G. Lefèvre

Sorption of selenium anionic species on apatites and iron oxides from aqueous solutions.

The sorption of selenite and selenate ions from aqueous solutions was investigated on hydroxyapatite, fluorapatite, goethite and hematite, in order to simulate the behavior of radioactive selenium in natural or artificial sorbing media. Correlation studies with acido-basic properties and solubility of the solids were also performed. The sorption is pH dependant, but these solids are very efficient for retaining selenite at pH values generally encountered in natural waters, with however higher K(d) values for oxides than apatites. Selenate ions are much less sorbed than selenite. Several methods such as electron microscopy and spectroscopic techniques were used to identify the sorption mechanisms. In the case of hydroxyapatite, sorption proceeds by substitution of phosphate groups in the lattice of the apatite crystal in the superficial layers of the solid. In the case of goethite and hematite, sorption can be interpreted and modeled by a surface complexation process, but there is a discrepancy between sorption site densities for selenite and for protons.

Towards a description of particulate fouling: from single particle deposition to clogging.

Particulate fouling generally arises from the continuous deposition of colloidal particles on initially clean surfaces, a process which can even lead to a complete blockage of the fluid cross-section. In the present paper, the initial stages of the fouling process (which include single-particle deposition and reentrainment) are first addressed and current modelling state-of-the-art for particle-turbulence and particle-wall interactions is presented. Then, attention is specifically focused on the later stages (which include multilayer formation, clogging and blockage). A detailed review of experimental works brings out the essential mechanisms occurring during these later stages: as for the initial stages, it is found that clogging results from the competition between particle-fluid, particle-surface and particle-particle interactions. Numerical models that have been proposed to reproduce the later stages of fouling are then assessed and a new Lagrangian stochastic approach to clogging in industrial cases is detailed. These models further confirm that, depending on hydrodynamical conditions (the flow velocity), fluid characteristics (such as the ionic strength) as well as particle and substrate properties (such as zeta potentials), particle deposition can lead to the formation of either a single monolayer or multilayers. The present paper outlines also future numerical developments and experimental works that are needed to complete our understanding of the later stages of the fouling process.

Morphology and surface heterogeneities in synthetic goethites

In the framework on a study of the acido-basic and sorption properties of iron oxides, a thorough characterization of two types of goethite powders was performed in several laboratories joined in a common project. Chemical analysis by ICPAES; high-resolution SEM, TEM, and AFM observations; XRD with line width analysis; and argon and nitrogen sorption isotherms were used for that purpose. The main crystallographic faces of goethite particles could be identified as {001}, {101}, and {121}, and their abundance correlated with the distribution of low-pressure argon adsorption local isotherms. These results will be very useful for further studies on the relationship between surface reactivity in aqueous solution and orientation of solid surfaces.

Numerical Study on the Deposition Rate of Hematite Particle on Polypropylene Walls: Role of Surface Roughness

In this paper, we investigate the deposition of nanosized and microsized particles on rough surfaces under electrostatic repulsive conditions in an aqueous suspension. This issue arises in the general context of modeling particle deposition which, in the present work, is addressed as a two-step process: first particles are transported by the motions of the flow toward surfaces and, second, in the immediate vicinity of the walls, the forces between the incoming particles and the walls are determined using the classical DLVO theory. The interest of this approach is to take into account both hydrodynamical and physicochemical effects within a single model. Satisfactory results have been obtained in attractive conditions but some discrepancies have been revealed in the case of repulsive conditions, in line with other studies which have noted differences between predictions based on the DLVO theory and experimental measurements for similar repulsive conditions. Consequently, the aim of the present work is to focus on this particular range and, more specifically, to assess the influence of surface roughness on the DLVO potential energy. For this purpose, we introduce a new simplified model of surface roughness where spherical protruding asperities are placed randomly on a smooth plate. On the basis of this geometrical description, approximate DLVO expressions are used and numerical calculations are performed. We first highlight the existence of a critical asperity size which brings about the highest reduction of the DLVO interaction energy. Then, the influence of the surface covered by the asperities is investigated as well as retardation effects which can play a role in the reduction of the interaction energy. Finally, by considering the random distribution of the energy barrier of the DLVO potential due to the random geometrical configurations, the overall effect of surface roughness is demonstrated with one application of the complete deposition model in an industrial test case. These new numerical results show that nonzero deposition rates are now obtained even in repulsive conditions, which confirms that surface roughness is a relevant aspect to introduce in general approaches to deposition.

Immobilization of iodide on copper(I) sulfide minerals

In the goal of finding efficient scavengers for radioiodide in conditions (pH, pE) close to those encountered in deep geological sites, sorption of iodide ions on cuprous sulfide minerals (especially roxbyite, Cu(1.75)S) has been studied. Surface analysis by X-ray photoelectron spectroscopy has shown that commercial cuprous sulfides are covered by an oxidized overlayer (mainly in the form of CuSO(4)). Therefore, a synthetic procedure to get roxbyite (typically by mixing Na(2)S with an aqueous suspension of commercial Cu(2)O) was applied to produce pure samples with clean surfaces. Batch equilibration of cuprous sulfide particles suspended in aqueous solutions containing iodide species has revealed significant consumption of iodide. The sorption mechanism involves the formation of a surface complex via the exchange of surface hydroxyl groups by iodide anions, as highlighted by a transient pH increase during the immobilization process. Other copper and mixed copper-iron sulfides (e.g. CuS, CuFeS(2)), which are stable over wide pH and potential ranges are also likely to accumulate iodide species. Because of the specific interaction between iodide and copper(I) centers on the minerals, high distribution coefficients (>1000 ml/g) were observed.

Sorption of uranyl ions on titanium oxide studied by ATR-IR spectroscopy.

ATR-IR spectroscopy was used to study the sorption of uranyl ions (10(-4) M) onto titanium oxide (mixture of rutile and anatase). A circulation setup, filled with a solution in D(2)O, allowed recording of the evolution of the antisymmetric O=U=O stretching of uranyl species onto titanium oxide particles deposited on the ATR crystal. The band centered at 915 cm(-1) has been decomposed in two Gaussian peaks at 920 and 905 cm(-1). From these values, and the observation that the ratio of the areas of the two peaks vs pH was constant, we have proposed that uranyl sorption on titanium oxide in the pH range 4-7 leads to the formation of one surface complex where uranium atoms have two different chemical environments. A trimer surface complex linked by two uranium atoms to the titanium oxide surface would be consistent with this interpretation.

Effect of solubility on the determination of the protonable surface site density of oxyhydroxides

The impact of the dissolved quantity of aluminum on the calculation of surface charge from titration experiments of hydrated gamma-alumina was investigated. Two methods were developed to correct this effect: direct determination of aluminum in solution in batch titration experiments and application of a dissolution rate model in continuous titration experiments. There is a large effect of dissolution on surface charge determination for pH>10 and pH < 4.5. Application of these correction methods to these pH ranges lead to apparent saturation surface charges of 1.3 and 2.3 at nm(-2), respectively. The last value seems to be the real proton-active site density, while the hydroxyl-active site density cannot be reached for easily achievable basic pH values.

Cuprite-modified electrode for the detection of iodide species

Abstract A cuprite-modified carbon paste electrode was evaluated as an electrochemical sensor for iodide species in aqueous medium. The overall analysis involved a two-step procedure: an open-circuit accumulation step followed by voltammetric quantification. In the preconcentration step, iodide was accumulated on cuprite (Cu 2 O) according to a surface precipitation mechanism leading to the formation of CuI. This solid was then detected either in the cathodic or in the anodic mode, the first process allowing multiple successive analyses without requiring any regeneration of the electrode surface, while the anodic scan resulted in the surface oxidation of Cu 2 O requiring the renewal of the electrode surface before any further accumulation experiment. The influence of various experimental parameters on the sensor response was investigated (i.e., pH, preconcentration time, detection mode, iodide concentration, Cu 2 O content into the paste). Reproducible results were obtained after optimization: a linear calibration was obtained in the 1×10 −6 M to 2×10 −5 M concentration range, with a detection limit of 5×10 −7 M. The effect of chloride interference was also discussed.

Numerical Study on the Adhesion and Reentrainment of Nondeformable Particles on Surfaces: The Role of Surface Roughness and Electrostatic Forces

In this paper, the reentrainment of nanosized and microsized particles from rough walls under various electrostatic conditions and various hydrodynamic conditions (either in air or aqueous media) is numerically investigated. This issue arises in the general context of particulate fouling in industrial applications, which involves (among other phenomena) particle deposition and particle reentrainment. The deposition phenomenon has been studied previously and, in the present work, we focus our attention on resuspension. Once particles are deposited on a surface, the balance between hydrodynamic forces (which tend to move particles away from the surface) and adhesion forces (which maintain particles on the surface) can lead to particle removal. Adhesion forces are generally described using van der Waals attractive forces, but the limit of these models is that any dependence of adhesion forces on electrostatic forces (due to variations in pH or ionic strength) cannot be reproduced numerically. For this purpose, we develop a model of adhesion forces that is based on the DLVO (Derjaguin and Landau, Verwey and Overbeek) theory and which includes also the effect of surface roughness through the use of hemispherical asperities on the surface. We first highlight the effect of the curvature radius on adhesion forces. Then some numerical predictions of adhesion forces or adhesion energies are compared to experimental data. Finally, the overall effects of surface roughness and electrostatic forces are demonstrated with some applications of the complete reentrainment model in some simple test cases.

Voltammetric Detection of Iodide after Accumulationby Friedel's Salt

Friedels salt, a mineral anion exchanger belonging to the family of the layered double hydroxides (LDHs), was synthesized and used as a novel electrode modifier for the accumulation of iodide species and their subsequent voltammetric determination at carbon paste. Beside the preconcentration features of Friedels salt towards iodide species, its presence at the electrode surface allowed to evidence the oxidation of molecular iodine into iodate (with transient IO−), contrary to most carbon-based electrodes, as demonstrated by cyclic voltammetry. Preconcentration was achieved at open circuit and iodide was then detected by differential pulse voltammetry in unbuffered chloride medium. The sensing process was further improved by optimization of the carbon paste composition, the detection medium, and the accumulation time. The detection limit was 0.06 µM (3σ), with linear calibration ranges extending from 0.1 to 1 µM, 1 to 10 µM, and 10 to 50 µM, giving a dynamic range of over several orders of magnitude. The effect of anionic interferences was evaluated and the sensor was applied to iodide analysis in synthetic ground- and seawaters.