Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Diffusion parameters for HTO, 36Cl−, and 125I− were determined on Upper Toarcian argillite samples from the Tournemire Underground Research Laboratory (Aveyron, France) using the through diffusion technique. The direction of diffusion was parallel to the bedding plane. The purpose of the present study was 3-fold; it was intended (i) to confirm the I− interaction with Upper Toarcian argillite and to verify the effects of initial I− concentration on this affinity, as previously observed by means of radial diffusion experiments, (ii) to highlight any discrepancy between Cl− and I− diffusivity, and (iii) to investigate the effect of an increase of the ionic strength of the solution on the anionic tracers' diffusive behaviour. The results show that the effective diffusion coefficient (De) and diffusion accessible porosity (εa) values obtained with an ionic strength (I.S.) synthetic pore water of 0.01 eq L−1 are: De = 2.35-2.50 × 10−11 m2 s−1 and εa = 12.0-15.0% for HTO, and De = 14.5-15.5 × 10−13 m2 s−1 and εa = 2.5-2.9% for 36Cl−. Because of anionic exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than HTO, taken as a water tracer. The associated effective diffusion coefficient (De) and rock capacity factor (α) obtained for 125I are: De = 7.00-8.60 × 10−13 m2 s−1 and α = 4.3-7.2%. Such values make it possible to calculate low 125I distribution ratios (0.0057 < RD < 0.0192 mL g−1) which confirm the trend indicating that the 125I rock capacity factor increases with the decrease of the initial I− concentration. Additional through-diffusion experiments were carried out with a higher ionic strength synthetic pore water (I.S. = 0.11 eq L−1). No evolution of HTO diffusion parameters was observed. The anionic tracers' effective diffusion coefficient increased by a factor of two but no clear evolution of their accessible porosity was observed. Such a paradox could be related to the particularly small mean pore size of the Upper Toarcian argillite of Tournemire. The most significant finding of this study is the large discrepancy (factor of two) between the values of the effective diffusion coefficient for 125I and 36Cl. Whatever the ionic strength of the synthetic solution used, 125I exhibited De values two times lower than those of 36Cl. A detailed explanation for this difference cannot be given at present even if a hypothesis based on ion-pairing or on steric-exclusion cannot be excluded. This makes questionable the assumption usually made for quantifying 125I sorption and postulating that 36Cl and 125I would diffuse in the same porosity. In other terms, at Tournemire, 125I sorption could be more pronounced than previously indicated.
ISSN: 0883-2927

hal-00757749
https://hal.archives-ouvertes.fr/hal-00757749
DOI : 10.1016/j.apgeochem.2011.12.017

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This paper proposes a new approach for the on-site detection of micropollutants in water in case of accidental or intentional contamination (characterized by high concentration). The technique is based on the use of an automatic multiple solid phase extraction step (MSPE) followed by direct or indirect UV spectrometry (MSPE/UV) for the detection of organic contaminants in water (such as regulated molecules (pesticides ...) as well as emerging pollutants (pharmaceutical products, endocrine disruptors ...)). The development of the system supposes firstly the choice of the most appropriate sorbent(s) and secondly conditions for the detection of targeted micropollutants, from several solid phase extraction cartridges and eluting solvents. Two different extraction sorbents were chosen. These sorbents and several eluting solvents allow the first separation of the compounds based on the physico-chemical properties of each substance (pKa, log Kow) and on the specific interactions with the sorbent. Finally, a UV analysis (either at the maximum of absorbance using a calibration curve or from the whole spectrum using a multicomponent (deconvolution) exploitation method) of each fraction allows a determination and a quantification of each compound. The method is rapid (less than 2 h), sensitive enough for an accidental/intentional contamination (between 5 and 40 μg*L− 1 according to the substances) and with a good precision (between 4 and 14%).
ISSN: 0026-265X

hal-00878024
https://hal.archives-ouvertes.fr/hal-00878024
DOI : 10.1016/j.microc.2012.10.025

Éditeur(s) : Springer Berlin / Heidelberg
Résumé : The role of particles in the fate and speciation of trace metals in macrotidal estuaries was studied using a surface complexation model (MOCO). Cadmium was selected as the target metal contaminant due to its reactivity in estuaries: cadmium behavior is mainly controlled by heterogeneous processes (sorption/desorption) related to salinity and suspended matter gradients. Various scenarios of suspended matter distribution according to salinity were simulated. The impact of surface properties (specific surface area, density of surface sites, acido-basic properties, and complexation constant) was evaluated using data collected on particles from the Gironde, Loire, and Seine estuaries. Our results show that particle surface properties, evaluated on the basis of various parameters, are instrumental in "non-conservative" contaminant speciation in the estuarine environment. Their evaluation enables us to understand and simulate, to a large extent, the fate of "Cd-type" contaminants (whose behavior is controlled by competition between sorption and desorption processes). The natural variations of these properties can be responsible for significant modifications of the Cd speciation in the macrotidal estuaries where salinity and SM gradients are very strong.
The Handbook of Environmental Chemistry (1433-6839) (Springer Berlin / Heidelberg), 2006 , Vol. 5H , P. 265-301

Droits : 2006 Springer
http://archimer.ifremer.fr/doc/2006/publication-2005.pdf
DOI:10.1007/b89479
http://archimer.ifremer.fr/doc/00000/2005/

Éditeur(s) : Université Bordeaux 1
Résumé : The mercury cycle was explored in the Petit-Saut reservoir / Sinnamary Estuary continuum in French Guiana. Main processes involve (i) photo-induced reduction, (ii) adsorption and desorption at the particle surfaces, (iii) methylating bacterial activity, (iv) precipitation and dissolution of iron oxyhydroxides and sulfides. Sources of mercury to the Petit-Saut reservoir consist of the partly impacted river-tributaries, the atmospheric deposition and the flooded soils or vegetation. Once into the reservoir, divalent mercury undergoes a large spectrum of transformations including speciation and phase changes. We, here, probe these processes and demonstrate that the Petit-Saut reservoir behaves as a privileged site for atmospheric recycling and in situ methylation. At the air / water interface, the mercury evasion exceeds by 50 % the direct atmospheric deposition. The in situ monomethylmercury (MMHg) production mostly occurs at the water-column chemocline and near the benthic interface. It reaches, for the whole reservoir, 8.1 moles yr-1 which corresponds to a 0.06 % d-1 methylation rate. We calculated that the 2003/04 period MMHg outputs from the reservoir to the Sinnamary Estuary averaged 13.5 moles yr-1 while the inputs were 5.4 moles yr-1. The dynamic Sinnamary Estuary is the genuine geochemical reactor of the continuum. There, the divalent mercury undergoes rapid yet profound partitioning among phases, recycling to the atmosphere and methylation processes. Those mostly originate from the long-scale oxygen paucity of the dam discharged waters. The expression of marked redox gradients and the intense organic matter turnover enhance the production of methylable inorganic mercurial species and tend to favor the sulfate reducing bacteria (methylating agents) activity. As a result, the dynamic Sinnamary Estuary exports 60 % more MMHg than it does import: 27 versus 17 moles yr-1. Further at large, in the saline estuary, we determined: (i) a non conservative behavior of dissolved (< 0.2 µm) mercury, (ii) a lowering of the mercury level of particles during mixing with the Amazon plume and (iii) a gradual dilution of the estuarine mercury concentrations by oceanic waters.
La retenue de Petit-Saut et, à l'aval, l'estuaire du Sinnamary sont deux centres d'altération du cycle naturel du mercure. Les processus sont, entre autres, (i) la photoréduction, (ii) la sorption / désorption en surface des particules, (iii) l'activité méthylante des bactéries, (iv) la dissolution / précipitation des oxyhydroxydes et des sulfures de fer. Les sources de mercure vers la retenue sont variées. Elles regroupent, en premier lieu, les affluents (partiellement orpaillés), l'atmosphère, les sols et la végétation ennoyés. Dans la colonne d'eau, les formes divalentes du mercure subissent un train complet de transformations couplant changements de phase et de spéciation. Nos résultats illustrent ces processus et démontrent que la retenue constitue un site privilégié de recyclage vers l'atmosphère et de méthylation. A l'interface air / eau, les exports en mercure de la retenue excèdent de 50 % le dépôt atmosphérique. La production endogène de monométhylmercure (MMHg) a lieu dans des sites particuliers : la chemocline et l'interface benthique. Elle atteint pour l'ensemble de la retenue 8,1 moles a-1 soit un taux de méthylation de 0,06 % j-1. On estime que la retenue exporte vers l'estuaire du Sinnamary 13,5 moles a-1 de MMHg alors qu'elle n'importe que 5,4 moles a-1. L'estuaire dynamique du Sinnamary constitue le véritable réacteur chimique du système fonctionnant en liaison avec celui de la retenue. Le mercure y décrit un cycle rapide aux processus de partition, de recyclage et de méthylation marqués. Ces processus résultent de l'oxygénation incomplète et durable des masses d'eau anoxiques exportées par la retenue de Petit-Saut. L'expression de gradients rédox prononcés conjuguée à un intense recyclage de la matière organique y favorise la production de formes méthylables de mercure ainsi que l'activité des bactéries sulfatoréductrices (agents de la méthylation). C'est pourquoi, l'estuaire dynamique du Sinnamary exporte 60 % plus de MMHg qu'il n'importe : 27 contre 17 moles a-1. Plus en aval, dans l'estuaire salin, nous avons mis en évidence : (i) un comportement non conservatif du mercure dissous, (ii) un appauvrissement du mercure des particules suite au mélange avec le panache de l'Amazone et (iii) une dilution des concentrations par les masses d'eau océaniques.

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/2006/these-1508.pdf
http://archimer.ifremer.fr/doc/00000/1508/

Éditeur(s) : HAL CCSD
Résumé : International audience
In this work, a series of zinc partially substituted magnetite nanoparticles (Fe3-xZnxO4, 0 ≤ x ≤ 0.4), were synthesised through a facile precipitation-oxidation method. The partial substitution of zinc into the magnetite (Fe3O4) structure was confirmed by the collective findings of nitrogen sorption, XRD and TG-DTG analysis. It was found that the partial substitution of zinc slightly changed the textural properties of the resultant Fe3-xZnxO4 nanoparticles. From the XRD analysis, there was no visible formation of secondary phase or impurity peaks in the nanoparticles. These findings indicated the partial substitution of zinc into the Fe3O4 crystal structure with a good dispersion within the Fe3O4 matrix. © 2016 Author(s).
1st International Conference on Advanced Science,
Penang, Malaysia

hal-01683217
https://hal.univ-antilles.fr/hal-01683217

Résumé : This study contributes to inventory programme on emerging pollutants in French waters and to the general reflection which will enable to update the list of relevant substnaces to be included in the new monitoring programmes to come. This work concerns the coastal part of the inventory programme on marine waters and sediments of France and five overseas french departments (OFD). In this goal, passive sampling techniques and direct extraction techniques have been tested through the implementation of in situ systems integrators POCIS (Polar Organic Chemical Integrative Sampler) and the extraction by SBSE bars (Stir bar sorptive extraction) directly in the waters sampled. Finally, analyzes of sediment completed the acquisition of data. Arount 40 stations were sampled for shore waters and sediments were collected from 7 stations in France and 5 stations in the OFD (one station/OFD). In analytical terms, 1054 analyzes were carried out on POCIS membranes and only 64 data exceeded the limit of detection (LD), 12726 analyzes came from SBSE extractions and 304 were above the LD and 1536 analyzes in sediment showed that 237 data were above the limit of quantification (LQ). Finally, 169 different substances were investigated and 68 of them were detected at least once in water or sediment. The lack of replicates for POCIS analyzes and those in the sediment limited the statistical treatment of data. The results were used to determine the level of contamination, the detection frequency (FD), the distribution of substances between France and OFD, the comparison with environmental thresholds (the PNEC) and the origin/use of the substances. In littoral waters, 32 substances were identified and 19 were quantified. In the sediment, 47 substances were quantified. Nine substances were detected in both water and sediment. In France, the 15 substances that were quantified at higher frequencies (> 50 %, one out of 2 sites) were quantified in sediments. These are the congeners of PAHs (11 substances), organic forms of tin (2 substances), diethyl lead and 209 PBDE congener. In the OFD, the 22 substances that were quantified at higher frequencies (> 50 %, one out of 2 sites) were measured in sediments. These are congeners of PAHs (13 substances) , alkylphenols ( 3 molecules: the mono and diethoxyate nonylphenol and the 4-ter butylphenol ), the organic forms of tin (2 substances), products of metabolism insecticide DDT ( 2 products), diethyl lead and the 209 PBDE congener. The study of the highest concentrations distribution of substances between France and OFD shows that the 5 (among 19 molecules) highest concentrations in water and the 6 (among 47 molecules) highest concentrations in sediments are found in OFD. Reference to PNEC indicates that four pesticides in water and 11 different substances in sediments exceed the environmental thresholds. Substances with highest detection frequency are found in the sediment. The distribution of data by use or nature of the substance shows that plasticizers and pesticides predominate in raw water, both in France and overseas departments while PAHs in sediments dominate in France and in OFD.
Cette étude contribue au programme d’inventaire des substances chimiques émergentes dans les eaux françaises et à la réflexion qui doit permettre d’actualiser la liste des substances pertinentes à surveiller de manière régulière dans le cadre des nouveaux programmes de surveillance. Ce travail concerne la partie littorale de l’inventaire, sur les eaux brutes et les sédiments de la métropole et des 5 DOM. Dans ce cadre, des techniques d’échantillonnage passif (EP) et d’extraction directe ont été testées grâce à la mise en place in situ de systèmes intégrateurs POCIS (Polar Organic Chemical Integrative Sampler) et à l’extraction par des barres SBSE (Stir Bar Sorptive Extraction) directement dans les eaux échantillonnées. Enfin des analyses de sédiments ont complété l’acquisition des données. L’eau d’une quarantaine de stations a été échantillonnée et des sédiments ont été prélevés sur 7 stations en métropole et dans 5 stations dans les DOM (une station par DOM). En termes analytiques, 1054 analyses ont été réalisées sur les membranes POCIS et 64 dépassaient la limite de détection (LD), 12726 analyses ont concerné les extractions par SBSE pour 304 résultats situés au dessus de la LD et 1536 analyses effectuées dans le sédiment ont donné 237 valeurs supérieures à la limite de quantification (LQ). Au bilan 169 substances différentes ont été recherchées et 68 d’entre elles ont été détectées au moins une fois dans l’eau brute ou le sédiment. L’absence de réplicats pour les analyses POCIS et celles dans le sédiment a limité le traitement statistique des données. Les résultats ont permis de déterminer le niveau de contamination, la fréquence de détection (FD), la distribution métropole/DOM des substances, la comparaison avec les seuils environnementaux (PNEC) et l’origine des substances. Dans l’eau 32 substances ont été identifiées et 19 ont été quantifiées. Dans le sédiment 47 substances sont quantifiées .Neuf substances sont détectées à la fois dans l’eau et le sédiment. En métropole, les 15 substances quantifiées aux plus hautes fréquences (> 50%, soit un site sur 2) sont quantifiées dans les sédiments. Ce sont les congénères de la famille des HAP (11 substances), des formes organiques de l’étain (2 substances), le plomb diéthyle et le congénère 209 des PBDE. Dans les DOM, les 22 substances quantifiées aux plus hautes fréquences (> 50%, soit un site sur 2) sont mesurées dans les sédiments. Ce sont des congénères de la famille des HAP dans (13 substances), des alkylphénols (3 substances : nonylphénols mono et diéthoxylés et 4-ter butylphénol), des formes organiques de l’étain (2 substances), des produits de métabolisation de l’insecticide DDT (2 produits), du plomb diéthyle et du congénère 209 des PBDE. L’étude de la répartition des plus fortes concentrations entre la métropole et les DOM montre que les 5 (sur 19) concentrations les plus élevées mesurées dans l’eau et les 6 (sur 47) plus fortes concentrations mesurées dans les sédiments sont trouvées dans les DOM. Les substances mesurées aux fortes fréquences sont observées dans le sédiment. La référence à la PNEC indique le dépassement de la norme pour 4 pesticides dans l’eau brute et 11 substances diverses dans les sédiments. L’exploitation des données par usage ou nature des substances montre que les plastifiants et les pesticides sont majoritaires dans les eaux brutes, à la fois en métropole et dans les DOM alors que ce sont les HAP qui dominent dans les sédiments, en métropole et dans les DOM.

Droits : 2014 ONEMA, Ifremer
http://archimer.ifremer.fr/doc/00259/36994/35483.pdf
http://archimer.ifremer.fr/doc/00259/36994/

Éditeur(s) : HAL CCSD Elsevier
Résumé : Among the radionuclides that can migrate from radioactive wastes buried within consolidated argillaceous rocks, I-129 poses a particular problem due to its high mobility in geomedia and its very long half-life of 1.6 10(7) years. Previous studies carried out on such rocks showed the existence of a low iodide retardation regarding the other anion species. The purpose of the present study was two-fold. It was hoped (1) to confirm this retardation by means of radial diffusion experiments and (2) to estimate the influence of the initial iodide concentrations towards the iodide uptake. The results obtained from in-diffusion stage show that (1) no iodide uptake occurs at high initial concentrations and (2) an uptake at low initial concentrations cannot be clearly evidenced. Finally. the most singular behaviour of iodide was highlighted for all the initial iodide concentrations, from the out-diffusion stage. during which some amount of iodide, available for out-diffusion, were not involved in the diffusion process. Although the origin of such phenomenon remains unclear, a kinetic effect for the iodide uptake was proposed, assuming that the period of 55days (corresponding to the in-diffusion stage duration) would be necessary for inducing the iodide uptake. This kinetic effect, already shown elsewhere by (Descostes. M., Blin, V., Bazer-Bachi, F., Meier, P., Grenut, B., Radwan. J., Schlegel, M.L., Buschaert, S.. Coelho, D, Tevissen, E. Diffusion of anionic species in Callovo-Oxfordian argillites and Oxfordian limestones. In press for Appl. Geochem.) on similar materials, needs to be deepened.
ISSN: 0079-1946

hal-00412393
https://hal.archives-ouvertes.fr/hal-00412393
DOI : 10.1016/j.pce.2008.05.020

Éditeur(s) : HAL CCSD
Résumé : International audience
Environmental context The safeguarding of water supplies and drinking water is a major issue when considering human health risk management. In this context, an automatic and on-site fractionation system for the detection of organic contaminants has been developed. The main goal of this system is to establish an initial diagnosis by identifying a class of substances involved in a case of pollution. Abstract This paper proposes a new approach for the preconcentration, fractionation, prediction and detection of organic micropollutants in water. The main aim of this study was to implement an innovative fractionation method and a prediction model based on the physicochemical properties of compounds and interactions with the sorbent of solid-phase extraction cartridges. Two sorbents (Strata-SAX and Oasis-HLB) and three specific eluting solvents (mixture of methanol and sodium chloride and mixtures of acetonitrile and ultrapure water) were used to separate organic compounds into five specific fractions according to their physicochemical properties (anionic and cationic or neutral compounds with various polarity). More than 75 molecules (43 molecules individually studied and a mixture with 43 molecules, including 11 molecules individually studied) including pesticides, pharmaceuticals, endocrine disruptors and polycyclic aromatic hydrocarbons, with various properties were studied, and the results showed that the elution fraction can be predicted for more than 85% of the compounds. This methodology could simplify the analytical chain by reducing detailed analysis on limited categories of compounds, and could be used for a rapid and on-site screening of organic compounds. © CSIRO 2016.
Environmental Chemistry

hal-01373945
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01373945
DOI : 10.1071/EN15135