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Clays under Nano- to Microscopic resolution, Karlsruhe : Allemagne (2011)
Effects of organics on the adsorption and mobility of metal cations in clay systems: Computational molecular modeling approach.
A. G. Kalinichev1, B. F. Ngouana Wakou1, N. Loganathan1
(2011)

Understanding and prediction of many natural and anthropogenic environmental processes ultimately depend on a fundamental understanding of the chemistry occurring at the mineral-fluid interfaces. Clay-related minerals and natural organic matter (NOM) are ubiquitous in the environment, and metal-NOM complexation induces strong correlations between the NOM concentration in water and the capacity of clay particles to bind metals, thus affecting their speciation, solubility and toxicity in the environment. Despite significant geochemical, environmental and technological interest, the molecular-level mechanisms and dynamics of the physical and chemical processes involving NOM are not yet well understood. In this presentation we compare three different molecular dynamics (MD) computer simulations of metal-NOM complexation in aqueous solutions. The simulation results indicate that despite some obvious quantitative variations in the computed values depending on the size of the simulated system and on the parameters of the force field models used, all three simulations are quite robust and consistent. In particular, approximately 35-50% of Ca2+ ions in all simulations are associated with the carboxylic groups of NOM at near-neutral pH. The stability of bidentate-coordinated contact ion pair complexes is also always strongly preferred. Easy association of metal cations with negatively charged NOM functional groups and negatively charged clay surfaces allows us to predict that cationic bridging could be the most probable mechanism of NOM association with clays in natural environments. New MD simulations are currently in progress to quantitatively assess these predictions on a molecular scale for nuclear waste disposal applications. New larger-scale clay models incorporate a more realistic representation of the structural and compositional disorder of natural illites and smectites and employ CLAYFF - a fully flexible general force field suitable for the molecular simulations of hydrated mineral systems in the presence of organics.
1 :  SUBATECH - Laboratoire SUBATECH Nantes
SUBATECH-Radiochimie
Chimie/Chimie théorique et/ou physique
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