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161.
Dissolved Cd (CdD) concentrations along the salinity gradient were measured in surface water of the Gironde Estuary during 15 cruises (2001–2007), covering a wide range of contrasting situations in terms of hydrology, turbidity and season. During all situations dissolved Cd concentrations displayed maximum values in the mid-salinity range, reflecting Cd addition by chloride-induced desorption and complexation. The daily net CdD fluxes from the Gironde Estuary to the coastal ocean were estimated using Boyle's method. Extrapolating CdD concentrations in the high salinity range to the freshwater end member using a theoretical dilution line produced 15 theoretical Cd concentrations (CdD0), each representative of one distinct situation. The obtained CdD0 concentrations were relatively similar (201 ± 28 ng L−1) when freshwater discharge Q was >500 m3 s−1 (508 ≤ Q ≤ 2600 m3 s−1), but were highly variable (340 ± 80 ng L−1; 247–490 ng L−1) for low discharge situations (169 ≤ Q ≤ 368 m3 s−1). The respective daily CdD net fluxes were 5–39 kg day−1, mainly depending on freshwater discharge. As this observation invalidates the existing method of estimating annual CdD net fluxes, we proposed an empirical model, using representative CdD0 values and daily freshwater discharges for the 2001–2007 period. Subsequent integration produced reliable CdD net flux estimates for the Gironde Estuary at the annual timescale that ranged between 3.8–5.0 t a−1 in 2005 and 6.0–7.2 t a−1 in 2004, depending on freshwater discharge. Comparing CdD net fluxes with the incoming CdD fluxes suggested that the annual net CdD addition in the Gironde Estuary ranged from 3.5 to 6.7 t a−1, without any clear temporal trend during the past seven years. The annual CdD net fluxes did not show a clearly decreasing trend in spite of an overall decrease by a factor 6 in Cd gross fluxes during the past decade. Furthermore, in six years out of seven (except 2003), the annual CdD net fluxes even exceeded river borne total (dissolved + particulate) gross Cd fluxes into the estuary. These observations were attributed to progressive Cd desorption from both suspended particles and bottom sediment during various sedimentation–resuspension cycles induced by tidal currents and/or continuous dredging (navigation channel) and diverse intra-estuarine sources (wet deposition, urban sources, and agriculture). Provided that gross fluxes remain stable over time, dissolved Cd exportation from the Gironde Estuary to the coastal ocean may remain at the present level for the coming decade and the estuarine sedimentary Cd stock is forecast to decrease slowly.  相似文献   
162.
Dissolved cadmium and copper species were measured in the Loire estuary and the North Biscay Bay continental shelf (France) in spring 2002. Metal behaviours along the salinity gradient, metal fluxes from the Loire system and surface distributions on the continental shelf were described and compared with the ones obtained at a period of higher discharge (i.e., winter 2001). Vertical distributions at different stations were also examined with the aim to assess whether the Loire inputs affect the Cu and Cd speciation over the continental shelf. In the Loire estuary, different metal behaviours were observed from winter. Cu and its various species mostly followed a theoretical dilution line whereas a Cd addition composed of chloro- and organic complexes was observed. According to our estimations, the Cu flux was composed, as in winter, of 40% hydrophobic organic complexes. On the other hand, Cd organic complexes accounted for less in the total dissolved metal flux than they did in winter (55 and 78% for spring and winter, respectively). On the continental shelf, a C18Cu-to-TDCu ratio of 40% was observed in the stratified area under Loire influence. For Cd, the organic fraction was relatively important in the surface waters near the mouth of the estuary and decreased deeper and seaward. Thus, the Cu and Cd speciation on the North Biscay Bay continental shelf are firstly determined by the extent of the estuarine plume. Beyond the estuarine influence, biological processes appeared to be the origin of the observed variations.  相似文献   
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