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

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

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

A detector interferometric calibration experiment for high precision astrometry

Context: Exoplanet science has made staggering progress in the last two decades, due to the relentless exploration of new detection methods and refinement of existing ones. Yet astrometry offers a unique and untapped potential of discovery of habitable-zone low-mass planets around all the solar-like stars of the solar neighborhood. To fulfill this goal, astrometry must be paired with high precision calibration of the detector. Aims: We present a way to calibrate a detector for high accuracy astrometry. An experimental testbed combining an astrometric simulator and an interferometric calibration system is used to validate both the hardware needed for the calibration and the signal processing methods. The objective is an accuracy of 5e-6 pixel on the location of a Nyquist sampled polychromatic point spread function. Methods: The interferometric calibration system produced modulated Young fringes on the detector. The Young fringes were parametrized as products of time and space dependent functions, based on various pixel parameters. The minimization of func- tion parameters was done iteratively, until convergence was obtained, revealing the pixel information needed for the calibration of astrometric measurements. Results: The calibration system yielded the pixel positions to an accuracy estimated at 4e-4 pixel. After including the pixel position information, an astrometric accuracy of 6e-5 pixel was obtained, for a PSF motion over more than five pixels. In the static mode (small jitter motion of less than 1e-3 pixel), a photon noise limited precision of 3e-5 pixel was reached

Photonuclear reactions cross-sections at energies up to 100 MeV for different experimental setups

In experiments on the electron linac LUE-40 of RDC "Accelerator" NSC KIPT, the flux-averaged cross-sections $\langle{\sigma(E_{\rm{\gamma max}})}\rangle_{\rm{exp}}$ of photonuclear reactions ${^{100}\rm{Mo}}(\gamma,n)^{99}\rm{Mo}$, ${^{27}\rm{Al}}(\gamma,x)^{24}\rm{Na}$, ${^{93}\rm{Nb}}(\gamma,n)^{92m}\rm{Nb}$, ${^{93}\rm{Nb}}(\gamma,3n)^{90}\rm{Nb}$, and ${^{181}\rm{Ta}}(\gamma,n)^{180g}\rm{Ta}$ were measured using the $\gamma$-activation technique. The theoretical flux-average cross-sections $\langle{\sigma(E_{\rm{\gamma max}})}\rangle_{\rm{th}}$ were computed using the partial cross-section $\sigma(E)$ values from the TALYS1.9-1.95 codes and bremsstrahlung $\gamma$-flux calculated using GEANT4.9.2. Two different experimental setups were used in the experiments: an aluminum electron absorber and a deflecting magnet to clean the bremsstrahlung $\gamma$-flux from electrons. A comparison of the flux-average cross-sections measured for two experimental setups was performed. The possibility of using the reactions ${^{100}\rm{Mo}}(\gamma,n)^{99}\rm{Mo}$, ${^{27}\rm{Al}}(\gamma,x)^{24}\rm{Na}$, ${^{93}\rm{Nb}}(\gamma,n)^{92m}\rm{Nb}$, ${^{93}\rm{Nb}}(\gamma,3n)^{90}\rm{Nb}$, and ${^{181}\rm{Ta}}(\gamma,n)^{180g}\rm{Ta}$ as monitors of the bremsstrahlung $\gamma$-flux for the energy range 30-100 MeV was investigated.Comment: 8 pages, 6 figures, 1 tabl

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

Structure and chemical bonds in reactively sputtered black Ti–C–N–O thin films

The evolution of the nanoscale structure and the chemical bonds formed in Ti–C–N–O films grown by reactive sputtering were studied as a function of the composition of the reactive atmosphere by increasing the partial pressure of an O2+N2 gas mixture from 0 up to 0.4 Pa, while that of acetylene (carbon source) was constant. The amorphisation of the films observed by transmission electron microscopy was confirmed by micro- Raman spectroscopy, but it was not the only effect associated to the increase of the O2+N2 partial pressure. The chemical environment of titanium and carbon, analysed by X-ray photoemission spectroscopy, also changes due to the higher affinity of Ti towards oxygen and nitrogen than to carbon. This gives rise to the appearance of amorphous carbon coexisting with poorly crystallized titanium oxynitride. The evolution of the films colour is explained on the basis of these structural changes.Fundação para a Ciência e a Tecnologia (FCT) - PTDC/CTM/69362/2006, SFRH/BPD/27114/2006CRUP (Acção Integrada Luso-francesa N° F-2307) and the GRICES/CNRS collaboration (Proc. 4.1.1 França

The interaction between the proliferating macroalga Asparagopsis taxiformis and the coral Astroides calycularis induces changes in microbiome and metabolomic fingerprints

Mediterranean Sea ecosystems are considered as hotspots of biological introductions, exposed to possible negative effects of non-indigenous species. In such temperate marine ecosystems, macroalgae may be dominant, with a great percentage of their diversity represented by introduced species. Their interaction with temperate indigenous benthic organisms have been poorly investigated. To provide new insights, we performed an experimental study on the interaction between the introduced proliferative red alga Asparagopsis taxiformis and the indigenous Mediterranean coral Astroides calycularis. The biological response measurements included meta-barcoding of the associated microbial communities and metabolomic fingerprinting of both species. Significant changes were detected among both associated microbial communities, the interspecific differences decreasing with stronger host interaction. No short term effects of the macroalga on the coral health, neither on its polyp activity or its metabolism, were detected. In contrast, the contact interaction with the coral induced a change in the macroalgal metabolomic fingerprint with a significant increase of its bioactivity against the marine bacteria Aliivibrio fischeri. This induction was related to the expression of bioactive metabolites located on the macroalgal surface, a phenomenon which might represent an immediate defensive response of the macroalga or an allelopathic offense against coral.ERA-NET Biome project "SEAPROLIF"; CNRS; Provence Alpes Cote d'Azur Region; TOTAL Fundation; Fundacao para a Ciencia e a Tecnologia (FCT) [Netbiome/0002/2011]; FCT fellowships [SFRH/BPD/63703/2009, SFRH/BPD/107878/2015]info:eu-repo/semantics/publishedVersio

Characterization of multinucleated giant cells in synovium and subchondral bone in knee osteoarthritis and rheumatoid arthritis

Background: Multinucleated giant cells have been noticed in diverse arthritic conditions since their first description in rheumatoid synovium. However, their role in the pathogenesis of osteoarthritis (OA) or rheumatoid arthritis (RA) still remains broadly unknown. We aimed to study the presence and characteristics of multinucleated giant cells (MGC) both in synovium and in subchondral bone tissues of patients with OA or RA. Methods: Knee synovial and subchondral bone samples were from age-matched patients undergoing total joint replacement for OA or RA, or non-arthritic post mortem (PM) controls. OA synovium was stratified by histological inflammation grade using index tissue sections. Synovitis was assessed by Krenn score. Histological studies employed specific antibodies against macrophage markers or cathepsin K, or TRAP enzymatic assay. Results: Inflamed OA and RA synovia displayed more multinucleated giant cells than did non-inflamed OA and PM synovia. There was a significant association between MGC numbers and synovitis severity. A TRAP negative/cathepsin K negative Langhans-like subtype was predominant in OA, whereas both Langhans-like and TRAP-positive/ cathepsin K negative foreign-body-like subtypes were most commonly detected in RA. Plasma-like and foam-like subtypes also were observed in OA and RA synovia, and the latter was found surrounding adipocytes. TRAP positive/ cathepsin K positive osteoclasts were only identified adjacent to subchondral bone surfaces. TRAP positive osteoclasts were significantly increased in subchondral bone in OA and RA compared to PM controls. Conclusions: Multinucleated giant cells are associated with synovitis severity, and subchondral osteoclast numbers are increased in OA, as well as in RA. Further research targeting multinucleated giant cells is warranted to elucidate their contributions to the symptoms and joint damage associated with arthritis