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

Relation entre notation sociale et structure financière des entreprises : une étude empirique.

Relation entre notation sociale et structure financière des entreprises : une étude empirique Cet article étudie le lien entre la structure du capital des entreprises et leur notation sociale. Notre modèle théorique montre que les entreprises les moins éthiques, pour échapper à la sanction du marché financier, recourent plus massivement à l'endettement, notamment à l'emprunt bancaire. En effet, l'intérêt croissant des investisseurs pour la responsabilité sociale fait que les entreprises non éthiques supportent un coût des capitaux propres plus élevé que leurs concurrentes éthiques. Inversement, le coût de la dette n'est pas lié à la qualité éthique de l'entreprise, les banques ne prenant pas en compte le critère éthique dans la fixation des taux d'intérêt. Nous proposons de vérifier que le niveau d'endettement des entreprises est en relation décroissante avec la note RSE (responsabilité sociale de l'entreprise). Nous tenons compte dans notre analyse de l'influence de plusieurs déterminants de la structure du capital, comme les coûts de faillite, le niveau de taxation, les variables d'agence et d'asymétrie d'information. L'étude porte sur un échantillon de 562 entreprises européennes pour lesquelles nous disposons de la note RSE fournie par l'agence de notation Vigéo. La période d'étude s'étend sur les années 1999 à 2007. Nos résultats montrent que la structure financière actuelle des entreprises est encore peu influencée par la note éthique. En revanche, lorsque l'on cherche à comprendre comment cette structure évolue, on identifie clairement la note éthique comme un facteur de changement : plus une entreprise a une bonne note éthique, plus elle se détourne de l'endettement.investissement socialement responsable ; notation éthique ; coût du capital ; endettement ; structure du capital ; optimum.

Alteraciones de la superficie del cuerpo vertebral en una población medieval de Logroño (s. XI y XII)

X Congreso Nacional de Paleopatología. Univesidad Autónoma de Madrid, septiembre de 200

Different regulation of haloperoxidation during agar oligosaccharide-activated defence mechanisms in two related red algae

The related red seaweeds Gracilaria sp. from the eastern Mediterranean and Gracilaria chilensis from Chile were similar in their enzymatic inventory for halogenation. In both species, halogenation was dependent upon H(2)O(2) and thus driven by haloperoxidases. These could be inhibited with phosphate and reversibly inhibited with azide and were therefore apparently dependent upon vanadate. Both species generated in the first line bromoform and other brominated halocarbons. Gel electrophoresis under non-denaturating conditions demonstrated that both species expressed halogenating peroxidases. Elicitation of Gracilaria sp. with agar oligosaccharides resulted in marked increases in bromination, iodination, and chlorination. Production rates of volatile halocarbons and phenol red bromination both increased by a factor of eight, presumably due to increased availability for haloperoxidases of H(2)O(2) during the oxidative burst response. Elicitation of Gracilaria sp. also triggered a release of bromide ions through DIDS-sensitive anion channels, which allowed for some bromination in bromide-free medium. However, this effect was relatively limited. By contrast, agar oligosaccharide oxidation in G. chilensis did not increase halogenation. Obviously, agar oligosaccharide oxidation does not provide sufficient amounts of hypohalous acids for such increases, because it does not deliver H(2)O(2) at the active site of vanadium-dependent haloperoxidases. These results correlate with earlier findings that the agar oligosaccharide-elicited oxidative burst controls microorganisms while agar oligosaccharide oxidation does not

Isomeric pair 95m,gNb{^{95\rm m,g}\rm{Nb}} in photonuclear reactions on nat^{\rm nat}Mo at end-point bremsstrahlung energy of 35-95 MeV

The ${^{\rm nat}\rm{Mo}}(\gamma,x\rm np)^{95\rm m,g}$Nb photonuclear reaction was studied using the electron beam from the NSC KIPT linear accelerator LUE-40. Experiment was performed using the activation and off-line $\gamma$-ray spectrometric technique. The experimental isomeric yield ratio $d(E_{\rm{\gamma max}}) = Y_{\rm m}(E_{\rm{\gamma max}}) / Y_{\rm g}(E_{\rm{\gamma max}})$ was determined for the reaction products $^{95\rm m,g}\rm{Nb}$ at the end-point bremsstrahlung energy $E_{\rm{\gamma max}}$ range of 35-95 MeV. The obtained values of $d(E_{\rm{\gamma max}})$ are in satisfactory agreement with the results of other authors and extend the range of previously known data. The theoretical values of the yields $Y_{\rm m,g}(E_{\rm{\gamma max}})$ and the isomeric yield ratio $d(E_{\rm{\gamma max}})$ for the isomeric pair $^{95\rm m,g}\rm{Nb}$ from the ${^{\rm nat}\rm{Mo}}(\gamma,x\rm np)$ reaction were calculated using the partial cross-sections $\sigma(E)$ from the TALYS1.95 code for six different level density models $LD$. The comparison showed a noticeable excess (more than 3.85 times) of the experimental isomeric yield ratio over all theoretical estimates. At the investigated range of $E_{\rm{\gamma max}}$ the theoretical dependence of $d(E_{\rm{\gamma max}})$ on energy was confirmed - the isomeric yield ratio smoothly decreases with increasing energy.Comment: 9 pages, 9 figures, 1 tabl

Interstrip resistance of a semiconductor microstrip detector

In this work the interelement (interstrip) resistance of the microstrip detector is studied. A few detectors with a different construction are investigated. The dependence of the interstrip resistance on the dose of detector irradiation with electrons is obtained. The possibility of application interstrip resistance measurement for the determination of the good strip yield is shown

Radiation Tolerance of Single-Sided Microstrip Detector with Si3N4Si_{3}N_{4} Insulator

The ALICE Collaboration is investigating the radiation tolerance and operation of silicon microstrip detectors for the inner tracking system. Detectors with and without an additional layer of Si3N4 insulator were made in one set, using the same thickness of SiO2 insulator. Measurements were made on both types of detectors after irradiation with 20 MeV electrons, using doses up to 2Mrad. The additional Si3N4 layer allows a coupling capacitor breakdown voltage larger than 100 V and capacitor yield larger than 99 percent. However, the leakage current for detectors with double layer insulator is about 20 nA per strip while the leakage current for the single layer SiO2 insulated detectors is only 0.5 nA. The 20 nA leakage current leads to 450 electrons noise when the ALICE 128C electronics with a peaking time of 1.4 microseconds is used. At a 1 nA leakage current the noise is 100 electrons. The ENC for an input capacitance of 5 pF is 300 electrons. Since all detectors show an increased leakage current after irradiation, the difference between the single and duoble layer insulation detectors becomes negligible when doses of the order of several hundreds of krad are applied

Production of 180m{^{180\rm{m}}}Hf in photoproton reaction 181{^{181}}Ta(γ,p)(\gamma,p) at energy EγmaxE_{\rm{\gamma max}} = 35-95 MeV

The production of the $^{180\rm{m}}\rm{Hf}$ nuclei in the photoproton reaction ${^{181}\rm{Ta}}(\gamma,p)$ was studied at end-point bremsstrahlung energies $E_{\rm{\gamma max}}$ = 35-95 MeV. The experiment was performed at the electron linear accelerator LUE-40 NSC KIPT with the use of the $\gamma$ activation and off-line $\gamma$-ray spectroscopy. The experimental values of the bremsstrahlung flux-averaged cross-sections $\langle{\sigma(E_{\rm{\gamma max}})}\rangle_{\rm{m}}$ for the ${^{181}\rm{Ta}}(\gamma,p)^{180\rm{m}}\rm{Hf}$ reaction were determined, and at $E_{\rm{\gamma max}} > 55$ MeV obtained for the first time. The measured values, also as the literature data, are significantly exceed the theoretical flux-averaged cross-sections $\langle{\sigma(E_{\rm{\gamma max}})}\rangle_{\rm{th}}$. The $\langle{\sigma(E_{\rm{\gamma max}})}\rangle_{\rm{th}}$ values were calculated using the cross-section $\sigma(E)$ computed with the TALYS1.95 code for six different level density models. A comparative analysis of the calculated total cross-sections for the reactions ${^{181}\rm{Ta}}(\gamma,p)^{180}\rm{Hf}$ and ${^{181}\rm{Ta}}(\gamma,n)^{180}\rm{Ta}$ was performed. It was shown that the photoproton $(\gamma,p)$ to photoneutron $(\gamma,n)$ strength ratio is consistent with the estimates based on the isospin selection rules and the value from the $(e,e'p)$ experiment.Comment: 9 pages, 4 figures, 2 table

First experimental results of very high accuracy centroiding measurements for the neat astrometric mission

NEAT is an astrometric mission proposed to ESA with the objectives of detecting Earth-like exoplanets in the habitable zone of nearby solar-type stars. NEAT requires the capability to measure stellar centroids at the precision of 5e-6 pixel. Current state-of-the-art methods for centroid estimation have reached a precision of about 2e-5 pixel at two times Nyquist sampling, this was shown at the JPL by the VESTA experiment. A metrology system was used to calibrate intra and inter pixel quantum efficiency variations in order to correct pixelation errors. The European part of the NEAT consortium is building a testbed in vacuum in order to achieve 5e-6 pixel precision for the centroid estimation. The goal is to provide a proof of concept for the precision requirement of the NEAT spacecraft. In this paper we present the metrology and the pseudo stellar sources sub-systems, we present a performance model and an error budget of the experiment and we report the present status of the demonstration. Finally we also present our first results: the experiment had its first light in July 2013 and a first set of data was taken in air. The analysis of this first set of data showed that we can already measure the pixel positions with an accuracy of about 1e-4 pixel.Comment: SPIE conference proceeding