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Molecular dynamics (MD) simulations of a montmorillonite/water interface at the pore scale were carried out at 0.1molL(-1) NaCl concentration in order to constrain cation, anion, and water distribution and mobility influenced by the mineral surface. MD results enabled anion exclusion and cation condensation at the surface to be quantified. MD-derived values could then be compared with macroscopic model results obtained from the Modified Gouy-Chapman (MGC) theory. While the Na concentration profile is well reproduced in the diffuse layer, anion exclusion is overestimated by the MGC theory under our experimental conditions. We also showed that MD simulations can be used to constrain Basic Stern model parameters or, in combination with zeta potential measurements, can be used to constrain triple layer model (TLM) parameters by providing suitable values for the capacitance values. Na sorption intrinsic equilibrium constant values for clay basal surfaces are given accordingly.

International audienceThe thermal and volumetric properties of complex aqueous solutions are described according to the Pitzer equation, explicitly taking into account the speciation in the aqueous solutions. The thermal properties are the apparent relative molar enthalpy (L_ϕ) and the apparent molar heat capacity (C_(p,ϕ)). The volumetric property is the apparent molar volume (V_ϕ). Equations describing these properties are obtained from the temperature or pressure derivatives of the excess Gibbs energy and make it possible to calculate the dilution enthalpy (〖∆H〗_ ^D), the heat capacity (c_p) and the density (ρ) of aqueous solutions up to high concentrations. Their implementation in PHREEQC V.3 (Parkhurst and Appelo, 2013) is described and has led to a new numerical tool, called PhreeSCALE. It was tested first, using a set of parameters (specific interaction parameters and standard properties) from the literature for two binary systems (Na2SO4-H2O and MgSO4-H2O), for the quaternary K-Na-Cl-SO4 system (heat capacity only) and for the Na-K-Ca-Mg-Cl-SO4-HCO3 system (density only). The results obtained with PhreeSCALE are in agreement with the literature data when the same standard solution heat capacity (C_p^0) and volume (V^0) values are used. For further applications of this improved computation tool, these standard solution properties were calculated independently, using the Helgeson-Kirkham-Flowers (HKF) equations. By using this kind of approach, most of the Pitzer interaction parameters coming from literature become obsolete since they are not coherent with the standard properties calculated according to the HKF formalism. Consequently a new set of interaction parameters must be determined. This approach was successfully applied to the Na2SO4-H2O and MgSO4-H2O binary systems, providing a new set of optimized interaction parameters, consistent with the standard solution properties derived from the HKF equations

To understand the main properties of cement, a ubiquitous material, a sound description of its chemistry and mineralogy, including its reactivity in aggressive environments and its mechanical properties, is vital. In particular, the porosity distribution and associated sample carbonation, both of which affect cement's properties and durability, should be quantified accurately, and their kinetics and mechanisms of formation known both in detail and in situ. However, traditional methods of cement mineralogy analysis (e.g. chemical mapping) involve sample preparation (e.g. slicing) that can be destructive and/or expose cement to the atmosphere, leading to preparation artefacts (e.g. dehydration). In addition, the kinetics of mineralogical development during hydration, and associated porosity development, cannot be examined. To circumvent these issues, X-ray diffraction computed tomography (XRD-CT) has been used. This allowed the mineralogy of ternary blended cement composed of clinker, fly ash and blast furnace slag to be deciphered. Consistent with previous results obtained for both powdered samples and dilute systems, it was possible, using a consolidated cement paste (with a water-to-solid ratio akin to that used in civil engineering), to determine that the mineralogy consists of alite (only detected in the in situ hydration experiment), calcite, calcium silicate hydrates (C-S-H), ettringite, mullite, portlandite, and an amorphous fraction of unreacted slag and fly ash. Mineralogical evolution during the first hydration steps indicated fast ferrite reactivity. Insights were also gained into how the cement porosity evolves over time and into associated spatially and time-resolved carbonation mechanisms. It was observed that macroporosity developed in less than 30 h of hydration, with pore sizes reaching about 100-150 mm in width. Carbonation was not observed for this time scale, but was found to affect the first 100 mm of cement located around macropores in a sample cured for six months. Regarding this carbonation, the only mineral detected was calcite.

The main objective of the VULSACO (VULnerability of SAndy COasts to climate change and anthropic pressure) project was to investigate present day and potential future vulnerability of sandy coasts at the 2030 horizon, i.e. on a time scale related to climate variability. The method, based on a multidisciplinary approach bringing together geologists, geographers, physicists, social psychologists, engineers and stakeholders, was structured around 4 axes: field data analysis; numerical modelling; analysis of governance and stakeholder perceptions; and development of vulnerability indexes. This approach was designed to investigate vulnerability at a local scale and was applied to 4 contrasting beaches located in France: Sète Lido (Mediterranean Sea), Truc Vert and La Tresson beaches (Atlantic Ocean), and Dewulf (English Channel). The results focus on decadal and multi-annual beach trends at the Truc Vert beach site. There is almost no trend in beach volume at Truc Vert beach, although there is a variation in this parameter on a cycle of 2 to 3 yr, with variations related to wave energy and probably to indexes of climate variability. Numerical modelling identified the sensitivity of beach responses to changes in wave height and direction, especially in terms of subtidal morphology and the potential development of shoreline instability. Together with the observed offshore wave angle at the Biscay Buoy, these model results suggest that a potential change in wave angle due to climate variability could significantly modify the bars' morphology. The combination of data analysis and numerical modelling contributed to the development of vulnerability indexes designed for sandy coasts, which take into account climate-dependant variables such as waves. This allowed the differentiation of the sites in terms of vulnerability to erosion: Sète Lido and Truc Vert beach were the most and least vulnerable sites, respectively. These indexes help in identifying the dominant components of beach vulnerability, and provide potential for the study of how anthropogenic factors affect vulnerability. The study of stakeholder perceptions and decision-making with regard to climate-related risk also highlighted potential anthropogenic effects on beach vulnerability, and identified possible site-specific outcomes.