Study of the behaviour of trace elements in estuaires : experimental approaches and modeling
Étude du comportement des élements traces en milieu estuarien : approche expérimentale et modélisation. Application à l’étude de la spéciation de Cd, Co et Cs dans les estuaires majeurs français (Seine, Loire, Gironde, Rhône)
Résumé
Most of trace elements have a non conservative behavior in estuarine environments. It is the case of cadmium, cobalt and caesium for which the fate in estuarine and coastal zones is largely controlled by their distribution between water and suspended particles, which generally have high residence times or can be definitely deposited in these areas. Metallic contaminants and radionuclides can be present under various species: dissolved (mineral and organic complexes), colloidal and particulate forms (adsorbed, precipitated) or integrated by various mechanisms in the organisms. Such distributions are the result of processes (physical, chemical, biological) which are controlled by many factors (ionic strength, pH, Eₕ, major cations concentration, nature and concentration of suspended matter, primary production,...). Geochemical modeling is a very useful approach to understand the dynamics of this type of contaminant, especially in the complex systems which are the estuaries. A speciation model was used to simulate the measurements of dissolved and particulate Cd, Co and Cs, taken during various cruises carried out in the Seine, Loire, Gironde and Rhone estuaries. The model is able to reproduce the distribution of metals between the dissolved and particulate phases, and also to evaluate the concentrations of various chemical species (especially those which are most bio-available). The approach presented treats adsorption processes as a formation of inner sphere complexes with functional surface groups (surface complexation model) or as an cationic exchange reaction. The calculation of chemical species takes into account the presence of dissolved ligands or major cations of seawater, which compete with the metal for the surface sites. The model can consider the various natural particle components (metal oxy-hydroxides, organic matter) as individual adsorbent phases or treat natural particles in a 'global manner'. The choice of modeled processes is based on studies of the biogeochemistry of Cd, Co and Cs in the estuarine environment and the knowledge obtained on the field. Experiments performed both in laboratory and in situ were necessary to check the validity of the assumptions of the model and to evaluate model parameters, which cannot be measured directly like to the sorption properties of natural particles. Radiotracers ("1"0"9Cd, "5"7Co,"1"3"4Cs) were used to determine physico-chemical key processes and environmental variables that control the speciation and the fate of Cd, Co and Cs. This approach, based on the use of spike with various radionuclides, allowed us to evaluate the affinity constants of particles to the four estuaries for the studied metals (global intrinsic complexation and exchange constants) and also the exchangeable particulate fraction estimated from the comparison of measured natural metals coefficients of distribution and coefficient of distribution of their radioactive equivalents. Other parameters, which are necessary to build the model (specific surface area, concentration of active surface sites, mean intrinsic acid-base constants,...), were independently estimated by various experimental approaches, applied in laboratory to particle samples taken throughout estuaries (electrochemical measurements, nitrogen adsorption using the BET method,...). The results of the validation indicate that in spite of its simplifications, the model reproduces in a satisfactory way the dissolved/particulate distributions measured for Cd, Co and Cs. With a predictive aim, this type of model must be coupled with a hydro-sedimentary transport model.
Un modèle de spéciation capable de reproduire le comportement géochimique de Cd, Cs et Co et de prédire les formes physico-chimiques sous lesquelles ils se trouvent lors de leur transit estuarien a été développé et appliqué à la simulation des profils dissous et particulaires de ces métaux au sein des principaux estuaires français (Seine, Loire, Gironde, Rhône). Le modèle élaboré permet de prendre en compte les processus majeurs qui gouvernent le comportement de ces éléments, à savoir la complexation et l'échange ionique de surface ainsi que la compétition avec les ligands dissous de l'eau de mer ou les cations majeurs pour les sites de surface. Les concentrations des différentes espèces chimiques sont calculées en considérant les caractéristiques physico-chimiques de surface et les propriétés de sorption moyennes des particules naturelles évaluées pour chaque estuaire par le biais d'expérimentations. . .