state flow model. The chloride profiles displayed large variations in concentrations and had (1) low chloride concentrations near the soil surface, (2) maximum chloride concentrations at depths of 11–14 cm beneath the soil surface, respectively in July and February, and (3) gradually decreasing chloride concentrations while depth increased below these peaks. Evaporative demands were found to be inversely proportional to the depth of evaporation fronts and proportional to evaporation fluxes. In addition, the evaporation along the profiles seems to be controlled by the soil composition and texture. The investigation of chloride profiles in February and July enabled the determination of a value for annual evaporation (～30 mm), which is in good agreement with the value estimated by the Allison-Barnes type model (～32 mm).     

Ancient harbors and Holocene morphogenesis of the Ras Ibn Hani peninsula (Syria)

Ras Ibn Hani peninsula, a wave-dominated tombolo (800 × 1000 m) on the Syrian coast, provides evidence for significant Holocene changes that can be linked to geological inheritance, rising post-glacial sea level, sediment supply and human impacts. Initial development of Ras Ibn Hani's coastal system began ~ 8000 years ago when shallow marine environments formed in a context of rising post-glacial sea level. Following relative sea-level stabilization ~ 6000 cal yr BP, beach facies trace the gradual formation of a wave-dominated sandbank fronted by a ~ 2300 × ~ 500 m palaeo-island whose environmental potentiality was attractive to Bronze Age societies. A particularly rapid phase of tombolo accretion is observed after ~ 3500 cal yr BP characterised by a two- to fourfold increase in sedimentation rates. This is consistent with (i) a pulse in sediment supply probably driven by Bronze Age/Iron Age soil erosion in local catchments, and (ii) positive feedback mechanisms linked to regionally attested neotectonics. Archaeological remains and radiocarbon datings confirm that the subaerial tombolo was probably in place by the Late Bronze Age. These data fit tightly with other eastern Mediterranean tombolo systems suggesting that there is a great deal of predictability to their geology and stratigraphy at the regional scale.     

Properties of a diffuse interface model based on a porous medium theory for solid–liquid dissolution problems

In this paper, a local non-equilibrium diffuse interface model is introduced for describing solid–liquid dissolution problems. The model is developed based on the analysis of Golfier et al. (J Fluid Mech 457:213–254, 2002) upon the dissolution of a porous domain, with the additional requirement that density variations with the mass fraction are taken into account. The control equations are generated by the upscaling of the balance equations for a solid–liquid dissolution using a volume averaging theory. This results into a diffuse interface model (DIM) that does not require an explicit treatment of the dissolving interface, e.g., the use of arbitrary Lagrangian–Eulerian (ALE) methods, for instance. Test cases were performed to study the features and influences of the effective coefficients inside the DIM. In particular, an optimum expression for the solid–liquid exchange coefficient is obtained from a comparison with the referenced solution by ALE simulations. Finally, a Ra–Pe diagram illustrates the interaction of natural convection and forced convection in the dissolution problem.     

Impact of coherent eddies on airborne measurements of vertical turbulent fluxes

During the Hydrological-Atmospheric Pilot Experiment (HAPEX)-Sahel, which took place in Niger in the transitional period between the wet and dry seasons, two French aircraft probed the Sahelian boundary layer to measure sensible and latent heat fluxes. The measurements over the Niamey area often revealed organised structures of a few km scale that were associated with both thermals and dry intrusions. We study the impact of these coherent structures using a single day’s aircraft-measured fluxes and a numerical simulation of that day with a mesoscale model. The numerical simulation at high horizontal resolution (250 m) contains structures that evolve from streaks in the early morning to cells by noon. This simulation shows distribution, variance and skewness similar to the observations. In particular, the numerical simulation shows dry intrusions that can penetrate deeply into the atmospheric boundary layer (ABL), and even reach the surface in some cases, which is in accordance with the observed highly negatively skewed water vapour fluctuations. Dry intrusions and thermals organised at a few km scale give skewed flux statistics and can introduce large errors in measured fluxes. We use the numerical simulation to: (i) evaluate the contribution of the organised structures to the total flux, and (ii) estimate the impact of the organised structures on the systematic and random errors resulting from the 1D sampling of the aircraft as opposed to the 2D numerical simulation estimate. We find a significant contribution by the organised structures to the total resolved fluxes. When rolls occur, and for a leg length of about 30 times the ABL depth, the 1D sampled flux is shown to be sometimes 20% lower than the corresponding 2D flux when the 1D sampling direction is the same as the main axis of the rolls, whereas the systematic error is much lower when the direction of the leg is transverse to the rolls. In the case of cells, an underestimate of around 10% can still be observed with the 1D approach independent of direction, due to poor sampling of the energy-containing scales.     

Interplay between urban communities and human‐crowd mobility: A study using contributed geospatial data sources

An intense process of urbanization, witnessed particularly in the last decade, has stressed the need to comprehend human mobility behavior in urban settings. Although the emergence of contributed geospatial data (i.e., pervasive activity‐based data) has contributed to substantial progress toward understanding human activity, the relationship between human‐crowd mobility and the functional structure of a city is not yet well understood. In this context, the present research focuses on the intra‐urban origin–destination matrix modeling founded on a combination of two major crowdsourced datasets as well as the inclusion of urban communities’ structure. Specifically, the well‐known “radiation” and “PWO” models were modified through first, identifying the communities embedded in the cyberspace network then employing the identified hierarchical structure of the spatial‐interaction network for the formulation of the users’ movement network and second, imposing proper input variables including the telecommunication activity volume and check‐in frequency. The results obtained by various empirical analyses suggest that the modified community‐constrained origin–destination flow estimation models exhibit better performance levels than those of alternative conventional mobility models.