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Sample records for hydrated caesium-smectite interlayers

  1. Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

    Directory of Open Access Journals (Sweden)

    Sposito Garrison

    2002-09-01

    Full Text Available Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

  2. Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

    Science.gov (United States)

    Sutton, Rebecca; Sposito, Garrison

    2002-01-01

    Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

  3. Role of interlayer hydration in lincomycin sorption by smectite clays.

    Science.gov (United States)

    Wang, Cuiping; Ding, Yunjie; Teppen, Brian J; Boyd, Stephen A; Song, Cunyi; Li, Hui

    2009-08-15

    Lincomycin, an antibiotic widely administered as a veterinary medicine, is frequently detected in water. Little is known about the soil-water distribution of lincomycin despite the fact that this is a major determinant of its environmental fate and potential for exposure. Cation exchange was found to be the primary mechanism responsible for lincomycin sorption by soil clay minerals. This was evidenced by pH-dependent sorption, and competition with inorganic cations for sorptive sites. As solution pH increased, lincomycin sorption decreased. The extent of reduction was consistent with the decrease in cationic lincomycin species in solution. The presence of Ca2+ in solution diminished lincomycin sorption. Clay interlayer hydration status strongly influenced lincomycin adsorption. Smectites with the charge deficit from isomorphic substitution in tetrahedral layers (i.e., saponite) manifest a less hydrated interlayer environment resulting in greater sorption than that by octahedrally substituted clays (i.e., montmorillonite). Strongly hydrated exchangeable cations resulted in a more hydrated clay interlayer environment reducing sorption in the order of Ca- smectite. X-ray diffraction revealed that lincomycin was intercalated in smectite clay interlayers. Sorption capacity was limited by clay surface area rather than by cation exchange capacity. Smectite interlayer hydration was shown to be a major, yet previously unrecognized, factor influencing the cation exchange process of lincomycin on aluminosilicate mineral surfaces.

  4. Influence of smectite hydration and swelling on atrazine sorption behavior.

    Science.gov (United States)

    Chappell, Mark A; Laird, David A; Thompson, Michael L; Li, Hui; Teppen, Brian J; Aggarwal, Vaneet; Johnston, Cliff T; Boyd, Stephen A

    2005-05-01

    Smectites, clay minerals commonly found in soils and sediments, vary widely in their ability to adsorb organic chemicals. Recent research has demonstrated the importance of surface charge density and properties of exchangeable cations in controlling the affinity of smectites for organic molecules. In this study, we induced hysteresis in the crystalline swelling of smectites to test the hypothesis that the extent of crystalline swelling (or interlayer hydration status) has a large influence on the ability of smectites to adsorb atrazine from aqueous systems. Air-dried K-saturated Panther Creek (PC) smectite swelled less (d(001) = 1.38 nm) than never-dried K-PC (d(001) = 1.7 nm) when rehydrated in 20 mM KCl. Correspondingly, the air-dried-rehydrated K-PC had an order of magnitude greater affinity for atrazine relative to the never-dried K-PC. Both air-dried-rehydrated and never-dried Ca-PC expanded to approximately 2.0 nm in 10 mM CaCl2 and both samples had similar affinities for atrazine that were slightly lower than that of never-dried K-PC. The importance of interlayer hydration status in controlling sorption affinity was confirmed by molecular modeling, which revealed much greater interaction between interlayer water molecules and atrazine in a three-layer hydrate relative to a one-layer hydrate. The entropy change on moving atrazine from a fully hydrated state in the bulk solution to a partially hydrated state in the smectite interlayers is believed to be a major factor influencing sorption affinity. In an application test, choice of background solution (20 mM KCl versus 10 mM CaCl2) and air-drying treatments significantly affected atrazine sorption affinities for three-smectitic soils; however, the trends were not consistent with those observed for the reference smectite. Further, extending the initial rehydration time from 24 to 240 h (prior to adding atrazine) significantly decreased the soil's sorption affinity for atrazine. We conclude that interlayer

  5. Influence of smectite crystal chemistry on the organization of interlayer water and cations

    International Nuclear Information System (INIS)

    Dazas, Baptiste

    2014-01-01

    Swelling clay minerals such as smectites are ubiquitous at the Earth surface and possess major hydration ability and contaminant uptake/retention capacity. As a consequence smectites exert a pivotal influence on elemental transfers in surficial environments. These properties are especially relevant also when smectites are used as sealant in engineered or geological barriers for waste disposal facilities. As interlayer H_2O molecules account for more than 80% of smectite water in under-saturated conditions, characterization of H_2O organization and dynamics in smectites interlayers is essential to determining the geometrical and dynamical properties of clay barriers for waste disposal and to predicting the mobility of contaminant whose principal vector is water. Within this general framework, the present works describe, in a first time, the structuration of interlayer water/cations in saturated conditions. Then, in a second time, review the influence of structural parameters such as the amount and location of layer charge deficit and the chemical composition (and more especially the presence of structural fluorine/hydroxyl) on smectite hydration properties. A set of samples covering the whole compositional range of swelling phyllosilicates has thus been synthesized and characterized chemically and structurally. Special attention was paid to determining the amount (water vapor sorption isotherms) and the distribution (X-ray diffraction) of interlayer water. Molecular modeling allowed unraveling the origin of the contrasting behaviors observed experimentally and to determine the influence of the different crystal-chemical parameters on smectite hydration. This step is essential for the prediction of smectite reactivity in the environment from a limited number of crystal-chemical parameters. Molecular modeling allowed unraveling the origin of the contrasting behaviors observed experimentally and to determine the influence of the different crystal-chemical parameters on

  6. Activation energies of diffusion for I and Cs in interlayer of smectite

    International Nuclear Information System (INIS)

    Sato, H.

    2009-01-01

    The apparent diffusivities (Da) and activation energies (ΔEa) for I - and Cs + ions in compacted Na-smectite with an interlayer space of only 2 water layers were measured at a dry density of 1.79 Mg/m 3 . In-diffusion experiments were carried out under the conditions that interlayer space, orientation of smectite stacks and dry density were controlled. Basal spacing was checked by X-ray diffractometry (XRD). All diffraction peaks to d(001) indicated basal spacing, of which interlayer space was equal to 2 water layers. The ΔEa of I - ions was at similar level as that for the ionic diffusivity of I - ions in free water (Do) at a dry density of 1.0 Mg/m 3 , but was 35.24 kJ/mol at a dry density of 1.79 Mg/m 3 . The ΔEa for Cs + ions was 46.27 kJ/mol which was higher than that for I? ions, at a dry density of 1.79 Mg/m 3 . Such high ΔEa for I - ions in the interlayer of smectite could be explained by the lowering in the activity (a H 2 O ) of interlayer water. Since Cs + ions sorb onto smectite by ion exchange, such high ΔEa for Cs + ions could be explained by the combined effects of the Cs+/Na+ ion exchange enthalpy (ΔH o ) in smectite and the lowering in the a H 2 O of interlayer water. (author)

  7. Experimental investigation of smectite hydration from the simulation of 001 X-ray diffraction lines. Implications for the characterization of mineralogical modifications of the 'argilite' from the Meuse - Haute Marne site as a result of a thermal perturbation; Etude experimentale de l'hydratation des smectites par simulation des raies OOl de diffraction des rayons X. Implications pour l'etude d'une perturbation thermique sur la mineralogie de l'argilite du site Meuse-Haute Marne

    Energy Technology Data Exchange (ETDEWEB)

    Ferrage, E

    2004-10-15

    The structural modifications affecting the reactive mineral constituents of the clay barriers (smectite) and possibly resulting from the thermal pulse related to nuclear waste storage are essentially limited to the amount and location of the layer charge deficit. These modifications likely impact the hydration properties of these minerals, and a specific methodology has thus been developed to describe, using simulation of X-ray diffraction profiles (001 reflections), these hydration properties and specifically the heterogeneity resulting from the inter-stratification of different layer types, each exhibiting a specific hydration state. The detailed study of the hydration properties of a low-charge montmorillonite (octahedral charge) has shown that the affinity of the interlayer cation for water rules the hydration state and the thickness of hydrated smectite layers. If the layer charge is increased, the transition between the different hydration states is shifted, following a water desorption isotherm, towards lower relative humidities. In addition, the hydration of studied beidellites (tetrahedral charge) was shown to be more heterogeneous than that of montmorillonites. The developed methodology also allowed describing the structural modifications resulting from a chemical perturbation (chlorinated anionic background, pH). Finally, the link between the thickness of elementary layers and the amount of interlayer water molecules has been evidenced. A new structure model has also been determined for these interlayer species allowing an improved description of their positional distribution in bi-hydrated interlayers. (author)

  8. Experimental investigation of smectite hydration from the simulation of 001 X-ray diffraction lines. Implications for the characterization of mineralogical modifications of the 'argilite' from the Meuse - Haute Marne site as a result of a thermal perturbation

    International Nuclear Information System (INIS)

    Ferrage, E.

    2004-10-01

    The structural modifications affecting the reactive mineral constituents of the clay barriers (smectite) and possibly resulting from the thermal pulse related to nuclear waste storage are essentially limited to the amount and location of the layer charge deficit. These modifications likely impact the hydration properties of these minerals, and a specific methodology has thus been developed to describe, using simulation of X-ray diffraction profiles (001 reflections), these hydration properties and specifically the heterogeneity resulting from the inter-stratification of different layer types, each exhibiting a specific hydration state. The detailed study of the hydration properties of a low-charge montmorillonite (octahedral charge) has shown that the affinity of the interlayer cation for water rules the hydration state and the thickness of hydrated smectite layers. If the layer charge is increased, the transition between the different hydration states is shifted, following a water desorption isotherm, towards lower relative humidities. In addition, the hydration of studied beidellites (tetrahedral charge) was shown to be more heterogeneous than that of montmorillonites. The developed methodology also allowed describing the structural modifications resulting from a chemical perturbation (chlorinated anionic background, pH). Finally, the link between the thickness of elementary layers and the amount of interlayer water molecules has been evidenced. A new structure model has also been determined for these interlayer species allowing an improved description of their positional distribution in bi-hydrated interlayers. (author)

  9. Development of swelling strain in smectite clays through exposure to carbon dioxide

    NARCIS (Netherlands)

    de Jong, S.M.; Spiers, C.J.; Busch, A.

    2014-01-01

    Smectites are common constituents of claystones, mudstones and shales and are often present in the caprocks and faults that seal potential CO2 storage reservoirs at depths up to 2 or even 3 km. Whilst the marked swelling behaviour of smectites caused by hydration through interlayer sorption of water

  10. Intercalation and retention of carbon dioxide in a smectite clay promoted by interlayer cations.

    Science.gov (United States)

    Michels, L; Fossum, J O; Rozynek, Z; Hemmen, H; Rustenberg, K; Sobas, P A; Kalantzopoulos, G N; Knudsen, K D; Janek, M; Plivelic, T S; da Silva, G J

    2015-03-05

    A good material for CO2 capture should possess some specific properties: (i) a large effective surface area with good adsorption capacity, (ii) selectivity for CO2, (iii) regeneration capacity with minimum energy input, allowing reutilization of the material for CO2 adsorption, and (iv) low cost and high environmental friendliness. Smectite clays are layered nanoporous materials that may be good candidates in this context. Here we report experiments which show that gaseous CO2 intercalates into the interlayer nano-space of smectite clay (synthetic fluorohectorite) at conditions close to ambient. The rate of intercalation, as well as the retention ability of CO2 was found to be strongly dependent on the type of the interlayer cation, which in the present case is Li(+), Na(+) or Ni(2+). Interestingly, we observe that the smectite Li-fluorohectorite is able to retain CO2 up to a temperature of 35°C at ambient pressure, and that the captured CO2 can be released by heating above this temperature. Our estimates indicate that smectite clays, even with the standard cations analyzed here, can capture an amount of CO2 comparable to other materials studied in this context.

  11. Effect of humidity and interlayer cation on frictional strength of montmorillonite

    Science.gov (United States)

    Tetsuka, H.; Katayama, I.; Sakuma, H.; Tamura, K.

    2016-12-01

    Smectite has been ubiquitously seen in fault gouge (Schleicher et al., 2006; Kuo et al., 2009; Si et al., 2014; Kameda, 2015) and is characteristic by low frictional coefficient (Saffer et al., 2001; Ikari et al., 2007); consequently, it has a key role in fault dynamics. The frictional strength of montmorillonite (a typical type of smectite) is affected by mainly two factors, 1) hydration state and 2) interlayer cation. Previous laboratory experiments have shown that the frictional strength of montmorillonite changes with hydration state (Ikari et al., 2007) and with interlayer cation (Behnsen and Faulkner, 2013). However, experimental study for frictional strengths of interlayer cation-exchanged montmorillonite under controlled hydration state has not been reported. We are developing humidity control system in biaxial friction testing machine and try to investigate the effect of relative humidity and interlayer cation on frictional strength of montmorillonite. The humidity control system consists of two units, 1) the pressure vessel (core holder) unit controlled by a constant temperature and 2) the vapor generating unit controlled by variable temperature. We control relative humidity around sample, which is calculated from the temperature around sample and the vapor pressure at vapor generating unit. Preliminary experiments under controlled humidity show frictional coefficient of montmorillonite decrease with increasing relative humidity. In the meeting, we will report the systematic study of frictional coefficient as function of relative humidity and interlayer cation species.

  12. Production of polyol carbonates and their intercalation into Smectite clays

    OpenAIRE

    Shaheen, Uzma

    2017-01-01

    In hyper-saline conditions, clays in geosynthetic clay liners contract and fail to form a hydraulic barrier due to removal of water from the interlayer spaces of smectite, which is the swelling mineral component of bentonites used in geosynthetic clay liners. Five-membered cyclic carbonates such as propylene carbonate have been reported to form stable intercalated complexes with hydrated Na-smectite, which maintain swollen states at 1M). Glycerol carbonate was selected as an alternative c...

  13. Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study; Hydratation des argiles gonflantes et influence des bacteries. Etude experimentale de reaction in situ

    Energy Technology Data Exchange (ETDEWEB)

    Berger, J

    2008-01-15

    This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, developed in the interlayer space, and the amount of water contained in different storage sites (interlayers, surfaces and pore spaces). Qualitative information on surface area and textural organization was also estimated based on calculated changes in the average particle thickness and the organization of water layer structures (ordering). Abiotic smectite hydration experiments, using a range of natural and industrial bentonites (SWy-2, IBECO, MX80, TIXOTON), focused on defining the role of the interlayer cation, variable clay packing densities and the ionic strength of the infiltrating solution. The rate of smectite hydration, as expected, was seen to be highly dependent on the type of interlayer cation (enhanced for Ca as opposed to Na) and the ionic strength of solution (enhanced uptake rates with saline solutions, particularly as they infiltrate Na-smectite). A range of dynamic changes in micro textural state occurred as a function of packing density. These changes explain the differences in hydration behaviour

  14. Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study

    International Nuclear Information System (INIS)

    Berger, J.

    2008-01-01

    This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, developed in the interlayer space, and the amount of water contained in different storage sites (interlayers, surfaces and pore spaces). Qualitative information on surface area and textural organization was also estimated based on calculated changes in the average particle thickness and the organization of water layer structures (ordering). Abiotic smectite hydration experiments, using a range of natural and industrial bentonites (SWy-2, IBECO, MX80, TIXOTON), focused on defining the role of the interlayer cation, variable clay packing densities and the ionic strength of the infiltrating solution. The rate of smectite hydration, as expected, was seen to be highly dependent on the type of interlayer cation (enhanced for Ca as opposed to Na) and the ionic strength of solution (enhanced uptake rates with saline solutions, particularly as they infiltrate Na-smectite). A range of dynamic changes in micro textural state occurred as a function of packing density. These changes explain the differences in hydration behaviour observed

  15. Thermodynamic of hydration of a Wyoming montmorillonite saturated with Ca, Mg, Na and K

    International Nuclear Information System (INIS)

    Vieillard, P.; Blanc, P.; Gailhanou, H.; Gaboreau, S.; Giffaut, E.

    2010-01-01

    enthalpy of immersion, and isotherms of adsorption - desorption has been done for Wyoming montmorillonite saturated by Mg 2+ , Ca 2+ , Na + and K + . Smectite water-vapor pressure isotherms represent the total concentration of H 2 O taken up the sample which is distributed among the interlayers, the outer surfaces of particles and the open pore space in the sample. In order to retrieve standard state thermodynamic properties for smectite hydration and dehydration from such data, the amount of H 2 O in excess of that in the interlayer must be assessed and subtracted from the total amount taken up by the clay sample. Berend et al. (1995), Cases et al. (1992, 1997) provide careful measurements of recovering waters in both processes (hydration and dehydration) on Wyoming saturated by monovalent and divalent cations. Despite the fact that neither the hydration, nor the dehydration isotherm necessarily represents the equilibrium state of the system, the two isotherms together can be considered to bracket the equilibrium values of Xhs and the activity of H 2 O. Paired hydration and dehydration isotherm in the one hand and enthalpy of immersion in the other hand, which constitute the limits of these brackets can be regressed to assess standard state thermodynamic parameters (enthalpy and entropy) for the hydration- dehydration process. Experimental enthalpies of hydration are used in the determination of ΔH deg. hyd. W H1 and W H2 by the minimization technique. For the adsorption-desorption isotherms, the determination of parameters ΔS deg. hyd. W S1 and W S2 are obtained by minimizing the difference between measured sets of data (relative humidity and number of adsorbed interlayer water) and calculated ones. For each Wyoming saturated with one cation, six parameters are requested and characterize the standard state thermodynamic properties of hydration between smectite and interlayer H 2 O. Relations between hydration parameters ΔH deg. hyd. and ΔS deg. hyd. in the one hand

  16. Hydration of swelling clays: multi-scale sequence of hydration and determination of macroscopic energies from microscopic properties; Hydratation des argiles gonflantes: sequence d'hydratation multi-echelle determination des energies macroscopiques a partir des proprietes microscopiques

    Energy Technology Data Exchange (ETDEWEB)

    Salles, F

    2006-10-15

    smectites: it is responsible for the structure of porosity in a dry state and of the evolution of the pore sizes as a function of the RH and it modifies the hydration sequence by its mobility inside the interlayer space. The distinction between various types of water in the smectite structure is also achieved by thermo-poro-metry at different RH: water bound to the cations and surfaces, water structured by porosity and free water. This distinction is important to understand the behaviour of smectite and in particular the diffusion properties in clayey materials. The importance of the cation nature is also highlighted by the energetic model. Electrostatic calculations using the PACHA formalism (Electronegativities Equalization method) show that, for the small cations, the hydration energy of the layers is predominant. To obtain these results, we determine the surface enthalpies for the dry state, which show a coherent evolution as a function of the cation partial charge with the increase of pore sizes and thus with particle sizes. Then, using a theoretical model, we calculated swelling energies, surface hydration energies and cation hydration energies. The behaviour of mixed purified clay displays a behaviour closer to that of a calcic clay for the experiments carried out, in contradiction with the fact that the Na cation is the most abundant. This observation implies results on the clay properties, different from that expected for hydration properties, swelling and interlayer cation mobility within the framework of the radioactive waste. (author)

  17. Mechanisms for adsorption of organic bases on hydrated smectite surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Laird, D.A.; Fleming, P.D.

    1999-08-01

    The environmental fate of anthropogenic organic bases introduced to soils and sediments, either deliberately as pesticides or inadvertently as contaminants, depends, to a large extent, on reactions between those compounds and the surfaces of soil mineral and organic constituents. Mechanisms by which organic bases are adsorbed on hydrated smectite surfaces were investigated. Three Ca-saturated reference smectites (Otay, SPV, and Panther Creek) were dispersed in distilled water containing 5 {micro}mol of pyridine or 3-butylpyridine. The pH was adjusted to between 7.5 and 3 using 0.01 M HCl. After a 2-h equilibration, the amounts of pyridine or 3-butylpyridine adsorbed on the clay and the amount of Ca desorbed from the clay were determined. Negligible amounts of pyridine were adsorbed by the Ca-smectites in the neutral systems (pH > 7); however, most of the added pyridine was adsorbed on the smectites in the acidified systems (pH < 5). Equivalent amounts of Ca{sup 2+} were desorbed from the clays, indicating that pyridine was adsorbed as a protonated species by cation exchange. By contrast, 40 to 90% of added 3-butylpyridine was adsorbed on the smectites at neutral pHs, whereas only small amounts of Ca{sup 2+} were desorbed. The results suggest that 3-butylpyridine is initially retained by hydrophobic bonding between the alkyl side chain of the molecule and hydrophobic nanosites located between the charge sites on smectite surfaces. Surface acidity catalyzed protonation 1 to 1.5 pH units above the pK{sub a} of the bases.

  18. Mechanisms associated with the high adsorption of dibenzo-p-dioxin from water by smectite clays.

    Science.gov (United States)

    Liu, Cun; Li, Hui; Teppen, Brian J; Johnston, Cliff T; Boyd, Stephen A

    2009-04-15

    Clay minerals may be an important unrecognized sorptive phase for dioxins in soils and clay deposits. Smectites, especially Cs-saponite, effectively adsorbed dibenzo-p-dioxin (DD) from water, reaching 0.8% (wt/wt). Adsorption was promoted by exchangeable cations with low hydration energies, and negative charge in the smectite arising from the tetrahedral siloxane sheets. X-ray diffraction measurements revealed that as DD loading increased to > or =8000 mg/kg the clay basal spacing increased abruptly from 12.3 to 15.2 A demonstrating DD intercalation. The 12.3 A spacing provides an interlayer distance that closely matches the molecular thickness of DD. In this configuration DD is essentially dehydrated as it interacts with the opposing hydrophobic siloxane sheets and with coplanar Cs+ via one of the dioxin ring oxygens. Ab initio calculations suggest that geometrical structures form at higher loadings in which intercalated DD molecules adopt a butterfly geometry sandwiched between dehydrated interlayer Cs+ and the siloxane surface, consistent with the 15.2 A spacing, wherein Cs+ interacts with dioxin ring oxygens and benzene ring pi-electrons. Fourier transformation infrared measurements confirm that adsorbed DD is present in orientations that are not parallel with the interlayer planar siloxane surfaces of smectite.

  19. Hydration of swelling clays: multi-scale sequence of hydration and determination of macroscopic energies from microscopic properties

    International Nuclear Information System (INIS)

    Salles, F.

    2006-10-01

    smectites: it is responsible for the structure of porosity in a dry state and of the evolution of the pore sizes as a function of the RH and it modifies the hydration sequence by its mobility inside the interlayer space. The distinction between various types of water in the smectite structure is also achieved by thermo-poro-metry at different RH: water bound to the cations and surfaces, water structured by porosity and free water. This distinction is important to understand the behaviour of smectite and in particular the diffusion properties in clayey materials. The importance of the cation nature is also highlighted by the energetic model. Electrostatic calculations using the PACHA formalism (Electronegativities Equalization method) show that, for the small cations, the hydration energy of the layers is predominant. To obtain these results, we determine the surface enthalpies for the dry state, which show a coherent evolution as a function of the cation partial charge with the increase of pore sizes and thus with particle sizes. Then, using a theoretical model, we calculated swelling energies, surface hydration energies and cation hydration energies. The behaviour of mixed purified clay displays a behaviour closer to that of a calcic clay for the experiments carried out, in contradiction with the fact that the Na cation is the most abundant. This observation implies results on the clay properties, different from that expected for hydration properties, swelling and interlayer cation mobility within the framework of the radioactive waste. (author)

  20. Ethylene glycol intercalation in smectites. molecular dynamics simulation studies

    International Nuclear Information System (INIS)

    Szczerba, Marek; Klapyta, Zenon; Kalinichev, Andrey

    2012-01-01

    Document available in extended abstract form only. Intercalation of ethylene glycol in smectites (glycolation) is widely used to discriminate smectites and vermiculites from other clays and among themselves. During this process, ethylene glycol molecules enter into the interlayer spaces of the swelling clays, leading to the formation of two-layer structure (∼17 A) in the case of smectites, or one-layer structure (∼14 A) in the case of vermiculites. In spite of the relatively broad literature on the understanding/characterization of ethylene glycol/water-clays complexes, the simplified structure of this complex presented by Reynolds (1965) is still used in the contemporary X-ray diffraction computer programs, which simulate structures of smectite and illite-smectite. The monolayer structure is only approximated using the assumption of the interlayer cation and ethylene glycol molecules lying in the middle of interlayer spaces. This study was therefore undertaken to investigate the structure of ethylene glycol/water-clays complex in more detail using molecular dynamics simulation. The structural models of smectites were built on the basis of pyrophyllite crystal structure (Lee and Guggenheim, 1981), with substitution of particular atoms. In most of simulations, the structural model assumed the following composition, considered as the most common in the mixed layer illite-smectites: EXCH 0.4 (Si 3.96 Al 0.04 )(Al 1.46 Fe 0.17 Mg 0.37 )O 10 (OH) 2 Atoms of the smectites were described with CLAYFF force field (Cygan et al., 2004), while atoms of water and ethylene glycol with flexible SPC and OPLS force fields, respectively. Ewald summation was used to calculate long range Coulombic interactions and the cutoff was set at 8.5 A. Results of the simulations show that in the two-layer glycolate the content of water is relatively small: up to 0.8 H 2 O per half of the smectite unit cell. Clear thermodynamic preference of mono- or two-layer structure of the complex is

  1. Dynamics of confined reactive water in smectite clay-zeolite composites.

    Science.gov (United States)

    Pitman, Michael C; van Duin, Adri C T

    2012-02-15

    The dynamics of water confined to mesoporous regions in minerals such as swelling clays and zeolites is fundamental to a wide range of resource management issues impacting many processes on a global scale, including radioactive waste containment, desalination, and enhanced oil recovery. Large-scale atomic models of freely diffusing multilayer smectite particles at low hydration confined in a silicalite cage are used to investigate water dynamics in the composite environment with the ReaxFF reactive force field over a temperature range of 300-647 K. The reactive capability of the force field enabled a range of relevant surface chemistry to emerge, including acid/base equilibria in the interlayer calcium hydrates and silanol formation on the edges of the clay and inner surface of the zeolite housing. After annealing, the resulting clay models exhibit both mono- and bilayer hydration structures. Clay surface hydration redistributed markedly and yielded to silicalite water loading. We find that the absolute rates and temperature dependence of water dynamics compare well to neutron scattering data and pulse field gradient measures from relevant samples of Ca-montmorillonite and silicalite, respectively. Within an atomistic, reactive context, our results distinguish water dynamics in the interlayer Ca(OH)(2)·nH(2)O environment from water flowing over the clay surface, and from water diffusing within silicalite. We find that the diffusion of water when complexed to Ca hydrates is considerably slower than freely diffusing water over the clay surface, and the reduced mobility is well described by a difference in the Arrhenius pre-exponential factor rather than a change in activation energy.

  2. Molecular Dynamics Study of Crystalline Swelling of Montmorillonite as Affected by Interlayer Cation Hydration

    Science.gov (United States)

    Li, Hongliang; Song, Shaoxian; Dong, Xianshu; Min, Fanfei; Zhao, Yunliang; Peng, Chenliang; Nahmad, Yuri

    2018-04-01

    Swelling of montmorillonite (Mt) is an important factor for many industrial applications. In this study, crystalline swelling of alkali-metal- and alkaline-earth-metal-Mt has been studied through energy optimization and molecular dynamics simulations using the clay force field by Materials Studio 8.0. The delamination and exfoliation of Mt are primarily realized by crystalline swelling caused by the enhanced interlayer cation hydration. The initial position of the interlayer cations and water molecules is the dominated factor for the accuracy of the Mt simulations. Crystalline swelling can be carried out in alkali-metal-Mt and Mg-Mt but with difficulty in Ca-Mt, Sr-Mt and Ba-Mt. The crystalline swelling capacity values are in the order Na-Mt > K-Mt > Cs-Mt > Mg-Mt. This order of crystalline swelling of Mt in the same group can be attributed to the differences between the interlayer cation hydration strengths. In addition, the differences in the crystalline swelling between the alkali-metal-Mt and alkaline-earth-metal-Mt can be primarily attributed to the valence of the interlayer cations.

  3. Smectite dehydration and stability: Applications to radioactive waste isolation at Yucca Mountain, Nevada

    International Nuclear Information System (INIS)

    Bish, D.L.

    1988-03-01

    Montmorillonite-beidellite smectites are present in amounts up to 50% in the rocks directly underlying the potential high-level radioactive waste repository horizon at Yucca Mountain, Nevada. The thermal reactions of concern include reversible collapse/expansion of the smectite layers due to loss/gain of interlayer water;irreversible collapse due to loss of interlayer water and migration of interlayer cations into the 2:1 silicate layers;irreversible reduction of the osmotic swelling ability through reaction in a steam atmosphere;and inhomogeneous transformation of the smectite into an interstratified illite/smectite. Reversible collapse should be of minor importance because any thermally driven collapse will be reversed when water is introduced and temperatures go down. The amounts of smectite in the potential repository horizon itself are probably insufficient to give rise to rock strength problems due to reversible collapse. The irreversible reduction of somotic selling capacity in a steam environment may be significant in the rocks near the repository horizon. This effect on naturally occurring Na-rich smectites would probably increase permeabilitie shut would also provide for increased cation exchange by the smectite. 60 refs., 9 figs

  4. Connecting the molecular scale to the continuum scale for diffusion processes in smectite-rich porous media.

    Science.gov (United States)

    Bourg, Ian C; Sposito, Garrison

    2010-03-15

    In this paper, we address the manner in which the continuum-scale diffusive properties of smectite-rich porous media arise from their molecular- and pore-scale features. Our starting point is a successful model of the continuum-scale apparent diffusion coefficient for water tracers and cations, which decomposes it as a sum of pore-scale terms describing diffusion in macropore and interlayer "compartments." We then apply molecular dynamics (MD) simulations to determine molecular-scale diffusion coefficients D(interlayer) of water tracers and representative cations (Na(+), Cs(+), Sr(2+)) in Na-smectite interlayers. We find that a remarkably simple expression relates D(interlayer) to the pore-scale parameter δ(nanopore) ≤ 1, a constrictivity factor that accounts for the lower mobility in interlayers as compared to macropores: δ(nanopore) = D(interlayer)/D(0), where D(0) is the diffusion coefficient in bulk liquid water. Using this scaling expression, we can accurately predict the apparent diffusion coefficients of tracers H(2)0, Na(+), Sr(2+), and Cs(+) in compacted Na-smectite-rich materials.

  5. Sorption of caesium and strontium onto calcium silicate hydrate in saline groundwater

    International Nuclear Information System (INIS)

    Sugiyama, D.; Fujita, T.

    2005-01-01

    Full text of publication follows: In the concept for radioactive waste disposal in Japan, cement is a potential waste packaging and backfilling material and is expected to provide chemical containment. The sorption of radionuclides onto cement materials, which controls the aqueous concentrations of elements in the pore-water, is a very important parameter when considering the release of radionuclides from the near field of a cementitious radioactive waste repository. Many safety assessment calculations currently assume radionuclide retardation as linear sorption equilibrium and describe it with a distribution ratio (R d value). In this study, the sorption mechanism is discussed by measuring the sorption isotherm of caesium, strontium (10 -5 ∼ 10 -2 mol dm -3 ) and sodium (10 -4 ∼ 10 -1 mol dm -3 ) onto Calcium Silicate Hydrate (C-S-H gel, Ca/Si 0.65 ∼ 1.2) at a liquid:solid ratio of 100:1, to support the assumption. In addition, the competitive sorption between caesium or strontium, and sodium is studied by sorption measurements using a range of sodium chloride concentration to simulate different ionic strengths in saline groundwater. The initial and equilibrated aqueous compositions were measured in the sorption experiments and it was found that caesium, strontium and sodium were sorbed by substitution for Ca in C-S-H phases by examining the mass balance. Based on the experimental results, we propose a modelling approach in which the ion-exchange model is employed and the presence of some calcium sites with different ion-exchange log K values in C-S-H is assumed by considering the composition and the structure of C-S-H. The modelling calculation results predict the measured Rd values well and also describe the competition of sorption of caesium or strontium, and sodium in the experiments. The log K values for sorption of each cation element decreased as Ca/Si ratio of C-S-H gel increased. This agrees with the trend that C-S-H gel is negatively charged at low

  6. Smectite alteration by anaerobic iron corrosion

    International Nuclear Information System (INIS)

    Sanders, D.; Kaufhold, S.; Hassel, A.W.; Dohrmann, R.

    2010-01-01

    Document available in extended abstract form only. The interaction of smectites with corroding steel/iron represents a crucial topic in the estimation of the long term confinement properties of clay barriers for the encasement of steel/iron containers. Especially in case of engineered clay barriers a possible deterioration of favourable smectite properties as response to corrosion could reduce the barrier capacity. The extent of this reduction is unknown, yet. The essential properties of bentonite clays in this context are on the one hand the relatively high swelling pressure together with low hydraulic conductivity, which results from the well known expandability of smectite interlayers in aqueous environments. On the other hand smectites are cation exchangers being able to long term encase radioactive cations in a way that negative charges of silicate layers are compensated by easily exchangeable hydrated cations. Both properties are directly related to the crystal and chemical composition of smectites. The nature of the corrosion of steel canisters in clay barriers will - after a first short aerobic phase - predominantly be anaerobic resulting in the formation of Fe(II) and two equivalents of hydroxide ions. In a set of exposition experiments anaerobic corroding iron in bentonite gels was studied in order to determine alteration of the smectite fraction. During the exposition a green coloration of the bentonite neighbouring to corroding iron was observed. Upon contact to oxygen in a humid state the bentonite turned reddish indicating the oxidation of Fe(II) to Fe(III). This observation is in accordance with reported results indicating the formation of an iron rich smectite. Chemical analysis of the 'green bentonite' reveals an increase of iron fraction e.g. from 3.4% mass to 9.3% mass . The adsorbed iron is predominantly Fe(II) which was proven by chromato-metric titration. The estimated ratio between silicon to increased iron content is Si: Fe ≅ 2

  7. Thermodynamic modelling of clay dehydration, stability and compositional evolution with temperature, pressure and H2O activity

    International Nuclear Information System (INIS)

    Vidal, O.; Dubacq, B.

    2010-01-01

    Document available in extended abstract form only. Full text of publication follows: The evaluation of the performance of clay-rich barrier considered for the disposal of radioactive waste and a reliable prediction of the impact of repository-induced disturbances upon the confinement properties of clay-rich geological formations requires reliable thermodynamic models for clay minerals. Such models have to take into account the variation of the hydration state of smectite as a function of temperature, pressure and water activity. We propose the first macroscopic thermodynamic model that account for the stepwise dehydration with increasing temperature or decreasing H 2 O activity of K, Na, Ca and Mg-smectite. The model relies on the relative stability of the different solid-solutions that describe the hydration of di- or tri-octahedral-smectites containing 0, 1, 2 or 3 interlayer water layers. The inclusion of anhydrous mica end-members makes it possible to cover, with the same solid-solution model, the entire range of composition from low-charge to high-charge smectite, through illite to mica. Non-ideal Margules parameters were used to describe the non-ideality of the solid solutions between the hydrated and dehydrated smectite end-members. Standard state properties of all smectite end-members as well as Ca- and Mg-muscovite and -phlogopite were initially estimated by oxide summation. These values were then refined and the other non-ideal interactions were estimated on the basis of different experimental data. The stepwise dehydration of smectite, and its stability and compatibility relations were calculated by Gibbs free energy minimizing. Our results account for the progressive evolution of smectite to inter-layered illite/smectite and then to mica, as observed in nature and experiments, and our model provides an explanation for the thermodynamic stability of smectite and illite/ smectite compared to mica + kaolinite or pyrophyllite assemblages. The results

  8. Influence of smectites on resistivity of rocks and soils; Smectite nendo kobutsu ga ganseki dojo no hi teiko ni oyobosu eikyo

    Energy Technology Data Exchange (ETDEWEB)

    Takakura, S; Nishizawa, O; Aoki, M [Geological Survey of Japan, Tsukuba (Japan); Kozake, K [University of Tsukuba, Ibaraki (Japan)

    1996-10-01

    This paper illustrates the measurement results of resistivity for specimens including smectite clay minerals artificially synthesized, and also discusses the influence of smectites on resistivity. Three kinds of bentonites, i.e., KN-1, Kawasaki ore, and Kawasaki Sanhaku, were used for preparing smectites. The KN-1 is Na type smectite, the Kawasaki ore is Ca type smectite, and the Kawasaki Sanhaku is acid clay. It is well known that smectites lower the resistivity of rocks. However, the experimental results suggested that the degree of decreasing the resistivity depends on the kind of smectites. The effect of decreasing the resistivity by the KN-1 was much superior to the other smectites. For the KN-1, a thick electrical double layer was formed by Na ions in the interlayers, which resulted in the larger effect of decreasing the resistivity. Swelling capacity and cation exchange capacity (CEC) of the KN-1 were large, which agreed with the above mentioned consideration. Reversely, it was considered that smectites having larger effect of decreasing the resistivity exhibited larger swelling capacity and CEC. 4 refs., 3 figs.

  9. Atomistic simulations of cation hydration in sodium and calcium montmorillonite nanopores

    Science.gov (United States)

    Yang, Guomin; Neretnieks, Ivars; Holmboe, Michael

    2017-08-01

    During the last four decades, numerous studies have been directed to the swelling smectite-rich clays in the context of high-level radioactive waste applications and waste-liners for contaminated sites. The swelling properties of clay mineral particles arise due to hydration of the interlayer cations and the diffuse double layers formed near the negatively charged montmorillonite (MMT) surfaces. To accurately study the cation hydration in the interlayer nanopores of MMT, solvent-solute and solvent-clay surface interactions (i.e., the solvation effects and the shape effects) on the atomic level should be taken into account, in contrast to many recent electric double layer based methodologies using continuum models. Therefore, in this research we employed fully atomistic simulations using classical molecular dynamics (MD) simulations, the software package GROMACS along with the CLAYFF forcefield and the SPC/E water model. We present the ion distributions and the deformation of the hydrated coordination structures, i.e., the hydration shells of Na+ and Ca2+ in the interlayer, respectively, for MMT in the first-layer, the second-layer, the third-layer, the fourth-layer, and the fifth-layer (1W, 2W, 3W, 4W, and 5W) hydrate states. Our MD simulations show that Na+ in Na-MMT nanopores have an affinity to the ditrigonal cavities of the clay layers and form transient inner-sphere complexes at about 3.8 Å from clay midplane at water contents less than the 5W hydration state. However, these phenomena are not observed in Ca-MMT regardless of swelling states. For Na-MMT, each Na+ is coordinated to four water molecules and one oxygen atom of the clay basal-plane in the first hydration shell at the 1W hydration state, and with five to six water molecules in the first hydration shell within a radius of 3.1 Å at all higher water contents. In Ca-MMT, however each Ca2+ is coordinated to approximately seven water molecules in the first hydration shell at the 1W hydration state and

  10. Molecular dynamics simulations of the three-layer hydrate of Na-montmorillonite

    International Nuclear Information System (INIS)

    Holmboe, Michael; Bourg, Ian C.

    2012-01-01

    Document available in extended abstract form only. In many nuclear waste repositories concepts, compacted and smectite-rich bentonite clay is considered as an engineered transport barrier surrounding the canisters holding the nuclear waste. One of the requirements in the safety assessment of these repositories is to predict the transport rate of radionuclides as well as the overall hydraulic conductivity through the bentonite barrier. Kozaki and co-workers have obtained important information from diffusion experiments in bentonite on the mechanisms that control solute transport by studying the temperature-dependence of apparent diffusivity for solutes such as Na + , Cs + and Sr 2+ . Their results showed that the apparent diffusivity follows an Arrhenius relation (ln D a ∝ -E A /RT) with distinct activation energies of diffusion (E A ) for certain montmorillonite compactions, ionic strengths, and types of interlayer cation (Na + vs. Ca 2+ ). Their results suggest that solutes follow different diffusion pathways in compacted montmorillonite at different experimental conditions. In order to identify these transport pathways in compacted montmorillonite one needs independent knowledge of the relative abundance of the different types of interlayer nano-pores, i.e. the different coexisting hydration states (1W-3W), and of the molecular-scale EA for solute diffusion on the external basal surfaces of montmorillonite particles and in the interlayer nano-pores. The latter property can be obtained using molecular dynamics (MD) simulations, an important tool in the characterization of clays and clay minerals that yields detailed atomistic insights into the structural, dynamical and thermodynamic properties of many different geochemically relevant systems. In particular, MD simulations yield insight into the behavior of individual atoms, where most experimental methods only would probe the average behavior of large numbers of atoms or molecules. Thus, by simulating systems of

  11. Sugar-influenced water diffusion, interaction, and retention in clay interlayer nanopores probed by theoretical simulations and experimental spectroscopies

    Science.gov (United States)

    Aristilde, Ludmilla; Galdi, Stephen M.; Kelch, Sabrina E.; Aoki, Thalia G.

    2017-08-01

    Understanding the hydrodynamics in clay nanopores is important for gaining insights into the trapping of water, nutrients, and contaminants in natural and engineered soils. Previous investigations have focused on the interlayer organization and molecular diffusion coefficients (D) of cations and water molecules in cation-saturated interlayer nanopores of smectite clays. Little is known, however, about how these interlayer dynamic properties are influenced by the ubiquitous presence of small organic compounds such as sugars in the soil environment. Here we probed the effects of glucose molecules on montmorillonite interlayer properties. Molecular dynamics simulations revealed re-structuring of the interlayer organization of the adsorptive species. Water-water interactions were disrupted by glucose-water H-bonding interactions. ;Dehydration; of the glucose-populated nanopore led to depletion in the Na solvation shell, which resulted in the accumulation of both Na ions (as inner-sphere complexes) and remaining hydrated water molecules at the mineral surface. This accumulation led to a decrease in both DNa and Dwater. In addition, the reduction in Dglucose as a function of increasing glucose content can be explained by the aggregation of glucose molecules into organic clusters H-bonded to the mineral surface on both walls of the nanopore. Experimental nuclear magnetic resonance and X-ray diffraction data were consistent with the theoretical predictions. Compared to clay interlayers devoid of glucose, increased intensities and new peaks in the 23Na nuclear magnetic resonance spectra confirmed increasing immobilization of Na as a function of increasing glucose content. And, the X-ray diffraction data indicated a reduced collapse of glucose-populated interlayers exposed to decreasing moisture conditions, which led to the maintenance of hydrated clay nanopores. The coupling of theoretical and experimental findings sheds light on the molecular to nanoscale mechanisms that

  12. The effect of pH on the stability of smectite

    International Nuclear Information System (INIS)

    Johnston, R.M.; Miller, H.G.

    1984-11-01

    The hydrothermal stability of smectite at temperatures less than 275 degrees C was investigated experimentally over a range of pH values. In the near-neutral pH region, the smectite to illite conversion predominated; in the mildly acid region, there was extensive formation of aluminum hydroxy interlayers in the clay; and in the alkaline region, framework silicates (feldspar and zeolites) were produced. The geological evidence for these reactions is also reviewed

  13. Interaction of calcium silicate hydrates (C-S-H), the main components of cement, with alkaline chlorides, analogy with clays; Interaction des silicates de calcium hydrates, principaux constituants du ciment, avec les chlorures d'alcalins. Analogie avec les argiles

    Energy Technology Data Exchange (ETDEWEB)

    Viallis-Terrisse, H

    2000-10-06

    This work, belonging to a more general study on the structure and reactivity of cement, deals with the experimental and theoretical analysis of the interaction of alkaline chlorides with calcium silicate hydrates (C-S-H), the main components of cement paste. The interaction of alkaline cations with C-S-H is interfacial, involving both electrostatic and surface complexation mechanisms. The C-S-H surface is constituted of silanol sites, partially dissociated due to the high pH of the interstitial solution. The calcium ions, present in large amounts in the equilibrium solution of C-S-H, constitute potential determining ions for the C-S-H surface. The alkaline ions seem to compete with calcium for the same surface sites. The adsorption isotherms show that caesium presents a better affinity than sodium and lithium for the C-S-H surface. Moreover, solid-state NMR suggests that caesium forms with the surface sites inner-sphere complexes, whereas sodium seems to keep its hydration sphere. These results are in agreement with zeta potential measurements, which let suppose a specific adsorption of caesium ions, and an indifferent behaviour of both other alkaline ions. A model for the C-S-H surface was proposed, from the electric double layer model, and mass action laws expressing the complexation of the different ionic species with the silanol sites. The whole study relies on a structural analogy with smectites, some clays presenting well-known cationic adsorption properties. The structural similarity between both minerals is enhanced by some similarities of reactivity, though significant behaviour differences could also be noted. (author)

  14. Ionic strength-induced formation of smectite quasicrystals enhances nitroaromatic compound sorption.

    Science.gov (United States)

    Li, Hui; Pereira, Tanya R; Teppen, Brian J; Laird, David A; Johnston, Cliff T; Boyd, Stephen A

    2007-02-15

    Sorption of organic contaminants by soils is a determinant controlling their transport and fate in the environment. The influence of ionic strength on nitroaromatic compound sorption by K+- and Ca2+ -saturated smectite was examined. Sorption of 1,3-dinitrobenzene by K-smectite increased as KCl ionic strength increased from 0.01 to 0.30 M. In contrast, sorption by Ca-smectite at CaCl2 ionic strengths of 0.015 and 0.15 M remained essentially the same. The "salting-out" effect on the decrease of 1,3-dinitrobenzene aqueous solubility within this ionic strength range was smectite with increasing KCl ionic strength. X-ray diffraction patterns and light absorbance of K-clay suspensions indicated the aggregation of clay particles and the formation of quasicrystal structures as KCI ionic strength increased. Sorption enhancement is attributed to the formation of better-ordered K-clay quasicrystals with reduced interlayer distances rather than to the salting-out effect. Dehydration of 1,3-dinitrobenzene is apparently a significant driving force for sorption, and we show for the first time that sorption of small, planar, neutral organic molecules, namely, 1,3-dinitrobenzene, causes previously expanded clay interlayers to dehydrate and collapse in aqueous suspension.

  15. Sorption characteristics of radioactive cesium and strontium on smectite

    International Nuclear Information System (INIS)

    Ohnuki, Toshihiko; Kozai, Naofumi

    1994-01-01

    Sorption of 137 Cs and 85 Sr on smectite has been studied by combining sorption and desorption experiments. In the desorption experiments, the 137 Cs and 85 Sr were desorbed from the smectite by 0.1 N different desorption reagents solution of Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ and Ba 2+ . The effects of Cs and Sr concentrations on sorption were examined by desorption experiments using 1 N KCl as a desorption reagent over a Cs and Sr concentrations range from 10 -8 to 1 N (saturated). All of Sr sorbed was desorbed with a 1 N KCl solution over Sr concentrations range of 10 -8 and 1 M. Approximately 50% of the 137 Cs sorbed at a concentration of 10 -8 M was desorbed with a 1 N KCl solution, and the fraction desorbed increased with increasing a Cs concentration. These results show that all Sr was reversibly sorbed on smectite, and a fraction of Cs was irreversibly sorbed on smectite. Thus, smectite has reversible sorption sites for Sr and both reversible and irreversible sorption sites for Cs. The fractions of Sr desorbed were related to the products of an ionic radius and charge of a desorption reagent, and those of Cs were related to the hydration energy. These results suggest that sorbed Sr and Cs reversibly on smectite form hydrated and dehydrated ions, respectively. (orig.)

  16. Interaction of calcium silicate hydrates (C-S-H), the main components of cement, with alkaline chlorides, analogy with clays

    International Nuclear Information System (INIS)

    Viallis-Terrisse, H.

    2000-01-01

    This work, belonging to a more general study on the structure and reactivity of cement, deals with the experimental and theoretical analysis of the interaction of alkaline chlorides with calcium silicate hydrates (C-S-H), the main components of cement paste. The interaction of alkaline cations with C-S-H is interfacial, involving both electrostatic and surface complexation mechanisms. The C-S-H surface is constituted of silanol sites, partially dissociated due to the high pH of the interstitial solution. The calcium ions, present in large amounts in the equilibrium solution of C-S-H, constitute potential determining ions for the C-S-H surface. The alkaline ions seem to compete with calcium for the same surface sites. The adsorption isotherms show that caesium presents a better affinity than sodium and lithium for the C-S-H surface. Moreover, solid-state NMR suggests that caesium forms with the surface sites inner-sphere complexes, whereas sodium seems to keep its hydration sphere. These results are in agreement with zeta potential measurements, which let suppose a specific adsorption of caesium ions, and an indifferent behaviour of both other alkaline ions. A model for the C-S-H surface was proposed, from the electric double layer model, and mass action laws expressing the complexation of the different ionic species with the silanol sites. The whole study relies on a structural analogy with smectites, some clays presenting well-known cationic adsorption properties. The structural similarity between both minerals is enhanced by some similarities of reactivity, though significant behaviour differences could also be noted. (author)

  17. Mineralogy of a Mudstone at Yellowknife Bay, Gale Crater, Mars

    Science.gov (United States)

    Vaniman, D. T.; Bish, D. L.; Ming, D. W.; Bristow, T. F.; Morris, R. V.; Blake, D. F.; Chipera, S. J.; Morrison, S. M.; Treiman, A. H.; Rampe, E. B.; Rice, M.; Achilles, C. N.; Grotzinger, J. P.; McLennan, S. M.; Williams, J.; Bell, J. F.; Newsom, H. E.; Downs, R. T.; Maurice, S.; Sarrazin, P.; Yen, A. S.; Morookian, J. M.; Farmer, J. D.; Stack, K.; Milliken, R. E.; Ehlmann, B. L.; Sumner, D. Y.; Berger, G.; Crisp, J. A.; Hurowitz, J. A.; Anderson, R.; Des Marais, D. J.; Stolper, E. M.; Edgett, K. S.; Gupta, S.; Spanovich, N.; Agard, Christophe; Alves Verdasca, José Alexandre; Anderson, Ryan; Archer, Doug; Armiens-Aparicio, Carlos; Arvidson, Ray; Atlaskin, Evgeny; Atreya, Sushil; Aubrey, Andrew; Baker, Burt; Baker, Michael; Balic-Zunic, Tonci; Baratoux, David; Baroukh, Julien; Barraclough, Bruce; Bean, Keri; Beegle, Luther; Behar, Alberto; Bender, Steve; Benna, Mehdi; Bentz, Jennifer; Berger, Jeff; Berman, Daniel; Blanco Avalos, Juan J.; Blaney, Diana; Blank, Jen; Blau, Hannah; Bleacher, Lora; Boehm, Eckart; Botta, Oliver; Böttcher, Stephan; Boucher, Thomas; Bower, Hannah; Boyd, Nick; Boynton, Bill; Breves, Elly; Bridges, John; Bridges, Nathan; Brinckerhoff, William; Brinza, David; Brunet, Claude; Brunner, Anna; Brunner, Will; Buch, Arnaud; Bullock, Mark; Burmeister, Sönke; Cabane, Michel; Calef, Fred; Cameron, James; Campbell, John “Iain”; Cantor, Bruce; Caplinger, Michael; Caride Rodríguez, Javier; Carmosino, Marco; Carrasco Blázquez, Isaías; Charpentier, Antoine; Choi, David; Clark, Benton; Clegg, Sam; Cleghorn, Timothy; Cloutis, Ed; Cody, George; Coll, Patrice; Conrad, Pamela; Coscia, David; Cousin, Agnès; Cremers, David; Cros, Alain; Cucinotta, Frank; d'Uston, Claude; Davis, Scott; Day, Mackenzie “Kenzie”; de la Torre Juarez, Manuel; DeFlores, Lauren; DeLapp, Dorothea; DeMarines, Julia; Dietrich, William; Dingler, Robert; Donny, Christophe; Drake, Darrell; Dromart, Gilles; Dupont, Audrey; Duston, Brian; Dworkin, Jason; Dyar, M. Darby; Edgar, Lauren; Edwards, Christopher; Edwards, Laurence; Ehresmann, Bent; Eigenbrode, Jen; Elliott, Beverley; Elliott, Harvey; Ewing, Ryan; Fabre, Cécile; Fairén, Alberto; Farley, Ken; Fassett, Caleb; Favot, Laurent; Fay, Donald; Fedosov, Fedor; Feldman, Jason; Feldman, Sabrina; Fisk, Marty; Fitzgibbon, Mike; Flesch, Greg; Floyd, Melissa; Flückiger, Lorenzo; Forni, Olivier; Fraeman, Abby; Francis, Raymond; François, Pascaline; Franz, Heather; Freissinet, Caroline; French, Katherine Louise; Frydenvang, Jens; Gaboriaud, Alain; Gailhanou, Marc; Garvin, James; Gasnault, Olivier; Geffroy, Claude; Gellert, Ralf; Genzer, Maria; Glavin, Daniel; Godber, Austin; Goesmann, Fred; Goetz, Walter; Golovin, Dmitry; Gómez Gómez, Felipe; Gómez-Elvira, Javier; Gondet, Brigitte; Gordon, Suzanne; Gorevan, Stephen; Grant, John; Griffes, Jennifer; Grinspoon, David; Guillemot, Philippe; Guo, Jingnan; Guzewich, Scott; Haberle, Robert; Halleaux, Douglas; Hallet, Bernard; Hamilton, Vicky; Hardgrove, Craig; Harker, David; Harpold, Daniel; Harri, Ari-Matti; Harshman, Karl; Hassler, Donald; Haukka, Harri; Hayes, Alex; Herkenhoff, Ken; Herrera, Paul; Hettrich, Sebastian; Heydari, Ezat; Hipkin, Victoria; Hoehler, Tori; Hollingsworth, Jeff; Hudgins, Judy; Huntress, Wesley; Hviid, Stubbe; Iagnemma, Karl; Indyk, Steve; Israël, Guy; Jackson, Ryan; Jacob, Samantha; Jakosky, Bruce; Jensen, Elsa; Jensen, Jaqueline Kløvgaard; Johnson, Jeffrey; Johnson, Micah; Johnstone, Steve; Jones, Andrea; Jones, John; Joseph, Jonathan; Jun, Insoo; Kah, Linda; Kahanpää, Henrik; Kahre, Melinda; Karpushkina, Natalya; Kasprzak, Wayne; Kauhanen, Janne; Keely, Leslie; Kemppinen, Osku; Keymeulen, Didier; Kim, Myung-Hee; Kinch, Kjartan; King, Penny; Kirkland, Laurel; Kocurek, Gary; Koefoed, Asmus; Köhler, Jan; Kortmann, Onno; Kozyrev, Alexander; Krezoski, Jill; Krysak, Daniel; Kuzmin, Ruslan; Lacour, Jean Luc; Lafaille, Vivian; Langevin, Yves; Lanza, Nina; Lasue, Jeremie; Le Mouélic, Stéphane; Lee, Ella Mae; Lee, Qiu-Mei; Lees, David; Lefavor, Matthew; Lemmon, Mark; Malvitte, Alain Lepinette; Leshin, Laurie; Léveillé, Richard; Lewin-Carpintier, Éric; Lewis, Kevin; Li, Shuai; Lipkaman, Leslie; Little, Cynthia; Litvak, Maxim; Lorigny, Eric; Lugmair, Guenter; Lundberg, Angela; Lyness, Eric; Madsen, Morten; Mahaffy, Paul; Maki, Justin; Malakhov, Alexey; Malespin, Charles; Malin, Michael; Mangold, Nicolas; Manhes, Gérard; Manning, Heidi; Marchand, Geneviève; Marín Jiménez, Mercedes; Martín García, César; Martin, Dave; Martin, Mildred; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F. Javier; Mauchien, Patrick; McAdam, Amy; McCartney, Elaina; McConnochie, Timothy; McCullough, Emily; McEwan, Ian; McKay, Christopher; McNair, Sean; Melikechi, Noureddine; Meslin, Pierre-Yves; Meyer, Michael; Mezzacappa, Alissa; Miller, Hayden; Miller, Kristen; Minitti, Michelle; Mischna, Michael; Mitrofanov, Igor; Moersch, Jeff; Mokrousov, Maxim; Molina Jurado, Antonio; Moores, John; Mora-Sotomayor, Luis; Mueller-Mellin, Reinhold; Muller, Jan-Peter; Muñoz Caro, Guillermo; Nachon, Marion; Navarro López, Sara; Navarro-González, Rafael; Nealson, Kenneth; Nefian, Ara; Nelson, Tony; Newcombe, Megan; Newman, Claire; Nikiforov, Sergey; Niles, Paul; Nixon, Brian; Noe Dobrea, Eldar; Nolan, Thomas; Oehler, Dorothy; Ollila, Ann; Olson, Timothy; Owen, Tobias; de Pablo Hernández, Miguel Ángel; Paillet, Alexis; Pallier, Etienne; Palucis, Marisa; Parker, Timothy; Parot, Yann; Patel, Kiran; Paton, Mark; Paulsen, Gale; Pavlov, Alex; Pavri, Betina; Peinado-González, Verónica; Pepin, Robert; Peret, Laurent; Perez, Rene; Perrett, Glynis; Peterson, Joe; Pilorget, Cedric; Pinet, Patrick; Pla-García, Jorge; Plante, Ianik; Poitrasson, Franck; Polkko, Jouni; Popa, Radu; Posiolova, Liliya; Posner, Arik; Pradler, Irina; Prats, Benito; Prokhorov, Vasily; Purdy, Sharon Wilson; Raaen, Eric; Radziemski, Leon; Rafkin, Scot; Ramos, Miguel; Raulin, François; Ravine, Michael; Reitz, Günther; Rennó, Nilton; Richardson, Mark; Robert, François; Robertson, Kevin; Rodriguez Manfredi, José Antonio; Romeral-Planelló, Julio J.; Rowland, Scott; Rubin, David; Saccoccio, Muriel; Salamon, Andrew; Sandoval, Jennifer; Sanin, Anton; Sans Fuentes, Sara Alejandra; Saper, Lee; Sautter, Violaine; Savijärvi, Hannu; Schieber, Juergen; Schmidt, Mariek; Schmidt, Walter; Scholes, Daniel “Dan”; Schoppers, Marcel; Schröder, Susanne; Schwenzer, Susanne; Sebastian Martinez, Eduardo; Sengstacken, Aaron; Shterts, Ruslan; Siebach, Kirsten; Siili, Tero; Simmonds, Jeff; Sirven, Jean-Baptiste; Slavney, Susie; Sletten, Ronald; Smith, Michael; Sobrón Sánchez, Pablo; Spray, John; Squyres, Steven; Stalport, Fabien; Steele, Andrew; Stein, Thomas; Stern, Jennifer; Stewart, Noel; Stipp, Susan Louise Svane; Stoiber, Kevin; Sucharski, Bob; Sullivan, Rob; Summons, Roger; Sun, Vivian; Supulver, Kimberley; Sutter, Brad; Szopa, Cyril; Tan, Florence; Tate, Christopher; Teinturier, Samuel; ten Kate, Inge; Thomas, Peter; Thompson, Lucy; Tokar, Robert; Toplis, Mike; Torres Redondo, Josefina; Trainer, Melissa; Tretyakov, Vladislav; Urqui-O'Callaghan, Roser; Van Beek, Jason; Van Beek, Tessa; VanBommel, Scott; Varenikov, Alexey; Vasavada, Ashwin; Vasconcelos, Paulo; Vicenzi, Edward; Vostrukhin, Andrey; Voytek, Mary; Wadhwa, Meenakshi; Ward, Jennifer; Webster, Chris; Weigle, Eddie; Wellington, Danika; Westall, Frances; Wiens, Roger Craig; Wilhelm, Mary Beth; Williams, Amy; Williams, Rebecca; Williams, Richard B. “Mouser”; Wilson, Mike; Wimmer-Schweingruber, Robert; Wolff, Mike; Wong, Mike; Wray, James; Wu, Megan; Yana, Charles; Yingst, Aileen; Zeitlin, Cary; Zimdar, Robert; Zorzano Mier, María-Paz

    2014-01-01

    Sedimentary rocks at Yellowknife Bay (Gale crater) on Mars include mudstone sampled by the Curiosity rover. The samples, John Klein and Cumberland, contain detrital basaltic minerals, calcium sulfates, iron oxide or hydroxides, iron sulfides, amorphous material, and trioctahedral smectites. The John Klein smectite has basal spacing of ~10 angstroms, indicating little interlayer hydration. The Cumberland smectite has basal spacing at both ~13.2 and ~10 angstroms. The larger spacing suggests a partially chloritized interlayer or interlayer magnesium or calcium facilitating H2O retention. Basaltic minerals in the mudstone are similar to those in nearby eolian deposits. However, the mudstone has far less Fe-forsterite, possibly lost with formation of smectite plus magnetite. Late Noachian/Early Hesperian or younger age indicates that clay mineral formation on Mars extended beyond Noachian time.

  18. Mineralogy of a mudstone at Yellowknife Bay, Gale crater, Mars.

    Science.gov (United States)

    Vaniman, D T; Bish, D L; Ming, D W; Bristow, T F; Morris, R V; Blake, D F; Chipera, S J; Morrison, S M; Treiman, A H; Rampe, E B; Rice, M; Achilles, C N; Grotzinger, J P; McLennan, S M; Williams, J; Bell, J F; Newsom, H E; Downs, R T; Maurice, S; Sarrazin, P; Yen, A S; Morookian, J M; Farmer, J D; Stack, K; Milliken, R E; Ehlmann, B L; Sumner, D Y; Berger, G; Crisp, J A; Hurowitz, J A; Anderson, R; Des Marais, D J; Stolper, E M; Edgett, K S; Gupta, S; Spanovich, N

    2014-01-24

    Sedimentary rocks at Yellowknife Bay (Gale crater) on Mars include mudstone sampled by the Curiosity rover. The samples, John Klein and Cumberland, contain detrital basaltic minerals, calcium sulfates, iron oxide or hydroxides, iron sulfides, amorphous material, and trioctahedral smectites. The John Klein smectite has basal spacing of ~10 angstroms, indicating little interlayer hydration. The Cumberland smectite has basal spacing at both ~13.2 and ~10 angstroms. The larger spacing suggests a partially chloritized interlayer or interlayer magnesium or calcium facilitating H2O retention. Basaltic minerals in the mudstone are similar to those in nearby eolian deposits. However, the mudstone has far less Fe-forsterite, possibly lost with formation of smectite plus magnetite. Late Noachian/Early Hesperian or younger age indicates that clay mineral formation on Mars extended beyond Noachian time.

  19. Microbial Effects in Promoting the Smectite to Illite Reaction: Role of Organic Matter Intercalated in the Interlayer

    Science.gov (United States)

    2007-01-01

    American Mineralogist, Volume 92. pages 1401-1410, 2007 Microbial effects in promoting the smectite to illite reaction: Role of organic matter...rich smectite (non- tronile, NAu-2). The illitization of these intercalated smectites as induced by microbial reduction of structural Fe" was...transmission electron microscopy did not detect any discrete illite, although illite/ smectite mixed layer or high charge smectite phases were observed. In

  20. Sorption and desorption of carbamazepine from water by smectite clays.

    Science.gov (United States)

    Zhang, Weihao; Ding, Yunjie; Boyd, Stephen A; Teppen, Brian J; Li, Hui

    2010-11-01

    Carbamazepine is a prescription anticonvulsant and mood stabilizing pharmaceutical administered to humans. Carbamazepine is persistent in the environment and frequently detected in water systems. In this study, sorption and desorption of carbamazepine from water was measured for smectite clays with the surface negative charges compensated with K+, Ca2+, NH4+, tetramethylammonium (TMA), trimethylphenylammonium (TMPA) and hexadecyltrimethylammonium (HDTMA) cations. The magnitude of sorption followed the order: TMPA-smectite≥HDTMA-smectite>NH4-smectite>K-smectite>Ca-smectite⩾TMA-smectite. The greatest sorption of carbamazepine by TMPA-smectite is attributed to the interaction of conjugate aromatic moiety in carbamazepine with the phenyl ring in TMPA through π-π interaction. Partitioning process is the primary mechanism for carbamazepine uptake by HDTMA-smectite. For NH4-smectite the urea moiety in carbamazepine interacts with exchanged cation NH4+ by H-bonding hence demonstrating relatively higher adsorption. Sorption by K-, Ca- and TMA-smectites from water occurs on aluminosilicate mineral surfaces. These results implicate that carbamazepine sorption by soils occurs primarily in soil organic matter, and soil mineral fractions play a secondary role. Desorption of carbamazepine from the sorbents manifested an apparent hysteresis. Increasing irreversibility of desorption vs. sorption was observed for K-, Ca-, TMA-, TMPA- and HDTMA-clays as aqueous carbamazepine concentrations increased. Desorption hysteresis of carbamazepine from K-, Ca-, NH4-smectites was greater than that from TMPA- and HDTMA-clays, suggesting that the sequestrated carbamazepine molecules in smectite interlayers are more resistant to desorption compared to those sorbed by organic phases in smectite clays. Copyright © 2010 Elsevier Ltd. All rights reserved.

  1. Probing the microscopic hydrophobicity of smectite surfaces. A vibrational spectroscopic study of dibenzo-p-dioxin sorption to smectite.

    Science.gov (United States)

    Rana, Kiran; Boyd, Stephen A; Teppen, Brian J; Li, Hui; Liu, Cun; Johnston, Cliff T

    2009-04-28

    The interaction of dibenzo-p-dioxin (DD), from aqueous suspension, with smectite was investigated using in situ vibrational spectroscopy (FTIR and Raman), structural and batch sorption techniques. Batch sorption isotherms were integrated with in situ attenuated total reflectance (ATR)-FTIR and Raman spectroscopy and X-ray diffraction. Sorption isotherms revealed that the affinity of DD for smectite in aqueous suspension was strongly influenced both by the type of smectite and by the nature of the exchangeable cation. Cs-saponite showed a much higher affinity over Rb-, K- and Na-exchange saponites. In addition, DD sorption was found to depend on clay type with DD showing a high affinity for the tetrahedrally substituted trioctahedral saponite over SWy-2 and Upton montmorillonites. A structural model is introduced to account for the influence of clay type. Raman and FTIR data provided complementary molecular-level insight into the sorption mechanisms. In the case of Cs-saponite, the selection rules of DD based on D(2h) symmetry were broken indicating a site-specific interaction between DD and intercalated Cs(+) ions in the interlayer of the clay. Polarized in situ ATR-FTIR spectra revealed that the molecular plane of sorbed DD was tilted with respect to the clay surface which was consistent with a d-spacing of 1.49 nm. Finally, cation-induced changes in both the skeletal ring vibrations and the asymmetric C-O-C stretching vibrations provided evidence for site specific interactions between the DD and exchangeable cations in the clay interlayer. Together, the combined macroscopic and spectroscopic data show a surprising link between a hydrophilic material and a planar hydrophobic aromatic hydrocarbon.

  2. Synthesis of Highly Reactive Subnano-sized Zero-valent Iron using Smectite Clay Templates

    Science.gov (United States)

    Gu, Cheng; Jia, Hanzhang; Li, Hui; Teppen, Brian J.; Boyd, Stephen A.

    2010-01-01

    A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH4, resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of discrete regions of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of ~ 5 Å. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the XRD results since the diameter of elemental Fe is 2.5 Å. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene:non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnano-scale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, e.g. as components of constructed reactive domains such as reactive caps for contaminated sediments. PMID:20446730

  3. Synthesis of highly reactive subnano-sized zero-valent iron using smectite clay templates.

    Science.gov (United States)

    Gu, Cheng; Jia, Hanzhong; Li, Hui; Teppen, Brian J; Boyd, Stephen A

    2010-06-01

    A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH(4), resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of approximately 5 A. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the X-ray diffraction (XRD) results since the diameter of elemental Fe is 2.5 A. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene/non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnanoscale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, for example, as components of constructed reactive domains such as reactive caps for contaminated sediments.

  4. Influence of Chemical, Physical, Biological and Geochemical Processes of Early Diagenesis and Material Exchange Across the Sediment/Seawater Interface in Margin Sediments

    National Research Council Canada - National Science Library

    Kastner, Miriam

    1997-01-01

    .... To this end, we provided high resolution characterizations of sediment microfabric, physical properties, chemistry, mineralogy, and organic matter content as well as theoretical work on smectite interlayer hydration...

  5. Relationship between interlayer hydration and photocatalytic water splitting of A'1-xNaxCa2Ta3O10.nH2O (A'=K and Li)

    International Nuclear Information System (INIS)

    Mitsuyama, Tomohiro; Tsutsumi, Akiko; Sato, Sakiko; Ikeue, Keita; Machida, Masato

    2008-01-01

    Partial replacement of alkaline metals in anhydrous KCa 2 Ta 3 O 10 and LiCa 2 Ta 3 O 10 was studied to control interlayer hydration and photocatalytic activity for water splitting under UV irradiation. A' 1-x Na x Ca 2 Ta 3 O 10 .nH 2 O (A'=K and Li) samples were synthesized by ion exchange of CsCa 2 Ta 3 O 10 in mixed molten nitrates at 400 deg. C. In K 1-x Na x Ca 2 Ta 3 O 10 .nH 2 O, two phases with the orthorhombic (C222) and tetragonal (I4/mmm) structures were formed at x≤0.7 and x≥0.5, respectively. Upon replacement by Na + having a larger enthalpy of hydration (ΔH h 0 ), the interlayer hydration occurred at x≥0.3 and the hydration number (n) was increased monotonically with an increase of x. Li 1-x Na x Ca 2 Ta 3 O 10 .nH 2 O showed a similar hydration behavior, but the phase was changed from I4/mmm (x 1-x Na x Ca 2 Ta 3 O 10 .nH 2 O exhibited the activity increasing in consistent with n, whereas Li 1-x Na x Ca 2 Ta 3 O 10 .nH 2 O exhibited the activity maximum at x=0.77, where the rates of H 2 /O 2 evolution were nearly doubled compared with those for end-member compositions (x=0 and 1). - Graphical abstract: The partial substitution of Na in the interlayer of anhydrous-layered perovskite has been found as useful structural modification toward highly active hydrated photocatalysts

  6. Interaction between tetracycline and smectite in aqueous solution.

    Science.gov (United States)

    Li, Zhaohui; Chang, Po-Hsiang; Jean, Jiin-Shuh; Jiang, Wei-Teh; Wang, Chih-Jen

    2010-01-15

    The fate and transport of commonly used antibiotics in soil and groundwater have attracted renewed studies due to increased sensitivities of analytical instruments and thus frequent detections of these compounds even in treated wastewater. Smectite, an important soil component, has large surface area and high cation exchange capacity, while tetracycline (TC) can exist in different forms and charges under different pH conditions. Thus, the interaction between smectite and TC in aqueous systems is of great importance. This research focused on elucidating the mechanisms of TC uptake by smectite, in terms of TC adsorption, cation desorption, and pH changes associated with TC adsorption by smectite and intercalation in smectite. TC adsorption onto smectite was a relatively fast process even though most of the adsorption sites were in the interlayer position involved in intercalation as confirmed by the expansion of d(001) spacing. The TC adsorption capacity was equivalent to 0.74-1.11 times the cation exchange capacity for three of the four smectite minerals studied. Accompanying TC adsorption was simultaneous adsorption of H(+), resulting in protonation of TC on the dimethylamine group. At higher TC input concentrations further adsorption of H(+) resulted in the ratio of H(+) adsorbed to TC adsorbed greater than one, suggesting that additionally adsorbed H(+) could serve as counterions to partially offset the negative charges on the tricarbonyl or phenolic diketone functional groups. The positive correlations between cations desorbed and TC adsorbed, as well as TC adsorbed and H(+) adsorbed, provided a first time evidence to confirm cation exchange as the main mechanism of TC uptake, even under neutral pH conditions.

  7. Transmission X-ray microscopy (TXM) reveals the nanostructure of a smectite gel.

    Science.gov (United States)

    Zbik, Marek S; Martens, Wayde N; Frost, Ray L; Song, Yen-Fang; Chen, Yi-Ming; Chen, Jian-Hua

    2008-08-19

    The unusual behavior of smectites, the ability to change volume when wetted (swelling) or dried (shrinking), makes soil rich in smectites very unstable and dangerous for the building industry because of the movement of building foundations and poor slope stability. These macroscopic properties are dominated by the structural arrangement of the smectites' finest fraction. Here, we show in three dimensions how the swelling phenomenon in smectite, caused by a combination of hydratation and electrostatic forces, may expand the dry smectite volume not 10-fold, as previously thought, but to more than 1000-fold. A new technique, transmission X-ray microscopy, makes it possible to investigate the internal structure and 3-D tomographic reconstruction of clay aggregates. This reveals, for the first time, the smectite gel arrangement in the voluminous cellular tactoid structure within a natural aqueous environment.

  8. New Composite Sorbents for Caesium and Strontium Ions Sorption

    Directory of Open Access Journals (Sweden)

    Mykola Kartel

    2017-06-01

    Full Text Available Composite lignocellulose-inorganic sorbents derived from plant residues of agriculture and food industry, modified with ferrocyanides of d-metals and hydrated antimony pentoxide were prepared. Caesium and strontium ions removal from water was tested by radiotracer method. Sorption of heavy metal ions, methylene blue, gelatin, vitamin B12 was also studied.

  9. Characterization of a hybrid-smectite nanomaterial formed by immobilizing of N-pyridin-2-ylmethylsuccinamic acid onto (3-aminopropyl)triethoxysilane modified smectite and its potentiometric sensor application

    Science.gov (United States)

    Topcu, Cihan; Caglar, Sema; Caglar, Bulent; Coldur, Fatih; Cubuk, Osman; Sarp, Gokhan; Gedik, Kubra; Bozkurt Cirak, Burcu; Tabak, Ahmet

    2016-09-01

    A novel N-pyridin-2-ylmethylsuccinamic acid-functionalized smectite nanomaterial was synthesized by immobilizing of N-pyridin-2-ylmethylsuccinamic acid through chemical bonding onto (3-aminopropyl)triethoxysilane modified smectite. The structural, thermal, morphological and surface properties of raw, silane-grafted and the N-pyridin-2-ylmethylsuccinamic acid-functionalized smectites were investigated by various characterization techniques. The thermal analysis data showed the presence of peaks in the temperature range from 200 °C to 600 °C due to the presence of physically adsorbed silanes, intercalated silanes, surface grafted silanes and chemically grafted silane molecules between the smectite layers. The powder x-ray diffraction patterns clearly indicated that the aminopropyl molecules also intercalated into the smectite interlayers as bilayer arrangement whereas N-pyridin-2-ylmethylsuccinamic acid molecules were only attached to 3-aminopropyltriethoxysilane molecules on the external surface and edges of clay and they did not intercalate. Fourier transform infrared spectroscopy confirms N-pyridin-2-ylmethylsuccinamic acid molecules bonding through the amide bond between the amine group of aminopropyltriethoxysilane molecules and a carboxylic acid functional group of N-pyridin-2-ylmethylsuccinamic acid molecules. The guest molecules functionalized onto the smectite caused significant alterations in the textural and morphological parameters of the raw smectite. The anchoring of N-pyridin-2-ylmethylsuccinamic acid molecules led to positive electrophoretic mobility values when compared to starting materials. N-pyridin-2-ylmethylsuccinamic acid-functionalized smectite was employed as an electroactive ingredient in the structure of potentiometric PVC-membrane sensor. The sensor exhibited more selective potentiometric response towards chlorate ions compared to the other common anionic species.

  10. Molecular Simulation Models of Carbon Dioxide Intercalation in Hydrated Sodium Montmorillonite

    Energy Technology Data Exchange (ETDEWEB)

    Myshakin, Evgeniy [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Saidi, Wissam [Univ. of Pittsburgh, PA (United States); Romanov, Vyacheslav [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Cygan, Randall [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Jordan, Kenneth [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Univ. of Pittsburgh, PA (United States); Guthrie, George [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-11-22

    In this study, classical molecular dynamics simulations and density functional theory (DFT)-based molecular dynamics are used to elucidate the process of CO2 intercalation into hydrated Na-montmorillonite at P-T conditions relevant to geological formations suitable for CO2 storage. Of particular interest are the structural and transport properties of interlayer species after CO2 intercalation. The conducted simulations allowed the research team to quantify expansion/contraction of smectite as a function of CO2 and H2O compositions. The resulting swelling curves can be used to gauge the amount of stored CO2, compare it to the experiment, and estimate changes in geomechanical properties of the storage formation. The obtained results showed that the infrared signal of the asymmetric stretch vibration of CO2 molecule is extremely sensitive to the solvent environment. The extent of the frequency shift relative to the gas-phase value can be used to probe hydration level in the interlayer with intercalated CO2. Interaction of supercritical CO2 with brine in deep geological formations promotes an increase of hydrophobicity of clay surfaces. As a result of wettability alteration, estimated diffusion constants of CO2 and H2O increase with the increased CO2 load; this can contribute to faster migration of CO2 throughout the formation.

  11. Chemical and physical stability of smectites and illite in electrolyte solutions: experimental study at 150 C

    International Nuclear Information System (INIS)

    Boutiche, M.

    1995-01-01

    Chemical interactions between electrolytic solutions commonly used i drilling muds and clays have been studies under P-T conditions similar to those of drillings (150 deg C) in order to determine the eventual consequences on the stability of clay rich formations. The experimental work has been carried out using several solutions (water, NaOH (pH 8, 10, 12), KCI (0,1, 1 2 mol./l), sea water, and K 2 CO 3 ) and clay minerals with low to high amounts of swelling layers (smectite (Na, Na-Ca, Ca), mixed layered illite-smectite minerals). Run products are studied by X-ray diffraction and electronic microprobe. Smectite layers show series of mineralogical changes (cation exchange in the interlayer site, formation of non-swelling layers, hydrolysis), which, however, do not yield to the formation of new minerals, except in the case of the interaction with K 2 CO 3 at 150 deg C (zeolite crystallisation). Cation exchange in the interlayer depends on the nature of the cation, cation concentration in the solution, exchange constants, and liquid/solid ratio. In dilute solutions ( 1 mol./l), because they favour the collapse of swelling layers, and dispersion. Solutions of K 2 CO 3 at 150 deg C are at the origin of the transformation of smectite to zeolites, and high pH - highly saline solutions are rather aggressive, and would probably not stabilize the argilites. (author)

  12. Factors that influence the design of modified clays - or how knowing your clay can save your day

    International Nuclear Information System (INIS)

    Gates, W.P.; Slade, P.G.

    1998-01-01

    tetrahedral sheets. Solvents (water, ethanol and toluene) were used to modify the basal spacings of the TMPA-clays, and changes to the orientation of TMPA in the interlayers were monitored with polarised FT-IR. The TMPA cation takes a different orientation in the interlayers of vermiculites than in those of smectites. For hydrated TMPA-vermiculites (layer charge X>0.7 e - per formula unit, predominantly tetrahedral), X-ray diffraction analysis indicates that the TMPA cation is orientated such that its A 1 symmetry axis is normal to the siloxane surface. In contrast, for hydrated TMPA smectites (X 1 symmetry axis parallel to the siloxane surface, but the plane of phenyl-ring (B 2 axis) varies from near normal (X∼0.55) to near parallel (X∼0.4) to the siloxane surface. However, clay type and solvent uptake also influence the orientation of organic cations where sufficient interlayer space exists. Hydration of the lower charged TMPA smectites with water or ethanol increased the d-spacing and causes the A 1 axis of TMPA to adopt a more inclined angle to the siloxane surface. Uptake of toluene only significantly increases the observed d-spacing of the lowest charged smectites, but results in the TMPA to orient with its B 2 axis parallel to the siloxane surface. Observed and calculated charge-space relations indicate that a layer charge density for smectites of Xμ0.7 e - per formula unit is required for TMPA to orientate in the manner observed for vermiculites. This value is the layer charge by which the smectites are classified separately from vermiculites

  13. Effects of Kapton Sample Cell Windows on the Detection Limit of Smectite: Implications for CheMin on the Mars Science Laboratory Mission

    Science.gov (United States)

    Achilles, C. N.; Ming, Douglas W.; Morris, R. V.; Blake, D. F.

    2012-01-01

    The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity is an X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of providing the mineralogical and chemical compositions of rocks and soils on the surface of Mars. CheMin uses a microfocus X-ray tube with a Co target, transmission geometry, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. CheMin has two different window materials used for sample cells -- Mylar and Kapton. Instrument details are provided elsewhere. Fe/Mg-smectite (e.g., nontronite) has been identified in Gale Crater, the MSL future landing site, by CRISM spectra. While large quantities of phyllosilicate minerals will be easily detected by CheMin, it is important to establish detection limits of such phases to understand capabilities and limitations of the instrument. A previous study indicated that the (001) peak of smectite at 15 Ang was detectable in a mixture of 1 wt.% smectite with olivine when Mylar is the window material for the sample cell. Complications arise when Kapton is the window material because Kapton itself also has a diffraction peak near 15 Ang (6.8 deg 2 Theta). This study presents results of mineral mixtures of smectite and olivine to determine smectite detection limits for Kapton sample cells. Because the intensity and position of the smectite (001) peak depends on the hydration state, we also analyzed mixtures with "hydrated" and "dehydrated"h smectite to examine the effects of hydration state on detection limits.

  14. Thermodynamic data of water on smectite surface and those applications to swelling pressure of compacted bentonite

    International Nuclear Information System (INIS)

    Sato, H.

    2009-01-01

    Swelling pressure was discussed focusing on the thermodynamic properties of water on smectite (montmorillonite) which is the major clay mineral constituent of the bentonite buffer. The thermodynamic data of the water on the smectite surface were obtained as a function of water content and temperature in a range of dry density 0.6-0.9 Mg/m 3 . Purified Na-smectite of which all interlayer cations were exchanged with Na+ ions, was used. The activity (a H 2 O ) and the relative partial molar Gibbs free energy (ΔG H 2 O ) of the water were obtained at 25 C. Both a H 2 O and ΔG H 2 O decreased with a decrease of water content, and similar results were obtained to data reported for montmorillonite (Kunipia-F bentonite). Since the specific surface area of smectite is about 800 m 2 /g, water up to approximately 2 water layers from smectite surface is thermodynamically evaluated to be bound. Swelling pressure versus smectite partial density was calculated based on ΔG H 2 O and compared to data experimentally obtained for various kinds of bentonites. The calculated results were in good agreement with the measured data over the range of smectite partial density between 1.0 and 2.0 Mg/m 3 . (author)

  15. Effects of smectite on the oil-expulsion efficiency of the Kreyenhagen Shale, San Joaquin Basin, California, based on hydrous-pyrolysis experiments

    Science.gov (United States)

    Lewan, Michael D.; Dolan, Michael P.; Curtis, John B.

    2014-01-01

    The amount of oil that maturing source rocks expel is expressed as their expulsion efficiency, which is usually stated in milligrams of expelled oil per gram of original total organic carbon (TOCO). Oil-expulsion efficiency can be determined by heating thermally immature source rocks in the presence of liquid water (i.e., hydrous pyrolysis) at temperatures between 350°C and 365°C for 72 hr. This pyrolysis method generates oil that is compositionally similar to natural crude oil and expels it by processes operative in the subsurface. Consequently, hydrous pyrolysis provides a means to determine oil-expulsion efficiencies and the rock properties that influence them. Smectite in source rocks has previously been considered to promote oil generation and expulsion and is the focus of this hydrous-pyrolysis study involving a representative sample of smectite-rich source rock from the Eocene Kreyenhagen Shale in the San Joaquin Basin of California. Smectite is the major clay mineral (31 wt. %) in this thermally immature sample, which contains 9.4 wt. % total organic carbon (TOC) comprised of type II kerogen. Compared to other immature source rocks that lack smectite as their major clay mineral, the expulsion efficiency of the Kreyenhagen Shale was significantly lower. The expulsion efficiency of the Kreyenhagen whole rock was reduced 88% compared to that of its isolated kerogen. This significant reduction is attributed to bitumen impregnating the smectite interlayers in addition to the rock matrix. Within the interlayers, much of the bitumen is converted to pyrobitumen through crosslinking instead of oil through thermal cracking. As a result, smectite does not promote oil generation but inhibits it. Bitumen impregnation of the rock matrix and smectite interlayers results in the rock pore system changing from water wet to bitumen wet. This change prevents potassium ion (K+) transfer and dissolution and precipitation reactions needed for the conversion of smectite to

  16. Illitization of Potassium, Cesium, and Ammonium Exchanged Smectite

    Science.gov (United States)

    Mills, M. M.; Wang, Y.; Payne, C.; Sanchez, A. C.; Boisvert, L.; Matteo, E. N.

    2017-12-01

    Bentonite clay is a primary choice for engineered barrier systems within geologic repositories for disposal of radioactive wastes due to its low permeability at saturated states, warranting diffusion as the dominant transport mechanism, and large swelling pressures that promote sealing. In order to predict how well the barrier will function over time at repository relevant temperatures, it is important to understand thermal alteration effects on montmorillonite, better known as smectite, a main constituent of bentonite. One type of thermal alteration is the conversion to illite, when exposed to elevated temperatures and a sufficient amount of potassium ions, thereby weakening barrier functions. To facilitate the conversion of smectite to illite and examine the influence of interlayer cations, illitization experiments on cation exchanged smectite were performed within hydrothermal reaction vessels over one week timescales. The detect any dissolved products and silica content. Results suggest the conversion rate is relatively fast, occurring within days, and is dependent on not only the amount of K, but also dissolved silica concentration related to total solid in solution. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. SAND2017-7856A

  17. Formation of a bioconjugate composed of hemin, smectite, and quaternary ammonium chloride that is soluble and active in hydrophobic media.

    Science.gov (United States)

    Kurosawa, Masaru; Itoh, Tetsuji; Kodera, Yoh; Matsushima, Ayako; Hiroto, Misao; Nishimura, Hiroyuki; Inada, Yuji

    2002-01-01

    Hemin (Fe(3+)) was adsorbed onto synthetic smectite (clay mineral) intercalated with a quaternary alkenylammonium compound, dioleyldimethylammonium chloride (DOA), to form a hemin-smectite-DOA conjugate. The hemin-smectite-DOA conjugate was soluble in organic solvents such as benzene and toluene to form a transparent colloidal solution with a light yellow color. Its absorption spectrum in benzene showed two bands, 600 and 568 nm, in the visible region and a sharp Soret band at 400 nm with the molar extinction coefficient of 7.5 x 10(4) M(-1) cm(-1). The formation of the conjugate of smectite and DOA was confirmed by X-ray diffraction analysis: the basal spacing, d(001), of hemin-smectite-DOA conjugate was 19 A which is an expansion of the interlayer space by 5 A based upon the basal spacing of smectite of 14 A. Hemin-smectite-DOA conjugate catalyzed the peroxidase-like reaction in organic solvents using benzoyl peroxide as the hydrogen acceptor and leucocrystal violet as the hydrogen donor. The temperature-dependent peroxidase-like activity of the conjugate was compared with peroxidase activity of horseradish peroxidase. The hemin-smectite-DOA conjugate exhibited higher activity as the temperature was increased from 30 to 70 degrees C, while horseradish peroxidase activity was reduced as the temperature was increased.

  18. Hydration behaviour of synthetic saponite at variable relative humidity

    Indian Academy of Sciences (India)

    Hydration behaviour of synthetic saponite was examined by X-ray powder diffraction simulation at various relative humidities (RH). The basal spacing of the Ca-saponite increased stepwise with increase in RH. The (00) reflections observed reflect single or dual hydration states of smectite. Quasi-rational, intermediate, or ...

  19. Interactions of oxytetracycline with a smectite clay: a spectroscopic study with molecular simulations.

    Science.gov (United States)

    Aristilde, Ludmilla; Marichal, Claire; Miéhé-Brendlé, Jocelyne; Lanson, Bruno; Charlet, Laurent

    2010-10-15

    Binding of antibiotics to clay minerals can decrease both their physical and biological availability in soils. To elucidate the binding mechanisms of tetracycline antibiotics on smectite clays as a function of pH, we probed the interactions of oxytetracycline (OTC) with Na-montmorillonite (MONT) using X-ray diffraction (XRD), infrared (IR), and solid-state nuclear magnetic resonance (NMR) spectroscopies, and Monte Carlo molecular simulations. The XRD patterns demonstrate the presence of OTC in the MONT interlayer space at acidic pH whereas complexation of OTC by external basal and edge sites seems to prevail at pH 8. At both pH, the (1)H-(13)C NMR profile indicates restricted mobility of the adsorbed OTC species; and, -CH(3) deformation and C-N stretching IR vibration bands confirm a binding mechanism involving the protonated dimethylamino group of OTC. Changes in the (23)Na NMR environments are consistent with cation-exchange and cation complexation reactions at the different sites of adsorption. Molecular simulations indicate that MONT interlayer spacing and structural charge localization dictate favorable binding conformations of the intercalated OTC, facilitating multiple interactions in agreement with the spectroscopic data. Our results present complementary insights into the mechanisms of adsorption of TETs on smectites important for their retention in natural and engineered soil environments.

  20. Enrofloxacin sorption on smectite clays: effects of pH, cations, and humic acid.

    Science.gov (United States)

    Yan, Wei; Hu, Shan; Jing, Chuanyong

    2012-04-15

    Enrofloxacin (ENR) occurs widely in natural waters because of its extensive use as a veterinary chemotherapeutic agent. To improve our understanding of the interaction of this emerging contaminant with soils and sediments, sorption of ENR on homoionic smectites and kaolinite was studied as a function of pH, ionic strength, exchangeable cations, and humic acid concentration. Batch experiments and in situ ATR-FTIR analysis suggested multiple sorption mechanisms. Cation exchange was a major contributor to the sorption of cationic ENR species on smectite. The decreased ENR sorption with increasing ionic strength indicated the formation of outer-sphere complexes. Exchangeable cations significantly influenced the sorption capacity, and the observed order was Csinterlayer intercalation is an important contributor to ENR sorption, while humic acid had a negligible contribution to the interlayer intercalation. The results of this study provide new insight into the molecular mechanisms of ENR sorption on clay minerals. Copyright © 2012 Elsevier Inc. All rights reserved.

  1. Structural stability of the smectite-doped lanthanum under high pressures and high temperatures

    International Nuclear Information System (INIS)

    Stefani, Vicente Fiorini

    2012-01-01

    Smectites are phyllosilicates that have a tetrahedron: octahedron structure ratio of 2:1, with high cation exchange capacity (CEC) in the interlayers. For these and other features, smectites have been used in many parts of the world as secondary barriers with the goal of containing a possible leak of radioactive elements in final disposal facilities for radioactive waste through cation exchange. Our aim in this work is to reach the cation exchange in calcium montmorillonite (smectite dioctahedral) by lanthanum to simulate trivalent radionuclides and to study the stability of this structure under high pressure and high temperature. To achieve high pressure it was used two different technique: DAC (Diamond Anvil Cell), achieving pressures up to 12GPa at room temperature and hydraulic press with a toroidal chamber profile to achieve pressures up to 7,7GPa and temperatures up to 900 degree C. The heating is achieved simultaneously by an electric system coupled in the hydraulic press. The outcomes show that the smectite structure doped with lanthanum remains stable under 12GPa at room temperature and 2.5GPa at 200 degree C. However, above 300 degree C at 2.5GPa the structure becomes a new phase of muscovite-like, rich of La, where it loses its interlayer water and turns out to be irreversible. Furthermore, it is important to point out that the higher temperature the better ordered is the structure and it is still stable under 7.7GPa and 900 degree C. Moreover, after all experiments the structure continues being dioctahedral. The new phase of muscovite-like, rich of La, in contact with a calcium solution remains partially unchanged, whereas the other part returns to the original structure (montmorillonite-Ca). The following analyses were performed: X-ray diffraction (XRD) for evaluating the spatial structure; Fourier transform infrared spectroscopy (FTIR) for getting information about the vibrational modes; scanning electron microscopy with dispersive Xray spectroscopy

  2. Adsorption of imidazolinone herbicides on smectite-humic acid and smectite-ferrihydrite associations.

    Science.gov (United States)

    Leone, P; Nègre, M; Gennari, M; Boero, V; Celis, R; Cornejo, J

    2002-01-16

    Adsorption of imazapyr (IMZ), imazethapyr (IMZT), and imazaquin (IMZQ) was studied on two smectite-humic acid and two smectite-ferrihydrite binary systems prepared by treating a Wyoming smectite with a humic acid extracted from soil (4 and 8% w/w of the smectite) and with just-precipitated synthetic ferrihydrite (8 and 16% w/w of the smectite). Adsorption of the three herbicides on the smectite was not measurable at pH >4.5, presumably because of negative charges on the surface of the smectite. Adsorption on the smectite-humic acid systems was also not measurable, presumably because of negative charges on the surface, despite the high affinity of the three herbicides for humic acid, the adsorption order of which was IMZ smectite-ferrihydrite systems and IMZQ smectite cannot adsorb herbicides, it modifies the adsorption capacity of ferrihydrite. The mutual interaction of active phases such as humic acid, ferrihydrite, and smectite alters the characteristics of the resulting surface and hence the adsorption process. Investigations of herbicide adsorption have been seen to produce more reliable results if conducted on polyphasic systems rather than on single soil components.

  3. Radiation-stability of smectite.

    Science.gov (United States)

    Sorieul, Stéphanie; Allard, Thierry; Wang, Lumin M; Grambin-Lapeyre, Caroline; Lian, Jie; Calas, Georges; Ewings, Rodney C

    2008-11-15

    The safety assessment of geological repositories for high-level nuclear waste and spent nuclear fuel requires an understanding of the response of materials to high temperatures and intense radiation fields. Clays, such as smectite, have been proposed as backfill material around waste packages, but their response to intense radiation from short-lived fission products and alpha decay of sorbed actinides remains poorly understood. Cumulative doses may amorphize clays and may alter their properties of sorption, swelling, or water retention. We describe the amorphization of smectites induced by electron and heavy ion irradiations to simulate ionizing radiation and alpha recoil nuclei, respectively. A new "bell-shaped" evolution of the amorphization dose with temperature has been determined. The maximum dose for amorphization occurs at about 300-400 degrees C, showing that temperature-induced dehydroxylation enhances amorphization. The exact shape of the bell-shaped curves depends on the interlayer cation. At ambient temperature, ionizing radiation and alpha-decay events do not show the same efficiency. The former results in amorphization at doses between 10(10)-10(11) Gy which are greater than the total radiation dose expected for radioactive waste over 10(6) years. In contrast, alpha-decay events amorphize clays at doses as low as 0.13-0.16 displacements per atom, i.e. doses consistent with nuclear waste accumulated over approximately 1000 yrs. However, the limited penetration of alpha particles and recoil nuclei, in the 100 nm - 20 microm range, will minimize damage. Clays will not be amorphized unless the waste package is breached and released actinides are heavily sorbed onto the clay overpack.

  4. Determination of caesium-137 in liquid milk

    International Nuclear Information System (INIS)

    Jankowska, S.

    1969-01-01

    A technique for determining caesium-137 in milk on the basis of caesium-137 sorption has been adapted according to the method of Broadbank. The caesium carrier is not added, because its addition decreases the sensitivity of measurement. Two procedures were used for the assay of caesium-137 in milk: (a) Sorption of caesium-137 from the solution of milk ash dissolved in 3M HNO 3 ; (b) Sorption of caesium-137 from whey. In both methods the radioactivity of caesium-137 was determined directly on the ammonium molybdophosphate (AMP) bed by means of counting

  5. The diagenesis-metamorphism limit in pelitic rocks: an X-ray diffraction and decomposition study of illite and interstratified illite/smectite minerals

    International Nuclear Information System (INIS)

    Gharrabi, M.

    1995-01-01

    The definition of the limit between diagenesis and metamorphism has long been debated. Various approaches have been used to describe this limit including mineral reaction such as the appearance of pyrophyllite, illite crystallinity and rock textures (i.e. the development of schistosity). The aim of this study is to characterize the illite clays transformation during this transition. Study of the (001) and (003) XRD peaks of illite and illite-rich interstratified illite/smectite (I/S) by decomposition of XRD spectra allows to define the transformation that affect these minerals in the transition from extensive diagenesis to low grade metamorphism. We studied Paleozoic pelites from the Illinois Basin (USA), Cornwall (UK), Brittany (France) and the Anti-Atlas mountains and the Eastern-Haou/Basin (Morocco) that have undergone this transition. Illite clays pass through three evolutionary stages during the transition from diagenesis to metamorphism: advanced diagenesis where the population of illite particles is composed of the following phases: interstratified illite/smectite (I/S), small illite crystallites (PCI) and large illite crystallites (WCI). The composition of I/S particles that contain approximately 95 % illite layers changes very little at low temperatures even over long periods of time. The most important change during this stage is the reduction in the amount of this phase. These I/S particles (<5% smectite layers) dissolve and furnish the chemical constituents necessary for the growth of PCI and WCI before they are transformed into 100 % illite. Particles of PCI also contain smectite interlayers in their structure. These smectite interlayers may be considered as a characteristic of diagenetic conditions. The second stage, corresponding to anchizone metamorphism is characterized by the disappearance of I/S. The disappearance is caused by higher thermal regime. In the last stage corresponding to epizone metamorphism there exists only one population of illite

  6. Heterogeneous reactions of dioctahedral smectites in illite-smectite and kaolinite-smectite mixed-layers: applications to clay materials for engineered barriers

    International Nuclear Information System (INIS)

    Meunier, A.; Proust, D.; Beaufort, D.; Lajudie, A.; Petit, J.-C.

    1992-01-01

    The clay materials selected for use in the engineered barriers of the French nuclear waste isolation programme are mainly composed of dioctahedral smectite, either bentonite of Wyoming type or kaolinite-smectites most often consist of randomly stacked layers with low and high charges. In the case of the Wyoming-type bentonite, these two differently charged layers do not react in the same way when subjected to hydrothermal alteration. Overall, the low-charge smectite layers react to form high-charge smectite layers + quartz + kaolinite. Then, fixing K ions, the high-charge smectite layers are transformed into illite-smectite mixed-layers (I/S) when the temperature conditions increase. A symmetrical process is observed in natural or experimental hydrothermal conditions when the high-charge smectite layers of I/S minerals react with quartz and/or kaolinite to produce low-charge smectite layers. The chemical properties of the bentonite-engineered barriers clearly depend on the low charge/high charge smectite layer proportion, which is in turn controlled by the temperature-dependent reactions in the vicinity of the waste disposal. Although there are fewer published data on the kaolinite-smectite mixed-layered minerals (K/S), a similar low charge-high charge reaction appears to affect their smectite component. The experimental alteration of K/S leads to the formation of a low-charge beidellite with an increase in the cation-exchange capacity and in the expandability of the clay material. Thus, the properties of the engineered barrier seems to be improved after hydrothermal alteration. (Author)

  7. Influence of microorganisms on swelling behavior of smectites

    International Nuclear Information System (INIS)

    Viefhaus, Hanna; Schanz, Tom

    2012-01-01

    stimulated microbial growth. This is all with respect to the fact that electrolyte concentration has to be unaltered in comparison to the liquid that was used for the reference samples without microbial accumulation. Therefore C 6 H 12 O 6 was added to tap water, with a concentration of 20 g/l, as it acted as the desired energy and carbon source for the microbial growth. Reference samples were treated with tap water as well. The changes measured in COD (chemical oxygen demand), which acted as an indicator for microbial growth, and the microscopic analysis of the samples in ESEM (environmental scanning electron microscope) were utilized to monitor the accumulation during and following the test. In the first series of tests 1-D volume change was measured and in the second series of tests it was added by weight measurement. This was in order to differentiate water adsorption from other volume changing effects, such as gas generation by metabolism processes, which seemed to appear during the first series of tests. Water content was plotted against time for each sample of Calcigel and MX80 mixtures. Both mixtures began to swell with the rapid occurring hydration of the cations and the charged surfaces, within the first 24 hours. This was followed by time intensive osmotic swelling in the case of MX80 smectite occupied with Na + . While hydration depends on the initial condition 'dry' or 'wet', osmotic swelling leads to water adsorption regardless of these conditions. Rapid occurring hydration of the charge carriers remains relatively unaffected by the presence of microorganisms. In comparison osmotic swelling exhibits considerable differences in water adsorption and volume change when samples have been accumulated with microorganisms. Therefore the influence reacts in different fashions, with negligible hydration increase and a significant decrease in osmotic swelling behavior of microbial accumulated samples. Also biological cells appear as charge carriers, and for this purpose

  8. Formulation of caesium based and caesium containing geo-polymers

    Energy Technology Data Exchange (ETDEWEB)

    Berger, S.; Joussot-Dubien, C.; Frizon, F. [CEA Valrho, Dir. de l' Energie Nucleaire, DEN, Decontamination and Conditioning Department, DEN/DTCD/SPDE/L2ED, 30 - Marcoule (France)

    2009-10-15

    Cement encapsulation is widely used as a low- and intermediate level radioactive waste immobilisation process. Among these wastes, caesium ions are poorly immobilised by Portland cement based materials. This work consists of an experimental investigation into the ability of geo-polymers to effectively encapsulate this chemical species and to determine the impact of caesium incorporation on the geo-polymer properties. Geo-polymers were synthesised with several compositions based on the activation of metakaolin with an alkali hydroxide solution containing caesium. The setting time, mineralogy, porosity and mechanical properties of the samples were examined for one month. Leach tests were conducted during the same period to determine the immobilisation efficiency. The results depend to a large extent on the composition of the activation solution in terms of soluble silica content and alkali used. These parameters determine both the degree of condensation and the geo-polymer composition. (authors)

  9. Formulation of caesium based and caesium containing geo-polymers

    International Nuclear Information System (INIS)

    Berger, S.; Joussot-Dubien, C.; Frizon, F.

    2009-01-01

    Cement encapsulation is widely used as a low- and intermediate level radioactive waste immobilisation process. Among these wastes, caesium ions are poorly immobilised by Portland cement based materials. This work consists of an experimental investigation into the ability of geo-polymers to effectively encapsulate this chemical species and to determine the impact of caesium incorporation on the geo-polymer properties. Geo-polymers were synthesised with several compositions based on the activation of metakaolin with an alkali hydroxide solution containing caesium. The setting time, mineralogy, porosity and mechanical properties of the samples were examined for one month. Leach tests were conducted during the same period to determine the immobilisation efficiency. The results depend to a large extent on the composition of the activation solution in terms of soluble silica content and alkali used. These parameters determine both the degree of condensation and the geo-polymer composition. (authors)

  10. Chromium rich smectites from Jordan: a sink for hazardous elements of a high pH plume

    International Nuclear Information System (INIS)

    Khoury, H.N.

    2010-01-01

    Document available in extended abstract form only. A green earthy chromium rich di-octahedral smectite is widely distributed in Jordan. The green clay mineral is associated with marbles and travertines in central Jordan and in Suweileh area near Amman. A wide range of chromium substitution in the octahedral layer of smectites is indicated in samples from the different localities. The chromium rich smectites followed the precipitation of calcite and preceded the precipitation of opaline silica from highly alkaline paleo-groundwater. SEM photo indicating the sequence of precipitation is shown. These waters were evolved as a result of retrograde alteration and hydration reactions in the metamorphic zone. The secondary mineral precipitation followed the thermal metamorphic event of the bituminous marls. The travertine in central Jordan indicates a long-term analogue of carbonation and remobilization of silica in cementitious barriers for radioactive waste repositories. The presence of Cr-rich smectites and relatively high levels of U in the associated opaline silica may suggest the use of central Jordan outcrops as analogues with the repository disturbed zone. Smectites and silica phases are expected to be a sink for alteration products in the late stage evolution of a high pH plume. (authors)

  11. Impact factors on the structuration and the rheological behavior of the clay-water system for smectite dispersions; Facteurs determinant l'organisation et la rheologie du systeme argile-eau pour des suspensions de smectites

    Energy Technology Data Exchange (ETDEWEB)

    Paumier, S

    2007-11-15

    Smectite are swelling clays widely used in industry. Their mechanical properties are unequal according to their mineralogical and physico-chemical characteristics. The aim of this study is to improve the knowledge of the interlayer cation impact on the structure built by the smectite-water system according to the concentration. Homo-ionic (Na{sup +} et Ca{sup 2+}) and bi-ionic systems are observed. This study cross checks mineralogical methods, physicochemical analysis and broad range of rheometric tests. At low concentration (less than 60 g/l) the calcium dispersions are shear thinning and few viscous due to the layer association in huge deformable flocks. The sodium smectite layers are dispersed; the dispersions are highly viscous. The lowest viscosity is detected for mix of 20 % of sodium smectite and 80 % of calcium smectite. At higher concentration (60 to 100 g/l), the yield stress and viscoelastic properties are studied by creep-recovery tests, oscillatory tests and imposed shear step. At the liquid state, the flow is first heterogeneous with a shear banding effect then homogeneous. The results make it possible to define the concentration area characteristic of each mechanical behavior (viscosity, shear thinning and yield stress) according to the saturation cation. The thixotropic properties are characterized with de-structuring-restructuring tests. Two kinetics are determined. Finally we realize a data base with 12 natural and industrial bentonite. The rheograms would be efficient to differentiate the natural calcium bentonite (Newtonian law), natural sodium bentonite (Herschel-Bulkley law) and activated calcium bentonite (Bingham law). (author)

  12. Structural characterization of hexadecyltrimethylammonium-smectite composites and their potentiometric electrode applications

    Energy Technology Data Exchange (ETDEWEB)

    Cubuk, Osman [Department of Chemistry, Faculty of Arts and Sciences, Erzincan University, 24100 Erzincan (Turkey); Caglar, Bulent, E-mail: bcaglar55@gmail.com [Department of Chemistry, Faculty of Arts and Sciences, Erzincan University, 24100 Erzincan (Turkey); Topcu, Cihan; Coldur, Fatih; Sarp, Gokhan [Department of Chemistry, Faculty of Arts and Sciences, Erzincan University, 24100 Erzincan (Turkey); Tabak, Ahmet [Department of Chemistry, Faculty of Arts and Sciences, Recep Tayyip Erdoğan University, 53100 Rize (Turkey); Sahin, Erdal [Department of Chemistry, Faculty of Arts and Sciences, Erzincan University, 24100 Erzincan (Turkey)

    2015-05-30

    Graphical abstract: - Highlights: • Surfactant cations intercalated with different molecular arrangements into smectite layers. • The electrophoretic mobility values indicate that excess surfactant loadings also create positive charges on the organosmectites surfaces. • A novel potentiometric SCN{sup −} selective electrode was fabricated based on modified smectite. - Abstract: Organosmectites were prepared by the intercalation of hexadecyltrimethylammonium cations at various ratios into interlayer of Unye smectite. Structural, thermal, morphological and textural properties of the synthesized organosmectites were characterized. Afterwards, a novel potentiometric PVC-membrane thiocyanate selective electrode was prepared based on the obtained hexadecyltrimethylammonium modified smectites as electroactive material. The basal spacing values of organosmectites were observed in the range of 15.61 and 35.50 Å. Powder X-ray diffraction data show that the surfactant cations penetrated into the smectite layers with different molecular arrangements. Modification of smectite with hexadecyltrimethylammonium led to appreciable decreases in the intensities of the FTIR bands at 3402 and 1635 cm{sup −1} and the new characteristic vibrational bands at 2927, 2850, 1472 and 722 cm{sup −1} originating from the surfactant molecules appeared. The thermal analysis data showed that the decomposition of surfactant species occurred in the temperature range of 170–720 °C and the amount of dehydrated water gradually decreased with the increase in surfactant amount. The intercalation of surfactant species within the gallery spacing led gradually to smaller surface areas. In addition, the electrophoretic mobility values indicate that excess surfactant loadings also generate positive charges on the organosmectite surfaces. The most convenient membrane composition resulting in the best potentiometric performance was investigated. The optimum membrane composition was determined to

  13. Physical capture and release of drug molecules, water and cations by a smectite clay

    DEFF Research Database (Denmark)

    Carvalho dos Santos, Éverton

    -fluorohectorite (LiFh, Li1.2(Mg4.8Li1.2)Si8O20F4), a synthetic clay mineral from the smectite family, have been experimentally analyzed. By means of X-rays powder diffraction (XRD), using both an in-house instrument and synchrotron radiation, UV-Vis spectroscopy, Thermogravimetric Analysis coupled to an Infrared......-analysis and inelastic neutron scattering data we established that the drug presence into the interlayer space of Fh is weakening the water-clay interactions. Furthermore, CIPRO’s release from Fh in synthetic gastric acid juice (SGA) as a function of time and temperature was also carefully followed. Our studies showed...... and toxicological tests, we demonstrated that the effectiveness and toxicity of pure CIPRO is unaffected in the clay-drug complex. To conclude, the high drug adsorption capacity as well as the slow and gradual release from CIPRO when intercalated in Fh adds this synthetic smectite to the list of promising drug...

  14. Densification of the interlayer spacing governs the nanomechanical properties of calcium-silicate-hydrate.

    Science.gov (United States)

    Geng, Guoqing; Myers, Rupert J; Qomi, Mohammad Javad Abdolhosseini; Monteiro, Paulo J M

    2017-09-08

    Calciuam-silicate-hydrate (C-S-H) is the principal binding phase in modern concrete. Molecular simulations imply that its nanoscale stiffness is 'defect-driven', i.e., dominated by crystallographic defects such as bridging site vacancies in its silicate chains. However, experimental validation of this result is difficult due to the hierarchically porous nature of C-S-H down to nanometers. Here, we integrate high pressure X-ray diffraction and atomistic simulations to correlate the anisotropic deformation of nanocrystalline C-S-H to its atomic-scale structure, which is changed by varying the Ca-to-Si molar ratio. Contrary to the 'defect-driven' hypothesis, we clearly observe stiffening of C-S-H with increasing Ca/Si in the range 0.8 ≤ Ca/Si ≤ 1.3, despite increasing numbers of vacancies in its silicate chains. The deformation of these chains along the b-axis occurs mainly through tilting of the Si-O-Si dihedral angle rather than shortening of the Si-O bond, and consequently there is no correlation between the incompressibilities of the a- and b-axes and the Ca/Si. On the contrary, the intrinsic stiffness of C-S-H solid is inversely correlated with the thickness of its interlayer space. This work provides direct experimental evidence to conduct more realistic modelling of C-S-H-based cementitious material.

  15. Impact factors on the structuration and the rheological behavior of the clay-water system for smectite dispersions

    International Nuclear Information System (INIS)

    Paumier, S.

    2007-11-01

    Smectite are swelling clays widely used in industry. Their mechanical properties are unequal according to their mineralogical and physico-chemical characteristics. The aim of this study is to improve the knowledge of the interlayer cation impact on the structure built by the smectite-water system according to the concentration. Homo-ionic (Na + et Ca 2+ ) and bi-ionic systems are observed. This study cross checks mineralogical methods, physicochemical analysis and broad range of rheometric tests. At low concentration (less than 60 g/l) the calcium dispersions are shear thinning and few viscous due to the layer association in huge deformable flocks. The sodium smectite layers are dispersed; the dispersions are highly viscous. The lowest viscosity is detected for mix of 20 % of sodium smectite and 80 % of calcium smectite. At higher concentration (60 to 100 g/l), the yield stress and viscoelastic properties are studied by creep-recovery tests, oscillatory tests and imposed shear step. At the liquid state, the flow is first heterogeneous with a shear banding effect then homogeneous. The results make it possible to define the concentration area characteristic of each mechanical behavior (viscosity, shear thinning and yield stress) according to the saturation cation. The thixotropic properties are characterized with de-structuring-restructuring tests. Two kinetics are determined. Finally we realize a data base with 12 natural and industrial bentonite. The rheograms would be efficient to differentiate the natural calcium bentonite (Newtonian law), natural sodium bentonite (Herschel-Bulkley law) and activated calcium bentonite (Bingham law). (author)

  16. Smectite alteration

    International Nuclear Information System (INIS)

    Anderson, D.M.

    1984-11-01

    This report contains the proceedings of a second workshop in Washington DC December 8-9, 1983 on the alteration of smectites intended for use as buffer materials in the long-term containment of nuclear wastes. It includes extended summaries of all presentations and a transcript of the detailed scientific discussion. The discussions centered on three main questions: What is the prerequisite for and what is the precise mechanism by which smectite clays may be altered to illite. What are likly sources of potassium with respect to the KBS project. Is it likely that the conversion of smectite to illite will be of importance in the 10 5 to the 10 6 year time frame. The workshop was convened to review considerations and conclusions in connection to these questions and also to broaden the discussion to consider the use of smectite clays as buffer materials for similar applications in different geographical and geological settings. SKBF/KBS technical report 83-03 contains the proceedings from the first workshop on these matters that was held at the State University of New York, Buffalo May 26-27, 1982. (Author)

  17. Visible and Near-IR Reflectance Spectra of Smectite Acquired Under Dry Conditions for Interpretation of Martian Surface Mineralogy

    Science.gov (United States)

    Morris, Richard V.; Achilles, Cherie N; Archer, Paul D.; Graff, Trevor G.; Agresti, David G.; Ming, Douglas W; Golden, Dadi C.; Mertzman, Stanley A.

    2011-01-01

    Visible and near-IR (VNIR) spectra from the MEx OMEGA and the MRO CRISM hyper-spectral imaging instruments have spectral features associated with the H2O molecule and M OH functional groups (M = Mg, Fe, Al, and Si). Mineralogical assignments of martian spectral features are made on the basis of laboratory VNIR spectra, which were often acquired under ambient (humid) conditions. Smectites like nontronite, saponite, and montmorillionite have interlayer H2O that is exchangeable with their environment, and we have acquired smectite reflectance spectra under dry environmental conditions for interpretation of martian surface mineralogy. We also obtained chemical, Moessbauer (MB), powder X-ray diffraction (XRD), and thermogravimetric (TG) data to understand variations in spectral properties. VNIR spectra were recorded in humid lab air at 25-35C, in a dynamic dry N2 atmosphere (50-150 ppmv H2O) after exposing the smectite samples (5 nontronites, 3 montmorillionites, and 1 saponite) to that atmosphere for up to approximately l000 hr each at 25-35C, approximately 105C, and approximately 215C, and after re-exposure to humid lab air. Heating at 105C and 215C for approximately 1000 hr is taken as a surrogate for geologic time scales at lower temperatures. Upon exposure to dry N2, the position and intensity of spectral features associated with M-OH were relatively insensitive to the dry environment, and the spectral features associated with H2O (e.g., approximately 1.90 micrometers) decreased in intensity and are sometimes not detectable by the end of the 215C heating step. The position and intensity of H2O spectral features recovered upon re-exposure to lab air. XRD data show interlayer collapse for the nontronites and Namontmorillionites, with the interlayer remaining collapsed for the latter after re-exposure to lab air. The interlayer did not collapse for the saponite and Ca-montmorillionite. TG data show that the concentration of H2O derived from structural OH was invariant

  18. Growth of Thermophilic and Hyperthermophilic Fe(III)-Reducing Microorganisms on a Ferruginous Smectite as the Sole Electron Acceptor▿

    Science.gov (United States)

    Kashefi, Kazem; Shelobolina, Evgenya S.; Elliott, W. Crawford; Lovley, Derek R.

    2008-01-01

    Recent studies have suggested that the structural Fe(III) within phyllosilicate minerals, including smectite and illite, is an important electron acceptor for Fe(III)-reducing microorganisms in sedimentary environments at moderate temperatures. The reduction of structural Fe(III) by thermophiles, however, has not previously been described. A wide range of thermophilic and hyperthermophilic Archaea and Bacteria from marine and freshwater environments that are known to reduce poorly crystalline Fe(III) oxides were tested for their ability to reduce structural (octahedrally coordinated) Fe(III) in smectite (SWa-1) as the sole electron acceptor. Two out of the 10 organisms tested, Geoglobus ahangari and Geothermobacterium ferrireducens, were not able to conserve energy to support growth by reduction of Fe(III) in SWa-1 despite the fact that both organisms were originally isolated with solid-phase Fe(III) as the electron acceptor. The other organisms tested were able to grow on SWa-1 and reduced 6.3 to 15.1% of the Fe(III). This is 20 to 50% less than the reported amounts of Fe(III) reduced in the same smectite (SWa-1) by mesophilic Fe(III) reducers. Two organisms, Geothermobacter ehrlichii and archaeal strain 140, produced copious amounts of an exopolysaccharide material, which may have played an active role in the dissolution of the structural iron in SWa-1 smectite. The reduction of structural Fe(III) in SWa-1 by archaeal strain 140 was studied in detail. Microbial Fe(III) reduction was accompanied by an increase in interlayer and octahedral charges and some incorporation of potassium and magnesium into the smectite structure. However, these changes in the major element chemistry of SWa-1 smectite did not result in the formation of an illite-like structure, as reported for a mesophilic Fe(III) reducer. These results suggest that thermophilic Fe(III)-reducing organisms differ in their ability to reduce and solubilize structural Fe(III) in SWa-1 smectite and that SWa-1

  19. Theoretical melting curve of caesium

    International Nuclear Information System (INIS)

    Simozar, S.; Girifalco, L.A.; Pennsylvania Univ., Philadelphia

    1983-01-01

    A statistical-mechanical model is developed to account for the complex melting curve of caesium. The model assumes the existence of three different species of caesium defined by three different electronic states. On the basis of this model, the free energy of melting and the melting curve are computed up to 60 kbar, using the solid-state data and the initial slope of the fusion curve as input parameters. The calculated phase diagram agrees with experiment to within the experimental error. Other thermodynamic properties including the entropy and volume of melting were also computed, and they agree with experiment. Since the theory requires only one adjustable constant, this is taken as strong evidence that the three-species model is satisfactory for caesium. (author)

  20. Anisotropy in diffusion and activation energies of I- and CS+ ions in compacted smectite

    International Nuclear Information System (INIS)

    Haruo Sato

    2005-01-01

    The anisotropies and the effect of salinity in the apparent diffusivities (D a ) and activation energies (ΔE a ) of I - and Cs + in compacted Na-smectite were studied. The diffusion experiments in the parallel and perpendicular directions to the orientated direction of smectite particles were performed as a function of smectite's dry density (0.9-1.4 Mg/m 3 ), salinity ([NaCl]=0.01, 0.51 M) and temperature (295-333 K). The Da-values for both ions tended to be higher in the parallel direction than in the perpendicular direction to the orientated direction of smectite particles. The Da-values of I - in the parallel direction decreased with increasing salinity only at low-dry density, but those of Cs + increased with increasing salinity in all conditions. Considering electrostatic effect from the surface of smectite aggregates and the change in tortuosity on dry density, salinity and diffusion direction, I - is interpreted to mainly diffuse in interstitial pores. While, Cs + can diffuse in both interlayer and interstitial pores, and the Da-values of Cs + are presumed to have elevated by the decrease in retardation by competition with Na + . The ΔE a -values of I - , similar levels (ΔE a =15.1-16.1 kJ/mol) to that of the ionic diffusivity in free water (Do) for I - (ΔE a =17.36 kJ/mol) at low-dry density, increased with increasing dry density. On the contrary, the ΔE a -values of Cs + , clearly higher (ΔE a =23.7-25.7 kJ/mol) than that of the Do for Cs + (ΔE a =16.47 kJ/mol) even at low-dry density, increased with increasing dry density. Such high ΔE a -values for Cs + can be explained by considering the ion exchange enthalpy between Cs + and Na + in smectite (ΔH 0 = -11.1 kJ/mol) at low-dry density, and are considered to be due to the effects of the decrease in the activity of porewater and ΔH 0 at high-dry density. (authors)

  1. Electrical properties of smectites; Smectite nendo kobutsu no denkiteki bussei

    Energy Technology Data Exchange (ETDEWEB)

    Takakura, S; Nishizawa, O; Aoki, M [Geological Survey of Japan, Tsukuba (Japan); Kozake, K [University of Tsukuba, Tsukuba (Japan)

    1997-05-27

    With an objective to evaluate effects of clayish minerals in the electric and electromagnetic exploration methods, resistivities were measured on samples which have adjusted contents of clayish minerals. Samples were prepared for an experiment by mixing 300 g of glass beads having a diameter of about 1 mm, 200 g of aqueous solutions, and 3 to 90 g of smectites. The aqueous solutions used KCL, NaCL and CaCL2 at concentrations of 0.1 to 0.001 mol/L. The result of the experiment may be summarized as follows: among the three kinds of smectites, KN-1 has the greatest effect to reduce the resistivity; the resistivity decreases when the smectite amount is increased except when the concentration of the solution is high; this phenomenon is thought to be caused by increase in the region of an electrically doubled layer which has higher ion concentration; change in the resistivity increases when the solution concentration is low, and decreases when the concentration is high; and in the case of the solution concentration being 0.1 mol/L, the resistivity increases with increase in the smectite content. 5 refs., 7 figs., 1 tab.

  2. Experimental study of smectite interaction with metal iron at low temperature: 1. Smectite destabilization.

    OpenAIRE

    Lantenois , Sébastien; Lanson , Bruno; Muller , Fabrice; Bauer , Andreas; Jullien , Michel; Plançon , Alain

    2005-01-01

    Interaction between metal Fe and a variety of natural and synthetic smectite samples with contrasting crystal chemistry was studied by scanning electron microscopy and X-ray diffraction from experiments conducted at 80°C. These experiments demonstrate an important reactivity contrast as a function of smectite crystal chemistry. An XRD method involving the use of an internal standard allowed quantification of the relative proportion of smectite destabilized as a function of initial pH conditio...

  3. Deposition of talc - kerolite-smectite - smectite at seafloor hydrothermal vent fields: Evidence from mineralogical, geochemical and oxygen isotope studies

    Science.gov (United States)

    Dekov, V.M.; Cuadros, J.; Shanks, Wayne C.; Koski, R.A.

    2008-01-01

    Talc, kerolite-smectite, smectite, chlorite-smectite and chlorite samples from sediments, chimneys and massive sulfides from six seafloor hydrothermal areas have been analyzed for mineralogy, chemistry and oxygen isotopes. Samples are from both peridotite- and basalt-hosted hydrothermal systems, and basaltic systems include sediment-free and sediment-covered sites. Mg-phyllosilicates at seafloor hydrothermal sites have previously been described as talc, stevensite or saponite. In contrast, new data show tri-octahedral Mg-phyllosilicates ranging from pure talc and Fe-rich talc, through kerolite-rich kerolite-smectite to smectite-rich kerolite-smectite and tri-octahedral smectite. The most common occurrence is mixed-layer kerolite-smectite, which shows an almost complete interstratification series with 5 to 85% smectitic layers. The smectite interstratified with kerolite is mostly tri-octahedral. The degree of crystal perfection of the clay sequence decreases generally from talc to kerolite-smectite with lower crystalline perfection as the proportion of smectite layers in kerolite-smectite increases. Our studies do not support any dependence of the precipitated minerals on the type/subtype of hydrothermal system. Oxygen isotope geothermometry demonstrates that talc and kerolite-smectite precipitated in chimneys, massive sulfide mounds, at the sediment surface and in open cracks in the sediment near seafloor are high-temperature (> 250????C) phases that are most probably the result of focused fluid discharge. The other end-member of this tri-octahedral Mg-phyllosilicate sequence, smectite, is a moderate-temperature (200-250????C) phase forming deep within the sediment (??? 0.8??m). Chlorite and chlorite-smectite, which constitute the alteration sediment matrix around the hydrothermal mounds, are lower-temperature (150-200????C) phases produced by diffuse fluid discharge through the sediment around the hydrothermal conduits. In addition to temperature, other two

  4. Correlation of erosion and erodibility assessments using caesium-137

    International Nuclear Information System (INIS)

    Elliott, G.L.; Campbell, B.L.; Loughran, R.J.

    1984-01-01

    Data are presented which show that in soils in which net erosion is occurring, the content of the environmental isotope caesium-137 is highly correlated with soil loss. Other soil characteristics which may be related to the caesium content and therefore to soil loss have also been examined. Of these factors, an improved index of soil aggregate stability explained the most variation in caesium content (52%). Soil organic matter content explained 27% of variation in caesium content and other soil erodibility indices based on quantitative measurement of aggregate stability, explained between 6% and 21% of the variation. Indices based on implied hydrologic characteristics, implied aggregation and clay dispersion explained between 1% and 3% of caesium variation. It is suggested that practical factors of soil protection are relevant to the prediction of erosion hazard and may be more relevant than some indices of soil resistance. It is noted further that caesium-137 content of a soil gives every indication of being a most suitable predictor of soil erosion status

  5. Visible and Near-IR Reflectance Spectra for Smectite, Sulfate And Perchlorate under Dry Conditions for Interpretation of Martian Surface Mineralogy

    Science.gov (United States)

    Morris, R.V.; Ming, W.; Golden, D.C.; Arvidson, R.E.; Wiseman, S.M.; Lichtenberg, K.A.; Cull, S.; Graff, T.G.

    2009-01-01

    Visible and near-IR (VNIR) spectral data for the martian surface obtained from orbit by the MRO-CRISM and OMEGA instruments are interpreted as having spectral signatures of H2O/OH-bearing phases, including smectites and other phyllosilicates, sulfates, and high-SiO2 phases [e.g., 1-4]. Interpretations of martian spectral signatures are based on and constrained by spectra that are obtained in the laboratory on samples with known mineralogical compositions and other physicochemical characteristics under, as appropriate, Mars-like environmental conditions (e.g., temperature, pressure, and humidity). With respect to environmental conditions, differences in the absolute concentration of atmospheric H2O can effect the hydration state and therefore the spectra signatures of smectite phyllosilicates (solvation H2O) and certain sulfates (hydration H2O) [e.g., 5-7]. We report VNIR spectral data acquired under humid (laboratory air) and dry (dry N2 gas) environments for two natural smectites (nontronite API-33A and saponite SapCa-1) to characterize the effect of solvation H2O on spectral properties. We also report spectral data for the thermal dehydration products of (1) melanterite (FeSO4.7H2O) in both air and dry N2 gas and (2) Mg-perchlorate (Mg(ClO4)2.6H2O) in dry N2 environments. Spectral measurements for samples dehydrated in dry N2 were made without exposing them to humid laboratory air.

  6. Thermodynamic properties of a smectite and an illite: comparison between solubility experiments and calorimetric results

    International Nuclear Information System (INIS)

    Gailhanou, H.; Gaboreau, S.; Gaucher, E.C.; Blanc, P.; Rogez, J.; Olives, J.; Amouric, M.; Van Miltenburg, J.C.; Michau, N.; Giffaut, E.

    2010-01-01

    Document available in extended abstract form only. In the context of nuclear waste repositories in argillaceous formations, it is necessary to assess the geochemical behaviour of natural and engineered clay barriers, namely by the stability of clay minerals over long periods of time. However, thermodynamic data of clay minerals, which are required for geochemical modelling, are still poorly known. The present study aims to improve our comprehension of clay mineral stability. The thermodynamic properties of smectite MX-80 and illite IMt-2 (Silver Hill, Montana) have already been determined using calorimetric methods between 0 K and 520 K, under both dried and hydrated states in the case of smectite. In parallel, solubility experiments were carried out in order to determine the solubility products of the clay minerals. Such experiments require some particular precautions as published by May et al. (1986) and Aja and Rosenberg (1992). According to these authors, it is namely important to reach the equilibrium from both under and over saturation and to characterize from a mineralogical point of view the end products. Taking advantage of previous calorimetric measurements, we propose to compare the solubility products obtained here from dissolution experiments with respect to calorimetry results, in order to assess the equilibrium achievement for the solubility experiments. The study is integrated in the Thermochimie project, which aims to provide a consistent thermodynamic database (Thermochimie) for modelling purposes. This work dealing with a smectite and an illite is being completed by the study of a set of typical clays, selected to be well-representative of the clay group. Enthalpies of formation of the minerals were determined by isothermal dissolution calorimetry at 25 deg. C, using a HF-HNO 3 solution. They were obtained by measuring the enthalpies of dissolution of (i) the sample (clay mineral + impurities) and (ii) the oxide or hydroxide constituent mixture

  7. Smectite formation in the presence of sulfuric acid: Implications for acidic smectite formation on early Mars

    Science.gov (United States)

    Peretyazhko, T. S.; Niles, P. B.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

    2018-01-01

    The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (∼200 °C). Smectites were analyzed by X-ray diffraction, Mössbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH ≤ 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH ∼3 and trioctahedral smectite saponite at final pH ∼4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model

  8. Separation of caesium-137 from fission products using phosphotungstic acid

    International Nuclear Information System (INIS)

    Murthy, T.S.; Balasubramaniam, K.R.; Ananthakrishnan, M.; Varma, R.N.

    1977-01-01

    Separation of caesium 137 from fission products using phosphotungstic acid is reported. Phosphotungstate caesium is precipitated as caesium from fission product waste solution in acid medium and subsequently purified. Separation of phosphate and tungstate ions has been done using a typical hydrous oxide like alumina. The exchange capacity of alumina for phosphate and tungstate ions, and the purity of the product are determined. Results are discussed. Based on the findings a procedure is recommended for caesium 137 separation. (A.K.)

  9. Correlation of index tests with smectite content determined with XRD in bentonite and smectite rich clays

    International Nuclear Information System (INIS)

    Kumpulainen, Sirpa; Kiviranta, Leena; Korkeakoski, Petri

    2012-01-01

    Document available in extended abstract form only. Various index tests are used by bentonite producers and users to assess the amount of swelling minerals in bentonites and smectite rich clays. Index tests are meant to provide relative fast and inexpensive way of testing the amount of swelling minerals, and their performance should not require sophisticated equipment. Such index tests are e.g. methylene blue absorption test, liquid limit and swelling index test (free swelling). In order to select appropriate index test to control the quality of buffer and backfill materials to be used in nuclear waste end disposal in Finland, results from various index tests were correlated with the smectite content determined with XRD and Rietveld refinement. Tests evaluated were: water absorption capacity (WAC) based on DIN 18132, swelling index (SI) based on ASTM D 5890-06, cation exchange capacity (CEC) based on Cu(II)-trien adsorption by Meier and Kahr (1999) and Ammann et al. (2005), liquid limit (LL) based on CEN ISO/TS 17892- 12:2004, methylene blue absorption (MB) based on SFS-EN 933-9, and specific surface area based on absorption of ethylene glycol monoethyl ether (EGME) described by Cerato and Lutenegger (2002). The number of samples tested was 6-25 (exact number of samples was dependent on the test method), and included natural Na-bentonites, natural Ca-bentonites, sodium activated Ca-bentonites and smectite rich clays from Wyoming/USA, Milos/Greece, Gujarat/India and Friedland/Germany. Smectite content in samples was determined after Kiviranta and Kumpulainen (2011) by x-ray diffraction (XRD), optical microscopy, chemical analyses, and full-pattern fitting with the Rietveld method using Siroquant software. Exchangeable cation composition was determined after Belyayeva (1967) and Jackson (1975). In order to achieve correlation of index test results with smectite content, water absorption capacity, liquid limit, and swelling index methods required additional information

  10. Thermochemically induced transformations in Al-smectites: A Spanish natural analogue of the bentonite barrier behaviour in a radwaste disposal

    International Nuclear Information System (INIS)

    Perez del Villar, L.; Delgado, A.; Reyes, E.; Pelayo, M.; Fernandez-Soler, J.M.; Cozar, J.S.; Tsige, M.; Quejido, A.J.

    2005-01-01

    The thermal effect induced by the Morron de Mateo volcanic dome (Cabo de Gata volcanic region, Spain) on the adjacent bentonitised tuffaceous beds has been studied as a natural analogue of the thermal behaviour of the bentonite-engineered barrier of a geological radwaste repository. These bentonites consist mainly of Fe-rich smectites and were formed in equilibrium with seawater at temperatures between 75 and 95 o C, according to the δ 18 O and δD values. In contrast, bentonites from other localities in the region consist mainly of Al-smectites, formed in equilibrium with meteoric water below 25 deg. C. This investigation is focussed on the detection of the chemical differences between smectites from proximal and distal zones to the dome, as well as to test whether the temperatures calculated based on the O and H isotopic values correspond to their formation or transformation. The initial hypothesis was that the chosen smectites could be formed under marine conditions, being later transformed and isotopically re-equilibrated as a result of the intrusion. To check this hypothesis, a detailed mineralogical, chemical, geochemical and isotopic study has been performed on the smectitised tuffaceous materials and the overlaying biocalcarenites outcropping near and far from the dome. The results show that distal smectites are dioctahedral Al-smectites, similar to those from other deposits in the region, while proximal smectites are Fe- and Mg-rich smectites, showing two evolutionary trends on a Fe-Mg-Al ternary diagram. Similar features are observed when their structural formulae are plotted on the muscovite-celadonite-pyrophylite diagram. Thus, they plot in the smectite domain with interlayer charge less than 1, which is mainly due to octahedral substitution for distal smectites, while for proximal ones it is caused by both octahedral and tetrahedral substitutions. In this ternary diagram, the domains of both proximal and distal smectites are partially overlapped. The

  11. Molecular dynamics simulation of polyacrylamides in potassium montmorillonite clay hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Junfang [CSIRO Petroleum Resources, Ian Wark Laboratory, Bayview Avenue, Clayton, Victoria 3168 (Australia); Rivero, Mayela [CSIRO Petroleum, PO Box 1130, Bentley, Western Australia, 6102 (Australia); Choi, S K [CSIRO Petroleum Resources, Ian Wark Laboratory, Bayview Avenue, Clayton, Victoria 3168 (Australia)

    2007-02-14

    We present molecular dynamics simulation results for polyacrylamide in potassium montmorillonite clay-aqueous systems. Interlayer molecular structure and dynamics properties are investigated. The number density profile, radial distribution function, root-mean-square deviation (RMSD), mean-square displacement (MSD) and diffusion coefficient are reported. The calculations are conducted in constant NVT ensembles, at T = 300 K and with layer spacing of 40 A. Our simulation results showed that polyacrylamides had little impact on the structure of interlayer water. Density profiles and radial distribution function indicated that hydration shells were formed. In the presence of polyacrylamides more potassium counterions move close to the clay surface while water molecules move away, indicating that potassium counterions are hydrated to a lesser extent than the system in which no polyacrylamides were added. The diffusion coefficients for potassium and water decreased when polyacrylamides were added.

  12. The New PTB Caesium Fountain Clock CSF2

    National Research Council Canada - National Science Library

    Wynands, R; Bauch, A; Griebsch, D; Schroeder, R; Weyers, S

    2005-01-01

    At PTB a second caesium fountain clock, CSF2, is in the process of being set up. It differs from the first PTB caesium fountain standard CSF1 in a number of details, which are consecutively specified...

  13. Smectite alteration

    International Nuclear Information System (INIS)

    Anderson, D.M.

    1983-02-01

    The colloquium was convened to compose a summary of the most recent data and the best scientific appraisal of present knowledge on the process of smectite conversion to illite. A brief account of a consensus view on the probable stability of smectite clays when employed as the buffer material in the Swedish nuclear fuel storage system. It is concluded that if the quantitiy of nuclear waste to be put in each bore hole is carefully limited, temperatures surrounding the cannister will not rise to an acceptable level and the clay buffer material can be relied upon to be effective throughout the life of the repository. (G.B.)

  14. Caesium contamination in human milk and transfer factor from diet

    International Nuclear Information System (INIS)

    Risica, S.; Campos Venuti, G.; Rogani, A.; Baronciani, D.; Petrone, M.

    1992-01-01

    A study on caesium contamination in human milk, as a consequence of the Chernobyl fallout, was conducted in 1989 on a group of women from one of the areas of northern Italy most heavily affected by the radioactive fallout. Their diet was studied, and the caesium intake was calculated by using the mean food activity concentration in that area. The caesium transfer factor was evaluated both as the ratio of caesium concentration in mother's milk to the daily intake, and by using a simplified milk compartment model. (author)

  15. Hydration states of AFm cement phases

    Energy Technology Data Exchange (ETDEWEB)

    Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Matschei, Thomas [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Scrivener, Karen L. [Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Saeidpour, Mahsa; Wadsö, Lars [Building Materials, Lund University, Box 124, 221 000 Lund (Sweden)

    2015-07-15

    The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFm phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.

  16. Translocation of the radioactive caesium via the calyx in persimmon fruit

    International Nuclear Information System (INIS)

    Sekizawa, Haruhito; Sato, Mari; Aihara, Takashi; Murakami, Toshifumi; Hachinohe, Mayumi; Hamamatsu, Shioka

    2016-01-01

    To elucidate pathways of radioactive caesium contamination of persimmon fruit, we investigated translocation via the calyx. We treated calyces of immature and mature fruits (at either stage and both stages) with water containing caesium-137 (1000 Bq/kg) and measured concentrations in the calyx, pericarp, and flesh with a germanium semiconductor detector. All treated fruits had higher levels of radioactive caesium in all tissues than untreated fruits at harvest. The translocated radioactive caesium was retained in the fruit and not retranslocated. These results indicate that radioactive caesium is translocated via the calyx of persimmon at all stages of fruit development and is accumulated in the flesh. (author)

  17. Studies on certain physical properties of modified smectite nanocatalysts

    International Nuclear Information System (INIS)

    Wu, Ming Ching; Kuo, Shu Lung; Lin, Jao Chuan; Ma, Chih Ming; Hong, Gui Bing; Chang, Chang Tang

    2011-01-01

    Most volatile organic compounds (VOCs) are toxic to humans in some manner. Generally, transitional metal catalysts have better conversion rates for controlling VOCs. However, catalyst activity will decay at high temperature, though the oxidizing catalyst is cheap. This study used smectite as the carrier to exchange with Ag + , Zn 2+ and Ti 4+ to modify the surface and form smectite catalysts. In addition, the transmission electron microscopy (TEM), FT-IR spectrum, and DSC-TGA instrument were applied to characterize their physical properties. After the FT-IR analysis of the modified smectite catalyst (smectite-Ag, smectite-Zn and smectite-Ti), both smectite and smectite catalyst had significant and complicated wave crests between the fingerprint area with the wave numbers of 415-600 cm -1 and 750-1170 cm -1 , that indicated the existence of a strong bond between impure silicates (Si-O) and silicates (O-Si-O). TEM observation proved that sintering at 350 deg. C results in the distribution of catalyst ions on clay carrier with a nanoscale. As thermal analysis reveals, the smectite reached endothermic peaks at the temperatures of 920 deg. C and 1057 deg. C, respectively, and shows the decomposition in a non-crystal form. Besides, the disappearance of the endothermic peak of smectite-Ag occurs at 920.5 deg. C and the exothermic peak occurs at 950 deg. C. The results indicating crystals formed of smectite-Ag are more comprehensive and stable than the other smectite or modified smectite catalysts at high temperature.

  18. Anatomy of a metabentonite: nucleation and growth of illite crystals and their colescence into mixed-layer illite/smectite

    Science.gov (United States)

    Eberl, D.D.; Blum, A.E.; Serravezza, M.

    2011-01-01

    The illite layer content of mixed-layer illite/smectite (I/S) in a 2.5 m thick, zoned, metabentonite bed from Montana decreases regularly from the edges to the center of the bed. Traditional X-ray diffraction (XRD) pattern modeling using Markovian statistics indicated that this zonation results from a mixing in different proportions of smectite-rich R0 I/S and illite-rich R1 I/S, with each phase having a relatively constant illite layer content. However, a new method for modeling XRD patterns of I/S indicates that R0 and R1 I/S in these samples are not separate phases (in the mineralogical sense of the word), but that the samples are composed of illite crystals that have continuous distributions of crystal thicknesses, and of 1 nm thick smectite crystals. The shapes of these distributions indicate that the crystals were formed by simultaneous nucleation and growth. XRD patterns for R0 and R1 I/S arise by interparticle diffraction from a random stacking of the crystals, with swelling interlayers formed at interfaces between crystals from water or glycol that is sorbed on crystal surfaces. It is the thickness distributions of smectite and illite crystals (also termed fundamental particles, or Nadeau particles), rather than XRD patterns for mixed-layer I/S, that are the more reliable indicators of geologic history, because such distributions are composed of well-defined crystals that are not affected by differences in surface sorption and particle arrangements, and because their thickness distribution shapes conform to the predictions of crystal growth theory, which describes their genesis.

  19. Alteration of Basaltic Glass to Mg/Fe-Smectite under Acidic Conditions: A Potential Smectite Formation Mechanism on Mars

    Science.gov (United States)

    Peretyazhko, Tanya; Sutter, Brad; Ming, Douglas W.

    2014-01-01

    Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed

  20. On the smectite-to-illite reaction

    International Nuclear Information System (INIS)

    Oscarson, D.W.; Hume, H.B.

    1993-08-01

    The smectite component of the buffer material in a nuclear fuel waste disposal vault could slowly transform over long periods of time to an inter-stratified illite/smectite (I/S) material. This has important implications for the long-term effectiveness of the buffer material. The smectite-to-illite reaction was examined by treating Wyoming bentonite at 150, 200 and 250 degrees C for periods ranging from 90 to 194 days in five synthetic solutions having widely varying compositions. The solution-to-clay ratio was 0.025 m 3 /kg. Progress of the smectite alteration reaction was determined by measuring the expandability of the reaction products by X-ray diffractometry after the exchange complex of the clay was saturated with K and solvated with ethylene glycol. In all systems, the expandability of the I/S run products generally decreased (increase in the amount of I/S formed) with increasing temperature and time. The cation-exchange capacity of the clay was not, however, markedly affected by the hydrothermal treatments. The results indicate the presence of K in solution is not necessary for the development of high-charge layers in smectite (an increase in layer charge is the first step in the formation of illite from smectite). The expandability of the I/S was greater in the solutions with comparatively high concentrations of Ca. This supports the observation that the presence of Ca, rather than Na, on the exchange complex of smectite inhibits the formation of high-charge layers. The data do not allow us to predict the rate at which smectite will transform to I/S in a disposal vault environment. But the reaction will undoubtedly be very slow given that the temperature in a disposal vault will be <100 C and the concentration of K in groundwaters deep in granite rock very low compared with that of Ca and Na. (author). 54 refs., 4 tabs., 3 figs

  1. Modeling of Cation Binding in Hydrated 2:1 Clay Minerals - Final Report

    International Nuclear Information System (INIS)

    Smith, David E.

    2000-01-01

    Hydrated 2:1 clay minerals are high surface area, layered silicates that play a unique role in determining the fate of radionuclides in the environment. This project consisted of developing and implementing computer simulation methods for molecular characterization of the swelling and ion exchange properties of Hydrated 2:1 clay minerals, and the subsequent analysis and theoretical modeling with a view toward improving contaminant transport modeling as well as soil remediation and radionuclide containment strategies. Project results included the (a) development of simulation methods to treat clays under environmentally relevant conditions of variable water vapor pressure; (b) calculation of clay swelling thermodynamics as a function of interlayer ion size and charge (calculated quantities include immersion energies, free energies, and entropies of swelling); and (c) calculation of ion exchange free energies, including contributions from changing interlayer water contents and layer spacing

  2. First-principles elasticity of monocarboaluminate hydrates

    KAUST Repository

    Moon, J.; Yoon, S.; Wentzcovitch, R. M.; Monteiro, P. J. M.

    2014-01-01

    The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

  3. First-principles elasticity of monocarboaluminate hydrates

    KAUST Repository

    Moon, J.

    2014-07-01

    The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

  4. Vapour pressure of caesium over nuclear graphite

    International Nuclear Information System (INIS)

    Faircloth, R.L.; Pummery, F.C.W.

    1976-01-01

    The vapour pressure of caesium over a fine-grained isotropic moulded gilsocarbon nuclear graphite intended for use in the manufacture of fuel tubes for the high temperature reactor has been determined as a function of temperature and concentration by means of the Knudsen effusion technique. The concentration range 0 to 10 μg caesium/g graphite was investigated and it was concluded that a Langmuir adsorption situation exists under these conditions. (author)

  5. Topotactic conversion of β-helix-layered silicate into AST-type zeolite through successive interlayer modifications.

    Science.gov (United States)

    Asakura, Yusuke; Takayama, Ryosuke; Shibue, Toshimichi; Kuroda, Kazuyuki

    2014-02-10

    AST-type zeolite with a plate morphology can be synthesized by topotactic conversion of a layered silicate (β-helix-layered silicate; HLS) by using N,N-dimethylpropionamide (DPA) to control the layer stacking of silicate layers and the subsequent interlayer condensation. Treatment of HLS twice with 1) hydrochloric acid/ethanol and 2) dimethylsulfoxide (DMSO) are needed to remove interlayer hydrated Na ions and tetramethylammonium (TMA) ions in intralayer cup-like cavities (intracavity TMA ions), both of which are introduced during the preparation of HLS. The utilization of an amide molecule is effective for the control of the stacking sequence of silicate layers. This method could be applicable to various layered silicates that cannot be topotactically converted into three-dimensional networks by simple interlayer condensation by judicious choice of amide molecules. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Influence of pH, layer charge location and crystal thickness distribution on U(VI) sorption onto heterogeneous dioctahedral smectite.

    Science.gov (United States)

    Guimarães, Vanessa; Rodríguez-Castellón, Enrique; Algarra, Manuel; Rocha, Fernando; Bobos, Iuliu

    2016-11-05

    The UO2(2+) adsorption on smectite (samples BA1, PS2 and PS3) with a heterogeneous structure was investigated at pH 4 (I=0.02M) and pH 6 (I=0.2M) in batch experiments, with the aim to evaluate the influence of pH, layer charge location and crystal thickness distribution. Mean crystal thickness distribution of smectite crystallite used in sorption experiments range from 4.8nm (sample PS2), to 5.1nm (sample PS3) and, to 7.4nm (sample BA1). Smaller crystallites have higher total surface area and sorption capacity. Octahedral charge location favor higher sorption capacity. The sorption isotherms of Freundlich, Langmuir and SIPS were used to model the sorption experiments. The surface complexation and cation exchange reactions were modeled using PHREEQC-code to describe the UO2(2+) sorption on smectite. The amount of UO2(2+) adsorbed on smectite samples decreased significantly at pH 6 and higher ionic strength, where the sorption mechanism was restricted to the edge sites of smectite. Two binding energy components at 380.8±0.3 and 382.2±0.3eV, assigned to hydrated UO2(2+) adsorbed by cation exchange and by inner-sphere complexation on the external sites at pH 4, were identified after the U4f7/2 peak deconvolution by X-photoelectron spectroscopy. Also, two new binding energy components at 380.3±0.3 and 381.8±0.3eV assigned to AlOUO2(+) and SiOUO2(+) surface species were observed at pH 6. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Instrumental characterization of the smectite clay–gentamicin hybrids

    Indian Academy of Sciences (India)

    This paper focusses on the intercalation of clay mineral with gentamicin (an aminoglycoside antibiotic). The smectite clay–gentamicin hybrids were prepared by a solution intercalation at 60°C and the process was carried out on unmodified smectite clay and on smectite after Na+ ionic activation. The resulting ...

  8. On the conditions of preparation of hydrated rare earth orthovanadates

    International Nuclear Information System (INIS)

    Nakhodnova, A.P.; Belousova, E.E.; Shuba, Yu.I.; Zaslavskij, L.V.

    1988-01-01

    The properties of Ln(NO 3 ) 3 -Na 3 VO 4 -H 2 O solution series, where Ln is Er, Ho, Eu are investigated by the methods of residual concentrations, conductometry and potentiometry. It is found that at equivalent ratios of the initial components LnVO 4 xmH 2 O hydrated orthovanadates are formed. Deviations towards excess of rare earths or vanadium result in contamination of the compounds by products of side reactions. According to the data on X-ray phase analysis, hydrated erbium, holmium, europium orthovanadates have the zirconium crystal structure typical for anhydrous compounds. It is shown that hydrate water, being a component of orthovanadates, can be referred to adsorbed and interlayer water

  9. A new aluminium-hydrate species in hydrated Portland cements characterized by 27Al and 29Si MAS NMR spectroscopy

    International Nuclear Information System (INIS)

    Andersen, Morten Daugaard; Jakobsen, Hans J.; Skibsted, Jorgen

    2006-01-01

    Recent 27 Al MAS NMR studies of hydrated Portland cements and calcium-silicate-hydrate (C-S-H) phases have shown a resonance from Al in octahedral coordination, which cannot be assigned to the well-known aluminate species in hydrated Portland cements. This resonance, which exhibits the isotropic chemical shift δ iso = 5.0 ppm and the quadrupole product parameter P Q = 1.2 MHz, has been characterized in detail by 27 Al MAS and 27 Al{ 1 H} CP/MAS NMR for different hydrated white Portland cements and C-S-H phases. These experiments demonstrate that the resonance originates from an amorphous or disordered aluminate hydrate which contains Al(OH) 6 3- or O x Al(OH) 6-x (3+x)- units. The formation of the new aluminate hydrate is related to the formation of C-S-H at ambient temperatures, however, it decomposes by thermal treatment at temperatures of 70-90 o C. From the experiments in this work it is proposed that the new aluminate hydrate is either an amorphous/disordered aluminate hydroxide or a calcium aluminate hydrate, produced as a separate phase or as a nanostructured surface precipitate on the C-S-H phase. Finally, the possibilities of Al 3+ for Ca 2+ substitution in the principal layers and interlayers of the C-S-H structure are discussed

  10. Evidence for Smectite Clays from MSL SAM Analyses of Mudstone at Yellowknife Bay, Gale Crater, Mars

    Science.gov (United States)

    McAdam, Amy; Franz, Heather; Mahaffy, Paul R.; Eigenbrode, Jennifer L.; Stern, Jennifer C.; Brunner, Anna; Archer, Paul Douglas; Ming, Douglas W.; Morris, Richard V.; Atreya, Sushil K.

    2013-01-01

    Drilled samples of mudstone from the Sheepbed unit at Yellowknife Bay were analyzed by MSL instruments including the Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments in MSL's Analytical Laboratory. CheMin analyses revealed the first in situ X-ray diffraction based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., saponite) and comprise approx 20% of the mudstone sample (e.g., Bristow et al., this meeting). SAM analyses, which heated the mudstone samples to 1000 C and monitored volatiles evolved to perform in situ evolved gas analysis mass spectrometry (EGA-MS), resulted in a H2O trace exhibiting a wide evolution at temperatures smectite interlayer H2O, and structural H2O/OH from bassanite and akaganeite (identified by CheMin) and H2O/OH from amorphous phases in the sample. The high temperature H2O is consistent with the evolution of H2O from the dehydroxylation of the smectite clay mineral. Comparison to EGA-MS data collected under SAM-like conditions on a variety of clay mineral reference materials indicate that a trioctahedral smectite, such as saponite, is most consistent with the high temperature H2O evolution observed. There may also be SAM EGA-MS evidence for a small high temperature H2O evolution from scoop samples from the Yellowknife Bay Rocknest sand shadow bedform. As in the mudstone samples, this evolution may indicate the detection of smectite clays, and the idea that minor clays may be present in Rocknest materials that could be expected to be at least partially derived from local sources is reasonable. But, because smectite clays were not definitively observed in CheMin analyses of Rocknest materials, they must be present at much lower abundances than the approx 20% observed in the mudstone samples. This potential detection underscores the complementary nature of the MSL CheMin and SAM instruments for investigations of martian sample mineralogy. Information on the nature of Yellowknife

  11. The caesium oxygen interactions in the crystalline solids

    International Nuclear Information System (INIS)

    Leclaire, Andre

    2008-01-01

    Through the study of the Cs-O bonds registered in the literature one observes that: (i)the bond lengths range from 2.46 to 3.60 A; (ii)the preferential coordination numbers adopted by the caesium ions are 8, 9 and 10 but values from 1 to 12 also exist; (iii)the average bond lengths increase with the coordination (CN) of the caesium ions with the following values: 2.714 A (CN=1), 2.98 A (CN=2), 3.057 A (CN=3), 3.104 A (CN=4), 3.149 A (CN=5), 3.188 A (CN=6), 3.224 A (CN=7), 3.245 A (CN=8), 3.261 A (CN=9), 3.269 A (CN=10), 3.293 A (CN=11) and 3.323 A (CN=12). A new R ij =2.469 constant is determined with all the caesium coordination polyhedra to compute electrostatic bond valence sums. The U eq values of caesium in crystal structure are about 0.03 and generally less than 0.06 similar to those of the oxygen atoms and often bigger. - Graphical abstract: A survey of more than 1000 of oxygen polyhedrons around caesium ions shows bond lengths ranging from 2.46 to 3.60 A with 32% of the shortest bonds in the polyhedrons less than 3.00 A. Coordination numbers from 1 to 12 are observed, in which the average bond lengths increase from 2.714 to 3.323 A with the coordination, and with a preference for 8, 9 and 10-fold surrounding

  12. USAGE OF DIOCTAHEDRAL SMECTITE IN CHILDREN WITH ATOPIC DERMATITIS

    Directory of Open Access Journals (Sweden)

    A.S. Botkina

    2008-01-01

    Full Text Available The results of enter sorbent — dioctahedral Smectite (Neosmektin — usage as part of complex therapy of children with atopic dermatitis (ATD. It is shown that the administration of Smectite favored better efficacy of baseline treatment of ATD, more express and quick regression of skin manifestations of the disease, decrease in number of children with eosinophilia. High efficacy of ATD treatment with Smectite indicates the pathogenetic justification of efferent therapy of the disease. Observation results witness the good tolerability of Smectite: side effects related to the treatment were only observed in 14 percent of children.Key words: children, atopic dermatits, smectite, treatment.

  13. Fired products of Cr-smectite clays in nitrogen

    Directory of Open Access Journals (Sweden)

    C. Volzone

    2004-12-01

    Full Text Available The products of Cr-smectite clays heated to 1350 ° C in nitrogen were evaluated by X-ray diffraction and chemical analysis. Cr-smectite clays were prepared at room temperature by contact between smectite clays and Cr species contained in OH-Cr solutions. The Cr species were prepared using chromium nitrate solution by addition of NaOH solution with OH/Cr = 2. Products of firing in nitrogen at the high temperature were different (magnesia chromite, donathite, iron chromium oxide and picrochromite depending on the type of isomorphous substitution of the smectite structure and the amount of retained chromium.

  14. Effect of the crystal chemistry on the hydration mechanism of swelling micas

    Science.gov (United States)

    Pavón, Esperanza; Alba, María D.; Castro, Miguel A.; Cota, A.; Osuna, Francisco J.; Pazos, M. Carolina

    2017-11-01

    Swelling and dehydration under minor changes in temperature and water vapor pressure is an important property that clays and clay minerals exhibit. In particular, their interlayer space, the solid-water interface and the layers' collapse and re-expansion have received much attention because it affects to the dynamical properties of interlayer cations and thus the transfer and fate of water and pollutants. In this contribution, the dehydration and rehydration mechanism of a swelling high-charge mica family is examined by in situ X-ray Diffraction. The effect of the aluminosilicate layer charge and the physicochemical properties of the interlayer cations on these processes are analyzed. The results showed that the dehydration temperature and the number of steps involved in this process are related to the layer charge of the silicate and the physicochemical properties of the interlayer cations. Moreover, the ability to adsorb water molecules in a confined space with high electric field by the interlayer cations does not only depend on their hydration enthalpy but also on the electrostatic parameters of these cations.

  15. Influence of pH, layer charge location and crystal thickness distribution on U(VI) sorption onto heterogeneous dioctahedral smectite

    Energy Technology Data Exchange (ETDEWEB)

    Guimarães, Vanessa [Instituto de Ciências da Terra – Porto, DGAOT, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal); Geobiotec. Departamento de Geociências da Universidade de Aveiro, Campo Universitário de Santiago, 3810-193 Aveiro (Portugal); Rodríguez-Castellón, Enrique; Algarra, Manuel [Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Málaga. Campus de Teatino s/n, 29071 Málaga (Spain); Rocha, Fernando [Geobiotec. Departamento de Geociências da Universidade de Aveiro, Campo Universitário de Santiago, 3810-193 Aveiro (Portugal); Bobos, Iuliu, E-mail: ibobos@fc.up.pt [Instituto de Ciências da Terra – Porto, DGAOT, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal)

    2016-11-05

    Highlights: • The UO{sub 2}{sup 2+} sorption at pH 4 and 6 on heterogeneous smectite structure. • The cation exchange process is affected by layer charge distribution. • Surface complexation and cation exchange modelling. • New binding energy components identified by X-ray photoelectron spectroscopy. - Abstract: The UO{sub 2}{sup 2+} adsorption on smectite (samples BA1, PS2 and PS3) with a heterogeneous structure was investigated at pH 4 (I = 0.02 M) and pH 6 (I = 0.2 M) in batch experiments, with the aim to evaluate the influence of pH, layer charge location and crystal thickness distribution. Mean crystal thickness distribution of smectite crystallite used in sorption experiments range from 4.8 nm (sample PS2), to 5.1 nm (sample PS3) and, to 7.4 nm (sample BA1). Smaller crystallites have higher total surface area and sorption capacity. Octahedral charge location favor higher sorption capacity. The sorption isotherms of Freundlich, Langmuir and SIPS were used to model the sorption experiments. The surface complexation and cation exchange reactions were modeled using PHREEQC-code to describe the UO{sub 2}{sup 2+} sorption on smectite. The amount of UO{sub 2}{sup 2+} adsorbed on smectite samples decreased significantly at pH 6 and higher ionic strength, where the sorption mechanism was restricted to the edge sites of smectite. Two binding energy components at 380.8 ± 0.3 and 382.2 ± 0.3 eV, assigned to hydrated UO{sub 2}{sup 2+} adsorbed by cation exchange and by inner-sphere complexation on the external sites at pH 4, were identified after the U4f{sub 7/2} peak deconvolution by X-photoelectron spectroscopy. Also, two new binding energy components at 380.3 ± 0.3 and 381.8 ± 0.3 eV assigned to ≡AlOUO{sub 2}{sup +} and ≡SiOUO{sub 2}{sup +} surface species were observed at pH 6.

  16. Influence of pH, layer charge location and crystal thickness distribution on U(VI) sorption onto heterogeneous dioctahedral smectite

    International Nuclear Information System (INIS)

    Guimarães, Vanessa; Rodríguez-Castellón, Enrique; Algarra, Manuel; Rocha, Fernando; Bobos, Iuliu

    2016-01-01

    Highlights: • The UO_2"2"+ sorption at pH 4 and 6 on heterogeneous smectite structure. • The cation exchange process is affected by layer charge distribution. • Surface complexation and cation exchange modelling. • New binding energy components identified by X-ray photoelectron spectroscopy. - Abstract: The UO_2"2"+ adsorption on smectite (samples BA1, PS2 and PS3) with a heterogeneous structure was investigated at pH 4 (I = 0.02 M) and pH 6 (I = 0.2 M) in batch experiments, with the aim to evaluate the influence of pH, layer charge location and crystal thickness distribution. Mean crystal thickness distribution of smectite crystallite used in sorption experiments range from 4.8 nm (sample PS2), to 5.1 nm (sample PS3) and, to 7.4 nm (sample BA1). Smaller crystallites have higher total surface area and sorption capacity. Octahedral charge location favor higher sorption capacity. The sorption isotherms of Freundlich, Langmuir and SIPS were used to model the sorption experiments. The surface complexation and cation exchange reactions were modeled using PHREEQC-code to describe the UO_2"2"+ sorption on smectite. The amount of UO_2"2"+ adsorbed on smectite samples decreased significantly at pH 6 and higher ionic strength, where the sorption mechanism was restricted to the edge sites of smectite. Two binding energy components at 380.8 ± 0.3 and 382.2 ± 0.3 eV, assigned to hydrated UO_2"2"+ adsorbed by cation exchange and by inner-sphere complexation on the external sites at pH 4, were identified after the U4f_7_/_2 peak deconvolution by X-photoelectron spectroscopy. Also, two new binding energy components at 380.3 ± 0.3 and 381.8 ± 0.3 eV assigned to ≡AlOUO_2"+ and ≡SiOUO_2"+ surface species were observed at pH 6.

  17. Wound healing effect of bioactive ion released from Mg-smectite.

    Science.gov (United States)

    Sasaki, Yu; Sathi, Gulsan Ara; Yamamoto, Osamu

    2017-08-01

    Bioactive ions like Mg 2+ and Si 4+ have been known as promotion factors of tissue regeneration. In the present work, Mg-smectite, consisting of Mg 2+ and Si 4+ ions, was synthesized by a solution process, and evaluated for the efficiency of the powder on wound healing in rats. White precipitates were obtained by mixing a magnesium chloride hexahydrate solution and a sodium silicate hexahydrate solution at room temperature. The precipitates mixed with a NaOH aqueous solution were subjected to hydrothermal reaction, and finally crystalline Mg-smectite powder was obtained. The crystal and molecular structure of Mg-smectite was identified by X-ray diffractometry (XRD) and Fourier-transform infrared spectroscopy (FT-IR). The synthesized material was determined to be crystalline Mg-smectite. The amount of Mg 2+ and Si 4+ ions released from Mg-smectite in physiological saline was analyzed by inductively coupled plasma mass spectroscopy (ICP-MS). The total amount of Si 4+ ion released from Mg-smectite was greater than that of Mg 2+ ion. To evaluate the wound healing effect of Mg-smectite, Mg-smectite powder was applied to a full-thickness surgical wound reaching the subcutaneous tissue in the rat's abdomen. At 1 and 2weeks, skin tissue was collected and subjected to histological analysis. The results for skin regeneration showed no significant difference in wound size between the control and Mg-smectite group. However, it was found that the neovascularization, collagen deposition, and maturation were notedly accelerated by applying Mg-smectite powder in comparison with the control. Mg-smectite can then be hypothesized to stimulate the regeneration of skin tissue by releasing Mg 2+ and Si 4+ ions. These results suggested that Mg-smectite could offer great potential as a wound dressing material. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. On the conditions of preparation of hydrated rare earth orthovanadates

    Energy Technology Data Exchange (ETDEWEB)

    Nakhodnova, A P; Belousova, E E; Shuba, Yu I; Zaslavskij, L V

    1988-10-01

    The properties of Ln(NO/sub 3/)/sub 3/-Na/sub 3/VO/sub 4/-H/sub 2/O solution series, where Ln is Er, Ho, Eu are investigated by the methods of residual concentrations, conductometry and potentiometry. It is found that at equivalent ratios of the initial components LnVO/sub 4/xmH/sub 2/O hydrated orthovanadates are formed. Deviations towards excess of rare earths or vanadium result in contamination of the compounds by products of side reactions. According to the data on X-ray phase analysis, hydrated erbium, holmium, europium orthovanadates have the zirconium crystal structure typical for anhydrous compounds. It is shown that hydrate water, being a component of orthovanadates, can be referred to adsorbed and interlayer water.

  19. Molecular dynamics of interfacial water and cations associated with clay minerals

    International Nuclear Information System (INIS)

    Cygan, Randall T.; Greathouse, Jeffery A.; Teich-McGoldrick, Stephanie L.; Nenoff, Tina M.; Daemen, Luke L.

    2012-01-01

    Document available in extended abstract form only. Clay mineral interfaces, including interlayer and external surfaces, play an essential role in many geochemical processes. Adsorption, dissolution, precipitation, nucleation, and growth mechanisms, in particular, are controlled by the interplay of structure, thermodynamics, kinetics, and transport at clay mineral-water interfaces. Molecular details of these geochemical processes are especially important in evaluating the fate of radionuclide waste in the environment. Such details are typically beyond the sensitivity of experimental and analytical methods and therefore require accurate models and simulations. Also, the basal surfaces and interlayers of clay minerals offer structurally constrained interfacial environments to better evaluate the local molecular chemistry. We have developed and used classical and quantum methods to examine the complex behavior of clay mineral-water interfaces and dynamics of interlayer species. Bulk structures, swelling behavior, diffusion, and adsorption processes are evaluated and compared to experimental and spectroscopic findings. In particular, inelastic neutron scattering methods provide a successful probe of vibrational behavior of interlayer species to help guide the simulations. Librations involving rock, wag, and twist motions of water molecules are particularly sensitive to the interlayer environment of smectite minerals such as montmorillonite and beidellite. Trends in librational modes for interlayer water as a function of clay structure and cation hydration energy are readily explained using structural and vibrational analysis derived from molecular simulation. Molecular dynamics simulations of virtual phases, including hydrated pyrophyllite, help to explain the behavior of interlayer water that is not associated with cation species. Additionally, we use large-scale molecular dynamics simulations of other layered minerals, such as muscovite, to evaluate adsorption

  20. Adsorption, aggregation, and desorption of proteins on smectite particles.

    Science.gov (United States)

    Kolman, Krzysztof; Makowski, Marcin M; Golriz, Ali A; Kappl, Michael; Pigłowski, Jacek; Butt, Hans-Jürgen; Kiersnowski, Adam

    2014-10-07

    We report on adsorption of lysozyme (LYS), ovalbumin (OVA), or ovotransferrin (OVT) on particles of a synthetic smectite (synthetic layered aluminosilicate). In our approach we used atomic force microscopy (AFM) and quartz crystal microbalance (QCM) to study the protein-smectite systems in water solutions at pH ranging from 4 to 9. The AFM provided insights into the adhesion forces of protein molecules to the smectite particles, while the QCM measurements yielded information about the amounts of the adsorbed proteins, changes in their structure, and conditions of desorption. The binding of the proteins to the smectite surface was driven mainly by electrostatic interactions, and hence properties of the adsorbed layers were controlled by pH. At high pH values a change in orientation of the adsorbed LYS molecules and a collapse or desorption of OVA layer were observed. Lowering pH to the value ≤ 4 caused LYS to desorb and swelling the adsorbed OVA. The stability of OVT-smectite complexes was found the lowest. OVT revealed a tendency to desorb from the smectite surface at all investigated pH. The minimum desorption rate was observed at pH close to the isoelectric point of the protein, which suggests that nonspecific interactions between OVT and smectite particles significantly contribute to the stability of these complexes.

  1. Fired products of Cr-smectite clays in nitrogen

    OpenAIRE

    C. Volzone; A. M. Cesio

    2004-01-01

    The products of Cr-smectite clays heated to 1350 ° C in nitrogen were evaluated by X-ray diffraction and chemical analysis. Cr-smectite clays were prepared at room temperature by contact between smectite clays and Cr species contained in OH-Cr solutions. The Cr species were prepared using chromium nitrate solution by addition of NaOH solution with OH/Cr = 2. Products of firing in nitrogen at the high temperature were different (magnesia chromite, donathite, iron chromium oxide and picrochromi...

  2. Smectite Formation in Acid Sulfate Environments on Mars

    Science.gov (United States)

    Peretyazhko, T. S.; Niles, P. B.; Sutter, B.; Clark, J. V.; Morris, R. V.; Ming, D. W.

    2017-01-01

    Phyllosilicates of the smectite group detected in Noachian and early Hesperian terrains on Mars were hypothesized to form under aqueous conditions that were globally neutral to alkaline. These pH conditions and the presence of a CO2-rich atmosphere should have been favorable for the formation of large carbonate deposits. However, large-scale carbonate deposits have not been detected on Mars. We hypothesized that smectite deposits are consistent with perhaps widespread acidic aqueous conditions that prevented carbonate precipitation. The objective of our work was to investigate smectite formation under acid sulfate conditions in order to provide insight into the possible geochemical conditions required for smectite formation on Mars. Hydrothermal batch incubation experiments were performed with Mars-analogue, glass-rich, basalt simulant in the presence of sulfuric acid of variable concentration.

  3. Production of intensive negative lithium beam with caesium sputter-type ion source

    Science.gov (United States)

    Lobanov, Nikolai R.

    2018-01-01

    Compounds of lithium oxide, hydroxide and carbonate, mixed with silver, were prepared for use as a cathode in caesium-sputter ion source. The intention was to determine the procedure which would produce the highest intensity negative lithium beams over extended period and with maximum stability. The chemical composition and properties of the samples were analysed using mass-spectrometry, optical microscopy, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analyses (EDX) and Raman spectroscopy. These analyses showed that the chemical transformations with components resulted from pressing, storage and bake out were qualitatively in agreement with expectations. Intensive negative lithium ion beams >1 μA were delivered using cathodes fabricated from materials with multicomponent chemical composition when the following conditions were met: (i) use of components with moderate enthalpy of formation; (ii) low moisture content at final stage of cathode production and (iii) small concentration of water molecules in hydrate phase in the cathode mixture.

  4. Thermodynamics of hydration of MX80-Na. What are the best approaches for evaluating the thermodynamic properties of hydration?

    International Nuclear Information System (INIS)

    Vieillard, P.; Lassin, A.; Blanc, P.; Gailhanou, H.; Gaboreau, S.; Gaucher, E.C.; Denoyel, R.; Bloch, E.; Fialips, C.; Giffaut, E.

    2012-01-01

    Document available in extended abstract form only. In the context of a waste disposal within clayey formations (Callovian-Oxfordian argillite) or using clayey barriers, the prediction of the long-term behavior requires the thermodynamic properties of clay minerals. It has been shown by Gailhanou et al. (submitted) that hydration reactions may have some dramatic consequences on the thermodynamic properties of clay minerals. Different theoretical models exist for extracting thermodynamic properties from water adsorption/desorption isotherms. The present work aims at investigating and comparing these methods, because they can provide very different results based on the assumptions of each models. First, three types of models are compared: 1) the Hill (1949) model based on heat of adsorption combined with adsorption isotherm, 2) the Jura and Hill (1951) model, based on the Clausius-Clapeyron relation, and 3) the BET theory. Both have been designed in order to describe surface sorption phenomena. For instance, they suppose that the number of sorption sites is constant during all the vapor sorption process (and at any relative humidity, P/P 0 ). The hydration reaction approach can also be used. Compared to the three previous models, it is not structurally constrained, except for mass balance considerations on the H 2 O component. It had been especially developed by Tardy and Touret, (1985) and modified into a solid solution model, first by Ransom and Helgeson, (1994). It relies simply on the reaction: Clay(dehydrated) + nH 2 O = Clay(hydrated).nH 2 O. The different families of models have been compared to experimental measurements performed on a sodic smectite MX80. The set of experiments includes a series of three adsorption/desorption isotherms obtained at 25, 45 and 60 C and a heat of adsorption combined with a adsorption isotherm obtained at 25 C. The heat of adsorption was derived from the 3 adsorption/desorption isotherms by using the different models. Then

  5. Caesium absorption by barley - influence of its retention by the soil - competitive action of potassium

    International Nuclear Information System (INIS)

    Ferron-Trosseau, F.

    1964-06-01

    We have studied, in various culture media, how the absorption of caesium by barley varies with its concentration, and how this absorption can be in competition with a similar alkali cation-potassium. We have also considered the caesium distribution in the ground in particular radio-active caesium, between the soil and solution, as a function of the amount of caesium. From our work it is clear that barley behaves very differently according to whether the caesium is in a nutritive solution or is in the soil: for a nutritive solution, the fraction of caesium (radioactive and stable) absorbed by barley remains practically constant in the presence of increasing amounts (relatively small) of stable caesium; in soil, the fraction of the radio-active caesium absorbed increases as the stable caesium content (fairly low) of the soil increases, in relationship with a rapidly decreasing selectivity of the soil for Cs + . The difference between these results is thus explained by the very pronounced selectivity of the illitic soil studied for Cs + , as long as the proportion of Cs remains low, about as low as that of most natural soils. Furthermore, the K + ion is in competition with the Cs + ion, for absorption by barley in a culture medium in a nutritive solution or in soil, only when the potassium concentrations are relatively low, of the order of the nutritive maximum. This shows that the addition of potassium to a medium already rich in this element does not reduce the absorption of caesium by barley. The choice of experimental conditions close to natural conditions (nutritive media strong in calcium) and the examination of the distribution of radioactive caesium between the soil, the soil solution and the plant in the presence of very low doses of stable caesium make these results interesting from the 'atomic health' point of view; it should be expected that a definite contamination risk exists for plants cultivated on synthetic media and for plants such as rice and cress

  6. Influence of Iltization on the Ion-sorbing Capacity of Smectitic Clay

    International Nuclear Information System (INIS)

    Lee, Jae Owan; Cho, Won Jin

    2008-01-01

    A high-level waste(HLW) repository uses smectitic clay as a buffer material to inhibit the penetration of groundwater and to retard the release of radionuclides from the radioactive wastes to the surrounding environment. However, when the smectitic clay is exposed to an elevated temperature due to radioactive decay heat and geochemical conditions for a long time, its physicochemical and mineralogical properties may be degradated and thus lose its barrier functions. It has been known in literature that the degradation of these properties of the smectitic clay occurs by a illitization in which the smectite transforms into illite. Therefore, an understanding of the illitization is essential to evaluate the long-term barrier performance of smectitic clay for the buffer of a HLW repository. This paper will carry out hydrothermal reaction tests with domestic smectitic clay which will be favorably considered for the buffer material of a Korean HLW repository, and also investigate the influence of illization on the ion-sorbing capacity of the smectitic clay

  7. A study of sorption mechanism onto cement hydrates by isotherm measurements

    International Nuclear Information System (INIS)

    Sugiyama, Daisuke; Fujita, Tomonari

    2003-01-01

    In the concept for TRU waste disposal in Japan, cement is a potential waste packaging and backfilling material and is expected to provide chemical containment. In particular, the sorption of radionuclides onto cement material, which controls the aqueous concentrations of elements in the porewater, is a very important parameter when considering the release of radionuclides from the near field of a repository. Many safety assessment calculations currently assume radionuclide retardation as linear sorption equilibrium and describe it with a distribution ratio (R d value). In this study, the sorption mechanism is discussed by measuring the sorption isotherm of caesium, strontium and thorium onto Ordinary Portland Cement (OPC) and Calcium Silicate Hydrate (C-S-H gel), to justify and support this assumption. In addition, the effect of competitive sorption between thorium and uranium and other groundwater ions is studied by examining sorption using a range of sodium chloride concentrations to simulate different groundwater ionic strengths. Based on the experimental results, we have showed that: Caesium and strontium sorb by substitution for Ca in C-S-H phases and the presence of some calcium sites with different ion-exchange log K values is suggested; Thorium would be fixed in a surface co-precipitation to form a solubility-limiting phase. The results of sorption experiments are reasonably well modelled by the ion-exchange model for caesium and strontium and the surface co-precipitation model for thorium, respectively. (author)

  8. Formation of interlayer gap and control of interlayer burr in dry drilling of stacked aluminum alloy plates

    Directory of Open Access Journals (Sweden)

    Tian Wei

    2016-02-01

    Full Text Available In aircraft assembly, interlayer burr formation in dry drilling of stacked metal materials is a common problem. Traditional manual deburring operation seriously affects the assembly quality and assembly efficiency, is time-consuming and costly, and is not conducive to aircraft automatic assembly based on industrial robot. In this paper, the formation of drilling exit burr and the influence of interlayer gap on interlayer burr formation were studied, and the mechanism of interlayer gap formation in drilling stacked aluminum alloy plates was investigated, a simplified mathematical model of interlayer gap based on the theory of plates and shells and finite element method was established. The relationship between interlayer gap and interlayer burr, as well as the effect of feed rate and pressing force on interlayer burr height and interlayer gap was discussed. The result shows that theoretical interlayer gap has a positive correlation with interlayer burr height and preloading pressing force is an effective method to control interlayer burr formation.

  9. The smectite to chlorite transition in the Chipilapa geothermal system, El Salvador

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, D. [Univ. of Bristol (United Kingdom). Dept. of Earth Sciences; Santana de Zamora, A. [Comision Ejecutiva Hidroelectrica del Rio Lempa (El Salvador)

    1999-04-01

    Clay mineralogical, X-ray diffraction and electron microprobe studies have been carried out on separated <2 {micro}m fractions from cutting and core material from three wells in the Chipilapa geothermal system in El Salvador. The data indicate that the smectite to chlorite transition is prevalent, but a secondary smectite to illite transition is also present. At depths approximately <750 m, smectite with very minor chlorite mixed-layers (approximately <15%) is dominant, and has a composition midway between a di- and tri-smectite. At {approximately}750 m there is a very clear distinction and sharp transition into discrete chlorite with very minor smectite mixed-layers (approximately <10%). Corrensite is recorded only as a rare and minor phase. Smectite occurs in abundance at temperatures up to {approximately}200 C, and the transition from a smectite-dominant to chlorite-dominant assemblage takes place over a narrow temperature range ({approximately}150 to 200 C). The stability range of smectite is very similar to that recorded in other geothermal systems, whereas the smectite to chlorite transition differs greatly from that recorded in other systems. The transition does not involve continuous chlorite/smectite mixed-layering but a marked step: It is the sharpest and most discontinuous stepped sequence of this mineralogical transition recorded.

  10. Laser spectroscopy of collisionally prepared target species: atomic caesium

    International Nuclear Information System (INIS)

    Moreau, J.-P.; Tremblay, Julien; Knystautas, E.J.; Laperriere, S.C.; Larzilliere, Michel

    1989-01-01

    Fast ion beam bombardment was used to collisionally prepare a target gas in excited states, to which conventional laser spectroscopy was then applied. The versatility of this method is demonstrated with atomic targets of caesium, for a state of Cs + that is 16 eV above the ground state, as well as for a short-lived state (38 ns) of the neutral atom. The local temperature in the caesium oven is also obtained. (Author)

  11. Siderophore-promoted dissolution of smectite by fluorescent Pseudomonas.

    Science.gov (United States)

    Ferret, Claire; Sterckeman, Thibault; Cornu, Jean-Yves; Gangloff, Sophie; Schalk, Isabelle J; Geoffroy, Valérie A

    2014-10-01

    Siderophores are organic chelators produced by microorganisms to fulfil their iron requirements. Siderophore-promoted dissolution of iron-bearing minerals has been clearly documented for some siderophores, but few studies have addressed metabolizing siderophore-producing bacteria. We investigated iron acquisition from clays by fluorescent Pseudomonads, bacteria that are ubiquitous in the environment. We focused on the interactions between smectite and Pseudomonas aeruginosa, a bacterium producing two structurally different siderophores: pyoverdine and pyochelin. The presence of smectite in iron-limited growth media promoted planktonic growth of P. aeruginosa and biofilm surrounding the smectite aggregates. Chemical analysis of the culture media indicated increases in the dissolved silicon, iron and aluminium concentrations following smectite supplementation. The use of P. aeruginosa mutants unable to produce either one or both of the two siderophores indicated that pyoverdine, the siderophore with the higher affinity for iron, was involved in iron and aluminium solubilization by the wild-type strain. However, in the absence of pyoverdine, pyochelin was also able to solubilize iron but with a twofold lower efficiency. In conclusion, pyoverdine and pyochelin, two structurally different siderophores, can solubilize structural iron from smectite and thereby make it available for bacterial growth.

  12. Natural sorptive barriers in Yucca Mountain, Nevada, for long-term isolation of high-level waste

    International Nuclear Information System (INIS)

    Bish, D.L.; Vaniman, D.T.; Rundberg, R.S.; Wolfsberg, K.; Daniels, W.R.; Broxton, D.E.

    1984-01-01

    There are several sorptive phases occurring naturally in the silicic tuffs at Yucca Mountain, Nevada, that can aid in the long-term isolation of high-level wastes. These phases include hydrated volcanic glasses, smectites and zeolites. Los Alamos has a continuing programme to investigate the mineralogy and stratigraphy of the tuffs at Yucca Mountain. In addition, extensive data have been obtained on the sorptive behaviour of technetium, strontium, caesium, barium, cerium, europium, uranium, neptunium, plutonium and americium on the minerals in tuffs. Sorption of elements by ion-exchange processes is high in tuffs containing smectite and the zeolites clinoptilolite-heulandite and mordenite. Moreover, sorption correlates with abundances of these minerals. Sorption is not as high for the zeolite analcime and for volcanic glass. Elements that may not sorb by ion exchange, e.g. plutonium, also tend to be sorbed when the zeolite abundance is high, but the correlations are less clearly defined. Because of the correlation between sorptive capacity and mineralogy, an accurate knowledge of mineral distribution and stratigraphy is essential. The distribution of hydrated glasses is stratigraphically controlled, and the glasses occur in narrow unaltered horizons as vitrophyres and as vitric tuff. Although glasses are of minor importance as sorptive phases, they are very reactive and can alter to other minerals if heated in the presence of water. Smectite clays are reversibly expandable and are widespread in tuffs, but their beneficial properties can be modified by prolonged exposure to elevated temperatures. The zeolites clinoptilolite-heulandite and mordenite occur in high concentrations in silicic tuffs, mostly as secondary alterations of non-welded and poorly welded tuffs; their distribution is therefore stratigraphically controlled

  13. Considering clay rock heterogeneity in radionuclide retention

    International Nuclear Information System (INIS)

    Grambow, B.; Montavon, G.; Tournassat, C.; Giffaut, E.; Altmann, S.

    2010-01-01

    considering the measured mass fraction of illite, I/S, and kaolinite. Five values were fitted simultaneous in the overall fit: the CECs of the kaolinite, the smectite and illite components as well as the illite fraction in both R0 and R1 I/S. For transport calculations of radionuclides it is important to know which part of the overall porosity belongs to the micropores and which to the interlayers of the smectite layers in the inter-stratified I/S. Making the hypothesis that, at the given degree of compaction, these interlayers are hydrated by two water layers one could calculate the fraction of micropores in total porosity from the measured I/S content and the fitted I/S ratio given for either R0 or R1. For high smectite contents there is about twice as much water in interlayers than in the micropores, while there is much more water in the micropores in case of low smectite contents. The retention and porosity models for Bentonite have been adapted successfully to argillite samples for various drill cores assuming additivity of the various mineralogical contributions, in particular illite and I/S and of the illite to smectite ratio in I/S. The approach leads to a reasonable quantitative representation of the CEC as well as of surface complexation site densities as a function of depth and mineralogical composition. Ratios of micropores to interlayer pore space were obtained as well. The good correlation of calculated and measured retention data for Cs and for Ni gave reasonable justification to apply the model for the prediction of K d variations of Cs all along a drill core. Predicted values vary by about a factor of 10. (authors)

  14. Experience of iodine, caesium and noble gas release from AGR failures

    International Nuclear Information System (INIS)

    Chapman, C.J.; Harris, A.M.; Phillips, M.E.

    1985-01-01

    In the event of a fuel failure in an Advanced Gas Cooled Reactor (AGR), the quantity of fission products available for release to the environment is determined by the transport of fission products in the UO 2 fuel, by the possible retention of fission products in the fuel can interspace and by the deposition of fission products on gas circuit surfaces ('plate-out'). The fission products of principal radiological concern are radioactive caesium (Cs-137 and Cs-134) and iodine (principally I-131). Results are summarised of a number of experiments which were designed to study the release of these fission products from individual fuel failures in the prototype AGR at Windscale. Results are also presented of fission product release from failures in commercial AGRs. Comparisons of measured releases of caesium and iodine relative to the release of the noble gas fission products show that, for some fuel failures, there is a significant retention of caesium and iodine within the fuel can interspace. Under normal conditions circuit deposition reduces caesium and iodine gas concentrations by several orders of magnitude. Differing release behaviour of caesium and iodine from the failures is examined together with subsequent deposition within the sampling equipment. These observations are important factors which must be considered in developing an understanding of the mechanisms involved in circuit deposition. (author)

  15. Rheological properties of sodium smectite clay

    International Nuclear Information System (INIS)

    Boergesson, L.; Hoekmark, H.; Karnland, O.

    1988-12-01

    The rheological properties of Na-smectite Mx-80 have been investigated by various laboratory tests. The investigations include determination of the hydraulic conductivity, the undrained stress-strain-strength properties, the creep properties, the compression and swelling properties in drained and undrained conditions and the undrained thermomechanical properties. Measurements have been made at different densities, clay/sand mixtures and pore water compositions. The influence of temperature, rate of strain and testing technique has also been considered. The investigation has led to a supply of basic data for the material models which will be used at performance calculations. The results have also increased the general understanding of the function of smectitic clay as buffer material. The microstructural behaviour has been considered at the validation of the different test results and the validity of the effective stress theory has been discussed. Comparisons with the properties of Ca-smectite have also been made. (orig.)

  16. New selective ligands for caesium. Application to Cs+/Na+ separation by nano-filtration-complexation in aqueous phase

    International Nuclear Information System (INIS)

    Pellet-Rostaing, S.; Chitry, F.; Lemaire, M.; Guy, A.; Foos, J.

    2000-01-01

    Separating traces of caesium from aqueous medium containing high sodium concentration is a harsh problem because caesium and sodium have a similar behaviour in aqueous medium. The aim of our study was to select a highly caesium-selective ligand in a nano-filtration-complexation process in order to achieve Cs + /Na + separation. This process involve a nano-filtration step combined with a preliminary complexation step. Caesium complexes are retained by the nano-filtration membrane whereas free sodium cations pass through it. We tried to find a relation between the ligands structure and their activity towards caesium-complexation. Among the synthesized receptors, Tetra-hydroxylated bis-crown-6 calix[4]arene was found to be the more caesium-selective ligand (S=β(Cs + )/β(Na+)=6600). Combined with a nano-filtration process, this ligand helped reaching 90% caesium retention in a highly concentrated aqueous medium ([NaNO 3 ] = 3 mol/L). (authors)

  17. Decreasing of transfer of caesium and strontium radionuclides from soil to vegetation - Use of modified aluminosilicates for decreasing of transfer of caesium and strontium radionuclides from soil to vegetation

    Energy Technology Data Exchange (ETDEWEB)

    Voronina, Anna V.; Blinova, Marina O.; Semenischev, Vladimir S.; Kutergin, Andrey S. [Ural federal university, 620002 Ekaterinburg (Russian Federation)

    2014-07-01

    The method of addition of sorbents to soils is seemed to be the most efficient for decreasing of transfer of radionuclides from soil to vegetation. Using sorbents should possess affinity to natural systems, high specificity and selectivity and also irreversibility of sorption of radionuclides for effective retention of radionuclides as well as to prevent their migration into vegetation and further movement through food chains. Specificity, selectivity and reversibility of sorption of caesium and strontium radionuclides by natural aluminosilicates (glauconite, clinoptilolite) and modified ferrocyanide sorbents based on them was studied in this work. It was shown that the natural glauconite sorbs caesium from tap water with distribution coefficient K{sub d} = 10{sup (3.5±0.1)} mL/g, static exchange capacity of Cs is 11.0 mg/g; it shows lower specificity to strontium: K{sub d} = 10(2.5±0.1) mL/g, static exchange capacity = 9 mg/g. For clinoptilolite these parameters are for caesium K{sub d} = 10(4.4±0.5) mL/g, static exchange capacity 210 mg/g; for strontium K{sub d} = 10(3.5±0.1) mL/g, capacity = 12 mg/g. Ferrocyanide sorbents concentrate caesium radionuclides more effectively: distribution coefficient of Cs from tap water by mixed nickel-potassium ferrocyanide based on glauconite is 10(5.9±1.6) mL/g, static exchange capacity of Cs is (63.0±2.0) mg/g; for mixed nickel-potassium ferrocyanide based on clinoptilolite these characteristics are respectively 10(7.4±1.3) mL/g, 500 mg/g. In case of modified sorbents specificity to strontium remains the same as for natural aluminosilicates. Reversibility of sorption of caesium by natural glauconite and ferrocyanide sorbent was determined as caesium leaching degree from saturated samples. High caesium leaching rates and degrees are typical for natural glauconite irrespective of leachant salinity: total degree of leaching after 35 days of leaching was: mineral water = 63.4%, tap water = 41.6% and rain water = 28.8%. For

  18. Mechanism of caesium ion exchange on potassium cobalt hexacyanoferrates(II)

    Energy Technology Data Exchange (ETDEWEB)

    Lehto, J.; Haukka, S.; Harjula, R. (Helsinki Univ. (Finland). Dept. of Radiochemistry); Blomberg, M. (Helsinki Univ. (Finland). Dept. of Physics)

    1990-03-01

    The caesium uptakes by K{sub 2}(CoFe(CN){sub 6}) and non-stoicheiometric compounds K{sub 2/x}Co{sub x/2}(CoFe(CN){sub 6}) were found to correlate directly with the specific surface areas of the products with x < 1. The exchange process is assumed to involve only the outermost surface layer of their crystals, which have cubic lattice, i.e. only potassium (or cobalt) ions inside the elementary cubes closest to the surface of the crystals are exchanged for caesium ions. Compounds with x > 1 are mixtures of cubic potassium cobalt hexacyanoferrate (ii) and tetragonal Co{sub 2}Fe(CN){sub 6}. The thermodynamic equilibrium constant of the caesium exchange on K{sub 2}(CoFe(CN){sub 6}) was found to have a high value of 125. (author).

  19. Caesium fallout as a tracer of erosion-sedimentation

    International Nuclear Information System (INIS)

    Bouhlassa, S.; Azenfar, A.; Machrouh, A.

    1994-01-01

    The purpose of this paper is to set up a methodology of use of radioactive caesium fallout, to measure erosion and sedimentation in a sub-catchment and to establish the effects of geomorphological parameters, land uses and soil nature, on the losses caesium by physical process. The result obtained by this new and elegant approach, on a watershed of 4114 ha., studied before by classical and conventional techniques, gives a good evaluation of erosion, but also sedimentation rate, and permit to stand up, a model and sampling strategy, to extend the method to large catchment. 1 tab., 2 refs. (author)

  20. Adsorption of poly(ethylene oxide) on smectite: Effect of layer charge.

    Science.gov (United States)

    Su, Chia-Chi; Shen, Yun-Hwei

    2009-04-01

    The adsorption of polymers on clay is important in many applications. However the mechanisms of poly(ethylene oxide) (PEO) adsorption on smectite is not well elucidated at present. The aim of this study was to investigate the effect of layer charge density on the adsorption of PEO by smectite. The results indicated that both the hydrophobic interaction (between CH(2)CH(2) groups and siloxane surface) and the hydrogen bonding (between ether oxygen of PEO and structure OH of smectite) lead to PEO preferential adsorption on the surface of low-charge smectite. In addition, the delamination of low-charge smectite in water is enhanced upon PEO adsorption presumably due to the hydrophilic ether oxygen of adsorbed PEO.

  1. Investigation of the elution by seawater of caesium and strontium from loaded clinoptilolite

    International Nuclear Information System (INIS)

    Harder, B.R.; Mitchell, I.H.; Smyth, M.J.

    1985-07-01

    Simple investigations of the elution of caesium and strontium from loaded clinoptilolite are described. The clinoptilolite was loaded to levels expected in the British Nuclear Fuels plc SIXEP plant and contacted with seawater at approx. 15 C. (The elution time was measured until about 99% of the caesium and strontium had been eluted.) It was found that 99% of the caesium was eluted in 35 hours but the strontium (with more variable results) took at least 400 hours for 99% elution. (author)

  2. Removal of lead and phosphate ions from aqueous solutions by organo-smectite.

    Science.gov (United States)

    Bajda, Tomasz; Szala, Barbara; Solecka, Urszula

    2015-01-01

    Smectite has been modified using hexadecyltrimethyl ammonium bromide in an amount of double cationic exchange capacity. This alteration makes it possible to use organo-smectite as a sorbent to remove anionic forms. The experiment consisted of the interchangeable sorption of phosphate(V) and lead(II) by organo-smectite. Research was carried out with varying pH (2-5) and various concentrations (0.1-5 mmol/L). Organo-smectite with previously adsorbed lead ions removed more phosphate than the untreated organo-smectite. Experimental data show that lead is more likely to absorb on the organo-smectite than on the organo-smectite with previously adsorbed phosphate ions. It follows that the most effective use of the organo-smectite is through the sorption of first - Pb cations and then PO4 anions. With an increasing concentration of Pb(II) or P(V), the sorption efficiency increases. The maximum sorption efficiency of lead and phosphate ions is observed at pH 5. This enables the removal of harmful lead and phosphorus compounds from waste water and immobilizes them on the sorbent's surface. The alternating reactions of lead and phosphorus ions result in the crystallization of brompyromorphite Pb5(PO4)3Br.

  3. Occurrence of Fe-Mg-rich smectites and corrensite in the Morron de Mateo bentonite deposit (Cabo de Gata region, Spain): A natural analogue of the bentonite barrier in a radwaste repository

    Energy Technology Data Exchange (ETDEWEB)

    Pelayo, M., E-mail: m.pelayo@ciemat.es [Departamento de Medio Ambiente, CIEMAT, Avda. Complutense 22, 28040 Madrid (Spain); Garcia-Romero, E. [Departamento de Cristalografia y Mineralogia, Facultad C.C. Geologicas, UCM, 28040 Madrid (Spain); Labajo, M.A.; Perez del Villar, L. [Departamento de Medio Ambiente, CIEMAT, Avda. Complutense 22, 28040 Madrid (Spain)

    2011-07-15

    Highlights: > A hydrothermal process transformed Fe-Mg smectites into corrensite. > This transformation was favoured by the intrusion of the Morron de Mateo dome. > The intrusion caused a temperature increased and a supply of Fe-Mg rich solutions. > The system can be a good natural analogue of bentonite barrier in a radwaste disposal. > Experimental studies of stability of bentonite are in agreement with the results. - Abstract: The Morron de Mateo bentonite deposit is being studied as a natural analogue of the thermal and geochemical effects on a bentonite barrier in a deep geological repository of high level radioactive wastes. This bentonite deposit and its host rocks were intruded by a rhyodacitic volcanic dome that induced a hydrothermal metasomatic process affecting the biocalcarenite beds close to the dome. In this work, the mineralogical and chemical features of the clay minerals of the hydrothermally altered pyroclastic (white tuffs) and epiclastic rocks (mass flow), located in the NE sector of the Morron de Mateo deposit are described. White tuffs have a high content of phyllosilicates, mainly composed of dioctahedral smectites, while mass flow have a higher proportion of inherited minerals, the neoformed phyllosilicates are dioctahedral smectites and an interlayer chlorite/smectite mineral of corrensite type. The chemical composition of smectites reflects the different nature of the parent rocks, in such a way that smectites from white tuffs have a quite homogeneous chemical composition and their structural formulae correspond to montmorillonite type, while smectites from mass flow show more chemical variability, higher Fe and Mg contents and a mean structural formulae corresponding to Fe-Mg-rich beidellite and/or to an intermediate smectite member between beidellite and saponite. In addition, chemical composition and textural features of corrensite-like clay minerals in relation to Fe-Mg-rich smectites in the samples have also been studied, suggesting

  4. Occurrence of Fe-Mg-rich smectites and corrensite in the Morron de Mateo bentonite deposit (Cabo de Gata region, Spain): A natural analogue of the bentonite barrier in a radwaste repository

    International Nuclear Information System (INIS)

    Pelayo, M.; Garcia-Romero, E.; Labajo, M.A.; Perez del Villar, L.

    2011-01-01

    Highlights: → A hydrothermal process transformed Fe-Mg smectites into corrensite. → This transformation was favoured by the intrusion of the Morron de Mateo dome. → The intrusion caused a temperature increased and a supply of Fe-Mg rich solutions. → The system can be a good natural analogue of bentonite barrier in a radwaste disposal. → Experimental studies of stability of bentonite are in agreement with the results. - Abstract: The Morron de Mateo bentonite deposit is being studied as a natural analogue of the thermal and geochemical effects on a bentonite barrier in a deep geological repository of high level radioactive wastes. This bentonite deposit and its host rocks were intruded by a rhyodacitic volcanic dome that induced a hydrothermal metasomatic process affecting the biocalcarenite beds close to the dome. In this work, the mineralogical and chemical features of the clay minerals of the hydrothermally altered pyroclastic (white tuffs) and epiclastic rocks (mass flow), located in the NE sector of the Morron de Mateo deposit are described. White tuffs have a high content of phyllosilicates, mainly composed of dioctahedral smectites, while mass flow have a higher proportion of inherited minerals, the neoformed phyllosilicates are dioctahedral smectites and an interlayer chlorite/smectite mineral of corrensite type. The chemical composition of smectites reflects the different nature of the parent rocks, in such a way that smectites from white tuffs have a quite homogeneous chemical composition and their structural formulae correspond to montmorillonite type, while smectites from mass flow show more chemical variability, higher Fe and Mg contents and a mean structural formulae corresponding to Fe-Mg-rich beidellite and/or to an intermediate smectite member between beidellite and saponite. In addition, chemical composition and textural features of corrensite-like clay minerals in relation to Fe-Mg-rich smectites in the samples have also been studied

  5. Dynamic weakening of smectite-rich faults at intermediate to high velocities

    Science.gov (United States)

    Oohashi, K.; Hirose, T.; Takahashi, M.

    2013-12-01

    Smectite, one of the hydrous clay mineral, is ubiquitous in incoming sediments to subduction zones and is thought to weaken and stabilize subduction thrust faults. However, frictional properties of smectite alone cannot explain the nucleation and propagation of earthquake slip at the shallow plate boundary thrust which potentially causes the devastating tsunamis. Here, we investigate for the first time the effect of smectite fraction in smectite-quartz mixtures on friction at 30 μm/s to 1.3 m/s, to shed a light on the frictional response for the intermediate to high slip rates where the conventional friction experiments have not been explored. In the low slip rate of 30 μm/s, the steady-state coefficient of friction decreases non-linearly increasing smectite fraction: it drops rapidly at moderate fraction of 30-50 vol%. On the other hand, at the faster slip rates of ≥ 150 μm/s the friction lowers from 10-20 vol% fraction since drastic slip weakening appears for the mixtures of ~20 vol % smectite. Hence the fault suddenly loses the strength by adding only 20 % of smectite. The weakening seems to be associated with an excess pore pressure invoked by shear compaction and thermal pressurization during the experiments. This property weakens the fault strength and accelerates the fault slip, even if clay content is small (c.a. 15-35 %), leading to the large stress drop. In contrast, the faults rich in smectite (≥ 50 %) may cause small stress drop during the faulting owing to low friction coefficient of smectite at any slip rates. The results highlight that smectite content significantly affects frictional properties of faults and may generates the diversity in the subduction zone earthquakes. ACKNOLEDGEMENTS We thank Kyuichi Kanagawa, Masaya Suzuki, Osamu Tadai, and Hiroko Kitajima for constructive discussions and technical help. This work was supported by a JSPS Grant-in-Aid for JSPS fellows (25-04960) to KO, a JSPS Grant-in-Aid for Young Scientists (B) (20740264

  6. Ion sieving in graphene oxide membranes via cationic control of interlayer spacing

    Science.gov (United States)

    Chen, Liang; Shi, Guosheng; Shen, Jie; Peng, Bingquan; Zhang, Bowu; Wang, Yuzhu; Bian, Fenggang; Wang, Jiajun; Li, Deyuan; Qian, Zhe; Xu, Gang; Liu, Gongping; Zeng, Jianrong; Zhang, Lijuan; Yang, Yizhou; Zhou, Guoquan; Wu, Minghong; Jin, Wanqin; Li, Jingye; Fang, Haiping

    2017-10-01

    Graphene oxide membranes—partially oxidized, stacked sheets of graphene—can provide ultrathin, high-flux and energy-efficient membranes for precise ionic and molecular sieving in aqueous solution. These materials have shown potential in a variety of applications, including water desalination and purification, gas and ion separation, biosensors, proton conductors, lithium-based batteries and super-capacitors. Unlike the pores of carbon nanotube membranes, which have fixed sizes, the pores of graphene oxide membranes—that is, the interlayer spacing between graphene oxide sheets (a sheet is a single flake inside the membrane)—are of variable size. Furthermore, it is difficult to reduce the interlayer spacing sufficiently to exclude small ions and to maintain this spacing against the tendency of graphene oxide membranes to swell when immersed in aqueous solution. These challenges hinder the potential ion filtration applications of graphene oxide membranes. Here we demonstrate cationic control of the interlayer spacing of graphene oxide membranes with ångström precision using K+, Na+, Ca2+, Li+ or Mg2+ ions. Moreover, membrane spacings controlled by one type of cation can efficiently and selectively exclude other cations that have larger hydrated volumes. First-principles calculations and ultraviolet absorption spectroscopy reveal that the location of the most stable cation adsorption is where oxide groups and aromatic rings coexist. Previous density functional theory computations show that other cations (Fe2+, Co2+, Cu2+, Cd2+, Cr2+ and Pb2+) should have a much stronger cation-π interaction with the graphene sheet than Na+ has, suggesting that other ions could be used to produce a wider range of interlayer spacings.

  7. Experimental studies of caesium iodide aerosol condensation: theoretical interpretation

    International Nuclear Information System (INIS)

    Beard, A.M.; Benson, C.G.; Horton, K.D.; Buckle, E.R.

    1990-07-01

    Caesium iodide is predicted to be a significant source of fission product aerosols during the course of a severe accident in a pressurised water reactor (PWR). The nucleation and growth of caesium iodide aerosols have been studied using a plume chamber and the results compared with theoretical values calculated using the approach developed by Buckle for aerosol nucleation. The morphology of the particles was studied using scanning electron microscopy (SEM) and transmission optical microscopy (TOM), whilst the particle size distributions were determined from differential mobility (DMPS) and aerodynamic (APS) measurements. (author)

  8. Kaolinite flocculation induced by smectite addition - a transmission X-ray microscopic study.

    Science.gov (United States)

    Zbik, Marek S; Song, Yen-Fang; Frost, Ray L

    2010-09-01

    The influence of smectite addition on kaolinite suspensions in water was investigated by transmission X-ray microscopy (TXM) and Scanning Electron Microscopy (SEM). Sedimentation test screening was also conducted. Micrographs were processed by the STatistic IMage Analysing (STIMAN) program and structural parameters were calculated. From the results of the sedimentation tests important influences of small smectite additions to about 3wt.% on kaolinite suspension flocculation has been found. In order to determine the reason for this smectite impact on kaolinite suspension, macroscopic behaviour micro-structural examination using Transmission X-ray Microscope (TXM) and SEM has been undertaken. TXM & SEM micrographs of freeze-dried kaolinite-smectite suspensions with up to 20% smectite showed a high degree of orientation of the fabric made of highly oriented particles and greatest density when 3wt.% of smectite was added to the 10wt.% dense kaolinite suspension. In contrast, suspensions containing pure kaolinite do not show such platelet mutual orientation but homogenous network of randomly oriented kaolinite platelets. This suggests that in kaolinite-smectite suspensions, smectite forms highly oriented basic framework into which kaolinite platelets may bond in face to face preferential contacts strengthening structure and allowing them to show plastic behaviour which is cause of platelets orientation. Copyright 2010 Elsevier Inc. All rights reserved.

  9. Reducing bioavailability and phytotoxicity of 2,4-dinitrotoluene by sorption on K-smectite clay.

    Science.gov (United States)

    Roberts, Michael G; Rugh, Clayton L; Li, Hui; Teppen, Brian J; Boyd, Stephen A

    2007-02-01

    Smectite clays demonstrate high affinities for nitroaromatics that strongly depend on the exchangeable cation. The K-smectites have high affinities for nitroaromatics, but Ca-smectites do not. Here we evaluate the ability of K-smectite to attenuate the bioavailability and hence toxicity of 2,4-dinitrotoluene (2,4-DNT) to the aquatic plant duckweed. In the absence of K-smectite, 2,4-DNT was highly toxic to duckweed. Small amounts of K-smectite reduced toxicity substantially, presumably by reducing 2,4-DNT bioavailability via sorption.

  10. Synthetic mullite fabrication from smectite clays

    International Nuclear Information System (INIS)

    Lima, L.N. de; Kiminami, R.H.G.A.

    1988-01-01

    The technological importance of mullite is mostly due to its refractory properties. Mullite in native form is very rare, and therefore it may be necessary to produced it by synthetic means. Brazil has a large reserve of smectite clays. In this work the process to produce synthetic mullite from these clays by treatment with aluminum sulphate was studied. X-ray analyses has shown the presence of mullite crystals in treated smectite clays of several colours, sinterized at 1100 0 C. By sintering at 1300 0 C, pure mullite was obtained in some colours. (author) [pt

  11. A simple way to constrain the stoichiometry of secondary smectites upon aqueous glass alteration

    International Nuclear Information System (INIS)

    Thien, Bruno M.J.

    2014-01-01

    Highlights: • Si/Al of different glasses were compared to Si/Al of associated secondary smectites. • Si/Al of secondary smectite is nearly equal to Si/Al of parent glass. • This is a simple way which can help to constrain smectite composition. • Accurate smectite composition cannot be measured in many cases. - Abstract: The comparison of the stoichiometry of several nuclear waste glasses and basaltic glasses with their associated secondary smectites evidenced that Si/Al ratios of secondary smectites are nearly equal to the Si/Al ratios of parent glasses. This information may be very useful in constraining secondary smectites structure and stoichiometry in cases where other identification methods are difficult to apply

  12. Uptake Evaluation Of Glass house Grown Grasses In Radio phyto remediation Of Caesium-Contaminated Soil

    International Nuclear Information System (INIS)

    Zal U'yun Wan Mahmood; Nur Humaira' Lau Abdullah; Khairuddin Abdul Rahim

    2014-01-01

    A glass house experiment was performed to evaluate the uptake of grasses viz. Napier and Vetiver in radiophytoremediation of caesium-contaminated soil. The glass house radiophytoremediation experiment was designed according to the Randomized Complete Block Design (RCBD). The grasses were grown in troughs filled with soil mixed with a known specific activity of 134 Cs. Initial Cs activity and activity after different cultivation time intervals of 1, 3, 6 and 9 months were analyzed using gamma spectrometer direct measurement. The results showed the uptake of caesium by Napier and Vetiver after 9 months with the transfer factors (TF) were 4.70 and 6.25, respectively. Meanwhile, the remediation of caesium from contaminated soil at the same time was 95.25 % (Napier) and 95.58 % (Vetiver). Both grasses have been found to accumulate caesium, with Vetiver accumulating higher than Napier. Thus, the present study suggests that Vetiver could be used as a potential plant for radiophytoremediation of caesium. (author)

  13. Mechanism of caesium ion exchange on potassium cobalt hexacyanoferrates(II)

    International Nuclear Information System (INIS)

    Lehto, J.; Haukka, S.; Harjula, R.; Blomberg, M.

    1990-01-01

    The caesium uptakes by K 2 [CoFe(CN) 6 ] and non-stoicheiometric compounds K 2/x Co x/2 [CoFe(CN) 6 ] were found to correlate directly with the specific surface areas of the products with x 1 are mixtures of cubic potassium cobalt hexacyanoferrate (ii) and tetragonal Co 2 Fe(CN) 6 . The thermodynamic equilibrium constant of the caesium exchange on K 2 [CoFe(CN) 6 ] was found to have a high value of 125. (author)

  14. A study of specific sorption of neptunium(V) on smectite in low pH solution

    International Nuclear Information System (INIS)

    Kozai, Naofumi; Ohnuki, Toshihiko; Matsumoto, Junko; Banba, Tsunetaka; Ito, Yoshimoto

    1996-01-01

    The 'specific sorption' of neptunium(V) on smectite, in other words, a strong sorption undesorbable by 1 M KCl, is studied with a combination of batch type sorption and desorption experiments over a pH range of 2 to 5. Six types of homoionic smectite (Li-, Na-, K-, Cs-, Mg-, and Ca-smectite) are used in this study. Distribution coefficients (K d ) of neptunium for smectite vary over a wide pH range; the maximum K d value of ∝300 cm 3 x g -1 at around pH 2 for Li- and Na-smectite and the minimum value of ∝2 cm 3 x g -1 for Cs-smectite. The specific sorption of neptunium depends on pH and on the affinity of the exchangeable cation for smectite; the lower the pH of solution or the affinity, the larger the specific sorption. The neptunium-smectite association varies with the elapse of contact time. Within the first day of the neptunium-smectite contact the neptunium sorbed on na-smectite at low pH is desorbable by 1 M KCl solution, and on the passage of time most of the neuptunium sorbed becomes undesorbable by KCl (the specific sorption). Hydronium ion in solution is sorbed on smectite at low pH and dissociates the exchangeable cation from smectite into solution, and the specific sorption of neuptunium increases with increasing the exchangeable cation that is dissociated from smectite. (orig.)

  15. Kinetics of caesium and potassium absorption by roots of three grass pastures and competitive effects of potassium on caesium uptake in Cynodon sp.

    Science.gov (United States)

    Ayub, J. Juri; Valverde, L. Rubio; Garcia-Sanchez, M. J.; Fernandez, J. A.; Velasco, R. H.

    2008-08-01

    Caesium uptake by plant roots has been normally associated with the uptake of potassium as the potassium transport systems present in plants have also the capacity to transport caesium. Three grass species (Eragrostis curvula, Cynodon sp and Distichlis spicata) growing in seminatural grassland of central Argentina were selected to study their capability to incorporate Cs+ (and K+) using electrophysiological techniques. Although the 137Cs soil inventory ranged between 328-730 Bq m-2 in this region, no 137Cs activity was detected in these plants. However, all the species, submitted previously to K+ starvation, showed the uptake of both Cs+ and K+ when micromolar concentrations of these cations were present in the medium. The uptake showed saturation kinetics for both cations that could be fitted to the Michelis-Menten model. KM values were smaller for K+ than for Cs+, indicating a higher affinity for the first cation. The presence of increasing K+ concentrations in the assay medium inhibited Cs+ uptake in Cynodon sp., as expected if both cations are transported by the same transport systems. This effect is due to the competition of both ions for the union sites of the high affinity potassium transporters. In field situation, where soil concentration of Cs+ is smaller than K+ concentration, is then expectable that caesium activity in plants is not detectable. Nevertheless, the studied plants would have the capacity to incorporate caesium if its availability in soil solution increases. In addition, studies of Cs/K interaction can help us to understand the variability in transfer factors.

  16. Kinetics of caesium and potassium absorption by roots of three grass pastures and competitive effects of potassium on caesium uptake in Cynodon sp

    International Nuclear Information System (INIS)

    Ayub, J. Juri; Velasco, R. H.; Valverde, L. Rubio; Garcia-Sanchez, M. J.; Fernandez, J. A.

    2008-01-01

    Caesium uptake by plant roots has been normally associated with the uptake of potassium as the potassium transport systems present in plants have also the capacity to transport caesium. Three grass species (Eragrostis curvula, Cynodon sp and Distichlis spicata) growing in seminatural grassland of central Argentina were selected to study their capability to incorporate Cs + (and K + ) using electrophysiological techniques. Although the 137 Cs soil inventory ranged between 328-730 Bq m -2 in this region, no 137 Cs activity was detected in these plants. However, all the species, submitted previously to K + starvation, showed the uptake of both Cs + and K + when micromolar concentrations of these cations were present in the medium. The uptake showed saturation kinetics for both cations that could be fitted to the Michelis-Menten model. K M values were smaller for K + than for Cs + , indicating a higher affinity for the first cation. The presence of increasing K + concentrations in the assay medium inhibited Cs + uptake in Cynodon sp., as expected if both cations are transported by the same transport systems. This effect is due to the competition of both ions for the union sites of the high affinity potassium transporters. In field situation, where soil concentration of Cs + is smaller than K + concentration, is then expectable that caesium activity in plants is not detectable. Nevertheless, the studied plants would have the capacity to incorporate caesium if its availability in soil solution increases. In addition, studies of Cs/K interaction can help us to understand the variability in transfer factors

  17. In-situ interferometric measurements of compacted smectite under hyper-alkaline condition - 59124

    International Nuclear Information System (INIS)

    Satoh, Hisao; Kurosawa, Susumu; Ishii, Tomoko; Owada, Hitoshi

    2012-01-01

    Document available in abstract form only. Full text of publication follows: Alteration of bentonite buffer at the repository for radioactive waste is an unavoidable phenomenon. However, precise kinetic data is useful for evaluation of the endurance for long-term safety. Alkaline attack to bentonite by cement-leachates may enhance alteration of smectite into the other phase such as zeolite. Until recently, there are a number of detailed dissolution studies (e.g., Cama et al., 2000; Yokoyama et al., 2005; Rozalen et al., 2008) for suspended smectite, using high precision measurements by ICPMS and AFM analyses. In contrast, dissolution study of compacted smectite is very limited (e.g., Nakayama et al., 2003). In order to verify the previous data, the dissolution rate of compacted smectite with realistic density needs to be confirmed experimentally. We have, for the first time, applied in-situ vertical scanning interferometry (VSI) along with the auto-compaction cell for measuring dissolution rates of smectite compacted at 0.04-20.0 MPa and 70 deg. C in 0.3 M NaOH (pH 12.1). At less-compaction (0.04 MPa), Kunipia-P smectite initially showed a relatively fast dissolution of ∼2E-11 mol/m 2 /s which is comparable to the rate for suspended smectite under same pH-T condition. At high-compaction ( 2 /s, but at higher compaction (>5 MPa), smectite dissolution was enhanced again to ∼5E-13 mol/ m 2 /s

  18. Meta-analysis: Smectite in the treatment of acute infectious diarrhoea in children.

    Science.gov (United States)

    Szajewska, H; Dziechciarz, P; Mrukowicz, J

    2006-01-15

    Although not currently recommended, dioctahedral smectite (smectite) is commonly used to treat acute infectious diarrhoea in many countries. To evaluate systematically the effectiveness of smectite in treating acute infectious diarrhoea in children. Using medical subject headings and free-language terms, the following electronic databases were searched for studies relevant to acute infectious diarrhoea and smectite: MEDLINE, EMBASE, CINAHL and The Cochrane Library; additional references were obtained from reviewed articles. Only randomized-controlled trials were included. Nine randomized-controlled trials (1238 participants) met the inclusion criteria. Combined data from six randomized-controlled trials showed that smectite significantly reduced the duration of diarrhoea compared with placebo. The pooled weighted mean difference was (-22.7 h, 95% CI: -24.8 to -20.6) with a fixed model and remained significant in a random effect model (-24.4 h, 95% CI: -29.8 to -19.1). The chance of cure on intervention day 3 was significantly increased in the smectite vs. the control group (RR 1.64, 95% CI: 1.36-1.98; number needed to treat 4, 95% CI: 3-5). Adverse effects were similar in both groups. Smectite may be a useful adjunct to rehydration therapy in treating acute paediatric gastroenteritis. However, the results of this meta-analysis should be interpreted with caution as most of the included studies had important limitations. Cost-effectiveness analyses should be undertaken before routine pharmacological therapy with smectite is recommended.

  19. Redistribution of strontium and cesium during alteration of smectite to illite

    International Nuclear Information System (INIS)

    Ohnuki, Toshihiko; Murakami, Takashi; Sato, Tsutomu; Isobe, Hiroshi

    1994-01-01

    The redistribution of strontium and cesium during the alteration of smectite to illite has been studied under hydrothermal conditions at 200 C using solutions of 1x10 -4 M Sr and Cs. Two different sorption conditions were applied for the hydrothermal experiments. One was the condition in which strontium and cesium were sorbed by smectite before the hydrothermal experiments (dynamic condition). The other was the condition in which strontium and cesium were sorbed by the alteration products, illite/smectite (I/S) interstratified minerals after the hydrothermal experiments (static condition). The sorption characteristics of strontium and cesium by smectite, I/S interstratified minerals were examined by a sequential extraction method. Most of the strontium was desorbed from smectite and the I/S interstratified minerals with a 1 M KCl solution under both the dynamic and static conditions. Less than 1% of cesium was desorbed from the I/S interstratified minerals with any solution of a 1 M KCl, a 1 M HCl and a 6 M HCl under the dynamic condition, while most of cesium was desorbed with either solution of a 1 M KCl and 1 M HCl from smectite and from the I/S interstratified minerals under the static condition. These suggest that cesium sorbed by smectite changes its sorption characteristic during the alteration process, but strontium does not. Possible sites for more strongly bounded cesium to the I/S interstratified minerals may be at the 'ditrigonal cavity' of adjacent tetrahedral layers. (orig.)

  20. Positron scattering by rubidium and caesium

    International Nuclear Information System (INIS)

    Kernoghan, A.A.; Walters, H.R.J.; McAlinden, M.T.

    1996-01-01

    We report results in the energy range 0.5 to 64 eV for positron scattering by ground state rubidium and caesium in Ps(1s,2s,2p,3s,3p,3d) + Rb(5s,5p,6s,6p,4d) and Ps(1s,2s,2p,3s,3p,3d) + Cs(6s,6p,7s,7p,5d) coupled-state approximations, respectively. The pattern of results is similar to analogous calculations made on potassium by McAlinden et al. Except at the lowest energies, positronium formation is found to be almost entirely into excited states, with there being a dramatic collapse of the Ps(1s) cross section in the case of caesium. Ps(n = 2), Ps(n = 3) and Ps(n≥ 4) cross sections are predicted to be of comparable size. Ps(n≥ 4) formation is estimated from the calculated Ps(n = 3) results using the n 3 scaling rule. Good agreement in shape and magnitude is obtained with the recent lower bound measurements of total positronium formation in rubidium by Surdutovich et al, although there are differences in detail. Good agreement is also achieved with the total cross section measurements of Parikh et al on rubidium after these have been corrected for discrimination against forward elastic scattering and renormalized upwards by 5%. These total cross section measurements display a pronounced peak near 6 eV which is well reproduced by the present theory but is at variance with the earlier Rb(5s,5p,6s,6p,4d) calculations of McEachran et al which neglect positronium formation. This peak, which also appears in the calculations on potassium and caesium, is primarily associated with the maximum in the total positronium formation cross section. At low energies elastic scattering is dominant, this dominance being directly taken over by the resonance excitation of the atom with increasing impact energy. The next most important cross section is positronium formation, followed by excitation of the lowest atomic d-state. The 5s → 6s and 5s → 6p transitions in rubidium and the 6s → 7s and 6s → 7p transitions in caesium are of relatively minor importance. (Author)

  1. XRD measurement of mean crystallite thickness of illite and illite/smectite: Reappraisal of the Kubler index and the Scherrer equation

    Science.gov (United States)

    Drits, Victor A.; Środoń, Jan; Eberl, D.D.

    1997-01-01

    The standard form of the Scherrer equation, which has been used to calculate the mean thickness of the coherent scattering domain (CSD) of illite crystals from X-ray diffraction (XRD) full width data at half maximum (FWHM) intensity, employs a constant, Ksh, of 0.89. Use of this constant is unjustified, even if swelling has no effect on peak broadening, because this constant is valid only if all CSDs have a single thickness. For different thickness distributions, the Scherrer “constant” has very different values.Analysis of fundamental particle thickness data (transmission electron microscopy, TEM) for samples of authigenic illite and illite/smectite from diagenetically altered pyroclastics and filamentous illites from sandstones reveals a unique family of lognormal thickness distributions for these clays. Experimental relations between the distributions' lognormal parameters and mean thicknesses are established. These relations then are used to calculate the mean thickness of CSDs for illitic samples from XRD FWHM, or from integral XRD peak widths (integrated intensity/maximum intensity).For mixed-layer illite/smectite, the measured thickness of the CSD corresponds to the mean thickness of the mixed-layer crystal. Using this measurement, the mean thickness of the fundamental particles that compose the mixed-layer crystals can be calculated after XRD determination of percent smectitic interlayers. The effect of mixed layering (swelling) on XRD peak width for these samples is eliminated by using the 003 reflection for glycolated samples, and the 001, 002 or 003 reflection for dehydrated, K-saturated samples. If this technique is applied to the 001 reflection of air-dried samples (Kubler index measurement), mean CSD thicknesses are underestimated due to the mixed-layering effect.The technique was calibrated using NEW MOD©-simulated XRD profiles of illite, and then tested on well-characterized illite and illite/smectite samples. The XRD measurements are in good

  2. Geological evidence of smectite longevity

    International Nuclear Information System (INIS)

    Pusch, R.; Karnland, O.

    1988-12-01

    Search is going on for geological evidence of natural smectite clay materials that have been exposed to conditions that are similar to those radioactive in repositories. Cases in which heating to 90 degree C or more for long periods has taken place, are of particular interest. The report describes two bentonite layers, one of Miocenic age located at central Sardinia (Busachi), and the other of Ordovician age, forming a basal stratum of southern Gotland, (Hamra), Sweden. They both serve as excellent examples of the survival potential of montmorillonite-rich clays. The more than 10 m thick Sardinian bentonite bed was very significantly heated when the magma moved in and covered it. The upper meter was heated to more than 200 degree C for several days, while at more than 4 m depth, the temperature did note exceed 80 degree C. The test show that the smectite content was not reduced to less than 60 percent in any part of the layer sequence, while slight cementation was caused by precipitation of heat-released silica in the uppermost layer. The 0.3 m thick bed on Gotland is presently located at 515 m depth. Various investigations indicate that it has been exposed to an effective pressure of 300 MPa and a temperature of 110 degree C for several million years due to burial under almost 3 km of Devonian sediments. The content of smectite is around 25 percent of the bulk material, and 30-40 percent of the clay fraction. Illite appears to have been neoformed in small voids of the smectite matrix and the identified apparent I/S material is suggested to consist of mixed-layer minerals with hydrous mica and Ca or Na locked in instead of K, which would be the conventional interpretation. The earlier developed alteration model appears to be valid and it is extended in the present report on the basis of the findings. (28 illustrations, 9 tables)

  3. Caesium inhibits the colonization of Medicago truncatula by arbuscular mycorrhizal fungi

    International Nuclear Information System (INIS)

    Wiesel, Lea; Dubchak, Sergiy; Turnau, Katarzyna; Broadley, Martin R.; White, Philip J.

    2015-01-01

    Contamination of soils with radioisotopes of caesium (Cs) is of concern because of their emissions of harmful β and γ radiation. Radiocaesium enters the food chain through vegetation and the intake of Cs can affect the health of organisms. Arbuscular mycorrhizal (AM) fungi form mutualistic symbioses with plants through colonization of the roots and previous studies on the influence of AM on Cs concentrations in plants have given inconsistent results. These studies did not investigate the influence of Cs on AM fungi and it is therefore not known if Cs has a direct effect on AM colonization. Here, we investigated whether Cs influences AM colonization and if this effect impacts on the influence of Rhizophagus intraradices on Cs accumulation by Medicago truncatula. M. truncatula was grown with or without R. intraradices in pots containing different concentrations of Cs. Here, we present the first evidence that colonization of plants by AM fungi can be negatively affected by increasing Cs concentrations in the soil. Mycorrhizal colonization had little effect on root or shoot Cs concentrations. In conclusion, the colonization by AM fungi is impaired by high Cs concentrations and this direct effect of soil Cs on AM colonization might explain the inconsistent results reported in literature that have shown increased, decreased or unaffected Cs concentrations in AM plants. - Highlights: • Colonization of plants by arbuscular mycorrhizal fungi is negatively affected by increasing soil caesium concentrations. • Shoot caesium concentrations are not influenced by AM fungi at soil caesium concentrations above about 3 μg Cs kg −1 . • The direct effect of caesium on AM fungi might impact on the influence of AM fungi on Cs accumulation in plants. • This might explain the inconsistent results reported in literature on Cs accumulation in AM plants

  4. Uptake and retention of radio-caesium in earthworms cultured in soil contaminated by the Fukushima nuclear power plant accident

    International Nuclear Information System (INIS)

    Fujiwara, K.; Takahashi, T.; Nguyen, P.; Kubota, Y.; Gamou, S.; Sakurai, S.; Takahashi, S.

    2015-01-01

    To understand the effects of radionuclides on non-human biota and the environment, it is essential to study the intake and metabolism of radio-isotopes in earthworms which are among the most important soil organisms, and Eisenia fetida, which were used in this study, are known to be sufficiently sensitive to chemicals and representative of common earthworms. In this study, we assessed the concentration ratios, uptake and retention, absorbed dose rate, and distribution of radio-caesium in earthworms. The concentration ratios of 137 Cs (i.e., the concentrations of radio-caesium in earthworms relative to those in dry soil) were higher early in the culturing period and decreased gradually over the experimental period. 137 Cs taken up by E. fetida was cleared rapidly after the worms were cultured in radio-caesium-free soil, suggesting that the metabolism of radio-caesium in earthworms is very rapid. Autoradiography demonstrated that the concentration of radio-caesium within the digestive tract was as high as that in the soil, while radio-caesium in the body tissue was lower than radio-caesium in the soil and was almost uniformly distributed among earthworm tissues. The highest absorbed dose rate of total exposure to radio-caesium ( 137 Cs + 134 Cs) was calculated to be 1.9 × 10 3 (μGy/day) in the earthworms. - Highlights: • We assessed the concentration ratios of 137 Cs in earthworms/dry soil. • The distribution of radio-caesium was relatively uniform throughout the earthworm body without any distinguishable accumulation in specific organs or tissues. • We estimated the absorbed dose rate of radio-caesium for earthworms

  5. Deposition of caesium and strontium substances on growing crops: Effects and countermeasures

    International Nuclear Information System (INIS)

    Bengtsson, S.

    2010-01-01

    Full text: To investigate how the two radionuclides caesium ( 134 Cs) and strontium ( 85 Sr) are taken up and transported to the harvested parts (the seeds) by fallout in a growing crop. Further on how this is related to the size and time of the fallout. From the information collected recommendation of suitable countermeasures at different scenarios to prevent further spreading to food stuff can be suggested. In the project a number of field trials where artificial deposited by the two radionuclides 134 Cs and 85 Sr in a contaminated rainfall, on the two agricultural crops Brassica napus L. (spring rape) and Triticum aestivum L. (spring wheat). The trial contained different treatments where the radionuclides where deposited by a rainfall simulator at different growing stages of the crops. The field trial continues for two more years and the reason for that is due to the variation of the climate for the different years. The radionuclides were applied in the form of a wet deposition and the rainfall was about 1 mm m -1 with a concentration of 20 kBq m -1 for each radionuclide. Samples were taken from the plots at the day(s) after the treatment of contaminated rainfall, both from the latest treated plots and from the earlier treated plots. The hypotheses are: 1. That the size of the deposition and the time in relation to the development stages of the crop will steer how much caesium and strontium that are coughed, detained and transferred to the harvested parts. 2. That the levels of caesium and strontium in the harvested parts of the crops are related to the insensitivity of the rainfall after a deposition and also how long time the first intensive rain will occur. 3. That the size of caesium and strontium in harvested plant parts are related to the size of uptake throw the leaves. 4. If the deposition of caesium and strontium will be the same, the levels of caesium will be much higher than strontium in the harvested parts. (author)

  6. Effects of cooking process on the changes of concentration and total amount of radioactive caesium in beef, wild plants and fruits

    International Nuclear Information System (INIS)

    Nabeshi, Hiromi; Tsutsumi, Tomoaki; Uekusa, Yoshinori; Matsuda, Rieko; Akiyama, Hiroshi; Teshima, Reiko; Hachisuka, Akiko

    2016-01-01

    In order to obtain information about effects of the cooking process on the changes of concentration and amount of radioactive materials in foods, we determined the concentration of radioactive caesium in several foods such as beef, edible wild plants, blueberries and mushrooms, before and after cooking. Our results showed that drying after soaking in liquid seasoning and the removal of astringent taste were effective in removing radioactive caesium from foods. More than 80% of radioactive caesium could be removed by these cooking methods. These results suggest that cooking processes such as boiling and soaking in liquid seasoning or water are effective to remove radioactive caesium from foods. Moreover, appropriate food additives such as baking soda were useful to promote the removal of radioactive caesium from foods. On the other hand, simple drying, jam making, grilling and tempura cooking could not remove radioactive caesium from foods. In addition, we showed that the concentration of radioactive caesium in foods was raised after simple drying, although the amount of radioactive caesium was unchanged. It would be necessary to monitor radioactive caesium concentration in processed foods because they might have undergone dehydration by cooking, which could result in concentrations exceeding regulatory levels. (author)

  7. The behaviour of radioactive caesium in a boreal forest ecosystem

    International Nuclear Information System (INIS)

    Bergman, R.; Nylen, T.; Lidstroem, K.; Palo, T.

    1991-01-01

    The distribution of radioactive caesium (Cs-134 and Cs-137) in a boreal forest ecosystem is studied with focus in the dynamics of the turnover in, and loss from, the system. Measurements of the distribution in soil and vegetation, as well as the loss of radioactive caesium by run-off from a catchment, constitute the basis for an analysis of the caesium budget in the system. Comparisons of the distribution of 'old' Cs-137, i.e. originating from fallout due to the atmospheric nuclear weapons test, and that due to deposition after the accident in Chernobyl 1986 are used for extrapolations to future situations concerning transport of Cs-137 via the food chains over berries and moose to man. The exposure in a long term perspective due to the average intake of Cs-137 in the Swedish population by consumption of meat, milk, and milk products (i.e. of an agricultural origin) is compared to that due to ingestion of the forest products: berries (bilberry, lingonberries, and cloudberries) and moose meat. (au) (34 refs.)

  8. Effects of humidity and interlayer cations on the frictional strength of montmorillonite

    Science.gov (United States)

    Tetsuka, Hiroshi; Katayama, Ikuo; Sakuma, Hiroshi; Tamura, Kenji

    2018-04-01

    We developed a humidity control system in a biaxial friction testing machine to investigate the effect of relative humidity and interlayer cations on the frictional strength of montmorillonite. We carried out the frictional experiments on Na- and Ca-montmorillonite under controlled relative humidities (ca. 10, 30, 50, 70, and 90%) and at a constant temperature (95 °C). Our experimental results show that frictional strengths of both Na- and Ca-montmorillonite decrease systematically with increasing relative humidity. The friction coefficients of Na-montmorillonite decrease from 0.33 (at relative humidity of 10%) to 0.06 (at relative humidity of 93%) and those of Ca-montmorillonite decrease from 0.22 (at relative humidity of 11%) to 0.04 (at relative humidity of 91%). Our results also show that the frictional strength of Na-montmorillonite is higher than that of Ca-montmorillonite at a given relative humidity. These results reveal that the frictional strength of montmorillonite is sensitive to hydration state and interlayer cation species, suggesting that the strength of faults containing these clay minerals depends on the physical and chemical environment.[Figure not available: see fulltext.

  9. Sorption behavior of cobalt on manganese dioxide, smectite and their mixture

    International Nuclear Information System (INIS)

    Ohnuki, T.; Kozai, N.

    1995-01-01

    The sorption behavior of cobalt on manganese dioxide, the clay mineral smectite and mixtures of the two was studied by batch type sorption/desorption experiments at neutral pH. Sorption behavior was examined by sequential extraction, in which the sorbents were contacted first with a 1 M CH 3 COONH 4 solution and then with a hydroxylamine solution (NH 2 OH of 1 M with 25 weight % CH 3 COOH). More than 70% of the sorbed cobalt was desorbed from smectite with a 1 M CH 3 COONH 4 solution: about 15% of the cobalt remained on the smectite after treatment with the hydroxylamine solution. Less than 1% of the remaining cobalt was desorbed from manganese dioxide with a 1 M CH 3 COONH 4 solution; with the hydroxylamine solution, all was desorbed. In mixtures of MnO 2 and smectite that were formulated to sorb equal amounts of cobalt regardless of the MnO 2 /smectite ratio in the mixture, less than 5% of the sorbed cobalt was desorbed by treatment with 1 M CH 3 COONH 4 . The fraction of the cobalt desorbed by treatment with the hydroxylamine solution increased with increased MnO 2 in the mixtures. The fraction of the cobalt sorbed on MnO 2 in the mixture was estimated from the desorption experiments. The results showed that higher fractions were sorbed onto MnO 2 than were estimated by the weighted averages of distribution coefficients for MnO 2 and smectite. Therefore, in minerals of the mixture, manganese dioxide is a more important component than smectite for the sorption of cobalt. (orig.)

  10. Uptake and retention of radio-caesium in earthworms cultured in soil contaminated by the Fukushima nuclear power plant accident.

    Science.gov (United States)

    Fujiwara, K; Takahashi, T; Nguyen, P; Kubota, Y; Gamou, S; Sakurai, S; Takahashi, S

    2015-01-01

    To understand the effects of radionuclides on non-human biota and the environment, it is essential to study the intake and metabolism of radio-isotopes in earthworms which are among the most important soil organisms, and Eisenia fetida, which were used in this study, are known to be sufficiently sensitive to chemicals and representative of common earthworms. In this study, we assessed the concentration ratios, uptake and retention, absorbed dose rate, and distribution of radio-caesium in earthworms. The concentration ratios of (137)Cs (i.e., the concentrations of radio-caesium in earthworms relative to those in dry soil) were higher early in the culturing period and decreased gradually over the experimental period. (137)Cs taken up by E. fetida was cleared rapidly after the worms were cultured in radio-caesium-free soil, suggesting that the metabolism of radio-caesium in earthworms is very rapid. Autoradiography demonstrated that the concentration of radio-caesium within the digestive tract was as high as that in the soil, while radio-caesium in the body tissue was lower than radio-caesium in the soil and was almost uniformly distributed among earthworm tissues. The highest absorbed dose rate of total exposure to radio-caesium ((137)Cs + (134)Cs) was calculated to be 1.9 × 10(3) (μGy/day) in the earthworms. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. The conversion of smectite to illite in hydrothermal systems

    International Nuclear Information System (INIS)

    Johnston, R.M.

    1983-06-01

    In natural diagenetic shale systems, smectite converts to illite and mixed-layer illite-smectite in less than a million years at temperatures between 75 degrees C and 200 degrees C. This has raised questions as to the stability of smectite-based bentonite buffers under nuclear waste disposal vault conditions. Experimental and geological evidence indicate that the reaction is dependent on the availability of K + , and that the rate of reaction in K + -poor systems (such as the disposal vault) may be much lower than that observed in shale. The presence of Na + , Ca 2+ and Mg 2+ in the system slows the reaction and may halt it altogether at lower temperatures. Two different reaction mechanisms have been proposed; the evidence for, and implication of, each are discussed

  12. Availability of caesium radionuclides to plants - classification of soils and role of mycorrhiza

    Energy Technology Data Exchange (ETDEWEB)

    Drissner, J.; Buermann, W.; Enslin, F.; Heider, R.; Klemt, E.; Miller, R.; Schick, G.; Zibold, G. [Fachhochschule Ravensburg-Weingarten, D-88241 Weingarten (Germany)

    1998-10-01

    At different locations in spruce stands spread rather homogeneously over southern Baden-Wuerttemberg, samples of soil and plants were taken and the vertical distribution of the caesium radionuclides in the soil was studied. As a direct measure of the bioavailability, the aggregated transfer factor, T{sub ag}, was determined for fern, bilberry, raspberry, blackberry, and clover. The T{sub ag} (in m2 kg{sup -1}) is defined by the specific caesium activity (in Bq kg{sup -1}) of the dry mass of the plants, divided by the total inventory (in Bq m{sup -2}) of the soil. It varies between 0{center_dot}5 and 0{center_dot}001 m2kg{sup -1}, being highest for fern and lowest for blackberry or clover at all sampling sites. Most decisive for the value of the T{sub ag} are kind of humus deposit, thickness and pH value of the humus layers. Also important are the soil properties, whereas geology has only a minor influence on T{sub ag}. At different sampling sites in spruce forests, the T{sub ag} can vary by two orders of magnitude for one plant species. Caesium desorption experiments were performed. We could not find a dependence of the transfer of caesium to the plant on the desorbability of caesium from the soil, which implies a more complex transport mechanism than simple ion exchange in the soil solution. It is suggested that the transport of caesium is mediated by mycorrhiza fungi. Therefore, we studied the density of mycorrhiza hyphae in the O{sub f}, O{sub h} and A{sub h} soil horizons of two sites differing in T{sub ag} by a factor of 10. The densities of mycorrhiza hyphae in the O{sub h} and A{sub h} soil horizons each differ by a factor of 2 for the two sites. Yet, the effect of the hyphae density on radiocaesium uptake has to be a subject of further investigation. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  13. Sensitivity of Clay Suspension Rheological Properties to pH, Temperature, Salinity, and Smectite-Quartz Ratio

    Science.gov (United States)

    Kameda, Jun; Morisaki, Tomonori

    2017-10-01

    Understanding the rheological properties of clay suspensions is critical to assessing the behavior of sediment gravity flows such as debris flow or turbidity current. We conducted rheological measurements of composite smectite-quartz suspensions at a temperature of 7°C and a salt concentration of 0.6 M. This is representative of smectite-bearing sediments under conditions on the seafloor. The flow curves obtained were fitted by the Bingham fluid model, from which we determined the Bingham yield stress and dynamic viscosity of each suspension. At a constant smectite-quartz mixing ratio, the yield stress and the dynamic viscosity tend to increase as the solid/water ratio of the suspension is increased. In the case of a constant solid/water ratio, these values increase with increasing smectite content in the smectite-quartz mixture. Additional experiments exploring differing physicochemical conditions (pH 1.0-9.0; temperature 2-30°C; and electrolyte (NaCl) concentration 0.2-0.6 M) revealed that the influence of temperature is negligible, while pH moderately affects the rheology of the suspension. More significantly, the electrolyte concentration greatly affects the flow behavior. These variations can be explained by direct and/or indirect (double-layer) interactions between smectite-smectite particles as well as between smectite-quartz particles in the suspension. Although smectite is known as a frictionally weak material, our experimental results suggest that its occurrence can reduce the likelihood that slope failure initiates. Furthermore, smectite can effectively suppress the spreading distance once the slope has failed.

  14. Transformation of adsorbed aflatoxin B1 on smectite at elevated temperatures

    Science.gov (United States)

    Aflatoxins cause liver damage and suppress immunity. Smectites can be used to reduce the bioavailability of aflatoxins through adsorption. To further reduce the toxicity of aflatoxins and to eliminate the treatments of aflatoxin-loaded smectites, degrading the adsorbed aflatoxin to nontoxic or less ...

  15. Leakage of caesium braquitherapy sources

    International Nuclear Information System (INIS)

    Lozada, J.A.

    1998-01-01

    In several Venezuelan public hospitals where cervix uteri tumours are treated by intracavitary radiotherapy, that use manual after loading Fletcher method, with Caesium 137 sources, the use of improper source holders, locally manufactured from pieces of drainage plastic tubing, which deteriorated and created a corrosive environment all around the sources, omission of manufacturer's recommendations regarding corrosion information, source storage, inspection and testing, violation of International Atomic Energy Agency Radiation Protection Procedures, and lack of proper regulatory control, resulted integrity damage to about sixty special form sources (ISO2919 C 63322), leakage of Cs-137 from a supposed insoluble refractory active content (caesium silicoaluminate), and contamination of applicators, floors and bedding. When the situation was detected by means removal contamination tests, after routine inspections, the sources were removed from the hospitals, decontaminated by means of immersion in 3% EDTA solution in ultrasonic bath, subjected to leaking assessment tests, and the ones that passed were placed in low cost stainless steel source holders, designed and built by the instituto Venezolano de Investigaciones Cientificas (IVIC) returned to the hospitals. The leaking sources were removed from use and considered radioactive waste. In order to avoid the occurrence of similar situations, all the importers of such sources are now required to send them to IVIC for testing and placement in proper source holders, before they are shipped to the hospitals. (author)

  16. Phonon dispersion relations for caesium thiocyanate

    International Nuclear Information System (INIS)

    Irving, M.A.; Smith, T.F.; Elcombe, M.M.

    1984-01-01

    Room temperature phonon dispersion relations for frequencies below 2 THz have been measured, along the three orthorhombic axes and selected diagonal directions by neutron inelastic scattering, for caesium thiocyanate. These curves, which represent 13 acoustic modes and 11 optic modes of vibration, do not agree with the dispersion behaviour calculated from the rigid-ion model developed by Ti and Ra to describe their Raman scattering observations

  17. Experimental study and modelling of selenite sorption onto illite and smectite clays.

    Science.gov (United States)

    Missana, T; Alonso, U; García-Gutiérrez, M

    2009-06-15

    This study provides a large set of experimental selenite sorption data for pure smectite and illite. Similar sorption behavior existed in both clays: linear within a large range of the Se concentrations investigated (from 1x10(-10) to 1x10(-3) M); and independent of ionic strength. Selenite sorption was also analysed in the illite/smectite system with the clays mixed in two different proportions, as follows: (a) 30% illite-70% smectite and (b) 43% illite-57% smectite. The objective of the study was to provide the simplest model possible to fit the experimental data, a model also capable of describing selenite sorption in binary illite/smectite clay systems. Selenite sorption data, separately obtained in the single mineral systems, were modeled using both a one- and a two-site non-electrostatic model that took into account the formation of two complexes at the edge sites of the clay. Although the use of a two-site model slightly improved the fit of data at a pH below 4, the simpler one-site model reproduced satisfactorily all the sorption data from pH 3 to 8. The complexation constants obtained by fitting sorption data of the individual minerals were incorporated into a model to predict the adsorption of selenium in the illite/smectite mixtures; the model's predictions were consistent with the experimental adsorption data.

  18. Structure of caesium selenate

    International Nuclear Information System (INIS)

    Zuniga, F.J.; Breczewski, T.; Arnaiz, A.

    1991-01-01

    Cs 2 SeO 4 , M 4 =408.77, orthorhombic, Pnam, a=8.3777 (8), b=11.276 (2), c=6.434 (2) A, V=607.8 (2) A 3 , Z=4, D x =4.46 Mg m -3 , MoKα, λ=0.71069 A, μ=185.06 cm -1 , F(000)=704, T=293 K, R=0.048, 3348 observed reflections. Average values of the Se-O and Cs-O distances are 1.637 (4) and 3.387 (3) A, respectively [range 3.038 (5)-3.872 (6) A with 9 and 11 coordination of caesium by oxygen]. (orig.)

  19. Formation of Fe/mg Smectite Under Acidic Conditions from Synthetic Adirondack Basaltic Glass: an Analog to Fe/mg Smectite Formation on Mars

    Science.gov (United States)

    Sutter, B.; Peretyazhko, T.; Morris, R. V.; Ming, D. W.

    2014-01-01

    Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Angstroms (02l) and 1.54Angstroms (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200 C for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060 peaks. Moessbauer analysis coupled with future experiments are planned to verify if nontronite can be formed under mildly acidic and oxic conditions. Results of this work demonstrate that acidic conditions could have occurred on an early Mars, which allowed for smectite formation but inhibited carbonate formation.

  20. Changes in the Expandability, Layer charge, and CEC of Smectitic Clay due to a Illitization

    International Nuclear Information System (INIS)

    Lee, Jae Owan; Cho, Won Jin

    2007-01-01

    In a high-level waste(HLW) repository, the major fucntions of the smectitic clay for use as a buffer material are to inhibit the penetration of groundwater and to retard the release of radionuclides from the radioactive wastes to the surrounding environment. However, when the smectite clay is exposed to an elevated temperature due to radioactive decay heat and geochemical conditions for a long time, its physicochemical and mineralogical properties may be degradated and thus lose its barrier functions. It has been known in literature that the degradation of these properties of the smectitic clay occurs by a illitization in which the smectite transforms into illite. Therefore, an understanding of the illitization is essential to evaluate the long-term barrier performance of smectitic clay for the buffer of a HLW repository. This paper will carry out hydrothermal reaction tests with domestic smectitic clay which will be favorably considered for the buffer material of a Korean HLW repository, and investigate changes in the expandibility, layer charge and cation exchange capacity(CEC) of the smectitic clay due to a illitization

  1. Adsorption of Caesium in Urine on Copper Hexacyanoferrate(II) - A Contamination Control Kit for Large-Scale In-Situ Use

    International Nuclear Information System (INIS)

    Johansson, L.; Samuelsson, C.; Holm, E.

    1999-01-01

    A kit containing copper hexacyanoferrate(II) was created for large scale distribution to caesium-contaminated subjects for in situ sampling in the event of radiocaesium release from a nuclear accident of other nuclear activities. This kit is to be used for screening the internal contamination level of a population exposed to radiocaesium fallout and could be seen as a fast method of whole-body counting, suitable for large scale determinations. The separation of caesium from urine by adsorption on the copper compound was studied and it was determined that caesium efficiently adsorbed from urine. The contamination control kit is a practical alternative to urine sampling since caesium is concentrated to a small volume, by the subject using the kit in situ, gaining advantages in handling, distribution, storage and measuring geometry in the subsequent gamma ray analysis. The kit consists of cotton filters impregnated with copper hexacyanoferrate(II) held by plastic filter holders and performs a rapid flow-through. In order to obtain full caesium adsorption, less than 0.5 g of the compound is required for a 2 litre urine sample. No chemical preparation or change in pH of the urine sample is needed before adsorption. When using the kit in an authentic internal caesium contamination situation, the adsorbed fraction of caesium was 97 ± 3% (SD) in ten samples. (author)

  2. Radioactive caesium in a boreal forest ecosystem and internally absorbed dose to man

    International Nuclear Information System (INIS)

    Bergman, R.; Johansson, L.

    1989-01-01

    Different aspects dealing with water-soil, soil-plant and plant-herbivore interactions are studied. The study area is located to the Forest Research Station at Svartberget 50 km west of Umea in Vaesterbotten. An important topic in this study concerns the transport of caesium in food chains to man. Consumption of forest products by man i.e. game (primarily moose) and berries constitutes the major pathway of radioactive caesium to man. Moose meat contributes to about 30% of the total meat consumption in Vaesterbotten and the average over the Swedish population has remained at the level of 5-10% during the present decade. In order to assess the absorbed dose resulting from intake via these food products over a long period of time, knowledge about the long term behaviour of caesium in the biotic community is studied. (orig./HP)

  3. The Formation of Fe/Mg Smectite Under Mildly Acidic Conditions on Early Mars

    Science.gov (United States)

    Sutter, B.; Golden, D. C.; Ming, Douglas W.; Niles, P. B.

    2011-01-01

    The detection of Fe/Mg smectites and carbonate in Noachian and early Hesperian terrain of Mars suggests that neutral to mildly alkaline conditions prevailed during the early history of Mars. If early Mars surface geochemical conditions were neutral to moderately alkaline with a denser CO2 atmosphere than today, then large carbonates deposits should be more widely detected in Noachian terrain. Why have so few carbonate deposits been detected compared to Fe/Mg smectites? Fe/Mg smectites on early Mars formed under mildly acidic conditions, which would preclude the extensive formation of carbonate deposits. The goal of the proposed work is to evaluate the formation of Fe/Mg smectites under mildly acidic conditions.

  4. Stability of deep-sited smectite minerals in crystalline rock-chemical aspects

    International Nuclear Information System (INIS)

    Pusch, R.

    1983-03-01

    A recent survey of possible conditions and mechanisms of smectite alteration, with special respect to the Swedish concept of radioactive waste disposal, has shown that the charge change by replacement of tetrahedral Si by Al is the key mechanism of the only practically important alteration, namely that of smectite/illite conversion. If K is available in sufficient quantities it will be fixed and permanent conversion to the unwanted illite-type minerals is a fact; if not, the smectite will be beidellitelike with practically unchanged physico/mechanical properties. Heating to more than about 100degreeC is thought to be the cause of the charge change. One other process may be critical and that is cementation of various substances. A possible cementation mechanism, i.e. that of quartz precipitation, is very probably associated with the smectite/illite conversion. Practical examples of smectite alteration and survival under reasonably well documented geological conditions with respect to temperature and pressure are available, one being that of the Kinnekulle bentonites, another one, although less well known, being the smectitic clay beds in the Hoeganaes depression. Rather comprehensive core sampling was made at both sites and elemental and mineral analyses were conducted as well as microstructural studies. They support the hypothesis that practically important charge change through Si/Al replacement requires a temperature of more than 100degreeC, and that such replacement does not yield permanent lattice collapse unless K is available in sufficient quantities. The Hoeganaes case also serves as an example of drastic loss in plasticity and swelling potential by cementation of other precipitates than quartz, namely iron compounds. (author)

  5. Smectite Formation from Basaltic Glass Under Acidic Conditions on Mars

    Science.gov (United States)

    Peretyazhko, T. S.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

    2015-01-01

    Massive deposits of phyllosilicates of the smectite group, including Mg/Fe-smectite, have been identified in Mars's ancient Noachian terrain. The observed smectite is hypothesized to form through aqueous alteration of basaltic crust under neutral to alkaline pH conditions. These pH conditions and the presence of a CO2-rich atmosphere suggested for ancient Mars were favorable for the formation of large carbonate deposits. However, the detection of large-scale carbonate deposits is limited on Mars. We hypothesized that smectite deposits may have formed under acidic conditions that prevented carbonate precipitation. In this work we investigated formation of saponite at a pH of approximately 4 from Mars-analogue synthetic Adirondack basaltic glass of composition similar to Adirondack class rocks located at Gusev crater. Hydrothermal (200º Centigrade) 14 day experiments were performed with and without 10 millimoles Fe(II) or Mg under anoxic condition [hereafter denoted as anoxic_Fe, anoxic_Mg and anoxic (no addition of Fe(II) or Mg)] and under oxic condition [hereafter denoted as oxic (no addition of Fe(II) or Mg)]. Characterization and formation conditions of the synthesized saponite provided insight into the possible geochemical conditions required for saponite formation on Mars.

  6. Low Level Caesium Mapping in Latvia Anno 1996

    DEFF Research Database (Denmark)

    Aage, Helle Karina

    1999-01-01

    In Latvia the caesium-137 contamination from the Chernobyl accident and from the nuclear weapon tests in the 1960´es is very low. Conventional techniques for extracting information from the measured spectra cannot be used here. Therefore a new, sensitive technique - the pseudo concentration method...

  7. Low Level Caesium Mapping in Latvia Anno 1995

    DEFF Research Database (Denmark)

    Aage, Helle Karina

    1999-01-01

    In Latvia the caesium-137 contamination from the Chernobyl accident and from the nuclear weapon tests in the 1960´es is very low. Conventional techniques for extracting information from the measured spectra cannot be used here. Therefore a new, sensitive technique - the pseudo concentration method...

  8. A Falls Dam, Otago, sedimentation rate measured by the caesium-137 profile

    International Nuclear Information System (INIS)

    McCabe, W.J.; Mason, W.J.

    1982-09-01

    Two cores from the dam were examined. The lead-210 was measured from Core D, but because of the high sedimentation rate the ''unsupported'' lead-210 was not detectable above the ''supported'' lead background. Caesium-137 was determined from Core A and the profile obtained related to the pattern of the ''fallout'' caesium in rainwater. From this a sedimentation rate of 11 kg per sq. metre per year was calculated. In terms of the length of the core sample, this is equivalent to 1.3 cm per year

  9. Clinical results in carcinoma of the cervix: radium compared to caesium using remote afterloading

    International Nuclear Information System (INIS)

    Jackson, S.M.; Fairey, R.N.; Kornelsen, R.O.; Young, M.E.J.; Wong, F.L.

    1989-01-01

    In 1979 the Cancer Control Agency of British Columbia changed from radium to remote controlled afterloaded caesium in the treatment of carcinoma of the cervix. In 3 years prior to the change, 139 patients received radium as part of their treatment and in the 3 years after the change, 158 patients received caesium. Overall referral patterns, patient and cancer demographics, and treatment policies were stable throughout the 6-year period. Radiotherapy technique, dose, dose distribution and dose rate were comparable for both radium and caesium treated patients. The results of treatment in the two time periods showed no difference in survival, local tumour control or complications. The use of afterloading has not compromised treatment results and has allowed better nursing care for patients and protection from radiation for all staff. (author)

  10. Superior thermoelectric response in the 3R phases of hydrated NaxRhO2

    KAUST Repository

    Saeed, Y.; Singh, Nirpendra; Schwingenschlö gl, Udo

    2014-01-01

    Density functional theory is used to investigate the thermoelectric properties of the 3R phases of NaxRhO2 for different Na vacancy configurations and concentrations. As compared to the analogous 2H phases, the modified stacking of the atomic layers in the 3R phases reduces the interlayer coupling. As a consequence, the 3R phases are found to be superior in the technologically relevant temperature range. The Rh d3z2-r2 orbitals still govern the valence band maxima and therefore determine the transport properties. A high figure of merit of 0.35 is achieved in hydrated Na0.83RhO2 at 580 K by water intercalation, which is 34% higher than in the non-hydrated phase.

  11. Superior thermoelectric response in the 3R phases of hydrated NaxRhO2

    KAUST Repository

    Saeed, Y.

    2014-03-17

    Density functional theory is used to investigate the thermoelectric properties of the 3R phases of NaxRhO2 for different Na vacancy configurations and concentrations. As compared to the analogous 2H phases, the modified stacking of the atomic layers in the 3R phases reduces the interlayer coupling. As a consequence, the 3R phases are found to be superior in the technologically relevant temperature range. The Rh d3z2-r2 orbitals still govern the valence band maxima and therefore determine the transport properties. A high figure of merit of 0.35 is achieved in hydrated Na0.83RhO2 at 580 K by water intercalation, which is 34% higher than in the non-hydrated phase.

  12. Caesium extraction from acidic high level liquid wastes with functionalized calixarenes

    International Nuclear Information System (INIS)

    Simon, N.; Eymard, S.; Tournois, B.; Dozol, J.F.

    2000-01-01

    In the framework of French law programme, studies are under way to selectively remove caesium from acidic high activity wastes. Calix[4]arene crown derivatives exhibit outstanding efficiency and selectivity for caesium. An optimisation of the formulation of a selective extractant system for Cs based on crown calixarenes and usable in a process which use liquid-liquid extraction is presented. A system involving a monoamide as a modifier is proposed. Besides these improvements, a reference solvent based on a standard 1,3-di-(n-octyl-oxy)2,4-calix(4)arene crown is studied. Flow-sheets related to this system are calculated and easily transferable to the optimised new system. (authors)

  13. Smectite for acute infectious diarrhoea in children.

    Science.gov (United States)

    Pérez-Gaxiola, Giordano; Cuello-García, Carlos A; Florez, Ivan D; Pérez-Pico, Víctor M

    2018-04-25

    As mortality secondary to acute infectious diarrhoea has decreased worldwide, the focus shifts to adjuvant therapies to lessen the burden of disease. Smectite, a medicinal clay, could offer a complementary intervention to reduce the duration of diarrhoea. To assess the effects of smectite for treating acute infectious diarrhoea in children. We searched the Cochrane Infectious Diseases Group Specialized Register, the Cochrane Central Register of Controlled Trials (CENTRAL), MEDLINE (Pubmed), Embase (Ovid), LILACS, reference lists from studies and previous reviews, and conference abstracts, up to 27 June 2017. Randomized and quasi-randomized trials comparing smectite to a control group in children aged one month to 18 years old with acute infectious diarrhoea. Two review authors independently screened abstracts and the full texts for inclusion, extracted data, and assessed risk of bias. Our primary outcomes were duration of diarrhoea and clinical resolution at day 3. We summarized continuous outcomes using mean differences (MD) and dichotomous outcomes using risk ratios (RR), with 95% confidence intervals (CI). Where appropriate, we pooled data in meta-analyses and assessed heterogeneity. We explored publication bias using a funnel plot. Eighteen trials with 2616 children met our inclusion criteria. Studies were conducted in both ambulatory and in-hospital settings, and in both high-income and low- or middle-income countries. Most studies included children with rotavirus infections, and half included breastfed children.Smectite may reduce the duration of diarrhoea by approximately a day (MD -24.38 hours, 95% CI -30.91 to -17.85; 14 studies; 2209 children; low-certainty evidence); may increase clinical resolution at day 3 (risk ratio (RR) 2.10, 95% CI 1.30 to 3.39; 5 trials; 312 children; low-certainty evidence); and may reduce stool output (MD -11.37, 95% CI -21.94 to -0.79; 3 studies; 634 children; low-certainty evidence).We are uncertain whether smectite reduces

  14. The removal of caesium ions using supported clinoptilolite

    International Nuclear Information System (INIS)

    De Haro-Del Rio, D.A.; Al-Joubori, S.; Kontogiannis, O.; Papadatos-Gigantes, D.; Ajayi, O.; Li, C.; Holmes, S.M.

    2015-01-01

    Highlights: • Natural clinoptilolite was supported over carbon structures produced from wastes. • Carbon–clinoptilolite showed an improved Cs + ions sorption capacity. • Overall kinetic rate was improved using carbon–clinoptilolite composite. • Diffusive resistances were modified using the composite and pure zeolite. • Final disposition volume can be reduced up to 60% by encapsulation. - Abstract: In this paper, the sorptive kinetic and diffusional characteristics of caesium ion removal from aqueous solution by carbon-supported clinoptilolite composites are presented. Natural clinoptilolite was supported on carbonaceous scaffolds prepared from date stones. Thermal treatment was applied to produce voids in the carbon which was conditioned using polydiallyldimethylammonium chloride to facilitate the clinoptilolite attachment. This method allowed the formation of a consistent zeolite layer on the carbon surface. The composite was applied in the removal of non-radioactive caesium ions showing an enhanced uptake from 55 mg g −1 to 120.9 mg g −1 when compared to clinoptilolite. Kinetic studies using Pseudo First Order model revealed an enhanced rate constant for carbon–clinoptilolite (0.0252 min −1 ) in comparison with clinoptilolite (0.0189 min −1 ). The Pseudo-First Order model described the process for carbon–clinoptilolite, meanwhile Pseudo Second Order model adjusted better for pure clinoptilolite. Diffusivity results suggested that mass transfer resistances involved in the Cs + sorption are film and intraparticle diffusion for natural clinoptilolite and intraparticle diffusion as the mechanism that controls the process for carbon–clinoptilolite composite. The most significant aspect being that the vitrified volume waste can be reduced by over 60% for encapsulation of the same quantity of caesium due to the enhanced uptake of zeolite

  15. Dehydrochlorination of 1,1,1-trichloroethane and pentachloroethane by microbially reduced ferruginous smectite.

    Science.gov (United States)

    Cervini-Silva, Javiera; Kostka, Joel E; Larson, Richard A; Stucki, Joseph W; Wu, Jun

    2003-05-01

    Reduction of structural Fe(III) in smectite clay minerals has been identified as a means to promote dechlorination of polychlorinated ethanes, but its environmental significance has yet to be fully assessed because Fe reduction has normally been achieved by agents uncommon in the environment (e.g., dithionite). This study reports the dehydrochlorination of pentachloroethane and 1,1,1-trichloroethane in the presence of ferruginous smectite reduced by two cultures of microorganisms, Shewanella oneidensis strain MR-1 (MR-R) and an enrichment culture from rice paddy soils (PS-R), in aqueous suspension under anoxic conditions. Microbially reduced ferruginous smectite facilitated dehydrochlorination of 1,1,1-trichloroethane to 1,1-dichloroethene with up to 60% conversion within 3 h of incubation time. In contrast, no formation of 1,1-dichloroethene was observed after incubation of 1,1,1-trichloroethane with chemically reduced ferruginous smectite for 24 h. Microbially reduced ferruginous smectite by MR-R and PS-R promoted the dehydrochlorination of pentachloroethane to tetrachloroethene by 80 and 15%, respectively, after 3 h of incubation time. The conversion of pentachloroethane to tetrachloroethene in the presence of chemically reduced ferruginous smectite after 24 h was 65%. These results indicate that structural Fe(II) in clay minerals has the potential to be an important reductant controlling the fate of organic chemicals in contaminated sediments.

  16. Investigation of chloritization of smectite. Document prepared by other institute, based on the trust contact

    International Nuclear Information System (INIS)

    Oba, Takanobu

    2003-03-01

    The stability of smectite under the bulk composition of high iron content is as follows: (1) and (2). (1) In early burial diagenesis, the chemical variations of chlorite and dioctahedral smectite in Tertiary formations of Niigata prefecture. (2) The experiment of the stability of smectite in iron - rich bulk composition under oxygen fugacity. In the present study, the results are as follows: (1) Samples were taken from the cores and cuttings of exploratory test well of Oguni. The trioctahedral smectite in tertiary formation decreases with a depth. Below 3800m, Si content of chlorite increases with a depth. In the study, corrensite at 2700m depth has higher Si content, as compared to chlorite at 3800m. Mg/(Mg+Fe) ratios of chlorite/smectite interstratified mineral increase with increasing Si content regardless of the depth. (2) Chlorite/smectite interstratified mineral forms at 250degC on the compositions of the starting material of Mont:Mt=5:5. Chlorite did not crystallize by using of the starting material of Sap:Mt 5:5 at 250degC. At 400degC, montomorillonite did not decompose on the starting material composition with low iron content. The iron density is very important for the stability of smectite. (author)

  17. Studies on the acid activation of Brazilian smectitic clays

    Directory of Open Access Journals (Sweden)

    Valenzuela Díaz Francisco R.

    2001-01-01

    Full Text Available Fuller's earth and acid activated smectitic clays are largely used as bleaching earth for the industrial processing of vegetable, animal and mineral oils and waxes. The paper comments about the nomenclature used for these materials, the nature of the acid activation of smectitic clays (bentonites, activation laboratory procedures and presents a review of the acid activation of bentonites from 20 deposits from several regions of Brazil. The activated clays were tested and show good decolorizing power for soybean, castor, cottonseed, corn and sunflower oils.

  18. Prediction of Intrinsic Cesium Desorption from Na-Smectite in Mixed Cation Solutions.

    Science.gov (United States)

    Fukushi, Keisuke; Fukiage, Tomo

    2015-09-01

    Quantitative understanding of the stability of sorbed radionuclides in smectite is necessary to assess the performance of engineering barriers used for nuclear waste disposal. Our previous study demonstrated that the spatial organization of the smectite platelets triggered by the divalent cations led to the apparent fixation of intrinsic Cs in smectite, because some Cs is retained inside the formed tactoids. Natural water is usually a mixture of Na(+) and divalent cations (Ca(2+) and Mg(2+)). This study therefore investigated the desorption behavior of intrinsic Cs in Na-smecite in mixed Na(+)-divalent cation solutions under widely various cation concentrations using batch experiments, grain size measurements, and cation exchange modeling (CEM). Results show that increased Na(+) concentrations facilitate Cs desorption because Na(+) serves as the dispersion agent. A linear relation was obtained between the logarithm of the Na(+) fraction and the accessible Cs fraction in smectite. That relation enables the prediction of accessible Cs fraction as a function of solution cationic compositions. The corrected CEM considering the effects of the spatial organization suggests that the stability of intrinsic Cs in the smectite is governed by the Na(+) concentration, and suggests that it is almost independent of the concentrations of divalent cations in natural water.

  19. Caesium dynamics in the peats and associated vegetation of northern Greece and northern Scotland

    International Nuclear Information System (INIS)

    Heaton, B.; Mitchell, R.D.J.; Killham, K.; Veresoglou, D.S.

    1990-01-01

    Sequential analyses have shown that Chernobyl-derived caesium has been largely retained in Greek basin peats (highly cultivated, base-rich, sedge peats) and retained/cycled in Scottish upland peats (uncultivated, base-poor, blanket peats). To investigate the mechanisms of retention and cycling in the Scottish peat/vegetation system, a laboratory experiment was carried out involving 'microcosms' intact peat cores. Festuca ovina was grown from seed in the cores prior to nebuliser-application of simulated rain containing caesium-134. The major factors investigated were competitive ion exchange from ammonium (designed to simulate animal waste inputs), freeze-thaw activity, and cropping (designed to simulate upland grazing). The effects of these factors are discussed in relation to the physio-cochemical and biological properties of the peat and vegetation and to our observations of the movement of caesium in the field. (author)

  20. Development of prediction models for radioactive caesium distribution within the 80-km radius of the Fukushima Daiichi nuclear power plant

    International Nuclear Information System (INIS)

    Kinase, Sakae; Sato, Satoshi; Saito, Kimiaki; Takahashi, Tomoyuki; Sakamoto, Ryuichi

    2014-01-01

    Preliminary prediction models have been studied for the radioactive caesium distribution within the 80-km radius of the Fukushima Daiichi nuclear power plant. The models were represented by exponential functions using ecological half-life of radioactive caesium in the environment. The ecological half-lives were derived from the changes in ambient dose equivalent rates through vehicle-borne surveys. It was found that the ecological half-lives of radioactive caesium were not constant within the 80-km radius of the Fukushima Daiichi nuclear power plant. The ecological half-life of radioactive caesium in forest areas was found to be much larger than that in urban and water areas. (authors)

  1. Microhydration of caesium compounds: Cs, CsOH, CsI and Cs₂I₂ complexes with one to three H₂O molecules of nuclear safety interest.

    Science.gov (United States)

    Sudolská, Mária; Cantrel, Laurent; Cernušák, Ivan

    2014-04-01

    Structure and thermodynamic properties (standard enthalpies of formation and Gibbs free energies) of hydrated caesium species of nuclear safety interest, Cs, CsOH, CsI and its dimer Cs₂I₂, with one up to three water molecules, are calculated to assess their possible existence in severe accident occurring to a pressurized water reactor. The calculations were performed using the coupled cluster theory including single, double and non-iterative triple substitutions (CCSD(T)) in conjunction with the basis sets (ANO-RCC) developed for scalar relativistic calculations. The second-order spin-free Douglas-Kroll-Hess Hamiltonian was used to account for the scalar relativistic effects. Thermodynamic properties obtained by these correlated ab initio calculations (entropies and thermal capacities at constant pressure as a function of temperature) are used in nuclear accident simulations using ASTEC/SOPHAEROS software. Interaction energies, standard enthalpies and Gibbs free energies of successive water molecules addition determine the ordering of the complexes. CsOH forms the most hydrated stable complexes followed by CsI, Cs₂I₂, and Cs. CsOH still exists in steam atmosphere even at quite high temperature, up to around 1100 K.

  2. Effect of radiation-induced amorphization on smectite dissolution.

    Science.gov (United States)

    Fourdrin, C; Allard, T; Monnet, I; Menguy, N; Benedetti, M; Calas, G

    2010-04-01

    Effects of radiation-induced amorphization of smectite were investigated using artificial irradiation. Beams of 925 MeV Xenon ions with radiation dose reaching 73 MGy were used to simulate the effects generated by alpha recoil nuclei or fission products in the context of high level nuclear waste repository. Amorphization was controlled by X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. An important coalescence of the smectite sheets was observed which lead to a loss of interparticle porosity. The amorphization is revealed by a loss of long-range structure and accompanied by dehydroxylation. The dissolution rate far-from-equilibrium shows that the amount of silica in solution is two times larger in the amorphous sample than in the reference clay, a value which may be enhanced by orders of magnitude when considering the relative surface area of the samples. Irradiation-induced amorphization thus facilitates dissolution of the clay-derived material. This has to be taken into account for the safety assessment of high level nuclear waste repository, particularly in a scenario of leakage of the waste package which would deliver alpha emitters able to amorphize smectite after a limited period of time.

  3. GMM - a general microstructural model for qualitative and quantitative studies of smectite clays

    International Nuclear Information System (INIS)

    Pusch, R.; Karnland, O.; Hoekmark, H.

    1990-12-01

    A few years ago an attempt was made to accommodate a number of basic ideas on the fabric and interparticle forces that are assumed to be valid in montmorillonite clay in an integrated microstructural model and this resulted in an SKB report on 'Outlines of models of water and gas flow through smectite clay buffers'. This model gave reasonable agreement between predicted hydraulic conductivity values and actually recorded ones for room temperature and porewater that is poor in electrolytes. The present report describes an improved model that also accounts for effects generated by salt porewater and heating, and that provides a basis for both quantitative determination of transport capacities in a more general way, and also for analysis and prediction of rheological behaviour in bulk. It has been understood very early by investigators in this scientific field that full understanding of the physical state of porewater is asked for in order to make it possible to develop models for clay particle interaction. In particular, a deep insight in the nature of the interlamellar water and of the hydration mechanisms leading to an equilibrium state between the two types of water, and of forcefields in matured smectite clay, requires very qualified multi-discipline research and attempts have been made by the senior author to initiate and coordinate such work in the last 30 years. Despite this effort it has not been possible to get an unanimous understanding of these things but a number of major features have become more clear through the work that we have been able to carry out in the current SKB research work. Thus, NMR studies and precision measurements of the density of porewater as well as comprehensive electron microscopy and rheological testing in combination with application of stochastical mechanics, have led to the hypothetical microstructural model - the GMM - presented in this report. (au)

  4. Nano-confined water in the interlayers of hydrocalumite: Reorientational dynamics probed by neutron spectroscopy and molecular dynamics computer simulations

    Science.gov (United States)

    Kalinichev, A. G.; Faraone, A.; Udovic, T.; Kolesnikov, A. I.; de Souza, N. R.; Reinholdt, M. X.; Kirkpatrick, R.

    2008-12-01

    Layered double hydroxides (LDHs, anionic clays) represent excellent model systems for detailed molecular- level studies of the structure, dynamics, and energetics of nano-confined water in mineral interlayers and nano-pores, because LDH interlayers can have a well-defined structures and contain H2O molecules and a wide variety of anions in structurally well-defined positions and coordinations. [Ca2Al(OH)6]Cl·2H2O, also known as hydrocalumite or Friedel's salt, has a well- ordered Ca,Al distribution in the hydroxide layer and a very high degree of H2O,Cl ordering in the interlayer. It is also one of the only LDH phase for which a single crystal structure refinement is available. Thus, it is currently the best model compound for understanding the structure and dynamical behavior of interlayer and surface species in other, less-ordered, LDHs. We investigated the structural and dynamic behavior of water in the interlayers of hydrocalumite using inelastic (INS) and quasielastic (QENS) neutron scattering and molecular dynamics computer simulations. The comperehensive neutron scattering studies were performed for one fully hydrated and one dehydrated sample of hydrocalumite using several complementary instruments (HFBS, DCS and FANS at NCNR; HRMECS and QENS at IPNS) at temperatures above and below the previously discovered order-disorder interlayer phase transition. Together the experimental and molecular modeling results capture the important details of the dynamics of nano-confined water and the effects of the orientational ordering of H2O molecules above and below the phase transition. They provide otherwise unobtainable experimental information about the transformation of H2O librational and diffusional modes across the order-disorder phase transition and significantly add to our current understanding of the structure and dynamics of water in LDH phases based on the earlier NMR, IR, X-ray, and calorimetric measurements. The approach can now be extended to probe the

  5. Smectite-zeolite envelope surrounding the Tsukiyoshi uranium deposit, central Japan. A natural analogue study

    International Nuclear Information System (INIS)

    Utada, Minoru

    2003-01-01

    The Tsukiyoshi uranium deposit in Gifu Prefecture is the largest one in Japan. It is embedded in lower part of the Mizunami Group of Miocene age. Relating to the existence of this uranium deposit, the constituent minerals in sediments were studied by XRD and SEM, using many drilling cores. The most abundant authigenic mineral is smectite. The amount of smectite increases generally from upper to lower horizons, and a highly smectitized zone is situated around the uranium deposit. Smectitization predominated in mafic glassy grains of sediments, which was probably formed in early burial diagenesis. Zeolites including clinoptilolite-heulandite, mordenite, analcime, chabazite and philipsite are secondly abundant authigenic minerals. They seem to have been formed at early to late diagenetic stages. Opaline silica is rather rare. Carbonate minerals, including calcite, dolomite, siderite and rhodocrosite are common. They may be formed by diagenesis as well. Gypsum and pyrite occur in upper horizons and lower horizons, respectively. In particular, a highly smectitized zone including pyrite probably played an important role for retarding the migration of uranium and as a result keeping the uranium deposit for past one million years. This smectite-zeolite envelope surrounding the Tsukiyoshi uranium deposit is regarded as a natural analogue of the buffer materials surrounding the high-level radioactive waste repository. (author)

  6. Rapid and extensive debromination of decabromodiphenyl ether by smectite clay-templated subnanoscale zero-valent iron.

    Science.gov (United States)

    Yu, Kai; Gu, Cheng; Boyd, Stephen A; Liu, Cun; Sun, Cheng; Teppen, Brian J; Li, Hui

    2012-08-21

    Subnanoscale zerovalent iron (ZVI) synthesized using smectite clay as a template was utilized to investigate reduction of decabromodiphenyl ether (DBDE). The results revealed that DBDE was rapidly debrominated by the prepared smectite-templated ZVI with a reaction rate 10 times greater than that by conventionally prepared nanoscale ZVI. This enhanced reduction is plausibly attributed to the smaller-sized smectite-templated ZVI clusters (∼0.5 nm) vs that of the conventional nanoscale ZVI (∼40 nm). The degradation of DBDE occurred in a stepwise debromination manner. Pentabromodiphenyl ethers were the terminal products in an alkaline suspension (pH 9.6) of smectite-templated ZVI, whereas di-, tri-, and tetrabromodiphenyl ethers formed at the neutral pH. The presence of tetrahydrofuran (THF) as a cosolvent at large volume fractions (e.g., >70%) in water reduced the debromination rates due to enhanced aggregation of clay particles and/or diminished adsorption of DBDE to smectite surfaces. Modification of clay surfaces with tetramethylammonium (TMA) attenuated the colsovent effect on the aggregation of clay particles, resulting in enhanced debromination rates. Smectite clay provides an ideal template to form subnanoscale ZVI, which demonstrated superior debromination reactivity with DBDE compared with other known forms of ZVIs. The ability to modify the nature of smectite clay surface by cation exchange reaction utilizing organic cations can be harnessed to create surface properties compatible with various contaminated sites.

  7. Kinetic Study of Denatonium Sorption to Smectite Clay Minerals.

    Science.gov (United States)

    Crosson, Garry S; Sandmann, Emily

    2013-06-01

    The denatonium cation, as a benzoate salt, is the most bitter cation known to modern society and is frequently added to consumer products to reduce accidental and intentional consumption by humans and animals. Denatonium can enter the environment by accidental discharges, potentially rendering water supplies undrinkable. Interactions of denatonium with soil components ( i.e. , smectite minerals) ultimately control the environmental fate of denatonium, but the current literature is devoid of studies that evaluate denatonium sorption to smectite minerals. This study investigated the mechanism and kinetics of denatonium sorption to smectite clay minerals as a function of smectite type, temperature, pH and ionic strength. Uptake by synthetic mica montmorillonite (Syn-1), Wyoming montmorillonite (SWy-2), and Texas montmorillonite (STx-1b) at 305K was rapid, with equilibrium being reached within 2 min for all clays. Complete removal of denatonium was observed for STx-1b at pH 6.9, while partial removal was observed for Syn-1 and SWy-2. Kinetic behavior of SWy-2 and Syn-1 is consistent with a pseudo-second-order model at 305K. An activation energy of +25.9 kJ/mol was obtained for sorption to Syn-1 and was independent of temperature between 286K and 338K. Activation-free energy (Δ G *), activation enthalpy (Δ H *), and activation entropy (Δ S *) for Syn-1 were found to be +62.91 kJ/mol, +23.36 kJ/mol, and -0.130 kJ/(K·mol), respectively. Sorption capacities at pH 3.6, 6.9, and 8.2 were constant at 1.3×10 -2 g denatonium/g clay; however, the kinetic rate constant increased by 56%, going from acidic to basic solution conditions. Distribution coefficients were negatively correlated with ionic strength, suggesting cation exchange. Collectively, results suggested that smectite minerals can serve as efficient sinks for denatonium cations. This is much-needed information for agencies developing regulations regarding denatonium usage and for water treatment professionals

  8. NIFSIL - a composite sorbent for caesium - properties and application

    International Nuclear Information System (INIS)

    Rajec, P.; Orechovska, J.

    1998-01-01

    Samples of the potassium-nickel ferrocyanides K 2 NiFe(CN) 6 , KNi 1,5 Fe(CN) 6 and Ni 2 Fe(CN) 6 were prepared and their properties studied with respect to their use as sorbents for caesium. Caesium is fixed on mixed alkaline-nickel ferrocyanide without structural change. The capacity of Cs retention never reached the theoretic value corresponding to a total release of the monovalent ions of the solid. High distribution coefficients (K D in the order of 10 4 cm 3 /g) determined in batch experiments show that these sorbents have a very high affinity for caesium ions, even in the presence of competing K + , Na + and Ca 2+ ions. The sorbents have a good chemical stability in a wide pH-range (2-12). The irradiation of some sorbent samples with high energy gamma-rays ( 60 Co) of a total dose of 1.10 5 Gy caused no remarkable changes in the sorbent properties (K D , sorption capacity and kinetics, mechanical stability). The sorbents were also tested for 85 Sr and 239 Pu and the results carried out under dynamic and batch experiments have shown that sorbents are not suitable for removal of these radionuclides. Potassium nickel hexacyanoferrate incorporated in silica-gel matrix could compete with others sorbents based on insoluble hexacyanoferrates, has the advantage of good radiation stability and suitable granulometry. The sorbent was prepared on a pilot scale with a capacity about 1000 kg per year with the prospect that it could be easily upgraded to an industrial scale

  9. Advanced study of transport analysis in bentonite (2)

    International Nuclear Information System (INIS)

    Kawamura, Katsuyuki

    2004-03-01

    Solute and radionuclide transport analysis in buffer material made of bentonite clay is essential in safety assessment of a geological disposal facility for high-level radioactive waste (HLW). It is keenly required to understand the true physical and chemical process of the transport phenomena and to improve reliability of the safety assessment, since any conventional methods based on experimental models involve difficulty to estimate the robustness for a very long-term behavior. In order to solve this difficulty we start with the molecular dynamics (MD) simulation method for understanding the molecular-based fundamental properties such as an ionic state and diffusion characteristics of hydrated smectite clay minerals, and we extend the microscale properties to the macroscale behaviors by applying the multiscale homogenization method. In the study of this year we improved the MD atomic model for the hydrated clay minerals, and a new adsorption-diffusion analysis scheme by the homogenization analysis (HA). In the MD simulation first we improved the interatomic potential model for the smectitic clays. Then the behaviors of hydrated Na-beidellite and its substitution products by Cs and Ca were calculated. Not only the swelling behaviors of the beidellite minerals but also the diffusion characteristics of cations in the interlayer space are calculated. A microscopic image is important to specify micro/macro behavior of bentonite. Last year we observed microstructures of bentonite by using a confocal laser scanning microscope (LSM). Based on the knowledge of the local material properties obtained by MD and the microscopic observation we simulated the micro-/macro-behavior of diffusion experiments of the bentonite which included the microscale adsorption characteristics at the edges of clay minerals. (author)

  10. A preliminary assessment of the potential for using caesium-137 to estimate rates of soil erosion in the Loess Plateau of China

    International Nuclear Information System (INIS)

    Zhang Xinbao

    1990-01-01

    The potential for using the radionuclide caesium-137 as an environmental tracer to indicate sources of soil erosion in the Chinese Loess Plateau is introduced. The caesium-137 contents of soil profiles have been used to estimate soil erosion losses from different topographic and land use conditions at Lishi, Shanxi Province, and Luochuan, Shaanxi Province. At uncultivated sites the caesium-137 has accumulated in the upper soil profile, whilst it has been mixed within the plough layer of cultivated soils. Eroded soils contain relatively less caesium-137, and simple calibration techniques are applied to quantify soil loss. Preliminary results suggest that caesium-137 may be of considerable value in assembling data on the rates and spatial distribution of soil loss and in identifying the source areas of eroded sediment. (author)

  11. Intercalated theophylline-smectite hybrid for pH-mediated delivery.

    Science.gov (United States)

    Trivedi, Vivek; Nandi, Uttom; Maniruzzaman, Mohammed; Coleman, Nichola J

    2018-01-23

    On the basis of their large specific surface areas, high adsorption and cation exchange capacities, swelling potential and low toxicity, natural smectite clays are attractive substrates for the gastric protection of neutral and cationic drugs. Theophylline is an amphoteric xanthine derivative that is widely used as a bronchodilator in the treatment of asthma and chronic obstructive pulmonary disease. This study considers the in vitro uptake and release characteristics of the binary theophylline-smectite system. The cationic form of theophylline was readily ion exchanged into smectite clay at pH 1.2 with a maximum uptake of 67 ± 2 mg g -1 . Characterisation of the drug-clay hybrid system by powder X-ray diffraction analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy confirmed that the theophylline had been exclusively intercalated into the clay system in an amorphous form. The drug remained bound within the clay under simulated gastric conditions at pH 1.2; and the prolonged release of approximately 40% of the drug was observed in simulated intestinal fluid at pH 6.8 and 7.4 within a 2-h timeframe. The incomplete reversibility of the intercalation process was attributed to chemisorption of the drug within the clay lattice. These findings indicate that smectite clay is a potentially suitable vehicle for the safe passage of theophylline into the duodenum. Protection from absorption in the stomach and subsequent prolonged release in the small intestine are advantageous in reducing fluctuations in serum concentration which may impact therapeutic effect and toxicity.

  12. Assessing the conditions favorable for the occurrence of gas hydrate in the Tuonamu area Qiangtang basin, Qinghai–Tibetan, China

    International Nuclear Information System (INIS)

    He Jianglin; Wang Jian; Fu Xiugen; Zheng Chenggang; Chen Yanting

    2012-01-01

    Highlights: ► This is a pioneer research on the exploration of gas hydrate in Qiangtang basin. ► The factors influencing the stable of gas hydrate in Tuonamu area were studied. ► Simulation shows that gas hydrate stable zone is about 300 m thick in target area. ► Source condition is the key factor for the formation of gas hydrate in this area. ► The areas around the deeper faults are favorable targets for gas hydrate. - Abstract: Qiangtang basin, which is located in the largest continuous permafrost area in Qinghai–Tibetan Plateau, is expected to be a strategic area of gas hydrate exploitation in China. However, relatively little work has been done on the exploration of gas hydrate in this area. In this work, we evaluated the factors controlling the formation of gas hydrate in the Tuonamu area and provided a preliminary insight into gas hydrate distribution in it on the basis of the core samples, seismic data and laboratory analysis. It can be concluded that the source rock in the deeper formation would be dominant thermogenic source for the formation of gas hydrate in Tuonamu area. The thickness of gas hydrate stable zone in this area is about 300 m. The gas hydrate in the area most probably is in the form of gas-hydrate-water. The source condition is the key factor for the formation of gas hydrate and the gas hydrate layer would be mainly present in the form of interlayer in this area. The areas around the deeper faults are the favorable targets for the exploration of gas hydrate in the Tuonamu area.

  13. Efficacy of Probiotics and Smectite in Rats with Non-Alcoholic Fatty Liver Disease.

    Science.gov (United States)

    Kobyliak, Nazarii; Abenavoli, Ludovico; Falalyeyeva, Tetyana; Beregova, Tetyana

    2018-01-01

    Today probiotics have been suggested as a treatment for the prevention of non-alcoholic fatty liver disease (NAFLD). Smectite is a natural silicate that binds to digestive mucous and has the ability to bind endo- and exotoxins. The present study was designed to determine whether probiotics plus smectite is superior to probiotic alone on the monosodium glutamate (MSG) induced NAFLD model in rats. We included 60 rats divided into 4 groups 15 animals in each. Rats of group I were intact. Newborns rats of groups II-IV were injected with MSG. The III (Symbiter) group received 2.5 ml/kg of multiprobiotic "Symbiter" containing concentrated biomass of 14 probiotic bacteria genera. The IV (Symbiter+Smectite) groups received "Symbiter Forte" combination of probiotic biomass with smectite gel (250 mg). In both interventional groups reduction of total NAS score as compared to MSG-obesity was observed. Indeed similar values of steatosis score (0.93 ± 0.22 vs. 0.87 ± 0.16) in both treatment groups, we observed that lower total score for Symbiter+ Smectite are associated with more pronounced reduction of lobular inflammation (0.13 ± 0.09 vs. 0.33 ± 0.15) as compared to administration of probiotic alone. This data accompanied with significant reduction of IL-1 and restoration of IL-10 between these 2 groups. Additional to alive probiotic administration of smectite gel due to his absorbent activity and mucus layer stabilization properties can impact on synergistic enhancement of single effect which manifested with reduction of lobular inflammation and at list partly steatohepatitis prevention.

  14. Morphology of Si/tungsten-silicides/Si interlayers

    International Nuclear Information System (INIS)

    Theodore, N.; Secco d'Aragona, F.; Blackstone, S.

    1992-01-01

    Tungsten and tungsten-silicides are of interest for semiconductor technology because of their refractory nature, low electrical-resistivity and high electromigration-resistance. This paper presents the first formation of buried tungsten-silicide layers in silicon, by proximity adhesion. The interlayers, created by a combination of chemical vapor-deposition (CVD) and proximity-adhesion were studied using transmission electron-microscopy (TEM). The behavior of the layers in the presence and absence of an adjacent silicon-dioxide interlayer was also investigated. Buried silicide layers were successfully formed with or without the adjacent silicon-dioxide. The silicide formed continuous layers with single grains encompassing the width of the interlayer. Individual grains were globular, with cusps at grain boundaries. This caused interlayer-thicknesses to be non-uniform, with lower thickness values being present at the cusps. Occasional voids were observed at grain-boundary cusps. The voids were smaller and less frequent in the presence of an adjacent oxide-layer, due to flow of the oxide during proximity adhesion. Electron-diffraction revealed a predominance of tungsten-disilicide in the interlayers, with some free tungsten being present. Stresses in the silicide layers caused occasional glide dislocations to propagate into the silicon substrate beneath the interlayers. The dislocations propagate only ∼100 nm into the substrate and therefore should not be detrimental to use of the buried layers. Occasional precipitates were observed at the end of glide-loops. These possibly arise due to excess tungsten from the interlayer diffusion down the glide dislocation to finally precipitate out as tungsten-silicide

  15. Measurement of clay surface areas by polyvinylpyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance

    Science.gov (United States)

    Blum, A.E.; Eberl, D.D.

    2004-01-01

    A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ~0.99 mg/m2, which corresponds to ~0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (~725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

  16. Chemical and Mineralogical Features of Smectite from the Morron de Mateo Bentonite Deposit (Cabo de Gata, Almeria) in Relation to the Parent Rocks and the Alteration Processes Occurred After the Bentonite Formation: Analogies and Implications for the Engineered Clayey Barrier of a Deep Geological Rad waste Repository

    International Nuclear Information System (INIS)

    Pelayo, M.; Labajo, M. A.; Garcia Romero, L.; Perez del Villar, L.

    2009-01-01

    The Morron de Mateo bentonite deposit is being studied as a natural analogue of the thermal and geochemical effects on the clayey barrier of a Deep Geological Rad waste Repository (DGRR) after its closure, in relation to the radioactive decay of the fission products and the container corrosion. This bentonite deposit and their host rocks were intruded by a rhyodacitic volcanic dome that induced a hydrothermal metasomatic process affecting the bioclastic calcarenite beds close to the dome. Bentonite from the NE sector of the deposit have been chemically and mineralogically characterized. Pyroclastic rocks (white tuffs), epyclastic rocks (mass flow) and andesitic breccia all of them hydrothermally altered, have been studied at the site. Samples are composed of feldspars, quartz and amphybols, as inherited minerals, and phyllosilicates, zeolites, crystoballite and calcite, as new formed minerals. White tuffs have the highest phyllosilicate contents, mainly dioctahedral smectite of montmorillonite type. Epyclastic rocks and andesitic breccia have a highest proportion of inherited minerals, the new formed phillosilicates being di octahedral smectite of beidellite type and an ordered interlayer chlorite/smectite mineral, of corrensite type. Smectite from the epyclastic rocks have higher Fe and Mg contents and chemical variability, as a consequence of nature of their parent rocks. The presence of corrensite in the epyclastic rocks suggests that in the Morron de Mateo area a propilitic alteration process occurred after bentonite formation, which transformed Fe-Mg-rich smectite into corrensite. This transformation was probably favoured by the sub volcanic intrusion, which also produced a temperature increase in the geological media and a supply of Fe-Mg-rich solutions, which also were the responsible for the metasomatic transformations observed in the calcarenite beds. (Author) 57 refs

  17. Enhancing the DEMO divertor target by interlayer engineering

    Energy Technology Data Exchange (ETDEWEB)

    Barrett, T.R., E-mail: tom.barrett@ccfe.ac.uk [CCFE, Culham Science Centre, Oxfordshire OX14 3DB (United Kingdom); McIntosh, S.C.; Fursdon, M.; Hancock, D.; Timmis, W.; Coleman, M. [CCFE, Culham Science Centre, Oxfordshire OX14 3DB (United Kingdom); Rieth, M.; Reiser, J. [Karlsruhe Institute for Technology, IMF-I, D-7602 Karlsruhe (Germany)

    2015-10-15

    Highlights: • The European ‘near-term’ DEMO forsees a water-cooled divertor. • Divertor targets typically use an interlayer between the armour and structure. • Engineering the properties of the interlayer can yield large gains in performance. • A response surface based design search and optimisation method is used. • A new design passes linear-elastic code rules up to applied heat flux of 18 MW/m{sup 2}. - Abstract: A robust water-cooled divertor target plate solution for DEMO has to date remained elusive. Common to all contemporary concepts is an interlayer at the boundary between the tungsten armour and the cooling structure. In this paper we show by design optimisation that an effectively designed interlayer can produce dramatic gains in power handling. By engineering the interlayer as part of the design study, it is found that divertor performance is enhanced by either a low conductivity ‘Thermal Break’ interlayer or an ‘Ultra-Compliant’ interlayer. For a 10 MW/m{sup 2} surface heat flux we find that a thermal conductivity of 15 W/mK and elastic modulus of 1 GPa are effective. A design is proposed which passes linear-elastic code rules up to an applied heat flux of 18 MW/m{sup 2}.

  18. Enhancing the DEMO divertor target by interlayer engineering

    International Nuclear Information System (INIS)

    Barrett, T.R.; McIntosh, S.C.; Fursdon, M.; Hancock, D.; Timmis, W.; Coleman, M.; Rieth, M.; Reiser, J.

    2015-01-01

    Highlights: • The European ‘near-term’ DEMO forsees a water-cooled divertor. • Divertor targets typically use an interlayer between the armour and structure. • Engineering the properties of the interlayer can yield large gains in performance. • A response surface based design search and optimisation method is used. • A new design passes linear-elastic code rules up to applied heat flux of 18 MW/m"2. - Abstract: A robust water-cooled divertor target plate solution for DEMO has to date remained elusive. Common to all contemporary concepts is an interlayer at the boundary between the tungsten armour and the cooling structure. In this paper we show by design optimisation that an effectively designed interlayer can produce dramatic gains in power handling. By engineering the interlayer as part of the design study, it is found that divertor performance is enhanced by either a low conductivity ‘Thermal Break’ interlayer or an ‘Ultra-Compliant’ interlayer. For a 10 MW/m"2 surface heat flux we find that a thermal conductivity of 15 W/mK and elastic modulus of 1 GPa are effective. A design is proposed which passes linear-elastic code rules up to an applied heat flux of 18 MW/m"2.

  19. Time-varying multiplex network: Intralayer and interlayer synchronization

    Science.gov (United States)

    Rakshit, Sarbendu; Majhi, Soumen; Bera, Bidesh K.; Sinha, Sudeshna; Ghosh, Dibakar

    2017-12-01

    A large class of engineered and natural systems, ranging from transportation networks to neuronal networks, are best represented by multiplex network architectures, namely a network composed of two or more different layers where the mutual interaction in each layer may differ from other layers. Here we consider a multiplex network where the intralayer coupling interactions are switched stochastically with a characteristic frequency. We explore the intralayer and interlayer synchronization of such a time-varying multiplex network. We find that the analytically derived necessary condition for intralayer and interlayer synchronization, obtained by the master stability function approach, is in excellent agreement with our numerical results. Interestingly, we clearly find that the higher frequency of switching links in the layers enhances both intralayer and interlayer synchrony, yielding larger windows of synchronization. Further, we quantify the resilience of synchronous states against random perturbations, using a global stability measure based on the concept of basin stability, and this reveals that intralayer coupling strength is most crucial for determining both intralayer and interlayer synchrony. Lastly, we investigate the robustness of interlayer synchronization against a progressive demultiplexing of the multiplex structure, and we find that for rapid switching of intralayer links, the interlayer synchronization persists even when a large number of interlayer nodes are disconnected.

  20. Behaviour of caesium-137 in the marine environment

    International Nuclear Information System (INIS)

    Gilat, E.; Laichter, Y.; Shafrir, N.H.

    1975-01-01

    The radiological impacts of radioactive release from nuclear facilities into aquatic environments can be studied by following the behaviour of fallout radionuclides in the sea, provided that they exist in the same physico-chemical state. Caesium-137 entering the sea from fallout, although found to be at extremely low levels in the marine environment, is still detectable and can be considered representative for the behaviour of 137 Cs appearing in cooling waters and effluents of nuclear installations and processing plants located near the sea. The relatively high radiotoxicity, long physical half-life and high fission yield of 137 Cs justify further investigation of its behaviour in aquatic environments. In this investigation the sampling of sea water, sediments and organisms in the Mediterranean Sea was undertaken. Caesium-137 determinations were carried out using an extremely low level Ge(Li) gamma spectrometry system specifically designed for studies of environmental marine radioactivity. The activity of 137 Cs on the surface of the sea was found to be 0.49+-0.17 pCi/1. Caesium-137 concentrations at depth profiles down to 1000 m below the surface show variations by a factor of ten (0.65-0.07), maximum concentrations being found at a depth of 100-300 m. These concentration peaks may be explained by good mixing in the upper layers and by the existence of a thermocline or pycnocline which serve as mixing barriers at depths down to approximately 300 m, at least during part of the year. Caesium-137 concentrations in a number of marine biota representing a marine food chain composed of benthic algae, invertebrates and fishes, were determined. With reference to the average 137 Cs content in the upper water layers of the sea, concentration factors for these organisms were calculated. In all the three taxonomic groups mentioned, values within the range 10-300 were found. Biological concentration factors for any particular radionuclide are independent of its content in the

  1. New ion selective materials. Application to the selective extraction of caesium

    International Nuclear Information System (INIS)

    Favre-Reguillon, Alain

    1996-01-01

    This research thesis addresses the synthesis and assessment of ion selective materials. The first part reports the development of a general method of assessment of ion selective materials. In the second part, the author describes different methods used to insolubilize macro-cycles on hydrophilic polymers. The obtained polyurethanes are synthesised. These hydrophilic polymers display interesting complexing properties and selectivities with respect to cations of alkali metals. Then the author addresses the improvement of selectivity with respect to caesium of ion exchange resorcinol-formaldehyde resins. Different factors affecting selectivity are identified, and the concept of molecular print is used to study the improvement of selectivity. The effect of macro-cyclic structures on phenolic resins with respect to caesium is highlighted [fr

  2. Swimming clusters in thallium-rich liquid caesium-thallium alloys

    NARCIS (Netherlands)

    van der Aart, SA; van der Lugt, W; Badyal, YS; Verkerk, P

    The purpose of the work presented here is to obtain structural information on thallium-rich caesium-thallium alloys by means of neutron diffraction. The alloys exhibit a long-range (>1 nm) superstructure. This range increases with the thallium content. The results are interpreted with the help of a

  3. Polarization and pressure effects in caesium 6S-8S two-photon spectroscopy

    International Nuclear Information System (INIS)

    Lee, Yi-Chi; Tsai, Chin-Chun; Chui, Hsiang-Chen; Chang, Yi-Hsiu; Chen, Ying-Yu

    2010-01-01

    This work analyses the effects of polarization and pressure in caesium 6S-8S two-photon spectroscopy. The linewidth was broadened and the frequency was shifted by a change of polarization states. The frequency shift and the linewidth broadening of the caesium 6S-8S two-photon transition were measured as a function of laser power using one single-frequency Ti:sapphire ring cavity laser, two caesium cells and two quarter-wave plates to ensure polarization states of light, and we showed that the linewidth cannot be evaluated just by fitting data to a Lorentzian shape. As determined by fitting the data to a Voigt profile, the natural linewidth is independent of the polarization states of the pump beams, the laser power and the pressure. Caesium 6S-8S two-photon transitions pumped by a circularly polarized beam have narrower linewidths and smaller shifts than those pumped by a linearly polarized beam. The light shift obtained by pumping with the circularly polarized beam is -6.75(57) Hz (mW mm -2 ) -1 , and that obtained by pumping with a linearly polarized beam is -7.25(45) Hz (mW mm -2 ) -1 . These results agree closely with theoretical calculations. The pressure shift is -588(387) Hz mPa -1 . This work shows how to evaluate two-photon transitions with a Voigt profile, and then helps us to understand two-photon transitions with different polarization states, and improve the signal quality obtained when they are used as frequency markers.

  4. An innovation wall model based on interlayer ventilation

    International Nuclear Information System (INIS)

    Feng Jinmei; Lian Zhiwei; Hou Zhijian

    2008-01-01

    The thermal characteristics of the external wall are important to the energy consumption of the air conditioning system. Great attention should also be paid to the energy loss of the air exhaust. An innovation wall model based on interlayer ventilation is presented in this paper. The interlayer ventilation wall combines the wall and air exhaust of heating, ventilating and air conditioning (HVAC). The results of the experiment show that the energy loss of the exhaust air can be fully recovered by the interlayer ventilation wall. The cooling load can be reduced greatly because the temperature difference between the internal surface of the interlayer ventilation wall and the indoor air is very small. Clearly, the small temperature difference can enhance thermal comfort. In order to popularize the interlayer ventilation wall, technical and economical analysis is presented in this paper. Based on the buildings in the Shanghai area and a standard air conditioning system, a 4 years payback period for interlayer ventilation wall implementation was found according to the analysis

  5. Porosity model for simultaneous radionuclide transfer in compact clay

    International Nuclear Information System (INIS)

    Grambow, B.; Ribet, S.; Landesman, C.; Altman, S.

    2010-01-01

    Document available in extended abstract form only. Both, a mono and a dual porosity model have been developed to describe diffusion in bentonite as function of compaction, which give similar results for the diffusion coefficients. There are little advantages but more computation time for the dual porosity model compared to the mono-porosity model. A significant change in paradigm has been proposed to describe diffusion accessible porosity in bentonite: Only a single micro-porosity value is considered for anions, cations and neutral species. Hydration water in the interlayers is considered as part of the solid phase and is not considered as a constitutive part of overall porosity. Since hydration water takes part of the solid phase, it is now possible to explicitly account for retention of HTO by formulating exchange between HTO and water in the interlayers. In the adaptation of the model to experimental data, a single fit constant, the geometric factor G = 7 was used, common to all ions and neutral species and for densities between 0.2 and 1.8 kg.dm -3 . The only input parameters to describe the effect of dry density on diffusion coefficients are the micro porosity (total porosity minus interlayer porosity) and the hydration numbers of exchanging cations in the interlayers, both of which can be measured by independent means (DRX, water sorption isotherms). The modelling of simultaneous mass transfer of HTO, Cs, Br and Ni has been undertaken. From the results apparent diffusion coefficients were obtained. Effective diffusion coefficients can of course only be compared to literature data if the the same porosity hypothesis is used for Da-De conversion as used in literature (total porosity for anions and HTO, micro-porosity for anions). Then, the calculated apparent diffusion coefficients for HTO match closely the measured values in the mentioned density range. Considering large experimental data uncertainty the agreement between anion diffusion data and calculations

  6. Chemical processes causing cementation in heat-affected smectite - the Kinnekulle bentonite

    Energy Technology Data Exchange (ETDEWEB)

    Pusch, R. [Geodevelopment AB, Lund (Sweden); Takase, Hiroyasu; Benbow, S. [Quantisci Ltd., Oxfordshire (United Kingdom)

    1998-12-01

    Numerical calculation of silica migration and precipitation that can cause cementation of smectite buffer clay has been made using the Grindrod/Takase chemical model. It is used here to investigate whether the silicification of the bentonite and surrounding sediments at Kinnekulle, southwestern Sweden, can be explained by the heat pulse caused by the diabase intrusion that took place in Permian time. Compilation of data concerning silica cementation and associated microstructural and rheological changes showed that significant silica precipitation should have occurred in the Kinnekulle case and this is also documented. Thus, precipitation of quartz has taken place to an extent that can be explained by the chemical model, which also showed conversion of smectite to illite by neoformation of the latter mineral but only for the 3000 years long heating period. Introduction of a criterion for non-reversible illitization is hence a necessary improvement of the model for explaining the actual presence of neoformed illite, which may in fact be wholly or partly responsible for the cementation. (The report is made up of two articles: `Cementation processes in smectite clay associated with conversion of smectite to illite as exemplified by the Kinnekulle bentonites` and `Nonisothermal modelling of geochemical evolution in the Kinnekulle bentonite layer. Mathematical modelling and simulation`) 33 refs, 40 figs.

  7. Chemical processes causing cementation in heat-affected smectite - the Kinnekulle bentonite

    International Nuclear Information System (INIS)

    Pusch, R.; Takase, Hiroyasu; Benbow, S.

    1998-12-01

    Numerical calculation of silica migration and precipitation that can cause cementation of smectite buffer clay has been made using the Grindrod/Takase chemical model. It is used here to investigate whether the silicification of the bentonite and surrounding sediments at Kinnekulle, southwestern Sweden, can be explained by the heat pulse caused by the diabase intrusion that took place in Permian time. Compilation of data concerning silica cementation and associated microstructural and rheological changes showed that significant silica precipitation should have occurred in the Kinnekulle case and this is also documented. Thus, precipitation of quartz has taken place to an extent that can be explained by the chemical model, which also showed conversion of smectite to illite by neoformation of the latter mineral but only for the 3000 years long heating period. Introduction of a criterion for non-reversible illitization is hence a necessary improvement of the model for explaining the actual presence of neoformed illite, which may in fact be wholly or partly responsible for the cementation. (The report is made up of two articles: 'Cementation processes in smectite clay associated with conversion of smectite to illite as exemplified by the Kinnekulle bentonites' and 'Nonisothermal modelling of geochemical evolution in the Kinnekulle bentonite layer. Mathematical modelling and simulation')

  8. Effect of crystallochemistry of starting materials on the rate of smectite to illite reaction

    International Nuclear Information System (INIS)

    Sato, Tsutomu; Isobe, Hiroshi; Ohnuki, Toshihiko; Murakami, Takashi

    1995-01-01

    A series of hydrothermal experiments was performed to determine the effect of layer charge of starting materials on the smectite to illite reaction rate that might be applied to nuclear-waste repository design. The experiments were conducted on K-saturated fractions of Wyoming smectite (SWy-1) and Tsukinuno smectite (SKu-F) in a closed system at temperatures of 95, 150, 200, 250, 300 C for run durations of up to 477 days with a 1:20 mass ratio of solid to deionized water. The mean layer charge and tetrahedral charge of SKu-F are larger than those of SWy-1. The proportion of smectite layers in illite/smectite interstratified minerals rapidly decreases, and then slowly decreases with increase in reaction time; a plot of ln (100/% smectite) vs. time produces two distinct straight lines in all experiments. These lines are suggestive of two first-order kinetic processes with different rates for this reaction; the first process has a greater rate than the second one. An Arrhenius plot of the reaction rates for each process produces a folding and straight lines for the first and second processes, respectively, suggesting that there are at least two parallel processes in the first process, and a dominant process is different between high- and low-temperature reactions. The activation energies of the first and second processes determined from the plots are the same for the two starting materials, meaning that the reaction mechanisms for the two starting materials are the same. However, the rate of the first process is different between the two starting materials, although that of the second process is similar. The difference in the rate of the first process results possibly from the difference in the amount of layer charge between the two starting smectites

  9. Influence of layer charge and charge distribution of smectites on the flow behaviour and swelling of bentonites

    Science.gov (United States)

    Christidis, G.E.; Blum, A.E.; Eberl, D.D.

    2006-01-01

    The influence of layer charge and charge distribution of dioctahedral smectites on the rheological and swelling properties of bentonites is examined. Layer charge and charge distribution were determined by XRD using the LayerCharge program [Christidis, G.E., Eberl, D.D., 2003. Determination of layer charge characteristics of smectites. Clays Clay Miner. 51, 644-655.]. The rheological properties were determined, after sodium exchange using the optimum amount of Na2CO3, from free swelling tests. Rheological properties were determined using 6.42% suspensions according to industrial practice. In smectites with layer charges of - 0.425 to - 0.470 per half formula unit (phfu), layer charge is inversely correlated with free swelling, viscosity, gel strength, yield strength and thixotropic behaviour. In these smectites, the rheological properties are directly associated with the proportion of low charge layers. By contrast, in low charge and high charge smectites there is no systematic relation between layer charge or the proportion of low charge layers and rheological properties. However, low charge smectites yield more viscous suspensions and swell more than high charge smectites. The rheological properties of bentonites also are affected by the proportion of tetrahedral charge (i.e. beidellitic charge), by the existence of fine-grained minerals having clay size, such as opal-CT and to a lesser degree by the ionic strength and the pH of the suspension. A new method for classification of smectites according to the layer charge based on the XRD characteristics of smecites is proposed, that also is consistent with variations in rheological properties. In this classification scheme the term smectites with intermediate layer charge is proposed. ?? 2006 Elsevier B.V. All rights reserved.

  10. Thermodynamic understanding on swelling pressure of bentonite buffer

    International Nuclear Information System (INIS)

    Sato, Haruo

    2007-01-01

    Smectite (montmorillonite) is a major clay mineral constituent of the bentonite buffer and backfilling materials to be used for the geological disposal of high-level radioactive waste. Swelling pressure of the bentonite buffer occurring in the permeation process of moisture was estimated based on thermodynamic theory and the thermodynamic data of interlayer water in smectite in this study. The relative partial molar Gibbs free energies (ΔG H2O ) of water on the smectite surface were measured as a function of water content (0-83%) in a dry density range of 0.6-0.9 Mg/m 3 . Purified Na-smectite of which interlayer cations were exchanged with Na + ions and soluble salts were completely removed, was used in this study. Obtained ΔG H2O decreased with an increase of water content in the range of water content lower than about 40%, and similar trends were obtained to data of Kunipia-F bentonite (Na-bentonite) of which smectite content was approximately 100 wt.%. From the specific surface area of smectite (ca. 800 m 2 /g) and the correlation between ΔG H2O and water content, water affected from the surface of smectite was estimated to be up to approximately 2 water layers. Swelling pressure versus smectite partial density (montmorillonite partial density) was estimated based on ΔG H2O from the chemical potential balance of water in equilibrium between the free water and moisturized smectite, and compared to data measured for various kinds of bentonites of which smectite contents were respectively different. The estimated swelling pressures were in good agreement with the measured data. (author)

  11. Composite interlayer for diffusion bonding

    International Nuclear Information System (INIS)

    1976-01-01

    A ductile interlayer is described, which is useful for transient liquid phase diffusion bonding of metallic articles; the interlayer consisting of a melting point depressant and a plurality of ductile lamellae which are free from carbides, aluminides and borides. The composition and fabrication of the lamellae, and the process for bonding the metallic articles, depend on the composition of the metals to be bonded, and are exemplified in the specification. (U.K.)

  12. Analysis of the improvement of selenite retention in smectite by adding alumina nanoparticles.

    Science.gov (United States)

    Mayordomo, Natalia; Alonso, Ursula; Missana, Tiziana

    2016-12-01

    Smectite clay is used as barrier for hazardous waste retention and confinement. It is a powerful material to retain cations, but less effective for retaining anionic species like selenite. This study shows that the addition of a small percentage of γ-Al 2 O 3 nanoparticles to smectite significantly improves selenite sorption. γ-Al 2 O 3 nanoparticles provide high surface area and positively charged surface sites within a wide range of pH, since their point of zero charge is at pH8-9. An addition of 20wt% of γ-Al 2 O 3 to smectite is sufficient to approach the sorption capacity of pure alumina. To analyze the sorption behavior of the smectite/oxide mixtures, a nonelectrostatic surface complexation model was considered, accounting for the surface complexation of HSeO 3 - and SeO 3 2- , the anion competition, and the formation of surface ternary complexes with major cations present in the solution. Selenite sorption in mixtures was satisfactorily described with the surface parameters and complexation constants defined for the pure systems, accounting only for the mixture weight fractions. Sorption in mixtures was additive despite the particle heteroaggregation observed in previous stability studies carried out on smectite/γ-Al 2 O 3 mixtures. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Prophylaxis of irradiation-induced Diarrhea with smectite. Results of a placebo-controlled investigation

    International Nuclear Information System (INIS)

    Hombrink, J.; Froehlich, D.; Glatzel, M.; Krauss, A.; Thiel, H.J.; Meier, J.; Hamann, D.; Muecke, R.; Glaser, F.H.; Koest, S.

    2000-01-01

    Between April 1994 and May 1995, a total of 176 patients obtaining radiotherapy of the pelvis or the abdomen were evaluated in a double-blind, randomized placebo-controlled investigation regarding the prophylactic effect of smectite (=Colina trademark ) against radiotherapy-induced diarrhea. During the whole period of radiotherapy 85 patients obtained 2x6 g smectite daily and 91 patients received 2x6 g placebo. The primary end point of the analysis was the time to the first appearance of diarrhea (≥3 pappy stools). Results: All 176 patients were evaluated according to an intent-to-treat analysis. There was no significant difference between the prophylactic effects of smectite and placebo. For an explorative post-hoc analysis the total study group was split up into 2 subgroups, one with an irradiated small bowel volume ≤837.5 ml, the other with a small bowel volume >837.5 ml (median); the analysis indicated that the first subgroup showed a benefit for the smectite-treated patients in contrast to the placebo treatment (32 vs. 18 calendar days to the first appearance of diarrhea). This benefit was statistically not significant. Conclusion: Prophylactic application of smectite during irradiation of the pelvis and the abdomen can delay the development of radiotherapy-induced diarrhea, a statistical significance could not be verified neither in the total study group nor in the post-hoc subgroup analysis. (orig.) [de

  14. Sorption of uranium and cesium by Hanford basalts and associated secondary smectite

    International Nuclear Information System (INIS)

    Ames, L.L.; McGarrah, J.E.; Walker, B.A.; Salter, P.F.

    1982-01-01

    Three characterized basalts and an associated secondary smectite were used in comparative uranium and cesium sorption studies. Experiments utilizing two synthetic characteristic basalt groundwaters at 23 and 60 0 C allowed comparison of increased temperature and carbonate concentration effects on Cs and U sorption. The sorption data were fitted to the Dubinin-Radushkevich (D-R) isotherm, and loading maxima and energetics derived. An increase in temperature caused a decrease in Cs sorption maxima on all solids from all groundwaters studied and an increase in U sorption maxima, especially from the higher-carbonate-content groundwater. Sorption energies were characteristic of ion exchange for both Cs and U sorption processes. Basalt U sorption maxima were relatively insignificant, but smectite U sorption maxima surpassed Cs sorption maxima in both groundwaters at 60 0 C. The uranyl carbonate complexes thus may be relatively temperature-sensitive. Upon removal of excess Fe-oxides from the secondary smectite, U sorption decreased and the D-R isotherm reverted to a normal Freundlich sorption isotherm. Removal of excess Fe-oxides from the basalts and secondary smectite would probably result in Freundlich sorption isotherms for both Cs and U. (Auth.)

  15. Chemical stability and physical properties of Caesium uranates

    International Nuclear Information System (INIS)

    Berton, J.P.; Baron, D.; Coquerelle, M.

    1998-01-01

    Caesium is one of the most abundant fission products in PWR nuclear fuel or in fast reactor fuel as well. A work program has been started at the TUI Karlsruhe, in collaboration with EDF Etudes et Recherches, to determine the thermal stability and conductivity, the mechanical properties and the thermal expansion coefficient of Cs 2 UO 4 . The Caesium mono-uranate was obtained by a chemical reaction between Cs 2 O 3 and U 3 O 8 powders mixed together, pressed and heated at 670 deg. C for 24 hours. The compound was found stable up to 830 deg. C. Mechanical compressive hardening tests allowed to evaluate the elastic modulus versus temperature in the range 200 to 800 deg. C. Furthermore the viscous behaviour of the compound above 400 deg. C was confirmed. The thermal expansion coefficient of Cs 2 UO 4 was found somewhat 40% higher than the thermal expansion coefficient of UO 2 . The thermal conductivity is about 1.5 to 1.8 W/m/K for temperatures ranging from 100 to 700 deg. C, a value very similar to the UO 2 fuel thermal conductivity at high burnup in the same temperature range. (author)

  16. An i.r. investigation on some calcium aluminate hydrates, Ca2Al(OH)6+X-.yH2O (= 3CaO.Al2O3.CaX2.nH2O, X- = univalent anion)

    NARCIS (Netherlands)

    Houtepen, C.J.M.; Stein, H.N.

    1976-01-01

    The i.r. spectra of some hydrated and dehydrated calcium aluminate hydrates of the type Ca2Al(OH)6+X-·yH2O with X- = Cl-, Br-, J-, ClO3-, NO3-, ClO4- (y = 2) and X- = BrO3-, JO3- (2 interlayer water with the anions

  17. Nano-engineered composites: interlayer carbon nanotubes effect

    Energy Technology Data Exchange (ETDEWEB)

    Carley, Glaucio, E-mail: carleyone@hotmail.com [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil); Geraldo, Viviany; Oliveira, Sergio de [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisica; Avila, Antonio Ferreira [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisica

    2013-11-01

    The concept of carbon nanotube interlayer was successfully introduced to carbon fiber/epoxy composites. This new hybrid laminated composites was characterized by Raman spectroscopy, X-ray diffraction, scanning electron microscopy and tensile tests. An increase on peak stress close to 85% was witnessed when CNTs interlayer with 206.30 mg was placed to carbon fiber/epoxy laminates. The failure mechanisms are associated to CNTs distribution between and around carbon fibers. These CNTs are also responsible for crack bridging formation and the increase on peak stress. Initial stiffness is strongly affected by the CNT interlayer, however, changes on stiffness is associated to changes on nano/micro-structure due to damage. Three different behaviors can be described, i.e. for interlayers with Almost-Equal-To 60 mg of CNT the failure mode is based on cracks between and around carbon fibers, while for interlayers with CNT contents between 136 mg and 185 mg cracks were spotted on fibers and inside the CNT/matrix mix. Finally, the third failure mechanism is based on carbon fiber breakage, as a strong interface between CNT/matrix mix and carbon fibers is observed. (author)

  18. Nano-engineered composites: interlayer carbon nanotubes effect

    International Nuclear Information System (INIS)

    Carley, Glaucio; Geraldo, Viviany; Oliveira, Sergio de; Avila, Antonio Ferreira

    2013-01-01

    The concept of carbon nanotube interlayer was successfully introduced to carbon fiber/epoxy composites. This new hybrid laminated composites was characterized by Raman spectroscopy, X-ray diffraction, scanning electron microscopy and tensile tests. An increase on peak stress close to 85% was witnessed when CNTs interlayer with 206.30 mg was placed to carbon fiber/epoxy laminates. The failure mechanisms are associated to CNTs distribution between and around carbon fibers. These CNTs are also responsible for crack bridging formation and the increase on peak stress. Initial stiffness is strongly affected by the CNT interlayer, however, changes on stiffness is associated to changes on nano/micro-structure due to damage. Three different behaviors can be described, i.e. for interlayers with ≈ 60 mg of CNT the failure mode is based on cracks between and around carbon fibers, while for interlayers with CNT contents between 136 mg and 185 mg cracks were spotted on fibers and inside the CNT/matrix mix. Finally, the third failure mechanism is based on carbon fiber breakage, as a strong interface between CNT/matrix mix and carbon fibers is observed. (author)

  19. Composition, oxygen isotope geochemistry, and origin of smectite in the metalliferous sediments of the Bauer Deep, southeast Pacific

    Energy Technology Data Exchange (ETDEWEB)

    Cole, T G [Imperial Coll. of Science and Technology, London (UK). Geology Dept.

    1985-01-01

    The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite. Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite. Infra-red and Mossbauer spectroscopy, and wet chemical analysis (LiBO/sub 2/ fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3 deg C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth. Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed. Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO/sub 3/ accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions.)

  20. Composition, oxygen isotope geochemistry, and origin of smectite in the metalliferous sediments of the Bauer Deep, southeast Pacific

    International Nuclear Information System (INIS)

    Cole, T.G.

    1985-01-01

    The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite. Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite. Infra-red and Mossbauer spectroscopy, and wet chemical analysis (LiBO 2 fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3 deg C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth. Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed. Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO 3 accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions.) (author)

  1. Smectite clay--inorganic nanoparticle mixed suspensions: phase behaviour and rheology.

    Science.gov (United States)

    Bailey, Louise; Lekkerkerker, Henk N W; Maitland, Geoffrey C

    2015-01-14

    Smectite clay minerals and their suspensions have long been of both great scientific and applications interest and continue to display a remarkable range of new and interesting behaviour. Recently there has been an increasing interest in the properties of mixed suspensions of such clays with nanoparticles of different size, shape and charge. This review aims to summarize the current status of research in this area focusing on phase behaviour and rheological properties. We will emphasize the rich range of data that has emerged for these systems and the challenges they present for future investigations. The review starts with a brief overview of the behaviour and current understanding of pure smectite clays and their suspensions. We then cover the work on smectite clay-inorganic nanoparticle mixed suspensions according to the shape and charge of the nanoparticles - spheres, rods and plates either positively or negatively charged. We conclude with a summary of the overarching trends that emerge from these studies and indicate where gaps in our understanding need further research for better understanding the underlying chemistry and physics.

  2. Monitoring of caesium-137 in food plants and muscle from moose, red deer and wild reindeer in 2010

    International Nuclear Information System (INIS)

    Veiberg, Vebjoern; Gaare, Eldar; Stokke, Sigbjoern; Solberg, Erling J.; Skuterud, Lavrans

    2011-01-01

    The monitoring of Cs-137 fall-out from the Chernobyl accident in 1986, started the same year. Several plants and wild reindeer in natural ecosystems in Nord-Rondane have been followed annually ever since. Four more wild reindeer ranges were included in 2001: Setesdal-Ryfylkeheiene, Hardangervidda, Nord-Ottadalen, Snoehetta and Nord-Rondane. From 2007 Forollhogna was also included. On fixed plots in Nord-Rondane and Snoehetta some of the reindeer forage plants, including both higher plants and fruticose lichens, have been sampled and analyzed annually since 1986. This was also done in 2010. In addition plants and lichens were sampled at five locations along an altitudinal gradient at Soendre Knutshoe, and at 7-8 locations along an east-west gradient from Kollaflata to Skarhoe in the Jora valley continuing along the Aursjoe to Torbudalen. All these locations were sampled annually between 1987-1990, but they have not been sampled since. In 2010 samples from red deer and moose was also collected from eight different regions located within the following counties: Oppland, Telemark, Vest-Agder, Rogaland, Sogn and Fjordane, Nord-Troendelag, Nordland and Troms. Red deer were sampled in four regions and moose in six. Both species were sampled in Oppland. In 2010 76, 49 and 61 samples were collected from wild reindeer, red deer and moose respectively. All measures of caesium levels were performed on dried samples. For the 596 samples of plants and lichen the results refer to caesium-levels in dried samples. For the meat samples, results refer to caesium-137 levels in raw meat. Due to large variation in measured levels of caesium within species and sampling area, we give median values instead of mean values.The highest caesium levels in wild reindeer were found in Snoehetta (1010 Bq/kg) and Nord-Rondane (2686 Bq/kg). The levels found in the other areas were considerably lower. The highest caesium levels in both red deer (Sel, 677 Bq/kg) and moose (Vaaga, 365 Bq/kg) were found

  3. XRD measurement of mean thickness, thickness distribution and strain for illite and illite-smectite crystallites by the Bertaut-Warren-Averbach technique

    Science.gov (United States)

    Drits, Victor A.; Eberl, Dennis D.; Środoń, Jan

    1998-01-01

    A modified version of the Bertaut-Warren-Averbach (BWA) technique (Bertaut 1949, 1950; Warren and Averbach 1950) has been developed to measure coherent scattering domain (CSD) sizes and strains in minerals by analysis of X-ray diffraction (XRD) data. This method is used to measure CSD thickness distributions for calculated and experimental XRD patterns of illites and illite-smectites (I-S). The method almost exactly recovers CSD thickness distributions for calculated illite XRD patterns. Natural I-S samples contain swelling layers that lead to nonperiodic structures in the c* direction and to XRD peaks that are broadened and made asymmetric by mixed layering. Therefore, these peaks cannot be analyzed by the BWA method. These difficulties are overcome by K-saturation and heating prior to X-ray analysis in order to form 10-Å periodic structures. BWA analysis yields the thickness distribution of mixed-layer crystals (coherently diffracting stacks of fundamental illite particles). For most I-S samples, CSD thickness distributions can be approximated by lognormal functions. Mixed-layer crystal mean thickness and expandability then can be used to calculate fundamental illite particle mean thickness. Analyses of the dehydrated, K-saturated samples indicate that basal XRD reflections are broadened by symmetrical strain that may be related to local variations in smectite interlayers caused by dehydration, and that the standard deviation of the strain increases regularly with expandability. The 001 and 002 reflections are affected only slightly by this strain and therefore are suited for CSD thickness analysis. Mean mixed-layer crystal thicknesses for dehydrated I-S measured by the BWA method are very close to those measured by an integral peak width method.

  4. Escherichia coli challenge and one type of smectite alter intestinal barrier of pigs.

    Science.gov (United States)

    Almeida, Juliana Abranches Soares; Liu, Yanhong; Song, Minho; Lee, Jeong Jae; Gaskins, H Rex; Maddox, Carol Wolfgang; Osuna, Orlando; Pettigrew, James Eugene

    2013-12-20

    An experiment was conducted to determine how an E. coli challenge and dietary clays affect the intestinal barrier of pigs. Two groups of 32 pigs (initial BW: 6.9 ± 1.0 kg) were distributed in a 2 × 4 factorial arrangement of a randomized complete block design (2 challenge treatments: sham or E. coli, and 4 dietary treatments: control, 0.3% smectite A, 0.3% smectite B and 0.3% zeolite), with 8 replicates total. Diarrhea score, growth performance, goblet cell size and number, bacterial translocation from intestinal lumen to lymph nodes, intestinal morphology, and relative amounts of sulfo and sialo mucins were measured. The E. coli challenge reduced performance, increased goblet cell size and number in the ileum, increased bacterial translocation from the intestinal lumen to the lymph nodes, and increased ileal crypt depth. One of the clays (smectite A) tended to increase goblet cell size in ileum, which may indicate enhanced protection. In conclusion, E. coli infection degrades intestinal barrier integrity but smectite A may enhance it.

  5. Determination of caesium in river and sea waters by electrothermal atomic-absorption spectrometry. Interference of cobalt and iron

    International Nuclear Information System (INIS)

    Frigieri, P.; Trucco, R.; Ciaccolini, I.; Pampurini, G.

    1980-01-01

    For the enrichment or the simple recovery of caesium from river and sea waters, selective inorganic exchangers were considered. Ammonium hexacyanocobalt ferrate (NCFC) was chosen because it can be used in strongly acidic solutions (with the exception of concentrated sulphuric acid). Caesium is fully retained by the NCFC chromatographic column and can then be recovered by dissolution in hot sulphuric acid. The solution is then diluted and analysed, either directly or following caesium separation, by atomic-absorption spectrometry. To check the reliability of the analytical procedure, a series of experiments were carried out in which the possible interfering species were added to the aqueous caesium solution prior to analysis. The well known ionic interference in flame atomisation processes caused by magnesium, calcium, strontium and metals was investigated by electrothermal atomisation measurements. The experimental data showed that this effect does not occur even when these elements are present in concentrations of the order of thousands of parts per million. However, strong interferences from iron and cobalt were observed. (author)

  6. Complexation of carboxylate on smectite surfaces.

    Science.gov (United States)

    Liu, Xiandong; Lu, Xiancai; Zhang, Yingchun; Zhang, Chi; Wang, Rucheng

    2017-07-19

    We report a first principles molecular dynamics (FPMD) study of carboxylate complexation on clay surfaces. By taking acetate as a model carboxylate, we investigate its inner-sphere complexes adsorbed on clay edges (including (010) and (110) surfaces) and in interlayer space. Simulations show that acetate forms stable monodentate complexes on edge surfaces and a bidentate complex with Ca 2+ in the interlayer region. The free energy calculations indicate that the complexation on edge surfaces is slightly more stable than in interlayer space. By integrating pK a s and desorption free energies of Al coordinated water calculated previously (X. Liu, X. Lu, E. J. Meijer, R. Wang and H. Zhou, Geochim. Cosmochim. Acta, 2012, 81, 56-68; X. Liu, J. Cheng, M. Sprik, X. Lu and R. Wang, Geochim. Cosmochim. Acta, 2014, 140, 410-417), the pH dependence of acetate complexation has been revealed. It shows that acetate forms inner-sphere complexes on (110) in a very limited mildly acidic pH range while it can complex on (010) in the whole common pH range. The results presented in this study form a physical basis for understanding the geochemical processes involving clay-organics interactions.

  7. Evolution of models for conversion of smectite to non-expandable minerals

    International Nuclear Information System (INIS)

    Pusch, R.

    1993-12-01

    Hydrothermal alteration of smectite has long been regarded as conversion to illite and chlorite as concluded from investigations of Gulf sediments. As manifested by statements given earlier at various international scientific meetings and in the literature, smectite-to-illite conversion (S→I) has been assumed to be a solid-state reaction with layer-by-layer alteration via mixed layer I/S to illite. In the last 10 years this opinion has successively changed and in recent years the concept of dissolution of smectite and accessory minerals and precipitation of illite and possibly I/S has been favored by many investigators. The present report reports laboratory and field investigations on bentonite and also calculations based on geochemical codes, which all support the dissolution/precipitation process. Applying Pytte's model for calculating the rate of conversion to illite, one finds good agreement with a number of experiments and field data, and this model is therefore recommended for practical use

  8. Lactobacillus GG (LGG) and smectite versus LGG alone for acute gastroenteritis: a double-blind, randomized controlled trial.

    Science.gov (United States)

    Pieścik-Lech, Małgorzata; Urbańska, Magdalena; Szajewska, Hania

    2013-02-01

    Diarrhea treatment with either Lactobacillus GG (LGG) or smectite as an adjuvant to standard rehydration therapy has proven efficacy. In countries where both LGG and smectite are available, concomitant use is frequently practiced. We investigated whether LGG plus smectite is superior to LGG alone in the management of children with acute gastroenteritis (AGE). A double-blind, placebo-controlled, randomized trial was performed. Children aged 4 to 60 months with AGE received LGG 6 × 10(9) colony forming units/day plus randomly either smectite (3 g) or placebo as an adjuvant to the standard rehydration therapy. Of the 88 children randomized, 81 (92 %) were available for intention-to-treat analysis. The duration of diarrhea in the LGG/smectite group (n = 44) compared with the LGG/placebo group (n = 37) was similar (P = 0.43). There were no significant differences between the study groups for the secondary outcomes, with three exceptions. On day 4, in the LGG/placebo group compared to the LGG/smectite group, there was significantly reduced stool frequency (P = 0.03). While there was a significant (P = 0.05) difference in stool consistency on the Bristol Stool Form Scale on day 4, it was not of clinical relevance. Finally, in the LGG/smectite group compared to the LGG/placebo group, there was a significantly shorter duration of intravenous therapy after randomization (P = 0.02). No adverse events were observed in the study groups. LGG plus smectite and LGG alone are equally effective for treating young children with AGE. Combined use of the two interventions is not justified.

  9. Instrumental characterization of the smectite clay–gentamicin hybrids

    Indian Academy of Sciences (India)

    use of conventional drugs may lead to fluctuations whereby drug concentrations in ... ence of smectite, as well as determination of the capacity of gentamicin to fill ... the pharmaceutical and cosmetic industries manufactured by. R.T. Vanderbilt ...

  10. Smectite flocculation structure modified by Al13 macro-molecules--as revealed by the transmission X-ray microscopy (TXM).

    Science.gov (United States)

    Zbik, Marek S; Martens, Wayde N; Frost, Ray L; Song, Yen-Fang; Chen, Yi-Ming; Chen, Jian-Hua

    2010-05-01

    The aggregate structure which occurs in aqueous smectitic suspensions is responsible for poor water clarification, difficulties in sludge dewatering and the unusual rheological behaviour of smectite rich soils. These macroscopic properties are dictated by the 3D structural arrangement of smectite finest fraction within flocculated aggregates. Here, we report results from a relatively new technique, transmission X-ray microscopy (TXM), which makes it possible to investigate the internal structure and 3D tomographic reconstruction of the smectite clay aggregates modified by Al(13) Keggin macro-molecule [Al(13)(O)(4)(OH)(24)(H(2)O)(12)](7+). Three different treatment methods were shown resulted in three different micro-structural environments of the resulting flocculation. In case of smectite sample prepared in Methods 1 and 3 particles fall into the primary minimum where Van der Waals forces act between FF oriented smectite flakes and aggregates become approach irreversible flocculation. In case of sample prepared using Method 2, particles contacting by edges (EE) and edge to face (EF) orientation fell into secondary minimum and weak flocculation resulted in severe gelation and formation of the micelle-like texture in fringe superstructure, which was first time observed in smectite based gel. Copyright 2010 Elsevier Inc. All rights reserved.

  11. Role of interlayer coupling in ultra thin MoS2

    KAUST Repository

    Cheng, Yingchun; Zhu, Zhiyong; Schwingenschlö gl, Udo

    2012-01-01

    The effects of interlayer coupling on the vibrational and electronic properties of ultra thin MoS 2 were studied by ab initio calculations. For smaller slab thickness, the interlayer distance is significantly elongated because of reduced interlayer

  12. Formation of Fe- and Mg-Rich Smectite under Hyperalkaline Conditions at Narra in Palawan, the Philippines

    OpenAIRE

    Shimbashi, Misato; Sato, Tsutomu; Yamakawa, Minoru; Fujii, Naoki; Otake, Tsubasa

    2018-01-01

    The formation of Fe- and Mg-rich smectite and zeolite under alkaline conditions, as secondary minerals after the alkaline alteration of bentonite in repositories for radioactive waste, is of major concern. It is crucial for safety assessments to know whether smectite is formed as a secondary mineral after the alkaline alteration of bentonite. In the present paper, Fe- and Mg-rich smectite, which interacted with the hyperalkaline groundwater at Narra in Palawan, Philippines, was used. Mineralo...

  13. Role of interlayer coupling in ultra thin MoS2

    KAUST Repository

    Cheng, Yingchun

    2012-01-01

    The effects of interlayer coupling on the vibrational and electronic properties of ultra thin MoS 2 were studied by ab initio calculations. For smaller slab thickness, the interlayer distance is significantly elongated because of reduced interlayer coupling. This explains the anomalous thickness dependence of the lattice vibrations observed by Lee et al. (ACS Nano, 2010, 4, 2695). The absence of interlayer coupling in mono-layer MoS 2 induces a transition from direct to indirect band gap behaviour. Our results demonstrate a strong interplay between the intralayer chemical bonding and the interlayer van-der-Waals interaction. This journal is © 2012 The Royal Society of Chemistry.

  14. Retention of alkali ions by hydrated low-pH cements: Mechanism and Na+/K+ selectivity

    International Nuclear Information System (INIS)

    Bach, T.T.H.; Chabas, E.; Pochard, I.; Cau Dit Coumes, C.; Haas, J.; Frizon, F.; Nonat, A.

    2013-01-01

    Low-pH cements, also referred to as low-alkalinity cements, can be designed by replacing significant amounts of Portland cement by pozzolanic materials. Their pore solution is characterized by a pH near 11, and an alkali concentration much lower than that of Portland cement. This work investigates the retention of sodium and potassium by a hydrated low-pH cement comprising 60% Portland cement and 40% silica fume. It is shown that sorption of potassium is higher than that of sodium and mainly results from counterion charge balancing of the C-S-H negative surface charge. To explain the greater retention of potassium compared to sodium, it is postulated that potassium, unlike sodium, may enter the interlayer of C-S-H to compensate the negative charges in the interlayer, in addition to the external surfaces. This assumption is supported by structural characterization of C-S-H using X-ray diffraction

  15. The accumulation of radioactive caesium from water by the brown trout (Salmo trutta) and its comparison with plaice and rays

    International Nuclear Information System (INIS)

    Hewett, C.J.; Jefferies, D.F.

    1976-01-01

    The patterns of accumulation of caesium-137 from water by the tissues and organs of the freshwater teleost, the brown trout (Salmo trutta) are described. Estimates of the biological half-times and steady-state concentrations are derived, using a simple exponential equation. In all tissues and organs examined, other than muscle, the rate processes of the trout fall between those of the plaice and the ray. It is concluded that most of the caesium accumulated by the brown trout from water enters other than by the gut, probably through the gills, but as with plaice and ray, the main source of the caesium, possibly 90%, must come from the food. Despite differences in the levels of accumulation, the ratios of the tissue to blood steady state concentrations were very similar in all three species. The steady state caesium concentration of the blood appeared to be directly related to the red blood cell count of the fish. (author)

  16. Electron paramagnetic resonance studies on silver atoms and clusters in regularly interstratified clay minerals

    International Nuclear Information System (INIS)

    Yamada, H.; Tamura, K.; Shimomura, S.; Sadlo, J.; Turek, J.; Michalik, J.

    2004-01-01

    The formation and stabilization of reduced silver species in the regularly interstratified clay minerals, trioctahedral smectite/chlorite (tri-Sm/Ch) and dioctahedral smectite/mica (di-Sm/M), have been studied by electron paramagnetic resonance (EPR) spectroscopy. Both minerals loaded with Ag + cations after degassing and dehydration were γ-irradiated at 77 K and monitored by EPR as the temperature increased. Some samples were exposed to water or methanol vapor after dehydration. In both hydrated and dehydrated samples only the doublets to Ag 0 atoms were observed with no evidence of the formation of Ag clusters. However, the EPR parameter of silver atoms in both matrices are different. In tri-Sm/Ch the narrow anisotropic EPR lines overlap with the broader isotropic lines, whereas in di-Sm/M only broad lines are recorded. The hyperfine splitting - A iso (Ag 0 ) is larger in tri-Sm/Ch than in di-Sm/M. Also the stability of Ag 0 in both clay minerals is distinctly different. Ag 0 doublet in di-Sm/M disappears completely above 230 K, Whereas in tri-Sm/Ch it is still recorded at 310 K. It is proposed, basing on the EPR results that Ag 0 atoms appear at different sites in both matrices: - in tri-Sm/Ch in the middle of smectite interlayer and in hexagonal cavities in the silicate sheets of tetrahedron layer and in di-Sm.M in hexagonal cavities only. When samples had been exposed to methanol before irradiation, the silver clusters become stabilized in the interlayer sites. In tri-Sm/M matrix the silver dimer Ag 2 + formed by gamma-irradiation at 77 K is transformed to tetrameric cluster, Ag 4 + at 150 K. In di-Sm/M the radiation-induced silver agglomeration proceeds in a similar way, but with a slower rate and Ag tetramer is formed only above 190 K. In both clay minerals, Ag 4 + clusters decay above 250 K. (author)

  17. Inter-layer potential for hexagonal boron nitride

    Science.gov (United States)

    Leven, Itai; Azuri, Ido; Kronik, Leeor; Hod, Oded

    2014-03-01

    A new interlayer force-field for layered hexagonal boron nitride (h-BN) based structures is presented. The force-field contains three terms representing the interlayer attraction due to dispersive interactions, repulsion due to anisotropic overlaps of electron clouds, and monopolar electrostatic interactions. With appropriate parameterization, the potential is able to simultaneously capture well the binding and lateral sliding energies of planar h-BN based dimer systems as well as the interlayer telescoping and rotation of double walled boron-nitride nanotubes of different crystallographic orientations. The new potential thus allows for the accurate and efficient modeling and simulation of large-scale h-BN based layered structures.

  18. Inter-layer potential for hexagonal boron nitride

    Energy Technology Data Exchange (ETDEWEB)

    Leven, Itai; Hod, Oded, E-mail: odedhod@tau.ac.il [Department of Chemical Physics, School of Chemistry, The Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Tel-Aviv 69978 (Israel); Azuri, Ido; Kronik, Leeor [Department of Materials and Interfaces, Weizmann Institute of Science, Rehovoth 76100 (Israel)

    2014-03-14

    A new interlayer force-field for layered hexagonal boron nitride (h-BN) based structures is presented. The force-field contains three terms representing the interlayer attraction due to dispersive interactions, repulsion due to anisotropic overlaps of electron clouds, and monopolar electrostatic interactions. With appropriate parameterization, the potential is able to simultaneously capture well the binding and lateral sliding energies of planar h-BN based dimer systems as well as the interlayer telescoping and rotation of double walled boron-nitride nanotubes of different crystallographic orientations. The new potential thus allows for the accurate and efficient modeling and simulation of large-scale h-BN based layered structures.

  19. Inter-layer potential for hexagonal boron nitride

    International Nuclear Information System (INIS)

    Leven, Itai; Hod, Oded; Azuri, Ido; Kronik, Leeor

    2014-01-01

    A new interlayer force-field for layered hexagonal boron nitride (h-BN) based structures is presented. The force-field contains three terms representing the interlayer attraction due to dispersive interactions, repulsion due to anisotropic overlaps of electron clouds, and monopolar electrostatic interactions. With appropriate parameterization, the potential is able to simultaneously capture well the binding and lateral sliding energies of planar h-BN based dimer systems as well as the interlayer telescoping and rotation of double walled boron-nitride nanotubes of different crystallographic orientations. The new potential thus allows for the accurate and efficient modeling and simulation of large-scale h-BN based layered structures

  20. In situ immobilisation of toxic metals in soil using Maifan stone and illite/smectite clay.

    Science.gov (United States)

    Ou, Jieyong; Li, Hong; Yan, Zengguang; Zhou, Youya; Bai, Liping; Zhang, Chaoyan; Wang, Xuedong; Chen, Guikui

    2018-03-15

    Clay minerals have been proposed as amendments for remediating metal-contaminated soils owing to their abundant reserves, high performance, simplicity of use and low cost. Two novel clay minerals, Maifan stone and illite/smectite clay, were examined in the in situ immobilisation of soil metals. The application of 0.5% Maifan stone or illite/smectite clay to field soils significantly decreased the fractions of diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Ni, Cr, Zn, Cu and Pb. Furthermore, reductions of 35.4% and 7.0% in the DTPA-extractable fraction of Cd were obtained with the Maifan stone and illite/smectite clay treatments, respectively, which also significantly reduced the uptake of Cd, Ni, Cr, Zn, Cu and Pb in the edible parts of Brassica rapa subspecies pekinensis, Brassica campestris and Spinacia oleracea. Quantitatively, the Maifan stone treatment reduced the metal uptake in B. rapa ssp. Pekinensis, B. campestris and S. oleracea from 11.6% to 62.2%, 4.6% to 41.8% and 11.3% to 58.2%, respectively, whereas illite/smectite clay produced reductions of 8.5% to 62.8% and 4.2% to 37.6% in the metal uptake in B. rapa ssp. Pekinensis and B. campestris, respectively. Therefore, both Maifan stone and illite/smectite clay are promising amendments for contaminated soil remediation.

  1. Elements of reflection on pathologies possibly induced by caesium 137

    International Nuclear Information System (INIS)

    Nifenecker, Herve

    2006-01-01

    The author discusses the content of few known publications on the possible pathological effects of caesium 137: a Belarus study on the consequences of Chernobyl, results of few autopsies performed on babies and adults, a study performed on rats, and a study performed on a set of 94 children in a sanatorium

  2. Investigations on caesium 134 and 137 contamination of game hunted for food in Hessia

    International Nuclear Information System (INIS)

    Hadlock, R.M.; Harju, H.; Sattler, E.L.; Wagner, G.

    1990-01-01

    The amount of caesium 134 and 137 in Hessian game hunted for food (556 animals) after the reactor accident at Chernobyl was investigated. Comparisons have been made before and after the accident. Although there was only a very low level of contamination, the contamination rate of different species varied; on average, the Red Deer showed the highest activity (130 Bq/kg). The level of caesium contamination was mostly influenced by the permanent habitat of the animals. The main influence was due to regional, geographical and meteorological conditions. The influence of age or sex could not be determined. The contamination rate was shown to decrease with time [de

  3. Sorption Behavior of Strontium-85 Onto Colloids of Silica and Smectite

    International Nuclear Information System (INIS)

    Lu, N.; Triay, I.R.; Mason, C.F.V.; Longmire, P.A.

    1998-01-01

    Strontium-90 is one of the sizable radioactive contaminants found in DP Canyon at Los Alamos, New Mexico. Radioactive surveys found the 90 Sr is present in surface and groundwater in DP Canyon and Los Alamos Canyon. Colloids may influence the transport of this radionuclide in surface water and groundwater environments in both canyons. In this study, we investigated the sorption/desorption behavior of Sr on colloids of smectite and silica. Laboratory batch sorption experiments were conducted using 85 Sr as a surrogate to 90 Sr. Groundwater, collected from DP Canyon and from Well J-13 at Yucca Mountain, Nevada, and deionized water were used in this study. Our results show that 92% to 100% of 85 Sr was rapidly adsorbed onto smectite colloids in all three waters. The concentrations of Ca 2+ significantly influence the adsorption of 85 Sr onto silica colloids. Desorption of 85 Sr from smectite colloids is much slower than the sorption process. Desorption of 85 Sr from silica colloids was rapid in DP groundwater and slow using J-13 groundwater and deionized water

  4. Evaluation of the organization of the homoionic smectite layers (Na(+) or Ca(2+)) in diluted dispersions using granulometry, microscopy and rheometry.

    Science.gov (United States)

    Paumier, S; Pantet, A; Monnet, P

    2008-09-01

    Smectites are swelling clay materials with pronounced colloidal properties that are widely used in industry. These properties originate in the electrokinetic properties of the smectite layers and their linkage capacities. Thin layers may be dispersed or aggregated according to many parameters, such as concentration, particle size and morphology, exchangeable cation nature and chemical environment (pH, ionic strength). The literature usually provides general rules, like the sodium dispersion contains a lot of small units whereas the calcium dispersion contains a few large units. A volume of water molecules bound to the clay surface is considered as the immobile water phase that behaves like the solid phase obstructing the flow. The water immobilized around layers and trapped inside aggregates cannot participate to the flow. In this study, we evaluated the volume occupied by calcium and sodium units inside the dispersion containing the immobile water phase. First, the smectite was cautiously extracted from a raw bentonite and its physicochemical properties were determined. A large quantity of extracted and saturated smectite (Na-smectite and Ca-smectite) was obtained. Second, the unit size and a shape factor for each sample were evaluated using granulometry and scanning transmission electron microscopy on wet samples (Wet STEM) and some flow curves. Na-smectite dispersions contain 0.13 microm(2) surface units with a shape factor of 50. Ca-smectite dispersions contain 0.32 microm(2) surface units with a shape factor of 3.3. Finally, rheometry allowed us to evaluate the unit occupancy using an adaptation of the Krieger-Dougherty law. We used shape factors and evaluated the concentration from which the entire immobile volume was connected (6.4% for Na-smectite and 11.9% for Ca-smectite). This study explains the evolution of flow properties with increasing concentrations by the evolution of layer interactions at the microscopic scale for homoionic smectite particles in

  5. Estimation of committed effective dose from radioactive caesium contained in kindergarten supply of food during one year after Fukushima Daiichi Nuclear Power Plant accident

    International Nuclear Information System (INIS)

    Midorikawa, Miho; Hayashi, Toru

    2013-01-01

    For the purpose of contributing to an understanding about the situation of radioactive contamination of kindergarten lunch, contents of radioactive caesium and 40 K in lunch supplied by the attached kindergarten of Seitoku University was calculated by using the data on radioactive contamination of foodstuffs published by the Japanese Government. The average value of daily intake of radioactive caesium was estimated at lower than 1Bq and that of 40 K was 8.6Bq. Total amount of radioactive caesium in the lunch for one year was about 100Bq and that of 40 K was 1100Bq, resulting in a committed effective dose from radioactive caesium at about 1μSv. (author)

  6. Macrostructure of smectite-water systems. Influence of anionic poly-electrolytes on the organisation of montmorillonite suspensions

    International Nuclear Information System (INIS)

    Morvan, Mikel

    1993-01-01

    In its first part, this research thesis reports a bibliographical study which aimed at highlighting the main aspects of smectite swelling, discusses the organisation of smectite suspension, and briefly presents the knowledge on clay-polymer mixtures. Then, the author describes the method he used to characterise clay suspensions (relaxation, MNR, osmometric techniques, small-angle X-ray diffraction), and theoretical elements required to interpret results. He addresses more particularly the organisation of smectite-water systems with either a natural smectite (montmorillonite) or a synthetic one (laponite) which have different geometries. The last part addresses the interactions between a montmorillonite suspension and sodium polyacrylates. The author, based on the use of small-angle X-ray diffraction and the measurement of the polyelectrolyte osmotic pressure, proposes a new interpretation of the action mechanism of an anionic polyelectrolyte of low molecular mass within a montmorillonite suspension

  7. Carbonized cellulose paper as an effective interlayer in lithium-sulfur batteries

    International Nuclear Information System (INIS)

    Li, Shiqi; Ren, Guofeng; Hoque, Md Nadim Ferdous; Dong, Zhihua; Warzywoda, Juliusz; Fan, Zhaoyang

    2017-01-01

    Highlights: • A facile and economical method to fabricate interlayer for high-performance lithium-sulfur battery was demonstrated. • The performance of lithium-sulfur batteries without and with interlayer was compared. • The mechanism for the function of interlayer was explained. - Abstract: One of the several challenging problems hampering lithium-sulfur (Li-S) battery development is the so-called shuttling effect of the highly soluble intermediates (Li_2S_8–Li_2S_6). Using an interlayer inserted between the sulfur cathode and the separator to capture and trap these soluble intermediates has been found effective in diminishing this effect. Previously, most reported interlayer membranes were synthesized in a complex and expensive process, and might not be suitable for practical cheap batteries. Herein, a facile method is reported to pyrolyze the commonly used cellulose filter paper into highly flexible and conductive carbon fiber paper. When used as an interlayer, such a carbon paper can improve the cell capacity by several folds through trapping the soluble polysulfides. The enhanced electronic conductivity of the cathode, due to the interlayer, also significantly improves the cell rate performance. In addition, it was demonstrated that such an interlayer can also effectively mitigate the self-discharge problem of the Li-S batteries. This study indicates that the cost-effective pyrolyzed cellulose paper has potential as interlayer for practical Li-S batteries.

  8. Carbonized cellulose paper as an effective interlayer in lithium-sulfur batteries

    Energy Technology Data Exchange (ETDEWEB)

    Li, Shiqi; Ren, Guofeng; Hoque, Md Nadim Ferdous [Department of Electrical and Computer Engineering and Nano Tech Center, Texas Tech University, Lubbock, TX 79409 (United States); Dong, Zhihua [Hangzhou Dianzi University, No. 1158, 2nd Street, Xiasha Higher Education District, Hangzhou City, Zhejiang Province (China); Warzywoda, Juliusz [Materials Characterization Center, Whitacre College of Engineering, Texas Tech University, Lubbock, TX 79409 (United States); Fan, Zhaoyang, E-mail: zhaoyang.fan@ttu.edu [Department of Electrical and Computer Engineering and Nano Tech Center, Texas Tech University, Lubbock, TX 79409 (United States)

    2017-02-28

    Highlights: • A facile and economical method to fabricate interlayer for high-performance lithium-sulfur battery was demonstrated. • The performance of lithium-sulfur batteries without and with interlayer was compared. • The mechanism for the function of interlayer was explained. - Abstract: One of the several challenging problems hampering lithium-sulfur (Li-S) battery development is the so-called shuttling effect of the highly soluble intermediates (Li{sub 2}S{sub 8}–Li{sub 2}S{sub 6}). Using an interlayer inserted between the sulfur cathode and the separator to capture and trap these soluble intermediates has been found effective in diminishing this effect. Previously, most reported interlayer membranes were synthesized in a complex and expensive process, and might not be suitable for practical cheap batteries. Herein, a facile method is reported to pyrolyze the commonly used cellulose filter paper into highly flexible and conductive carbon fiber paper. When used as an interlayer, such a carbon paper can improve the cell capacity by several folds through trapping the soluble polysulfides. The enhanced electronic conductivity of the cathode, due to the interlayer, also significantly improves the cell rate performance. In addition, it was demonstrated that such an interlayer can also effectively mitigate the self-discharge problem of the Li-S batteries. This study indicates that the cost-effective pyrolyzed cellulose paper has potential as interlayer for practical Li-S batteries.

  9. Molecular modeling of the structure and dynamics of the interlayer and surface species of mixed-metal layered hydroxides: Chloride and water in hydrocalumite (Friedel's salt)

    Energy Technology Data Exchange (ETDEWEB)

    KALINICHEV,ANDREY G.; KIRKPATRICK,R. JAMES; CYGAN,RANDALL T

    2000-01-17

    The dynamical behavior of Cl{sup {minus}} and H{sub 2}O molecules in the interlayer and on the (001) surface of the Ca-aluminate hydrate hydrocalumite (Friedel's salt) over a range of temperatures from {minus}100 to 300 C is studied using the technique of isothermal-isobaric molecular dynamics computer simulations. This phase is currently the best available model compound for other, typically more disordered, mixed-metal layered hydroxides. The computed crystallographic parameters and density are in good agreement with available X-ray diffraction data and the force field developed for these simulations preserves the structure and density to within less than 2% of their measured values. In contrast to the highly ordered arrangement of the interlayer water molecules interpreted from the X-ray data, the simulations reveal significant dynamic disorder in water orientations. At all simulated temperatures, the interlayer water molecules undergo rapid librations (hindered hopping rotations) around an axis essentially perpendicular to the layers. This results in breaking and reformation of hydrogen bonds with the neighboring Cl{sup {minus}} anions and in a time-averaged nearly uniaxial symmetry at Cl{sup {minus}}, in good agreement with recent {sup 35}Cl NMR measurements. Power spectra of translational, vibrational, and vibrational motions of interlayer and surface Cl{sup {minus}} and H{sub 2}O were calculated as Fourier transforms of the atomic velocity autocorrelation functions and compared with the corresponding spectra and dynamics for a bulk aqueous solution. The ordered interlayer space has significant effects on the motions. Strong electrostatic attraction between interlayer water molecules and Ca atoms in the principal layer makes the Ca{hor_ellipsis}OH{sub 2} bond direction the preferred axis for interlayer water librations. The calculated diffusion coefficient of Cl{sup {minus}} as an outer-sphere surface complex is almost three times that of inner-sphere Cl

  10. Measurement of metabolism of worker ants by using the elimination of caesium-134

    International Nuclear Information System (INIS)

    Nielsen, M.G.; Jensen, T.F.

    1977-01-01

    In order to find a method for measuring field metabolism of worker ants the elimination of 134 Cs by two ant species has been investigated. Equations relating temperature to radiocaesium elimination and metabolism have been found. From these equations the relationship between elimination and metabolism is calculated. Consequently, the elimination of the isotope can be used for measuring metabolism. A pilot field experiment with Lasius alienus (Foerst.) reveals that the traditional methods of estimating field metabolism give values which are considerably lower than the value based on caesium elimination rate. This difference is supposed to be mainly due to greater motor activity of the animals in the field. Consequently, the value of the caesium elimination method is closer to the 'true' value of field metabolism. (orig.) [de

  11. Can inter-cultivar variation in caesium and strontium uptake reduce contamination of forage grasses? - Can inter-cultivar variation in caesium and strontium accumulation by forage grasses be used to reduce contamination of cows' milk in radiologically contaminated areas?

    Energy Technology Data Exchange (ETDEWEB)

    Penrose, B. [NERC Centre for Ecology and Hydrology, Lancaster Environment Centre, Library Avenue, Lancaster, LA1 4AP (United Kingdom); School of Biosciences, University of Nottingham, Sutton Bonington Campus, Leicestershire, LE12 5RD (United Kingdom); Beresford, N. [NERC Centre for Ecology and Hydrology, Lancaster Environment Centre, Library Avenue, Lancaster, LA1 4AP (United Kingdom); Broadley, M.; Crout, N.M.J.; King, J.; Young, S. [School of Biosciences, University of Nottingham, Sutton Bonington Campus, Leicestershire, LE12 5RD (United Kingdom); Lovatt, A. [Institute of Biological, Environmental and Rural Sciences (IBERS), Aberystwyth University, Gogerddan, Aberystwyth, Ceredigion, SY23 3E E (United Kingdom); Thomson, R. [Science and Advice for Scottish Agriculture (SASA), Roddinglaw Road, Edinburgh, EH12 9FJ (United Kingdom)

    2014-07-01

    Radiocaesium and radiostrontium primarily enter the food chain via plant root uptake, including indirectly via animal fodders. Inter-species variation in caesium and strontium accumulation in plants has previously been reported to be over two orders of magnitude. This variation could be exploited to select crops with relatively low uptake to reduce transfer of these radionuclides to consumers in contaminated areas. Exploiting intra-species (i.e. inter-cultivar) variation in caesium and strontium uptake has not yet been evaluated as a remediation strategy as sufficient data have not been available. As cows' milk has been one of the main contributors to human dose following the Chernobyl and Mayak accidents, we have chosen to focus on elucidating the extent and nature of inter-cultivar variation in caesium and strontium uptake in forage grasses. A total of 412 cultivars from four species of forage grass; perennial ryegrass (Lolium perenne; 284 cultivars), Italian ryegrass (Lolium multiflorum; 17 cultivars), hybrid ryegrass (Lolium hybridum; 101 cultivars) and tall fescue (Festuca arundinacea; 10 cultivars) were sampled from 20 sets of experimental plots in Aberystwyth (Wales, UK) and Edinburgh (Scotland, UK). Fifty-nine cultivars were grown in both locations. At least three replicates of the same cultivar were grown in each set of plots. Vegetation samples from 2208 plots were collected both in spring 2013 (May-June) and summer 2013 (August-September). The samples were oven-dried and milled then analysed for elemental composition using inductively coupled plasma mass spectrometry (ICP-MS). Stable caesium and strontium were measured as a proxy measurement for radiocaesium and radiostrontium concentrations. Concentrations of chemical analogues of caesium and strontium (potassium and calcium) and a number of other elements were measured. Soil samples from the experimental plots were also collected, dried, milled and analysed using ICP-MS. This paper will present

  12. [Mechanism Study of the Smectite-OR-SH Compound for Reducing Cadmium Uptake by Plants in Contaminated Soils].

    Science.gov (United States)

    Zeng, Yan-jun; Zhou, Zhi-jun; Zhao, Qiu-xiang

    2015-06-01

    Adsorption and desorption experiments, pot experiments and characterization test were performed to investigate the immobilization effect and mechanism of the smectite-OR-SH compound for reducing cadmium uptake by plants in contaminated soils. The results showed that the saturated adsorption capacity for the adsorption of Cd2+ on smectite raised distinctly after functionalized. The adsorption of Cd2+ on smectite-OR-SH compound was very stable and it was difficult for Cd2+ to be desorbed from it. Crop yields promoted differently in original soil, Cd 3 mg x kg(-1) soil and Cd 10 mg x kg(-1) soil after adding the smectite-OR-SH compound. And the cadmium content of the cabbage reduced 61.00%, 62.10% and 83.73% respectively compare with the control. Characterization test analysis showed that Cd was adsorbed by the compound successfully and ligand interaction occurred between Cd and the thiol group. Floc amount on the compound surface increased correspondingly. In addition to electrostatic adsorption, ion exchange and hydroxyl ligand adsorption, the reaction mechanism of smectite-OR-SH compound with Cd was mainly sulfhydryl ligand adsorption.

  13. Improved efficiency in OLEDs with a thin Alq3 interlayer

    International Nuclear Information System (INIS)

    Lian Jiarong; Yuan Yongbo; Cao Lingfang; Zhang Jie; Pang Hongqi; Zhou Yunfei; Zhou Xiang

    2007-01-01

    We demonstrate an improved efficiency in OLEDs with a thin Alq 3 interlayer, which is inserted into the hole-transport layer for adjusting the hole-injection and transport, and improving the hole-electron balance. The thin Alq 3 interlayer can effectively influence the electrical performance and electroluminescence (EL) efficiency of the devices. The devices with an optimum Alq 3 interlayer exhibit a maximum EL efficiency of around 3.3 cd/A, which is improved by a factor of two over the conventional devices (1.6 cd/A) without the interlayer

  14. Studies of adsorption of pillarized and organofunctionalized smectite clay for Th"4"+ removal

    International Nuclear Information System (INIS)

    Guerra, D.J.L.; Menonca, E.S.; Silva, R.A.R.; Lara, W.

    2012-01-01

    A natural smectite clay sample was taken from the Amazon region, Amazonas State, Brazil. Zirconium polyoxycations were inserted into the smectite structure in a pillaring process. The pillarized smectite was organofunctionalized with the compound 3-mercaptopropyltrimethoxysilane. The natural and modified clay samples were used for the adsorption of tetravalent thorium cation from aqueous solution in a batch process. The adsorption process was fitted to equilibrium and kinetic models. The effects of stirring time, adsorbent dosage and pH on the adsorption capacity demonstrated that 90 min is sufficient to reach equilibrium at room temperature at pH 6.0. From the cation/basic center interactions for each smectite at the solid-liquid interface, the equilibrium constant and exothermic thermal effects were calculated with calorimetric methodology. By considering the net interactive number of moles for thorium cation and the equilibrium constant, the enthalpy, (-7.2 ± 0.11 to -7.0 ± 0.11 kJ mol"-"1) and negative Gibbs free energy, (-22.4 ± 0.1 to -23.1 ± 0.1 kJ mol"-"1) were calculated. These values enabled determination of the positive entropy, (51.2 ± 0.1 to 54.1 ± 0.1 JK"-"1mol"-"1). All liquid/solid interface adsorptions were spontaneous in nature and enthalpically driven.

  15. Stable hydrogen production from ethanol through steam reforming reaction over nickel-containing smectite-derived catalyst.

    Science.gov (United States)

    Yoshida, Hiroshi; Yamaoka, Ryohei; Arai, Masahiko

    2014-12-25

    Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH4 are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H2 reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H2.

  16. Robustly Engineering Thermal Conductivity of Bilayer Graphene by Interlayer Bonding

    Science.gov (United States)

    Zhang, Xiaoliang; Gao, Yufei; Chen, Yuli; Hu, Ming

    2016-01-01

    Graphene and its bilayer structure are the two-dimensional crystalline form of carbon, whose extraordinary electron mobility and other unique features hold great promise for nanoscale electronics and photonics. Their realistic applications in emerging nanoelectronics usually call for thermal transport manipulation in a controllable and precise manner. In this paper we systematically studied the effect of interlayer covalent bonding, in particular different interlay bonding arrangement, on the thermal conductivity of bilayer graphene using equilibrium molecular dynamics simulations. It is revealed that, the thermal conductivity of randomly bonded bilayer graphene decreases monotonically with the increase of interlayer bonding density, however, for the regularly bonded bilayer graphene structure the thermal conductivity possesses unexpectedly non-monotonic dependence on the interlayer bonding density. The results suggest that the thermal conductivity of bilayer graphene depends not only on the interlayer bonding density, but also on the detailed topological configuration of the interlayer bonding. The underlying mechanism for this abnormal phenomenon is identified by means of phonon spectral energy density, participation ratio and mode weight factor analysis. The large tunability of thermal conductivity of bilayer graphene through rational interlayer bonding arrangement paves the way to achieve other desired properties for potential nanoelectronics applications involving graphene layers. PMID:26911859

  17. Textural and structural modifications of one smectite treated with different 0.1 M Zr solutions, with and without thermal treatment

    International Nuclear Information System (INIS)

    Volzone, Cristina; Hipedinger, Nora E.

    1997-01-01

    Smectite treated with with hydrolyzed Zr-solutions and posterior thermal treatment provide a product generally known as pillared inter layered clays (PILC), with interest as adsorbents, gas separation and catalysis. The smectite was dispersed in distilled water for one day at room temperature. The hydroxy-zirconium solutions were prepared from 0.1 M Zr O Cl 2 .8 H 2 O and hydrolyzed at different conditions: a) at room temperature 15 days; b) at 60 deg C one day; C) refluxed 2 hours and d) refluxed 12 hours. These solutions were slowly added to the dispersed smectite with stirring. After one day of contact at room temperature the solid was separated and washed several times. The amount of Zr added was 2.5 mmol per gram of smectite. The different Zr-smectites, at room temperature and 350 deg C, were characterized by: XRD, DTA, TGA and adsorption-desorption of N 2 . Textural and structural changes were observed in Zr-smectites depending on the prepared Zr solutions. (author)

  18. Interlayer toughening of fiber composite flywheel rotors

    Science.gov (United States)

    Groves, Scott E.; Deteresa, Steven J.

    1998-01-01

    An interlayer toughening mechanism to mitigate the growth of damage in fiber composite flywheel rotors for long application. The interlayer toughening mechanism may comprise one or more tough layers composed of high-elongation fibers, high-strength fibers arranged in a woven pattern at a range from 0.degree. to 90.degree. to the rotor axis and bound by a ductile matrix material which adheres to and is compatible with the materials used for the bulk of the rotor. The number and spacing of the tough interlayers is a function of the design requirements and expected lifetime of the rotor. The mechanism has particular application in uninterruptable power supplies, electrical power grid reservoirs, and compulsators for electric guns, as well as electromechanical batteries for vehicles.

  19. Caesium-137 in a boreal forest ecosystem. Aspects on the long-term behaviour

    International Nuclear Information System (INIS)

    Bergman, R.; Nylen, T.; Nelin, P.; Palo, T.

    1993-11-01

    Cycling of radioactive caesium, particularly the isotope Cs-137, is studied in boreal forest biotopes mainly located at the Vindeln experimental forest, 60 km NW of Umeaa, Sweden, (64 degrees 16'N, 19 degrees 48'E). The distribution of radioactive caesium in this forest ecosystem, prior to and in different periods after the Chernobyl accident, reflects the existence of fast changes particularly at an early stage after the deposition, superimposed on slow redistribution over long time periods. The definite causes to this complex dynamic behaviour are not yet unambiguously established. In this work we use the specific results from local field studies as a basis to describe the general pattern and time dependence of Cs-137 redistribution in a boreal forest. We raise the hypothesis that: 'Cs-137 present in a boreal forest tends towards a homogenous distribution among the living cells of that system'. This hypothesis is based on physiological characteristics concerning transport over cell membranes and intracellular distribution in comparison to potassium, and the apparently conservative conditions prevailing for caesium in boreal ecosystems - e.g. the facts that very little of the radioactive caesium deposited over the forest area is lost from the system by run off, more than 90% of the total deposition of Cs-137 resides in the upper organic horizon in podzol areas, and that the availability in the ecosystem, as can be seen from the Cs-137 concentration in moose meat, is not significantly different in 1985 (i.e. prior to the Chernobyl accident) in comparison to the period 1986-1990. The aim of this work is to elucidate how predictions, based on our hypothesis about redistribution processes in the boreal forest, corroborates with the main features in the time-dependent change of Cs-137 activity, according to measurements on perennial vegetation from the local sites. In particular the implicit dependence of the dynamics of the redistribution processes on primary

  20. Estimation of illitization rate of smectite from the thermal history of Murakami deposit, Japan

    International Nuclear Information System (INIS)

    Kamei, G.; Arai, T.; Yusa, Y.; Sasaki, N.; Sakuramoto, Y.

    1990-01-01

    The research on illitization of smectite in the natural environment affords information on the long-term durability of bentonite which is the candidate for buffer material for high-level radioactive waste disposal facilities. Murakami bentonite deposit in central Japan, where the bentonite and rhyolitic intrusive rock were distributed, was surveyed and the lateral variation of smectite to illite in the aureole of the rhyolite was studied. The radiometric ages of some minerals from the intrusive rock and the clay deposit were determined. Comparison of the mineral ages with closure temperature estimated for the various isotopic systems allowed the thermal history of the area. The age of the intrusion was 7.1 ± 0.5 Ma, and the cooling rate of the intrusive rock was estimated to be approximately 45C/Ma. Sedimentation ages of the clay bed were mostly within the range from 18 to 14 Ma. However, the fission-track age of zircon in the clay containing illite/smectite mixed layers was 6.4 ± 0.4 Ma, which was close to that of the intrusion. The latter value could be explained as the result of annealing of fission-tracks in zircon. The presence of annealing phenomena and the estimated cooling rate concluded that illitization had occurred in the period of 3.4 Ma at least under the temperature range from above 240 ± 50 to 105C. Illite-smectite mixed layers occurred from smectite in the process. The proportion of illite was about 40%. Approximately, 29 kcal/mol as a value of activation energy was calculated to the illitization

  1. Molecular Dynamics Study of Water Molecules in Interlayer of 14 ^|^Aring; Tobermorite

    KAUST Repository

    Yoon, Seyoon

    2013-01-01

    The molecular structure and dynamics of interlayer water of 14 Å tobermorite are investigated based on molecular dynamics (MD) simulations. Calculated structural parameters of the interlayer water configuration are in good agreement with current knowledge of the refined structure. The MD simulations provide detailed information on the position and mobility of the hydrogen and oxygen of interlayer water, as well as its self-diffusion coefficient, through the interlayer of 14 Å tobermorite. Comparison of the MD simulation results at 100 and 300 K demonstrates that water molecules in the interlayer maintain their structure but change their mobility. The dominant configuration and self-diffusion coefficient of interlayer water are obtained in this study. Copyright © 2013 Japan Concrete Institute.

  2. Enrichment and activation of smectite-poor clay

    Energy Technology Data Exchange (ETDEWEB)

    Sarcevica, Inese; Kostjukovs, Juris; Actint, Andris, E-mail: inese.sarcevicha@gmail.com [Department of Chemistry, University of Latvia, Kr. Valdemara street 48, Riga (Latvia)

    2011-06-23

    A new method of smectite clay enrichment has been developed. The method is based on dispersing clay in a phosphate solution and sequential coagulation. The product of enrichment is characterized with X-ray powder diffraction, wavelength dispersive X-ray fluorescence spectrometry, differential thermal analysis and thermogravimetry. Sorption of methylene blue and hexadecylpyridinium bromide on raw and purified clays was studied.

  3. Transfer of radioactive caesium from soil to vegetation and comparison with potassium in upland grasslands

    International Nuclear Information System (INIS)

    Coughtrey, P.J.; Kirton, J.A.; Mitchell, N.G.; Morris, C.

    1989-01-01

    The distribution and transfer of caesium and potassium between soils and vegetation has been investigated by field sampling and experimental studies on soils and vegetation typical of upland grassland in north west England. Total 137 Cs content to a depth of 0.05 m below root matt ranged from 13 000 to 18 000 Bq m -2 . This caesium content derives from three sources: the Windscale accident of 1957, weapons-testing fallout which peaked in the early 1960s, and the Chernobyl accident in May 1986. From 2200 to 6200 Bq m -2 is attributed to the first two sources, and the remainder to Chernobyl. During accelerated growth of vegetation, on monoliths in glasshouse conditions over the winter of 1986/87, 137 Cs was transferred from soil and root matt to new growth, such that concentrations in fresh growth were similar to or higher than those observed in the field during December 1986. Removal of caesium by successive cuts resulted in up to 25% of the original estimated total being removed over a 240 day period. Increased concentrations coincided with the emergence of Carex sp. and Trichophorum caespitosum, as well

  4. Organofunctionalized Amazon smectite for dye removal from aqueous medium-Kinetic and thermodynamic adsorption investigations

    Energy Technology Data Exchange (ETDEWEB)

    Guerra, Denis L., E-mail: denis@cpd.ufmt.br [Universidade Federal de Mato Grosso, DRM-UFMT, Mato Grosso, Brasil 78060 900 (Brazil); Silva, Weber L.L. [Universidade Federal de Mato Grosso, DRM-UFMT, Mato Grosso, Brasil 78060 900 (Brazil); Oliveira, Helen C.P. [Universidade Estadual do Norte Fluminense, UENF, Rio de Janeiro, Brasil 28013 602 (Brazil); Viana, Rubia R. [Universidade Federal de Mato Grosso, DRM-UFMT, Mato Grosso, Brasil 78060 900 (Brazil); Airoldi, Claudio [Chemistry Institute, State University of Campinas, P.O. Box 6154, 13084-971 Campinas, Sao Paulo (Brazil)

    2011-02-15

    The objective of this study is to examine the adsorption behavior of Sumifix Brilliant Orange 3R textile dye from aqueous solution on smectite sample, an abundant Amazon clay. The original smectite clay mineral has been collected from Amazon region, Brazil. The compound 2-aminomethylpyridine was anchored onto smectite surface by heterogeneous route. The ability of these materials to remove the Sumifix Brilliant Orange 3R textile dye from aqueous solution was followed by a series of adsorption isotherms, using a batchwise process. The maximum number of moles adsorbed was determined to be 1.26 and 2.07 mmol g{sup -1} for natural and modified clay samples, respectively. The energetic effects caused by dye cations adsorption were determined through calorimetric titrations. Thermodynamics indicated the existence of favorable conditions for such dye-nitrogen interactions.

  5. Organofunctionalized Amazon smectite for dye removal from aqueous medium-Kinetic and thermodynamic adsorption investigations

    International Nuclear Information System (INIS)

    Guerra, Denis L.; Silva, Weber L.L.; Oliveira, Helen C.P.; Viana, Rubia R.; Airoldi, Claudio

    2011-01-01

    The objective of this study is to examine the adsorption behavior of Sumifix Brilliant Orange 3R textile dye from aqueous solution on smectite sample, an abundant Amazon clay. The original smectite clay mineral has been collected from Amazon region, Brazil. The compound 2-aminomethylpyridine was anchored onto smectite surface by heterogeneous route. The ability of these materials to remove the Sumifix Brilliant Orange 3R textile dye from aqueous solution was followed by a series of adsorption isotherms, using a batchwise process. The maximum number of moles adsorbed was determined to be 1.26 and 2.07 mmol g -1 for natural and modified clay samples, respectively. The energetic effects caused by dye cations adsorption were determined through calorimetric titrations. Thermodynamics indicated the existence of favorable conditions for such dye-nitrogen interactions.

  6. Amorphization and Frictional Processes in Smectite-Quartz Gouge Mixtures Sheared from Sub-seismic to Seismic Slip Rates

    Science.gov (United States)

    Aretusini, S.; Mittempergher, S.; Spagnuolo, E.; Di Toro, G.; Gualtieri, A.; Plümper, O.

    2015-12-01

    Slipping zones in shallow sections of megathrusts and large landslides are often made of smectite and quartz gouge mixtures. Experiments aimed at investigating the frictional processes operating at high slip rates (>1 m/s) may unravel the mechanics of these natural phenomena. Here we present a new dataset obtained with two rotary shear apparatus (ROSA, Padua University; SHIVA, INGV-Rome). Experiments were performed at room humidity and temperature on four mixtures of smectite (Ca-Montmorillonite) and quartz with 68, 50, 25, 0 wt% of smectite. The gouges were slid for 3 m at normal stress of 5 MPa and slip rate V from 300 µm/s to 1.5 m/s. Temperature during the experiments was monitored with four thermocouples and modeled with COMSOL Multiphysics. In smectite-rich mixtures, the friction coefficient µ evolved with slip according to three slip rate regimes: in regime 1 (V0.3 m/s) µ had strong slip-weakening behavior. Instead, in quartz-rich mixtures the gouge had a monotonic slip-weakening behavior, independently of V. Temperature modelling showed that the fraction of work rate converted into heat decreased with increasing smectite content and slip rate. Quantitative X-ray powder diffraction (Rietveld method) indicates that the production of amorphous material from smectite breakdown increased with frictional work but was independent of work rate. Scanning Electron Microscopy investigation evidenced strain localization and presence of dehydrated clays for V≥0.3 m/s; instead, for V<0.3 m/s, strain was distributed and the gouge layer pervasively foliated. In conclusion, amorphization of the sheared gouges was not responsible of the measured frictional weakening. Instead, slip-weakening was concomitant to strain localization and possible vaporization of water adsorbed on smectite grain surfaces.

  7. Experimental Study and modelling of the Sorption of Selenite and Europium Onto Smectite and Illite Clays

    Energy Technology Data Exchange (ETDEWEB)

    Missana, T.; Alonso, U.; Garcia-Gutierrez, M.

    2009-10-12

    This study provides a large set of experimental selenite sorption data for pure smectite and illite. Similar sorption behavior existed in both clays: linear within a large range of the Se concentrations investigated and independent of ionic strength. Selenite sorption was also analysed in the illite/smectite system with the clays mixed in two different proportions. The objective of the study was to provide the simplest model possible to fit the experimental data, a model also capable of describing selenite sorption in binary illite/smectite clay systems. Selenite sorption data were modeled using both a one-and a two-site non-electrostatic model that took into account the formation of two complexes at the edge sites of the clay. The complexation constants obtained by fitting sorption data of the individual minerals were incorporated into a model to predict the adsorption of selenium in the illite/ smectite mixtures; the models predictions were consistent with the experimental adsorption data. (Author) 42 refs.

  8. Experimental Study and modelling of the Sorption of Selenite and Europium Onto Smectite and Illite Clays

    International Nuclear Information System (INIS)

    Missana, T.; Alonso, U.; Garcia-Gutierrez, M.

    2009-01-01

    This study provides a large set of experimental selenite sorption data for pure smectite and illite. Similar sorption behavior existed in both clays: linear within a large range of the Se concentrations investigated and independent of ionic strength. Selenite sorption was also analysed in the illite/smectite system with the clays mixed in two different proportions. The objective of the study was to provide the simplest model possible to fit the experimental data, a model also capable of describing selenite sorption in binary illite/smectite clay systems. Selenite sorption data were modeled using both a one-and a two-site non-electrostatic model that took into account the formation of two complexes at the edge sites of the clay. The complexation constants obtained by fitting sorption data of the individual minerals were incorporated into a model to predict the adsorption of selenium in the illite/ smectite mixtures; the models predictions were consistent with the experimental adsorption data. (Author) 42 refs

  9. Acid–base properties of pillared interlayered clays with single and mixed Zr–Al oxide pillars prepared from Tunisian-interstratified illite–smectite

    Directory of Open Access Journals (Sweden)

    Saida Mnasri

    2017-12-01

    Full Text Available Interstratified illite–smectite clay samples from Tunisia have been used in order to prepare Al, Zr and Zr–Al-pillared clays. Several Al/metal, OH/metal ratios were used in order to investigate the effect on the chemical and physical properties, specifically the point of zero charge (PZC of the synthesized pillared clays. The structure of the pillared materials is studied by XRD and cationic exchange capacity. The textural property is investigated by the nitrogen adsorption/desorption method. The acid–base chemistry “surface acidity” of these products was analysed by using mass and potentiometric titration in order to determine the PZC and the equilibrium constants (pKa of each sample. The resulting materials exhibited basal spacings in the range of 17.4–20.5 Å, with high surface areas (134–199 m2 g−1. Titration curves obtained by acid–base potentiometric titration for the starting material showed an indistinct cross-over point at about pH = 7.3, whereas in the case of pillared samples, points were observed at the acidic region between 4 and 6. In addition, the calculated pKas values of pillared clays show a shifting to the acidic values compared to the untreated sample.

  10. The swelling behavior of montmorillonite as affected by the grain size by in situ X-ray diffraction experiments

    International Nuclear Information System (INIS)

    Morodome, S.; Kawamura, K.; Owada, H.; Yahagi, R.; Kobayashi, I.

    2012-01-01

    -samples measured by SEM was ambiguous. These results show that jet mill pulverization made a stacked layer cleave rather than broke a sheet crystal. The swelling pressure measurement and X-ray diffraction measurement using of the same samples conducted in RWMC-project, was shown in Figure 2 and 3. As shown in Figure 2, the swelling behavior depended on the grain size. The swelling pressure of pulverized Kunipia-F was approximately 1.4 times larger than that of intact sample, and MX-80 was approximately 2.3 times larger. Moreover, XRD patterns of the intact and pulverized Kunipia-F and MX-80 were different, respectively. Although the swelling behavior of the intact sample showed distinct zero-, one-, and two-layer water molecular hydration states, the pulverized sample showed the continuous swelling from one- and two-layer hydration state. According to RWMC-project, pulverizing the smectitic materials increases the swelling pressure and the ratio of the low hydration states in montmorillonite in spite of the same hydrous conditions as intact specimen. This result is consistent with the result in this paper. It is thought that a small part of montmorillonite sheets is difficult to swell potentially. Since the stacked layer was cleft forcibly by the pulverization and the hydration area of montmorillonite increased, the montmorillonite hydrated uniformly. In the constant hydrous conditions, the increment of hydration area causes the montmorillonite content with low hydration state to increase, and the swelling behavior changes stepwise hydration to continuous hydration. By using of MX-80 (Wyoming bentonite), the same measurements have been carried out, and we will also report the difference between Kunipia-F and MX-80. This research is constituted from an additional experimental research and a part of 'Development of the technique for the evaluation of long-term performance of EBS, FY2011' under a grant from the Japanese Ministry of Economy, Trade and Industry (METI). (authors)

  11. Oscillatory interlayer magnetic coupling and induced magnetism in ...

    Indian Academy of Sciences (India)

    Unknown

    lating interlayer magnetic coupling (IMC) (Grunberg et al 1986; Parkin et al 1990; Unguris et al 1991) and giant magnetoresistance (GMR). Such oscillations in interlayer magnetic coupling and the saturation magnetoresistance were reported by Parkin et al (1990) with a period 15–. 20 Å in Fe/Cr, Co/Cr, Co/Ru multilayers.

  12. Research and development on groundwater dating. Part 6. Extraction of pore water from low permeability rocks

    International Nuclear Information System (INIS)

    Nakata, Kotaro; Oyama, Takahiro; Higashihara, Tomohiro; Hasegawa, Takuma; Kitsukawa, Takashi

    2007-01-01

    The squeezing method is one of the most promising methods to obtain the pore water from rock cores. However, in previous studies, ion composition of squeezed water was found to have dependency on squeezing pressure. In this study, squeezing method was applied to both natural and artificial standard samples and concentration of Cl ion in squeezed water and basal spacing of smectite included in samples were investigated as a function of squeezing pressure. Furthermore, bentonite sample was prepared by suspending the bentonite powder in NaCl solution and supplied for squeezing. The relation between concentration of Cl ion in squeezed water and the amount of inter-layer water squeezed from smectite was discussed quantitatively, for this bentonite sample. The concentration of Cl ion in squeezed water was found to decrease with increase of squeezing pressure. The inter-layer water from smectite is assumed to be one of the most effective cause of the decrease of Cl ion with increase of squeezing pressure, because of following 3 reasons; 1) Basal spacing of smectite included in rocks decreased with increase of squeezing pressure, 2) The decrease of Cl ion strongly depended on the amount of smectite included in rocks and no decrease was observed in glass filter sample in which no smectite is included, 3) The agreement between concentration of Cl estimated from obtained pore water and that calculated with basal spacing and amount of pore water was obtained in bentonite sample. These results indicated squeezing pressure should be limited so that basal spacing of smectite do not change during squeezing to estimate the concentration of Cl in pore water precisely. (author)

  13. Analysis of the structural stability of the smectite submitted to high pressures and temperatures

    International Nuclear Information System (INIS)

    Alabarse, Frederico Gil

    2009-10-01

    The thermal stability of bentonite is of particular interest for containment barrier in nuclear waste disposal facilities. However, very little is known about the stability of smectite (principal component of bentonite) under high-pressure and high-temperature conditions (HPHT). The objective of this work was to investigate the stability of the smectite structure under HP-HT conditions. The HP-HT experiments were performed on toroidal chambers (TC) with pressure up 7.7 GPa and temperatures of 1000 deg C. The samples were characterized by X-ray diffraction after the HP-HT processing. Furthermore, one sample from the original material was analyzed using Fourier transformed infra-red (FTIR) in situ measurements on a diamond anvil cell (DAC) in experiments up to 12 GPa. The original sample of bentonite, calcium dioctahedral montmorillonite with small fraction of quartz, was characterized by FTIR, XRD, X-ray fluorescence (XRF), scanning electron microscopy (SEM), surface area, thermogravimetric analysis (TGA) and differential thermal analysis (DTA). In the experiment performed using the DAC up to 12 GPa, the FTIR in situ measurements analysis showed that the smectite structure is stable with a reversible deformation in the Si-O bond and that the smectite did not loose water. Experiments performed in TC at 7.7 GPa of pressure and 250 deg C of temperature, during 3.5 h showed, after analysis by XRD and FTIR, that the smectite structure is stable and did not loose water. Experiments performed in TC at 7.7 GPa of pressure and 1000 deg C of temperature, during 3.5 h showed, after analysis by XRD and SEM, the transformation of bentonite to the mineral assemblage: Coesite, Quartz, Kyanite and Pyrope. (author)

  14. Josephson junctions with ferromagnetic interlayer

    International Nuclear Information System (INIS)

    Wild, Georg Hermann

    2012-01-01

    We report on the fabrication of superconductor/insulator/ferromagnetic metal/superconductor (Nb/AlO x /Pd 0.82 Ni 0.18 /Nb) Josephson junctions (SIFS JJs) with high critical current densities, large normal resistance times area products, and high quality factors. For these junctions, a transition from 0- to π-coupling is observed for a thickness d F =6 nm of the ferromagnetic Pd 0.82 Ni 0.18 interlayer. The magnetic field dependence of the critical current of the junctions demonstrates good spatial homogeneity of the tunneling barrier and ferromagnetic interlayer. Magnetic characterization shows that the Pd 0.82 Ni 0.18 has an out-of-plane anisotropy and large saturation magnetization indicating negligible dead layers at the interfaces. A careful analysis of Fiske modes up to about 400 GHz provides valuable information on the junction quality factor and the relevant damping mechanisms. Whereas losses due to quasiparticle tunneling dominate at low frequencies, at high frequencies the damping is explained by the finite surface resistance of the junction electrodes. High quality factors of up to 30 around 200 GHz have been achieved. They allow to study the junction dynamics, in particular the switching probability from the zero-voltage into the voltage state with and without microwave irradiation. The experiments with microwave irradiation are well explained within semi-classical models and numerical simulations. In contrast, at mK temperature the switching dynamics without applied microwaves clearly shows secondary quantum effects. Here, we could observe for the first time macroscopic quantum tunneling in Josephson junctions with a ferromagnetic interlayer. This observation excludes fluctuations of the critical current as a consequence of an unstable magnetic domain structure of the ferromagnetic interlayer and affirms the suitability of SIFS Josephson junctions for quantum information processing.

  15. Josephson junctions with ferromagnetic interlayer

    Energy Technology Data Exchange (ETDEWEB)

    Wild, Georg Hermann

    2012-03-04

    We report on the fabrication of superconductor/insulator/ferromagnetic metal/superconductor (Nb/AlO{sub x}/Pd{sub 0.82}Ni{sub 0.18}/Nb) Josephson junctions (SIFS JJs) with high critical current densities, large normal resistance times area products, and high quality factors. For these junctions, a transition from 0- to {pi}-coupling is observed for a thickness d{sub F}=6 nm of the ferromagnetic Pd{sub 0.82}Ni{sub 0.18} interlayer. The magnetic field dependence of the critical current of the junctions demonstrates good spatial homogeneity of the tunneling barrier and ferromagnetic interlayer. Magnetic characterization shows that the Pd{sub 0.82}Ni{sub 0.18} has an out-of-plane anisotropy and large saturation magnetization indicating negligible dead layers at the interfaces. A careful analysis of Fiske modes up to about 400 GHz provides valuable information on the junction quality factor and the relevant damping mechanisms. Whereas losses due to quasiparticle tunneling dominate at low frequencies, at high frequencies the damping is explained by the finite surface resistance of the junction electrodes. High quality factors of up to 30 around 200 GHz have been achieved. They allow to study the junction dynamics, in particular the switching probability from the zero-voltage into the voltage state with and without microwave irradiation. The experiments with microwave irradiation are well explained within semi-classical models and numerical simulations. In contrast, at mK temperature the switching dynamics without applied microwaves clearly shows secondary quantum effects. Here, we could observe for the first time macroscopic quantum tunneling in Josephson junctions with a ferromagnetic interlayer. This observation excludes fluctuations of the critical current as a consequence of an unstable magnetic domain structure of the ferromagnetic interlayer and affirms the suitability of SIFS Josephson junctions for quantum information processing.

  16. Organofunctionalized Amazon smectite for dye removal from aqueous medium--kinetic and thermodynamic adsorption investigations.

    Science.gov (United States)

    Guerra, Denis L; Silva, Weber L L; Oliveira, Helen C P; Viana, Rúbia R; Airoldi, Claudio

    2011-02-15

    The objective of this study is to examine the adsorption behavior of Sumifix Brilliant Orange 3R textile dye from aqueous solution on smectite sample, an abundant Amazon clay. The original smectite clay mineral has been collected from Amazon region, Brazil. The compound 2-aminomethylpyridine was anchored onto smectite surface by heterogeneous route. The ability of these materials to remove the Sumifix Brilliant Orange 3R textile dye from aqueous solution was followed by a series of adsorption isotherms, using a batchwise process. The maximum number of moles adsorbed was determined to be 1.26 and 2.07 mmol g(-1) for natural and modified clay samples, respectively. The energetic effects caused by dye cations adsorption were determined through calorimetric titrations. Thermodynamics indicated the existence of favorable conditions for such dye-nitrogen interactions. Copyright © 2010. Published by Elsevier B.V.

  17. Caesium 137: Properties and biological effects resulting of an internal contamination

    International Nuclear Information System (INIS)

    Lestaevel, P.; Racine, R.; Bensoussan, H.; Rouas, C.; Gueguen, Y.; Dublineau, I.; Bertho, J.M.; Gourmelon, P.; Jourdain, J.R.; Souidi, M.

    2010-01-01

    Caesium-137 ( 137 Cs) is a radionuclide present in the environment mainly as the result of the atmospheric nuclear weapons testing and accidents arising in nuclear power plants like the Chernobyl accident in 1986. Nowadays, the health consequences resulting from a chronic exposure to this radionuclide remain unknown. After absorption, the caesium is distributed relatively homogeneously within the body, with a more important load in children than in adults. The toxicity of 137 Cs is mainly due to its radiological properties. A high dose of 137 Cs is responsible for a medullar dystrophy, disorders of the reproductive function, and effects on liver and renal functions. Disorders of bone mineralization and brain damages were also described in human beings. At lowest dose, 137 Cs induces disturbances of wakefulness-sleep cycle, but not accompanied with behavioural disorders. The cardiovascular system was also perturbed. Biological effects of 137 Cs on the metabolisms of the vitamin D, cholesterol and steroid hormones were described, but do not lead to clinical symptoms. In human beings, 137 Cs leads to an immune deficiency, congenital and foetal deformations, an increased of thyroid cancer, as well as neurological disorders. It seems that children are more sensitive to the toxic effects of caesium than the adults. At present, the only effective treatment for the decorporation of the ingested 137 Cs is the Prussian Blue (Radiogardase). The use of pectin to de-corporate the ingested 137 Cs, in children notably, is sometimes proposed, but its administration still remains an open question. To conclude, the available scientific data suggest that 137 Cs could affect a number of physiological and metabolic functions and consequently, could participate in the health risks associated to the presence of other contaminants in the environment. (authors)

  18. Caesium transfer to placenta, urine and human milk

    International Nuclear Information System (INIS)

    Risica, S.; Rogani, A.; Tancredi, F.; Grisanti, A.; Grisanti, G.; Baronciani, D.; Del Prete, A.; Zanini, R.

    1997-01-01

    After the Chernobyl accident few measurements on radioactive contamination of maternal milk, placenta and urine of nursing mothers were carried out. Two previous studies on breast milk contamination were conducted in different Italian areas by the Physics Department of the National Institute of Health (Laboratorio di Fisica, Istituto Superiore di Sanita). In the first study conducted in collaboration with the Epidemiological Unit of the Lazio District, I-131, Cs-134 and Cs-137 concentrations were measured in mixed breast milk samples pooled from 5-10 women in the first week after delivery, from May 1986 to December 1987, in the Rome area. The second research was conducted, in collaboration with the Lecco Hospital, in 1989 on a group of women living in the Como Lake area (Lombardia), which was one of the areas of Northern Italy most heavily affected by Chernobyl fallout, because of intensive rainfall in the first few days after the accident. The specific diet and caesium content in maternal milk were studied recruiting pregnant women at the ''respiratory autogen training'' course. In this case, Cs-l37, Cs-134 and K-40 concentration in placenta and urine of the mothers under study had also been measured. Aim of this paper is to discuss these data and investigate the relationship between Cs-137 contamination of maternal milk, placenta and urine as a contribution to a better understanding of caesium metabolism in pregnant and nursing women

  19. NPL's contribution to the introduction of the caesium second

    Energy Technology Data Exchange (ETDEWEB)

    Whibberley, Peter [National Physical Laboratory, Teddington (United Kingdom). Time and Frequency Group

    2017-09-15

    For centuries timekeeping was the preserve of astronomers. The fundamental unit of time measurement was the day, sub-divided by clocks for everyday use into hours, minutes and seconds. By the early 20th century, clocks were sufficiently stable to indicate that the length of the mean solar day varied, though their lack of intrinsic accuracy (the rate of a clock depended on its mechanical properties) ensured that the Earth's rotation remained the global reference standard for timekeeping. This situation changed fundamentally in June 1955, when Louis Essen and Jack Parry brought the first caesium atomic clock into operation at the National Physical Laboratory, in Teddington, UK. The atomic clock not only provided a much more stable timekeeper than the Earth's rotation; its reference was the frequency of an atomic transition - a fundamental constant of nature, determined by the laws of quantum mechanics. As a result all caesium clocks will run at essentially the same rate, limited only by noise processes and their local environment, regardless of time or place.

  20. Reduction of radioactive caesium in meat and fish by soaking

    International Nuclear Information System (INIS)

    Petaejae, E.; Puolanne, E.

    1992-01-01

    The removal of radioactive caesium from meat by soaking in brine or water and the effect of injection curing, temperature, size of meat piece and cooking on this removal were studied. The availability of the brined meat for the manufacture of cured, smoked and cooked meat, oven-cooked meat and cooked sausages was also investigated. The soaking method was also tested on fish. (Author)

  1. Comparative study of strontium adsorption on dioctahedral and trioctahedral smectites

    International Nuclear Information System (INIS)

    Galambos, M.; Rosskopfova, O.; Krajnak, A.; Rajec, P.; Osacky, M.; Comenius University, Bratislava

    2012-01-01

    Slovak bentonites characterized by good rheological, mineralogical and chemical stability are considered as suitable sealing barriers for construction of Slovak deep geological repository for high-level radioactive waste and spent nuclear fuel. There is several Slovak bentonite deposits, bentonites of which have appropriate adsorption properties meeting the geotechnical requirements for this type of barriers. Study of adsorption properties of bentonites (mainly smectites) is an essential step for developing the migration model long-lived corrosion and activation products, and fission products of uranium. Nuclear wastes contain the most important nuclear fission products, β-emitter 90 Sr with long half-life, biological half-life and high mobility. The present paper investigates and compares the strontium adsorption properties of bentonites of different mineral composition consisted mainly of dioctahedral and trioctahedral smectites. (author)

  2. Promoting information diffusion through interlayer recovery processes in multiplex networks

    Science.gov (United States)

    Wang, Xin; Li, Weihua; Liu, Longzhao; Pei, Sen; Tang, Shaoting; Zheng, Zhiming

    2017-09-01

    For information diffusion in multiplex networks, the effect of interlayer contagion on spreading dynamics has been explored in different settings. Nevertheless, the impact of interlayer recovery processes, i.e., the transition of nodes to stiflers in all layers after they become stiflers in any layer, still remains unclear. In this paper, we propose a modified ignorant-spreader-stifler model of rumor spreading equipped with an interlayer recovery mechanism. We find that the information diffusion can be effectively promoted for a range of interlayer recovery rates. By combining the mean-field approximation and the Markov chain approach, we derive the evolution equations of the diffusion process in two-layer homogeneous multiplex networks. The optimal interlayer recovery rate that achieves the maximal enhancement can be calculated by solving the equations numerically. In addition, we find that the promoting effect on a certain layer can be strengthened if information spreads more extensively within the counterpart layer. When applying the model to two-layer scale-free multiplex networks, with or without degree correlation, similar promoting effect is also observed in simulations. Our work indicates that the interlayer recovery process is beneficial to information diffusion in multiplex networks, which may have implications for designing efficient spreading strategies.

  3. Evaluation of caesium atomic fountain NICT-CsF1

    International Nuclear Information System (INIS)

    Kumagai, M.; Ito, H.; Kajita, M.; Hosokawa, M.

    2008-01-01

    In this paper, we describe the first caesium atomic fountain primary frequency standard NICT-CsF1 of National Institute of Information Communications Technology (NICT) in Tokyo, Japan. The structure of the NICT-CsF1 system and evaluation procedure of the systematic frequency shifts and their uncertainties are presented. Typically, NICT-CsF1 has a frequency stability of 4 * 10 -13 /τ 1/2 and a frequency uncertainty of 1.9 * 10 -15 . (authors)

  4. Alteration of isolating properties of dense smectite clay in repository environment as exemplified by seven pre-quaternary clays

    International Nuclear Information System (INIS)

    Pusch, R.; Boergesson, L.; Erlstroem, M.

    1987-12-01

    Seven pre-quaternary clays with a smectite content ranging between zero and about 25% were taken as possible reaction products resulting from chemical alteration of dense sodium bentonite. They were characterized with respect to the mineral composition and microstructural constitution and tested with reference to their hydraulic conductivity, swelling ability and creep properties. It was found that since they were all less permeable than a typical large granitic rock mass they would serve as flow barriers in a repository. Thus, even rather extreme chemical attack is not expected to eliminate the most important barrier function of Na bentonite in repository environment. However, slight mechanical disturbance of a heterogeneously altered smectite clay buffer or seal, may be critical. Thus, the investigated, less smectitic clays experienced a rather dramatic increase in hydraulic conductivity on expansion and remolding. This is explained by the inability of a microstructurally discontinuous smectite component - particularly in the Ca-form - to swell and fill voids. The minimum content of Na smectite to preserve the self-healing capacity is estimated at 15-25%. Slight or moderate cementation was indicated by two of the clays by the creep tests. At a smectite content of 15-25% it is probable that self-healing will take place after a mechanically induced breakage of the cementing bonds. The tests gave a good basis for future development of rational, routine tests as well as for a relevant characterization of buffer material candidates. (orig.)

  5. Interlayer shear of nanomaterials: Graphene-graphene, boron nitride-boron nitride and graphene-boron nitride

    Institute of Scientific and Technical Information of China (English)

    Yinfeng Li; Weiwei Zhang; Bill Guo; Dibakar Datta

    2017-01-01

    In this paper,the interlayer sliding between graphene and boron nitride (h-BN) is studied by molecular dynamics simulations.The interlayer shear force between h-BN/h-BN is found to be six times higher than that of graphene/graphene,while the interlayer shear between graphene/h-BN is approximate to that of graphene/graphene.The graphene/h-BN heterostructure shows several anomalous interlayer shear characteristics compared to its bilayer counterparts.For graphene/graphene and h-BN/h-BN,interlayer shears only exit along the sliding direction while interlayer shear for graphene/h-BN is observed along both the translocation and perpendicular directions.Our results provide significant insight into the interlayer shear characteristics of 2D nanomaterials.

  6. Radioactive caesium in Boreal forest landscapes - Dynamics and transport in food webs. Summary of research 1986-1996

    International Nuclear Information System (INIS)

    Bergman, R.; Nylen, T.; Palo, T.

    1998-12-01

    The need for - but also the paucity of - radioecological knowledge concerning the boreal forest became particularly apparent after the nuclear power plant accident in Chernobyl in April 1986. As a consequence several new projects were initiated in the Nordic countries with particular focus on the behaviour of radioactive caesium in terrestrial and aquatic systems characteristic for the Fenno-Scandinavian landscapes. Among these new projects a multi-disciplinary co-operation in Umeaa between scientists at the Swedish University of Agricultural Sciences, and the Defence Research Establishment emerged. Initially this joint work focused mainly on descriptions of the dynamic changes of the content of radioactive caesium in soil-plant and animal communities in the county of Vaesterbotten. Most of the studies have been performed at the Vindeln experimental forest, 60 km NW of Umeaa. Plants of key interest were: bilberry (Vaccinium myrtillus), birch (Betula spp.), and pine (Pinus sylvestris), and among the animals: the moose (Alces alces) and a small rodent, the forest vole (Clethrionomus glareolus). Gradually over the past ten years the research has entered the stage where the specific causes of the caesium behaviour have been addressed - partly by the help of models developed for simulating forest ecosystems, partly by complementary field experiments. This paper reviews our main findings on this theme concerning the behaviour of radioactive caesium in boreal landscapes and significant pathways to man, as has become apparent from the radioecological co-operation dating from about ten years back. A list of the publications arising from these studies since 1986 is also presented in this report

  7. Density functional theory study of inter-layer coupling in bulk tin selenide

    Science.gov (United States)

    Song, Hong-Yue; Lü, Jing-Tao

    2018-03-01

    We study the inter-layer coupling in bulk tin selenide (SnSe) through density functional theory based calculations. Different approximations for the exchange-correlation functionals and the van der Waals interaction are employed. By performing comparison with graphite, MoS2 and black phosphorus, we analyze the inter-layer coupling from different points of view, including the binding energy, the low frequency inter-layer optical phonons, and the inter-layer charge transfer. We find that, there is a strong charge transfer between layers of SnSe, resulting in the strongest inter-layer coupling. Moreover, the charge transfer renders the inter-layer coupling in SnSe not of van der Waals type. Mechanical exfoliation has been used to fabricate mono- or few-layer graphene, MoS2 and black phosphorus. But, our results show that it may be difficult to apply similar technique to SnSe.

  8. Behavioural Changes in Rats Internally Contaminated with Caesium-137

    International Nuclear Information System (INIS)

    Ramboiu, S.

    2001-01-01

    Full text: The effect of low doses of 137 Cs on the exercise performances, behavioural and learning processes in rats is analysed. The experiments were performed on albino male and female Wistar rats. The animals were divided as follows: two groups, M 1 and F 1 (males and females) internally contaminated with 490 Bq 137 Cs by milk ingestion during 34 days, groups M 2 and F 2 , internally contaminated with 283 Bq by ingestion of milk during 38 days and two control groups. The duration of forced swimming, the active avoidance reaction and the total latency time in the shuttle-box and the score of aggressive behaviour were analysed. The following results were obtained: (1) the duration of forced swimming decreased significantly in the contaminated groups as compared with controls. (2) The active avoidance reaction in the shuttle-box increased in female groups and decrease in male groups. (3) The total latency time of the same reaction was lower in animals internally contaminated with 137 Cs in the first day of learning. (4) The score of aggressive behavioural rise significantly, especially in female groups. The results can be explained by neurotoxic action of the caesium on several central neural areas including monoaminergic and endocrine mechanisms and sex dependence of caesium accumulation in the organism. (author)

  9. Temperature-dependent residual shear strength characteristics of smectite-rich landslide soils

    Science.gov (United States)

    Shibasaki, Tatsuya; Matsuura, Sumio; Okamoto, Takashi

    2015-04-01

    On gentle clayey slopes in weathered argillaceous rock areas, there exist many landslides which repeatedly reactivate with slow movement. The slip surface soils of these landslides are sometimes composed dominantly of swelling clay mineral (smectite) which is well known to show extremely low residual friction angle. From field data monitored at landslide sites in Japan, it has become clear that some landslides with relatively shallow slip surface begin to move and become active in late autumn or early winter every year. In such cases, the triggering mechanisms of landslides have not been understood well enough, because landslide initiation and movement are not always clearly linked with rises in pore water pressures (ground water levels). In this study, we focus on the influence of seasonal variation in ground temperature on slope stability and have investigated the effect of temperature on the shear strength of slip surface soils. Undisturbed soil samples were collected by boring from the Busuno landslide in Japan. We performed box shear experiments on undisturbed slip surface soils at low temperature ranges (approximately 5-25 °C). XRD analysis revealed that these soils contain high fraction of smectite. Slickensided slip surface within test specimen was coincided with the shearing plane of the shear box and shear displacement was applied precisely along the localized slip surface. Experiments were performed under slow shearing rate condition (0.005mm/min) and the results showed that shear strength decreased with decreasing temperature. Temperature effect was rather significant on frictional angle than on cohesion. Ring shear experiments were also performed on normally-consolidated remoulded samples. Under residual strength condition, temperature-change experiments (cooling-event tests) ranging approximately from 5 to 25 °C were performed on smectite-rich landslide soils and commercial bentonites. As well as the results by box shear test, shear weakening

  10. Caesium-137 as an indicator of geomorphic processes in a drainage basin system

    International Nuclear Information System (INIS)

    Campbell, B.L.; Elliott, G.L.

    1982-01-01

    Caesium-137 from fallout from nuclear weapons tests is adsorbed on fine sediments and becomes an effective tracer. It is hypothesised that within a drainage basin, sites undergoing little or no erosion accumulate Cs-137 in their upper layers; cultivated soils will have Cs-137 uniformly distributed within the cultivated layer; eroded soils, cultivated or not, will have relatively less Cs-137, depending on the severity of erosion. Accumulated sediments will have characteristic Cs-137 profiles reflecting temporal fallout variations and sedimentation history. This hypothetical model is largely confirmed by results from Maluna Creek basin, where erosion and accumulation of sediments has taken place. Soils under viticulture have about one third the Cs-137 content of soils with grass cover, indicating more severe erosion under cultivation. Caesium-137 profiles in alluvial fan and flood plain deposits correlate with sediment layers and known cultivation history

  11. The transition time induced narrow linewidth of the electromagnetically induced transparency in caesium vapour

    International Nuclear Information System (INIS)

    Li Luming; Peng Xiang; Liu Cheng; Guo Hong; Chen Xuzong

    2004-01-01

    We observed a narrow linewidth (∼60 kHz) in a Doppler-broadened system showing electromagnetically induced transparency in caesium atomic vapour. The transition time induced reduction of the linewidth is illustrated both theoretically and experimentally

  12. Effect of interlayer bonding quality of asphalt layers on pavement performance

    Science.gov (United States)

    Jaskula, Piotr; Rys, Dawid

    2017-09-01

    The quality of interlayer bonding at the interfaces between the asphalt layers in flexible pavements affects the overall pavement performance. Lack or partial lack of interlayer bonding between asphalt layers can cause pavement’s premature failures such as rutting, slippage of the wearing course, cracking or simply a reduction in the calculated fatigue life of the pavement structure. This paper shows the case studies of investigation of actual or potential premature failure of newly reconstructed and constructed pavements where low quality of interlayer bonding has a dominant meaning. In situ and laboratory tests were performed and followed by analytical calculation of pavement structure where thicknesses of layers and maximum shear strengths obtained from the tests were used. During the investigation it was found out that a low quality of tack coat as well as the same aggregate gradation in the bonded asphalt mixtures were the main reasons behind the weak quality of interlayer bonding. Partial interlayer bonding has a strong influence on reduction of calculated fatigue life of pavement. The summary of the paper includes recommendations on how to avoid the low quality of interlayer bonding of asphalt layers.

  13. The selectivity of zirconium phosphate for caesium in electrochemical ion exchange

    International Nuclear Information System (INIS)

    Lain, M.J.

    1988-11-01

    The properties of amorphous zirconium phosphate are investigated as an inorganic ion exchanger for use in liquid waste treatment by electrochemical ion exchange. Experiments to determine and increase the selectivity for caesium exchange over sodium are discussed, including various pulsed waveforms and studies with rotating membranes. Automation of a sampling system with pH and atomic absorption measurements is described. (author)

  14. Effects of lactic acid bacteria and smectite after aflatoxin B1 challenge on the growth performance, nutrient digestibility and blood parameters of broilers.

    Science.gov (United States)

    Liu, N; Ding, K; Wang, J; Deng, Q; Gu, K; Wang, J

    2018-04-11

    This study aimed to investigate the effect of lactic acid bacteria (LAB) and smectite on the growth performance, nutrient digestibility and blood parameters of broilers that were fed diets contaminated with aflatoxin B 1 (AFB 1 ). A total of 480 newly hatched male Arbor Acres broilers were randomly allocated into four groups with six replicates of 20 chicks each. The broilers were fed diets with the AFB 1 (40 μg/kg) challenge or without (control) it and supplemented with smectite (3.0 g/kg) or LAB (4.0 × 10 10  CFU/kg) based on the AFB 1 diet. The trial lasted for 42 days. The results showed that during days 1-42 of AFB 1 challenge, the feed intake (FI) and body weight gain (BWG) were depressed (p smectite increased (p smectite. LAB and smectite also increased (p smectite affected (p smectite have similar effects on the growth and health of the broilers, suggesting that LAB could be an alternative against AFB 1 in commercial animal feeds. © 2018 Blackwell Verlag GmbH.

  15. Role of interatomic bonding in the mechanical anisotropy and interlayer cohesion of CSH crystals

    Energy Technology Data Exchange (ETDEWEB)

    Dharmawardhana, C.C. [Department of Physics and Astronomy, University of Missouri—Kansas City, Kansas City, MO 64110 (United States); Misra, A. [Department of Civil, Environmental, and Architectural Engineering, University of Kansas, Lawrence, KS 66045 (United States); Aryal, S.; Rulis, P. [Department of Physics and Astronomy, University of Missouri—Kansas City, Kansas City, MO 64110 (United States); Ching, W.Y., E-mail: ccdxz8@mail.umkc.edu [Department of Physics and Astronomy, University of Missouri—Kansas City, Kansas City, MO 64110 (United States)

    2013-10-15

    Atomic scale properties of calcium silicate hydrate (CSH), the main binding phase of hardened Portland cement, are not well understood. Over a century of intense research has identified almost 50 different crystalline CSH minerals which are mainly categorized by their Ca/Si ratio. The electronic structure and interatomic bonding in four major CSH crystalline phases with structures close to those found in hardened cement are investigated via ab initio methods. Our result reveals the critical role of hydrogen bonding and importance of specifying precise locations for water molecules. Quantitative analysis of contributions from different bond types to the overall cohesion shows that while the Si-O covalent bonds dominate, the hydrogen bonding and Ca-O bonding are also very significant. Calculated results reveal the correlation between bond topology and interlayer cohesion. The overall bond order density (BOD) is found to be a more critical measure than the Ca/Si ratio in classifying different CSH crystals.

  16. Magnetic properties of nickel halide hydrates including deuteration effects

    Energy Technology Data Exchange (ETDEWEB)

    DeFotis, G.C., E-mail: gxdefo@wm.edu [Chemistry Department, College of William & Mary, Williamsburg, VA, 23187 United States (United States); Van Dongen, M.J.; Hampton, A.S.; Komatsu, C.H.; Trowell, K.T.; Havas, K.C.; Davis, C.M.; DeSanto, C.L. [Chemistry Department, College of William & Mary, Williamsburg, VA, 23187 United States (United States); Hays, K.; Wagner, M.J. [Chemistry Department, George Washington University, Washington, DC, 20052 United States (United States)

    2017-01-01

    Magnetic measurements on variously hydrated nickel chlorides and bromides, including deuterated forms, are reported. Results include locations and sizes of susceptibility maxima, T{sub max} and χ{sub max}, ordering temperatures T{sub c}, Curie constants and Weiss theta in the paramagnetic regime, and primary and secondary exchange interactions from analysis of low temperature data. For the latter a 2D Heisenberg model augmented by interlayer exchange in a mean-field approximation is applied. Magnetization data to 16 kG as a function of temperature show curvature and hysteresis characteristics quite system dependent. For four materials high field magnetization data to 70 kG at 2.00 K are also obtained. Comparison is made with theoretical relations for spin-1 models. Trends are apparent, primarily that T{sub max} of each bromide hydrate is less than for the corresponding chloride, and that for a given halide nD{sub 2}O (n=1 or 2) deuterates exhibit lesser T{sub max} than do nH{sub 2}O hydrates. A monoclinic unit cell determined from powder X-ray diffraction data on NiBr{sub 2}·2D{sub 2}O is different from and slightly larger than that of NiBr{sub 2}·2H{sub 2}O. This provides some rationale for the difference in magnetic properties between these. - Highlights: • The magnetism of Ni(II) chloride and bromide dihydrates and monohydrates is studied. • Effects of replacing H{sub 2}O by D{sub 2}O are examined for both hydration states and both halides. • Exchange interactions in bromides are weaker than in corresponding chlorides. • Exchange interactions are weaker in D{sub 2}O than in corresponding H{sub 2}O containing systems. • The unit cell of NiBr{sub 2}·2D{sub 2}O is different from and slightly larger than that of NiBr{sub 2}·2H{sub 2}O.

  17. Effect of sputtered titanium interlayers on the properties of nanocrystalline diamond films

    Energy Technology Data Exchange (ETDEWEB)

    Li, Cuiping, E-mail: licp226@126.com, E-mail: limingji@163.com; Li, Mingji, E-mail: licp226@126.com, E-mail: limingji@163.com; Wu, Xiaoguo; Yang, Baohe [Tianjin Key Laboratory of Film Electronic and Communicate Devices, School of Electronics Information Engineering, Tianjin University of Technology, Tianjin 300384 (China); Dai, Wei; Xu, Sheng [Tianjin Key Laboratory of Film Electronic and Communicate Devices, School of Electronics Information Engineering, Tianjin University of Technology, Tianjin 300384 (China); College of Precision Instrument and Optoelectronics Engineering, Tianjin University, Tianjin 300072 (China); Li, Hongji [Tianjin Key Laboratory of Organic Solar Cells and Photochemical Conversion, School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384 (China)

    2016-04-07

    Ti interlayers with different thicknesses were sputtered on Si substrates and then ultrasonically seeded in a diamond powder suspension. Nanocrystalline diamond (NCD) films were deposited using a dc arc plasma jet chemical vapor deposition system on the seeded Ti/Si substrates. Atomic force microscopy and scanning electron microscopy tests showed that the roughness of the prepared Ti interlayer increased with increasing thickness. The effects of Ti interlayers with various thicknesses on the properties of NCD films were investigated. The results show nucleation, growth, and microstructure of the NCD films are strongly influenced by the Ti interlayers. The addition of a Ti interlayer between the Si substrate and the NCD films can significantly enhance the nucleation rate and reduce the surface roughness of the NCD. The NCD film on a 120 nm Ti interlayer possesses the fastest nucleation rate and the smoothest surface. Raman spectra of the NCD films show trans-polyacetylene relevant peaks reduce with increasing Ti interlayer thickness, which can owe to the improvement of crystalline at grain boundaries. Furthermore, nanoindentation measurement results show that the NCD film on a 120 nm Ti interlayer displays a higher hardness and elastic modulus. High resolution transmission electron microscopy images of a cross-section show that C atoms diffuse into the Ti layer and Si substrate and form TiC and SiC hard phases, which can explain the enhancement of mechanical properties of NCD.

  18. Reconsideration on Hydration of Sodium Ion: From Micro-Hydration to Bulk Hydration

    Science.gov (United States)

    Yongquan, Zhou; Chunhui, Fang; Yan, Fang; Fayan, Zhu; Haiwen, Ge; Hongyan, Liu

    2017-12-01

    Micro hydration structures of the sodium ion, [Na(H2O) n ]+, n = 1-12, were probed by density functional theory (DFT) at B3LYP/aug-cc-pVDZ level in both gaseous and aqueous phase. The predicted equilibrium sodium-oxygen distance of 0.240 nm at the present level of theory. The four-, five- and six-coordinated cluster can transform from each other at the ambient condition. The analysis of the successive water binding energy and natural charge population (NBO) on Na+ clearly shows that the influence of Na+ on the surrounding water molecules goes beyond the first hydration shell with the hydration number of 6. The Car-Parrinello molecular dynamic simulation shows that only the first hydration sphere can be found, and the hydration number of Na+ is 5.2 and the hydration distance ( r Na-O) is 0.235 nm. All our simulations mentioned in the present paper show an excellent agreement with the diffraction result from X-ray scattering study.

  19. Dehydration of moulding sand in simulated casting process examined with neutron radiography

    Energy Technology Data Exchange (ETDEWEB)

    Schillinger, B., E-mail: Burkhard.Schillinger@frm2.tum.de [Technische Universitaet Muenchen, FRM II and Faculty for Physics E21, Lichtenbergstr. 1, 85748 Garching (Germany); Calzada, E. [Technische Universitaet Muenchen, FRM II and Faculty for Physics E21, Lichtenbergstr. 1, 85748 Garching (Germany); Eulenkamp, C.; Jordan, G.; Schmahl, W.W. [Ludwig-Maximilians-Universitaet Muenchen, Department fuer Geo- und Umweltwissenschaften, Sektion Kristallographie, Theresienstr. 41, 80333 Muenchen (Germany)

    2011-09-21

    Natural bentonites are an important material in the casting industry. Smectites as the main component of bentonites plasticize and stabilise sand moulds. Pore water as well as interlayer water within the smectites are lost as a function of time, location and temperature. Although rehydration of the smectites should be a reversible process, the industrially dehydrated smectites lose their capability to reabsorb water. This limits the number of possible process cycles of the mould material. A full understanding of the dehydration process would help to optimise the amount of fresh material to be added and thus save resources. A simulated metal casting was investigated with neutron radiography at the ANTARES neutron imaging facility of the FRM II reactor of Technische Universitaet Muenchen, Germany.

  20. Microbial reduction of structural Fe3+ in nontronite by a thermophilic bacterium and its role in promoting the smectite to illite reaction

    Science.gov (United States)

    Zhang, G.; Dong, H.; Kim, J.; Eberl, D.D.

    2007-01-01

    The illitization process of Fe-rich smectite (nontronite NAu-2) promoted by microbial reduction of structural Fe3+ was investigated by using a thermophilic metal-reducing bacterium, Thermoanaerobacter ethanolicus, isolated from the deep subsurface. T. ethanolicus was incubated with lactate as the sole electron donor and structural Fe3+ in nontronite as the sole electron acceptor, and anthraquinone-2, 6-disulfonate (AQDS) as an electron shuttle in a growth medium (pH 6.2 and 9.2, 65 ??C) with or without an external supply of Al and K sources. With an external supply of Al and K, the extent of reduction of Fe3+ in NAu-2 was 43.7 and 40.4% at pH 6.2 and 9.2, respectively. X-ray diffraction and scanning and transmission electron microscopy revealed formation of discrete illite at pH 9.2 with external Al and K sources, while mixed layers of illite/smectite or highly charged smectite were detected under other conditions. The morphology of biogenic illite evolved from lath and flake to pseudo-hexagonal shape. An external supply of Al and K under alkaline conditions enhances the smectite-illite reaction during microbial Fe3+ reduction of smectite. Biogenic SiO2 was observed as a result of bioreduction under all conditions. The microbially promoted smectite-illite reaction proceeds via dissolution of smectite and precipitation of illite. Thermophilic iron reducing bacteria have a significant role in promoting the smectite to illite reaction under conditions common in sedimentary basins.

  1. Selective Dissolution Techniques, X-Ray Diffraction and Moessbauer Spectroscopy Studies of Forms of Fe in Particle-Size Fractions of an Entic Haplustoll

    International Nuclear Information System (INIS)

    Acebal, S. G.; Aguirre, M. E.; Santamaria, R. M.; Mijovilovich, A.; Petrick, S.; Saragovi, C.

    2003-01-01

    Particle-size fractions (o = mean diameter, 5-2 μm, 2-1 μm, and 57 Fe Moessbauer spectroscopy (MS). Quartz, feldspar, smectite, illite and interstratified illite-smectite are the dominant minerals whereas Fe oxides and oxy-hydroxides are present in low concentration but increase as particle size decreases. Poorly crystallized oxides (highly Al-substituted hematite and goethite) amounts are lower, comparable to or slightly higher than the hematite amounts in the o 5-2 μm, 2-1 μm and 3+ and Fe 2+ are associated to the clay minerals and/or hydroxyl-interlayered 2:1 type material present; part of this Fe 3+ is located in the hydroxy-interlayers its amount being higher in the smallest fraction. Any possible changes after the PY and NaOH treatments were not detected by MS.

  2. Thermogravimetric analysis and dissociation pressure of caesium trihalides

    International Nuclear Information System (INIS)

    Harris, G.S.; McKechnie, J.S.

    1982-01-01

    We have carried out a thermogravimetric study of caesium trihalides to obtain, from the procedural decomposition temperatures, an order of apparent thermal stability which could be compared with the order of thermodynamic stability obtained from vapour pressure measurements. Thermogravimetric analysis could also prove to be a useful method for rapid analysis of metal polyhalides. The thermograms indicated a one-step decomposition for each compound; the procedural decomposition temperatures and percentage weight losses obtained are given. Dissociation pressures were measured and values of equilibrium constant and enthalpy of dissociation were calculated. The results are given. The 'stability' order obtained is discussed. (U.K.)

  3. Electrical properties of a charge-transfer interlayer modified organic heterojunction

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Shuwen; Salzmann, Ingo; Koch, Norbert [Humboldt-Universitaet zu Berlin (Germany). Institut f. Physik; Vollmer, Antje [HZB-BESSY, Berlin (Germany)

    2010-07-01

    We investigated the effect of a thin interlayer (ca. monolayer) of tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) between prototypical hole and electron transport layers (HTL and ETL) on interface energetics and current transport. As HTL we used 4,4{sup '},4''-tris(N,N-diphenyl-amino)triphenylamine (TDATA) and tris (8-hydroxyquinoline)aluminium (Alq{sub 3}) as ETL, which are commonly employed in organic light emitting diodes. The hole injection barrier into TDATA is 0.5 eV, as measured by photoemission spectroscopy. Deposition of an F4-TCNQ interlayer on top of TDATA does not further change the energy level position. However, after applying the F4-TCNQ interlayer the energy levels of Alq3 deposited on top of TDATA are 0.15 eV closer to the Fermi-level than without the interlayer. Diodes fabricated without interlayer had a 0.6 V higher onset-voltage one order of magnitude lower current density than those with F4-TCNQ. These observations can be rationalized by an increased (non-radiative) electron-hole recombination rate at the modified organic heterojunction and a changed internal electric field distribution.

  4. Redox properties of structural Fe in clay minerals: 3. Relationships between smectite redox and structural properties.

    Science.gov (United States)

    Gorski, Christopher A; Klüpfel, Laura E; Voegelin, Andreas; Sander, Michael; Hofstetter, Thomas B

    2013-01-01

    Structural Fe in clay minerals is an important redox-active species in many pristine and contaminated environments as well as in engineered systems. Understanding the extent and kinetics of redox reactions involving Fe-bearing clay minerals has been challenging due to the inability to relate structural Fe(2+)/Fe(total) fractions to fundamental redox properties, such as reduction potentials (EH). Here, we overcame this challenge by using mediated electrochemical reduction (MER) and oxidation (MEO) to characterize the fraction of redox-active structural Fe (Fe(2+)/Fe(total)) in smectites over a wide range of applied EH-values (-0.6 V to +0.6 V). We examined Fe(2+)/Fe(total )- EH relationships of four natural Fe-bearing smectites (SWy-2, SWa-1, NAu-1, NAu-2) in their native, reduced, and reoxidized states and compared our measurements with spectroscopic observations and a suite of mineralogical properties. All smectites exhibited unique Fe(2+)/Fe(total) - EH relationships, were redox active over wide EH ranges, and underwent irreversible electron transfer induced structural changes that were observable with X-ray absorption spectroscopy. Variations among the smectite Fe(2+)/Fe(total) - EH relationships correlated well with both bulk and molecular-scale properties, including Fe(total) content, layer charge, and quadrupole splitting values, suggesting that multiple structural parameters determined the redox properties of smectites. The Fe(2+)/Fe(total) - EH relationships developed for these four commonly studied clay minerals may be applied to future studies interested in relating the extent of structural Fe reduction or oxidation to EH-values.

  5. Tunneling Photocurrent Assisted by Interlayer Excitons in Staggered van der Waals Hetero-Bilayers.

    Science.gov (United States)

    Luong, Dinh Hoa; Lee, Hyun Seok; Neupane, Guru Prakash; Roy, Shrawan; Ghimire, Ganesh; Lee, Jin Hee; Vu, Quoc An; Lee, Young Hee

    2017-09-01

    Vertically stacked van der Waals (vdW) heterostructures have been suggested as a robust platform for studying interfacial phenomena and related electric/optoelectronic devices. While the interlayer Coulomb interaction mediated by the vdW coupling has been extensively studied for carrier recombination processes in a diode transport, its correlation with the interlayer tunneling transport has not been elucidated. Here, a contrast is reported between tunneling and drift photocurrents tailored by the interlayer coupling strength in MoSe 2 /MoS 2 hetero-bilayers (HBs). The interfacial coupling modulated by thermal annealing is identified by the interlayer phonon coupling in Raman spectra and the emerging interlayer exciton peak in photoluminescence spectra. In strongly coupled HBs, positive photocurrents are observed owing to the inelastic band-to-band tunneling assisted by interlayer excitons that prevail over exciton recombinations. By contrast, weakly coupled HBs exhibit a negative photovoltaic diode behavior, manifested as a drift current without interlayer excitonic emissions. This study sheds light on tailoring the tunneling transport for numerous optoelectronic HB devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Sources of present Chernobyl-derived caesium concentrations in surface air and deposition samples

    International Nuclear Information System (INIS)

    Hoetzl, H.; Rosner, G.; Winkler, R.; Gesellschaft fuer Strahlen- und Umweltforschung mbH Muenchen, Neuherberg

    1992-01-01

    The sources of Chernobyl-derived caesium concentrations in air and deposition samples collected from mid-1986 to end-1990 at Munich- Neuherberg, Germany, were investigated. Local resuspension has been found to be the main source. By comparison with deposition data from other locations it is estimated that within a range from 20 Bq m -2 to 60 kBq m -2 of initially deposited 137 Cs activity ∼2% is re-deposited by the process of local resuspension in Austria, Germany, Japan and United Kingdom, while significantly higher total resuspension is to be expected for Denmark and Finland. Stratospheric contribution to present concentrations is shown to be negligible. This is confirmed by cross correlation analysis between the time series of 137 Cs in air and precipitation before and after the Chernobyl accident and the respective time series of cosmogenic 7 Be, which is an indicator of stratospheric input. Seasonal variations of caesium concentrations with maxima in winter were observed. (author). 32 refs.; 5 figs.; 1 tab

  7. Smectite clay-inorganic nanoparticle mixed suspensions : Phase behaviour and rheology

    NARCIS (Netherlands)

    Bailey, Louise; Lekkerkerker, Henk N W; Maitland, Geoffrey C.

    2015-01-01

    Smectite clay minerals and their suspensions have long been of both great scientific and applications interest and continue to display a remarkable range of new and interesting behaviour. Recently there has been an increasing interest in the properties of mixed suspensions of such clays with

  8. Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light.

    Science.gov (United States)

    Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

    2015-04-28

    Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe(3+)>Al(3+)>Cu(2+)>Ca(2+)>K(+)>Na(+), which is consistent with the binding energy of cation-π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation-π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na(+)-smectite and K(+)-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe(3+), Al(3+), and Cu(2+) are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O2(-) , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Human metabolism of caesium

    International Nuclear Information System (INIS)

    Raeaef, C.L.; Falk, R.; Lauridsen, Bente; Rahola, T.; Soogard-Hansen, J.

    2006-04-01

    A study of the human biokinetics of caesium in two forms, i.) incorporated in foodstuff (137Cs in perch and mushrooms) and ii.) in ionic state ( 134 Cs in aqueous solution) has been carried out at the department of Radiation Physics in Malmoe, starting in 2001. The results of the pilot study were published in 2004, and a continuation of that study has now been carried out by means of NKS funding (NKS-B Cskinetik). The aim is to, i.) investigate whether Scandinavian populations exhibit shorter biological half-time of radiocaesium than other populations; ii.) extend the biokinetic study to additional human subjects from the other Nordic countries. Results from the continued study further indicate a near complete absorption of radiocaesium in the gastro-intestinal tract, be it in ion state or contained in food matrix. So far, the literature survey of Nordic studies on biokinetics of Cs suggests that the biological half time is somewhat shorter among Scandinavian males (84 days vs. ICRP-value of 110 days), although females do not exhibit any significant difference (64 days vs ICRP value of 65 days). (au)

  10. Human metabolism of caesium

    Energy Technology Data Exchange (ETDEWEB)

    Raeaef, C.L. [Lund Univ., Dept. of Radiation Physics in Malmoe (Sweden); Falk, R. [Swedish Radiation Protection Authority (Sweden); Lauridsen, Bente [Risoe National Lab. (Denmark); Rahola, T. [STUK - Radiation and Nuclear Safety Authority (Finland); Soogard-Hansen, J. [NRPA - Norwegian Radiation Protection Authority (Norway)

    2006-04-15

    A study of the human biokinetics of caesium in two forms, i.) incorporated in foodstuff (137Cs in perch and mushrooms) and ii.) in ionic state ({sup 134}Cs in aqueous solution) has been carried out at the department of Radiation Physics in Malmoe, starting in 2001. The results of the pilot study were published in 2004, and a continuation of that study has now been carried out by means of NKS funding (NKS-B Cskinetik). The aim is to, i.) investigate whether Scandinavian populations exhibit shorter biological half-time of radiocaesium than other populations; ii.) extend the biokinetic study to additional human subjects from the other Nordic countries. Results from the continued study further indicate a near complete absorption of radiocaesium in the gastro-intestinal tract, be it in ion state or contained in food matrix. So far, the literature survey of Nordic studies on biokinetics of Cs suggests that the biological half time is somewhat shorter among Scandinavian males (84 days vs. ICRP-value of 110 days), although females do not exhibit any significant difference (64 days vs ICRP value of 65 days). (au)

  11. Hydrate-CASM for modeling Methane Hydrate-Bearing Sediments

    Science.gov (United States)

    De La Fuente Ruiz, M.; Vaunat, J.; Marin Moreno, H.

    2017-12-01

    A clear understanding of the geomechanical behavior of methane hydrate-bearing sediments (MHBS) is crucial to assess the stability of the seafloor and submarine infrastructures to human and natural loading changes. Here we present the Hydrate-CASM, a new elastoplastic constitutive model to predict the geomechanical behavior of MHBS. Our model employs the critical state model CASM (Clay and Sand Model) because of its flexibility in describing the shape of the yield surface and its proven ability to predict the mechanical behavior of sands, the most commercially viable hydrate reservoirs. The model considers MHBS as a deformable elastoplastic continuum, and hydrate-related changes in the stress-strain behavior are predicted by a densification mechanism. The densification attributes the mechanical contribution of hydrate to; a reduction of the available void ratio; a decrease of the swelling line slope; and an increase of the volumetric yield stress. It is described by experimentally derived physical parameters except from the swelling slope coefficient that requires empirical calibration. The Hydrate-CASM is validated against published triaxial laboratory tests performed at different confinement stresses, hydrate saturations, and hydrate morphologies. During the validation, we focused on capturing the mechanical behavior of the host sediment and consider perturbations of the sediment's mechanical properties that could result from the sample preparation. Our model successfully captures the experimentally observed influence of hydrate saturation in the magnitude and trend of the stiffness, shear strength, and dilatancy of MHBS. Hence, we propose that hydrate-related densification changes might be a major factor controlling the geomechanical response of MHBS.

  12. Direct observation of grafting interlayer phosphate in Mg/Al layered double hydroxides

    International Nuclear Information System (INIS)

    Shimamura, Akihiro; Kanezaki, Eiji; Jones, Mark I.; Metson, James B.

    2012-01-01

    The grafting of interlayer phosphate in synthetic Mg/Al layered double hydroxides with interlayer hydrogen phosphate (LDH-HPO 4 ) has been studied by XRD, TG/DTA, FT-IR, XPS and XANES. The basal spacing of crystalline LDH-HPO 4 decreases in two stages with increasing temperature, from 1.06 nm to 0.82 nm at 333 K in the first transition, and to 0.722 nm at 453 K in the second. The first stage occurs due to the loss of interlayer water and rearrangement of the interlayer HPO 4 2− . In the second transition, the interlayer phosphate is grafted to the layer by the formation of direct bonding to metal cations in the layer, accompanied by a change in polytype of the crystalline structure. The grafted phosphate becomes immobilized and cannot be removed by anion-exchange with 1-octanesulfonate. The LDH is amorphous at 743 K but decomposes to Mg 3 (PO 4 ) 2 , AlPO 4 , MgO and MgAl 2 O 4 after heated to 1273 K. - Graphical abstract: The cross section of the synthetic Mg, Al layered double hydroxides in Phase 1, with interlayer hydrogen phosphate Phase 2, and with grafted phosphate, Phase 3. Highlights: ► The grafting of hydrogen phosphate intercalated Mg/Al-LDH has been studied. ► The basal spacing of crystalline LDH-HPO 4 decreases in two stages with increasing temperature. ► The first decrease is due to loss of interlayer water, the second is attributed to phosphate grafting. ► The grafted interlayer phosphate becomes immobilized and cannot be removed by anion-exchange.

  13. Effects of Electrospun Carbon Nanofibers’ Interlayers on High-Performance Lithium–Sulfur Batteries

    Directory of Open Access Journals (Sweden)

    Tianji Gao

    2017-03-01

    Full Text Available Two different interlayers were introduced in lithium–sulfur batteries to improve the cycling stability with sulfur loading as high as 80% of total mass of cathode. Melamine was recommended as a nitrogen-rich (N-rich amine component to synthesize a modified polyacrylic acid (MPAA. The electrospun MPAA was carbonized into N-rich carbon nanofibers, which were used as cathode interlayers, while carbon nanofibers from PAA without melamine was used as an anode interlayer. At the rate of 0.1 C, the initial discharge capacity with two interlayers was 983 mAh g−1, and faded down to 651 mAh g−1 after 100 cycles with the coulombic efficiency of 95.4%. At the rate of 1 C, the discharge capacity was kept to 380 mAh g−1 after 600 cycles with a coulombic efficiency of 98.8%. It apparently demonstrated that the cathode interlayer is extremely effective at shutting down the migration of polysulfide ions. The anode interlayer induced the lithium ions to form uniform lithium metal deposits confined on the fiber surface and in the bulk to strengthen the cycling stability of the lithium metal anode.

  14. Electronic cooling via interlayer Coulomb coupling in multilayer epitaxial graphene

    Science.gov (United States)

    Mihnev, Momchil T.; Tolsma, John R.; Divin, Charles J.; Sun, Dong; Asgari, Reza; Polini, Marco; Berger, Claire; de Heer, Walt A.; MacDonald, Allan H.; Norris, Theodore B.

    2015-01-01

    In van der Waals bonded or rotationally disordered multilayer stacks of two-dimensional (2D) materials, the electronic states remain tightly confined within individual 2D layers. As a result, electron–phonon interactions occur primarily within layers and interlayer electrical conductivities are low. In addition, strong covalent in-plane intralayer bonding combined with weak van der Waals interlayer bonding results in weak phonon-mediated thermal coupling between the layers. We demonstrate here, however, that Coulomb interactions between electrons in different layers of multilayer epitaxial graphene provide an important mechanism for interlayer thermal transport, even though all electronic states are strongly confined within individual 2D layers. This effect is manifested in the relaxation dynamics of hot carriers in ultrafast time-resolved terahertz spectroscopy. We develop a theory of interlayer Coulomb coupling containing no free parameters that accounts for the experimentally observed trends in hot-carrier dynamics as temperature and the number of layers is varied. PMID:26399955

  15. Long-term loss rates of radioisotopes of cobalt, zinc, ruthenium, caesium and silver by Mytilus edulis under field conditions

    International Nuclear Information System (INIS)

    Dahlgaard, H.

    1999-01-01

    Long-term loss rates of cobalt, zinc, ruthenium, caesium and silver by Mytilus edulis soft parts as well as shells were measured under field conditions in the Mediterranean Sea at Monaco during a period of 13 months after experimental contamination. For all 5 elements, the loss could be described by two exponential functions for the soft parts and one for the shells. Biological half lives for the long-lived compartment ranged from ∼20 days for caesium to 100 - 200 days for cobalt, zinc, ruthenium and silver for soft parts as well as for shells. A comparison with results from similar experiments performed under very different environmental conditions in the Baltic Sea indicated that caesium and maybe silver had a faster turnover in the warm and saline Mediterranean, whereas loss rates for cobalt and zinc were comparable. It is argued, that reliable deduction of loss rates require experiments running over several months to a year, and it is pointed out that shorter term experiments - even up to 3 months - may give biased results. (author)

  16. Testing candidate interlayers for an enhanced water-cooled divertor target

    International Nuclear Information System (INIS)

    Hancock, David; Barrett, Tom; Foster, James; Fursdon, Mike; Keech, Gregory; McIntosh, Simon; Timmis, William; Rieth, Michael; Reiser, Jens

    2015-01-01

    Highlights: • We introduce an optimised divertor target concept: the “Thermal Break”. • We suggest a candidate interlayer material for this concept: FeltMetal. • We describe a bespoke rig for testing the thermal conductivity of this material. • We present preliminary results for a number of samples. - Abstract: The design of a divertor target for DEMO remains one of the most challenging engineering tasks to be overcome on the path to fusion power. Under the European DEMO programme, a promising concept known as Thermal Break has been developed at CCFE. This concept is a variation of the ITER tungsten divertor in which the pure Copper interlayer between Copper Chrome Zirconium coolant pipe and Tungsten monoblock armour is replaced with a low thermal conductivity compliant interlayer, with the aim of reducing the thermal mismatch stress between the armour and structure. One candidate material for this interlayer is FeltMetal™ (Technetics Group, USA). This material consists of an amorphous matrix of fine copper wires which are sintered onto a thin copper foil, creating a sheet of approximately 1 mm thickness. FeltMetal has been successfully used for many years to provide compliant sliding electrical contacts for the MAST TF coils and on ALCATOR C-Mod and extensive material testing has therefore been undertaken to quantify thermal and mechanical properties. These tests, however, have not been performed under vacuum or DEMO-relevant conditions. A bespoke experimental test rig has therefore been designed and constructed with which to measure the interlayer thermal conductance as a function of temperature and pressure under vacuum conditions. The design of this apparatus and the results of experiments on FeltMetal as well as other candidate interlayers are presented here. In parallel, joint mockups using the candidate interlayers have been prepared and Thermal Break divertor target mockups have been manufactured, requiring the development of a dedicated

  17. Testing candidate interlayers for an enhanced water-cooled divertor target

    Energy Technology Data Exchange (ETDEWEB)

    Hancock, David, E-mail: david.hancock@ccfe.ac.uk [CCFE, Culham Science Centre, Oxfordshire OX14 3DB (United Kingdom); Barrett, Tom; Foster, James; Fursdon, Mike; Keech, Gregory; McIntosh, Simon; Timmis, William [CCFE, Culham Science Centre, Oxfordshire OX14 3DB (United Kingdom); Rieth, Michael; Reiser, Jens [Karlsruhe Institute of Technology, IAM-AWP, P.O. Box 3640, 76021 Karlsruhe (Germany)

    2015-10-15

    Highlights: • We introduce an optimised divertor target concept: the “Thermal Break”. • We suggest a candidate interlayer material for this concept: FeltMetal. • We describe a bespoke rig for testing the thermal conductivity of this material. • We present preliminary results for a number of samples. - Abstract: The design of a divertor target for DEMO remains one of the most challenging engineering tasks to be overcome on the path to fusion power. Under the European DEMO programme, a promising concept known as Thermal Break has been developed at CCFE. This concept is a variation of the ITER tungsten divertor in which the pure Copper interlayer between Copper Chrome Zirconium coolant pipe and Tungsten monoblock armour is replaced with a low thermal conductivity compliant interlayer, with the aim of reducing the thermal mismatch stress between the armour and structure. One candidate material for this interlayer is FeltMetal™ (Technetics Group, USA). This material consists of an amorphous matrix of fine copper wires which are sintered onto a thin copper foil, creating a sheet of approximately 1 mm thickness. FeltMetal has been successfully used for many years to provide compliant sliding electrical contacts for the MAST TF coils and on ALCATOR C-Mod and extensive material testing has therefore been undertaken to quantify thermal and mechanical properties. These tests, however, have not been performed under vacuum or DEMO-relevant conditions. A bespoke experimental test rig has therefore been designed and constructed with which to measure the interlayer thermal conductance as a function of temperature and pressure under vacuum conditions. The design of this apparatus and the results of experiments on FeltMetal as well as other candidate interlayers are presented here. In parallel, joint mockups using the candidate interlayers have been prepared and Thermal Break divertor target mockups have been manufactured, requiring the development of a dedicated

  18. Effect of doped ceria interlayer on cathode performance of the electrochemical cell using proton conducting oxide

    International Nuclear Information System (INIS)

    Sakai, Takaaki; Matsushita, Shotaro; Hyodo, Junji; Okuyama, Yuji; Matsuka, Maki; Ishihara, Tatsumi; Matsumoto, Hiroshige

    2012-01-01

    Highlights: ► Ce 0.8 Yb 0.2 O 2−δ (YbDC) interlayer conducted a large amount of protons. ► YbDC can work as cathode interlayer for proton conducting electrolyte cells. ► Cathode overpotential of the YbDC interlayer cells showed a plateau at about 400 mV. - Abstract: Introduction of doped ceria interlayer to cathode/electrolyte interface of the electrochemical cell with proton conducting electrolyte was investigated using thin Ce 0.8 Yb 0.2 O 2−δ (YbDC) interlayer of about 500 nm thickness. YbDC interlayer conducted a large amount of protons as much as 170 mA cm −2 . It was also found that cathode overpotential of the YbDC interlayer cells consistently showed a plateau at about 400 mV, at which that of the non-interlayer cells did not show, suggesting a possibility that cathode reaction is changed by introducing the doped ceria interlayer. This result also indicates that the interlayer showed high activity for cathode reaction when enough cathodic bias was applied. Especially, the interlayer showed high activity for the improvement of poor cathode reaction between SrZr 0.9 Y 0.1 O 3−α (SZY-91) electrolyte and platinum cathode.

  19. Contact-metamorphic illitization and related consequences for the functioning of backfill barriers in high level radioactive waste repositories (South Africa)

    International Nuclear Information System (INIS)

    Buehmann, C.

    2000-01-01

    A clay barrier, consisting of smectite, is common to most disposal designs for HLW repositories. Concerns are that elevated temperatures and long time periods may alter the two properties, the barrier is employed: a high swelling as well as cation exchange capacity (CEC). A ''natural analogue'' approach has therefore been attempted to predict smectite characteristics and stability in relation to time/temperature. The following investigations were performed in order to determine changes in swelling capacity and CEC: (1) Conversion of smectite to other clay minerals. (2) Changes in the layer charge characteristics of the clay minerals. (3) Swelling potential measurements of the smectitic interlayer. Smectite was thermally unstable and transformed into illite via illite/smectite interstratifications (I/S) and chlorite at temperature exceeding about 100 deg. C. The swelling potential was directly related to the proportion of smectite. As a conclusion it can be stated that elevated temperatures (> 70 deg. C) result in the transformation of smectite into illite. For backfill purposes it is recommended that the clay content in the backfill barrier should be as high as technically possible and that mixing the bentonite with K-bearing minerals (granite) should be avoided. (author)

  20. Hydrothermal alterations of Bentonites in Almeria (Spain); Alteracion hidrotermal de las bentonitas de Almeria

    Energy Technology Data Exchange (ETDEWEB)

    Linares Gonzalez, J; Barahona Fernandez, E; Huertas Garcia, F; Caballero Mesa, E; Cuadros Ojeda, J

    1996-12-01

    The use of bentonite as backfilling and sealing material in the high level radioactive waste disposals has been treated in previous studies accomplished by different authors. However, the use of this clayey barrier needs the resolution of different problems so that its efficiency will be enhanced. between those could be cited the study of the actual capacity of sealing the space around the canister and the accommodation to the pressure of the rocky environment; the possible variations in plasticity; the diffusion and reaction processes that can be produced through the barrier by groundwater, the capacity of radionuclides adsorption, etc. These studies, show that the bentonites with high content in smectite fulfill satisfactorily with the physical and chemical conditions to be used as sealing material, but it is known that the smectite can be unstable in diagenetic conditions similar to those are given in a deep repository of radioactive wastes, being transformed into illite. A conclusion of immediate interest is deduced from this last study. The bentonites used as sealing material in radioactive waste repositories must no contain Na as interlayer cation since it is very easily exchangeable by K. It is better to select those smectites with Ca and Mg that detain the entry of K in the interlayer and as a consequence the transformation process of smectite into illite is made more difficult. (Author)

  1. Hydrothermal alterations of Bentonites in Almeria (Spain)

    International Nuclear Information System (INIS)

    Linares Gonzalez, J.; Barahona Fernandez, E.; Huertas Garcia, F.; Caballero Mesa, E.; Cuadros Ojeda, J.

    1996-01-01

    The use of bentonite as backfilling and sealing material in the high level radioactive waste disposals has been treated in previous studies accomplished by different authors. However, the use of this clayey barrier needs the resolution of different problems so that its efficiency will be enhanced. between those could be cited the study of the actual capacity of sealing the space around the canister and the accommodation to the pressure of the rocky environment; the possible variations in plasticity; the diffusion and reaction processes that can be produced through the barrier by groundwater, the capacity of radionuclides adsorption, etc. These studies, show that the bentonites with high content in smectite fulfill satisfactorily with the physical and chemical conditions to be used as sealing material, but it is known that the smectite can be unstable in diagenetic conditions similar to those are given in a deep repository of radioactive wastes, being transformed into illite. A conclusion of immediate interest is deduced from this last study. The bentonites used as sealing material in radioactive waste repositories must no contain Na as interlayer cation since it is very easily exchangeable by K. It is better to select those smectites with Ca and Mg that detain the entry of K in the interlayer and as a consequence the transformation process of smectite into illite is made more difficult. (Author)

  2. Analysis of the kinetic behaviour of iodine and caesium isotopes in the primary circuit of LWR's during severe fuel damage accidents

    International Nuclear Information System (INIS)

    Alonso, A.; Fernandez, S.; Buron, J.M.; Lopez, J.V.

    1991-01-01

    This State of the Art report deals with the chemical behaviour of caesium and iodine in the primary system, focusing particularly on kinetic chemical aspects. In case of a postulated severe accident in a nuclear reactor, cesium and iodine fission products are among the major contributors to health harm because of their high volatility and radiotoxicity. The extent of the release of such fission products to the environment depends on the effectiveness of transport through different structures in the reactor coolant system and within the reactor building. The release from fuel has been briefly studied; only those aspects concerning to iodine and caesium chemical forms when released have been reviewed; nevertheless the emphasis has been put on the transport of such elements and their species through the primary system. Some thermochemical equilibrium studies, applied to primary circuit conditions in LWR's, have been analyzed. The revision of the few kinetic studies existing on this matter has shown that kinetic behaviour of iodine and caesium isotopes in the primary circuit is an aspect poorly studied, despite the fact that kinetic aspects could have great importance on the chemical species formed under certain conditions. Other phenomena affecting iodine and caesium transport, besides chemical reactions, such as interactions with surfaces, aerosols or other chemical species have also been examined from available information on diverse experiments

  3. Contribution to the use in analysis of ammonium phosphomolybdate- separation of radio-caesium in solution

    International Nuclear Information System (INIS)

    Scheidhauer, J.; Chabidon, M.; Ordinaire, L.

    1964-01-01

    The use in analysis of ammonium phosphomolybdate has been studied for the separation of barium from caesium 137. The cases have been studied of small and medium-sized volumes, and of large volumes of about 100 litres. (authors) [fr

  4. The influence of interlayer interactions on the mechanical properties of polymeric nanocomposites

    Directory of Open Access Journals (Sweden)

    Jabbarzadeh Mehrdad

    2015-01-01

    Full Text Available In this paper the influence of types of interlayer interactions on the elastic modules of multilayer graphene sheets (GS and nanocomposites is studied. The modeling and investigation of mechanical properties of graphite layers are performed using molecular mechanics (MM method. Initially, due to improving the model and decreasing the amount of computations, three types of elements such as beam, linear spring and nonlinear spring are used. To continue, the mechanical properties of multilayers and nanocomposites are compared using three types of interlayer interactions. Initially, nonlinear spring defined by Leonard Jones potential is used to define interlayer interactions (ordinary case. To continue, linear spring with certain stiffness, to obtain an equal linear spring and also to investigate the ultimate capacity of interlayer interactions in the force translation, by increasing the stiffness of linear springs, is employed (chemical change. Then once by omitting all Van der Waals interactions and defects creation in graphite layers, they are devoted to create covalent interlayer interactions (using Morse potential and another time, Van der Waals and covalent interlayer interactions are created spontaneously to study the properties of multilayers and nanocomposites (functionalization. The results are compared with other available literatures in this case to validate the modeling.

  5. Interlayer expanded molybdenum disulfide nanosheets assembly for electrochemical supercapacitor with enhanced performance

    International Nuclear Information System (INIS)

    Xiao, Huaqing; Wang, Shutao; Zhang, Shuo; Wang, Yihe; Xu, Qingfei; Hu, Wenjie; Zhou, Yan; Wang, Zhaojie; An, Changhua; Zhang, Jun

    2017-01-01

    Rational structural design for electrode materials is essential for fabricating high performance supercapacitors. In this work, we demonstrated a novel way to prepare incompact MoS_2 nanosheets assembled nanorods with the interlayer of MoS_2 nanosheets expanded to 0.89 nm, namely layer expanded MoS_2 nanorods (LE-MoS_2 NRs). The material was characterized by XRD, XPS and electron microscopes. The XRD data and HRTEM images confirmed the existence of expanded interlayer of MoS_2 nanosheets. N_2 adsorption-desorption isotherms of LE-MoS_2 NRs indicated high specific area up to 37.0 m"2 g"−"1. It was found that the expanded interlayer spacing can benefit the ion transportation within the MoS_2 interlayers. The as-prepared electrode material showed capacitance up to 231 F g"−"1 at 1 A g"−"1 charge-discharge current and cycling stability test indicated high capacitance of 177 F g"−"1 was retained after 1000 cycles. - Highlights: • High performance electrochemical supercapacitor electrode material. • Interlayer expanded MoS_2 to achieve enhanced capacitance. • Facile hydrothermal synthesis of interlayer expanded MoS_2. • MoS_2 nanosheets assembled incompact nanorods.

  6. Nuclear dynamics in the metastable phase of the solid acid caesium hydrogen sulfate.

    Science.gov (United States)

    Krzystyniak, Maciej; Drużbicki, Kacper; Fernandez-Alonso, Felix

    2015-12-14

    High-resolution spectroscopic measurements using thermal and epithermal neutrons and first-principles calculations within the framework of density-functional theory are used to investigate the nuclear dynamics of light and heavy species in the metastable phase of caesium hydrogen sulfate. Within the generalised-gradient approximation, extensive calculations show that both 'standard' and 'hard' formulations of the Perdew-Burke-Ernzerhof functional supplemented by Tkatchenko-Scheffler dispersion corrections provide an excellent description of the known structure, underlying vibrational density of states, and nuclear momentum distributions measured at 10 and 300 K. Encouraged by the agreement between experiment and computational predictions, we provide a quantitative appraisal of the quantum contributions to nuclear motions in this solid acid. From this analysis, we find that only the heavier caesium atoms reach the classical limit at room temperature. Contrary to naïve expectation, sulfur exhibits a more pronounced quantum character relative to classical predictions than the lighter oxygen atom. We interpret this hitherto unexplored nuclear quantum effect as arising from the tighter binding environment of this species in this technologically relevant material.

  7. Sources of present Chernobyl-derived caesium concentrations in surface air and deposition samples

    Energy Technology Data Exchange (ETDEWEB)

    Hoetzl, H.; Rosner, G.; Winkler, R. (Gesellschaft fuer Strahlen-und Umweltforschung Munich, Neuherberg (Germany). Forschungszentrum fuer Umwelt und Gesundheit Gesellschaft fuer Strahlen- und Umweltforschung mbH Muenchen, Neuherberg (Germany). Inst. fuer Strahlenschutz)

    1992-06-01

    The sources of Chernobyl-derived caesium concentrations in air and deposition samples collected from mid-1986 to end-1990 at Munich- Neuherberg, Germany, were investigated. Local resuspension has been found to be the main source. By comparison with deposition data from other locations it is estimated that within a range from 20 Bq m[sup -2] to 60 kBq m[sup -2] of initially deposited [sup 137]Cs activity [approx]2% is re-deposited by the process of local resuspension in Austria, Germany, Japan and United Kingdom, while significantly higher total resuspension is to be expected for Denmark and Finland. Stratospheric contribution to present concentrations is shown to be negligible. This is confirmed by cross correlation analysis between the time series of [sup 137]Cs in air and precipitation before and after the Chernobyl accident and the respective time series of cosmogenic [sup 7]Be, which is an indicator of stratospheric input. Seasonal variations of caesium concentrations with maxima in winter were observed. (author). 32 refs.; 5 figs.; 1 tab.

  8. A 3D conductive carbon interlayer with ultrahigh adsorption capability for lithium-sulfur batteries

    Science.gov (United States)

    Zhao, Qian; Zhu, Qizhen; An, Yabin; Chen, Renjie; Sun, Ning; Wu, Feng; Xu, Bin

    2018-05-01

    To improve the cycling performance of the Li-S batteries, a 3D interwoven hollow interlayer with extremely high electrolyte adsorption capability up to 9.64 g g-1 was simply prepared by carbonization of cotton fabric (CCF). For comparison, an interlayer coated on separator was obtained by the slurry-coating method of powdery CCF. The key role of the adsorption capability is confirmed by comparing the electrochemical performance of Li-S batteries with these two interlayers. In the Li-S batteries with 3D CCF interlayer, massive dissolved polysulfides, together with the electrolyte, can be adsorbed and confined in the 3D CCF interlayer, providing substantial extra active sites and alleviating the shuttle effect effectively. As a result, the Li-S batteries with 3D CCF interlayer show much enhanced utilization of active materials (1346.9 mAh g-1 at 0.1C), prolonged cycle life (capacity retention of 80% after 100 cycles), and improved rate performance (553.2 mAh g-1 at 4C). Even for cathodes with high sulfur loading of 5 mg cm-2, the cells with 3D CCF interlayer perform a high capacity of 1085 mAh g-1 and retain 870.6 mAh g-1 after 75 cycles at 0.5 mA cm-2. These results not only provide a sustainable, low cost and easy-prepared 3D CCF interlayer, but also offer a promising strategy based on interlayer with high adsorption capability in designing high-performance Li-S batteries.

  9. Analytical electron microscopy study of surface layers formed on the French SON68 nuclear waste glass during vapor hydration at 200 C

    International Nuclear Information System (INIS)

    Gong, W.L.; Wang, L.M.; Ewing, R.C.; Bates, J.K.; Ebert, W.L.

    1998-01-01

    Extensive solid-state characterization (AEM/SEM/HRTEM) was completed on six SON68 (inactive R7T7) waste glasses which were altered in the presence of saturated water vapor (200 C) for 22, 91, 241, 908, 1000, 1013, and 1021 days. The samples were examined by AEM in cross-section (lattice-fringe imaging, micro-diffraction, and quantitative thin-film EDS analysis). The glass monoliths were invariably covered by a thin altered rind, and the surface layer thickness increased with increasing time of reaction, ranging from 0.5 to 30 μm in thickness. Six distinctive zones, based on phase chemistry and microstructure, were distinguished within the well-developed surface layers. Numerous crystalline phases such as analcime, gyrolite, tobermorite, apatite, and weeksite were identified on the surfaces of the reacted glasses as precipitates. The majority of the surface layer volume was composed of two basic structures that are morphologically and chemically distinct: The A-domain consisted of well-crystallized fibrous smectite aggregates; and the B-domain consisted of poorly-crystallized regions containing smectite, possibly montmorillonite, crystallites and a ZrO 2 -rich amorphous silica matrix. The retention of the rare-earth elements, Mo, and Zr mostly occurred within the B-domain; while transition metal elements, such as Zn, Cr, Ni, Mn, and Fe, were retained in the A-domain. The element partitioning among A-domains and B-domains and recrystallization of the earlier-formed B-domains into the A-domain smectites were the basic processes which have controlled the chemical and structural evolution of the surface layer. The mechanism of surface layer formation during vapor hydration are discussed based on these cross-sectional AEM results. (orig.)

  10. EXAFS and FTIR studies of selenite and selenate sorption by alkoxide-free sol–gel generated Mg–Al–CO 3 layered double hydroxide with very labile interlayer anions

    KAUST Repository

    Chubar, Natalia

    2014-01-01

    © the Partner Organisations 2014. Current research on Layered Double Hydroxides (LDHs, also known as hydrotalcites, HTs) is predominantly focused on their intercalations, but the industrial application of LDHs for anion exchange adsorption has not yet been achieved. It was recently recognized that, to develop LDH applications, these materials should be produced using methods other than direct co-precipitation. Mg-Al-CO3LDH produced using an alkoxide-free sol-gel synthesis showed exceptional removal properties for aqueous selenium species. Se K-edge EXAFS/XANES and FTIR studies (supporting the data by XRD patterns) were performed to explain the unusual adsorptive performance of Mg-Al LDH by revealing the molecular-level mechanism of HSeO3 -, SeO4 2-and {HSeO3 -+ SeO4 2-} uptake at pH 5, 7 and 8.5. The role of inner-sphere complexation (exhibited by inorganic adsorbents with good performance) in adsorption of both selenium aqueous species was not confirmed. However, Mg-Al LDH fully met the other expectations regarding the involvement of the interlayer anions. The interlayer carbonate (due to its favorable speciation and generous HT hydration) gave a "second breath" to selenite sorption and was the only mechanism that controlled the removal of Se(vi). Because inner sphere complexation was the leading mechanism for selenite removal, ion exchange via surface OH-and interlayer CO3 2-species was the only mechanism for selenate removal; both of these species were easily bound to Mg-Al LDH (on its surface and gently parked into the interlayer forming a multilayer without violation of the structure of Mg-Al-CO3LDH). This work provides the first theoretical explanation of why it is more difficult to sorb selenate than selenite and which material should be used for this purpose. This journal is

  11. EXAFS and FTIR studies of selenite and selenate sorption by alkoxide-free sol–gel generated Mg–Al–CO 3 layered double hydroxide with very labile interlayer anions

    KAUST Repository

    Chubar, Natalia

    2014-08-08

    © the Partner Organisations 2014. Current research on Layered Double Hydroxides (LDHs, also known as hydrotalcites, HTs) is predominantly focused on their intercalations, but the industrial application of LDHs for anion exchange adsorption has not yet been achieved. It was recently recognized that, to develop LDH applications, these materials should be produced using methods other than direct co-precipitation. Mg-Al-CO3LDH produced using an alkoxide-free sol-gel synthesis showed exceptional removal properties for aqueous selenium species. Se K-edge EXAFS/XANES and FTIR studies (supporting the data by XRD patterns) were performed to explain the unusual adsorptive performance of Mg-Al LDH by revealing the molecular-level mechanism of HSeO3 -, SeO4 2-and {HSeO3 -+ SeO4 2-} uptake at pH 5, 7 and 8.5. The role of inner-sphere complexation (exhibited by inorganic adsorbents with good performance) in adsorption of both selenium aqueous species was not confirmed. However, Mg-Al LDH fully met the other expectations regarding the involvement of the interlayer anions. The interlayer carbonate (due to its favorable speciation and generous HT hydration) gave a "second breath" to selenite sorption and was the only mechanism that controlled the removal of Se(vi). Because inner sphere complexation was the leading mechanism for selenite removal, ion exchange via surface OH-and interlayer CO3 2-species was the only mechanism for selenate removal; both of these species were easily bound to Mg-Al LDH (on its surface and gently parked into the interlayer forming a multilayer without violation of the structure of Mg-Al-CO3LDH). This work provides the first theoretical explanation of why it is more difficult to sorb selenate than selenite and which material should be used for this purpose. This journal is

  12. Analyte-Size-Dependent Ionization and Quantification of Monosaccharides in Human Plasma Using Cation-Exchanged Smectite Layers.

    Science.gov (United States)

    Ding, Yuqi; Kawakita, Kento; Xu, Jiawei; Akiyama, Kazuhiko; Fujino, Tatsuya

    2015-08-04

    Smectite, a synthetic inorganic polymer with a saponite structure, was subjected to matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). Typical organic matrix molecules 2,4,6-trihydroxyacetophenone (THAP) and 2,5-dihydroxybenzoic acid (DHBA) were intercalated into the layer spacing of cation-exchanged smectite, and the complex was used as a new matrix for laser desorption/ionization mass spectrometry. Because of layer spacing limitations, only a small analyte that could enter the layer and bind to THAP or DHBA could be ionized. This was confirmed by examining different analyte/matrix preparation methods and by measuring saccharides with different molecular sizes. Because of the homogeneous distribution of THAP molecules in the smectite layer spacing, high reproducibility of the analyte peak intensity was achieved. By using isotope-labeled (13)C6-d-glucose as the internal standard, quantitative analysis of monosaccharides in pretreated human plasma sample was performed, and the value of 8.6 ± 0.3 μg/mg was estimated.

  13. Particle clogging in porous media. Filtration of a smectite solution

    Energy Technology Data Exchange (ETDEWEB)

    Richards, Tobias (Chalmers University of Technology, Goeteborg (Sweden))

    2010-01-15

    The goal of this project is to find out if it is possible for bentonite clay to self heal during leaching with deionized water. The investigation has focused on the formation of a filter cake made of accessory material from MX 80 and the separation of solid material when a smectite solution (1%) is pushed through the cake using a pressure difference of 5 bar. It was also in the scope of this project to design and build the necessary equipment for these experiments. In the literature review it was not found any example that the phenomenon of clogging has been used as a self-healing method previously. It was rather separated also between the clogging of a filter cake (deep bed filtration or cake filtration) and the filtration of colloidal particles. Probably because the latter are in such low concentrations in natural systems and the focus have mainly been in the transport properties of colloids within a filter cake or deep bed filter. An experimental equipment was designed and built. It consists of seven filtration cells that could operate in parallel. All of them are connected to the same source of pressure to ensure equal conditions. A system was also prepared to prevent air from dissolving in the solution because it could create an unwanted expansion in the filter cake due to lower solubility at lower pressure. The experiment showed good separation of smectite particles from the solution when it passed through the filter cake. In all tested cases, the separation was almost complete after long enough time, indicating that the cake has small enough pores to act as a geometrical hinder for the small particles. Comparison between the materials prepared at Chalmers University of Technology and at Clay Technology showed a very good agreement indicating similar properties of the produced smectite

  14. Particle clogging in porous media. Filtration of a smectite solution

    International Nuclear Information System (INIS)

    Richards, Tobias

    2010-01-01

    The goal of this project is to find out if it is possible for bentonite clay to self heal during leaching with deionized water. The investigation has focused on the formation of a filter cake made of accessory material from MX 80 and the separation of solid material when a smectite solution (1%) is pushed through the cake using a pressure difference of 5 bar. It was also in the scope of this project to design and build the necessary equipment for these experiments. In the literature review it was not found any example that the phenomenon of clogging has been used as a self-healing method previously. It was rather separated also between the clogging of a filter cake (deep bed filtration or cake filtration) and the filtration of colloidal particles. Probably because the latter are in such low concentrations in natural systems and the focus have mainly been in the transport properties of colloids within a filter cake or deep bed filter. An experimental equipment was designed and built. It consists of seven filtration cells that could operate in parallel. All of them are connected to the same source of pressure to ensure equal conditions. A system was also prepared to prevent air from dissolving in the solution because it could create an unwanted expansion in the filter cake due to lower solubility at lower pressure. The experiment showed good separation of smectite particles from the solution when it passed through the filter cake. In all tested cases, the separation was almost complete after long enough time, indicating that the cake has small enough pores to act as a geometrical hinder for the small particles. Comparison between the materials prepared at Chalmers University of Technology and at Clay Technology showed a very good agreement indicating similar properties of the produced smectite

  15. Interlayer expanded molybdenum disulfide nanosheets assembly for electrochemical supercapacitor with enhanced performance

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Huaqing; Wang, Shutao; Zhang, Shuo; Wang, Yihe; Xu, Qingfei; Hu, Wenjie [College of Science, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China); Zhou, Yan, E-mail: yanzhou@upc.edu.cn [College of Science, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China); State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China); Wang, Zhaojie [College of Science, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China); An, Changhua [College of Science, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China); College of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin, 300384 (China); Zhang, Jun, E-mail: zhangj@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China)

    2017-05-01

    Rational structural design for electrode materials is essential for fabricating high performance supercapacitors. In this work, we demonstrated a novel way to prepare incompact MoS{sub 2} nanosheets assembled nanorods with the interlayer of MoS{sub 2} nanosheets expanded to 0.89 nm, namely layer expanded MoS{sub 2} nanorods (LE-MoS{sub 2} NRs). The material was characterized by XRD, XPS and electron microscopes. The XRD data and HRTEM images confirmed the existence of expanded interlayer of MoS{sub 2} nanosheets. N{sub 2} adsorption-desorption isotherms of LE-MoS{sub 2} NRs indicated high specific area up to 37.0 m{sup 2} g{sup −1}. It was found that the expanded interlayer spacing can benefit the ion transportation within the MoS{sub 2} interlayers. The as-prepared electrode material showed capacitance up to 231 F g{sup −1} at 1 A g{sup −1} charge-discharge current and cycling stability test indicated high capacitance of 177 F g{sup −1} was retained after 1000 cycles. - Highlights: • High performance electrochemical supercapacitor electrode material. • Interlayer expanded MoS{sub 2} to achieve enhanced capacitance. • Facile hydrothermal synthesis of interlayer expanded MoS{sub 2}. • MoS{sub 2} nanosheets assembled incompact nanorods.

  16. Feasibility Study of Interlayer Slide Monitoring Using Postembedded Piezoceramic Smart Aggregates

    Directory of Open Access Journals (Sweden)

    Jianchao Wu

    2018-01-01

    Full Text Available Utilizing embedded transducers is an effective approach to monitor a landslide. However, for existing structures, sensors can only be postembedded, which involves drilling and grouting, and may change the original state of the structure, which calls for the need to study the effectiveness of postembedded transducers. The main focus of this paper is the feasibility study of the interlayer slide detection using postembedded piezoceramic smart aggregates (SAs. In this study, a small landslide structure that involves a weak layer is studied and two pairs of SAs were embedded in predetermined positions inside the structure. To study the difference, one pair of transducer was preembedded and the other pair was postembedded. Within each pair, one SA was employed as an actuator to generate stress waves, and another SA used as a sensor to detect wave responses. Active-sensing approach was developed to perform continuous monitoring during structural loading that was used to induce an interlayer slide. The occurrence of interlayer slide attenuates wave energy and decreases signal intensity. A wavelet-packed index was proposed to detect the occurrence and development of interlayer slide. Experimental results demonstrated that SA installation through postembedding process is an innovative yet effective approach to monitor interlayer slide.

  17. The CNEN Helium-Caesium Blow-Down MPD Facility and Experiments with a Prototype Duct

    Energy Technology Data Exchange (ETDEWEB)

    Bertolini, E.; Toschi, R. [CNEN, Frascati (Italy); Lindley, B. C. [C.A. Parsons and Co. Ltd (United Kingdom); Brown, R.; McNab, I. R. [International Research and Development Co. Ltd., Newcastle Upon Tyne (United Kingdom)

    1966-11-15

    The CNEN blow-down loop has been designed to study a helium-caesium MPD generator with particular regard to non-equilibrium ionization effects. An operating condition of the loop is: gas mass flow 0.2 kg/sec, seed fraction 1 at, wt.%, useful pulse duration 20 sec, stagnation temperature 2000 Degree-Sign K, stagnation pressure 5 atm abs, thermal power 1.6 MW, Mach number 0.6, magnetic field 4 Wb/m2, total impurity level less than 100 ppm. A sufficiently wide range of the stagnation conditions can be obtained with the present arrangement of the loop (temperature up to 2000*K, pressure from slightly sub-atmospheric to 6atmabs, gas mass flow from 50 g/sec to 400 g/sec, seed fraction from 0.1 to 2 at. wt.%. The storage heater is an alumina pebble bed electrically heated with tungsten elements and thermally insulated with zirconia fibre; the thermal capacity at 2000 Degree-Sign K is about 1000 MJ. Pure helium is obtained by evaporation of liquid helium at between 4.5 and 5 Degree-Sign K; liquid caesium is injected into a limited section of the pebble bed to provide a mixture of the two gases uniform in density and temperature. The duct is made of boron nitride (5 cm x 3 cm x 22 cm) with 25 pairs of tantalum electrodes whose geometry (electrode width 3 mm, segmentation pitch 9 mm) should prevent current leakage between adjacent electrodes; the duct walls and transfer can be pre-heated up to 1700 Degree-Sign K. A magnetic field of 4 Wb/m{sup 2} is obtained with a pulsed cryogenic magnet with pulse duration of 6 sec. Two series of experiments have been completed to assess the feasibility of the helium-caesium heating system and the generator duct. Heating system experiments, (a) Compatibility of alumina with tungsten, tantalum and caesium, with thermal cycling at 2000 Degree-Sign K; (b) Purification of zirconia fibre and its behaviour at high temperature, with thermal cycling at 2000 Degree-Sign K; (c) Capability of an alumina pebble bed of evaporating, heating and mixing

  18. Industrial treatment of solutions of fission products. Separation of caesium-137; Traitement industriel de solutions de produits de fission. Separation du cesium-137

    Energy Technology Data Exchange (ETDEWEB)

    Fisher, C; Raggenbass, A [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1959-07-01

    Two types of chemical treatment can be considered for the manufacture of solid sources for industrial uses from fission product solutions remaining after plutonium extraction: a) concentration of the solution and preparation of solid sources from the bulk material, without separation, b) separation of one or several fission products from which the sources are made. Examination of the radio-chemical composition of the mixture of fission products that will be available from the Marcoule reactors (G1, G2 and G3) shows that caesium-137 accounts for 30 per cent of the {gamma} energy available immediately after the plutonium separation, 70 per cent two years after and 100 per cent after five years. There is practically no advantage in making sources from bulk fission products, since the separation of caesium-137 is no more complicated and yet it results in a material with more potential uses. The separation of caesium-137 by a method based on the standard phospho-tungstate precipitation method has been considered. Previously, the precipitated caesium phospho-tungstate was dissolved and caesium was recovered from the solution by cation-exchange or by removal of phosphate and tungstate ions by anion-exchange. A study has now been made, of the metathesis of caesium phospho-tungstate to barium phosphate and tungstate by the action of barium hydroxide, the caesium being obtained in solution as the hydroxide. The advantages of this new procedure are: - greater decontamination of caesium-137 without further purification, - possibility of direct transformation to caesium sulphate, - general simplification of the procedure and, consequently, of the equipment. (author) [French] Deux types de traitement chimique peuvent etre envisages pour amener a l'etat de sources solides utilisables industriellement les produits de fission contenus dans les solutions residuaires de l'extraction du plutonium. Ces traitements sont les suivants: a) concentration des solutions et confection de

  19. Industrial treatment of solutions of fission products. Separation of caesium-137; Traitement industriel de solutions de produits de fission. Separation du cesium-137

    Energy Technology Data Exchange (ETDEWEB)

    Fisher, C.; Raggenbass, A. [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1959-07-01

    Two types of chemical treatment can be considered for the manufacture of solid sources for industrial uses from fission product solutions remaining after plutonium extraction: a) concentration of the solution and preparation of solid sources from the bulk material, without separation, b) separation of one or several fission products from which the sources are made. Examination of the radio-chemical composition of the mixture of fission products that will be available from the Marcoule reactors (G1, G2 and G3) shows that caesium-137 accounts for 30 per cent of the {gamma} energy available immediately after the plutonium separation, 70 per cent two years after and 100 per cent after five years. There is practically no advantage in making sources from bulk fission products, since the separation of caesium-137 is no more complicated and yet it results in a material with more potential uses. The separation of caesium-137 by a method based on the standard phospho-tungstate precipitation method has been considered. Previously, the precipitated caesium phospho-tungstate was dissolved and caesium was recovered from the solution by cation-exchange or by removal of phosphate and tungstate ions by anion-exchange. A study has now been made, of the metathesis of caesium phospho-tungstate to barium phosphate and tungstate by the action of barium hydroxide, the caesium being obtained in solution as the hydroxide. The advantages of this new procedure are: - greater decontamination of caesium-137 without further purification, - possibility of direct transformation to caesium sulphate, - general simplification of the procedure and, consequently, of the equipment. (author) [French] Deux types de traitement chimique peuvent etre envisages pour amener a l'etat de sources solides utilisables industriellement les produits de fission contenus dans les solutions residuaires de l'extraction du plutonium. Ces traitements sont les suivants: a) concentration des solutions et

  20. Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium.

    Science.gov (United States)

    Liu, D; Dong, H; Bishop, M E; Zhang, J; Wang, H; Xie, S; Wang, S; Huang, L; Eberl, D D

    2012-03-01

    Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate-reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu-2, mixed-layer illite-smectite RAr-1 and ISCz-1, and illite IMt-1) were exposed to D. vulgaris in a non-growth medium with and without anthraquinone-2,6-disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X-ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals. © 2011 Blackwell Publishing Ltd.

  1. Molecular Dynamics Study of Water Molecules in Interlayer of 14 ^|^Aring; Tobermorite

    KAUST Repository

    Yoon, Seyoon; Monteiro, Paulo J.M.

    2013-01-01

    The molecular structure and dynamics of interlayer water of 14 Å tobermorite are investigated based on molecular dynamics (MD) simulations. Calculated structural parameters of the interlayer water configuration are in good agreement with current

  2. Hydraulic/mechanical modeling of smectitic materials for HMC analytical evaluation of the long term performance of TRU geological repository - 59090

    International Nuclear Information System (INIS)

    Kobayashi, Ichizo; Owada, Hitoshi; Ishii, Tomoko

    2012-01-01

    Aiming at evaluation of the long term performance of transuranic (TRU) geological repositories, the hydraulic/ mechanical/chemical (HMC) analysis method has been studied. In this phase of research (four years) the hydraulic/mechanical modeling of smectitic materials for HMC analyses has been studied. In this paper, new experimental methods for investigation of the hydraulic/mechanical behavior of smectitic materials were developed. For hydraulic modeling, the measurement method of the specific surface area of compacted smectitic materials was developed using X-ray diffraction (XRD). The results of the method were applied to the Kozeny-Carman law. Since the specific surface area represents the microstructure of smectitic materials such as the degree of swelling, it was found that the Kozeny-Carman law using measured specific surface area of compacted smectitic materials was useful in evaluating the hydraulic performance of smectitic materials. Moreover, since the Kozeny-Carman law can take the alteration of content of pore water into consideration by not only a coefficient of viscosity but also by changes in specific surface area, the Kozeny-Carman law will be more suitable to chemical and mechanical couple analyses than the ordinary Darcy's law. For the mechanical modeling, the procedure of one dimensional exhausting compression test was developed. The tests gave the dry density and compression stress relation in the state of full-saturation of smectitic materials with varying water content. The relations between the dry density and compression stress in the state of fully saturation were termed fully saturation lines. The group of iso-grams of degree of saturation and water content were also given with this test. It was found that the fully-saturation line is consistent with swelling deformation-pressure relation in the equilibrium state. The results indicated that the swelling deformation-pressure relation does not depend on the saturation manner, such as the

  3. Toward Increasing Micropore Volume between Hybrid Layered Perovskites with Silsesquioxane Interlayers.

    Science.gov (United States)

    Kataoka, Sho; Kamimura, Yoshihiro; Endo, Akira

    2018-04-10

    Hybrid organic-inorganic layered perovskites are typically nonporous solids. However, the incorporation of silsesquioxanes with a cubic cage structure as interlayer materials creates micropores between the perovskite layers. In this study, we increase in the micropore volume in layered perovskites by replacing a portion of the silsesquioxane interlayers with organic amines. In the proposed method, approximately 20% of the silsesquioxane interlayers can be replaced without changing the layer distance owing to the size of the silsesquioxane. When small amines (e.g., ethylamine) are used in this manner, the micropore volume of the obtained hybrid layered perovskites increases by as much as 44%; when large amines (e.g., phenethylamine) are used, their micropore volume decreases by as much as 43%. Through the variation of amine fraction, the micropore volume can be adjusted in the range. Finally, the magnetic moment measurements reveal that the layered perovskites with mixed interlayers exhibit ferromagnetic ordering at temperature below 20 K, thus indicating that the obtained perovskites maintain their functions as layered perovskites.

  4. Images of interlayer Josephson vortices in single-layer cuprates

    International Nuclear Information System (INIS)

    Moler, K. A.; Kirtley, J. R.; Liang, R.; Bonn, D. A.; Hardy, W. N.; Williams, J. M.; Schlueter, J. A.; Hinks, D.; Villard, G.; Maignan, A.; Nohara, M.; Takagi, H.

    2000-01-01

    The interlayer penetration depth in layered superconductors may be determined from scanning Superconducting QUantum Interference Device (SQUID) microscope images of interlayer Josephson vortices. The authors compare their findings at 4 K for single crystals of the organic superconductor κ-(BEDT-TTF) 2 Cu(NCS) 2 and three near-optimally doped cuprate superconductors: La 2-x Sr x CuO 4 , (Hg, Cu)Ba 2 CuO 4+δ , and Tl 2 Ba 2 CuO 6+δ

  5. Pressure induced reactions amongst calcium aluminate hydrate phases

    KAUST Repository

    Moon, Ju-hyuk

    2011-06-01

    The compressibilities of two AFm phases (strätlingite and calcium hemicarboaluminate hydrate) and hydrogarnet were obtained up to 5 GPa by using synchrotron high-pressure X-ray powder diffraction with a diamond anvil cell. The AFm phases show abrupt volume contraction regardless of the molecular size of the pressure-transmitting media. This volume discontinuity could be associated to a structural transition or to the movement of the weakly bound interlayer water molecules in the AFm structure. The experimental results seem to indicate that the pressure-induced dehydration is the dominant mechanism especially with hygroscopic pressure medium. The Birch-Murnaghan equation of state was used to compute the bulk modulus of the minerals. Due to the discontinuity in the pressure-volume diagram, a two stage bulk modulus of each AFm phase was calculated. The abnormal volume compressibility for the AFm phases caused a significant change to their bulk modulus. The reliability of this experiment is verified by comparing the bulk modulus of hydrogarnet with previous studies. © 2011 Elsevier Ltd. All rights reserved.

  6. [An experimental study on the prevention of enteral bacterial translocation in scalded rats by smectite powder].

    Science.gov (United States)

    Su, Hai-tao; Li, Yi-shu; Lu, Shu-liang; Sun, Man; Qing, Chun; Li, Zong-yu; Shao, Tie-bing; Huang, Li-bing; Qu, Bing; Yang, Xin-bo

    2005-04-01

    To explore the preventive and treatment effects of smectite powder on enteral bacterial translocation in scalded rats. Fifty-four Sprague-Dawley (SD) rats were randomly divided into three groups, i.e. normal control (A, n = 6), burn control (B, n = 24), and burn treatment (T, n = 24) groups. The rats in B and T groups were fed with tracing bacteria JM109, which was transfected with PUC19 plasmid in advance. The rats were subjected to 30% TBSA scald injury after the plasmid was shown to have colonized in the intestine. Smectite powder (0.6 g/day/kg) was fed to rats of T group immediately after the scalding, while those in B group received no smectite powder. Bacterial translocation in blood and mesenteric lymph nodes in all groups was observed and identified by enzyme digestion at 12 post scald hour (PSH) and on 1, 3 and 5 post-scald days (PSD). The contents of malondialdehyde (MDA) and superoxide dismutase (SOD) were determined in rat intestinal tissue. And the degree of injury to the entire small intestine was observed pathologically. The villus height of intestinal mucosa was measured, and the rate of epithelial nuclear splitting of mucosal crypts was calculated. The number of rats with positive blood bacterial culture in B group was obviously higher than that in A and T groups (P Smectite powder is beneficial to the protection of the intestinal mucosa in scalded rats, and can effectively prevent postburn intestinal bacterial translocation in rats.

  7. Photoluminescence properties of Er-doped Ge–In(Ga)–S glasses modified by caesium halides

    Czech Academy of Sciences Publication Activity Database

    Ivanova, Z.G.; Zavadil, Jiří; Kostka, P.; Djouama, T.; Reinfelde, M.

    2017-01-01

    Roč. 254, č. 6 (2017), č. článku 1600662. ISSN 0370-1972 Institutional support: RVO:67985882 Keywords : caesium halides * chalcohalide glasses * erbium doping * transmission spectroscopy * photoluminiscence Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 1.674, year: 2016

  8. Photoluminescence properties of Er-doped Ge–In(Ga)–S glasses modified by caesium halides

    Czech Academy of Sciences Publication Activity Database

    Ivanova, Z.G.; Zavadil, Jiří; Kostka, Petr; Djouama, T.; Reinfelde, M.

    2017-01-01

    Roč. 254, č. 6 (2017), č. článku 1600662. ISSN 0370-1972 Institutional support: RVO:67985891 Keywords : caesium halides * chalcohalide glasses * erbium doping * transmission spectroscopy * photoluminiscence Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 1.674, year: 2016

  9. Can hydrate dissolution experiments predict the fate of a natural hydrate system?

    Energy Technology Data Exchange (ETDEWEB)

    Hester, K.C.; Peltzer, E.T.; Dunk, R.M.; Walz, P.M.; Brewer, P.G. [Monterey Bay Aquarium Research Inst., Moss Landing, CA (United States); Dendy Sloan, E. [Colorado School of Mines, Golden, CO (United States). Center for Hydrate Research

    2008-07-01

    Gas hydrates are naturally occurring compounds found in permafrost regions and in oceans. In the natural environment, sufficient temperature and pressure conditions for hydrate formation exist over a significant portion of the ocean. However, in addition to pressure and temperature, the chemical potential of the gas in the hydrate must be equal to the surrounding waters. If the concentration of the gas in surrounding water is under-saturated with respect to the gas in the hydrate, the hydrate will dissolve to drive the system towards chemical equilibrium. This paper presented a dissolution study of exposed hydrate from outcrops at Barkley Canyon, located off Vancouver Island, British Columbia. A previous field experiment on synthetic methane hydrate samples had demonstrated that mass transfer controlled dissolution in under-saturated seawater. However, seafloor hydrate outcrops have been shown to have significant longevity compared to expected dissolution rates based upon convective boundary layer diffusion calculations. An in-situ dissolution experiment was performed on two distinct natural hydrate fabrics in order to help resolve this apparent disconnect between the dissolution rates of synthetic and natural hydrate. The paper presented a map of Barkley Canyon and discussed the field measurements and methods for the study. Exposed outcrops of gas hydrates were cored using a specially constructed stainless steel coring device and a hydraulic ram was located inside the corer. Hydrate samples were cored directly using the a manipulator arm and then injected into a sampling cell. The hydrate was then added to an open mesh exposure container, which allowed for exposure to ambient benthic currents with minimal disturbance. As well, in order to observe the slow dissolution of the hydrate in seawater at Barkley Canyon, time-lapse photography was employed. Last, the paper presented the results of the hydrate fabric porosities and hydrate dissolution rates. It was

  10. Analytical modeling of effect of interlayer on effective moduli of layered graphene-polymer nanocomposites

    Institute of Scientific and Technical Information of China (English)

    C.C.Roach; Y.C.Lu

    2017-01-01

    Nanocomposites enhanced with two-dimensional,layered graphene fillers are a new class of engineering materials that exhibit superior properties and characteristics to composites with conventional fillers.However,the roles of "interlayers" in layered graphene fillers have yet to be fully explored.This paper examines the effect of interlayers on mechanical properties of layered graphene polymer composites.As an effective filler,the fundamental properties (in-plane Young's modulus EL1,out-of-plane Young's modulus EL2;shear modulus GL12,major Poisson's ratio 1L12) of the layered graphene were computed by using the Arridge's lamellar model.The effects of interlayers on effective moduli of layered graphene epoxy composites were examined through the Tandon-Weng model.The properties of the interlayer show noticeable impact on elastic properties of the composites,particular the out-of-plane properties (Young's modulus E2 and shear modulus G12).The interlayer spacing is seen to have much great influence on properties of the composites.As the interlayer spacing increases from 0.34 nm to 2 nm,all elastic properties of the composites have been greatly decreased.

  11. INFLUENCE OF THE SILICON INTERLAYER ON DIAMOND-LIKE CARBON FILMS DEPOSITED ON GLASS SUBSTRATES

    Directory of Open Access Journals (Sweden)

    Deiler Antonio Lima Oliveira

    2012-06-01

    Full Text Available Diamond-like carbon (DLC films as a hard protective coating have achieved great success in a diversity of technological applications. However, adhesion of DLC films to substrates can restrict their applications. The influence of a silicon interlayer in order to improve DLC adhesion on glass substrates was investigated. Amorphous silicon interlayer and DLC films were deposited using plasma enhanced chemical vapor deposition from silane and methane, respectively. The bonding structure, transmittance, refraction index, and adherence of the films were also evaluated regarding the thickness of the silicon interlayer. Raman scattering spectroscopy did not show any substantial difference in DLC structure due to the interlayer thickness of the silicon. Optical measurements showed a sharp decrease of transmittance in the ultra-violet region caused by the fundamental absorption of the light. In addition, the absorption edge of transmittance shifted toward longer wavelength side in the ultra-violet region as the thickness of the silicon interlayer increased. The tribological results showed an increase of DLC adherence as the silicon interlayer increased, which was characterized by less cracks around the grooves.

  12. Interactions among K+-Ca2+ exchange, sorption of m-dinitrobenzene, and smectite quasicrystal dynamics.

    Science.gov (United States)

    Chatterjee, Ritushree; Laird, David A; Thompson, Michael L

    2008-12-15

    The fate of organic contaminants in soils and sediments is influenced by sorption of the compounds to surfaces of soil materials. We investigated the interaction among sorption of an organic compound, cation exchange reactions, and both the size and swelling of smectite quasicrystals. Two reference smectites that vary in location and amount of layer charge, SPV (a Wyoming bentonite) and SAz-1 were initially Ca- and K-saturated and then equilibrated with mixed 0.01 M KCl and 0.005 M CaCl2 salt solutions both with and without the presence of 200 mg L(-1) m-dinitrobenzene (m-DNB). In general, sorption of m-DNB increased with the amount of K+ in the system for both clays, and the SPV sorbed more m-DNB than the SAz-1. Sorption of m-DNB increased the preference of Ca-SPV for K+ relative to Ca2+ but had little effect on K+-Ca2+ selectivity for K-SPV. Selectivity for K+ relative to Ca2+ was slightly higher for both K-SAz-1 and Ca-SAz-1 in the presence of m-DNB than in its absence. Distinct hysteresis loops were observed for the K+-Ca2+ cation exchange reactions for both clays, and the legacy of having been initially Ca- or K-saturated influenced sorption of m-DNB by SPV but had little effect for SAz-1. Suspension X-ray diffraction was used to measure changes in d-spacing and the relative thickness of smectite quasicrystals during the cation exchange and m-DNB sorption reactions. The results suggest that interactions among cation exchange and organic sorption reactions are controlled byan inherently hysteretic complex feedback process that is regulated by changes in the size and extent of swelling of smectite quasicrystals.

  13. Chemical and Mineralogical Features of Smectite from the Morron de Mateo Bentonite Deposit (Cabo de Gata, Almeria) in Relation to the Parent Rocks and the Alteration Processes Occurred After the Bentonite Formation: Analogies and Implications for the Engineered Clayey Barrier of a Deep Geological Rad waste Repository; Naturaleza de las Esmectitas del Yacimiento de Morron de Mateo (Cabo de Gata, Almeria) en Relacion con la Roca Madre y con los Procesos Posteriores a la Bentonitizacion: Implicaciones Analogicas para la Barrera de Ingenieria de un Almacenamiento Geologico de Residuos Radiactivos

    Energy Technology Data Exchange (ETDEWEB)

    Pelayo, M; Labajo, M A; Garcia Romero, L; Perez del Villar, L

    2009-10-12

    The Morron de Mateo bentonite deposit is being studied as a natural analogue of the thermal and geochemical effects on the clayey barrier of a Deep Geological Rad waste Repository (DGRR) after its closure, in relation to the radioactive decay of the fission products and the container corrosion. This bentonite deposit and their host rocks were intruded by a rhyodacitic volcanic dome that induced a hydrothermal metasomatic process affecting the bioclastic calcarenite beds close to the dome. Bentonite from the NE sector of the deposit have been chemically and mineralogically characterized. Pyroclastic rocks (white tuffs), epyclastic rocks (mass flow) and andesitic breccia all of them hydrothermally altered, have been studied at the site. Samples are composed of feldspars, quartz and amphybols, as inherited minerals, and phyllosilicates, zeolites, crystoballite and calcite, as new formed minerals. White tuffs have the highest phyllosilicate contents, mainly dioctahedral smectite of montmorillonite type. Epyclastic rocks and andesitic breccia have a highest proportion of inherited minerals, the new formed phillosilicates being di octahedral smectite of beidellite type and an ordered interlayer chlorite/smectite mineral, of corrensite type. Smectite from the epyclastic rocks have higher Fe and Mg contents and chemical variability, as a consequence of nature of their parent rocks. The presence of corrensite in the epyclastic rocks suggests that in the Morron de Mateo area a propilitic alteration process occurred after bentonite formation, which transformed Fe-Mg-rich smectite into corrensite. This transformation was probably favoured by the sub volcanic intrusion, which also produced a temperature increase in the geological media and a supply of Fe-Mg-rich solutions, which also were the responsible for the metasomatic transformations observed in the calcarenite beds. (Author) 57 refs.

  14. The desorption of caesium from Peach Bottom HTGR steam generator materials

    International Nuclear Information System (INIS)

    Clark, M.J.

    1979-03-01

    The work at Harwell on the Peach Bottom End-of-Life Program in co-operation with the General Atomic Company (U.S.A.) is described. Materials taken from the Economiser, Evaporator and Superheater Sections of the Peach Bottom Unit No. 1. High Temperature Gas Cooled Reactor (HTGR) Heat Exchanger were placed in a reducing atmosphere comparable to the composition of an HTGR helium coolant gas, and the desorption of caesium isotopes measured under known conditions of flow, temperature and oxygen pressure. (author)

  15. Neural network analysis of crosshole tomographic images: The seismic signature of gas hydrate bearing sediments in the Mackenzie Delta (NW Canada)

    Science.gov (United States)

    Bauer, K.; Pratt, R. G.; Haberland, C.; Weber, M.

    2008-10-01

    Crosshole seismic experiments were conducted to study the in-situ properties of gas hydrate bearing sediments (GHBS) in the Mackenzie Delta (NW Canada). Seismic tomography provided images of P velocity, anisotropy, and attenuation. Self-organizing maps (SOM) are powerful neural network techniques to classify and interpret multi-attribute data sets. The coincident tomographic images are translated to a set of data vectors in order to train a Kohonen layer. The total gradient of the model vectors is determined for the trained SOM and a watershed segmentation algorithm is used to visualize and map the lithological clusters with well-defined seismic signatures. Application to the Mallik data reveals four major litho-types: (1) GHBS, (2) sands, (3) shale/coal interlayering, and (4) silt. The signature of seismic P wave characteristics distinguished for the GHBS (high velocities, strong anisotropy and attenuation) is new and can be used for new exploration strategies to map and quantify gas hydrates.

  16. Clay Mineralogy of Soils on Quaternary Sediment in Northeast of Urmia

    Directory of Open Access Journals (Sweden)

    Parisa Farzamnia

    2017-03-01

    10.83 °C respectively and the soil moisture and temperature regimes are dry xeric and mesic respectively. In this study, eight soil profiles in quaternary sediments were dug and sampled and the morphological, physical, chemical and mineralogical properties were determined using standard methods. Results and Discussion: According to the results, Illite, smectite, Kaolinite, chlorite, vermiculite and hydroxy interlayer vermiculite (HIV were the dominant clay minerals in these soils. The origin of illite, chlorite and kaolinite were related to inheritance from parent material. Regarding to the present of some smectite in the parent material of these soils, some of smectites have been inherited from parent material. Nevertheless it seems that, the most of smectites in these soils have pedogenic origin. Based on mineralogical results and trends variation of smectite and illite along studied profiles, we concluded that some of smectites in these soils have been formed from illite transformation. In profiles 4 and 6, regarding to low depth water table and consequently poor drainage, high pH and high values of calcium and magnesium cations, provide suitable conditions for the neoformation of smectit and so, some of smectites have been formed via neoformation from soil solution. In these soils, vermiculites were pedogenic and have been formed during transformation of illite to smectite. Small amounts of hydroxy interlayer vermiculites were present in buried horizons and regarding that they were not present in parent material, it might be because these minerals are pedogenic and have been formed in a past wetter climate. The transformation of illite to smectite in lower horizons needs high moisture and regarding to recent semiarid climate of study area, the suitable amount of moisture for this transformation, especially in lower depths and also in buried horizons, is not present. Thus, it seems the transformation of illite to smectite in lower depths and buried horizons has

  17. Stable and biocompatible genipin-inducing interlayer-crosslinked micelles for sustained drug release

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Yu; Zhang, Xiaojin, E-mail: zhangxj@cug.edu.cn [China University of Geosciences, Faculty of Materials Science and Chemistry (China)

    2017-05-15

    To develop the sustained drug release system, here we describe genipin-inducing interlayer-crosslinked micelles crosslinked via Schiff bases between the amines of amphiphilic linear-hyperbranched polymer poly(ethylene glycol)-branched polyethylenimine-poly(ε-caprolactone) (PEG-PEI-PCL) and genipin. The generation of Schiff bases was confirmed by the color changes and UV-Vis absorption spectra of polymeric micelles after adding genipin. The particle size, morphology, stability, in vitro cytotoxicity, drug loading capacity, and in vitro drug release behavior of crosslinked micelles as well as non-crosslinked micelles were characterized. The results indicated that genipin-inducing interlayer-crosslinked micelles had better stability and biocompatibility than non-crosslinked micelles and glutaraldehyde-inducing interlayer-crosslinked micelles. In addition, genipin-inducing interlayer-crosslinked micelles were able to improve drug loading capacity, reduce the initial burst release, and achieve sustained drug release.

  18. The valve effect of the carbide interlayer of an electric resistance plug

    International Nuclear Information System (INIS)

    Lakomskii, V.

    1998-01-01

    The welded electric resistance plug (ERP) usually contains a carbide interlayer at the plug-carbon material interface. The interlayer forms during welding the contact metallic alloy with the carbon material when the oxide films of the alloy are reduced on the interface surface by carbon to the formation of carbides and the surface layer of the plug material dissolves carbon to saturation. Subsequently, during solidification of the plug material it forms carbides with the alloy components. The structural composition of the carbide interlayer is determined by the chemical composition of the contact alloy. In alloys developed by the author and his colleagues the carbide forming elements are represented in most cases by silicon and titanium and, less frequently, by chromium and manganese. Therefore, the carbide interlayers in the ERP consisted mainly of silicon and titanium carbides

  19. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

  20. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

    The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

  1. Gas hydrates

    Digital Repository Service at National Institute of Oceanography (India)

    Ramprasad, T.

    , not all of them are white like snow. Some hydrates from the deep Gulf of Mexico are richly colored in shades of yellow, orange, or even red. The ice-like masses are beautiful, and contrast with the dull gray of deep sea muds. Hydrates from the Blake... volcanoes and associated gas hydrates: Marine Geology, v. 167, p. 29-42. Milkov, A.V. and R. Sassen, 2001a, Estimate of gas hydrate resource, northwestern Gulf of Mexico continental slope: Marine Geology, v. 179, pp. 71-83. Milkov, A.V., Sassen, R...

  2. Shifting Focus: From Hydration for Performance to Hydration for Health.

    Science.gov (United States)

    Perrier, Erica T

    2017-01-01

    Over the past 10 years, literature on hydration biomarkers has evolved considerably - from (de)hydration assessment towards a more global definition of biomarkers of hydration in daily life. This shift in thinking about hydration markers was largely driven by investigating the differences that existed between otherwise healthy individuals whose habitual, ad-libitum drinking habits differ, and by identifying physiological changes in low-volume drinkers who subsequently increase their water intake. Aside from obvious differences in urinary volume and concentration, a growing body of evidence is emerging that links differences in fluid intake with small, but biologically significant, differences in vasopressin (copeptin), glomerular filtration rate, and markers of metabolic dysfunction or disease. Taken together, these pieces of the puzzle begin to form a picture of how much water intake should be considered adequate for health, and represent a shifting focus from hydration for performance, toward hydration for health outcomes. This narrative review outlines the key areas of research in which the global hydration process - including water intake, urinary hydration markers, and vasopressin - has been associated with health outcomes, focusing on kidney and metabolic endpoints. It will also provide a commentary on how various hydration biomarkers may be used in hydration for health assessment. Finally, if adequate water intake can play a role in maintaining health, how might we tell if we are drinking enough? Urine output is easily measured, and can take into account differences in daily physical activity, climate, dietary solute load, and other factors that influence daily water needs. Today, targets have been proposed for urine osmolality, specific gravity, and color that may be used by researchers, clinicians, and individuals as simple indicators of optimal hydration. However, there remain a large number of incomplete or unanswered research questions regarding the

  3. SORPTION AND ABIOTIC REDOX TRANSFORMATION OF NITROBENZENE AT THE SMECTITE-WATER INTERFACE

    Science.gov (United States)

    The effect of the redox state of structural Fe on the surface reactivity of iron-bearing phyllosilicates in aqueous suspension was investigated using a molecular probe. For this purpose the structural Fe in montmorillonite and ferruginous smectite was chemically reduced by sodium...

  4. Impacts of Hydrate Distribution on the Hydro-Thermo-Mechanical Properties of Hydrate-Bearing Sediments

    Science.gov (United States)

    Dai, S.; Seol, Y.

    2015-12-01

    In general, hydrate makes the sediments hydraulically less conductive, thermally more conductive, and mechanically stronger; yet the dependency of these physical properties on hydrate saturation varies with hydrate distribution and morphology. Hydrate distribution in sediments may cause the bulk physical properties of their host sediments varying several orders of magnitude even with the same amount of hydrate. In natural sediments, hydrate morphology is inherently governed by the burial depth and the grain size of the host sediments. Compare with patchy hydrate, uniformly distributed hydrate is more destructive to fluid flow, yet leads to higher gas and water permeability during hydrate dissociation due to the easiness of forming percolation paths. Water and hydrate have similar thermal conductivity values; the bulk thermal conductivity of hydrate-bearing sediments depends critically on gas-phase saturation. 60% of gas saturation may result in evident thermal conductivity drop and hinder further gas production. Sediments with patchy hydrate yield lower stiffness than that with cementing hydrate but higher stiffness than that with pore filling and loading bearing hydrate. Besides hydrate distribution, the stress state and loading history also play an important role in the mechanical behavior of hydrate-bearing sediments.

  5. Effect of water molecule distribution on the quantitative XRD analysis in the case of Na-montmorillonite exchanged Cu2+

    International Nuclear Information System (INIS)

    Oueslati, W.; Meftah, M.; Ben Rhaiem, H.; Ben Haj Amara, A.

    2010-01-01

    Document available in extended abstract form only. Several theoretical models are proposed to describe hydration process for Wyoming-montmorillonite clay exchanged Na + or Cu 2+ . They propose some theoretical distribution and disposition for water molecule in the inter-lamellar space in the case of homogeneous and inter-stratified hydration states. For example, Ben Brahim et al. (1983a) studied the interlayer structure (atomic positions of interlayer cations) and associated H 2 O molecules of Na-saturated montmorillonite and beidellite samples. Moore and Hower (1986) studied ordered structures composed of mono-hydrated and collapsed interlayers in montmorillonite, and Cuadros (1996) estimated the H 2 O content of smectite as a function of the interlayer cation. Using similar approach, Ferrage et al (2005b) proposed a discreet distribution of water molecule layer in the same z coordinate of the exchangeable cation with inhomogeneous distribution. This heterogeneity was attributed to the surface charge. The main objective of this study is to characterize the structural changes in the theoretical XRD profile, induced by different water molecule distribution, used to simulate experimental XRD patterns in the case of Na-montmorillonite exchanged Cu 2+ . This problem was achieved by quantitative XRD analysis using an indirect method based on the comparison of the experimental 001 reflections obtained from oriented films patterns with those calculated from structural models. The starting materials were Ca-montmorillonite originated from bentonites of Wyoming (USA). The XRD patterns were obtained by reflection setting with a D8 ADVANCE Bruker installation using Cu-Kα radiation and equipped with solid state detector. Intensities were measured at an interval of 2Θ 0.04 deg. and 40-50 s counting time per step. The diffracted intensity was calculated according to the matrix formalism detailed by Drits and Tchoubar, (1990). The fitting strategies was detailed by Ferrage et

  6. Doses and risk estimates to the human conceptus due to internal prenatal exposure to radioactive caesium

    International Nuclear Information System (INIS)

    Kalef-Ezra, J.A.

    1997-01-01

    The 1986 nuclear reactor accident at Chernobyl resulted in widespread internal contamination by radioactive caesium. The aim of the present study was to estimate the doses to embryos/fetus in Greece attributed to maternal 134 Cs and 137 Cs intake and the consequent health risks to their offspring. In pregnant women the concentration of total-body caesium (TBCs) was lower than in age-matched non-pregnant women measured during the same month. A detailed study of intake and retention in the members of one family carried out during the three years that followed the accident indicated that the biological half-time of caesium in the women decreased by a factor of two shortly after conception. Then at partus, there was an increase in the biological half-time, reaching a value similar to that before conception. The total-body potassium concentration was constant over the entire period. Doses to the embryo/fetus due to maternal intake was estimated to be about 150 μGy maximally in those conceived between November 1986 and March 1987. When conception took place later, the prenatal dose followed an exponential reduction with a half-time of about 170 d. These prenatal doses do not exceed the doses from either the natural internal potassium, or from the usual external background sources. The risks attributed to maternal 134 Cs and 137 Cs intake were considerably lower than levels that would justify consideration of termination of a pregnancy. In the absence of these data however, 2500 otherwise wanted pregnancies in Greece were terminated following the Chernobyl accident. (author)

  7. Interlayer excitons in a bulk van der Waals semiconductor

    DEFF Research Database (Denmark)

    Arora, Ashish; Drueppel, Matthias; Schmidt, Robert

    2017-01-01

    Bound electron-hole pairs called excitons govern the electronic and optical response of many organic and inorganic semiconductors. Excitons with spatially displaced wave functions of electrons and holes (interlayer excitons) are important for Bose-Einstein condensation, superfluidity......, dissipationless current flow, and the light-induced exciton spin Hall effect. Here we report on the discovery of interlayer excitons in a bulk van der Waals semiconductor. They form due to strong localization and spin-valley coupling of charge carriers. By combining high-field magneto-reflectance experiments...

  8. Modification of magnetoresistance and magnetic properties of Ni thin films by adding Dy interlayer

    Science.gov (United States)

    Vorobiov, S. I.; Shabelnyk, T. M.; Shutylieva, O. V.; Pazukha, I. M.; Chornous, A. M.

    2018-03-01

    The paper reports the influence of dysprosium (Dy) interlayer addition on structure, magnetoresistance and magnetic properties of nickel (Ni) thin films. Trilayer film systems Ni/Dy/Ni have been prepared by alternate electron-beam evaporation. It is demonstrated that all as-prepared and annealed Ni thin films have face-centered cubic structure. The composition of the samples after addition of the Dy interlayer corresponds to the combination of face-centered cubic (Ni) and hexagonal close-packed (Dy) structures. The structure of Ni/Dy/Ni film systems changes from amorphous to polycrystalline when Dy interlayer thickness (t Dy) is more than 15 nm. The value of magnetoresistance increases with the adding the Dy interlayer in both longitudinal and transverse geometries, meanwhile the anisotropic character of magnetoresistance field dependences retained. The saturation and reversal magnetizations are reduced with the increasing of the Dy thickness interlayer, while the coercivity takes the minimum value at t Dy = 15 nm. The following increasing of t Dy leads to increasing of coercivity near to three times. This result indicates the influence of the crystal structure on the magnetic properties of Ni thin films at adding Dy interlayer.

  9. Effects of a Ta interlayer on the phase transition of TiSi2 on Si(111)

    Science.gov (United States)

    Jeon, Hyeongtag; Jung, Bokhee; Kim, Young Do; Yang, Woochul; Nemanich, R. J.

    2000-09-01

    This study examines the effects of a thin Ta interlayer on the formation of TiSi2 on Si(111) substrate. The Ta interlayer was introduced by depositing Ta and Ti films sequentially on an atomically clean Si(111) substrate in an ultrahigh vacuum (UHV) system. Samples of 100 Å Ti with 5 and 10 Å Ta interlayers were compared to similar structures without an interlayer. After deposition, the substrates were annealed for 10 min, in situ, at temperatures between 500 and 750 °C in 50 °C increments. The TiSi2 formation with and without the Ta interlayer was analyzed with an X-ray diffractometer, Auger electron spectroscopy (AES), Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and a four-point probe. The AES analysis data showed a 1:2 ratio of Ti:Si in the Ti-silicide layer and indicated that the Ta layer remained at the interface between TiSi2 and the Si(111) substrate. The C 49-C 54 TiSi2 phase transition temperature was lowered by ˜200 °C. The C 49-C 54 TiSi2 phase transition temperature was 550 °C for the samples with a Ta interlayer and was 750 °C for the samples with no Ta interlayer. The sheet resistance of the Ta interlayered Ti silicide showed lower values of resistivity at low temperatures which indicated the change in phase transition temperature. The C 54 TiSi2 displayed different crystal orientation when the Ta interlayer was employed. The SEM and TEM micrographs showed that the TiSi2 with a Ta interlayer significantly suppressed the tendency to islanding and surface agglomeration.

  10. Efficient hole injection in organic light-emitting diodes using polyvinylidenefluoride as an interlayer

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Soon Ok; Soo Yook, Kyoung [Department of Polymer Science and Engineering, Dankook University, Jukjeon-dong, Suji-gu, Yongin-si, Gyeonggi 448-701 (Korea, Republic of); Lee, Jun Yeob, E-mail: leej17@dankook.ac.k [Department of Polymer Science and Engineering, Dankook University, Jukjeon-dong, Suji-gu, Yongin-si, Gyeonggi 448-701 (Korea, Republic of)

    2010-10-15

    The effect of the polyvinylidenefluoride (PVDF) interlayer on the hole injection and the device performances of the green phosphorescent organic light-emitting diodes (PHOLEDs) was investigated. The hole current density of the hole only device was improved and the power efficiency of the green PHOLEDs was enhanced from 10.5 to 12.5 lm/W by the PVDF interlayer. The reduction of the interfacial energy barrier was responsible for the high hole current density in the PVDF interlayer based green PHOLEDs.

  11. Influence of various thickness metallic interlayers on opto-electric and mechanical properties of AZO thin films on PET substrates

    Science.gov (United States)

    Chang, R. C.; Li, T. C.; Lin, C. W.

    2012-02-01

    Various thickness metallic interlayers to improve the opto-electric and mechanical properties of aluminum-doped zinc oxide (AZO) thin films deposited on flexible polyethylene terephtalate (PET) substrates are studied. The effects of the interlayers on the resistance and transmittance of the AZO thin films are discussed. The result shows that the metallic interlayers effectively improve the electric resistance but reduce the optical transmittance of the AZO thin films. These phenomena become more obvious as the interlayer thickness increases. However, the AZO with an aluminum interlayer still behaves an acceptable transmittance. Moreover, mechanical tests indicate that the aluminum interlayer increases the hardness and modulus, and reduce the residual stress of the AZO thin films. In contrast, the silver and copper interlayers decrease the AZO's mechanical properties. Comparing to those without any interlayer, the results show that the best interlayer is the 6 nm thick aluminum film.

  12. Molecular Simulation Study of Montmorillonite in Contact with Variably Wet Supercritical Carbon Dioxide

    KAUST Repository

    Kadoura, Ahmad Salim

    2017-03-07

    We perform grand canonical Monte Carlo simulations to study the detailed molecular mechanism of intercalation behavior of CO2 in Na-, Ca-, and Mg- montmorillonite exposed to variably hydrated supercritical CO2 at 323.15 K and 90 bar, The simulations indicate that the intercalation of CO2 strongly depends on the relative humidity (RH). The intercalation of CO2 in the dehydrated interlayer is inhibited, followed by the swelling of the interlayer region due to uptake of water and CO2 as the RH increases. In all of the hydrated clay samples, the amount of the intercalated CO2 generally decreases as a function of increasing RH, which is attributed mainly to the weakening of the interaction between CO2 and clay. At low RH values, Ca- and Mg- montmorillonite are relatively more efficient in capturing CO2. The amount of CO2 trapped in all clay samples shows similar values above RH of similar to 60%. Molecular dynamics simulations show that the diffusion coefficient of each species generally increases with increasing RH due to the associated expansion of the interlayer distance of the clay. For all the hydrated samples, the diffusion coefficients of CO2 and water in the interlayers are mostly comparable due to the fact that CO2 molecules are well solvated. The diffusion of CO2 in each hydration state is mostly independent of the type of cation in accordance with the fact that CO2 molecules hardly migrate into the first hydration shell of the interlayer cations.

  13. Standard Guide for Selection of Test Methods for Interlayer Materials for Aerospace Transparent Enclosures

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2002-01-01

    1.1 This guide summarizes the standard test methods available for determining physical and mechanical characteristics of interlayer materials used in multi-ply aerospace transparent enclosures. 1.2 Interlayer materials are used to laminate glass-to-glass, glass-to-plastic, and plastic-to-plastic. Interlayer materials are basically transparent adhesives with high-quality optical properties. They can also serve as an energy absorbing medium, a fail-safe membrane to contain cockpit pressure and to prevent entry of impact debris; a strain insulator to accommodate different thermal expansion rates of members being laminated and as an adherent to prevent spalling of inner surface ply material fragments. The relative importance of an interlayer characteristic will be a function of the prime use it serves in its particular application. 1.3 This guide, as a summary of various methods in Section 2, is intended to facilitate the selection of tests that can be applied to interlayer materials. 1.4 The test methods list...

  14. Petrophysics of shale intervals in the Skjold Field, Danish North Sea

    DEFF Research Database (Denmark)

    Mbia, Ernest Ncha; Fabricius, Ida Lykke; Oji, C. O.

    2011-01-01

    interval 6 is mainly shale. X-ray diffraction analysis reveals the dominance of inter-layered smectite/illite in interval 1–3 and upper part of interval 4, whereas illite dominates interval 5 and 6. Other minerals include kaolinite, chlorite, quartz, calcite, Opal-CT, dolomite and plagioclase...

  15. Surface conductivity of the single crystal aluminum oxide in vacuum and caesium vapors

    International Nuclear Information System (INIS)

    Vasilchenko, A.V.; Izhvanov, O.L.

    1996-01-01

    Results of measurements of surface conductivity of single-crystal aluminum oxide samples in vacuum and cesium vapors at T=620 endash 830 K and P Cs =0.13 endash 2 Pa are shown in the paper. Analysis of caesium vapor influence is carried out and ultimate characteristics of samples conductivity under operation conditions in thermionic nuclear power system (NPP) TFE are estimated. copyright 1996 American Institute of Physics

  16. Prepubertal changes in the metabolism of caesium in girls?

    International Nuclear Information System (INIS)

    Rundo, J.

    1987-01-01

    The results are presented of determinations from 1963 to 1967 of the 137 Cs/K ratio in three children (two girls and a younger boy). In the two girls the ratio was at a maximum in late 1963. The decline by a factor of more than four during 1965-1967 was consistent with the contemporaneous reduction in dietary contamination. When adjusted to allow for the decreasing intake, the ratio shows an increase from the age of about 9.5 in each girl. It is suggested that this is a reflection of an increase in the biological half-life of caesium in the girls, associated with prepubertal hormonal changes. 5 refs.; 4 figs.; 2 tabs

  17. Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Hanzhong, E-mail: jiahz@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Li, Li [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Chen, Hongxia; Zhao, Yue [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); School of Geology and Mining Engineering, Xinjiang University, Urumqi 830046 (China); Li, Xiyou [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Wang, Chuanyi, E-mail: cywang@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China)

    2015-04-28

    Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe{sup 3+} > Al{sup 3+} > Cu{sup 2+} >> Ca{sup 2+} > K{sup +} > Na{sup +}, which is consistent with the binding energy of cation–π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation–π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na{sup +}-smectite and K{sup +}-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe{sup 3+}, Al{sup 3+}, and Cu{sup 2+} are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O{sub 2}{sup −}· , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation.

  18. Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light

    International Nuclear Information System (INIS)

    Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

    2015-01-01

    Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe 3+ > Al 3+ > Cu 2+ >> Ca 2+ > K + > Na + , which is consistent with the binding energy of cation–π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation–π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na + -smectite and K + -smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe 3+ , Al 3+ , and Cu 2+ are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O 2 − · , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation

  19. Tunable states of interlayer cations in two-dimensional materials

    International Nuclear Information System (INIS)

    Sato, K.; Numata, K.; Dai, W.; Hunger, M.

    2014-01-01

    The local state of cations inside the Ångstrom-scale interlayer spaces is one of the controlling factors for designing sophisticated two-dimensional (2D) materials consisting of 2D nanosheets. In the present work, the molecular mechanism on how the interlayer cation states are induced by the local structures of the 2D nanosheets is highlighted. For this purpose, the local states of Na cations in inorganic 2D materials, in which the compositional fluctuations of a few percent are introduced in the tetrahedral and octahedral units of the 2D nanosheets, were systematically studied by means of 23 Na magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and 23 Na multiple-quantum MAS (MQMAS) NMR spectroscopy. In contrast with an uniform distribution of Na cations expected so far, various well-defined cation states sensitive to the local structures of the 2D nanosheets were identified. The tunability of the interlayer cation states along with the local structure of the 2D nanosheets, as the smallest structural unit of the 2D material, is discussed

  20. Tunable states of interlayer cations in two-dimensional materials

    Energy Technology Data Exchange (ETDEWEB)

    Sato, K.; Numata, K. [Department of Environmental Sciences, Tokyo Gakugei University, Koganei, Tokyo 184-8501 (Japan); Dai, W. [Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071 (China); Hunger, M. [Institute of Chemical Technology, University of Stuttgart, 70550 Stuttgart (Germany)

    2014-03-31

    The local state of cations inside the Ångstrom-scale interlayer spaces is one of the controlling factors for designing sophisticated two-dimensional (2D) materials consisting of 2D nanosheets. In the present work, the molecular mechanism on how the interlayer cation states are induced by the local structures of the 2D nanosheets is highlighted. For this purpose, the local states of Na cations in inorganic 2D materials, in which the compositional fluctuations of a few percent are introduced in the tetrahedral and octahedral units of the 2D nanosheets, were systematically studied by means of {sup 23}Na magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and {sup 23}Na multiple-quantum MAS (MQMAS) NMR spectroscopy. In contrast with an uniform distribution of Na cations expected so far, various well-defined cation states sensitive to the local structures of the 2D nanosheets were identified. The tunability of the interlayer cation states along with the local structure of the 2D nanosheets, as the smallest structural unit of the 2D material, is discussed.

  1. Importance of interlayer pair tunneling: A variational perspective

    International Nuclear Information System (INIS)

    Medhi, Amal; Basu, Saurabh

    2011-01-01

    We study the effect of interlayer pair tunneling in a bilayer superconductor where each layer is described by a two dimensional t-J model and the two layers are connected by the Josephson pair tunneling term. We study this model using a grand canonical variational Monte Carlo (GVMC) method, for which we develop a new algorithm to perform Monte Carlo simulation of a system with fluctuating particle number. The variational wavefunction is taken to be the product of two Gutzwiller projected d-wave BCS wavefunctions with variable particle densities, one for each layer. We calculate the energy of the above state as a function of the d-wave superconducting gap parameter, Δ. We find that the interlayer pair tunneling energy, E perpendicular shows interesting variation with Δ. E perpendicular tends to enhance the optimal value of Δ, thereby the superconducting pairing. However the magnitude of the tunneling energy is found to be too small to have any appreciable effect on the physical properties. While the result is supported by early experiments and hence may appear known to the community, the current work presents a new approach to the problem and confirms the diminished role of interlayer pair tunneling by directly calculating its contribution to superconducting condensation energy.

  2. Radioactive caesium in Boreal forest landscapes - Dynamics and transport in food webs. Summary of research 1986-1996

    Energy Technology Data Exchange (ETDEWEB)

    Bergman, R.; Nylen, T.; Palo, T

    1998-12-01

    The need for - but also the paucity of - radioecological knowledge concerning the boreal forest became particularly apparent after the nuclear power plant accident in Chernobyl in April 1986. As a consequence several new projects were initiated in the Nordic countries with particular focus on the behaviour of radioactivecaesium in terrestrial and aquatic systems characteristic for the Fenno-Scandinavian landscapes. Among these new projects a multi-disciplinary co-operation in Umeaa between scientists at the Swedish University of Agricultural Sciences, and the Defence Research Establishment emerged. Initially this joint work focused mainly on descriptions of the dynamic changes of the content of radioactive caesium in soil-plant and animal communities in the county of Vaesterbotten. Most of the studies have been performed at the Vindeln experimental forest, 60 km NW of Umeaa. Plants of key interest were: bilberry (Vaccinium myrtillus), birch (Betula spp.), and pine (Pinus sylvestris), and among the animals: the moose (Alces alces) and a small rodent, the forest vole (Clethrionomus glareolus). Gradually over the past ten years the research has entered the stage where the specific causes of the caesium behaviour have been addressed - partly by the help of models developed for simulating forest ecosystems, partly by complementary field experiments. This paper reviews our main findings on this theme concerning the behaviour of radioactive caesium in boreal landscapes and significant pathways to man, as has become apparent from the radioecological co-operation dating from about ten years back. A list of the publications arising from these studies since 1986 is also presented in this report.

  3. Characterisation of bentonites from Kutch, India and Milos, Greece - some candidate tunnel back-fill materials?

    Energy Technology Data Exchange (ETDEWEB)

    Olsson, Siv; Karnland, Ola (Clay Technology AB, Lund (Sweden))

    2009-12-15

    During the past decades comprehensive investigations have been made on bentonite clays in order to find optimal components of the multi-barrier system of repositories for radioactive waste. The present study gives a mineralogical characterisation of some selected bentonites, in order to supply some of the necessary background data on the bentonites for evaluating their potential as tunnel back-fill materials. Two bentonites from the island of Milos, Greece (Milos BF 04 and BF 08), and two bentonites from Kutch, India (Kutch BF 04 and BF 08) were analysed for their grain size distribution, cation exchange properties and chemical composition. The mineralogical composition was determined by X-ray diffraction analysis and evaluated quantitatively by use of the Siroquant software. Both the bulk bentonite and the <1mum fraction were analyzed when relevant. Prior to the chemical analyses the <1 mum fractions were converted to homo-ionic clays and purified by dialysis. The chemical data were used for calculating the structural formula of the smectites. Milos BF 04 contains ca. 10% particles >63 mum. The bentonite is distinguished by a high content of dolomite and calcite, which make up almost 25% of the bulk sample. The major accessory minerals are K-feldspars and plagioclase, whereas the content of sulphur-bearing minerals is very low (0.06% total S). Smectite makes up around 60% of the bulk sample, which has a CEC value of 73 meq/100 g. The pool of interlayer cations has a composition Mg>Ca>>Na>>K. The X-ray diffraction characteristics and the high potassium content (1.03% K{sub 2}O) of the <1 mum fraction suggest that the smectite is interstratified with ca. 10% illitic layers. Based on the charge distribution the smectite should be classified as montmorillonite and according to the structural formula, Mg predominates over Fe in the octahedral sheet. However, remnants of Mg-carbonates, if present, may be a source of error in the formula calculation. Milos BF 08 has a

  4. Controlled Synthesis of Carbon-Encapsulated Copper Nanostructures by Using Smectite Clays as Nanotemplates

    NARCIS (Netherlands)

    Tsoufis, Theodoros; Colomer, Jean-Francois; Maccallini, Enrico; Jankovic, Lubos; Rudolf, Petra; Gournis, Dimitrios; Jankovič, Lubos

    Rhomboidal and spherical metallic-copper nanostructures were encapsulated within well-formed graphitic shells by using a simple chemical method that involved the catalytic decomposition of acetylene over a copper catalyst that was supported on different smectite clays surfaces by ion-exchange. These

  5. Mean residence time of soil organic matter associated with kaolinite and smectite

    NARCIS (Netherlands)

    Wattel-Koekkoek, E.J.W.; Buurman, P.; Plicht, van der J.; Wattel, J.T.; Breemen, van N.

    2003-01-01

    To gain insight into the effect of clay mineralogy on the turnover of organic matter, we analysed the C-14 activity of soil organic matter associated with clay in soils dominated by kaolinite and smectite in natural savanna systems in seven countries. Assuming that carbon inputs and outputs are in

  6. Mean residence time of soil organic matter associated with kaolinite and smectite

    NARCIS (Netherlands)

    Wattel-Koekkoek, E.J.W.; Buurman, P.; Plicht, J. van der; Wattel, E.; Breemen, N. van

    To gain insight into the effect of clay mineralogy on the turnover of organic matter, we analysed the C-14 activity of soil organic matter associated with clay in soils dominated by kaolinite and smectite in natural savanna systems in seven countries. Assuming that carbon inputs and outputs are in

  7. Thermal decomposition of hydrotalcite with chromate, molybdate or sulphate in the interlayer

    Energy Technology Data Exchange (ETDEWEB)

    Frost, Ray L. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia)]. E-mail: r.frost@qut.edu.au; Musumeci, Anthony W. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia); Bostrom, Thor [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia); Adebajo, Moses O. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia); Weier, Matt L. [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia); Martens, Wayde [Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001 (Australia)

    2005-05-15

    The thermal decomposition of hydrotalcites with chromate, molybdate and sulphate in the interlayer has been studied using thermogravimetric analysis coupled to a mass spectrometer measuring the gas evolution. X-ray diffraction shows the hydrotalcites have a d(0 0 3) spacing of 7.98 A with very small differences in the d-spacing between the three hydrotalcites. XRD was also used to determine the products of the thermal decomposition. For the sulphate-hydrotalcite decomposition the products were MgO and a spinel MgAl{sub 2}O{sub 4}, for the chromate interlayered hydrotalcite MgO, Cr{sub 2}O{sub 3} and spinel. For the molybdate interlayered hydrotalcite the products were MgO, spinel and MgMoO{sub 4}. EDX analyses enabled the formula of the hydrotalcites to be determined. Two processes are observed in the thermal decomposition namely dehydration and dehydroxylation and for the case of the sulphate interlayered hydrotalcite, a third process is the loss of sulphate. Both the dehydration and dehydroxylation take place in three steps each for each of the hydrotalcites.

  8. Crystal structure of caesium hydrogen (L)-aspartate and an overview of crystalline compounds of aspartic acid with inorganic constituents

    Energy Technology Data Exchange (ETDEWEB)

    Fleck, M. [Universitaet Wien (Austria). Institut fuer Mineralogie und Kristallographie; Emmerich, R.; Bohaty, L. [Universitaet zu Koeln (Austria). Institut fuer Kristallographie

    2010-08-15

    The crystal structure of the new polar compound caesium hydrogen (L)-aspartate, Cs(C{sub 4}H{sub 6}NO{sub 4}), (abbreviated: Cs(L -AspH)) was determined from single crystal X-ray diffraction data; it comprises two crystallographically different L -AspH anions that are connected via caesium cations to form a three dimensional framework. The Cs ions are irregularly sevenfold[Cs1O{sub 7}] respectively eightfold[Cs2O{sub 8}] coordinated to all {alpha}- and {beta}- carboxylate oxygen atoms. Cs(L -AspH) represents a novel structure type of its own, as do most compounds of (L)-aspartic acid with inorganic constituents. A brief summary of such structurally known aspartates is given. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  9. Synthesis and characterization of organophilic clay from Cuban Chiqui Gomez bentonite

    International Nuclear Information System (INIS)

    Cortes, Guillermo R. Martin; Hennies, Wildor T.; Valera, Ticiane S.; Esper, Fabio J.; Diaz, Francisco R. Valenzuela

    2009-01-01

    Smectite are clay minerals with a layered structure and nanometric thickness, high specific area and a huge variety of uses. Consisting on stacked layers of about 1nm thickness, including two silica tetrahedral and one octahedral sheet. Properties of natural Smectite can be enhanced by organic modification, due to the substitution of the exchangeable cations in the interlayer area. In fact, the properties of the modified smectite (organophilic clay) are related to its modified chemical composition and structural parameters. The interaction of smectite clays with surfactants has an important interest in the fields of drilling fluids, paints, cosmetic, ceramic industries and others. Recent applications are: remediation of contaminated areas and polymer/clay nanocomposites. The aim of this paper is to obtain organophilic clays using a bentonite from the Chiqui Gomez deposit in Central Cuba. The raw and organophilic clays were analyzed by DRX, SEM, swelling capacity in organic solvents and others. (author)

  10. The Effect of Interlayer Materials on the Joint Properties of Diffusion-Bonded Aluminium and Magnesium

    Directory of Open Access Journals (Sweden)

    Stefan Habisch

    2018-02-01

    Full Text Available Diffusion bonding is a well-known technology for a wide range of advanced joining applications, due to the possibility of bonding different materials within a defined temperature-time-contact pressure regime in solid state. For this study, aluminium alloys AA 6060, AA 6082, AA 7020, AA 7075 and magnesium alloy AZ 31 B are used to produce dissimilar metal joints. Titanium and silver were investigated as interlayer materials. SEM and EDXS-analysis, micro-hardness measurements and tensile testing were carried out to examine the influence of the interlayers on the diffusion zone microstructures and to characterize the joint properties. The results showed that the highest joint strength of 48 N/mm2 was reached using an aluminium alloy of the 6000 series with a titanium interlayer. For both interlayer materials, intermetallic Al-Mg compounds were still formed, but the width and the level of hardness across the diffusion zone was significantly reduced compared to Al-Mg joints without interlayer.

  11. Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

    Science.gov (United States)

    Circone, S.; Kirby, S.H.; Stern, L.A.

    2005-01-01

    The composition of methane hydrate, namely nW for CH 4??nWH2O, was directly measured along the hydrate equilibrium boundary under conditions of excess methane gas. Pressure and temperature conditions ranged from 1.9 to 9.7 MPa and 263 to 285 K. Within experimental error, there is no change in hydrate composition with increasing pressure along the equilibrium boundary, but nW may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n W = 5.81-6.10 H2O describes the entire range of measured values, with an average composition of CH4??5.99(??0.07) H2O along the equilibrium boundary. These results, consistent with previously measured values, are discussed with respect to the widely ranging values obtained by thermodynamic analysis. The relatively constant composition of methane hydrate over the geologically relevant pressure and temperature range investigated suggests that in situ methane hydrate compositions may be estimated with some confidence. ?? 2005 American Chemical Society.

  12. A comparison using the caesium-137 technique of the relative importance of cultivation and overland flow on soil erosion in a steep semi-tropical sub-catchment

    International Nuclear Information System (INIS)

    Wiranatha, A.S.; Rose, C.W.; Salama, M.S.

    2001-01-01

    The spatial pattern of net soil loss on 6 downslope transects in a small semi-tropical sub-catchment was measured in 1990-91 using the resident caesium-137 deficit technique. The sub-catchment consisted of 2 opposing hillslopes which shed water to an intermittent stream in the valley bottom of the sub-catchment. There were 3 transects on each of the opposing hillslopes, and measurement indicated net soil loss from all 6 transects. Furthermore, the spatial pattern of caesium- 37 deficit did not indicate the accumulation of soil expected due to the slope decrease toward the bottom of the valley. Possible explanations of this finding could be the effect of periodic flooding of the intermittent valley stream, or seepage-accelerated erosion. Pineapple cultivation in the sub-catchment since 1950 included intensive cultivation at 4-year intervals by downslope-moving rotary hoe. The paper develops a theoretical prediction of the spatial pattern of net soil loss expected due to such cultivation, as well as the expected pattern of soil loss due to overland flow on the hillslopes. The spatial patterns of soil loss due to these 2 different soil erosion mechanisms were then compared with the pattern of net soil loss indicated by caesium- 137 depletion to provide an assessment of their likely relative importance in contributing to soil loss. In the upper part of each hillslope, this comparison of spatial trends did not allow the dominant cause of soil erosion to be distinguished. Both the model of erosion due to cultivation and that due to hillside overland flow predicted soil accumulation in the lower valley sides where slope decreased. Neither model represented the net loss of such accumulated soil indicated by caesium- 137 deficit, and this loss possibly occurred during periodically observed flooding of the valley floor, or due to surface burial with caesium-137 depleted subsoil. Copyright (2001) CSIRO Publishing

  13. Polytypism and unexpected strong interlayer coupling in two-dimensional layered ReS2

    Science.gov (United States)

    Qiao, Xiao-Fen; Wu, Jiang-Bin; Zhou, Linwei; Qiao, Jingsi; Shi, Wei; Chen, Tao; Zhang, Xin; Zhang, Jun; Ji, Wei; Tan, Ping-Heng

    2016-04-01

    Anisotropic two-dimensional (2D) van der Waals (vdW) layered materials, with both scientific interest and application potential, offer one more dimension than isotropic 2D materials to tune their physical properties. Various physical properties of 2D multi-layer materials are modulated by varying their stacking orders owing to significant interlayer vdW coupling. Multilayer rhenium disulfide (ReS2), a representative anisotropic 2D material, was expected to be randomly stacked and lack interlayer coupling. Here, we demonstrate two stable stacking orders, namely isotropic-like (IS) and anisotropic-like (AI) N layer (NL, N > 1) ReS2 are revealed by ultralow- and high-frequency Raman spectroscopy, photoluminescence and first-principles density functional theory calculation. Two interlayer shear modes are observed in AI-NL-ReS2 while only one shear mode appears in IS-NL-ReS2, suggesting anisotropic- and isotropic-like stacking orders in IS- and AI-NL-ReS2, respectively. This explicit difference in the observed frequencies identifies an unexpected strong interlayer coupling in IS- and AI-NL-ReS2. Quantitatively, the force constants of them are found to be around 55-90% of those of multilayer MoS2. The revealed strong interlayer coupling and polytypism in multi-layer ReS2 may stimulate future studies on engineering physical properties of other anisotropic 2D materials by stacking orders.Anisotropic two-dimensional (2D) van der Waals (vdW) layered materials, with both scientific interest and application potential, offer one more dimension than isotropic 2D materials to tune their physical properties. Various physical properties of 2D multi-layer materials are modulated by varying their stacking orders owing to significant interlayer vdW coupling. Multilayer rhenium disulfide (ReS2), a representative anisotropic 2D material, was expected to be randomly stacked and lack interlayer coupling. Here, we demonstrate two stable stacking orders, namely isotropic-like (IS) and

  14. Enhancing charge transfer kinetics by nanoscale catalytic cermet interlayer.

    Science.gov (United States)

    An, Jihwan; Kim, Young-Beom; Gür, Turgut M; Prinz, Fritz B

    2012-12-01

    Enhancing the density of catalytic sites is crucial for improving the performance of energy conversion devices. This work demonstrates the kinetic role of 2 nm thin YSZ/Pt cermet layers on enhancing the oxygen reduction kinetics for low temperature solid oxide fuel cells. Cermet layers were deposited between the porous Pt cathode and the dense YSZ electrolyte wafer using atomic layer deposition (ALD). Not only the catalytic role of the cermet layer itself but the mixing effect in the cermet was explored. For cells with unmixed and fully mixed cermet interlayers, the maximum power density was enhanced by a factor of 1.5 and 1.8 at 400 °C, and by 2.3 and 2.7 at 450 °C, respectively, when compared to control cells with no cermet interlayer. The observed enhancement in cell performance is believed to be due to the increased triple phase boundary (TPB) density in the cermet interlayer. We also believe that the sustained kinetics for the fully mixed cermet layer sample stems from better thermal stability of Pt islands separated by the ALD YSZ matrix, which helped to maintain the high-density TPBs even at elevated temperature.

  15. Interlayer excitons in a bulk van der Waals semiconductor.

    Science.gov (United States)

    Arora, Ashish; Drüppel, Matthias; Schmidt, Robert; Deilmann, Thorsten; Schneider, Robert; Molas, Maciej R; Marauhn, Philipp; Michaelis de Vasconcellos, Steffen; Potemski, Marek; Rohlfing, Michael; Bratschitsch, Rudolf

    2017-09-21

    Bound electron-hole pairs called excitons govern the electronic and optical response of many organic and inorganic semiconductors. Excitons with spatially displaced wave functions of electrons and holes (interlayer excitons) are important for Bose-Einstein condensation, superfluidity, dissipationless current flow, and the light-induced exciton spin Hall effect. Here we report on the discovery of interlayer excitons in a bulk van der Waals semiconductor. They form due to strong localization and spin-valley coupling of charge carriers. By combining high-field magneto-reflectance experiments and ab initio calculations for 2H-MoTe 2 , we explain their salient features: the positive sign of the g-factor and the large diamagnetic shift. Our investigations solve the long-standing puzzle of positive g-factors in transition metal dichalcogenides, and pave the way for studying collective phenomena in these materials at elevated temperatures.Excitons, quasi-particles of bound electron-hole pairs, are at the core of the optoelectronic properties of layered transition metal dichalcogenides. Here, the authors unveil the presence of interlayer excitons in bulk van der Waals semiconductors, arising from strong localization and spin-valley coupling of charge carriers.

  16. Characterisation of bentonites from Kutch, India and Milos, Greece - some candidate tunnel back-fill materials?

    International Nuclear Information System (INIS)

    Olsson, Siv; Karnland, Ola

    2009-12-01

    During the past decades comprehensive investigations have been made on bentonite clays in order to find optimal components of the multi-barrier system of repositories for radioactive waste. The present study gives a mineralogical characterisation of some selected bentonites, in order to supply some of the necessary background data on the bentonites for evaluating their potential as tunnel back-fill materials. Two bentonites from the island of Milos, Greece (Milos BF 04 and BF 08), and two bentonites from Kutch, India (Kutch BF 04 and BF 08) were analysed for their grain size distribution, cation exchange properties and chemical composition. The mineralogical composition was determined by X-ray diffraction analysis and evaluated quantitatively by use of the Siroquant software. Both the bulk bentonite and the 63 μm. The bentonite is distinguished by a high content of dolomite and calcite, which make up almost 25% of the bulk sample. The major accessory minerals are K-feldspars and plagioclase, whereas the content of sulphur-bearing minerals is very low (0.06% total S). Smectite makes up around 60% of the bulk sample, which has a CEC value of 73 meq/100 g. The pool of interlayer cations has a composition Mg>Ca>>Na>>K. The X-ray diffraction characteristics and the high potassium content (1.03% K 2 O) of the Na>Mg>>K. The 2 O) which indicates that also this smectite may be interstratified with a few percent illitic layers. Based on the charge distribution the smectite should be classified as montmorillonite but in this case Fe predominates over Mg in the octahedral sheet. The structural formula suggests that this smectite has the lowest total layer charge of the smectites examined. Kutch BF 04 contains essentially no particles >63 μm. The bentonite has a high content of titanium and iron-rich accessory minerals, such as anatase, magnetite, hematite and goethite. Other accessory minerals of significance are feldspars and quartz, whereas the content of sulphur

  17. Gas hydrate in nature

    Science.gov (United States)

    Ruppel, Carolyn D.

    2018-01-17

    Gas hydrate is a naturally occurring, ice-like substance that forms when water and gas combine under high pressure and at moderate temperatures. Methane is the most common gas present in gas hydrate, although other gases may also be included in hydrate structures, particularly in areas close to conventional oil and gas reservoirs. Gas hydrate is widespread in ocean-bottom sediments at water depths greater than 300–500 meters (m; 984–1,640 feet [ft]) and is also present in areas with permanently frozen ground (permafrost). Several countries are evaluating gas hydrate as a possible energy resource in deepwater or permafrost settings. Gas hydrate is also under investigation to determine how environmental change may affect these deposits.

  18. One step deposition of highly adhesive diamond films on cemented carbide substrates via diamond/β-SiC composite interlayers

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Tao; Zhuang, Hao; Jiang, Xin, E-mail: xin.jiang@uni-siegen.de

    2015-12-30

    Graphical abstract: - Highlights: • Novel diamond/beta-silicon carbide composite gradient interlayers were synthesized. • The interlayer features a cross-sectional gradient with increasing diamond content. • Diamond top layers and the interlayers were deposited in one single process. • The adhesion of the diamond film is drastically improved by employing the interlayer. • The stress was suppressed by manipulating the distribution of diamond and silicon carbide. - Abstract: Deposition of adherent diamond films on cobalt-cemented tungsten carbide substrates has been realized by application of diamond/beta-silicon carbide composite interlayers. Diamond top layers and the interlayers were deposited in one single process by hot filament chemical vapor deposition technique. Two different kinds of interlayers have been employed, namely, gradient interlayer and interlayer with constant composition. The distribution of diamond and beta-silicon carbide phases was precisely controlled by manipulating the gas phase composition. X-ray diffraction and Raman spectroscopy were employed to determine the existence of diamond, beta-silicon carbide and cobalt silicides (Co{sub 2}Si, CoSi) phases, as well as the quality of diamond crystal and the residual stress in the films. Rockwell-C indentation tests were carried out to evaluate the film adhesion. It is revealed that the adhesion of the diamond film is drastically improved by employing the interlayer. This is mainly influenced by the residual stress in the diamond top layer, which is induced by the different thermal expansion coefficient of the film and the substrate. It is even possible to further suppress the stress by manipulating the distribution of diamond and beta-silicon carbide in the interlayer. The most adhesive diamond film on cemented carbide is thus obtained by employing a gradient composite interlayer.

  19. On the Stress Transfer of Nanoscale Interlayer with Surface Effects

    Directory of Open Access Journals (Sweden)

    Quan Yuan

    2018-01-01

    Full Text Available An improved shear-lag model is proposed to investigate the mechanism through which the surface effect influences the stress transfer of multilayered structures. The surface effect of the interlayer is characterized in terms of interfacial stress and surface elasticity by using Gurtin–Murdoch elasticity theory. Our calculation result shows that the surface effect influences the efficiency of stress transfer. The surface effect is enhanced with decreasing interlayer thickness and elastic modulus. Nonuniform and large residual surface stress distribution amplifies the influence of the surface effect on stress concentration.

  20. Temperature dependence of interlayer coupling in perpendicular magnetic tunnel junctions with GdOX barriers

    Science.gov (United States)

    Newhouse-Illige, T.; Xu, Y. H.; Liu, Y. H.; Huang, S.; Kato, H.; Bi, C.; Xu, M.; LeRoy, B. J.; Wang, W. G.

    2018-02-01

    Perpendicular magnetic tunnel junctions with GdOX tunneling barriers have shown a unique voltage controllable interlayer magnetic coupling effect. Here, we investigate the quality of the GdOX barrier and the coupling mechanism in these junctions by examining the temperature dependence of the tunneling magnetoresistance and the interlayer coupling from room temperature down to 11 K. The barrier is shown to be of good quality with the spin independent conductance only contributing a small portion, 14%, to the total room temperature conductance, similar to AlOX and MgO barriers. The interlayer coupling, however, shows an anomalously strong temperature dependence including sign changes below 80 K. This non-trivial temperature dependence is not described by previous models of interlayer coupling and may be due to the large induced magnetic moment of the Gd ions in the barrier.

  1. Analysis on groundwater evolution and interlayer oxidation zone position at the southern margin of Yilin basin

    International Nuclear Information System (INIS)

    Zhang Guanghui

    2007-01-01

    This paper discusses the development and evolution history of groundwater and its reworking to the interlayer oxidation zone, hydrogeochemical zonation of interlayer oxidation zone, mechanism of water-rock interaction and transportation pattern of uranium in the water in Yili Basin. It is suggested that groundwater is one of the important factors to control the development of interlayer oxidation zone and uranium mineralization. (authors)

  2. Se interlayer in CIGS absorption layer for solar cell devices

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seung-Kyu; Sim, Jae-Kwan [Semiconductor Materials Process Laboratory, School of Advanced Materials Engineering, Research Center for Advanced Materials Development, Chonbuk National University, Deokjin-Dong 664-14, Jeonju 561-756 (Korea, Republic of); Kissinger, N.J. Suthan [Department of General Studies, Physics Group, Jubail University College, Royal Commission for Jubail, Jubail 10074 (Saudi Arabia); Song, Il-Seok; Kim, Jin-Soo; Baek, Byung-Joon [Semiconductor Materials Process Laboratory, School of Advanced Materials Engineering, Research Center for Advanced Materials Development, Chonbuk National University, Deokjin-Dong 664-14, Jeonju 561-756 (Korea, Republic of); Lee, Cheul-Ro, E-mail: crlee7@jbnu.ac.kr [Semiconductor Materials Process Laboratory, School of Advanced Materials Engineering, Research Center for Advanced Materials Development, Chonbuk National University, Deokjin-Dong 664-14, Jeonju 561-756 (Korea, Republic of)

    2015-06-05

    Highlights: • Se interlayer is deposited between the CuGa and CuIn/In/Mo/STS stacked layer. • Both CIG precursor layers were selenized at 500 °C for 1 h. • SIMS depth profile shows that Ga distribution is uniform by Se interlayer. • The efficiency was improved for the CIGS solar cell by Se interlayer. - Abstract: A CIGS absorber layer with high gallium contents in the space-charge region can reduce the carrier recombination and improve the open circuit voltage V{sub oc}. Therefore, controlling Ga grading on top of CIGS thin film solar cells is the main objective of this experiment. To reduce Selenium (Se) vacancy, it is important that the diffusion of Ga elements into Se vacancy between Mo back contact and CIGS absorption layer would be controlled. In order to reduce Se vacancy and confirm Ga inter-diffusion, two CIGS solar cells were fabricated by converting CIG precursor with and without Se interlayer. The copper-indium metallic precursors were fabricated corresponding to the sequence CuIn/In/Mo/STS on stainless steel (STS) substrates by sequential direct current magnetron sputtering while Se layer was evaporated by rapid thermal annealing (RTA) system to obtain a Se/CuIn/In/Mo/STS stack. CuGa precursor layer was also fabricated on the Se/CuIn/In/Mo/STS stack. Finally, both CuGa/Se/CuIn/In/Mo/STS and CuGa/CuIn/In/Mo/STS stacks were selenized at 500 °C for 1 h. It was clearly observed from the secondary ion mass spectroscopy (SIMS) and X-ray diffraction (XRD) that there was a change between the fabricated CIGS absorption layers and the amount of Ga elements. Furthermore, the Ga elements gradually decreased from the top to the bottom layer of the CIGS absorption layer. We also discussed the effect of Se interlayer in the CIGS absorption layer and its influence on the solar cell’s performance.

  3. Se interlayer in CIGS absorption layer for solar cell devices

    International Nuclear Information System (INIS)

    Lee, Seung-Kyu; Sim, Jae-Kwan; Kissinger, N.J. Suthan; Song, Il-Seok; Kim, Jin-Soo; Baek, Byung-Joon; Lee, Cheul-Ro

    2015-01-01

    Highlights: • Se interlayer is deposited between the CuGa and CuIn/In/Mo/STS stacked layer. • Both CIG precursor layers were selenized at 500 °C for 1 h. • SIMS depth profile shows that Ga distribution is uniform by Se interlayer. • The efficiency was improved for the CIGS solar cell by Se interlayer. - Abstract: A CIGS absorber layer with high gallium contents in the space-charge region can reduce the carrier recombination and improve the open circuit voltage V oc . Therefore, controlling Ga grading on top of CIGS thin film solar cells is the main objective of this experiment. To reduce Selenium (Se) vacancy, it is important that the diffusion of Ga elements into Se vacancy between Mo back contact and CIGS absorption layer would be controlled. In order to reduce Se vacancy and confirm Ga inter-diffusion, two CIGS solar cells were fabricated by converting CIG precursor with and without Se interlayer. The copper-indium metallic precursors were fabricated corresponding to the sequence CuIn/In/Mo/STS on stainless steel (STS) substrates by sequential direct current magnetron sputtering while Se layer was evaporated by rapid thermal annealing (RTA) system to obtain a Se/CuIn/In/Mo/STS stack. CuGa precursor layer was also fabricated on the Se/CuIn/In/Mo/STS stack. Finally, both CuGa/Se/CuIn/In/Mo/STS and CuGa/CuIn/In/Mo/STS stacks were selenized at 500 °C for 1 h. It was clearly observed from the secondary ion mass spectroscopy (SIMS) and X-ray diffraction (XRD) that there was a change between the fabricated CIGS absorption layers and the amount of Ga elements. Furthermore, the Ga elements gradually decreased from the top to the bottom layer of the CIGS absorption layer. We also discussed the effect of Se interlayer in the CIGS absorption layer and its influence on the solar cell’s performance

  4. INTERLAYER OPTICAL CONDUCTIVITY OF A SUPERCONDUCTING BILAYER

    NARCIS (Netherlands)

    GARTSTEIN, YN; RICE, MJ; VANDERMAREL, D

    1994-01-01

    We employ the Bardeen-Cooper-Schrieffer theory to calculate the frequency-dependent interlayer conductivity of a superconducting bilayer, the two layers of which are coupled by weak single-particle tunneling. The effect of the superconducting transition on the normal-state absorption band is to

  5. [Skin hydration and hydrating products].

    Science.gov (United States)

    Duplan, H; Nocera, T

    2018-05-01

    One of the skin's principal functions is to protect the body against its environment by maintaining an effective epidermal barrier, not only against external factors, but also to prevent water loss from the body. Indeed, water homeostasis is vital for the normal physiological functioning of skin. Hydration levels affect not only visible microscopic parameters such as the suppleness and softness of skin, but also molecular parameters, enzyme activities and cellular signalling within the epidermis. The body is continually losing some of its water, but this phenomenon is limited and the optimal hydration gradient in skin is ensured via a set of sophisticated regulatory processes that rely on the functional and dynamic properties of the uppermost level of the skin consisting of the stratum corneum. The present article brings together data recently acquired in the fields of skin hydration and the characterisation of dehydrated or dry skin, whether through study of the regulatory processes involved or as a result of changes in the techniques used for in situ measurement, and thus in optimisation of management. Copyright © 2018. Published by Elsevier Masson SAS.

  6. Hydration Properties of Ground Granulated Blast-Furnace Slag (GGBS Under Different Hydration Environments

    Directory of Open Access Journals (Sweden)

    Shuhua LIU

    2017-02-01

    Full Text Available The hydration properties of various cementitious materials containing Ground Granulated Blast-furnace Slag (GGBS, two alkali-activated slag cements (AAS-1 and AAS-2 in which sodium silicate and sodium hydroxide act as alkaline activators respectively, supersulfated cement (SSC and slag Portland cement(PSC, are compared with ordinary Portland cement (OPC to investigate the effect of activating environment on the hydration properties in this study by determining the compressive strength of the pastes, the hydration heat of binders within 96 hours, and the hydration products at age of 28 days. The results show that C-S-H gels are the main hydrated products for all cementitious systems containing GGBS. Ca(OH2 is the hydration products of OPC and PSC paste. However, ettringite and gypsum crystals instead of Ca(OH2 are detected in SSC paste. Additionally, tobermorite, a crystalline C-S-H, and calcite are hydrated products in AAS-1. Tobermorite, cowlesite and calcite are hydrated products of AAS-2 as well. Based on strength results, AAS-1 paste exhibits the highest compressive strength followed by POC, PSC, SSC in order at all testing ages and AAS-2 give the lowest compressive strength except for the early age at 3 days, which is higher than SSC but still lower than PSC. From hydration heat analysis, alkalinity in the reaction solution is a vital factor influencing the initial hydration rate and the initial hydration rate from higher to lower is AAS-2, AAS-1, OPC, PSC and SSC. Although AAS possesses a faster reaction rate in the initial hours, cumulative hydration heat of AAS is comparably lower than that of OPC, but higher than those of PSC and SSC in turn, which indicates that the hydration heat of clinkers is much higher than that of slag.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14934

  7. Interlayer growth in Mo/B4C multilayered structures upon thermal annealing

    International Nuclear Information System (INIS)

    Nyabero, S. L.; Kruijs, R. W. E. van de; Yakshin, A. E.; Zoethout, E.; Bosgra, J.; Loch, R. A.; Blanckenhagen, G. von; Bijkerk, F.

    2013-01-01

    Both multilayer period thickness expansion and compaction were observed in Mo/B 4 C multilayers upon annealing, and the physical causes for this were explored in detail. Using in situ time-dependent grazing incidence X-ray reflectometry, period changes down to picometer-scale were resolved. It was shown that the changes depend on the thickness of the B 4 C layers, annealing temperature, and annealing time. Although strong stress relaxation during annealing was observed, it was excluded as a cause for period expansion. Auger electron spectroscopy and wide angle X-ray diffraction measurements revealed the growth of interlayers, with associated period changes influenced by the supply of B and C atoms to the growing compound interlayers. For multilayers with a Mo thickness of 3 nm, two regimes were recognized, depending on the deposited B 4 C thickness: in multilayers with B 4 C ≤ 1.5 nm, the supply of additional Mo into the already formed MoB x C y interlayer was dominant and led to densification, resulting in period compaction. For multilayers with B 4 C ≥ 2 nm, the B and C enrichment of interlayers formed low density compounds and yielded period expansion.

  8. Experimental and numerical study of the stability of phyllosilicates in a strong thermal gradient. Test in the geothermal site of Soultz-sous-Forets

    International Nuclear Information System (INIS)

    Baldeyrou-Bailly, A.

    2003-01-01

    Thermodynamic data of hydrated phyllosilicates, in particular clay minerals are not well known. The stability fields of these minerals are not well determined; following some authors they even do not exist. We have developed an experimental approach, in which a sequence of local equilibrium states between a fluid and minerals take place in a closed gold cell along a strong thermal gradient. The experiments were conducted in the chemical systems: Mg-Al-Si-H 2 O (MASH), K-Al-Si-H 2 O (KASH), and K-Mg-Al-Si-H 2 O (KMASH). The sequences of crystallization observed along the thermal gradient are the same if one exchanges the position of the cells containing the initial reacting materials with respect to the thermal gradient end-members. The crystallization sequences correspond to local equilibrium states. Following the temperature increase (from 200 to 350 C) one observes the following sequences: di-octahedral smectite? tri-octahedral smectite; kaolinite? donbassite? tri-octahedral chlorite; smectite? illite? muscovite; or even kaolinite? illite + smectite? donbassite; commonly observed in hydrothermal systems. They allow to develop a thermodynamic model for hydrated phyllosilicates, taking into account their hydration state as a function of temperature. This model shows the stability fields of clay minerals between 200 and 350 C.The chemical and mineralogical dynamics showed in these experimental systems has been applied to predict the possible dissolutions and/or precipitations which may take place between the circulated hot fluid and the geothermal granitic reservoir in the geothermal system at Soultz-sous-Forets. These processes may affect the duration of the geothermal reservoir, as a function of evolution in the morphology of the porosity. Our experimental approach shows that feldspars and smectites are forming the major part of the total volume of silicates which may precipitate in addition to carbonates already described in previous studies. (author)

  9. Factors influencing caesium-137 levels in moose (Alces alces) and small game in Northern Sweden

    International Nuclear Information System (INIS)

    Nelin, P.; Palo, T.R.

    1989-01-01

    In the third annual hunting season after the Chernobyl accident the concentration of Cs-137 in meat of northern Swedish moose was significantly higher than in the first one (1986). In September 1986 the mean Cs concentration was 500 Bq/kg in calves but in September 1988 it has risen 1300 Bq/kg. This increase was only temporary and a rapid decline occured after September and by December 1988 the concentration of Cs was the same as in late 1986. Adult moose showed the same increase during the hunt 1988 but to a lower magnitude. Typical food plants of moose such as bilberry (Vaccinum myrtillus) and birch (Betula pubescens) showed, contradictory to expected by the level in moose, a decline of concentration caesium from 1986 to 1988. A probable explanation to the dramatically increased concentration of Cs in moose is a change in diet selection during 1988. Small mammals such as voles and lemmings showed a variation in concentration of caesium-137 which was more dependent on other factors than on their body size. This emphasize the necessity to study diet selection by herbivores in detail in order to predict uptake and changes in environmental contaminants. (orig.)

  10. Distribution and origin of authigenic smectite clays in Cape Roberts Project Core 3, Victoria Land Basin, Antarctica

    Science.gov (United States)

    Priestas, A.W.; Wise, S.W.

    2007-01-01

    Of some 800 m of lower Oligocene marine sediments cored continuously from the seafloor in the Victoria Land Basin of Antarctica at Cape Roberts Site CRP-3, the lower 500 m exhibit authigenic smectite clay coats on shallow-water sandstone grains. A scanning electron microscope/EDS study of 46 fracture sections confirms that the distribution of the clay coats through the unit is not uniform or evenly distributed, but rather varies with depth, original porosity, and the kinds and abundance of source materials. Our results suggest that smectite emplacement resulted from in-situ, low-temperature burial diagenesis rather than hydrothermal or fault-focused thermobaric fluids.

  11. Influence of in-situ deposited SiNx interlayer on crystal quality of GaN epitaxial films

    Science.gov (United States)

    Fan, Teng; Jia, Wei; Tong, Guangyun; Zhai, Guangmei; Li, Tianbao; Dong, Hailiang; Xu, Bingshe

    2018-05-01

    GaN epitaxial films with SiNx interlayers were prepared by metal organic chemical vapor deposition (MOCVD) on c-plane sapphire substrates. The influences of deposition times and locations of SiNx interlayers on crystal quality of GaN epitaxial films were studied. Under the optimal growth time of 120 s for the SiNx interlayer, the dislocation density of GaN film is reduced to 4.05 × 108 cm-2 proved by high resolution X-ray diffraction results. It is found that when the SiNx interlayer deposits on the GaN nucleation islands, the subsequent GaN film has the lowest dislocation density of only 2.89 × 108 cm-2. Moreover, a model is proposed to illustrate the morphological evolution and associated propagation processes of TDs in GaN epi-layers with SiNx interlayers for different deposition times and locations.

  12. Study of adsorption of zinc in clay smectite type Bofe in system of finite bath

    International Nuclear Information System (INIS)

    Souza, R.S.; Mota, J.D.; Lima, W.S.; Rodrigues, M.G.F.

    2012-01-01

    Clays are demonstrably excellent adsorbents, both for their physical and chemical characteristics and the wide coverage and low cost. Among the various groups of clay minerals, the smectite are noted for having large surface areas. The initial objective of this study was to characterize the clay Bofe through the techniques of X-Ray Diffraction (XRD), X-Ray Spectrometry by Energy Dispersive (EDX) and nitrogen adsorption (BET). To evaluate the adsorption of metal ions zinc (synthetic sewage), we used a system in finite bath, following a factorial design 2 2 , taking as input variables: pH and initial concentrations of zinc (Zn2 +) and output variables: percentage removal and removal capacity. The characterization results showed that Bofe clay belongs to the family of smectite and therefore has great potential for adsorption. (author)

  13. Hydration water and microstructure in calcium silicate and aluminate hydrates

    International Nuclear Information System (INIS)

    Fratini, Emiliano; Ridi, Francesca; Chen, Sow-Hsin; Baglioni, Piero

    2006-01-01

    Understanding the state of the hydration water and the microstructure development in a cement paste is likely to be the key for the improvement of its ultimate strength and durability. In order to distinguish and characterize the reacted and unreacted water, the single-particle dynamics of water molecules in hydrated calcium silicates (C 3 S, C 2 S) and aluminates (C 3 A, C 4 AF) were studied by quasi-elastic neutron scattering, QENS. The time evolution of the immobile fraction represents the hydration kinetics and the mobile fraction follows a non-Debye relaxation. Less sophisticated, but more accessible and cheaper techniques, like differential scanning calorimetry, DSC, and near-infrared spectroscopy, NIR, were validated through QENS results and they allow one to easily and quantitatively follow the cement hydration kinetics and can be widely applied on a laboratory scale to understand the effect of additives (i.e., superplasticizers, cellulosic derivatives, etc) on the thermodynamics of the hydration process. DSC provides information on the free water index and on the activation energy involved in the hydration process while the NIR band at 7000 cm -1 monitors, at a molecular level, the increase of the surface-interacting water. We report as an example the effect of two classes of additives widely used in the cement industry: superplasticizers, SPs, and cellulose derivatives. SPs interact at the solid surface, leading to a consistent increment of the activation energy for the processes of nucleation and growth of the hydrated phases. In contrast, the cellulosic additives do not affect the nucleation and growth activation energy, but cause a significant increment in the water availability: in other words the hydration process is more efficient without any modification of the solid/liquid interaction, as also evidenced by the 1 H-NMR. Additional information is obtained by scanning electron microscopy (SEM), ultra small angle neutron scattering (USANS) and wide

  14. Novel understanding of calcium silicate hydrate from dilute hydration

    KAUST Repository

    Zhang, Lina; Yamauchi, Kazuo; Li, Zongjin; Zhang, Xixiang; Ma, Hongyan; Ge, Shenguang

    2017-01-01

    The perspective of calcium silicate hydrate (C-S-H) is still confronting various debates due to its intrinsic complicated structure and properties after decades of studies. In this study, hydration at dilute suspension of w/s equaling to 10

  15. Synchronization and Inter-Layer Interactions of Noise-Driven Neural Networks.

    Science.gov (United States)

    Yuniati, Anis; Mai, Te-Lun; Chen, Chi-Ming

    2017-01-01

    In this study, we used the Hodgkin-Huxley (HH) model of neurons to investigate the phase diagram of a developing single-layer neural network and that of a network consisting of two weakly coupled neural layers. These networks are noise driven and learn through the spike-timing-dependent plasticity (STDP) or the inverse STDP rules. We described how these networks transited from a non-synchronous background activity state (BAS) to a synchronous firing state (SFS) by varying the network connectivity and the learning efficacy. In particular, we studied the interaction between a SFS layer and a BAS layer, and investigated how synchronous firing dynamics was induced in the BAS layer. We further investigated the effect of the inter-layer interaction on a BAS to SFS repair mechanism by considering three types of neuron positioning (random, grid, and lognormal distributions) and two types of inter-layer connections (random and preferential connections). Among these scenarios, we concluded that the repair mechanism has the largest effect for a network with the lognormal neuron positioning and the preferential inter-layer connections.

  16. Historical methane hydrate project review

    Science.gov (United States)

    Collett, Timothy; Bahk, Jang-Jun; Frye, Matt; Goldberg, Dave; Husebo, Jarle; Koh, Carolyn; Malone, Mitch; Shipp, Craig; Torres, Marta

    2013-01-01

    In 1995, U.S. Geological Survey made the first systematic assessment of the volume of natural gas stored in the hydrate accumulations of the United States. That study, along with numerous other studies, has shown that the amount of gas stored as methane hydrates in the world greatly exceeds the volume of known conventional gas resources. However, gas hydrates represent both a scientific and technical challenge and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of gas hydrates in nature, (2) assessing the volume of natural gas stored within various gas hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural gas hydrates, and (5) analyzing the effects of methane hydrate on drilling safety.Methane hydrates are naturally occurring crystalline substances composed of water and gas, in which a solid water-­‐lattice holds gas molecules in a cage-­‐like structure. The gas and water becomes a solid under specific temperature and pressure conditions within the Earth, called the hydrate stability zone. Other factors that control the presence of methane hydrate in nature include the source of the gas included within the hydrates, the physical and chemical controls on the migration of gas with a sedimentary basin containing methane hydrates, the availability of the water also included in the hydrate structure, and the presence of a suitable host sediment or “reservoir”. The geologic controls on the occurrence of gas hydrates have become collectively known as the “methane hydrate petroleum system”, which has become the focus of numerous hydrate research programs.Recognizing the importance of methane hydrate research and the need for a coordinated

  17. Thallium (Tl) sorption onto illite and smectite: Implications for Tl mobility in the environment

    Science.gov (United States)

    Martin, Loïc A.; Wissocq, Aubéry; Benedetti, M. F.; Latrille, Christelle

    2018-06-01

    Clay minerals play a relevant role in the transport and fate of trace elements in the environment. Though illite has been referred as an important Thallium (Tl) bearing phase in soils, mechanisms and affinity of thallium for clay minerals remain poorly known. This study investigated the sorption behavior of thallium as Tl(I) onto illite and smectite, two clay minerals occurring mainly in soils and sediments. Different sorption experiments were carried out under various pH conditions and Tl concentrations, in competition with sodium and calcium at a constant ionic strength of 0.01 mol L-1. Our results showed that illite displayed more affinity than smectite for thallium. With illite, the distribution coefficients (Kd in L kg-1) varied between 102.75 ± 0.17 and 104.0 ± 0.17 in Na solutions versus between 102.25 ± 0.17 and 103.0 ± 0.17 in Ca solutions, depending on pH. With smectite, Kd (in L kg-1) ranged between 102.50 ± 0.16 and 103.20 ± 0.16 and between 101.25 ± 0.16 and 101.95 ± 0.16 in Na and Ca solutions, respectively. Sorption behavior was described with the Multi-Site Ion Exchanger model and selectivity coefficients with respect to protons were calculated for the first time. In all cases, independently of clay mineral and background electrolyte, low capacity but highly reactive sites were dominant in thallium uptake, highlighting Tl affinity for those sites. Moreover, the exchangeable and reversible interactions between Tl+ and clays reactive sites suggested that in changing conditions, thallium could be released in solution. The role of clay minerals in thallium environmental cycle is evident and confirmed illite to be a dominant Tl bearing phase, in some environment competing with manganese oxides. Compared to others Tl bearing mineral phases, clays are ranked as follows: MnO2 > illite > smectite ∼ ferrihydrite ≥ Al2O3 ∼ goethite > SiO2. Finally, over the three monovalent cations (Tl, Rb, Cs) Tl is the one less sorbed on illite independently of

  18. Lipase immobilization on smectite nanoclays : Characterization and application to the epoxidation of alpha-pinene

    NARCIS (Netherlands)

    Tzialla, Aikaterini A.; Pavlidis, Ioannis V.; Felicissimo, Marcella P.; Rudolf, Petra; Gournis, Dimitrios; Stamatis, Haralambos

    The immobilization of lipase B from Candida antarctica on smectite group nanoclays (Laponite, SWy-2 and Kunipia), as well as on their organically modified derivatives, was investigated. A combination of techniques, namely X-ray diffraction, thermal analysis, X-ray photoelectron and FT-IR

  19. Hydraulic and Mechanical Effects from Gas Hydrate Conversion and Secondary Gas Hydrate Formation during Injection of CO2 into CH4-Hydrate-Bearing Sediments

    Science.gov (United States)

    Bigalke, N.; Deusner, C.; Kossel, E.; Schicks, J. M.; Spangenberg, E.; Priegnitz, M.; Heeschen, K. U.; Abendroth, S.; Thaler, J.; Haeckel, M.

    2014-12-01

    The injection of CO2 into CH4-hydrate-bearing sediments has the potential to drive natural gas production and simultaneously sequester CO2 by hydrate conversion. The process aims at maintaining the in situ hydrate saturation and structure and causing limited impact on soil hydraulic properties and geomechanical stability. However, to increase hydrate conversion yields and rates it must potentially be assisted by thermal stimulation or depressurization. Further, secondary formation of CO2-rich hydrates from pore water and injected CO2 enhances hydrate conversion and CH4 production yields [1]. Technical stimulation and secondary hydrate formation add significant complexity to the bulk conversion process resulting in spatial and temporal effects on hydraulic and geomechanical properties that cannot be predicted by current reservoir simulation codes. In a combined experimental and numerical approach, it is our objective to elucidate both hydraulic and mechanical effects of CO2 injection and CH4-CO2-hydrate conversion in CH4-hydrate bearing soils. For the experimental approach we used various high-pressure flow-through systems equipped with different online and in situ monitoring tools (e.g. Raman microscopy, MRI and ERT). One particular focus was the design of triaxial cell experimental systems, which enable us to study sample behavior even during large deformations and particle flow. We present results from various flow-through high-pressure experimental studies on different scales, which indicate that hydraulic and geomechanical properties of hydrate-bearing sediments are drastically altered during and after injection of CO2. We discuss the results in light of the competing processes of hydrate dissociation, hydrate conversion and secondary hydrate formation. Our results will also contribute to the understanding of effects of temperature and pressure changes leading to dissociation of gas hydrates in ocean and permafrost systems. [1] Deusner C, Bigalke N, Kossel E

  20. Structural evolution of Ti destroyable interlayer in large-size diamond film deposition by DC arc plasma jet

    Science.gov (United States)

    Guo, Jianchao; Li, Chengming; Liu, Jinlong; Wei, Junjun; Chen, Liangxian; Hua, Chenyi; Yan, Xiongbo

    2016-05-01

    The addition of titanium (Ti) interlayer was verified to reduce the residual stress of diamond films by self-fracturing and facilitate the harvest of a crack-free free-standing diamond film prepared by direct current (DC) arc plasma jet. In this study, the evolution of the Ti interlayer between large-area diamond film and substrate was studied and modeled in detail. The evolution of the interlayer was found to be relevant to the distribution of the DC arc plasma, which can be divided into three areas (arc center, arc main, and arc edge). The formation rate of titanium carbide (TiC) in the arc main was faster than in the other two areas and resulted in the preferred generation of crack in the diamond film in the arc main during cooling. Sandwich structures were formed along with the growth of TiC until the complete transformation of the Ti interlayer. The interlayer released stress via self-fracture. Avoiding uneven fragile regions that formed locally in the interlayer and achieving cooperatively released stress are crucial for the preparation of large crack-free diamond films.

  1. Heterogeneities in illite/smectite mixed/layers clays: some comments and recollections

    International Nuclear Information System (INIS)

    Johns, W.D.

    1995-01-01

    A review of some studies of heterogeneities, structure and surface in illite/smectite mixed-layer clays of Vienna Basin using X-ray diffraction, high resolution-transmission electron microscopy, infra-red spectroscopy, laser microprobe mass analysis, Auger electron spectroscopy, secondary ion mass spectroscopy, x-ray photoelectron spectroscopy, and ultraviolet photoelectron spectroscopy is given. The models of hexyl ammonium ion configuration complexed between silica sheets is discussed. 1 tab., 10 figs., 6 refs

  2. Caesium accumulation by microorganisms: uptake mechanisms, cation competition, compartmentalization and toxicity

    International Nuclear Information System (INIS)

    Avery, S.V.

    1995-01-01

    The continued release of caesium radioisotopes into the environment has led to a resurgence of interest in microbe-Cs interactions. Caesium exists almost exclusively as the monovalent cation Cs + in the natural environment. Although Cs + is a weak Lewis acid that exhibits a low tendency to form complexes with ligands, its chemical similarity to the biologically essential alkali cation K + facilitates high levels of metabolism-dependent intracellular accumulation. Microbial Cs + (K + ) uptake is generally mediated by monovalent cation transport systems located on the plasma membrane. These differ widely in specificity for alkali cations and consequently microorganisms display large differences in their ability to accumulate Cs + ; Cs + appears to have an equal or greater affinity than K + for transport in certain microorganisms. Microbial Cs + accumulation is markedly influenced by the presence of external cations, e.g. K + , Na + , NH 4 + and H + , and is generally accompanied by an approximate stoichiometric exchange for intracellular K + . However, stimulation of growth of K + -starved microbial cultures by Cs + is limited and it has been proposed that it is not the presence of Cs + in cells that is growth inhibitory but rather the resulting loss of K + . Increased microbial tolerance to Cs + may result from sequestration of Cs + in vacuoles or changes in the activity and/or specificity of transport systems mediating Cs + uptake. The precise intracellular target(s) for Cs + - induced toxicity has yet to be clearly defined, although certain internal structures, e.g. ribosomes, become unstable in the presence of Cs + and Cs + is known to substitute poorly for K + in the activation of many K + -requiring enzymes. (author)

  3. Strength Estimation for Hydrate-Bearing Sediments From Direct Shear Tests of Hydrate-Bearing Sand and Silt

    Science.gov (United States)

    Liu, Zhichao; Dai, Sheng; Ning, Fulong; Peng, Li; Wei, Houzhen; Wei, Changfu

    2018-01-01

    Safe and economic methane gas production, as well as the replacement of methane while sequestering carbon in natural hydrate deposits, requires enhanced geomechanical understanding of the strength and volume responses of hydrate-bearing sediments during shear. This study employs a custom-made apparatus to investigate the mechanical and volumetric behaviors of carbon dioxide hydrate-bearing sediments subjected to direct shear. The results show that both peak and residual strengths increase with increased hydrate saturation and vertical stress. Hydrate contributes mainly the cohesion and dilatancy constraint to the peak strength of hydrate-bearing sediments. The postpeak strength reduction is more evident and brittle in specimens with higher hydrate saturation and under lower stress. Significant strength reduction after shear failure is expected in silty sediments with high hydrate saturation Sh ≥ 0.65. Hydrate contribution to the residual strength is mainly by increasing cohesion at low hydrate saturation and friction at high hydrate saturation. Stress state and hydrate saturation are dominating both the stiffness and the strength of hydrate-bearing sediments; thus, a wave velocity-based peak strength prediction model is proposed and validated, which allows for precise estimation of the shear strength of hydrate-bearing sediments through acoustic logging data. This method is advantageous to geomechanical simulators, particularly when the experimental strength data of natural samples are not available.

  4. Formation conditions and prospecting criteria for sandstone uranium deposit of interlayer oxidation type

    International Nuclear Information System (INIS)

    Huang Shijie

    1994-01-01

    This paper comprehensively analyses the geotectonic setting and favourable conditions, such as structure of the basin, sedimentary facies and paleogeography, geomorphology and climate, hydrodynamics and hydrogeochemistry, the development of interlayered oxidation etc, necessary for the formation of sandstone uranium deposit of interlayered oxidation type. The following prospecting criteria is proposed, namely: abundant uranium source, arid climate, stable big basin, flat-lying sandstone bed, big alluvial fan, little change in sedimentary facies, intercalation of sandstone and mudstone beds, shallow burying of sandstone bed, well-aquiferous sandstone bed, high permeability of sandstone bed, development of interlayered oxidation, and high content of reductant in sandstone. In addition, the 6 in 1 hydrogenic genetic model is proposed

  5. Gas hydrate concentration and characteristics within Hydrate Ridge inferred from multicomponent seismic reflection data

    Science.gov (United States)

    Kumar, Dhananjay; Sen, Mrinal K.; Bangs, Nathan L.

    2007-12-01

    A seismic experiment composed of streamer and ocean bottom seismometer (OBS) surveys was conducted in the summer of 2002 at southern Hydrate Ridge, offshore Oregon, to map the gas hydrate distribution within the hydrate stability zone. Gas hydrate concentrations within the reservoir can be estimated with P wave velocity (Vp); however, we can further constrain gas hydrate concentrations using S wave velocity (Vs), and use Vs through its relationship to Vp (Vp/Vs) to reveal additional details such as gas hydrate form within the matrix (i.e., hydrate cements the grains, becomes part of the matrix frame or floats in pore space). Both Vp and Vs can be derived simultaneously by inverting multicomponent seismic data. In this study, we use OBS data to estimate seismic velocities where both gas hydrate and free gas are present in the shallow sediments. Once Vp and Vs are estimated, they are simultaneously matched with modeled velocities to estimate the gas hydrate concentration. We model Vp using an equation based on a modification of Wood's equation that incorporates an appropriate rock physics model and Vs using an empirical relation. The gas hydrate concentration is estimated to be up to 7% of the rock volume, or 12% of the pore space. However, Vp and Vs do not always fit the model simultaneously. Vp can vary substantially more than Vs. Thus we conclude that a model, in which higher concentrations of hydrate do not affect shear stiffness, is more appropriate. Results suggest gas hydrates form within the pore space of the sediments and become part of the rock framework in our survey area.

  6. Low-Frequency Interlayer Raman Modes to Probe Interface of Twisted Bilayer MoS2.

    Science.gov (United States)

    Huang, Shengxi; Liang, Liangbo; Ling, Xi; Puretzky, Alexander A; Geohegan, David B; Sumpter, Bobby G; Kong, Jing; Meunier, Vincent; Dresselhaus, Mildred S

    2016-02-10

    van der Waals homo- and heterostructures assembled by stamping monolayers together present optoelectronic properties suitable for diverse applications. Understanding the details of the interlayer stacking and resulting coupling is crucial for tuning these properties. We investigated the low-frequency interlayer shear and breathing Raman modes (frequency and intensity changes of low-frequency modes. The frequency variation can be up to 8 cm(-1) and the intensity can vary by a factor of ∼5 for twisting angles near 0° and 60°, where the stacking is a mixture of high-symmetry stacking patterns and is thus sensitive to twisting. For twisting angles between 20° and 40°, the interlayer coupling is nearly constant because the stacking results in mismatched lattices over the entire sample. It follows that the Raman signature is relatively uniform. Note that for some samples, multiple breathing mode peaks appear, indicating nonuniform coupling across the interface. In contrast to the low-frequency interlayer modes, high-frequency intralayer Raman modes are much less sensitive to interlayer stacking and coupling. This research demonstrates the effectiveness of low-frequency Raman modes for probing the interfacial coupling and environment of twisted bilayer MoS2 and potentially other two-dimensional materials and heterostructures.

  7. Al/Cu Dissimilar Friction Stir Welding with Ni, Ti, and Zn Foil as the Interlayer for Flow Control, Enhancing Mechanical and Metallurgical Properties

    Science.gov (United States)

    Sahu, Prakash Kumar; Pal, Sukhomay; Pal, Surjya K.

    2017-07-01

    This research investigates the effects of Ni, Ti, and Zn foil as interlayer, inserted between the faying edges of Al and Cu plates, for controlled intermetallic compound (IMC) formation. The weld tensile strength with Ti and Zn as interlayer is superior to Al base metal strength. This is due to controlled flow of IMCs by diffused Ti interlayer and thin, continuous, and uniform IMC formation in the case of Zn interlayer. Improved flexural stress was observed with interlayer. Weld microhardness varied with different interlayers and purely depends on IMCs present at the indentation point, flow of IMCs, and interlayer hardness. Specimens with interlayer failed at the interface of the nugget and thermomechanical-affected zone (TMAZ) with complete and broken three-dimensional (3-D) grains, indicating transgranular fracture. Phase analysis revealed that Al/Cu IMCs are impeded by Ni and Ti interlayer. The minor binary and ternary IMC phases form adjacent to the interlayer due to diffusion of the material with Al/Cu. Line scan and elemental mapping indicate thin, continuous, and uniform IMCs with enhanced weld metallurgical and mechanical properties for the joints with Zn interlayer. Macrostructural analysis revealed IMC flow variations with and without interlayer. Variation in grain size at different zones is also observed for different interlayers.

  8. The distinguishing characteristics of interlayer oxidation zone and burial ancient ground oxidation zone

    International Nuclear Information System (INIS)

    Zhang Zhanshi; Zhou Wenbin

    1998-01-01

    The author discusses the main characteristics of interlayer oxidation zones and the burial ancient ground oxidation zones of Uranium deposit No. 512 in Xinjiang Uigur municipality. The epigenetic genesis, depending on some aquifer, the tongue-like in section, having the zonation along dip direction and having certain mineral assemblage are the typical features for interlayer oxidation zones

  9. Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate

    Science.gov (United States)

    Geng, Guoqing; Myers, Rupert J.; Li, Jiaqi; Maboudian, Roya; Carraro, Carlo; Shapiro, David A.; Monteiro, Paulo J. M.

    2017-03-01

    The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is more deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach.

  10. Patients blood serum ferritin concentrations changes associated with Caesium-137 incorporation

    International Nuclear Information System (INIS)

    Shishkyina, V.V.; Chebotar'ova, E.D.; Zamyatyin, S.S.; Vlasenko, O.O.

    1993-01-01

    The results of radioimmune study of ferritin and carcinoembryonic antigen in 60 persons: 35 those who took part in liquidation of the Chernobyl accident and incorporated 25.9-70.4 MBq of Cesium-137,25 residents of Rivno Region with 7.4-203.5 MBq of the radionuclide in the organism are reported. The increased concentration of ferritin and carcinoembryonic antigen in blood serum was noted to be determined more often in the residents of the areas polluted with Caesium-137 than in l iquidators . The tumor markers levels depended to some extent on bad habits (smoking, alcohol) and existing chronic diseases of the alimentary system

  11. Mechanical characterization and modeling of brazed tungsten and Cu-Cr-Zr alloy using stress relief interlayers

    Science.gov (United States)

    Qu, Dandan; Zhou, Zhangjian; Yum, Youngjin; Aktaa, Jarir

    2014-12-01

    A rapidly solidified foil-type Ti-Zr based amorphous filler with a melting temperature of 850 °C was used to braze tungsten to Cu-Cr-Zr alloy for water cooled divertors and plasma facing components application. Brazed joints of dissimilar materials suffer from a mismatch in coefficients of thermal expansion. In order to release the residual stress caused by the mismatch, brazed joints of tungsten and Cu-Cr-Zr alloy using different interlayers were studied. The shear strength tests of brazed W/Cu joints show that the average strength of the joint with a W70Cu30 composite plate interlayer reached 119.8 MPa, and the average strength of the joint with oxygen free high conductivity copper (OFHC Cu)/Mo multi-interlayers reached 140.8 MPa, while the joint without interlayer was only 16.6 MPa. Finite element method (FEM) has been performed to investigate the stress distribution and effect of stress relief interlayers. FEM results show that the maximum von Mises stress occurs in the tungsten/filler interface and that the filler suffers the peak residual stresses and becomes the weakest zone. And the use of OFHC Cu/Mo multi-interlayers can reduce the residual stress significantly, which agrees with the mechanical experiment data.

  12. Mechanical characterization and modeling of brazed tungsten and Cu–Cr–Zr alloy using stress relief interlayers

    Energy Technology Data Exchange (ETDEWEB)

    Qu, Dandan, E-mail: dandan.qu@partner.kit.edu [School of Materials Science and Engineering, University of Science and Technology Beijing, 100083 Beijing (China); Karlsruhe Institute of Technology, Institute for Applied Materials, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Zhou, Zhangjian, E-mail: zhouzhangjianustb@163.com [School of Materials Science and Engineering, University of Science and Technology Beijing, 100083 Beijing (China); Yum, Youngjin [School of Mechanical Engineering, University of Ulsan, Ulsan 680-749 (Korea, Republic of); Aktaa, Jarir [Karlsruhe Institute of Technology, Institute for Applied Materials, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)

    2014-12-15

    A rapidly solidified foil-type Ti–Zr based amorphous filler with a melting temperature of 850 °C was used to braze tungsten to Cu–Cr–Zr alloy for water cooled divertors and plasma facing components application. Brazed joints of dissimilar materials suffer from a mismatch in coefficients of thermal expansion. In order to release the residual stress caused by the mismatch, brazed joints of tungsten and Cu–Cr–Zr alloy using different interlayers were studied. The shear strength tests of brazed W/Cu joints show that the average strength of the joint with a W70Cu30 composite plate interlayer reached 119.8 MPa, and the average strength of the joint with oxygen free high conductivity copper (OFHC Cu)/Mo multi-interlayers reached 140.8 MPa, while the joint without interlayer was only 16.6 MPa. Finite element method (FEM) has been performed to investigate the stress distribution and effect of stress relief interlayers. FEM results show that the maximum von Mises stress occurs in the tungsten/filler interface and that the filler suffers the peak residual stresses and becomes the weakest zone. And the use of OFHC Cu/Mo multi-interlayers can reduce the residual stress significantly, which agrees with the mechanical experiment data.

  13. Diffusion bonding of commercially pure titanium to low carbon steel using a silver interlayer

    International Nuclear Information System (INIS)

    Atasoy, Evren; Kahraman, Nizamettin

    2008-01-01

    Titanium and low carbon steel plates were joined through diffusion bonding using a silver interlayer at various temperatures for various diffusion times. In order to determine the strength of the resulting joints, tensile-shear tests and hardness tests were applied. Additionally, optical, scanning electron microscopy examinations and energy dispersive spectrometry elemental analyses were carried out to determine the interface properties of the joint. The work showed that the highest interface strength was obtained for the specimens joined at 850 deg. C for 90 min. It was seen from the hardness results that the highest hardness value was obtained for the interlayer material and the hardness values on the both sides of the interlayer decreased gradually as the distance from the joint increased. In energy dispersive spectrometry analyses, it was seen that the amount of silver in the interlayer decreased markedly depending on the temperature rise. In addition, increasing diffusion time also caused some slight decrease in the amount of silver

  14. Application of empirical hydration distribution functions around polar atoms for assessing hydration structures of proteins

    International Nuclear Information System (INIS)

    Matsuoka, Daisuke; Nakasako, Masayoshi

    2013-01-01

    Highlights: ► Empirical distribution functions of water molecules in protein hydration are made. ► The functions measure how hydrogen-bond geometry in hydration deviate from ideal. ► The functions assess experimentally identified hydration structures of protein. - Abstract: To quantitatively characterize hydrogen-bond geometry in local hydration structures of proteins, we constructed a set of empirical hydration distribution functions (EHDFs) around polar protein atoms in the main and side chains of 11 types of hydrophilic amino acids (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 113 (2009) 11274). The functions are the ensemble average of possible hydration patterns around the polar atoms, and describe the anisotropic deviations from ideal hydrogen bond geometry. In addition, we defined probability distribution function of hydration water molecules (PDFH) over the hydrophilic surface of a protein as the sum of EHDFs of solvent accessible polar protein atoms. The functions envelop most of hydration sites identified in crystal structures of proteins (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 114 (2010) 4652). Here we propose the application of EHDFs and PDFHs for assessing crystallographically identified hydration structures of proteins. First, hydration water molecules are classified with respect to the geometry in hydrogen bonds in referring EHDFs. Difference Fourier electron density map weighted by PDFH of protein is proposed to identify easily density peaks as candidates of hydration water molecules. A computer program implementing those ideas was developed and used for assessing hydration structures of proteins

  15. Dual functional MoS2/graphene interlayer as an efficient polysulfide barrier for advanced lithium-sulfur batteries

    International Nuclear Information System (INIS)

    Guo, Pengqian; Liu, Dequan; Liu, Zhengjiao; Shang, Xiaonan; Liu, Qiming; He, Deyan

    2017-01-01

    Highlights: •Dual functional MoS 2 /graphene interlayer was first used as an efficient polysulfide-trapping shield for lithium-sulfur batteries. •MoS 2 /graphene interlayer shows strong chemical interactions with LiPSs. •MoS 2 /graphene interlayer forms a 3D network to facilitate electron and ion transfer during the discharge-charge processes. •The resultant lithium-sulfur batteries exhibit a superior rate capacity and improved cycling capacity. -- Abstract: A dual functional interlayer consisted of composited two-dimensional MoS 2 and graphene has been developed as an efficient polysulfide barrier for lithium-sulfur batteries (LSBs). With such a configuration, LSBs show a superior rate capacity and improved cycling capacity. The excellent electrochemical performance can be attributed to the strong bonding interactions between the MoS 2 /graphene interlayer and the formed lithium polysulfides (LiPSs) as well as the good electrical conductivity of the MoS 2 /graphene composite. The MoS 2 /graphene interlayer can physically block LiPSs by the graphene nanosheets and chemically suppress the dissolution of LiPSs by the polar MoS 2 nanoflowers. Such a dual functional interlayer further provides a good contact with the surface of the sulfur cathode, acts as an upper current collector and greatly improves the sulfur utilization and the rate capability of LSBs.

  16. Characterization of the porous anodic alumina nanostructures with a metal interlayer on Si substrates

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Chia-Hui; Chen, Hung-Ing; Hsiao, Jui-Ju; Wang, Jen-Cheng; Nee, Tzer-En, E-mail: neete@mail.cgu.edu.tw

    2014-04-15

    Porous anodic alumina (PAA) films produced by the anodization technique have made possible the mass production of porous nano-scale structures where the pore height and diameter are controllable. A metal interlayer is observed to have a significant influence on the characteristics of these PAA nanostructures. In this study, we investigate in-depth the effect of the current density on the properties of porous anodic alumina nanostructures with a metal interlayer. A thin film layer of tungsten (W) and titanium (Ti) was sandwiched between a porous anodic alumina film and a silicon (Si) substrate to form PAA/W/Si and PAA/Ti/Si structures. The material and optical characteristics of the porous anodic alumina nanostructures, with and without a metal interlayer, on silicon substrates were studied using the scanning electron microscopy, X-ray diffraction (XRD), and temperature-dependent photoluminescence (PL) measurements. The current densities of the porous anodic alumina nanostructures with the metal interlayer are higher than for the PAA/Si, resulting in an increase of the growth rate of the oxide layer. It can be observed from the X-ray diffraction curves that there is more aluminum oxide inside the structure with the metal interlayer. Furthermore, it has been found that there is a reduction in the photoluminescence intensity of the oxygen vacancy with only one electron due to the formation of oxygen vacancies inside the aluminum oxide during the re-crystallization process. This leads to competition between the two kinds of different oxygen-deficient defect centers (F+ and F centers) in the carrier recombination mechanism from the PL spectra of the porous anodic alumina nanostructures, with and without a metal interlayer, on silicon substrates. -- Highlights: • Study of porous anodic alumina (PAA) films with metal interlayers on silicon. • The highly ordered PAA film with a fairly regular nano-porous structure. • The luminescence properties of PAA films were

  17. Thickness effects of yttria-doped ceria interlayers on solid oxide fuel cells

    Science.gov (United States)

    Fan, Zeng; An, Jihwan; Iancu, Andrei; Prinz, Fritz B.

    2012-11-01

    Determining the optimal thickness range of the interlayed yttria-doped ceria (YDC) films promises to further enhance the performance of solid oxide fuel cells (SOFCs) at low operating temperatures. The YDC interlayers are fabricated by the atomic layer deposition (ALD) method with one super cycle of the YDC deposition consisting of 6 ceria deposition cycles and one yttria deposition cycle. YDC films of various numbers of ALD super cycles, ranging from 2 to 35, are interlayered into bulk fuel cells with a 200 um thick yttria-stabilized zirconia (YSZ) electrolyte. Measurements and analysis of the linear sweep voltammetry of these fuel cells reveal that the performance of the given cells is maximized at 10 super cycles. Auger elemental mapping and X-ray photoelectron spectroscopy (XPS) techniques are employed to determine the film completeness, and they verify 10 super cycles of YDC to be the critical thickness point. This optimal YDC interlayer condition (6Ce1Y × 10 super cycles) is applied to the case of micro fuel cells as well, and the average performance enhancement factor is 1.4 at operating temperatures of 400 and 450 °C. A power density of 1.04 W cm-2 at 500 °C is also achieved with the optimal YDC recipe.

  18. Caesium concentration factors in wild herbivores and the fox (Vulpes vulpes L.)

    International Nuclear Information System (INIS)

    Lowe, V.P.W.; Horrill, A.D.

    1991-01-01

    A selection of wild animals was sampled in the winter of 1986/87. The sites chosen for sampling were based on information obtained from surveys carried out by The Institute of Terrestrial Ecology in the spring and autumn of 1986. Animals included deer, grouse, hares and rabbits, and foxes which were collected as a top carnivore in the food chain. Variation in concentration of caesium between species from the same area was unpredictable; rabbits never exceeded 200 Bq kg -1 (fresh wt) of 137 Cs in their flesh, even when adjacent to deer forests with over 1000 Bq kg -1 in the venison. The greatest complication arose from areas of peaty uplands where the pre-Chernobyl 137 Cs from weapons-testing was much higher than expected. This pre-Chernobyl contribution amounted to 630 Bq kg -1 in a red grouse from the Pennines, and 650 Bq kg -1 in a roe deer from near the Borders, being c. 60% of the total. Significant differences in concentration factors were found depending on species, food, sex, breeding condition and age. Contrasting the decrease of the two caesium isotopes in roe deer from forestry on peat with those from woodlands on mineral soils, it appeared that after an initial fall in concentration, the only decrease thereafter occurred on the mineral soils. Nowhere were radiocaesium concentrations high enough to cause concern amongst consumers of game and other wild animals, even when levels exceed 3000 Bq kg -1 (fresh wt) as they did in red deer, red grouse and the blue hare. (author)