Capillary geochemistry in non-saturated zone of soils. Water content and geochemical signatures.

International audienceThe unsaturated zone (UZ) retains aqueous solutions against gravity by capillary forces. This suction state corresponds to a decreasing internal pressure of the water, which modifies its thermodynamic properties. Accordingly, the speciation of solutes and the solubility of solids and gases in such capillary solutions change. The volumetric capillary water content of the soil at high suction can be calculated extrapolating the water retention curves (WRC) with the Rossi–Nimmo model. Interestingly, several tens of liters per cubic meter of soil can be thus suctioned, a sufficiently large volume to support that: (1) capillary water is not restricted to nanosized pores, which means it disobeys the Young–Laplace law and is metastable with respect to vapor (superheating); and (2) the geochemistry of capillary solutions might significantly influence the subsurface mass transfer. Two field situations are here interpreted using the capillary thermodynamic properties: (1) the trapping of sand grains during the growth of desert roses (gypsum), and (2) the development of abnormal paragenetic sequences in some saprolites. The capillary approach is extended to the soil solids, so that the micro-mineralogy can be explicitly (though sketchily) integrated in the calculations. The key conclusion is that capillarity changes the saturation indexes (and so the reaction rates) at given solution composition, in a way consistent with the field observations. This perspective amounts to geochemically distinguishing the capillary and percolating solutions, which is interestingly analogous to the immobile and mobile water distinction already often integrated in UZ flow model

Solubility of platinum in aqueous solutions at 25°C and pHs 4 to 10 under oxidizing conditions

Platinum has been found to be mobile under supergene conditions, including placers and weathering profiles. To elucidate the nature of Pt mobility in supergene environments, the dissolution of platinum metal was investigated under physicochemical conditions similar to those found in such environments. The solubility of platinum metal was measured at 25°C in several systems: Pt-K-HC8H4O4-H2O (pH 4.02), Pt-Na-HCO3-Cl-H2O (pH 6.40), Pt-Na-K-H2PO4-HPO4-H2O (pH 6.90), Pt-Na-HCO3-H2O (pH 8.30), Pt-Na-OH-H2O (pH 8.54), and Pt-Na-HCO3-H2O (pH 9.91). The redox conditions of these experiments were relatively oxidizing, with measured Eh values ranging from +280 to +590 mV. The ionic strength of the aqueous solutions did not exceed 0.30 (molal scale). The interpretation of the solubility results, in terms of the following reaction and its equilibrium constant, Pt(s)+nH2O left right double arrow Pt(OH)2−nn+nH++2e− served to identify the importance of the hydroxylated complex PtOH+ in the pH range (4 to 10) and to determine its stability constant at 25°C. Linear regression of the solubility data using the function log [Pt]−2pe=n pH+log Kn yielded a value of 1.01 ± 0.07 for n, the average ligand number, and −31.76 ± 0.55 for the thermodynamic equilibrium constant of reaction. The resulting stability constant (β1) of PtOH+ (Pt2+ + OH− left right double arrow PtOH+) is 24.91 ± 0.50, assuming the same value of the free energy of formation of Pt2+, ΔGfo(Pt2+) as that given by Glushko et al. (Thermodynamic Constants of Matter, Academy of Science, USSR, 1972). The range of values of ΔGfo(Pt2+) proposed to date is +185.63 to +258.74 kJ/mol. The value of Glushko et al. (1972) (+244.11 kJ/mol) appears to fit better with our measurements at pH 4 to 10 and with those of Wood (Wood S. A., “Experimental determination of the hydrolysis constants of Pt2+ and Pd2+ at 25°C from the solubility of Pt and Pd in aqueous hydroxide solutions,” Geochim. Cosmochim. Acta 55, 1759–1767, 1991) at pH 9 to 15.5. Finally, according to these new measurements of the solubility of platinum, the recommended values for Gibbs free energy (ΔGfo, in kiloJoule per mole) of the different aqueous species of Pt are +244.11 (Pt2+), −55.96 (PtOH+), and −234.48 (Pt(OH)2(aq)). The integration of data from the literature for chloride and sulfate complexes was used to calculate the speciation of platinum in seawater and in solutions with variable chlorinity (0.1, 1, and 3 mol/L NaCl) at 25°C. These calculations showed that in the absence of strong ligands (i.e., S2O32−, CN−), the transport of platinum in supergene environments primarily occurs in the form of PtOH+ (90%) and Pt(OH)2(aq) (9.7%). Chloride complexes (PtCl42− and PtCl3−) account for less than 1% of the dissolved platinum. This study clearly shows that the hydroxylated complexes (PtOH+ and Pt(OH)2(aq)) can play a very important role in controlling platinum transfer mechanisms in surface fluids (soils, placers, weathering profiles, etc.). Because the charged species PtOH+ is largely predominant, the mobility and transfer of platinum can also be affected by adsorption-desorption mechanisms onto oxides and hydroxides

Response to the comment by R. H. Byrne on ''Solubility of platinum in aqueous solutions at 25°c and pHs 4 to 10 under oxidizing conditions'' (2001) Geochim. Cosmochim. Acta 65, 4453-4466

In Byrne's comment (this issue) on the solubility of platinum in aqueous solutions (Azaroual et al., 2001), he claims that our recommended values for the formation constant of PtOH+ (OHβ1) are unreasonably high. We would like to thank him for his interest in our work and for the opportunity to clarify certain points that were not fully explicit in our initial paper

Influence of surface conductivity on the apparent zeta potential of TiO2 nanoparticles: application to the modeling of their aggregation kinetics

International audienceTitanium dioxide nanoparticles (TiO2 NPs) are extensively used in consumer products. The release of these NPs into aquatic environments raises the question of their possible risks to the environment and human health. The magnitude of the threat may depend on whether TiO2 NPs are aggregated or dispersed. Currently, limited information is available on this subject. A new approach based on DLVO theory is proposed to describe aggregation kinetics of TiO2 NPs in aqueous dispersions. It has the advantage of using zeta potentials directly calculated by an electrostatic surface complexation model whose parameters are calibrated by ab-initio calculations, crystallographic studies, potentiometric titration and electrophoretic mobility experiments. Indeed, the conversion of electrophoretic mobility measurements into zeta potentials is very complex for metal oxide nanoparticles. This is due to their very high surface electrical conductivity associated with the electromigration of counter and co-ions in their electrical double layer. Our model has only three adjustable parameters (the minimum separation distance between NPs, the Hamaker constant, and the effective interaction radius of the particle), and predicts very well the stability ratios of TiO2 NPs measured at different pH values and over a broad range of ionic strengths (KCl aqueous solution). We found an effective interaction radius that is significantly smaller than the radius of the aggregate and corresponds to the radius of surface crystallites or small clusters of surface crystallites formed during synthesis of primary particles. Our results confirm that DLVO theory is relevant to predict aggregation kinetics of TiO2 NPs if the double layer interaction energy is estimated accurately

In-Pore stress by drying-induced capillary bridges inside porous materials.

International audienceWe present here some evidences that capillary liquid bridges are able to deform micrometric cylindrical pores by tensile stress. Brine-soaked filter membranes are submitted to drying conditions leading to NaCl precipitation inside the 5-10 μm pores. A close examination demonstrated that two forms of NaCl crystallites are successively generated. First, primary cubic crystals grow, driven by the permanent evaporation. When this angular primary solid gets near the pore wall, while the evaporation makes the pore volume to be partly invaded by air, capillary liquid can bridge the nowsmall gap between the halite angles and the pore wall. In a second step, these small capillary bridges are frozen by a secondary precipitation event of concave-shaped NaCl. The proposed interpretation is that the liquid capillary bridges deform the host matrix of the membrane, and the situation is fossilized by the growth of solid capillary bridges. A quantitative interpretation is proposed and the consequences towards the natural media outlined

CO2 Injectivity in geological storages: an overview of program and results of the GeoCarbone-Injectivity Project

International audienceThe objective of the GeoCarbone-Injectivity project was to develop a methodology to study the complex phenomena involved in the near wellbore region during CO2 injection. This paper presents an overview of the program and results of the project, and some further necessary developments. The proposed methodology is based on experiments and simulations at the core scale, in order to understand (physical modelling and definition of constitutive laws) and quantify (calibration of simulation tools) the mechanisms involved in injectivity variations: fluid/rock interactions, transport mechanisms, geomechanical effects. These mechanisms and the associated parameters have then to be integrated in the models at the wellbore scale. The methodology has been applied for the study of a potential injection of CO2 in the Dogger geological formation of the Paris Basin, in collaboration with the other ANR GeoCarbone projects

Role of Impurities on CO2 Injection: Experimental and Numerical Simulations of Thermodynamic Properties of Water-salt-gas Mixtures (CO2 + Co-injected Gases) Under Geological Storage Conditions

International audienceRole of impurities on CO 2 injection: experimental and numerical simulations of thermodynamic properties of water-salt-gas mixtures (CO 2 + co-injected gases) under geological storage conditions Abstract Regarding the hydrocarbon source and CO 2 capture processes, fuel gas from boilers may be accompanied by so-called "annex gases" which could be co-injected in a geological storage. These gases, such as SOx, NOx, or oxygen for instance, are likely to interact with reservoir fluids and rocks and well materials (casing and cement) and could potentially affect the safety of the storage. However, there are currently only few data on the behaviour of such gas mixtures, as well as on their chemical reactivity, especially in the presence of water. One reason for this lack comes from the difficulty in handling because of their dangerousness and their chemical reactivity. Therefore, the purpose of the Gaz Annexes was to develop new experimental and analytical protocols in order to acquire new thermodynamic data on these annex gases, in fine for predicting the behaviour of a geological storage of CO 2 + co-injected gases in the short, medium and long terms. This paper presents Gaz Annexes concerning acquisition of PVT experimental and pseudo-experimental data to adjust and validate thermodynamic models for water / gas / salts mixtures as well as the possible influence of SO 2 and NO on the geological storage of CO 2. The Gaz Annexes s new insights for the establishment of recommendations concerning acceptable content of annex gases

O-ZNS, un oeil sur la nappe phréatique de Beauce

International audienc

O-ZNS, un oeil sur la nappe phréatique de Beauce

International audienc