Competition between organic matter and solid surface for cation sorption: Ce and rare earth element as Proxy. In : American Geophysical Union (AGU) Fall Meeting, San Francisco, 11-15 Déc. 2006
Résumé
Aquatic or soil organic matter are well-known to be strong adsorbent of many cations due to their adsorption capacity. Among these cations, the trivalent rare earth element (REE) and particularly Ce seem to be promising tools to investigate the impact of competition in between organic or inorganic ligands. Ce (III) is oxidized into Ce (IV) by oxidative surface such as Fe and Mn oxyhydroxides. Since Ce (IV) is preferentially adsorbed (as compared to other REE), a positive and negative Ce anomaly is developed respectively onto the solid and within the solution. Previous studies (Davranche et al., 2004, 2005) highlighted the suppression of this feature when Ce occurs to be complexed with organic matter (as humate species). Recent experiments were designed to evaluate the competition between humate and Mn oxide for REE complexation (each reactant being added simultaneously). Two parameters control the competition: time and pH. While organic matter does adsorb immediately the free REE, a desorption of REE occurs through time. Desorption is marked by the development of a Ce anomaly in the REE pattern that reflects the complexation with Mn oxide surface. Along the time, solid surface becomes thus more competitive than the organic matter. PH still influences the competition since at basic pH, REE and organic matter - probably as REE-organic complexes - are adsorbed onto the solid surface. Ultrafiltration analyses at 5 KD were also performed to separate organic matter and organic complexes from the solution. Results provide evidence that in presence of a solid surface, HREE (high rare earth element) desorption from the organic matter occurs through time. This leads to HREE enrichment in solution. All these results suggest that complexation of organic matter is kinetically favoured as compared to the complexation with solid surfaces. However, the organic complex formed during the first stage of the complexation process involves weak bindings. These bindings are easily broken in presence of a competitor ligand such as a sorptive surface. However, it is important to note that organic matter stay the major complexing ligand.