26 results on '"Sylvain Topin"'
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2. 6 months of radioxenon detection in western Europe with the SPALAX-New generation system - Part 2: Atmospheric transport modelling
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S. Generoso, Pascal Achim, Sylvain Topin, Mireille Morin, P. Gross, Gilbert Le Petit, Marguerite Monfort, Christophe Moulin, G. Douysset, CEA- Saclay (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
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010504 meteorology & atmospheric sciences ,Spalax ,Health, Toxicology and Mutagenesis ,[SDV]Life Sciences [q-bio] ,010501 environmental sciences ,Atmospheric sciences ,01 natural sciences ,Prevailing winds ,Air pollutants ,Belgium ,Radiation Monitoring ,Environmental Chemistry ,Animals ,Waste Management and Disposal ,0105 earth and related environmental sciences ,Family Characteristics ,biology ,Family characteristics ,General Medicine ,biology.organism_classification ,Pollution ,Europe ,Air Pollutants, Radioactive ,Western europe ,Environmental science ,Nuclear test ,Xenon Radioisotopes - Abstract
International audience; Atmospheric transport modeling has been used to interpret the unprecedented number of multi-isotope detections of radioxenons observed during the six months of the qualification process by the Comprehensive Nuclear-Test-Ban Treaty Organization of the new SPALAX-NG system (Système de Prélèvement Automatique en Ligne avec l’Analyse du Xénon - Nouvelle Génération). Highest $^{133}$Xe activity concentrations were found to be systematically associated with the concomitant measurement of several other radioxenons at the prevailing wind direction of north/northeast pointing to the Institute for Radio Elements (IRE), a medical isotope production facility located in Fleurus (Belgium). The lowest $^{133}$Xe activity concentrations were not associated with a prevailing wind direction or other radioxenons, indicating the contribution of distant sources (global background). The IRE's average source terms for $^{133}$mXe and to a lesser extent for $^{133}$Xe (slightly overestimated by a factor of 1.7) showed good agreement with the literature values, while corrections by a factor of ~23 and ~53 were proposed for $^{131}$mXe and $^{135}$Xe since the initial values were underestimated. However, detections of $^{131}$mXe alone and some low-activity concentrations of $^{133}$Xe associated with only one of the other radioxenons could not be linked to the IRE releases. Analysis of these cases suggests the contribution of local source releases that have been difficult to identify to date. In addition to the global background, releases from such local sources, if not identified, could affect the analysis of the isotopic ratios measured following a nuclear test. The characterization of these local contributions is now possible owing to the capacity of the SPALAX-NG and other new generation measurements systems.
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- 2020
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3. 6 months of radioxenon detection in western Europe with the SPALAX-New generation system - Part1: Metrological capabilities
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P. Gross, Mireille Morin, Christophe Moulin, Gilbert Le Petit, S. Generoso, G. Douysset, Sylvain Topin, A. Cagniant, Pascal Achim, Jean-Pierre Fontaine, Thomas Philippe, O. Delaune, CEA- Saclay (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
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Nuclear explosion ,010504 meteorology & atmospheric sciences ,Spalax ,Health, Toxicology and Mutagenesis ,[SDV]Life Sciences [q-bio] ,Data reliability ,010501 environmental sciences ,01 natural sciences ,Radiation Monitoring ,Environmental Chemistry ,Animals ,Waste Management and Disposal ,0105 earth and related environmental sciences ,Remote sensing ,Family Characteristics ,biology ,Reproducibility of Results ,General Medicine ,biology.organism_classification ,Pollution ,Data availability ,Metrology ,Europe ,Air Pollutants, Radioactive ,Western europe ,Environmental science ,Nuclear test ,France ,Xenon Radioisotopes - Abstract
International audience; The SPALAX-NG is a new-generation system that is designed to detect radioactive xenon at trace levels in the atmosphere following a nuclear explosion or civilian source release. This new system formed part of a validation program led by the Provisional Technical Secretary of the Comprehensive Nuclear-Test-Ban Treaty (CTBT) Organization. In this study, the first SPALAX-NG unit was tested for six months between October 2018 and April 2019 at the CEA/DIF premises near Paris, France. This test period provided an outstanding opportunity to illustrate the high level of detectability and reliability of the system. The data availability obtained over this period was approximately 99%, which was well above the CTBT Data Availability criteria of 95%. The data reliability was demonstrated by a comparison with a collocated SPALAX-1 unit (former version of SPALAX) and by re-measuring several samples at the CTBT-certified French laboratory FRL08. The high sensitivity to the detection of the four relevant radioxenon isotopes was fully demonstrated and enabled the recording of a major dataset for western Europe. A large set of isotopic ratios was measured, which enabled the discrimination criteria between civilian sources and nuclear test signatures to be refined.
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- 2020
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4. Development of a highly sensitive radon-222 amplifier (HiSRA) for low-level atmospheric measurements
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Sylvain Topin, J. Moulin, Claire Gréau, Ludovic Deliere, Patrick Richon, Vincent Thomas, Alexandre Hovesepian, and Julie Pujos
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Turbulent diffusion ,010504 meteorology & atmospheric sciences ,Atmosphere ,Health, Toxicology and Mutagenesis ,Analytical chemistry ,chemistry.chemical_element ,Radon ,General Medicine ,010502 geochemistry & geophysics ,01 natural sciences ,Pollution ,Particle detector ,Gas analyzer ,chemistry ,Air Pollutants, Radioactive ,Radiation Monitoring ,Ionization chamber ,Measuring instrument ,Environmental Chemistry ,Waste Management and Disposal ,Radioactive decay ,0105 earth and related environmental sciences - Abstract
Radon ( 222 Rn), a radioactive gas with a half-life of 3.82 days, is continuously emanated from soil, rocks, and water by the radioactive decay of 226 Ra. Radon-222 is released from the ground into the atmosphere, where it is transported mainly by turbulent diffusion or convection. For precise measurement of radon-222 atoms in the atmosphere, the detectors typically used present a small volume or surface area and are therefore not very sensitive, especially for online measurements and short sample intervals ( 3 h −1 ). The radon-222 concentration is increased instantaneously by at least a factor of 30 across the HiSRA system. Therefore, in this study, when coupling to an ionization chamber (AlphaGUARDTM) at the outlet of the HiSRA system, the detection limit of the overall system is multiplied by factor of 30 and induces a new LD for a radon 222 gas analyzer lower than 1 Bq m −3 for an integrating time of 10 min and 0.1 Bq m −3 for 1 h. We constructed one radon amplifier prototype that provided the preliminary results for amplification efficiency and the initial measurements presented herein.
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- 2017
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5. Effect of Chlorine-Containing VOCs on Silver Migration and Sintering in ZSM-5 Used in a TSA Process
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Gabriel Couchaux, Vincent Thomas, Antoine Artheix, Luis Cardenas, David Farrusseng, Arnaud Monpezat, Claire Gréau, Sylvain Topin, Ludovic Deliere, Lucian Roiban, Benoit Coasne, IRCELYON-Etudes & analyse de surfaces, XPS, LEIS (XPS), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and IRCELYON-Ingéniérie, du matériau au réacteur (ING)
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silver nanoparticles ,Materials science ,Sintering ,Nanoparticle ,010402 general chemistry ,010502 geochemistry & geophysics ,lcsh:Chemical technology ,01 natural sciences ,Catalysis ,Silver nanoparticle ,Nanomaterials ,lcsh:Chemistry ,Silver chloride ,chemistry.chemical_compound ,Adsorption ,lcsh:TP1-1185 ,Physical and Theoretical Chemistry ,zeolite ,0105 earth and related environmental sciences ,sintering ,[CHIM.CATA]Chemical Sciences/Catalysis ,[SDE.ES]Environmental Sciences/Environmental and Society ,0104 chemical sciences ,poisoning ,Chemical engineering ,chemistry ,lcsh:QD1-999 ,adsorption ,Particle ,Dispersion (chemistry) - Abstract
Silver nanoparticles are currently one of the most studied nanostructured nanomaterials. Because nanoparticle size and dispersion act together in determining a material&rsquo, s physical and chemical properties, there is a continuous quest to develop size-controlled synthesis methods. Nonetheless, the instability of the nanometer-sized particles, which is caused by their tendency to aggregate irreversibly into larger particles, remains a recurrent problem. The use of confining scaffolds, such as the regular system of cages in a crystalline zeolite-type material, is often reported in the literature as an efficient solution to overcome particle migration at the surface. Silver nanoparticles encapsulated in ZSM-5 (Ag@ZSM-5) represent a new generation of adsorbent for Xe enrichment from the atmosphere that is currently being developed at the pilot scale in a Temperature Swing Adsorption (TSA) process. In this study, we have found that the presence of Cl-containing compounds in the air (VOCs) leads to a poisoning of the active silver phase by the formation of silver chloride. By a careful study of process parameters, we have found that most of the chlorine can be removed by heat treatment above 573 K so that the adsorption properties of silver are regenerated. That said, when applying 573 K temperature regeneration at the pilot scale, we observe a very minor but observable decay of xenon adsorption capacity that continues cycle after cycle. The mechanism of capacity decay is discussed in terms of (i) the residual presence of Cl at the surface of silver nanoparticles, (ii) the aggregation of silver nanoparticles into larger particles (sintering mechanism), and (iii) the acceleration of silver particle migration to the surface and sintering.
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- 2019
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6. 6 months of radioxenon detection in western Europe with the SPALAX-New generation system - Part 1: Metrological capabilities [J. Environ. Radioact. 225, 2020, 106442]
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Sylvain Topin, Christophe Moulin, P. Gross, O. Delaune, Jean-Pierre Fontaine, S. Generoso, G. Douysset, Mireille Morin, Gilbert Le Petit, Thomas Philippe, A. Cagniant, and Pascal Achim
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Geography ,biology ,Spalax ,Health, Toxicology and Mutagenesis ,Western europe ,Environmental Chemistry ,General Medicine ,biology.organism_classification ,Pollution ,Waste Management and Disposal ,Cartography - Published
- 2021
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7. Development toward a double focusing isotopic separator for noble gas isotope enrichment
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Bertrand Thomas, Fabien Pointurier, Gregory Canchel, Sylvain Topin, Christophe Moulin, Denis Horlait, E. Gilabert, and B. Lavielle
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010504 meteorology & atmospheric sciences ,Isotope ,Chemistry ,Radiochemistry ,Analytical chemistry ,Noble gas ,Separator (oil production) ,010501 environmental sciences ,Mass spectrometry ,01 natural sciences ,7. Clean energy ,Ion source ,Ion ,Isotopic signature ,Ion implantation ,Spectroscopy ,0105 earth and related environmental sciences - Abstract
A double focusing sector field mass filter used in Nier-Johnson geometry has been built in order to perform Kr isotope enrichment for 81 Kr and 85 Kr isotopes. The principle consists in implanting Kr+ ions accelerated at 7 keV in Al foils after separation using the magnetic sector. A specific ion source has been designed capable of generating high Kr+ ion beams (>0.5 μA) to transfer into the collecting Al foils in 3 to 5 h significant fractions of large Kr samples (1015 to 1016 atoms) initially introduced in the instrument. Implanted Kr isotopes can be further selectively released from the Al foil by surface ablation using an infrared laser beam. Implantation yields and enrichment factors are measured using a conventional mass spectrometer. Copyright © 2016 John Wiley & Sons, Ltd.
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- 2016
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8. Adsorption in heterogeneous porous media: Hierarchical and composite solids
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Sylvain Topin, Ludovic Deliere, François Villemot, David Farrusseng, Benoit Coasne, Anne Galarneau, IRCELYON-Ingéniérie, du matériau au réacteur (ING), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interdisciplinaire de Physique [Saint Martin d’Hères] [2016-2019] (LIPhy [2016-2019]), and Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])
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Materials science ,Capillary action ,Composite number ,Thermodynamics ,[CHIM.MATE]Chemical Sciences/Material chemistry ,[CHIM.CATA]Chemical Sciences/Catalysis ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,[SDE.ES]Environmental Sciences/Environmental and Society ,01 natural sciences ,0104 chemical sciences ,Characterization (materials science) ,Hysteresis ,Adsorption ,Mechanics of Materials ,General Materials Science ,0210 nano-technology ,Porous medium ,Porosity ,Linear combination ,ComputingMilieux_MISCELLANEOUS - Abstract
SSCI-VIDE+ING+DFA; International audience; Experiment and molecular simulation are used to investigate adsorption in heterogeneous porous media consisting of hierarchical solids (combining different porosity scales) or composite solids (such as silver nanoparticles adsorbed at the external surface of zeolite). It is shown that adsorption in such heterogeneous materials can be written as a linear combination of the adsorption isotherms in its different domains (i.e. porosity scales for the hierarchical sample and constituents for the composite sample). In the case of the composite material, we also show that the linear combination can be used with weighing parameters obtained for a different adsorbate. Such a superimposition principle, which is validated using well-characterized experimental samples, is of interest for characterization purpose as well as industrial applications as they can be used to determine accurately the amount of phases in a given sample (volume corresponding to a given porosity scale or constituent). In contrast, significant departure between the experimental adsorption isotherm and the linear combination can be used to detect coupling effects between the different domains or restrained access to a given domain type. Such a characterization strategy of complex heterogeneous media is complementary to other experiments, such as those probing capillary hysteresis shapes, scanning curves and subloops, which allow determining the distribution of domains within the framework of the independent domain theory. (C) 2016 Elsevier Inc. All rights reserved.
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- 2016
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9. Evaluation Methods of Adsorbents for Air Purification and Gas Separation at Low Concentration: Case Studies on Xenon and Krypton
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Benoit Coasne, Arnaud Monpezat, Sylvain Topin, David Farrusseng, Ludovic Deliere, IRCELYON-Ingéniérie, du matériau au réacteur (ING), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
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Air purification ,Chromatography ,Materials science ,General Chemical Engineering ,Krypton ,chemistry.chemical_element ,02 engineering and technology ,General Chemistry ,[CHIM.CATA]Chemical Sciences/Catalysis ,021001 nanoscience & nanotechnology ,[SDE.ES]Environmental Sciences/Environmental and Society ,Industrial and Manufacturing Engineering ,Adsorption ,Xenon ,020401 chemical engineering ,chemistry ,Evaluation methods ,Gas separation ,0204 chemical engineering ,0210 nano-technology ,Volume concentration - Abstract
The development of gas separation processes dealing with very low concentration ranges is a rapidly growing domain with key applications such as trace detection, air purification from harmful pollu...
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- 2019
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10. Revisiting actinide–DTPA complexes in aqueous solution by CE-ICPMS and ab initio molecular dynamics
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Jean Aupiais, M. Kerbaa, L. Bonin, Sylvain Topin, Philippe Moisy, and Bruno Siberchicot
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Aqueous solution ,010405 organic chemistry ,Chemistry ,General Chemical Engineering ,Ab initio ,Analytical chemistry ,General Chemistry ,Actinide ,010402 general chemistry ,Mass spectrometry ,01 natural sciences ,0104 chemical sciences ,Electrophoresis ,Capillary electrophoresis ,Stability constants of complexes ,Inductively coupled plasma - Abstract
Although thermodynamics of AnIVDTPA− (DTPA = diethylenetriaminepentaacetic acid) complexation have been reported for 50 years, reliable data at low ionic strength is still missing. Owing to the use of capillary electrophoresis coupled with an inductively coupled plasma mass spectrometer, it is possible to simultaneously detect at ultra-trace level all AnIVDTPA− species in various conditions (concentration of ligand, pH) and to determine the formation constants. New values were obtained for tetravalent actinides with DTPA as well as with nitrilotriacetate (NTA) used as a competitor. Besides, the formation constants of hydrolyzed An(OH)DTPA2− species (An = Np, Pu) were also obtained for the first time using the variation of electrophoretic mobility as a function of pH at a constant DTPA concentration. The use of these data in radiotoxicology indicates that two stable species, namely PuDTPA− and Pu(OH)DTPA2− are present at approximately the same concentration in blood. From ab initio molecular dynamic (AIMD), the metal–oxygen distances dAn–O were calculated, and a linear relation was shown between dAn–O and the formation constants. The interpolation of data allowed determination of K values along the tetravalent actinide series, e.g. KNpDTPA−, KPaDTPA− and KU(OH)DTPA2−.
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- 2016
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11. Ultratrace analysis of krypton isotopes by resonant ionization spectroscopy-time of flight mass spectrometry (RIS-TOF)
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Sylvain Topin, E. Gilabert, Fabien Pointurier, Christophe Moulin, Bertrand Thomas, and B. Lavielle
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Isotope ,Electron multiplier ,010401 analytical chemistry ,Krypton ,Analytical chemistry ,Isotopes of krypton ,chemistry.chemical_element ,Mass spectrometry ,01 natural sciences ,Ion source ,0104 chemical sciences ,Analytical Chemistry ,010309 optics ,chemistry ,Ionization ,0103 physical sciences ,Time-of-flight mass spectrometry ,Spectroscopy - Abstract
A new RIS-TOF instrument, called FAKIR (Facility for Analyzing Krypton Isotope Ratios), has been developed at CENBG in order to measure Kr isotope ratios with an extremely high sensitivity. The instrument uses a single color Kr ionization scheme with tunable coherent UV photons near 216.6 nm. A two-photon resonance excitation allows it to reach the 5p[5/2]2 excitation level followed by a single-photon ionization. Krypton ions are accelerated towards an electron multiplier. The instrument includes a cryogenic concentrator that increases the efficiency of the ion source and a new selecting system allowing the deflection of the abundant isotopes before they impact the detector. This device eliminates the blinding effect on the detector that alters the detection of the less abundant Kr isotopes. The current sensitivity of the instrument of ∼6700 atoms has been demonstrated by extracting the gas from 37 mg of the Boguslavka iron meteorite. The associated errors on the 81Kr isotope ratio measurements did not exceed ∼12%. A good agreement is observed with conventional mass spectrometry analysis, which requires several grams of material, by measuring the cosmic ray exposure age of the Boguslavka meteorite.
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- 2016
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12. SPALAX new generation: New process design for a more efficient xenon production system for the CTBT noble gas network
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Christophe Moulin, Claire Gréau, G. Douysset, T. Taffary, Ludovic Deliere, Sylvain Topin, Alexandre Hovesepian, and Gilbert Le Petit
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biology ,business.industry ,Spalax ,Health, Toxicology and Mutagenesis ,Mineralogy ,Noble gas ,chemistry.chemical_element ,Monitoring system ,Retention capacity ,Process design ,General Medicine ,biology.organism_classification ,Pollution ,Xenon ,chemistry ,Air Pollutants, Radioactive ,Radiation Monitoring ,Comprehensive Nuclear-Test-Ban Treaty ,Environmental Chemistry ,Adsorption ,Process engineering ,business ,Waste Management and Disposal ,Xenon Radioisotopes ,Production system - Abstract
The SPALAX (Système de Prélèvement Automatique en Ligne avec l'Analyse du Xénon) is one of the systems used in the International Monitoring System of the Comprehensive Nuclear Test Ban Treaty (CTBT) to detect radioactive xenon releases following a nuclear explosion. Approximately 10 years after the industrialization of the first system, the CEA has developed the SPALAX New Generation, SPALAX-NG, with the aim of increasing the global sensitivity and reducing the overall size of the system. A major breakthrough has been obtained by improving the sampling stage and the purification/concentration stage. The sampling stage evolution consists of increasing the sampling capacity and improving the gas treatment efficiency across new permeation membranes, leading to an increase in the xenon production capacity by a factor of 2-3. The purification/concentration stage evolution consists of using a new adsorbent Ag@ZSM-5 (or Ag-PZ2-25) with a much larger xenon retention capacity than activated charcoal, enabling a significant reduction in the overall size of this stage. The energy consumption of the system is similar to that of the current SPALAX system. The SPALAX-NG process is able to produce samples of almost 7 cm(3) of xenon every 12 h, making it the most productive xenon process among the IMS systems.
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- 2015
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13. Spalax™ new generation: A sensitive and selective noble gas system for nuclear explosion monitoring
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Christophe Moulin, G. Douysset, T. Taffary, Jean-Pierre Fontaine, G. Le Petit, P. Gross, A. Cagniant, and Sylvain Topin
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Nuclear explosion ,Fission products ,Radionuclide ,Radiation ,Nuclear engineering ,Poison control ,chemistry.chemical_element ,Noble gas ,Context (language use) ,Nuclear physics ,Xenon ,chemistry ,Comprehensive Nuclear-Test-Ban Treaty ,Environmental science - Abstract
In the context of the verification regime of the Comprehensive nuclear Test ban Treaty (CTBT), CEA is developing a new generation (NG) of SPALAX™ system for atmospheric radioxenon monitoring. These systems are able to extract more than 6cm(3) of pure xenon from air samples each 12h and to measure the four relevant xenon radioactive isotopes using a high resolution detection system operating in electron-photon coincidence mode. This paper presents the performances of the SPALAX™ NG prototype in operation at Bruyères-le-Châtel CEA centre, integrating the most recent CEA developments. It especially focuses on an innovative detection system made up of a gas cell equipped with two face-to-face silicon detectors associated to one or two germanium detectors. Minimum Detectable activity Concentrations (MDCs) of environmental samples were calculated to be approximately 0.1 mBq/m(3) for the isotopes (131m)Xe, (133m)Xe, (133)Xe and 0.4 mBq/m(3) for (135)Xe (single germanium configuration). The detection system might be used to simultaneously measure particulate and noble gas samples from the CTBT International Monitoring System (IMS). That possibility could lead to new capacities for particulate measurements by allowing electron-photon coincidence detection of certain fission products.
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- 2015
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14. Xenon Capture on Silver-Loaded Zeolites: Characterization of Very Strong Adsorption Sites
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Marie-Anne Springuel-Huet, Sonia Aguado, Cécile Daniel, T. Taffary, Jean-Pierre Fontaine, David Farrusseng, Yves Schuurman, Sylvain Topin, Andrei Nossov, Ludovic Deliere, Adnane Elbaraoui, Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), INGENIERIE (INGENIERIE), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie de la Matière Condensée de Paris (site Paris VI) (LCMCP (site Paris VI)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Génie Chimique et Biochimique (LGCB), Université Blaise Pascal - Clermont-Ferrand 2 (UBP), Laboratoire de Détection et de Géophysique (CEA) (LDG), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)
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Range (particle radiation) ,Atmospheric pressure ,Chemistry ,Inorganic chemistry ,Analytical chemistry ,chemistry.chemical_element ,02 engineering and technology ,Orders of magnitude (numbers) ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Characterization (materials science) ,[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry ,General Energy ,Adsorption ,Xenon ,Physical and Theoretical Chemistry ,0210 nano-technology ,Zeolite ,Equilibrium constant - Abstract
INGENIERIE+SAG:YSC:DFA; The number and strength of adsorption sites for Xe in silver-modified zeolites are estimated from isotherm measurements at various temperatures over a broad range of pressure (from 1 ppm to atmospheric pressure). Fully and partially exchanged silver zeolites were synthesized starting from Na-ZSM-5(25), Na-ZSM-5(40), Na-Beta, NaX, and NaY. We have discovered that silver-modified zeolites may present one or two distinct adsorption sites depending on the nature of the material and silver loadings. The strongest adsorption sites are characterized by isosteric heat of adsorption in the order of -40 to -50 kJ.mol(-1). For Pentasil-type zeolites, we observe a linear 2:1 correlation between the total amount of silver and the number of strong sites. The highest concentration of strong sites is found for fully silver exchanged ZSM-5 (5.7 X 10(-4) mol/g), which presents the largest silver content for Pentasil-type zeolite. The equilibrium constant of Ag-ZSM-5 at low pressure is about 50 times larger than that of AgX. Qualitative correlations were established between Xe adsorption isotherms and Xe NMR signals. We show that Xe NMR could be used as a quantitative method for the characterization of the strength and of the number of strong Xe adsorption sites on silver-exchanged zeolites. The numbers of strong adsorption sites responsible for the Xe adsorption at 10-1000 ppm can be determined by the length of the plateau observed at low Xe uptake. In practice, our findings give guidelines for the discovery and optimization of silver-loaded zeolites for the capture of Xe at ppm levels. It appears that the amount of silver is a key parameter. Silver-modified ZSM-5 shows adsorption capacities 2-3 orders of magnitude larger than currently applied adsorbents for atmospheric Xe capture.
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- 2013
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15. Thermodynamic Study of the Complexation of Protactinium(V) with Diethylenetriaminepentaacetic Acid
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Mickaël Mendes, Sylvain Topin, Sébastien Leguay, Séna Hamadi, Jean Aupiais, Christophe Den Auwer, Jérôme Roques, Philippe Moisy, Christoph Hennig, Dominique Guillaumont, Claire Le Naour, Institut de Physique Nucléaire d'Orsay (IPNO), Université Paris-Sud - Paris 11 (UP11)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Département RadioChimie et Procédés (DRCP), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Institut de Chimie de Nice (ICN), Université Nice Sophia Antipolis (1965 - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université Paris-Sud - Paris 11 (UP11), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA)-Université Nice Sophia Antipolis (... - 2019) (UNS), and COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)
- Subjects
Pa(V) ,010405 organic chemistry ,Chemistry ,Analytical chemistry ,Protactinium ,Ionic bonding ,chemistry.chemical_element ,diethylenetriaminepentaacetic acid ,010402 general chemistry ,01 natural sciences ,Endothermic process ,0104 chemical sciences ,Inorganic Chemistry ,Capillary electrophoresis ,Stability constants of complexes ,Ionic strength ,Density functional theory ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] ,Physical and Theoretical Chemistry ,Stoichiometry - Abstract
The complex formation of protactinium(V) with DTPA was studied at different temperatures (25-50 °C) and ionic strengths (0.1-1 M) with the element at tracer scale. Irrespective of the temperature and ionic strength studied, only one neutral complex with (1:1) stoichiometry was identified from solvent extraction and capillary electrophoresis coupled to ICP-MS (CE-ICP-MS) experiments. Density Functional Theory (DFT) calculations revealed that two complexes can be considered: Pa(DTPA) and PaO(H2DTPA). The associated formation constants were determined from solvent extraction data at different ionic strengths and temperatures and then extrapolated to zero ionic strength by SIT methodology. These constants are valid, regardless of complex form, Pa(DTPA) or PaO(H2DTPA). The standard thermodynamic data determined with these extrapolated constants revealed a very stable complex formed energetically by an endothermic contribution which is counter balanced by a strong entropic contribution. Both, the positive enthalpy and entropy energy terms suggest the formation of an inner sphere complex.
- Published
- 2013
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16. New Insights into Formation of Trivalent Actinides Complexes with DTPA
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Sylvain Topin, Claire Le Naour, Manuel Miguirditchian, Philippe Moisy, Thomas Vercouter, Dominique Guillaumont, Jean Aupiais, Sébastien Leguay, Institut de Physique Nucléaire d'Orsay (IPNO), Université Paris-Sud - Paris 11 (UP11)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Département RadioChimie et Procédés (DRCP)
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Actinoid Series Elements ,Coordination sphere ,Curium ,Inorganic chemistry ,chemistry.chemical_element ,Protonation ,010402 general chemistry ,01 natural sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,Spectrophotometry ,Organometallic Compounds ,medicine ,Molecule ,Physical and Theoretical Chemistry ,medicine.diagnostic_test ,010405 organic chemistry ,Hydrogen-Ion Concentration ,Pentetic Acid ,0104 chemical sciences ,chemistry ,Stability constants of complexes ,Ionic strength ,Diethylenetriamine ,Quantum Theory ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] - Abstract
Complexation of trivalent actinides with DTPA (diethylenetriamine pentaacetic acid) was studied as a function of pcH and temperature in (Na,H)Cl medium of 0.1 M ionic strength. Formation constants of both complexes AnHDTPA(-) and AnDTPA(2-) (where An stands for Am, Cm, and Cf) were determined by TRLFS, CE-ICP-MS, spectrophotometry, and solvent extraction. The values of formation constants obtained from the different techniques are coherent and consistent with reinterpreted literature data, showing a higher stability of Cf complexes than Am and Cm complexes. The effect of temperature indicates that formation constants of protonated and nonprotonated complexes are exothermic with a high positive entropic contribution. DFT calculations were also performed on the An/DTPA system. Geometry optimizations were conducted on AnDTPA(2-) and AnHDTPA(-) considering all possible protonation sites. For both complexes, one and two water molecules in the first coordination sphere of curium were also considered. DFT calculations indicate that the lowest energy structures correspond to protonation on oxygen that is not involved in An-DTPA bonds and that the structures with two water molecules are not stable.
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- 2012
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17. Stability constants determination of successive metal complexes by hyphenated CE-ICPMS
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Sylvain Topin, Valérie Geertsen, Jean Aupiais, Catherine Beaucaire, Jeremy Petit, Moncef Stambouli, Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), and CentraleSupélec
- Subjects
Clinical Biochemistry ,Analytical chemistry ,02 engineering and technology ,01 natural sciences ,Biochemistry ,Stability (probability) ,Mass Spectrometry ,Analytical Chemistry ,Metal ,[CHIM.ANAL]Chemical Sciences/Analytical chemistry ,Lanthanum ,Beta (velocity) ,Oxalates ,Ligand ,Chemistry ,Osmolar Concentration ,010401 analytical chemistry ,Electrophoresis, Capillary ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Dilution ,Models, Chemical ,Nonlinear Dynamics ,Ionic strength ,visual_art ,visual_art.visual_art_medium ,Regression Analysis ,Thermodynamics ,Uranium ,0210 nano-technology ,Algorithms - Abstract
International audience; The study of radionuclides speciation requires accurate evaluation of stability constants, which can be achieved by CE-ICPMS. We have previously described a method for 1:1 metal complexes stability constants determination. In this paper, we present its extension to the case of successive complexations and its application to uranyl-oxalate and lanthanum-oxalate systems. Several significant steps are discussed: analytical conditions choice, mathematical treatment by non-linear regression, ligand concentration and ionic strength corrections. The following values were obtained: at infinite dilution, log(beta(1) degrees (UO(2)Oxa))=6.93+/-0.05, log(beta(2) degrees (UO(2)(Oxa)(2) (2-)))=11.92+/-0.43 and log(beta(3) degrees (UO(2)(Oxa)(3) (4-)))=15.11+/-0.12; log(beta(1) degrees (LaOxa(+)))=5.90+/-0.07, log(beta(2) degrees (La(Oxa)(2) (-)))=9.18+/-0.19 and log(beta(3) degrees (La(Oxa)(3) (3-)))=9.81+/-0.33. These values are in good agreement with the literature data, even though we suggest the existence of a new lanthanum-oxalate complex: La(Oxa)(3) (3-). This study confirms the suitability of CE-ICPMS for complexation studies
- Published
- 2010
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18. Trace Metal Speciation by Capillary Electrophoresis Hyphenated to Inductively Coupled Plasma Mass Spectrometry: Sulfate and Chloride Complexes of Np(V) and Pu(V)
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Pierre Vitorge, N. Baglan, Sylvain Topin, Philippe Moisy, Thomas Vercouter, and Jean Aupiais
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Aqueous solution ,Valence (chemistry) ,chemistry ,Ligand ,Oxidation state ,Neptunium ,Analytical chemistry ,Protactinium ,Physical chemistry ,chemistry.chemical_element ,Inner sphere electron transfer ,Analytical Chemistry ,Waste disposal - Abstract
In the framework of nuclear waste disposal, it is very important to well understand the behavior of actinides in the presence of the common environmental inorganic ligands such as sulfate and chloride. In this work, the AnO 2SO4 - and AnO2Cl 1-1 complexes have been evi- denced by capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICPMS) in perchlor- ate/chloride and in perchlorate/sulfate media for An ) Np and Pu. Their binding constants have been measured: logPuO2SO4 - 0 ) 1.30 ( 0.11, log � PuO2Cl 1 M NaCl ) -(0.40 ( 0.07), logNpO2SO4 - 0 ) 1.34 ( 0.12, and log � NpO2Cl 1 M NaCl )- (0.40 ( 0.07). These results are consistent with published values for Np(V). They confirm the expected analogy between Np(V) and Pu(V) for the weak bonding with chloride ligand, log10 � PuO2Cl ≈ log10 � NpO2Cl, attributed to mainly electrostatic interactions. Conversely, a slight shift is observed for the bonding with sulfate ligand, log10 � NpO2SO4 - > log10 � PuO2SO4 -, indicating that some covalency might stabilize the sulfate complexes. Actinides are usually chemical analogues when in the same oxidation state, i.e., forming cations of the same charge and similar sizes, which form complexes of the same stoichiometry and similar stabilities. This analogy is often used to predict the chemistry of actinides in oxidation states when they are difficult to study. It is typically the case for the actinides at the +5 oxidation state among which protactinium, neptunium, and plutonium can be stabilized in the environment. Indeed, the soluble Pu(V) can be quite stable at trace concentrations in environmental surface waters, and its aqueous chemistry is essentially known by analogy with Np(V), which is the most stable An(V).1 Conversely, Pa(V) is not a chemical analogue of the other An(V) ions since it has been recently shown that its aqua ion is not of the same form. 2-4 Therefore, it seems that such analogy rules need experimental verifications. Only few thermodynamical data are published for plutonium and protactinium in the +5 oxidation state (Pu(V) and Pa(V)), while more data are available in the literature for Np(V).1 Np(V) is stable as the linear NpO2 + neptunyl ion with solvent or ligand molecules in its equatorial plan. The Pu(V) aqua ion has a similar structure and a size close to that of Np(V), and the available complexing constants are similar for Np(V) and Pu(V). 1 Furthermore, Pu(V) is the second more stable An(V) after Np(V); therefore, their behavior versus complexation is compared here. The complexation can be driven by two components: electro- static interactions including possible outer sphere interactions and covalent bonding which exists only in inner sphere complexes. The electrostatic interactions between Np(V) and anionic ligands might be slightly weaker than those for Pu(V), since its density of charge is smaller. Conversely, Np covalent binding with anions might be stronger than for Pu since the 5f electrons of Np (electrons which participate in the bond) are less localized. The only binding constants selected by the NEA review1 for both Np(V) and Pu(V) are for carbonate complexes: log10 � AnO2CO3 - 0 ) 5.12 ± 0.06 and 4.96 ± 0.06 for An ) Pu and Np, respectively. The Pu complex is slightly more stable, but the difference is only a little more than the uncertainties. We recently measured similar values (log10 � AnO2CO3
- Published
- 2009
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19. On the use of speciation techniques and ab initio modelling to understand tetravalent actinide behavior in a biological medium: An(IV)DTPA case
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L. Bonin, Sylvain Topin, Jean Aupiais, C. Den Auwer, Ph. Moisy, and Bruno Siberchicot
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Actinoid Series Elements ,Extended X-ray absorption fine structure ,Chemistry ,Ab initio ,Analytical chemistry ,Molecular Conformation ,02 engineering and technology ,Actinide ,Molecular Dynamics Simulation ,Pentetic Acid ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Characterization (materials science) ,Ion ,Inorganic Chemistry ,Electrophoresis ,Capillary electrophoresis ,Computational chemistry ,Organometallic Compounds ,Quantum Theory ,Absorption (chemistry) ,0210 nano-technology - Abstract
In the case of an accidental nuclear event, contamination of human bodies by actinide elements may occur. Such elements have the particularity to exhibit both radiological and chemical toxicities that may induce severe damages at several levels, depending on the biokinetics of the element. In order to eliminate the actinide elements before they are stored in target organs (liver, kidneys, or bone, depending on the element), sequestering agents must be quickly injected. However, to date, there is still no ideal sequestering agent, despite the recent interest in this topic due to contamination concerns. DTPA (diethylene triamine pentaacetic acid) is currently generating interest for the development of oral or alternative self-administrable forms. Although biokinetics data are mostly available, molecular scale characterization of actinide-DTPA complexes is still scarce. Nevertheless, strong interest is growing in the characterization of An(IV)DTPA(-) complexes at the molecular level because this opens the way for predicting the stability constants of unknown systems or even for developing new analytical strategies aimed at better and more selective decorporation. For this purpose, Extended X-ray Absorption Fine Structure (EXAFS) and Ab Initio Molecular Dynamics (AIMD) investigations were undertaken and compared with capillary electrophoresis (CE) used in a very unusual way. Indeed, it is commonly believed that CE is incapable of extracting structural information. In capillary electrophoresis, the electrophoretic mobility of an ion is a function of its charge and size. Despite very similar ratios, partial separations between An(IV)DTPA(-) species (An(IV) = Th, U, Np, Pu) were obtained. A linear relationship between the electrophoretic mobility and the actinide--oxygen distance calculated by AIMD was evidenced. As an example, the interpolated U-O distances in U(IV)DTPA(-) from CE-ICPMS experiments, EXAFS, AIMD, and the relationship between the stability constants and the ratio z/dAn-O, are all in agreement. This results in the capability to evaluate the stability constants for the formation of Pa(IV)DTPA(-), Am(IV)DTPA(-) or Bk(IV)DTPA(-).
- Published
- 2016
20. Breakthrough in Xenon Capture and Purification Using Adsorbent-Supported Silver Nanoparticles
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Ludovic Deliere, David Farrusseng, Sylvain Topin, Claire Gréau, Christophe Moulin, Benoit Coasne, IRCELYON-Ingéniérie, du matériau au réacteur (ING), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
- Subjects
Chemical substance ,Chemistry ,Organic Chemistry ,chemistry.chemical_element ,Nanotechnology ,02 engineering and technology ,General Chemistry ,[CHIM.CATA]Chemical Sciences/Catalysis ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,7. Clean energy ,[SDE.ES]Environmental Sciences/Environmental and Society ,Catalysis ,Silver nanoparticle ,Spent nuclear fuel ,0104 chemical sciences ,Nuclear reprocessing ,Adsorption ,Xenon ,13. Climate action ,0210 nano-technology ,Selectivity ,Science, technology and society - Abstract
SSCI-VIDE+ING+DFA; International audience; Rare gas capture and purification is a major challenge for energy, environment, and health applications. Of utmost importance for the nuclear industry, novel separation processes for Xe are urgently needed for spent nuclear fuel reprocessing and nuclear activity monitoring. The recovered, non-radioactive Xe is also of high economic value for lighting, surgical anesthetic, etc. Here, using adsorption and breakthrough experiments and statistical mechanics molecular simulation, we show the outstanding performance of zeolite-supported silver nanoparticles to capture/separate Xe at low concentrations (0.087-100 ppm). We also establish the efficiency of temperature swing adsorption based on such adsorbents for Xe separation from Kr/Xe mixtures and air streams corresponding to off-gases generated by nuclear reprocessing. This study paves the way for the development of novel, cost-efficient technologies relying on the large selectivity/capacity of adsorbent-supported silver nanoparticles which surpass all materials ever tested.
- Published
- 2016
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21. Development toward a double focusing isotopic separator for noble gas isotope enrichment
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Bernard, Lavielle, Bertrand, Thomas, Eric, Gilabert, Gregory, Canchel, Denis, Horlait, Sylvain, Topin, Fabien, Pointurier, and Christophe, Moulin
- Abstract
A double focusing sector field mass filter used in Nier-Johnson geometry has been built in order to perform Kr isotope enrichment for
- Published
- 2015
22. The pentavalent actinide solution chemistry in the environment
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Jean Aupiais and Sylvain Topin
- Subjects
Actinoid Series Elements ,Health, Toxicology and Mutagenesis ,Inorganic chemistry ,chemistry.chemical_element ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Chloride ,Oxalate ,Mass Spectrometry ,Neptunium ,chemistry.chemical_compound ,Capillary electrophoresis ,Radiation Monitoring ,medicine ,Environmental Chemistry ,Sulfate ,Waste Management and Disposal ,Radiochemistry ,Electrophoresis, Capillary ,General Medicine ,Actinide ,021001 nanoscience & nanotechnology ,Pollution ,Plutonium ,0104 chemical sciences ,Solutions ,chemistry ,Carbonate ,Thermodynamics ,0210 nano-technology ,medicine.drug - Abstract
With regard to environmental monitoring of certain nuclear facilities, pentavalent actinides, in particular neptunium and plutonium, play a key role, as the chief soluble, mobile forms of actinides. In the past five years, investigations carried out by hyphenating capillary electrophoresis to ICP-MS (CE-ICP-MS) have allowed a number of hitherto unknown thermodynamic data to be determined for Np(V) and Pu(V) interactions with the chief environmentally abundant anions. For the first time, data were provided for Pu(V) interactions with carbonate, sulfate, oxalate, chloride, and nitrate ions, allowing the Np(V)/Pu(V) analogy to be verified experimentally. Knowledge of Np(V) chemistry, especially in carbonate, and sulfate media, was also refined. These CE-ICP-MS studies, combined with some earlier findings, have brought about a renewal in the knowledge of An(V) chemistry in solution.
- Published
- 2015
23. Role of Silver Nanoparticles in Enhanced Xenon Adsorption Using Silver-Loaded Zeolites
- Author
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Benoit Coasne, Cécile Daniel, Yves Schuurman, Sophie De Vito, Sylvain Topin, Pier Lorenzo Solari, Christophe Den Auwer, David Farrusseng, Ludovic Deliere, Jean-Pierre Fontaine, Laboratoire de Détection et de Géophysique (CEA) (LDG), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Department of Civil and Environmental Engineering [Cambridge] (CEE), Massachusetts Institute of Technology (MIT), Multiscale Material Science for Energy and Environment (MSE 2), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut de Chimie de Nice (ICN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA)-Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Soleil grant 99130072, Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Nice Sophia Antipolis (1965 - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Université Nice Sophia Antipolis (... - 2019) (UNS), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), IRCELYON-Ingéniérie, du matériau au réacteur (ING), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
- Subjects
Chabazite ,Absorption spectroscopy ,Inorganic chemistry ,chemistry.chemical_element ,RADIOACTIVE XENON ,SORPTION ,Silver nanoparticle ,Adsorption ,Xenon ,Physisorption ,TEMPERATURES ,Physical and Theoretical Chemistry ,Zeolite ,XE-129 NMR ,Chemistry ,[CHIM.CATA]Chemical Sciences/Catalysis ,[CHIM.MATE]Chemical Sciences/Material chemistry ,[SDE.ES]Environmental Sciences/Environmental and Society ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,HIGH-PRESSURES ,[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry ,General Energy ,KRYPTON ,MOLECULAR-DYNAMICS ,SIMULATION ,CHABAZITE ,Crystallite ,EXCHANGED Y-ZEOLITES - Abstract
SSCI-VIDE+ING+CDA:YSC:DFA; International audience; Molecular simulation is used to unravel the adsorption mechanisms of xenon on Ag-doped ZSM-5 zeolite. We show that silver nanoparticles, which form at the external surface of zeolite crystallites, are responsible for enhanced xenon physisorption at very low pressure. We also propose a simple model of adsorption on such composite materials made up of silver-exchanged zeolites and silver nanoparticles adsorbed at the zeolite surface. This model, which allows predicting the adsorption of other gases without any additional parameters, provides a tool to characterize the amount of reduced silver as well as the silver particle size distribution (in good agreement with transmission electron microscopy images). The presence of a majority of silver nanoparticles is further characterized by means of X-ray diffraction and X-ray Absorption Spectroscopy at the silver K edge.
- Published
- 2014
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24. Thermodynamical and structural study of protactinium(V) oxalate complexes in solution
- Author
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Mickaël Mendes, Sylvain Topin, Christophe Den Auwer, Aurélie Jeanson, Jean Aupiais, Séna Hamadi, Philippe Moisy, Claire Le Naour, Maria-Vita Di Giandomenico, Christoph Hennig, Jérôme Roques, Institut de Physique Nucléaire d'Orsay (IPNO), Université Paris-Sud - Paris 11 (UP11)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Service de Chimie des Procédés de Séparation (SCPS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), EDF R&D (EDF R&D), and EDF (EDF)
- Subjects
Absorption spectroscopy ,Protactinium ,Analytical chemistry ,chemistry.chemical_element ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Oxalate ,Mass Spectrometry ,Inorganic Chemistry ,chemistry.chemical_compound ,Capillary electrophoresis ,Pa(V) oxalate ,Physical and Theoretical Chemistry ,Inductively coupled plasma mass spectrometry ,X-ray absorption spectroscopy ,Oxalates ,Molecular Structure ,Electrophoresis, Capillary ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Solutions ,EXAFS ,chemistry ,Stability constants of complexes ,Thermodynamics ,Density functional theory ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] ,0210 nano-technology - Abstract
The complexation of protactinium(V) by oxalate was studied by X-ray absorption spectroscopy (XAS), density functional theory (DFT) calculations, capillary electrophoresis coupled with inductively coupled plasma mass spectrometry (CE-ICP-MS) and solvent extraction. XAS measurements showed unambiguously the presence of a short single oxo-bond, and the deduced structure agrees with theoretical calculations. CE-ICP-MS results indicated the formation of a highly charged anionic complex. The formation constants of PaO(C(2)O(4))(+), PaO(C(2)O(4))(2)(-), and PaO(C(2)O(4))(3)(3-) were determined from solvent extraction data by using protactinium at tracer scale (C(Pa) < 10(-10) M). Complexation reactions of Pa(V) with oxalate were found to be exothermic with relatively high positive entropic variation.
- Published
- 2010
- Full Text
- View/download PDF
25. Determination of the stability constants of nitrate complexes of Np(V) and Pu(V) using CE-ICP-MS
- Author
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Sylvain Topin, Jean Aupiais, and N. Baglan
- Subjects
Perchlorate ,chemistry.chemical_compound ,Capillary electrophoresis ,Nitrate ,Chemistry ,Neptunium ,Inorganic chemistry ,Analytical chemistry ,chemistry.chemical_element ,Physical and Theoretical Chemistry ,Mass spectrometry ,Binding constant ,Inductively coupled plasma mass spectrometry - Abstract
The interactions of pentavalent Np and Pu with nitrate ligands has been investigated in perchlorate/ nitrate media by capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS). The binding constant for the complex PuO 2 NO 3 , logl 10 β° PuO2NO3 =0.14 ± 0.14, is established for the first time while a new value for NpO 2 NO 3 , log 10 β° NpO2NO3 = 0.13 ± 0.14, is proposed. The usual analogy applied between Np(V) and Pu(V) interactions seems to be valid for nitrates.
- Published
- 2010
- Full Text
- View/download PDF
26. Direct determination of plutonium(V) and neptunium(V) complexation by carbonate ligand with CE-ICP-sector field MS
- Author
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Sylvain Topin, Jean Aupiais, and Philippe Moisy
- Subjects
Field (physics) ,Chemistry ,Ligand ,Neptunium ,Clinical Biochemistry ,Inorganic chemistry ,Analytical chemistry ,Carbonates ,chemistry.chemical_element ,Electrophoresis, Capillary ,Actinide ,Ligands ,Biochemistry ,Mass Spectrometry ,Plutonium ,Analytical Chemistry ,chemistry.chemical_compound ,Ionic strength ,Carbonate - Abstract
Direct determination of the stability constants of some pentavalent actinides (Np and Pu) with carbonate ligands was investigated by CE-ICP-sector field MS (SFMS). The high sensitivity of ICP-SFMS coupled with the high separation power of CE makes it possible to determine the mobility of each species as well as the stability constants with good accuracy. A procedure for preparing pentavalent plutonium at trace level has been successfully tested enabling the study of Pu(V) complexation by CE-ICP-SFMS. Stability constants beta1, beta2 and beta3 have been obtained at 25 +/- 1 degrees C at a constant ionic strength of 0.37 M in NaClO4 for K1 and NaCl for beta2 and beta3. The results were extrapolated to zero ionic strength and compared with data available in the literature for Np(V). The following stability constants were obtained for a Pu(V)/CO3 system: logbeta(1)(0) = 4.95 +/- 0.10, logbeta(2)(0) = 6.34 +/- 0.10, and logbeta(3)(0) = 5.61 +/- 0.16.
- Published
- 2009
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