This study presents trace elements levels in surface and deep sediments of the Toulon bay (SE France) subjected to anthropogenic inputs (navy base, harbors, etc.). The studied elements (As, Cd, Cr, Cu, Hg, Ni, Pb, Zn) are defined as priority contaminants in aquatic systems. Fifty-five points scattered on the entire bay were sampled, allowing the determination of contaminants distribution with a high resolution. Several approaches were used to assess the degree of contamination and the potential toxicity of the Toulon bay sediments: comparison to the French legislation, surface-weighted average metal concentrations, enrichment factors (EF), geoaccumulation indices (Igeo), trace element stock calculation and comparison to sediment quality guidelines. A principal component analysis was performed to reveal common behavior of the studied contaminants. Results demonstrated the very high contamination of the small bay, especially in Hg (EF up to 1500), Cu, Pb and Zn, with export to the large bay further governed by hydrodynamics.

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To cite this version:Yoann Louis, Cédric Garnier, Véronique Lenoble, Stéphane Mounier, Neven Cukrov, et al.. Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia). Marine Chemistry, Elsevier, 2009, 114, pp.An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K i equ ), total ligands concentration (L iT ) and association/dissociation rate constants (k i 1 ,k i -1 ). A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater-seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K 1 equ : 11.2-13.0, log K 2 equ :8.8-10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter. Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by atequilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k 1 1 :6.1-20 × 10 3 (M s) − 1 , k 2 1 : 1.3-6.3 × 10 3 (M s) − 1 ) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h. It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM C , i.e. 1 mg C L − 1 ) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).

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