Etude cinétique de la complexation du cuivre en milieu hydrogénocarbonate par électrochimie

La détermination de la capacité complexante des eaux naturelles est généralement effectuée par titrage ampérométrique du cuivre à pH fixé. Beaucoup, sinon tous les tampons classiques utilisés perturbent les études de spéciation du cuivre par formation de complexes peu stables. Dans ce travail nous nous sommes intéressés à la complexation du cuivre par les ions carbonates généralement présents dans les eaux naturelles. Afin de mener à bien notre étude, nous avons mesuré, dans un milieu synthétique de force ionique et pH contrôlés (KNO3 0,02 M + NaHCO3 2,38.10-3 M) toutes les constantes des divers équilibres prévisibles : produits de solubilité de l'hydroxyde de cuivre Cu(OH)2 et de la malachite Cu2 (OH)2 CO3, constante de formation du carbonate de cuivre dissous CuCO3. A des valeurs de pH suffisamment faibles, la formation du complexe CUOH+ peut étre négligée. Les trois autres réactions ont été suivies race aux mesures combinées, d'une part du pH et, d'autre part, de l'activité en ion Cu2+ libre ou hydraté par ionométrie. Compte tenu des propriétés acido-basiques des diverses espèces, les mesures ont été effectuées à divers pH compris entre 5,5 et 8. Le complexe CuCO30étant l'espèce majoritaire dans ces solutions, sa labilité, pouvant perturber follement les déterminations des capacités complexantes par titrage ampérométrique, a été étudiée par diverses méthodes électrochimiques. La polarographie à tension sinusoïdale surimposée (AC) a indiqué une réduction rapide du cuivre (II) sur électrode de mercure. Deux vagues ont été obtenues en voltampérométrie sur électrode tournante à disque de platine (RDE), ce dédoublement étant d'origine cinétique compte tenu de l'évolution de ces vagues avec la température. Une estimation des valeurs des constantes de vitesse de formation kf et de dissociation kb, a permis de montrer la rapidité des réactions mises en jeu et la labilité du complexe CuCO30.The determination of the complexing capacity of natural waters by amperometric copper (II) titrations must be made in pH-buffered solutions. Most if not all of classical buffers influence copper speciation through the formation of weak complexes. This paper deals with an attempt to use the naturally occurring hydrogenocarbonate buffet. A detailed study of copper (II) chemistry in synthetic solutions at controlled ionic strength and pH (0.02 mol.l-1 KNO3, 2.38 mol.l-1 NaHCO3, controlled Pco2) was carried out. In these solutions copper (Il) chemistry may involve precipitation of copper hydroxide Cu(OH)2, copper hydroxycarbonate Cu2(OH)2 CO3 (malachite) and formation of the soluble complexes CuCO30 and CuOH+. At low enough values of pH CuOH+ formation may be neglected. The three other reactions are studied using copper ionometry with a specific electrode and equilibrium constants determined in the 5.5 to 8.0 pH range. As CuCO30 is a major species in these solutions its lability is of major concern for the validity of the amperometric determination of the complexing capacity by copper (II) titration and bas been studied by several electrochemical approaches. AC polarography indicated a rapid reduction of copper (II) on the mercury electrode. Two waves were obtained for the deposition of copper (Il) by voltamperometry with a rotated platinum disk electrode (RDE) presenting the characteristics of a kinetic control. However the values of the forward (kf) and backward (kb) reaction rate constants for CuCO30 formation or dissociation seem too high for a precise determination

The significance of Anomalocaris and other Radiodonta for understanding paleoecology and evolution during the Cambrian explosion

One of the most widespread and diverse animal groups of the Cambrian Explosion is a clade of stem lineage arthropods known as Radiodonta, which lived exclusively in the early Paleozoic. First reported in 1892 with Anomalocaris canadensis, radiodonts are now one of the best known early animal groups with excellent representation in the fossil record, and are ubiquitous components of <jats:italic>Konservat-Lagerstätten</jats:italic> from the Cambrian and the Early Ordovician. These large swimmers were characterised by a segmented body bearing laterally-oriented flaps, and a head with a distinct radial oral cone, a pair of large frontal appendages adapted for different feeding modes, compound eyes on stalks, and prominent head carapaces. Radiodonts inform on the paleoecology of early animal communities and the steps involved in euarthropod evolution. Four families within Radiodonta have been established. The raptorial predator families Anomalocarididae and Amplectobeluidae were dominant early in the evolutionary history of Radiodonta, but were later overtaken by the mega-diverse and widespread Hurdiidae, which has a more generalised sediment-sifting predatory mode. Suspension feeding, notably in the families Tamisiocarididae and Hurdiidae, also evolved at least twice in the history of the clade. The well-preserved anatomical features of the radiodont body and head have also provided insights into the evolution of characteristic features of Euarthropoda, such as the biramous limbs, compound eyes, and organisation of the head. With 37 species recovered from all major paleocontinents of the Cambrian and Early Ordovician, Radiodonta provides a unique opportunity for revealing evolutionary patterns during the Cambrian Explosion

Spéciation des organoétains dans les eaux et sédiments du bassin Adour-Garonne

De par leurs nombreuses propriétés physico- chimiques, les organoétains sont très utilisés dans l’industrie et en agriculture et entrent dans la composition de nombreux produits domestiques. Ils sont cependant extrêmement toxiques et la Communauté Européenne les a classés parmi les substances prioritaires dans le domaine de l’eau.Un suivi des organoétains a été réalisé sur onze rivières du bassin Adour-Garonne et sur l’estuaire de l’Adour. Ces composés y sont systématiquement présents, les butylétains et les octylétains étant les espèces les plus fréquemment détectées. Les concentrations varient de la limite de détection (0.2-0.5 ng(Sn)/l en moyenne) à 50 ng(Sn)/l dans les eaux, et de 15 à 300 µg(Sn)/kg dans les sédiments dulcicoles. Des pics de contamination ont été observés en fin de printemps et d’été, dans plusieurs rivières. Ils correspondent à la présence des mono- butyl- et -phénylétains principalement, leurs concentrations pouvant atteindre 700 à 900 ng(Sn)/l d’eau. Les rivières les plus contaminées sont la Garonne, le Gave de Pau, l’Adour, la Charente et le Thoré. Dans les matières en suspension de l’estuaire de l’Adour les concentrations atteignent quelques mg(Sn)/kg. L’ensemble des données recueillies a permis de mieux comprendre les origines et le devenir des organoétains dans le cycle hydrologique.Because of their physico-chemical properties, organotin compounds (OTC) are widely used in industry and are present in a significant number of agricultural pesticides and domestic products. They are highly toxic and the European Community has listed them as priority pollutants in the aquatic environment. Organotins have been monitored in the Adour- Garonne basin and the Adour estuary. They are systematically present in the rivers, with butyl- and octyltins being the species most frequently detected. These species, especially octyltins, probably come from the continuous leaching of plastic tubes. The OTC concentrations ranged from just over detection limits (≥ 0.2-0.5 ng (Sn)/L) to 50 ng (Sn)/L in water and from 15 to 300 µg (Sn)/kg in freshwater sediment. Important seasonal variations were also observed. Thus, at the end of spring and summer, very high monophenyltin (MPhT) concentrations of up to 700-900 ng (Sn)/L were found in the dissolved phase. This phenomenon could be partly attributed to specific triphenyltin (TPhT)-based agricultural treatments, MPhT being one of the TPhT degradation products. High monobutyltin (MBT) concentrations of up to 150 ng (Sn)/L were also detected during the same period. This latter compound comes from leaching of plastics and from tri- and di-butyltin (TBT, DBT) degradation. It represents 80 to 100% of the butyl species found in sediments.Considering OTC concentrations, speciation and toxicity, the most contaminated rivers appeared to be the Garonne, Gave de Pau, Adour, Charente and Thoré. Urban activities have significant influence on the levels of OTC contamination for most of the rivers, demonstrating continuous OTC inputs from domestic and industrial treatment plants. This is especially the case for the Charente and Thoré rivers, where some specific industrial activities devoted to leather and wood are present close to the sampling points.A statistical study was performed on the different physico-chemical parameters (temperature, water flow rate, dissolved oxygen concentration) and OTC concentrations. A significant positive correlation between water flow rate and organotin concentrations in the dissolved phase was observed. This correlation was very important when only sampling points far from potential OTC sources were considered, the octyltin concentrations showing the strongest correlation. These observations confirm the presence of a continuous OTC diffusion into aquatic media. A comparison between the present results in Adour-Garonne and OTC monitoring performed in the Rhin- Meuse basin shows that the level of contamination was quite similar in the two basins, especially considering rivers without fluvial traffic. A similar correlation existed between OTC concentrations in the dissolved phase and water flow rate.Special attention was given to the Adour sub-basin because of its particular geographic position and especially the large built-up area in the estuary. Butyltins remain the main OTC compound present, in terms both of frequency and concentration. According to the different sampling points in this sub-basin, mean OTC concentrations in the estuary did not appear to be really influenced by human activities located upstream, the concentrations in this part reaching 50 ng (Sn)/L in the dissolved phase. In contrast, OTC amounts found in the estuary were considerable higher. The built-up area of the estuary had a strong influence on concentrations, which were 6 to 14 times higher in the city centre than those upstream from the city (in an agricultural region). In addition to the influence of local sources, both a strong dilution effect and significant adsorption/ sedimentation phenomena in the downstream region of the estuary could be important. In the suspended matter of the Adour estuary, organotin concentrations were extremely high, reaching concentrations as high as mg (Sn)/kg. Such concentrations have already been reported for nearby regions of the harbour [Bravo et al. (2004)]. However, in the present case, there should be considerable concern considering the possible environmental consequences. The estuarine sediments appeared obviously contaminated by butyltins, but the concentrations were lower than those that could be expected (2000 µg (Sn)/ kg maximum). This observation could be explained by water flow rates as well as the tide, which could export large amounts of suspended matter outside the estuary. MPhT and TPhT were also detected, especially in sediments from the extreme downstream region of the estuary. Their presence could be attributed to the marina. The different solid/ dissolved partition coefficients were also evaluated. These partition coefficients ranged from over 40x104 for sediments up to 200x104 for suspended matter. Finally, the information on the Adour sub-basin showed that the estuary was more strongly contaminated than the upstream region.Generally, all these data have contributed to the first evaluation of OTC contamination in the Adour-Garonne basin, and identified organotin sources. The statistical study, comparisons between the different parts of the aquatic environment, and the observation of solid/ liquid distributions lead to a better understanding of the environmental fate of OTCs. Even if differences exist between the level of contamination in freshwater and estuarine environments, the ubiquitous presence of OTC must remain a subject of concern, especially with regard to the high toxicity of organotins. For example, TBT and TPhT have lethal effects on trout and algal species at aquatic concentrations in the µg (Sn)/L range or even below this concentration [TOOBY et al. (1975), WONG et al. (1982)]. Considering this high toxicity, other studies will have to be performed in order to increase the current database concerning OTC in rivers. It is also important to know the conditions that control OTC uptake by biota, and in order to propose effective environmental management strategies

Mise au point de techniques analytiques pour la spéciation du sélénium dans les boues de stations d'épuration d'eaux résiduaires urbaines

Les stations d'épuration d'eaux résiduaires sont une des étapes du cycle du sélénium dans l'environnement et contribuent à sa redistribution dans le milieu naturel. Très peu étudié jusqu'à présent dans ces milieux, le sélénium n'en est pas moins un élément très important du point de vue écotoxicologique, sa teneur dans les boues de stations d'épuration destinées à l'épandage agricole faisant par ailleurs l'objet d'une norme.Nous avons mis au point des techniques permettant la détermination spécifique de l'élément total dans ce type d'échantillon, par minéralisation classique ou assistée par micro-ondes et dosage par Voltamétrie de Redissolution Cathodique Différentielle Pulsée (DPCSV) et Spectrométrie d'Absorption Atomique ElectroThermique (ETAAS). Le contrôle qualité a été effectué sur deux échantillons certifiés fournis par le Bureau Communautaire de Référence (BCR) : la boue CRM 145 R et la boue CRM 007.Cependant, lorsqu'on parle de risque toxicologique, il est important de s'intéresser à la détermination des différentes formes sous lesquelles cet élément peut être présent. Nous avons pour cela réalisé des extractions parallèles (spéciation de phases) du sélénium contenu dans les boues afin de déterminer quel pourcentage du sélénium total est réellement et potentiellement disponible pour les végétaux lors d'un épandage sur sol agricole. La spéciation d'espèces a été brièvement abordée dans le but de déterminer les teneurs en Se(IV) et Se(VI), espèces les plus toxiques.The great effort undertaken for about twenty years to improve the quality of surface waters has led to the construction of numerous waste water treatment plants, generating an increasing amount of sludge. Waste water and sludge treatment processes represent an important point in the hydrological cycle at which the disposal of substantial quantities of trace elements to the environment may be regulated. From the law on waste recovery and disposal in 1975 to the European guideline about wastes in 1991, the priority has been given to waste recovery and recycling. With increasing pressure to ban all sludge dumping at sea, and considering the prohibitive costs of land-filling and incineration, there is a great tendency to dispose of sludge on land (40% in 1988 to 60% in 1992).Although numerous studies have demonstrated the intrinsic value of sludge for soil amendment, given its nitrogen, phosphorus and homogeneous organic matter content, evidence has accumulated in recent years that numerous environmental problems can arise because of the presence in sludges of high amounts of certain trace elements (potentially toxic to plants and to human beings and liable to be concentrated along the food chain), among which selenium is particularly interesting.Selenium presents a complex case, as it is also an essential element for living organisms (including humans). The amendment with sewage sludge is sometimes used to increase the selenium content in crops, and afterwards in cattle, when there is a proven lack of this element in a given place. Nevertheless the boundary between essentiality and toxicity is relatively narrow and is expressed at trace levels. It is thus particularly important to survey the selenium concentrations encountered in sewage sludge, especially as guidelines and regulations concerning these data will probably be strengthened. Presently, in France, sludge must not contain more than 200 mg Se·kg-1 dry weight and must not be used on soils containing more than 10 mg Se·kg-1 dry weight (AFNOR U 44-041 norm). This norm concerns only the total amount of selenium contained in sludge and does not take into account the different species (organic and inorganic Se(-II), Se(0), Se(IV) and Se(VI)) that could be present.First of all we had to develop methods for the classical and microwave-assisted wet digestion of sewage sludge, and the determination of their total selenium concentration by Differential Pulse Cathodic Stripping Voltammetry (DPCSV) and ElectroThermal Atomic Absorption Spectrometry (ETAAS). Quality assurance involved the analysis of two BCR (Community Bureau of Reference) certified sewage sludge reference materials (CRM 145 R and CRM 007) and the different techniques were then applied to natural samples from a representative French sewage treatment plant located in the city of Tarbes (South-West of France). The mixture HNO3-H2O2-H2O led to the best results for the digestion and analysis of certified samples, caused few problems for the analysis by DPCSV and ETAAS, and was therefore retained. The decrease of the digestion duration obtained by the use of microwaves was particularly interesting (from one to three days on a hot plate to less than one hour by the Microdigest 301 (PROLABO, France)), and reproducibility was also acceptable (between 3 and 10%). Concentrations obtained for the sewage sludge from the Tarbes treatment plant were very much lower than those for NF U 44-041: 1.08±0.11 mg Se·kg-1 dry weight.However knowledge of speciation, that is to say the determination of the different physicochemical forms of selenium present in a given medium, is necessary when speaking of the toxicological risk represented by an element. The mobility of selenium and its toxicity to the biosphere are related to its association with various sludge or soil constituents as well as to its total concentration. "Soft" or partial extraction techniques are necessary when the aim of the study to determine trace element speciation. The extractants used must separate selenium from the matrix without inducing any loss or change in the partitioning of individual chemical species. In parallel extractions the mechanisms involved for each extractant must correspond to processes occurring in nature and are then associated with special fractions of selenium: soluble, exchangeable, "oxidizable", and "mineral" fractions .Parallel extractions with three types of extractants were chosen for this study and applied first to CRM 007: warm water (soluble fraction), ammonium phosphate-citric acid (soluble + exchangeable fraction) and sodium hydroxide (soluble + exchangeable + "oxidizable" fraction). The soluble, exchangeable, "oxidizable" and "mineral" fractions represent respectively : 11%, 14%, 39% and 36%. The same procedure was then applied to natural samples from Tarbes giving the following results: 36% soluble, 22% exchangeable, 42% "oxidizable". The sodium hydroxide extraction procedure allowed us to extract the entire Se content of this sludge (1.07±0.03 mg Se·kg-1 dry weight), showing that all the selenium present is potentially available after agricultural land application. It was then possible in this fraction to deal with the species speciation of selenium by the mean of a separation of inorganic and organic species on an Amberlite CG-400 resin and a specific analysis by DPCSV. Se(IV) and Se(VI) represent respectively between 30 and 40% and between 2 and 20% of total selenium in the sludges from Tarbes

Radiodont frontal appendages from the Fezouata Biota (Morocco) reveal high diversity and ecological adaptations to suspension-feeding during the Early Ordovician

Introduction: The Early Ordovician Fezouata Shale Formation (485–475Ma, Morocco) is a critical source of evidence for the unfolding Great Ordovician Biodiversification Event (GOBE), the largest radiation in animal diversity during the Paleozoic. The Fezouata Shale preserves abundant remains of ancient marine organisms, including hundreds of specimens of radiodonts, a diverse and globally distributed group of stem lineage arthropods that first appeared as raptorial predators during the Cambrian Explosion. Methods: In this work, we study 121 radiodont frontal appendages from the Fezouata Shale. Frontal appendages are the most commonly preserved body parts of radiodonts, and their well-preserved anatomical characters are crucial for describing taxonomic diversity at the species level, while also providing essential data on mode of life, paleoecology, and feeding behaviour. Results: Our data allow for a systematic review of suspension-feeding Hurdiidae radiodonts from Fezouata. The genus Pseudoangustidontus is recognised as a radiodont and ascribed to Hurdiidae, and a new second species of this genus is identified, Pseudoangustidontus izdigua sp. nov. Aegirocassis benmoulai is also reviewed and its diagnosis amended with new details of differentiated endites in this appendage. The morphological similarity between both genera allows us to erect Aegirocassisinae subfam. nov., which groups together the suspension-feeding hurdiids of the Fezouata Shale. Discussion: Suspension-feeding radiodont appendages are more abundant than those of sediment sifting or raptorial radiodonts, with the Fezouata Shale showing the highest diversity of suspension-feeding radiodonts in the history of the group. This dominance and diversity of frontal filter-feeding appendages follows the “Ordovician Plankton Revolution”, which started in the upper Cambrian and saw a huge radiation in plankton diversity

The heterogeneous spatial and temporal patterns of behavior of small pelagic fish in an array of Fish Aggregating Devices (FADs)

Identifying spatial and temporal patterns can reveal the driving factors that govern the behavior of fish in their environment. In this study, we characterized the spatial and temporal occupation of 37 acoustically tagged bigeye scads (Selar Crumenophthalmus) in an array of shallow Fish Aggregating Devices (FADs) to clarify the mechanism that leads fish to associate with FADs. A comparison of the number of visits and residence times exhibited by the fish at different FADs revealed a strong variability over the array of FADS, with the emergence of a leading FAD, which recorded the majority of visits and retained the fish for a longer period of time. We found diel variability in the residence times, with fish associated at daytime and exploring the array of FADs at nighttime. We demonstrated that this diel temporal pattern was amplified in the leading FAD. We identified a 24-hour periodicity for a subset of individuals aggregated to the leading FAD, thus suggesting that those fish were able to find this FAD after night excursions. The modeling of fish movements based on a Monte Carlo sampling of inter-FAD transitions revealed that the observed spatial heterogeneity in the number of visits could not be explained through simple array-connectivity arguments. Similarly, we demonstrated that the high residence times recorded at the leading FAD were not due to the spatial arrangement of individual fish having different associative characters. We discussed the relationships between these patterns of association with the FADs, the exploration of the FAD array and the possible effects of social interactions and environmental factors.Comment: 21 pages, 9 figures + 2 supplementary figure

Radiodont frontal appendages from the Fezouata Biota (Morocco) reveal high diversity and ecological adaptations to suspension-feeding during the Early Ordovician

IntroductionThe Early Ordovician Fezouata Shale Formation (485–475Ma, Morocco) is a critical source of evidence for the unfolding Great Ordovician Biodiversification Event (GOBE), the largest radiation in animal diversity during the Paleozoic. The Fezouata Shale preserves abundant remains of ancient marine organisms, including hundreds of specimens of radiodonts, a diverse and globally distributed group of stem lineage arthropods that first appeared as raptorial predators during the Cambrian Explosion.MethodsIn this work, we study 121 radiodont frontal appendages from the Fezouata Shale. Frontal appendages are the most commonly preserved body parts of radiodonts, and their well-preserved anatomical characters are crucial for describing taxonomic diversity at the species level, while also providing essential data on mode of life, paleoecology, and feeding behaviour.ResultsOur data allow for a systematic review of suspension-feeding Hurdiidae radiodonts from Fezouata. The genus Pseudoangustidontus is recognised as a radiodont and ascribed to Hurdiidae, and a new second species of this genus is identified, Pseudoangustidontus izdigua sp. nov. Aegirocassis benmoulai is also reviewed and its diagnosis amended with new details of differentiated endites in this appendage. The morphological similarity between both genera allows us to erect Aegirocassisinae subfam. nov., which groups together the suspension-feeding hurdiids of the Fezouata Shale.DiscussionSuspension-feeding radiodont appendages are more abundant than those of sediment sifting or raptorial radiodonts, with the Fezouata Shale showing the highest diversity of suspension-feeding radiodonts in the history of the group. This dominance and diversity of frontal filter-feeding appendages follows the “Ordovician Plankton Revolution”, which started in the upper Cambrian and saw a huge radiation in plankton diversity