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The determination of copper (Cu) speciation and its bioavailability in natural waters is an important issue due to its specific role as an essential micronutrient but also a toxic element at elevated concentrations. Here, we report an improved anodic stripping voltammetry (ASV) method for organic Cu speciation, intended to eliminate the important problem of surface-active substances (SAS) interference on the voltammetric signal, hindering measurements in samples with high organic matter concentration. The method relies on the addition of nonionic surfactant Triton-X-100 (T-X-100) at a concentration of 1 mg L−1. T-X-100 competitively inhibits the adsorption of SAS on the Hg electrode, consequently 1) diminishing SAS influence during the deposition step and 2) strongly improving the shape of the stripping Cu peak by eliminating the high background current due to the adsorbed SAS, making the extraction of Cu peak intensities much more convenient. Performed tests revealed that the addition of T-X-100, in the concentration used here, does not have any influence on the determination of Cu complexation parameters and thus is considered "interference-free." The method was tested using fulvic acid as a model of natural organic matter and applied for the determination of Cu speciation in samples collected in the Arno River estuary (Italy) (in spring and summer), characterized by a high dissolved organic carbon (DOC) concentration (up to 5.2 mgC L−1) and anthropogenic Cu input during the tourist season (up to 48 nM of total dissolved Cu). In all the samples, two classes of ligands (denoted as L1 and L2) were determined in concentrations ranging from 3.5 ± 2.9 to 63 ± 4 nM eq Cu for L1 and 17 ± 4 to 104 ± 7 nM eq Cu for L2, with stability constants logKCu,1 = 9.6 ± 0.2–10.8 ± 0.6 and logKCu,2 = 8.2 ± 0.3–9.0 ± 0.3. Different linear relationships between DOC and total ligand concentrations between the two seasons suggest a higher abundance of organic ligands in the DOM pool in spring, which is linked to a higher input of terrestrial humic substances into the estuary. This implies that terrestrial humic substances represent a significant pool of Cu-binding ligands in the Arno River estuary.

Location of river-groundwater exchange zones and biodiversity hotspot is essential for a river management plan, especially for Mediterranean karstic rivers. This location is often difficult and timeconsuming when long river sectors are considered. We studied a 13 km-long sector of the Cèze River (Southern France) located in a karstic canyon. We compared five indicators of river-groundwater exchanges: longitudinal profiles of temperature, electrical conductivity and 222Rn concentrations in the surface water of the river, chemical characteristics of the hyporheic water and hyporheic biodiversity.Upwelling zones occurred downstream of geomorphological heterogeneities (here at the tail of gravel bars). Surface water chemistry, especially electrical conductivity and 222Rn concentrations, clearly traces large scale gaining sections, which were not associated to valley narrowing but with lateral springs, suggesting a crucial role of the geological structuration of the karstic plateau of Méjanne-le-Clap. Hyporheic water chemistry fits with the large-scale hydrological pattern, but with a high variability corresponding to local heterogeneities. The stygobite fauna (obligate groundwater organisms) and benthic EPTC (Ephemeroptera, Plecoptera, Trichoptera and Coleoptera) occurred preferentially in the gaining sections fed by groundwater, likely because of oligotrophic water and cooler temperature. The spatial distribution of river-groundwater exchange zone and hyporheic biodiversity may be thus predicted using changes in surface water chemistry, especially for electrical conductivity and 222Rn concentrations.

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Reviewer 1 Highlights corrected Sediment dynamic differed during flushing operations and flood events Line 15 corrected The Rhône River (France) has been used for energy production for decades and 21 dams have been built. Line 29-In general it is not advisable to start a sentence with an acronym, rather right it out in full corrected The SPM contamination was generally lower than during baseflow and flood regimes. Line 131 corrected More than 3 x 106 m3 of SPM were thus stored in the Verbois reservoir between 2003 and 2012 (Services industriels de Genève, 2014). Line 133 corrected [...] which transports ~0.7 x 106 m3 of SPM per year (approx. 1 to 3 tons dry weight) [...] Line 309-314-This section reads as introduction or as part of the discussion According to reviewer 4, this section was moved in the Materials and Method part.

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