3D Modelling for the Dispersion of Sediments Dredged in the Port of La Rochelle with Open TELEMAC-MASCARET

Hydrodynamic

Simple and Rapid Voltammetric Method Using a Gold Microwire Electrode to Measure Inorganic Arsenic in Holopelagic <i>Sargassum</i> (Fucales, Phaeophyceae)

The valorization of massive strandings of holopelagic Sargassum spp. is strongly limited by high levels of inorganic arsenic (Asi) that are potentially above the limit of current regulations. Monitoring Asi in algal biomass is currently achieved using standard chromatographic separation followed by spectroscopic detection. Here, we propose an alternative simpler procedure based on the extraction of Asi from the freeze-dried algal powder in deionized water and the electroanalytical detection of the diluted extract at a gold-microwire electrode. The protocol was optimized both in terms of extraction (powder/water ratio, extraction time, temperature) and electrolyte used for the voltammetric detection. Two electrolytes were tested: one composed of citric acid, sulfamic acid and KCl (pH 2.0) and another composed of an acetate buffer (pH 4.7) and NaCl. We demonstrate here that Asi determination is possible with the first electrolyte but it is necessary to deal with a relative unstable signal. Measurement of Asi was best achieved with the second electrolyte (acetate buffer and NaCl) with the following optimized electrochemical conditions: deposition potential of −1.2 V, deposition time of 30 seconds and linear scan voltammetry. Voltammetric results were then compared to a reference method (HPLC-ICP-MS) using different morphotypes of holopelagic Sargassum spp. (S. natans VIII, S. natans I and S. fluitans III), using commercial extracts of brown seaweeds and using a Hijiki certified reference material. Very good agreement was obtained between our novel method and HPLC-ICP-MS. Both methods show that inorganic arsenic is almost entirely present as As(V) in Sargassum spp. extracts

Electrochemical methods for speciation of trace elements in marine waters. Dynamic aspects

The contribution of electrochemical methods to the knowledge of dynamic speciation of toxic trace elements in marine waters is critically reviewed. Due to the importance of dynamic considerations in the interpretation of the electrochemical signal, the principles and recent developments of kinetic features in the interconversion of metal complex species will be presented. As dynamic electrochemical methods, only stripping techniques (anodic stripping voltammetry and stripping chronopotentiometry) will be used because they are the most important for the determination of trace elements. Competitive ligand ex- change-adsorptive cathodic stripping voltammetry, which should be considered an equilibrium technique rather than a dynamic method, will be also discussed because the complexing parameters may be affected by some kinetic limitations if equilibrium before analysis is not attained and/or the flux of the adsorbed complex is in fluenced by the lability of the natural complexes in the water sample. For a correct data interpretation and system characterization the comparison of results obtained from different techniques seems essential in the articulation of a serious discussion of their meaning

Bedform migration in a mixed sand and cohesive clay intertidal environment and implications for bed material transport predictions

Many coastal and estuarine environments are dominated by mixtures of non-cohesive sand and cohesive mud. The migration rate of bedforms, such as ripples and dunes, in these environments is important in determining bed material transport rates to inform and assess numerical models of sediment transport and geomorphology. However, these models tend to ignore parameters describing the physical and biological cohesion (resulting from clay and extracellular polymeric substances, EPS) in natural mixed sediment, largely because of a scarcity of relevant laboratory and field data. To address this gap in knowledge, data were collected on intertidal flats over a spring-neap cycle to determine the bed material transport rates of bedforms in biologically-active mixed sand-mud. Bed cohesive composition changed from below 2 vol% up to 5.4 vol% cohesive clay, as the tide progressed from spring towards neap. The amount of EPS in the bed sediment was found to vary linearly with the clay content. Using multiple linear regression, the transport rate was found to depend on the Shields stress parameter and the bed cohesive clay content. The transport rates decreased with increasing cohesive clay and EPS content, when these contents were below 2.8 vol% and 0.05 wt%, respectively. Above these limits, bedform migration and bed material transport was not detectable by the instruments in the study area. These limits are consistent with recently conducted sand-clay and sand-EPS laboratory experiments on bedform development. This work has important implications for the circumstances under which existing sand-only bedform migration transport formulae may be applied in a mixed sand-clay environment, particularly as 2.8 vol% cohesive clay is well within the commonly adopted definition of “clean sand”

Metals impact into the Paranaguá Estuarine Complex (Brazil) during the exceptional flood of 2011

Abstract Particulate and dissolved metal concentrations were determined after the largest flood in the last 30 years on the east-west axis of the Paranaguá Estuarine Complex (PEC) and compared to the those of the dry period at two stations. Results confirmed that the flood greatly affected riverine outflows and the behavior of metals in the PEC. In particular, a sharp decrease in salinity was followed by extremely high SPM concentrations leading to a decrease in DO concentrations at both stations. For the dissolved phase, ANOSIM analysis showed a significant dissimilarity at each station between the sampled periods, whereas for the particulate phase this dissimilarity was found only for the samplings taken at the Antonina Station. KD values suggested dissolved Cu behavior was related to the presence of organic complexes and dissolved Mn had sediment resuspension of redox sediments and or/pore water injection as sources. Metal concentrations were lower than in polluted estuaries, though high enrichment factors found after the flood pointed to the influence of anthropogenic sources. In conclusion, the flood's influence was more evident at the Antonina Station, due to its location in the upper estuary, whereas in Paranaguá a high SPM content with low metal concentration was found, following the common pattern generally found in other marine systems subject to heavy rainfall events

Off Congo waters (Angola Basin, Atlantic Ocean) : a hot spot for cadmium-phosphate fractionation

We report the distribution of cadmium at 13 stations along 5.83 degrees S in the Angola Basin. The studied area (which is influenced by the plume of the Congo River, doming, and relatively high primary production) is characterized by relatively low-circulation regime, which results in a strong oxygen minimum. In subsurface, very low cadmium : phosphate (Cd : P) ratios (0.05-0.10 nmol L-1 : mu mol L-1) were observed below the euphotic zone (depth range = 50-200 m), indicating that mineralization is the main process explaining the Cd-P fractionation. Cd-P decoupling is not restricted to subsurface waters, but occurs also throughout the oxygen minimum zone. An isopycnal analysis of the Cd : P ratio throughout the Atlantic Ocean shows that upper and intermediate waters in the South-east Atlantic are highly altered in terms of Cd-P properties. Benthic inputs at 4000 m were associated with degradation of organic matter with an important siliceous component, but were not accompanied by substantial changes in the Cd : P ratio

Sulfide determination in hydrothermal seawater samples using a vibrating gold micro-wire electrode in conjunction with stripping chronopotentiometry.

International audienceA rapid electrochemical stripping chronopotentiometric procedure to determined sulfide in unaltered hydrothermal seawater samples is presented. Sulfide is deposited at -0.25V (vs Ag/AgCl, KCl 3M) at a vibrating gold microwire and then stripped through the application of a reductive constant current (typically -2μA). The hydrodynamic conditions are modulated by vibration allowing a short deposition step, which is shown here to be necessary to minimize H(2)S volatilization. The limit of detection (LOD) is 30nM after a deposition step of 7s. This LOD is in the same range as the most sensitive cathodic voltammetric technique using a mercury drop electrode and is well below those reported previously for other electrodes capable of being implemented in situ

Simple and Rapid Voltammetric Method Using a Gold Microwire Electrode to Measure Inorganic Arsenic in Holopelagic <i>Sargassum</i> (Fucales, Phaeophyceae)

The valorization of massive strandings of holopelagic Sargassum spp. is strongly limited by high levels of inorganic arsenic (Asi) that are potentially above the limit of current regulations. Monitoring Asi in algal biomass is currently achieved using standard chromatographic separation followed by spectroscopic detection. Here, we propose an alternative simpler procedure based on the extraction of Asi from the freeze-dried algal powder in deionized water and the electroanalytical detection of the diluted extract at a gold-microwire electrode. The protocol was optimized both in terms of extraction (powder/water ratio, extraction time, temperature) and electrolyte used for the voltammetric detection. Two electrolytes were tested: one composed of citric acid, sulfamic acid and KCl (pH 2.0) and another composed of an acetate buffer (pH 4.7) and NaCl. We demonstrate here that Asi determination is possible with the first electrolyte but it is necessary to deal with a relative unstable signal. Measurement of Asi was best achieved with the second electrolyte (acetate buffer and NaCl) with the following optimized electrochemical conditions: deposition potential of −1.2 V, deposition time of 30 seconds and linear scan voltammetry. Voltammetric results were then compared to a reference method (HPLC-ICP-MS) using different morphotypes of holopelagic Sargassum spp. (S. natans VIII, S. natans I and S. fluitans III), using commercial extracts of brown seaweeds and using a Hijiki certified reference material. Very good agreement was obtained between our novel method and HPLC-ICP-MS. Both methods show that inorganic arsenic is almost entirely present as As(V) in Sargassum spp. extracts.</p

Eutrophication, oxygen status and nutrient fluxes in a macrotidal estuarine reservoir: the case of the Ria Penfeld, Bay of Brest

Excessive nutrient inputs are generally perceived to be responsible for the eutrophication of estuarine and coastal systems. Here, we show that the alteration of estuarine water circulation may be a very critical driver in the case of macrotidal systems. For this study, we intensively sampled the upstream part of the Ria Penfeld in June 2021, in a period of maximum irradiance and after a period of ~7 days of closure of the Kervallon dam gate. We observed that the physico-chemical structure of the Ria Penfeld reservoir (RPR), with very high biomass (chl-a values up to 120 µg L−1) and anoxic conditions in the bottom, was radically different from what is usually observed in the other estuaries of the region. The very high net primary production (~1700 mg C m−2 d−1) in the RPR was associated with an important removal of nutrients, especially phosphate, resulting in a strong nutritional imbalance (molar N:Si:P ratio of 2100:1500:1) for the water exported to the downstream estuary.Les apports excessifs de nutriments sont généralement considérés comme responsables de l’eutrophisation des systèmes estuariens et côtiers. Nous montrons ici que la modification de la circulation des eaux estuariennes peut être un facteur particulièrement critique dans le cas des systèmes macrotidaux. Dans cette étude, nous avons intensivement échantillonné la partie amont de la Ria Penfeld en juin 2021, dans une période d’ensoleillement maximal et après une période de ~7 jours de fermeture des vannes du barrage de Kervallon. Nous avons observé que la structure physico-chimique du réservoir de Ria Penfeld (RPR), avec une biomasse très élevée (chl-a jusqu’à 120 μg L-1) et des conditions anoxiques dans le fond, était radicalement différente de ce qui est habituellement observé dans les autres estuaires de la région. La production primaire nette très élevée (~1700 mg C m−2 d−1) était associée à une importante utilisation des nutriments, en particulier du phosphate, ce qui a entraîné un fort déséquilibre nutritionnel (rapport molaire N:Si:P de 2100:1500:1) pour l’eau exportée vers l’estuaire en aval