WorldWideScience

Sample records for calcite buffered solutions

  1. Calcite growth kinetics: Modeling the effect of solution stoichiometry

    NARCIS (Netherlands)

    Wolthers, M.; Nehrke, G.; Gustafsson, J.P.; Van Cappellen, P.

    2012-01-01

    Until recently the influence of solution stoichiometry on calcite crystal growth kinetics has attracted little attention, despite the fact that in most aqueous environments calcite precipitates from non-stoichiometric solution. In order to account for the dependence of the calcite crystal growth rat

  2. Single-contact pressure solution creep on calcite monocrystals

    CERN Document Server

    Zubtsov, Sergei; Gratier, Jean-Pierre; Dysthe, Dag; Traskine, Vladimir

    2005-01-01

    Pressure solution creep rates and interface structures have been measured by two methods on calcite single crystals. In the first kind of experiments, calcite monocrystals were indented at 40 degrees C for six weeks using ceramic indenters under stresses in the 50-200 MPa range in a saturated solution of calcite and in a calcite-saturated aqueous solution of NH4Cl. The deformation (depth of the hole below the indenter) is measured ex-situ at the end of the experiment. In the second type of experiment, calcite monocrystals were indented by spherical glass indenters for 200 hours under stresses in the 0-100 MPa range at room temperature in a saturated aqueous solution of calcite. The displacement of the indenter was continuously recorded using a specially constructed differential dilatometer. The experiments conducted in a calcite-saturated aqueous solution of NH4Cl show an enhanced indentation rate owing to the fairly high solubility of calcite in this solution. In contrast, the experiments conducted in a calc...

  3. X-ray scattering of calcite thin films deposited by atomic layer deposition: Studies in air and in calcite saturated water solution

    International Nuclear Information System (INIS)

    Carbonates are one of the most abundant groups of minerals in earth systems and are important in many geological settings and industrial processes. Calcite (CaCO3) thin films produced by atomic layer deposition offer a method to evaluate the surficial properties of carbonates as well as interactions at the carbonate–fluid interface. Using synchrotron X-ray reflectivity and X-ray diffraction, these films are observed to be porous, polycrystalline, and have crystallites oriented with the major (104) calcite cleavage plane parallel to the surface of the z-cut single crystal quartz substrate. An Al2O3 buffer layer, present between quartz and the calcite film, does not affect the as-deposited film, but does influence how the films reorganize in contact with fluid. Without a buffer layer, calcite reorients its crystallites to have populations of (006) and (030) parallel to the substrate, while those with an Al2O3 buffer layer become more amorphous. Amorphous films may represent an analog to amorphous calcium carbonate and provide insights into that material's thermophysical behavior. Due to a higher percentage of pore spaces available for fluid infiltration, films deposited at higher temperature make the calcite thin films more susceptible to amorphization. These films are chemically similar, but structurally dissimilar to bulk natural calcite. Nevertheless, they can be a complementary system to traditional single crystal X-ray surface scattering studies on carbonates, particularly for important but less common minerals, to evaluate mineral–fluid interfacial interactions. - Highlights: • Atomic layer deposition (ALD) used to produce calcite films. • Calcite film orientation and crystallinity depend on ALD parameters. • ALD calcite films can be both crystalline and amorphous. • Interaction of water with films can re-orient or amorphize the films. • ALD calcite films may be useful to study carbonate–fluid interfacial interactions

  4. Crystal growth of calcite from calcium bicarbonate solutions at constant PCO2 and 25°C: a test of a calcite dissolution model

    Science.gov (United States)

    Reddy, Michael M.; Plummer, L. Neil; Busenberg, E.

    1981-01-01

    A highly reproducible seeded growth technique was used to study calcite crystallization from calcium bicarbonate solutions at 25°C and fixed carbon dioxide partial pressures between 0.03 and 0.3 atm. The results are not consistent with empirical crystallization models that have successfully described calcite growth at low PCO2 (crystallization rates and those calculated from the calcite dissolution rate law and mechanism proposed by Plummer et al. (1978).

  5. Calcite interaction with acidic sulphate solutions: a vertical scanning interferometry and energy-dispersive XRF study

    OpenAIRE

    Atanassova, Radostina; Cama, Jordi; Soler, Josep M.; Offeddu, Francesco G.; Queralt Mitjans, Ignacio; Casanova, Ignasi

    2013-01-01

    Calcite dissolution on (10 (1) over bar4) cleavage surface was investigated by means of ex situ vertical scanning interferometry (VSI) measurements using flow-through and batch experiments at ambient pCO(2), pH 1-7 and room temperature in metal (Fe(II), Zn, Cu and Cd) and metal-free chloride solutions, and metal sulphate and metal-free sulphate solutions, undersaturated with respect to calcite and undersaturated or in equilibrium with respect to gypsum.Based on the VSI measurements, surface r...

  6. Experimental study of the effect of mica on pressure solution of single crystal calcite

    Science.gov (United States)

    Karcz, Z.; Laronne, L.; Polizzotti, R. S.; Ertas, D.; Aharonov, E.

    2007-12-01

    Field and experimental studies suggest that clays and micas accelerate the rate of pressure solution in various geomaterials. It is not clear however whether the "clay effect" is purely mechanical (i.e., maintaining a thick conduit for fluids at the contact) or whether its surface chemistry plays a critical role. A case in point is the insoluble clay filling of stylolites, which are thought by some to be merely an inert byproduct of dissolution, or by others to be a necessary feature for the propagation of the seam. To study the effect of mica on carbonate pressure solution, the corner of a cleaved calcite single crystal rhomb was polished into a triangular face (edge length ~ 200micron) and pressed against either muscovite or quartz discs to yield a nominal stress of 10-20MPa. Immersing the contact in pre-saturated (with respect to microcrystalline calcite) solutions of distilled water or 0.25M NH4Cl caused axial shortening of the crystal. This axial strain was measured with a capacitance sensor (perimeter roughens. The second stage is distinguished by high axial strain rates (~40nm/h) and changes in the size and spatial position of isolated contacts (diameterfaces adjacent to it. At this point we see no significant difference between the calcite quartz and calcite muscovite experiments under similar load conditions.

  7. Interactions of Ni and Ca at the calcite-solution interface

    International Nuclear Information System (INIS)

    The performance assessment of repositories for spent nuclear fuel need, among other things, data describing the solubilities of radionuclides in the near field and far field. The solubility limits are often used in order to estimate the maximum concentrations of radionuclides during their possible transport to the biosphere. The solubilities used are mostly the individual solubilities for pure solids of the actual radionuclides. This way of using solubility limits represents a conservative performance assessment where the estimated nuclide concentrations are unrealistically high. This is acceptable from a performance assessment point of view but very unsatisfactory for an optimal design of the repository. In order to make the assessment more realistic, coprecipitation and solid solution formation should be taken into account. Only solids which are, in geological terms, formed in fast reactions need to be considered, which in practice restricts the number of radionuclide scavengers to calcite and iron(III)oxihydroxide. This work focuses on the Ni coprecipitation with calcite. The systems were studied under anoxic conditions and consisted of calcite-saturated 0.05 M NaCl solutions in equilibrium with synthetic calcite. The solutions were initially spiked with 63Ni and 45Ca and the concentrations of these elements were determined using liquid scintillation counting. (18 refs.)

  8. Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

    Science.gov (United States)

    Busenberg, Eurybiades; Plummer, L. Niel

    1989-01-01

    The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and

  9. The influence of solution composition and grain boundaries on the replacement of calcite by dolomite

    Science.gov (United States)

    Moraila Martinez, Teresita de Jesus; Putnis, Christine V.; Putnis, Andrew

    2016-04-01

    Dolomite formation is a mineral replacement reaction that affects extensive rock volumes and comprises a large fraction of oil and gas reservoirs [1,2]. The most accepted hypothesis is the 'dolomitization' of limestone by Mg-rich fluids [3]. The objective of this research is to study the replacement mechanism of calcite by dolomite, the role of grain boundaries, highlighted by Etschmann et al. (2014), and the possible influence of solutions in dolomite formation under the presence of ions that are normally in crustal aqueous fluids. To accomplish this purpose, we performed hydrothermal experiments using Carrara marble cubes of ~1.5 mm size and 7-9 mg weight as starting material, reacted with 1M (Mg,Ca)Cl2 aqueous solutions, with Mg/Ca ratios of 3 and 5 at 200°C, for different reaction times. Additional experiments were performed adding 1mM of Na2SO4, NaCl or NaF to the previous solutions. After the reaction, the product phases were identified using Raman spectroscopy, X-Ray powder diffraction (XRD), electron microprobe analysis (EMPA), and the textural evolution was studied by scanning electron microscopy (SEM). Samples reacted with aqueous solutions resulted in the replacements of the calcite rock into magnesite and dolomite. The amount and type of reaction strongly depends on the Mg/Ca ratio. Samples reacted with a Mg/Ca ratio of 5 resulted in an almost complete replacement reaction and more favorable for magnesite formation than for dolomite. When the Mg/Ca ratio was 3 dolomite formed but the replacement was located in the core of the sample. We show that grain boundaries are very important for the infiltration of solution and the progress of a replacement reaction, acting as fluid pathways. Solution composition controls the nature of the replacement product. Acknowledgment: This work is funded within a Marie Curie EU Initial Training Network- CO2-React. 1. Etschmann B., Brugger J., Pearce M.A., Ta C., Brautigan D., Jung M., Pring A. (2014). Grain boundaries as

  10. A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

    Science.gov (United States)

    Davis, J.A.; Fuller, C.C.; Cook, A.D.

    1987-01-01

    The rate of Cd2+ sorption by calcite was determined as a function of pH and Mg2+ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO3. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca2+ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd2+ sorption decrease with increasing pH or with increasing Mg2+. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer. A model is presented which is consistent with the rates of Cd2+ sorption and Ca2+ isotopic exchange. In the model, the first step in Cd2+ sorption involves a fast adsorption reaction that is followed by diffusion of Cd2+ into a surface layer of hydrated CaCO3 that overlies crystalline calcite. Desorption of Cd2+ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO3, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution. ?? 1987.

  11. Stability of biodegradable waterborne polyurethane films in buffered saline solutions.

    Science.gov (United States)

    Lin, Ying Yi; Hung, Kun-Che; Hsu, Shan-Hui

    2015-01-01

    The stability of polyurethane (PU) is of critical importance for applications such as in coating industry or as biomaterials. To eliminate the environmental concerns on the synthesis of PU which involves the use of organic solvents, the aqueous-based or waterborne PU (WBPU) has been developed. WBPU, however, may be unstable in an electrolyte-rich environment. In this study, the authors reported the stability of biodegradable WBPU in the buffered saline solutions evaluated by atomic force microscopy (AFM). Various biodegradable WBPU films were prepared by spin coating on coverslip glass, with a thickness of ∼300 nm. The surface AFM images of poly(ε-caprolactone) (PCL) diol-based WBPU revealed nanoglobular structure. The same feature was observed when 20% molar of the PCL diol soft segment was replaced by polyethylene butylenes adipate diol. After hydration in buffered saline solutions for 24 h, the surface domains generally increased in sizes and became irregular in shape. On the other hand, when the soft segment was replaced by 20% poly(l-lactide) diol, a meshlike surface structure was demonstrated by AFM. When the latter WBPU was hydrated, the surface domains appeared to be disconnected. Results from the attenuated total reflectance infrared spectroscopy and x-ray photoelectron spectroscopy indicated that the surface chemistry of WBPU films was altered after hydration. These changes were probably associated with the neutralization of carboxylate by ions in the saline solutions, resulting in the rearrangements of soft and hard segments and causing instability of the WBPU. PMID:26296357

  12. Buffer Sizing in Wireless Networks: Challenges, Solutions, and Opportunities

    KAUST Repository

    Showail, Ahmad

    2016-04-01

    Buffer sizing is an important network configuration parameter that impacts the Quality of Service (QoS) characteristics of data traffic. With falling memory costs and the fallacy that \\'more is better\\', network devices are being overprovisioned with large bu ers. This may increase queueing delays experienced by a packet and subsequently impact stability of core protocols such as TCP. The problem has been studied extensively for wired networks. However, there is little work addressing the unique challenges of wireless environment such as time-varying channel capacity, variable packet inter-service time, and packet aggregation, among others. In this paper we discuss these challenges, classify the current state-of-the-art solutions, discuss their limitations, and provide directions for future research in the area.

  13. Biocompatibility and tolerability of a purely bicarbonate-buffered peritoneal dialysis solution.

    NARCIS (Netherlands)

    Weiss, L.; Stegmayr, B.; Malmsten, G.; Tejde, M.; Hadimeri, H.; Siegert, C.E.; Ahlmen, J.; Larsson, R.; Ingman, B.; Simonsen, O.; Hamersvelt, H.W. van; Johansson, A.C.; Hylander, B.; Mayr, M.; Nilsson, P.H.; Andersson, P.O.; Los Rios, T. De

    2009-01-01

    BACKGROUND: Novel peritoneal dialysis solutions are characterized by a minimal content of glucose degradation products and a neutral pH. Many studies have shown the biocompatibility of neutral lactate-buffered solutions; however, until now, the effect of purely bicarbonate-buffered solutions has not

  14. The role of silicate surfaces on calcite precipitation kinetics

    DEFF Research Database (Denmark)

    Stockmann, Gabrielle J.; Wolff-Boenisch, Domenik; Bovet, Nicolas Emile;

    2014-01-01

    H equal to 9.1. Although the inlet fluid composition, flow rate, and temperature were identical for all experiments, the onset of calcite precipitation depended on the identity of the seeds present in the reactor. Calcite precipitated instantaneously and at a constant rate in the presence of calcite......The aim of this study is to illuminate how calcite precipitation depends on the identity and structure of the growth substrate. Calcite was precipitated at 25°C from supersaturated aqueous solutions in the presence of seeds of either calcite or one of six silicate materials: augite, enstatite......, labradorite, olivine, basaltic glass and peridotite rock. Calcite saturation was achieved by mixing a CaCl2-rich aqueous solution with a NaHCO3-Na2CO3 aqueous buffer in mixed-flow reactors containing 0.5-2g of mineral, rock, or glass seeds. This led to an inlet fluid calcite saturation index of 0.6 and a p...

  15. Impact of solute concentration on the electrocatalytic conversion of dissolved gases in buffered solutions

    KAUST Repository

    Shinagawa, Tatsuya

    2015-04-24

    To maintain local pH levels near the electrode during electrochemical reactions, the use of buffer solutions is effective. Nevertheless, the critical effects of the buffer concentration on electrocatalytic performances have not been discussed in detail. In this study, two fundamental electrochemical reactions, oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR), on a platinum rotating disk electrode are chosen as model gas-related aqueous electrochemical reactions at various phosphate concentrations. Our detailed investigations revealed that the kinetic and limiting diffusion current densities for both the ORR and HOR logarithmically decrease with increasing solute concentration (log|jORR|=-0.39c+0.92,log|jHOR|=-0.35c+0.73). To clarify the physical aspects of this phenomenon, the electrolyte characteristics are addressed: with increasing phosphate concentration, the gas solubility decrease, the kinematic viscosity of the solution increase and the diffusion coefficient of the dissolved gases decrease. The simulated limiting diffusion currents using the aforementioned parameters match the measured ones very well (log|jORR|=-0.43c+0.99,log|jHOR|=-0.40c+0.54), accurately describing the consequences of the electrolyte concentration. These alterations of the electrolyte properties associated with the solute concentration are universally applicable to other aqueous gas-related electrochemical reactions because the currents are purely determined by mass transfer of the dissolved gases. © 2015 The Authors.

  16. Experimental determination of calcite solubility in H2O-KCl-NaCl-LiCl solutions at 700 °C and 8 kbar

    OpenAIRE

    Eguchi, James Hiro

    2014-01-01

    Understanding the interactions between calcite and aqueous solutions is important when studying the deep carbon cycle. The present study investigates the solubility of calcite in salt-H2O fluids at 700 °C and 8 kbar. The investigated salts included NaCl, KCl, LiCl, and CsCl. All experiments were conducted in a piston cylinder apparatus. The results show that calcite solubility increases with increasing concentration of any individual salt. The data were successfully fit to simple functions of...

  17. Pressure solution of minerals in quartz-type buffer materials

    International Nuclear Information System (INIS)

    Two samples, pure quartz sand and a sand-bentonite (10%) mixture, were tested under conditions of high pressure (200 bar) and temperature (1150C). The experiment was carried out over a period of 70 days. A series of thin slides were prepared on a resin embedded sample at the end of the test period. A microscopical study was performed as to obtain data concerning the effects of pressure and temperature. It showed that no pressure solution had taken place in the pure quartz sand. However, the individual grains had been severely fractured, thus causing significant internal sedimentation. The mixed sample showed that the clay component coated the quartz grains and significantly decreased the effect of stress in the grains by having a cushioning effect. Relative grain movement was facilitated by the clay, by which the grains rotated and slipped into stable positions with large contact areas and low contact stresses. This probably minimized pressure solution. However, a few contact regions indicated the presence of precipitated silica. The investigation shows no definite evidence of pressure solution after an experiment duration of 70 days. Since the effect of solution may be time dependent at the applied temperature, it is recommended that further experiments be conducted at higher effective and porewater pressures but still at 1150C. (orig.)

  18. Comparison of Ring-Buffer-Based Packet Capture Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Barker, Steven Andrew [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2015-10-01

    Traditional packet-capture solutions using commodity hardware incur a large amount of overhead as packets are copied multiple times by the operating system. This overhead slows sensor systems to a point where they are unable to keep up with high bandwidth traffic, resulting in dropped packets. Incomplete packet capture files hinder network monitoring and incident response efforts. While costly commercial hardware exists to capture high bandwidth traffic, several software-based approaches exist to improve packet capture performance using commodity hardware.

  19. Thick lanthanum zirconate buffer layers from water-based precursor solutions on Ni-5%W substrates

    International Nuclear Information System (INIS)

    In this work, water-based precursor solutions suitable for dip-coating of thick La2Zr2O7 (LZO) buffer layers for coated conductors on Ni-5%W substrates were developed. The solutions were prepared based on chelate chemistry using water as the main solvent. The effect of polymer addition on the maximum crack-free thickness of the deposited films was investigated. This novel solution preparation method revealed the possibility to grow single, crack-free layers with thicknesses ranging 100-280 nm with good crystallinity and an in-plane grain misalignment with average FWHM of 6.55o. TEM studies illustrated the presence of nanovoids, typical for CSD-LZO films annealed under Ar-5%H2 gas flow. The appropriate buffer layer action of the film in preventing the Ni diffusion was studied using XPS. It was found that the Ni diffusion was restricted to the first 30 nm of a 140 nm thick film. The surface texture of the film was improved using a seed layer. - Graphical abstract: Thick LZO buffer layers from water-based precursor solutions were synthesized and their crystallinity, microstructure and buffer layer action were studied. The buffer layer action of the LZO layer was substantial to restrict the Ni penetration within 30 nm of a 140 nm thick film. Highlights: → LZO buffer layers with high thicknesses for use in coated conductors were prepared. → Prepared from water-based solutions. → Polymeric PVP increases the crack-free critical thickness of thick films. → Thick films showed good barrier action against Ni penetration. → Seed layers promote epitaxial growth of thick layers.

  20. Induction of Root Hair Growth in a Phosphorus-Buffered Culture Solution

    Institute of Scientific and Technical Information of China (English)

    LIU Guo-dong; James Dunlop; Thai Phung

    2006-01-01

    A system to control the release of phosphate in water was successfully established, based on solubility product of [Ca2+] and [PO43-] using tricalcium phosphate as P source in the hydroponic solution, and adding CaC12 for supplementing extra Ca2+. The system, similar to soil solutions, was a P nutrient buffer solution with very low bioavailable P. The buffer solution induced the roots of both monocotyledon and dicotyledon species to grow abundant root hairs, 3 mm in maximum length. The monocotyledons were corn (Zea mays L.) (var. Yellow Rose), wheat (Triticum aestivum L.) (var.Yanzhong 144), Triticale secale L. (var. Jingsong 5), and ryegrass (Lolium rigidum L.) (var. Ruanni), and the dicotyledons were Arabidopsis thaliana L. (var. Columbia), white clover (Trifolium repens) (var. Kopu), Lotus (Lotus peduncucatus Cav. Luliginosus Schkuhr) (var. Grasslands Maku). For these species we proved that the root environment controls the induction of root hair formation. However, the hydroponic buffer solution failed to induce root hairs on the roots of onion (Allium cepa L.). Other investigators have concluded that corn does not form root hairs in hydroponics, but abundant long root hairs on corn were induced by this buffer system. The roots with abundant long root hairs are called "hedgehog roots" because they have hairs everywhere just like a hedgehog.

  1. Interaction mode and nanoparticle formation of bovine serum albumin and anthocyanin in three buffer solutions

    International Nuclear Information System (INIS)

    Investigation of interaction mode of bovine serum albumin (BSA) and anthocyanin (ACN) in different solutions will help us understand the interaction mechanism and functional change of bioactive small molecule and biomacromolecule. This study investigated the binding mode, including binding constant, number of binding sites, binding force of BSA and ACN interaction in three buffer solutions of phosphate (PBS), sodium chloride (NaCl), and PBS-NaCl, using fluorescence spectroscopy and synchronous fluorescence spectroscopy. Formation and characteristics of BSA–ACN complex were also investigated using dynamic light scattering (DLS) and transmission electron microscopy (TEM). The results showed that ACN could interact with BSA at both tyrosine (Tyr) and tryptophan (Trp) residues through both hydrogen bonds and van der Waals force, and the same binding mode was seen in dH2O and three buffer solutions. The value of binding constant K was decreased as the temperature increased from 298 K to 308 K, and the decreasing degree was in the order of dH2O (9.0×104)>NaCl (2.64×104)/PBS (2.37×104)>PBS-NaCl (0.88×104), which was inversely correlated with the ionic strength of the buffer solutions of PBS-NaCl>NaCl>PBS. It indicated that stability of BSA–ACN complex was affected most in dH2O than in three buffer solutions. The BSA and ACN interaction led to formation of BSA–ACN nanoparticles. The sizes of BSA–ACN nanoparticles in dH2O were smaller than that in three buffer solutions, which correlated with stronger binding force between BSA and ACN in dH2O than in three buffer solutions at room temperature (25 °C, 298 K). - Highlights: • We report the influences of four solutions on the BSA–ACN interaction. • We report the relationship between BSA–ACN interaction and particle size of complex. • The stability of BSA–ACN complex was affected most in dH2O than in buffer solutions

  2. Interaction mode and nanoparticle formation of bovine serum albumin and anthocyanin in three buffer solutions

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Rui; Dong, Xueyan; Song, Lanlan; Jing, Hao, E-mail: hao.haojing@gmail.com

    2014-11-15

    Investigation of interaction mode of bovine serum albumin (BSA) and anthocyanin (ACN) in different solutions will help us understand the interaction mechanism and functional change of bioactive small molecule and biomacromolecule. This study investigated the binding mode, including binding constant, number of binding sites, binding force of BSA and ACN interaction in three buffer solutions of phosphate (PBS), sodium chloride (NaCl), and PBS-NaCl, using fluorescence spectroscopy and synchronous fluorescence spectroscopy. Formation and characteristics of BSA–ACN complex were also investigated using dynamic light scattering (DLS) and transmission electron microscopy (TEM). The results showed that ACN could interact with BSA at both tyrosine (Tyr) and tryptophan (Trp) residues through both hydrogen bonds and van der Waals force, and the same binding mode was seen in dH{sub 2}O and three buffer solutions. The value of binding constant K was decreased as the temperature increased from 298 K to 308 K, and the decreasing degree was in the order of dH{sub 2}O (9.0×10{sup 4})>NaCl (2.64×10{sup 4})/PBS (2.37×10{sup 4})>PBS-NaCl (0.88×10{sup 4}), which was inversely correlated with the ionic strength of the buffer solutions of PBS-NaCl>NaCl>PBS. It indicated that stability of BSA–ACN complex was affected most in dH{sub 2}O than in three buffer solutions. The BSA and ACN interaction led to formation of BSA–ACN nanoparticles. The sizes of BSA–ACN nanoparticles in dH{sub 2}O were smaller than that in three buffer solutions, which correlated with stronger binding force between BSA and ACN in dH{sub 2}O than in three buffer solutions at room temperature (25 °C, 298 K). - Highlights: • We report the influences of four solutions on the BSA–ACN interaction. • We report the relationship between BSA–ACN interaction and particle size of complex. • The stability of BSA–ACN complex was affected most in dH{sub 2}O than in buffer solutions.

  3. The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

    International Nuclear Information System (INIS)

    Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H2SO4, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L-1, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe-oxyhydroxysulfates (Fe(III)-SO4-H+ solutions) or Fe-oxyhydroxychlorides (Fe(III)-Cl-H+ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to ∼6-7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)-SO4-H+ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)-Cl-H+ solutions

  4. Acanthamoeba encystment: multifactorial effects of buffers, biocides, and demulcents present in contact lens care solutions

    Directory of Open Access Journals (Sweden)

    Kovacs CJ

    2015-10-01

    Full Text Available Christopher J Kovacs, Shawn C Lynch, Marjorie J Rah, Kimberly A Millard, Timothy W Morris Bausch & Lomb Incorporated, Rochester, NY, USA Purpose: To determine whether agents which are purportedly capable of inducing encystment of Acanthamoeba can recapitulate the signal when tested in differing formulations. Methods: In accordance with the International Standard ISO 19045, Acanthamoeba castellanii ATCC 50370 trophozoites were cultured in antibiotic-free axenic medium, treated with test solutions, and encystment rates plus viability were measured via bright field and fluorescent microscopy. Test solutions included phosphate-buffered saline (PBS, borate-buffered saline, biguanide- and hydrogen peroxide (H2O2-based biocides, propylene glycol (PG and povidone (POV ophthalmic demulcents, and one-step H2O2-based contact lens disinfection systems. Results: Only PBS solutions with 0.25 ppm polyaminopropyl biguanide (PAPB and increasing concentrations of PG and POV stimulated A. castellanii encystment in a dose-dependent manner, whereas PBS solutions containing 3% H2O2 and increasing concentrations of PG and POV did not stimulate encystment. Borate-buffered saline and PBS/citrate solutions containing PG also did not stimulate encystment. In addition, no encystment was observed after 24 hours, 7 days, or 14 days of exposures of trophozoites to one-step H2O2 contact lens disinfection products or related solutions. Conclusion: The lack of any encystment observed when trophozoites were treated with existing or new one-step H2O2 contact lens care products, as well as when trophozoites were exposed to various related test solutions, confirms that Acanthamoeba encystment is a complex process which depends upon simultaneous contributions of multiple factors including buffers, biocides, and demulcents. Keywords: propylene glycol, contact lens care system, hydrogen peroxide disinfecting solution

  5. The separation of radionuclide migration by solution and particle transport in LLRW repository buffer material

    International Nuclear Information System (INIS)

    Laboratory-scale lysimeter experiments were performed with simulated waste forms placed in candidate buffer materials which have been chosen for a low-level radioactive waste repository. Radionuclide releases into the effluent water and radionuclide capture by the buffer material were determined. The results could not be explained by traditional solution transport mechanisms, and transport by particles released from the waste form and/or transport by buffer particles were suspected as the dominant mechanism for radionuclide release from the lysimeters. To elucidate the relative contribution of particle and solution transport, the waste forms were replaced by a wafer of neutron-activated buffer soaked with selected soluble isotopes. Particle transport was determined by the movement of gamma-emitting neutron-activation products through the lysimeter. Solution transport was quantified by comparing the migration of soluble radionuclides relative to the transport of neutron activation products. The new approach for monitoring radionuclide migration in soil is presented. It facilitates the determination of most of the fundamental coefficients required to model the transport process

  6. A new single buffer layer for YBCO coated conductors prepared by chemical solution deposition

    Energy Technology Data Exchange (ETDEWEB)

    Li Guo [Key Laboratory of Advanced Technologiesof Materials (Ministry of Education of China), Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Pu Minghua [Key Laboratory of Advanced Technologiesof Materials (Ministry of Education of China), Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Du Xiaohua [Key Laboratory of Advanced Technologiesof Materials (Ministry of Education of China), Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Zhang Yanbing [Key Laboratory of Advanced Technologiesof Materials (Ministry of Education of China), Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Zhou Huaming [Key Laboratory of Advanced Technologiesof Materials (Ministry of Education of China), Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Zhao Yong [Key Laboratory of Advanced Technologiesof Materials (Ministry of Education of China), Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China)]. E-mail: yzhao@home.swjtu.edu.cn

    2007-02-01

    A new single buffer layer YBiO{sub 3} has been proposed for YBCO coated conductors. Highly c-axis oriented YBiO{sub 3} buffer layer has been deposited on single crystal LaAlO{sub 3} by a low-cost chemical solution deposition method in a temperature range as low as 730-800 C in air. A very dense, smooth, pinhole-free morphology has been observed for YBiO{sub 3} buffer layer. Dense, homogeneous and epitaxially grown YBCO film has been obtained with its onset critical temperature 90 K and J {sub c} (77 K, 0 T) = 3.1 MA/cm{sup 2}. The addition of Bi{sub 2}O{sub 3}, which melts at around 817 C, has been argued to be responsible for the densification as well as low-process temperature of YBiO{sub 3} buffer layer. These results offer an alternative to prepare desirable buffer layer(s) for YBCO coated conductors via a cost-effective and easily scalable route.0.

  7. A new single buffer layer for YBCO coated conductors prepared by chemical solution deposition

    International Nuclear Information System (INIS)

    A new single buffer layer YBiO3 has been proposed for YBCO coated conductors. Highly c-axis oriented YBiO3 buffer layer has been deposited on single crystal LaAlO3 by a low-cost chemical solution deposition method in a temperature range as low as 730-800 C in air. A very dense, smooth, pinhole-free morphology has been observed for YBiO3 buffer layer. Dense, homogeneous and epitaxially grown YBCO film has been obtained with its onset critical temperature 90 K and J c (77 K, 0 T) = 3.1 MA/cm2. The addition of Bi2O3, which melts at around 817 C, has been argued to be responsible for the densification as well as low-process temperature of YBiO3 buffer layer. These results offer an alternative to prepare desirable buffer layer(s) for YBCO coated conductors via a cost-effective and easily scalable route

  8. Nickel adsorption on chalk and calcite

    DEFF Research Database (Denmark)

    Belova, Dina Alexandrovna; Lakshtanov, Leonid; Carneiro, J.F.;

    2014-01-01

    Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite...

  9. Simple solution-processed CuOX as anode buffer layer for efficient organic solar cells

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Simple solution-processed CuOX hole transport layer for efficient organic solar cell. • Good photovoltaic performances as hole transport layer in OSCs with P3HT and PBDTTT-C as donor materials. • The device with CuOX as hole transport layer shows great improved stability compared with that of device with PEDOT:PSS as hole transport layer. - Abstract: A simple, solution-processed ultrathin CuOX anode buffer layer was fabricated for high performance organic solar cells (OSCs). XPS measurement demonstrated that the CuOX was the composite of CuO and Cu2O. The CuOX modified ITO glass exhibit a better surface contact with the active layer. The photovoltaic performance of the devices with CuOX layer was optimized by varying the thickness of CuOX films through changing solution concentration. With P3HT:PC61BM as the active layer, we demonstrated an enhanced PCE of 4.14% with CuOX anode buffer layer, compared with that of PEDOT:PSS layer. The CuOX layer also exhibits efficient photovoltaic performance in devices with PBDTTT-C:PC71BM as the active layer. The long-term stability of CuOX device is better than that of PEDOT:PSS device. The results indicate that the easy solution-processed CuOX film can act as an efficient anode buffer layer for high-efficiency OSCs

  10. Hydrogen production in microbial reverse-electrodialysis electrolysis cells using a substrate without buffer solution.

    Science.gov (United States)

    Song, Young-Hyun; Hidayat, Syarif; Kim, Han-Ki; Park, Joo-Yang

    2016-06-01

    The aim of this work was to use substrate without buffer solution in a microbial reverse-electrodialysis electrolysis cell (MREC) for hydrogen production under continuous flow condition (10 cell pairs of RED stacks, HRT=5, 7.5, and 15h). Decreasing in the HRT (increasing in the organic matter) made cell current stable and increased. Hydrogen gas was produced at a rate of 0.61m(3)-H2/m(3)-Van/d in H-MREC, with a COD removal efficiency of 81% (1.55g/L/d) and a Coulombic efficiency of 41%. This MREC system without buffer solution could successfully produce hydrogen gas at a consistent rate. PMID:26888336

  11. Anodic dissolution of electrodeposited iron group elements in phthalate buffer solution

    International Nuclear Information System (INIS)

    The anodic dissolution of electrodeposited iron group elements (Fe, Co, Ni) were studied in phthalate buffer solution. The pH dependence of the corrosion potential, the corrosion current and Tafel slope was measured for each element. Based on the electrochemical parameters including Tafel slopes, we proposed the redox mechanism of the corrosion and the passivation. The adsorption of various phthalate species on the electrodeposited iron group elements seemed to be affected the corrosion mechanisms

  12. Growth Kinetics and Electronic Properties of Passive Film of Zinc in Borate Buffer Solution

    International Nuclear Information System (INIS)

    We have investigated the growth kinetics and electronic properties of passive film of zinc in borate buffer solution. The oxide film formed in passivation process of zinc has showed the electronic properties of n-type semiconductor based on the Mott-Schottky equation. And it was found out that the oxide film consisted ZnO and Zn(OH)2 was composed of deep and shallow donors

  13. Corrosion behaviour of niobium in phosphate buffered saline solutions with different concentrations of bovine serum albumin

    International Nuclear Information System (INIS)

    Highlights: ► Corrosion of Nb was investigated in phosphate buffered saline solutions. ► Addition of bovine serum albumin lowered the open circuit potential of Nb. ► Open circuit potential, polarization resistance and impedance increased with time. ► Bovine serum albumin molecules and PO43− competitively adsorbed on Nb surface. ► A surface distribution of time-constants was proposed. - Abstract: The corrosion behaviour of Nb was studied in phosphate buffered saline (PBS) solutions at a presence of 0–6 g L−1 bovine serum albumin (BSA). Addition of BSA to PBS solutions lowered the open circuit potential (OCP). OCP, polarization resistance and impedance increased over immersion time. The adsorption process of BSA on Nb surface was found to be faster than that of the PO43−. According to X-ray Photoelectron Spectroscopy (XPS) a competitive adsorption between PO43− and BSA was in effect during the immersion process. Based on the analysis of effective capacitances, a surface distribution of time-constants was proposed.

  14. [Bicarbonate instead of lactate buffered substitution solution for continuous hemofiltration in intensive care].

    Science.gov (United States)

    Olbricht, C J; Huxmann-Nägeli, D; Bischoff, H

    1990-04-01

    The substitution fluids applied in continuous haemofiltration contain 40 mmol/l of lactate. This is unphysiological, since administration of large amounts of lactate lowers the phosphorylation potential and increases catabolism. With bicarbonate-buffered fluid three problems may arise: 1. Precipitation of calcium carbonate and magnesium carbonate; 2. pH is usually 8.4; 3. evaporation of CO2 increases pH. To solve these problems we applied a two-component system consisting of a glass bottle with 160 ml sodium bicarbonate 8.4% and a bag with 4.5 l of acidic solution. Prior to use, the bicarbonate was infused into the bag. The values of Ca++, Mg++, bicarbonate, and pH in this final substitution solution were constant during a 24 hr period after mixing. Precipitation of Ca++ and Mg++ carbonate was prevented by 3 mmol/l of lactic acid in the solution. The pH was 7.37. Evaporation of CO2 was prevented by bags made of special plastic sheeting. The solution was then applied in 7 intensive-care patients suffering from acute renal failure treated by continuous arteriovenous haemofiltration. No side effects of the solution were observed during six days of treatment. The values of Ca++, bicarbonate, pH, and pCO2 remained constant under clinical routine conditions. Hence, bicarbonate-buffered substitution solution is recommended for continuous haemofiltration. Continuous haemofiltration is now also available for patients with impaired liver function and increased lactate levels. PMID:2360710

  15. A resin-buffered nutrient solution for controlling metal speciation in the algal bottle assay

    Energy Technology Data Exchange (ETDEWEB)

    Verheyen, L., E-mail: liesbeth.verheyen@ees.kuleuven.be [Division of Soil and Water Management, Department of Earth and Environmental Sciences, K.U.Leuven, Kasteelpark Arenberg 20 - box 2459, 3001 Heverlee (Belgium); Merckx, R.; Smolders, E. [Division of Soil and Water Management, Department of Earth and Environmental Sciences, K.U.Leuven, Kasteelpark Arenberg 20 - box 2459, 3001 Heverlee (Belgium)

    2012-06-15

    Metal speciation in solution is uncontrolled during algal growth in the traditional algal bottle assay. A resin-buffered nutrient solution was developed to overcome this problem and this was applied to test the effect of chloride (Cl{sup -}) on cadmium (Cd) uptake. Standard nutrient solution was enriched with 40 mM of either NaNO{sub 3} or NaCl, and was prepared to contain equal Cd{sup 2+} but varying dissolved Cd due to the presence of CdCl{sub n}{sup 2-n} complexes. Both solutions were subsequently used in an algal assay in 100 mL beakers that contained only the solution (designated '-R') or contained the solution together with a cation exchange sulfonate resin (2 g L{sup -1}, designated '+R') as a deposit on the bottom of the beaker. Pseudokirchneriella subcapitata was grown for 72 h (1.4 Multiplication-Sign 10{sup 5}-1.4 Multiplication-Sign 10{sup 6} cells mL{sup -1}) in stagnant solution and shaken three times a day. Growth was unaffected by the presence of the resin (p > 0.05). The Cd concentrations in solution of the -R devices decreased with 50-58% of initial values due to Cd uptake. No such changes were found in the +R devices or in abiotic controls. Cd uptake was unaffected by either NaNO{sub 3} or NaCl treatment in the +R device, confirming that Cd{sup 2+} is the preferred Cd species in line with the general concept of metal bioavailability. In contrast, Cd uptake in the -R devices was two-fold larger in the NaCl treatment than in the NaNO{sub 3} treatment (p < 0.001), suggesting that CdCl{sub n}{sup 2-n} complexes are bioavailable in this traditional set-up. However this bioavailability is partially, but not completely, an apparent one, because of the considerable depletion of solution {sup 109}Cd in this set-up. Resin-buffered solutions are advocated in the algal bottle assay to control trace metal supply and to better identify the role of metal complexes on bioavailability.

  16. A resin-buffered nutrient solution for controlling metal speciation in the algal bottle assay

    International Nuclear Information System (INIS)

    Metal speciation in solution is uncontrolled during algal growth in the traditional algal bottle assay. A resin-buffered nutrient solution was developed to overcome this problem and this was applied to test the effect of chloride (Cl−) on cadmium (Cd) uptake. Standard nutrient solution was enriched with 40 mM of either NaNO3 or NaCl, and was prepared to contain equal Cd2+ but varying dissolved Cd due to the presence of CdCln2−n complexes. Both solutions were subsequently used in an algal assay in 100 mL beakers that contained only the solution (designated “−R”) or contained the solution together with a cation exchange sulfonate resin (2 g L−1, designated “+R”) as a deposit on the bottom of the beaker. Pseudokirchneriella subcapitata was grown for 72 h (1.4 × 105–1.4 × 106 cells mL−1) in stagnant solution and shaken three times a day. Growth was unaffected by the presence of the resin (p > 0.05). The Cd concentrations in solution of the −R devices decreased with 50–58% of initial values due to Cd uptake. No such changes were found in the +R devices or in abiotic controls. Cd uptake was unaffected by either NaNO3 or NaCl treatment in the +R device, confirming that Cd2+ is the preferred Cd species in line with the general concept of metal bioavailability. In contrast, Cd uptake in the −R devices was two-fold larger in the NaCl treatment than in the NaNO3 treatment (p n2−n complexes are bioavailable in this traditional set-up. However this bioavailability is partially, but not completely, an apparent one, because of the considerable depletion of solution 109Cd in this set-up. Resin-buffered solutions are advocated in the algal bottle assay to control trace metal supply and to better identify the role of metal complexes on bioavailability.

  17. Two new solid solutions in calcite-magnesite system identified in a sample from coral reefs in the northern Perth basin

    International Nuclear Information System (INIS)

    Full text: Dolomite, CaMg(CO3)2, is an economically important mineral, being of particular significance in petroleum geology. Carbonate rocks have long been a focus of investigation because these rocks contain an estimated 60 percent of the world's recoverable petroleum, and include most of the world's largest reservoirs. Correct phase identification in carbonates has concerned sedimentologists and petroleum geologists for decades. A new type of solid solution in the calcite (CaCO3) - magnesite (MgCO3) system has been identified at Curtin University by Rietveld XRD and neutron diffraction data analysis in a sample from late Pleistocene reefs in the northern Perth Basin. It is known that the structure of calcite (space group R3C) will be transformed to dolomite (R3), which has an ordered distribution of Ca and Mg in the structure, if 50% of its Ca atoms are substituted by Mg in terms of the Ca-Mg atomic ratio. However, the upper limit of Mg substitution for Ca in calcite under sedimentary-geological conditions without there being a change in structure to dolomite is still unknown. Two carbonates examined at Curtin showed Mg substitution for Ca in calcite under coral reef sedimentary conditions of 18.1% and 37.7%, whereas Bragg peak shifts for a 'dolomite, line for these samples were interpreted by geologists as indicative of dolomite with a certain extent of order-disorder distribution between Ca and Mg atoms. The observations have provided an opportunity to re-examine the origins of dolomite and aspects of dolomitization in a coral reef environment in the Quaternary

  18. The corrosion behaviour of rare-earth containing magnesium alloys in borate buffer solution

    International Nuclear Information System (INIS)

    In this work, the corrosion behaviour of magnesium alloys ZK31, EZ33 and WE54 was studied in sodium borate buffer solution at pH 9.2. The electrochemical processes were studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The composition and morphology of the alloys and corrosion products formed were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The experimental findings highlighted the differences in the corrosion mechanisms of the different alloys tested. The results showed that the presence of rare-earth elements (RE) only increases the corrosion resistance when present in solid solution, as is the case of the WE54 alloy. At pH 9.2, an amorphous yttrium oxide/hydroxide thick film was formed, which possesses greater stability when compared to magnesium oxide/hydroxide. The role of RE in the corrosion mechanism was discussed.

  19. Activity and stability of recombinant human superoxide dismutase in buffer solutions and hypothermic perfusates.

    Directory of Open Access Journals (Sweden)

    Senoo,Yoshimasa

    1988-06-01

    Full Text Available The stability of recombinant human superoxide dismutase (r-hSOD in buffer solutions was studied in solutions at various pH and temperatures. Additionally, we studied the effects of incubation with proteases, serum and two types of hypothermic perfusates. R-hSOD was stable in the pH range of 6-11 and at temperatures up to 80 degrees C for 30 min. R-hSOD activity was not affected by incubation with trypsin, aminopeptidase M or serum for 2 h. R-hSOD activity determined at various temperatures (4-37 degrees C did not vary remarkably. R-hSOD in hypothermic perfusates was stable at 4-37 degrees C for 24 h.

  20. The corrosion behaviour of rare-earth containing magnesium alloys in borate buffer solution

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, R. [ICEMS, Instituto Superior Tecnico, Technical University of Lisbon (Portugal); Ferreira, M.G.S. [ICEMS, Instituto Superior Tecnico, Technical University of Lisbon (Portugal); CICECO, Universidade de Aveiro (Portugal); Carmezim, M.J. [ICEMS, Instituto Superior Tecnico, Technical University of Lisbon (Portugal); Instituto Politecnico de Setubal, ESTSetubal, DEM (Portugal); Montemor, M.F., E-mail: mfmontemor@ist.utl.p [ICEMS, Instituto Superior Tecnico, Technical University of Lisbon (Portugal)

    2011-01-01

    In this work, the corrosion behaviour of magnesium alloys ZK31, EZ33 and WE54 was studied in sodium borate buffer solution at pH 9.2. The electrochemical processes were studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The composition and morphology of the alloys and corrosion products formed were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The experimental findings highlighted the differences in the corrosion mechanisms of the different alloys tested. The results showed that the presence of rare-earth elements (RE) only increases the corrosion resistance when present in solid solution, as is the case of the WE54 alloy. At pH 9.2, an amorphous yttrium oxide/hydroxide thick film was formed, which possesses greater stability when compared to magnesium oxide/hydroxide. The role of RE in the corrosion mechanism was discussed.

  1. Electrochemical passivation behaviour of nanocrystalline Fe80Si20 coating in borate buffer solution

    Indian Academy of Sciences (India)

    G Gupta; A P Moon; K Mondal

    2013-02-01

    Passivation behaviour of nanocrystalline coating (Fe80Si20) obtained by in situ mechanical alloying route is studied and compared with that of the commercial pure iron and cast Fe80Si20 in sodium borate buffer solution at two different pH values (7.7 and 8.4). The coating reveals single passivation at a pH of 7.7 and double stage passivity at a pH of 8.4. The first passive layer is due to the dissolution mechanism and second passivity is related to stable passivation. The cast sample shows single stage passivity in the solution of pH 8.4. The difference in the passivation behaviour for the cast alloy (Fe80Si20) and the coating is related to the presence of highly iron-enriched localized regions, formed during the processing stage of coating.

  2. Cyclic growth and branching phenomena of calcite grown in Mg(2+) containing solutions and in natural systems

    Science.gov (United States)

    Wiethoff, Felix; Richter, Detlef K.; Neuser, Rolf D.; Immenhauser, Adrian; Gies, Hermann; Schreuer, Jürgen

    2016-04-01

    Undulosity in calcites (radiaxial fibrous calcite (RFC) and fascicular-optic fibrous calcite (FOFC)) is a common phenomenon in paleozoic and mesozoic limestones. Despite their importance as archives for climate reconstruction the underlying mechanisms and processes of their formation are still poorly understood [1]. To improve the application of such archives for climate reconstruction a better knowledge of their formation and possible alteration scenarios is necessary. In Mg2+ containing gel based growth experiments calcite crystals develop pathological morphologies. The morphology can be described as a product of a geometrical selective branching process at the rhombohedral crystal faces. Multiple sheet like building blocks evolve at the branching crystal face; each slightly tilted in respect to their substrate. The product is a crystal aggregate consisting out of several misoriented sub domains. In polarized light thin section microscopy the extinction behaviour of these sub units resemble the optical undulosity of radiaxial fibrous cements. In a multi method approach the local Mg2+ concentration was measured using EMPA and compared with maps of the local crystal orientation (via electron backscatter diffraction (EBSD)) and thin section microscopy. We found that Mg2+ is enriched at the sub-domain boundaries and deduced that lattice misfit as a consequence of impurity incorporation causes the crystal branching. We propose that this process is cyclic and each new misoriented sheet represents a growth period after a phase of inhibited growth caused by crystal faces covered by Mg2+‑ions. In comparison to natural systems we found that radiaxial-fibrous cave cements show a pathological morphology based on the same formation principles. [1] Richter et al. (2011) Sediment. Geol. 239, 23-36 [2] Reeder & Paquette (1989) Sediment. Geol. 65, 239-247 [3] Davis et al. (2004) Am. Min. 89, 714-720

  3. Critical zinc[sup +2] activities for sour orange determined with chelator-buffered nutrient solutions

    Energy Technology Data Exchange (ETDEWEB)

    Swietlik, D.; Zhang, L. (Texas A M Univ., Weslaco, TX (United States))

    1994-07-01

    Chelator-buffered nutrient solutions were used to study the effect of different levels of Zn activity in the rhizosphere on growth and nutritive responses of various tissues of sour orange seedlings. The seedlings were grown for 3 months in a growth chamber in a hydroponic culture containing from 5 to 69 [mu]m and 5 to 101 [mu]m total Zn in Expts. 1 and 2, respectively. Zn[sup +2] activities were calculated with a computerized chemical equilibrium model, and buffered by inclusion of a chelator, diethylenetriamine pentaacetate (DTPA), at 74 and 44 [mu]m in excess of the sum of Fe, Mn, Zn, Cu, Ni, and Co in Expts. 1 and 2, respectively. The use of DTPA-buffered solutions proved successful in imposing varying degrees of Zn deficiency. The deficiency was confirmed by leaf symptomatology, leaf chemical analyses, i.e., <16 mg[center dot]kg[sup [minus]1] Zn, and responses to foliar sprays and application of Zn to the roots. Growth parameters varied in their sensitivity to Zn deficiency, i.e., root dry weight < leaf number and white root growth < stem dry weight < leaf dry weight < shoot elongation and leaf area. The critical activities, expressed as pZn = [minus]log(Zn[sup +2]), were [approximately]10.2 [+-] 0.2 for root dry weight, 10.1 [+-] 0.2 for leaf number and white root growth, 10.0 [+-] 0.2 for stem dry weight, 9.9 [+-] 0.2 for leaf dry weight, and 9.8 [+-] 0.2 for shoot growth and leaf area. Increases in growth were observed in response to Zn applications even in the absence of visible Zn-deficiency symptoms. Seedlings containing > 23 mg[center dot]kg[sup [minus]1] Zn in leaves did not respond to further additions of Zn to the nutrient solution. Zinc foliar sprays were less effective than Zn applications to the roots in alleviating severe Zn deficiency because foliar-absorbed Zn was not translocated from the top of the roots and thus could not correct Zn deficiency in the roots.

  4. Corrosion and Passivation of Nickel Rotating Disk Electrode in Borate Buffer Solution

    International Nuclear Information System (INIS)

    The electrochemical corrosion and passivation of Ni rotating disk electrod in borate buffer solution was studied with potentiodynamic and electrochemical impedance spectroscopy. The mechanisms of both the active dissolution and passivation of nickel and the hydrogen evolution in reduction reaction were hypothetically established while utilizing the Tafel slope, impedance data, the rotation speed of Ni-RDE and the pH dependence of corrosion potential and current. Based on the EIS data, an equivalent circuit was suggested. In addition, carefully measured were the electrochemical parameters for specific anodic dissolution regions. It can be concluded from the data collected that the Ni(OH)2 oxide film, which is primarily formed by passivation, is converted to NiO by dehydration under the influence of an electrical field

  5. Luminescence quenching effect for the interaction of prulifloxacin with trypsin-Britton-Robinson buffer solution system

    Energy Technology Data Exchange (ETDEWEB)

    Huang Yabei; Liu Benzhi; Yu Zhang [School of Chemistry and Materials Science, Huaibei Coal Normal College, Huaibei 235000 (China); Zi Yanqin, E-mail: ziyanqin@163.co [School of Chemistry and Materials Science, Huaibei Coal Normal College, Huaibei 235000 (China)

    2010-03-15

    Prulifloxacin is a kind of new oral taking antibiotic of fluoroquinolone. Conjugation reaction of prulifloxacin with trypsin in Britton-Robinson buffer solution of pH 7.96 was analyzed by UV-vis spectrophotometry and fluorescence spectrometry. The intrinsic fluorescence of trypsin was strongly quenched by prulifloxacin. This effect was rationalized in terms of a static quenching procedure. The binding parameters have been evaluated by fluorescence quenching methods. Negative values DELTAG{sup 0} for the formation of prulifloxacin-trypsin complex implied that both hydrogen bonds and hydrophobic interactions might play a significant role in prulifloxacin binding to trypsin. The binding distance deduced from the efficiency of energy transfer was 0.84 nm for prulifloxacin-trypsin. Furthermore, association constants and binding mechanism were successfully derived from the fluorescence spectra. UV-vis detections supported a change in the secondary structure of proteins caused by the interaction of prulifloxacin with trypsin.

  6. Luminescence quenching effect for the interaction of prulifloxacin with trypsin-Britton-Robinson buffer solution system

    International Nuclear Information System (INIS)

    Prulifloxacin is a kind of new oral taking antibiotic of fluoroquinolone. Conjugation reaction of prulifloxacin with trypsin in Britton-Robinson buffer solution of pH 7.96 was analyzed by UV-vis spectrophotometry and fluorescence spectrometry. The intrinsic fluorescence of trypsin was strongly quenched by prulifloxacin. This effect was rationalized in terms of a static quenching procedure. The binding parameters have been evaluated by fluorescence quenching methods. Negative values ΔG0 for the formation of prulifloxacin-trypsin complex implied that both hydrogen bonds and hydrophobic interactions might play a significant role in prulifloxacin binding to trypsin. The binding distance deduced from the efficiency of energy transfer was 0.84 nm for prulifloxacin-trypsin. Furthermore, association constants and binding mechanism were successfully derived from the fluorescence spectra. UV-vis detections supported a change in the secondary structure of proteins caused by the interaction of prulifloxacin with trypsin.

  7. The passivity of Type 316L stainless steel in borate buffer solution

    Science.gov (United States)

    Nicic, Igor; Macdonald, Digby D.

    2008-09-01

    The passivity of Type 316 SS in borate buffer solution (pH 8.35), in the steady-state, has been explored using a variety of electrochemical techniques, including potentiostatic polarization, Mott Schottky analysis, and electrochemical impedance spectroscopy. The study shows that the passive film is an n-type semiconductor with a donor density that is essentially independent of voltage across the passive state. The passive current density is also found to be voltage-independent, but the thickness of the barrier layer depends linearly on the applied voltage. These observations are consistent with the predictions of the Point Defect Model, noting that the point defects within the barrier layer of the passive film are metal interstitials or oxygen vacancies, or both. No evidence for p-type behavior was obtained, indicating that cation vacancies do not have a significant population density in the film compared with the two donors (cation interstitials and oxygen vacancies).

  8. The passivity of Type 316L stainless steel in borate buffer solution

    International Nuclear Information System (INIS)

    The passivity of Type 316 SS in borate buffer solution (pH 8.35), in the steady-state, has been explored using a variety of electrochemical techniques, including potentiostatic polarization, Mott Schottky analysis, and electrochemical impedance spectroscopy. The study shows that the passive film is an n-type semiconductor with a donor density that is essentially independent of voltage across the passive state. The passive current density is also found to be voltage-independent, but the thickness of the barrier layer depends linearly on the applied voltage. These observations are consistent with the predictions of the Point Defect Model, noting that the point defects within the barrier layer of the passive film are metal interstitials or oxygen vacancies, or both. No evidence for p-type behavior was obtained, indicating that cation vacancies do not have a significant population density in the film compared with the two donors (cation interstitials and oxygen vacancies)

  9. Relationship between Virucidal Efficacy and Free Iodine Concentration of Povidone-Iodine in Buffer Solution.

    Science.gov (United States)

    Wada, Hideki; Nojima, Yasuhiro; Ogawa, Satoko; Hayashi, Nobuyuki; Sugiyama, Noriyoshi; Kajiura, Takumi; Ueda, Tomofumi; Morimoto, Shota; Yokota, Katuhiro

    2016-01-01

    Povidone-iodine solutions prepared to various concentrations (0.01, 0.1, 1 and 10%) with 0.2M phosphate buffer (pH 7.0) (PVP-I PB) were analyzed to determine their free iodine concentrations using membrane permeation cells, and their inactivation effects on three viruses (influenza A virus, poliovirus type 1 and adenovirus type 3) were examined. The free iodine concentrations in the 0.01-10% PVP-I PB were determined to be 1.84, 4.88, 1.58 and 0.17 ppm (approximate values), respectively, with the maximum obtained for the 0.1% solution. The virucidal efficacy of these PVP-I PB against poliovirus type 1 and adenovirus type 3 was found to be generally dependent on free iodine concentration, with the 0.1% solution being the most effective. Influenza A virus was inactivated with an action time of 15 s at all four concentrations examined. The results of this study suggested an association between free iodine concentration and virucidal efficacy for the 0.01-10% PVP-I PB. PMID:27009506

  10. Labile synthetic cadmium complexes are not bioavailable to Pseudokirchneriella subcapitata in resin buffered solutions

    International Nuclear Information System (INIS)

    The Free Ion Activity Model (FIAM) predicts that cadmium (Cd) uptake by organisms is identical for solutions with the same free Cd2+ concentration and inorganic composition. Clear exceptions to the FIAM have been shown for Cd uptake by plant roots, periphyton and human cells where labile Cd complexes increase bioavailability and which has been attributed to their role in enhancing Cd diffusion towards the uptake cells. Here, we assessed the role of labile Cd complexes on Cd uptake by algae, for which diffusion limitations should be less pronounced due to their smaller size. Long-term (3 days) Cd uptake by the green algae Pseudokirchneriella subcapitata was measured in resin buffered solutions with or without synthetic ligands and at three Cd2+ ion activities (pCd 8.2–5.7). The free Cd2+ activity was maintained during the test using a metal-selective resin located in the algal bottles. Total dissolved Cd increased up to 35-fold by adding the synthetic ligands at constant Cd2+ activity. In contrast, Cd uptake by algae increased maximally 2.8 fold with increasing concentration of the synthetic ligands and the availability of the complexes were maximally 5.2% relative to Cd2+ for NTA and CDTA complexes. It is concluded that labile Cd complexes do not greatly enhance Cd bioavailability to the unicellular algae and calculations suggest that Cd transport from solution to these small cells is not rate limiting.

  11. Performance improvement of polymer solar cells by using a solution processible titanium chelate as cathode buffer layer

    Science.gov (United States)

    Tan, Zhan'ao; Yang, Chunhe; Zhou, Erjun; Wang, Xiang; Li, Yongfang

    2007-07-01

    A solution processible titanium chelate, titanium (diisopropoxide) bis (2,4-pentanedionate) (TIPD), was used as the cathode buffer layer in the polymer solar cells (PSCs) based on the blend of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] and [6,6]-phenyl-C61-butyric acid methyl ester. Introducing TIPD buffer layer reduced the interface resistance between the active layer and Al electrode, leading to a lower device resistance. The power conversion efficiency of the PSC with TIPD buffer layer reached 2.52% under the illumination of AM1.5, 100mW/cm2, which is increased by 51.8% in comparison with that (1.66%) of the device without TIPD buffer layer under the same experimental conditions.

  12. BIOKID: Randomized controlled trial comparing bicarbonate and lactate buffer in biocompatible peritoneal dialysis solutions in children [ISRCTN81137991

    Directory of Open Access Journals (Sweden)

    Misselwitz Joachim

    2004-10-01

    Full Text Available Abstract Background Peritoneal dialysis (PD is the preferred dialysis modality in children. Its major drawback is the limited technique survival due to infections and progressive ultrafiltration failure. Conventional PD solutions exert marked acute and chronic toxicity to local tissues. Prolonged exposure is associated with severe histopathological alterations including vasculopathy, neoangiogenesis, submesothelial fibrosis and a gradual loss of the mesothelial cell layer. Recently, more biocompatible PD solutions containing reduced amounts of toxic glucose degradation products (GDPs and buffered at neutral pH have been introduced into clinical practice. These solutions contain lactate, bicarbonate or a combination of both as buffer substance. Increasing evidence from clinical trials in adults and children suggests that the new PD fluids may allow for better long-term preservation of peritoneal morphology and function. However, the relative importance of the buffer in neutral-pH, low-GDP fluids is still unclear. In vitro, lactate is cytotoxic and vasoactive at the concentrations used in PD fluids. The BIOKID trial is designed to clarify the clinical significance of the buffer choice in biocompatible PD fluids. Methods/design The objective of the study is to test the hypothesis that bicarbonate based PD solutions may allow for a better preservation of peritoneal transport characteristics in children than solutions containing lactate buffer. Secondary objectives are to assess any impact of the buffer system on acid-base status, peritoneal tissue integrity and the incidence and severity of peritonitis. After a run-in period of 2 months during which a targeted cohort of 60 patients is treated with a conventional, lactate buffered, acidic, GDP containing PD fluid, patients will be stratified according to residual renal function and type of phosphate binding medication and randomized to receive either the lactate-containing Balance solution or the

  13. Uncertainty in geochemical modelling of CO2 and calcite dissolution in NaCl solutions due to different modelling codes and thermodynamic databases

    International Nuclear Information System (INIS)

    Highlights: • CO2 and calcite dissolution is calculated. • The codes PHREEQC, Geochemist’s Workbench, EQ3/6, and FactSage are used. • Comparison with Duan and Li (2008) shows lowest deviation using phreeqc.dat and wateq4f.dat. • Using Pitzer databases does not improve accurate calculations. • Uncertainty in dissolved CO2 is largest using the geochemical models. - Abstract: A prognosis of the geochemical effects of CO2 storage induced by the injection of CO2 into geologic reservoirs or by CO2 leakage into the overlaying formations can be performed by numerical modelling (non-invasive) and field experiments. Until now the research has been focused on the geochemical processes of the CO2 reacting with the minerals of the storage formation, which mostly consists of quartzitic sandstones. Regarding the safety assessment the reactions between the CO2 and the overlaying formations in the case of a CO2 leakage are of equal importance as the reactions in the storage formation. In particular, limestone formations can react very sensitively to CO2 intrusion. The thermodynamic parameters necessary to model these reactions are not determined explicitly through experiments at the total range of temperature and pressure conditions and are thus extrapolated by the simulation code. The differences in the calculated results lead to different calcite and CO2 solubilities and can influence the safety issues. This uncertainty study is performed by comparing the computed results, applying the geochemical modelling software codes The Geochemist’s Workbench, EQ3/6, PHREEQC and FactSage/ChemApp and their thermodynamic databases. The input parameters (1) total concentration of the solution, (2) temperature and (3) fugacity are varied within typical values for CO2 reservoirs, overlaying formations and close-to-surface aquifers. The most sensitive input parameter in the system H2O–CO2–NaCl–CaCO3 for the calculated range of dissolved calcite and CO2 is the fugacity of CO2

  14. Substituent Effects on the Photodeprotection Reactions of Selected Ketoprofen Derivatives in Phosphate Buffered Aqueous Solutions

    Science.gov (United States)

    Liu, Mingyue; Li, Ming-De; Huang, Jinqing; Li, Tianlu; Liu, Han; Li, Xuechen; Phillips, David Lee

    2016-02-01

    Photodeprotection is an important reaction that has been attracting broad interest for use in a variety of applications. Recent advances in ultrafast and vibrational time-resolved spectroscopies can facilitate obtaining data to help unravel the reaction mechanisms involving in the photochemical reactions of interest. The kinetics and reaction mechanisms for the photodeprotection reactions of ketoprofen derivatives containing three different substituents (ibuprofen, Br and I) were investigated by femtosecond transient absorption (fs-TA) and nanosecond time-resolved resonance Raman (ns-TR3) spectroscopy methods in phosphate buffered solutions (PBS). Fs-TA allows us to detect the decay kinetics of the triplet species as the key precursor for formation of a carbanion species for three different substituents attached to ketoprofen. To characterize the structural and electronic properties of the corresponding carbanion and triplet intermediates, TR3 spectroscopic experiments were conducted. The transient spectroscopy work reveals that the different substituents affect the photodecarboxylation reaction to produce carbon dioxide which in turn influences the generation of the carbanion species which determines the rate of the photorelease of the functional groups attached on the ketoprofen parent molecule. The fingerprint TR3 spectroscopy results suggest that ketoprofen derivatives may be deactivated to produce a triplet carbanion when increasing the atom mass of the halogen atoms.

  15. Corrosion behavior of pristine and added MgB2 in Phosphate Buffered Saline Solution

    International Nuclear Information System (INIS)

    We have obtained by Spark Plasma Sintering (SPS), dense samples of MgB2 added with Ho2O3. Starting composition was (MgB2)0.975(HoO1.5)0.025 and we used addition powders with an average particle size below and above 100 nm. For Mg, pristine and added MgB2 samples we measured potentiodynamic polarization curves in Phosphate Buffered Saline (PBS) solution media at room temperature. MgB2 based composites show corrosion/ degradation effects. This behavior is in principle similar to Mg based alloys in the same media. Our work suggests that the different morphologies and phase compositions of the SPS-ed samples influence the interaction with corrosion medium; hence additions can play an important role in controlling the corrosion rate. Pristine MgB2 show a significant improvement of the corrosion resistance, if compared with Mg. The best corrosion resistance is obtained for pristine MgB2, followed by MgB2 with nano-Ho2O3 and μ-Ho2O3 additions.

  16. An advice concerning the quantity of buffer solution used in lanthanide complexometric analysis

    International Nuclear Information System (INIS)

    The influence of buffer quantity used in the titration of complexometric analysis of lanthanides is presented. This allows to determine the optimum quantity of buffer which shows reproducible results. La (NO3)3.4 dmSO samples are used in the analysis. (A.R.H.)

  17. The stability of DLC film on nitrided CoCrMo alloy in phosphate buffer solution

    International Nuclear Information System (INIS)

    CoCrMo alloy is often used as the material for metal artificial joint, but metal debris and metal ions are the main concern on tissue inflammation or tissue proliferation for metal prosthesis. In this paper, nitrogen ion implantation and diamond like carbon (DLC) film composite treatment was used to reduce the wear and ion release of biomedical CoCrMo substrate. The mechanical properties and stability of N-implanted/DLC composite layer in phosphate buffer solution (PBS) was evaluated to explore the full potential of N-implanted/DLC composite layer as an artificial joint surface modification material. The results showed that the DLC film on N implanted CoCrMo (N-implanted/DLC composite layer) had the higher surface hardness and wear resistance than the DLC film on virgin CoCrMo alloy, which was resulted from the strengthen effect of the N implanted layer on CoCrMo alloy. After 30 days immersion in PBS, the structure of DLC film on virgin CoCrMo or on N implanted CoCrMo had no visible change. But the adhesion and corrosion resistance of DLC on N implanted CoCrMo (N-implanted/DLC composite layer) was weakened due to the dissolution of the N implanted layer after 30 days immersion in PBS. The adhesion reduction of N-implanted/DLC composite layer was adverse for in vivo application in long term. So researcher should be cautious to use N implanted layer as an inter-layer for increasing CoCrMo alloy load carrying capacity in vivo environment.

  18. The stability of DLC film on nitrided CoCrMo alloy in phosphate buffer solution

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, T.F.; Liu, B.; Wu, B.J.; Liu, J.; Sun, H.; Leng, Y.X., E-mail: yxleng@263.net; Huang, N.

    2014-07-01

    CoCrMo alloy is often used as the material for metal artificial joint, but metal debris and metal ions are the main concern on tissue inflammation or tissue proliferation for metal prosthesis. In this paper, nitrogen ion implantation and diamond like carbon (DLC) film composite treatment was used to reduce the wear and ion release of biomedical CoCrMo substrate. The mechanical properties and stability of N-implanted/DLC composite layer in phosphate buffer solution (PBS) was evaluated to explore the full potential of N-implanted/DLC composite layer as an artificial joint surface modification material. The results showed that the DLC film on N implanted CoCrMo (N-implanted/DLC composite layer) had the higher surface hardness and wear resistance than the DLC film on virgin CoCrMo alloy, which was resulted from the strengthen effect of the N implanted layer on CoCrMo alloy. After 30 days immersion in PBS, the structure of DLC film on virgin CoCrMo or on N implanted CoCrMo had no visible change. But the adhesion and corrosion resistance of DLC on N implanted CoCrMo (N-implanted/DLC composite layer) was weakened due to the dissolution of the N implanted layer after 30 days immersion in PBS. The adhesion reduction of N-implanted/DLC composite layer was adverse for in vivo application in long term. So researcher should be cautious to use N implanted layer as an inter-layer for increasing CoCrMo alloy load carrying capacity in vivo environment.

  19. Physico-chemical investigation of cement carbonation in aqueous solution in equilibrium with calcite and with a controlled CO2 partial pressure at 25 and 50 deg. C

    International Nuclear Information System (INIS)

    In the framework of radioactive waste geological disposal, structural concretes have to be adapted to underground chemical conditions. For concrete in water saturated medium, it is believed that carbonation will have a major impact on the interaction between concrete and the geological medium. So, to understand the complex degradation of the cement paste in that context, it is interesting to study a simplified system such as degradation in carbonated water solution. This solution must be at equilibrium with a CO2 partial pressure 30 times higher than the atmospheric pCO2, to reproduce underground natural conditions of Callovo-Oxfordian clayey rock of Bure (France). In this study, the behaviour of a new low pH material (CEM I + silica fume + fly ashes) is compared with a CEM I cement paste, both of them being submitted to carbonation in aqueous solution in equilibrium with calcite and with a pCO2 equal to 1.32 kPa (1.3 10-2 atm). Two different temperatures, 25 and 50 C, are considered. To realize these experiments, two different original types of devices were developed

  20. Solution-processed In2S3 buffer layer for chalcopyrite thin film solar cells

    Science.gov (United States)

    Wang, Lan; Lin, Xianzhong; Ennaoui, Ahmed; Wolf, Christian; Lux-Steiner, Martha Ch.; Klenk, Reiner

    2016-02-01

    We report a route to deposit In2S3 thin films from air-stable, low-cost molecular precursor inks for Cd-free buffer layers in chalcopyrite-based thin film solar cells. Different precursor compositions and processing conditions were studied to define a reproducible and robust process. By adjusting the ink properties, this method can be applied in different printing and coating techniques. Here we report on two techniques, namely spin-coating and inkjet printing. Active area efficiencies of 12.8% and 12.2% have been achieved for In2S3-buffered solar cells respectively, matching the performance of CdS-buffered cells prepared with the same batch of absorbers.

  1. Solution-processed In2S3 buffer layer for chalcopyrite thin film solar cells

    Directory of Open Access Journals (Sweden)

    Wang Lan

    2016-01-01

    Full Text Available We report a route to deposit In2S3 thin films from air-stable, low-cost molecular precursor inks for Cd-free buffer layers in chalcopyrite-based thin film solar cells. Different precursor compositions and processing conditions were studied to define a reproducible and robust process. By adjusting the ink properties, this method can be applied in different printing and coating techniques. Here we report on two techniques, namely spin-coating and inkjet printing. Active area efficiencies of 12.8% and 12.2% have been achieved for In2S3-buffered solar cells respectively, matching the performance of CdS-buffered cells prepared with the same batch of absorbers.

  2. Aspartate buffer and divalent metal ions affect oxytocin in aqueous solution and protect it from degradation

    DEFF Research Database (Denmark)

    Avanti, Christina; Oktaviani, Nur Alia; Hinrichs, Wouther L.J.;

    2013-01-01

    favorable. These interactions may explain the protection of the disulfide bridge against intermolecular reactions that lead to dimerization.Mg or Zn, using 2D NOESY, TOCSY, H-C HSQC and H- N HSQC NMR spectroscopy. Almost all H, C and N resonances of oxytocin could be assigned using HSQC spectroscopy....... Furthermore, LC–MS (MS) measurements indicated that the combination of aspartate buffer and Zn2+ in particular suppressed intermolecular degradation reactions near the Cys1,6 disulfide bridge. These results lead to the hypothesis that in aspartate buffer, Zn2+ changes the conformation of oxytocin in such a...... way that the Cys1,6 disulfide bridge is shielded from its environment thereby suppressing intermolecular reactions involving this region of the molecule. To verify this hypothesis, we investigate here the conformation of oxytocin in aspartate buffer in the presence of Mg2+ or Zn2+, using 2D NOESY...

  3. Aspartate buffer and divalent metal ions affect oxytocin in aqueous solution and protect it from degradation

    NARCIS (Netherlands)

    Avanti, Christina; Oktaviani, Nur Alia; Hinrichs, Wouter L J; Frijlink, Henderik W; Mulder, Frans A A

    2013-01-01

    Oxytocin is a peptide drug used to induce labor and prevent bleeding after childbirth. Due to its instability, transport and storage of oxytocin formulations under tropical conditions is problematic. In a previous study, we have found that the stability of oxytocin in aspartate buffered formulation

  4. Use of multiple attributes decision-making Technique for Order Preference by Similarity to Ideal Solution (TOPSIS for Ghare-Gheshlagh calcite in determination of optimum geochemical sampling sites

    Directory of Open Access Journals (Sweden)

    Mansour Rezaei Azizi

    2015-04-01

    for green, white and pink calcites were varied 0.087, 0.247 and 0.997 respectively. The low amounts of Eu anomaly for green and white calcites attributed to low rock/fluid ratio (Nesbitt et al., 1990 and relatively more pH value (Cheng et al., 2013, however, increasing the Eu anomaly may be due to high rock/fluid ratio and less pH value. Ce anomalies are 0.0241, 0.0113 and 0.0131 in pink, white and green calcites respectively. The most negative Ce anomaly values show that calcite have precipitated under reduction conditions (Nesbitt et al., 1990. Discussion Recently, multiple attributes decision-making techniques help scientist to solve decision-making problems related to various controlling factors (Zhijun et al., 2013. One of these techniques is a Technique for Order Preference by Similarity to Ideal Solution (TOPSIS which is a quantitative weighted method (Momenei 2006. The identified criteria are CaO abundant in solution (C1, Eu anomaly (C2, Ce anomaly (C3, Sr abundant (C4 and volume (C5. The Index-Rock matrix also includes A1, A2 and A3 alternatives; as pink, green and white calcite respectively. The weighted normalized decision matrix can be calculated by multiplying the normalized evaluation matrix with its associated weight to obtain the result. The result show that Eu anomaly, volume, Sr abundant and Ce anomaly in order have higher role to investigate the geochemical study of area. Calculation of the relative closeness to the ideal solution (Cl * for pink, green and white calcites are 0.837, 0.445 and 0.157 respectively. It can be deduced that the most preferable calcite to be sampled for investigating geochemically are pink and green calcites. References Cheng, D.L., Jiang-haob, L., Shou-pengc, Z., Lianga, L., Zhao-bina, Y., Guo-lina, G. and Tinga, L., 2013. Geochemical characteristics of calcite and dolomite in sandstone of Dongying Sinking, Shandong Province, China. Procedia Earth and Planetary Science, 7(4: 504 – 507. Eftekharnezhad, J., 1973

  5. Matching phosphate and maleate buffer systems for dissolution of weak acids: Equivalence in terms of buffer capacity of bulk solution or surface pH?

    Science.gov (United States)

    Cristofoletti, Rodrigo; Dressman, Jennifer B

    2016-06-01

    The development of in vitro dissolution tests able to anticipate the in vivo fate of drug products has challenged pharmaceutical scientists over time, especially in the case of ionizable compounds. In the seminal model proposed by Mooney et al. thirty-five years ago, the pH at the solid-liquid interface (pH0) was identified as a key parameter in predicting dissolution rate. In the current work it is demonstrated that the in vitro dissolution of the weak acid ibuprofen in maleate and phosphate buffer systems is a function of the pH0, which in turn is affected by properties of the drug and the medium. The reported pH0 for ibuprofen dissolution in bicarbonate buffer, the predominant buffer species in the human small intestine under fasting conditions, can be achieved by reducing the phosphate buffer concentration to 5.0mM or the maleate buffer concentration to 2.2mM. Using this approach to identify the appropriate buffer/buffer capacity combination for in vitro experiments in FaSSIF-type media, it would be possible to increase the physiological relevance of this important biopharmaceutics tool. However, the necessity of monitoring and adjusting the bulk pH during the experiments carried out in 5.0mM phosphate or 2.2mM maleate buffers must also be taken into consideration. PMID:27032508

  6. Enhanced efficiency of inverted polymer solar cells by using solution-processed TiOx/CsOx cathode buffer layer

    OpenAIRE

    Zhou, Xiaodong; Fan, Xi; Sun, Xianke; ZHANG, YUNLI; Zhu, Ziqiang

    2015-01-01

    In this work, a double-buffer film of TiOx coated with CsOx (TiOx/CsOx) was solution prepared to be applied in poly(3-hexylthiophene):indene-C60 bisadduct (P3HT:ICBA) and P3HT:[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) inverted polymer solar cells (PSCs). Compared with TiOx films and CsOx films, the TiOx/CsOx double-buffer film exhibited a favorable energy-level alignment among TiOx, CsOx, and the electron acceptor of PCBM or ICBA a better surface morphology; and an enhanced wetting an...

  7. The effect of undissociated acetic-acid concentration of buffer solutions on artificial caries-like lesion formation in human tooth enamel

    NARCIS (Netherlands)

    Groeneveld, A.; Theuns, H.M.; Dijk, J.W.E. van; Driessens, F.C.M.

    1984-01-01

    A chemical system for lesion production was used. The influence on lesion characteristics of the concentration of undissociated acetic acid in a calcium and phosphate-containing buffer solution was investigated. Artificial lesions obtained after demineralization in buffers with a pH of 4.0, 4.5, 5.0

  8. Proposing buffer zones and simple technical solutions for safeguarding river water quality and public health

    Science.gov (United States)

    Podimata, M. V.; Bekri, E. S.; Yannopoulos, P. C.

    2012-04-01

    Alfeios River Basin (ARB) constitutes one of the major hydrologic basins (≈3650km2) of Peloponnisos peninsula in Southern Greece. It is drained by Alfeios River and its tributaries, such as Lousios, Ladhon, Erymanthos, Kladheos, Selinous etc. The present manuscript takes a closer look at the importance of tributary basins and focuses on Erymanthos sub-basin that covers about 360 km2. Erymanthos River springs from Erymanthos Mountain that reaches altitudes of 2200 m and discharges 10 m3/sec, approximately, during the winter period, presenting a sound decrease from half to about an order of magnitude during summertime. Two factors stand out as reasons to select Erymanthos sub-basin as a case study. First, the sub-basin presents a significant variety of ecosystems and comprises a very important river system, since Erymanthos Tributary satisfies, among other uses, drinking water supply for a great majority of citizens in the region. Second, authors' experience of the study area in Research Program Pythagoras II, funded by the European Social Fund (ESF) and the Operational Program for Educational and Vocational Training II (EPEAEK II) of Greece, offers a basis for better understanding of the real problems in the area. Erymanthos watershed, in fact, faces a lot of pressures, in several levels, provoked by human activities and Erymanthos Tributary is vulnerable to pollution. Recognizing the importance of clean water for healthy people, a developing economy, and a sustainable environment, the challenge of the present paper is elaborating human-induced pressures in the study area, analyzing their effects, estimating pollution factors and proposing integrated solutions/tools and a number of methodologies/initiatives used to overcome the problem of contaminating water supply in a catchment that lacks of wastewater treatment and disposal systems. The preservation of a good ecological status in Erymanthos River is not only a necessity for achieving the goals of EU Water

  9. The Effect of Crystallizing and Non-crystallizing Cosolutes on Succinate Buffer Crystallization and the Consequent pH Shift in Frozen Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Sundaramurthi, Prakash; Suryanarayanan, Raj (UMM)

    2011-09-06

    To effectively inhibit succinate buffer crystallization and the consequent pH changes in frozen solutions. Using differential scanning calorimetry (DSC) and X-ray diffractometry (XRD), the crystallization behavior of succinate buffer in the presence of either (i) a crystallizing (glycine, mannitol, trehalose) or (ii) a non-crystallizing cosolute (sucrose) was evaluated. Aqueous succinate buffer solutions, 50 or 200 mM, at pH values 4.0 or 6.0 were cooled from room temperature to -25 C at 0.5 C/min. The pH of the solution was measured as a function of temperature using a probe designed to function at low temperatures. The final lyophiles prepared from these solutions were characterized using synchrotron radiation. When the succinic acid solution buffered to pH 4.0, in the absence of a cosolute, was cooled, there was a pronounced shift in the freeze-concentrate pH. Glycine and mannitol, which have a tendency to crystallize in frozen solutions, remained amorphous when the initial pH was 6.0. Under this condition, they also inhibited buffer crystallization and prevented pH change. At pH 4.0 (50 mM initial concentration), glycine and mannitol crystallized and did not prevent pH change in frozen solutions. While sucrose, a non-crystallizing cosolute, did not completely prevent buffer crystallization, the extent of crystallization was reduced. Sucrose decomposition, based on XRD peaks attributable to {beta}-D-glucose, was observed in frozen buffer solutions with an initial pH of 4.0. Trehalose completely inhibited crystallization of the buffer components when the initial pH was 6.0 but not at pH 4.0. At the lower pH, the crystallization of both trehalose dihydrate and buffer components was evident. When retained amorphous, sucrose and trehalose effectively inhibited succinate buffer component crystallization and the consequent pH shift. However, when trehalose crystallized or sucrose degraded to yield a crystalline decomposition product, crystallization of buffer was

  10. Simple solution-processed CuO{sub X} as anode buffer layer for efficient organic solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Wenfei [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Songling Road, Qingdao 266101 (China); Institute of Hybrid Materials, The Growing Base for State Key Laboratory, Qingdao University, 308 Ningxia Road, Qingdao 266071 (China); Yang, Chunpeng [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Songling Road, Qingdao 266101 (China); Bao, Xichang, E-mail: baoxc@qibebt.ac.cn [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Songling Road, Qingdao 266101 (China); Sun, Liang; Wang, Ning [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Songling Road, Qingdao 266101 (China); Tang, Jianguo [Institute of Hybrid Materials, The Growing Base for State Key Laboratory, Qingdao University, 308 Ningxia Road, Qingdao 266071 (China); Chen, Weichao [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Songling Road, Qingdao 266101 (China); Yang, Renqiang, E-mail: yangrq@qibebt.ac.cn [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Songling Road, Qingdao 266101 (China)

    2015-10-15

    Graphical abstract: - Highlights: • Simple solution-processed CuO{sub X} hole transport layer for efficient organic solar cell. • Good photovoltaic performances as hole transport layer in OSCs with P3HT and PBDTTT-C as donor materials. • The device with CuO{sub X} as hole transport layer shows great improved stability compared with that of device with PEDOT:PSS as hole transport layer. - Abstract: A simple, solution-processed ultrathin CuO{sub X} anode buffer layer was fabricated for high performance organic solar cells (OSCs). XPS measurement demonstrated that the CuO{sub X} was the composite of CuO and Cu{sub 2}O. The CuO{sub X} modified ITO glass exhibit a better surface contact with the active layer. The photovoltaic performance of the devices with CuO{sub X} layer was optimized by varying the thickness of CuO{sub X} films through changing solution concentration. With P3HT:PC{sub 61}BM as the active layer, we demonstrated an enhanced PCE of 4.14% with CuO{sub X} anode buffer layer, compared with that of PEDOT:PSS layer. The CuO{sub X} layer also exhibits efficient photovoltaic performance in devices with PBDTTT-C:PC{sub 71}BM as the active layer. The long-term stability of CuO{sub X} device is better than that of PEDOT:PSS device. The results indicate that the easy solution-processed CuO{sub X} film can act as an efficient anode buffer layer for high-efficiency OSCs.

  11. Sorption and desorption of arsenate and arsenite on calcite

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt; Postma, Diederik Jan; Jakobsen, Rasmus;

    2008-01-01

    The adsorption and desorption of arsenate (As(V)) and arsenite (As(111)) oil calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic concentrat......The adsorption and desorption of arsenate (As(V)) and arsenite (As(111)) oil calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic...

  12. In situ measurement of reaction volume and calculation of pH of weak acid buffer solutions under high pressure.

    Science.gov (United States)

    Min, Stephen K; Samaranayake, Chaminda P; Sastry, Sudhir K

    2011-05-26

    Direct measurements of reaction volume, so far, have been limited to atmospheric pressure. This study describes a method for in situ reaction volume measurements under pressure using a variable volume piezometer. Reaction volumes for protonic ionization of weak acid buffering agents (MES, citric acid, sulfanilic acid, and phosphoric acid) were measured in situ under pressure up to 400 MPa at 25 °C. The methodology involved initial separation of buffering agents within the piezometer using gelatin capsules. Under pressure, the volume of the reactants was measured at 25 °C, and the contents were heated to 40 °C to dissolve the gelatin and allow the reaction to occur, and cooled to 25 °C, where the volume of products was measured. Reaction volumes were used to calculate pH of the buffer solutions as a function of pressure. The results show that the measured reaction volumes as well as the calculated pH values generally quite agree with their respective theoretically predicted values up to 100 MPa. The results of this study highlight the need for a comprehensive theory to describe the pressure behavior of ionization reactions in realistic systems especially at higher pressures. PMID:21542618

  13. Size Control of (99m)Tc-tin Colloid Using PVP and Buffer Solution for Sentinel Lymph Node Detection.

    Science.gov (United States)

    Kim, Eun-Mi; Lim, Seok Tae; Sohn, Myung-Hee; Jeong, Hwan-Jeong

    2015-06-01

    Colloidal particle size is an important characteristic that allows mapping sentinel nodes in lymphoscintigraphy. This investigation aimed to introduce different ways of making a (99m)Tc-tin colloid with a size of tens of nanometers. All agents, tin fluoride, sodium fluoride, poloxamer-188, and polyvinylpyrrolidone (PVP), were mixed and labeled with (99m)Tc. Either phosphate or sodium bicarbonate buffers were used to adjust the pH levels. When the buffers were added, the size of the colloids increased. However, as the PVP continued to increase, the size of the colloids was controlled to within tens of nanometers. In all samples, phosphate buffer added PVP (30 mg) stabilized tin colloid ((99m)Tc-PPTC-30) and sodium bicarbonate solution added PVP (50 mg) stabilized tin colloid ((99m)Tc-BPTC-50) were chosen for in vitro and in vivo studies. (99m)Tc-BPTC-50 (PPTC-30 (>100 nm) mainly accumulated in the liver. When a rabbit was given a toe injection, the node uptake of (99m)Tc-PPTC-30 decreased over time, while (99m)Tc-BPTC-50 increased. Therefore, (99m)Tc-BPTC-50 could be a good candidate radiopharmaceutical for sentinel node detection. The significance of this study is that nano-sized tin colloid can be made very easily and quickly by PVP. PMID:26028937

  14. High surface area calcite

    Science.gov (United States)

    Schultz, L. N.; Andersson, M. P.; Dalby, K. N.; Müter, D.; Okhrimenko, D. V.; Fordsmand, H.; Stipp, S. L. S.

    2013-05-01

    Calcite (CaCO3) is important in many fields—in nature, because it is a component of aquifers, oil reservoirs and prospective CO2 storage sites, and in industry, where it is used in products as diverse as paper, toothpaste, paint, plastic and aspirin. It is difficult to obtain high purity calcite with a high surface area but such material is necessary for industrial applications and for fundamental calcite research. Commercial powder is nearly always contaminated with growth inhibitors such as sugars, citrate or pectin and most laboratory synthesis methods deliver large precipitates, often containing vaterite or aragonite. To address this problem, we (i) adapted the method of carbonating a Ca(OH)2 slurry with CO2 gas to develop the first simple, cheap, safe and reproducible procedure using common laboratory equipment, to obtain calcite that reproducibly had a surface area of 14-17 m2/g and (ii) conducted a thorough characterization of the product. Scanning electron microscopy (SEM) revealed nanometer scale, rhombohedral crystals. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR) confirmed highly crystalline, pure calcite that more closely resembles the dimensions of the biogenic calcite produced by algae in coccoliths than other methods for synthesizing calcite. We suggest that this calcite is useful when purity and high surface area are important.

  15. Physicochemistry of hexadecylammonium bromide and its methyl and ethanolic head group analogues in buffered aqueous and gelatin solution

    Indian Academy of Sciences (India)

    Debolina Mitra; Satya P Moul

    2010-05-01

    In this work, the interfacial and bulk behaviour of the amphiphiles hexadecylammonium bromide and its methyl and ethanolic head group analogues in buffered aqueous and gelatin solution has been examined. The analogues are of two categories: the methyl and the combined methyl and ethanolic head group representatives are considered as Group A compounds, and all non-methyl but ethanolic head group species are taken as Group B compounds. Different physical techniques have been employed to ascertain the amphiphilic behaviour in solution. The self-aggregation of these surfactants at different pH has been studied along with pH dependent interfacial activity of gelatin. The interaction of the two categories of the surfactants with gelatin at different pH has been investigated. A scheme for this interaction at various stages of the process has been proposed. The influence of the surfactant head groups on the interaction process has been assessed.

  16. In situ ellipsometric investigation of stainless steel corrosion behavior in buffered solutions with amino acids

    Science.gov (United States)

    Vinnichenko, M. V.; Pham, M. T.; Chevolleau, T.; Poperenko, L. V.; Maitz, M. F.

    2003-02-01

    The corrosion of metals is associated both with a release of ions and changes in optical surface properties. In this study, these two effects were correlated by a potentiodynamic corrosion test and in situ probing of the surface by ellipsometry. The studies were carried out with stainless steel (SS) AISI 304 and 316 in phosphate buffered saline (PBS) and in Dulbecco's modified minimal essential medium (DMEM) at pH 7.4. In both media, 304 steel is more susceptible to corrosion than 316 grade. The 316 steel shows a higher corrosion potential and higher corrosion current density in PBS than in DMEM, for 304 steel this behavior is vice versa. Ellipsometry demonstrated a higher sensitivity than potentiodynamics to surface modification in the cathodic area. In DMEM the removal of a surface layer at negative potential and a further repassivation with increasing potential was characteristic. In PBS a surface layer started to grow immediately. X-ray photoelectron spectra of this layer formed in PBS are consistent with iron phosphate. Its formation is inhibited in DMEM; the presence of amino acids is discussed as the reason.

  17. Seed layer, solution concentration and thickness effects on CSD-derived La2Zr2O7 buffer layers for coated conductors

    International Nuclear Information System (INIS)

    La2Zr2O7/NiW buffer layers as very promising buffer layers for coated conductors were fabricated by chemical solution deposition using cheap precursors, La-acetate and Zr-(IV) n-propoxide (70% w/w in n-propanol). The effects on the orientation and microstructure of La2Zr2O7 buffer layers, including seed layer, thickness and solution concentration, were investigated. The results showed that insertion of a seed layer could obviously improve the crystallization and orientation, and decrease of single layer thickness could also obviously improve the in-plane orientation. The results of all metalorganic depositions derived YBCO/CeO2/La2Zr2O7/NiW showed that the prepared La2Zr2O7 buffer layers were suitable for coated conductors using all metalorganic depositions

  18. An evaluation of MES (2(N-Morpholino)ethanesulfonic acid) and Amberlite IRC-50 as pH buffers for nutrient solution studies

    Science.gov (United States)

    Bugbee, B. G.; Salisbury, F. B.

    1985-01-01

    All buffering agents used to stabilize pH in hydroponic research have disadvantages. Inorganic buffers are absorbed and may become phytotoxic. Solid carbonate salts temporarily mitigate decreasing pH but provide almost no protection against increasing pH, and they alter nutrient absorption. Exchange resins are more effective, but we find that they remove magnesium and manganese from solution. We have tested 2(N-Morpholino)ethanesulfonic acid (MES) as a buffering agent at concentrations of 1 and 10 mol m-3 (1 and 10 mM) with beans, corn, lettuce, tomatoes, and wheat. MES appears to be biologically inert and does not interact significantly with other solution ions. Relative growth rates among controls and MES treatments were nearly identical for each species during the trial period. The pH was stabilized by 1 mol m-3 MES. This buffer warrants further consideration in nutrient research.

  19. Aqueous Chemical Solution Deposition of Novel, Thick and Dense Lattice-Matched Single Buffer Layers Suitable for YBCO Coated Conductors: Preparation and Characterization

    Directory of Open Access Journals (Sweden)

    Isabel van Driessche

    2012-09-01

    Full Text Available In this work we present the preparation and characterization of cerium doped lanthanum zirconate (LCZO films and non-stoichiometric lanthanum zirconate (LZO buffer layers on metallic Ni-5% W substrates using chemical solution deposition (CSD, starting from aqueous precursor solutions. La2Zr2O7 films doped with varying percentages of Ce at constant La concentration (La0.5CexZr1−xOy were prepared as well as non-stoichiometric La0.5+xZr0.5−xOy buffer layers with different percentages of La and Zr ratios. The variation in the composition of these thin films enables the creation of novel buffer layers with tailored lattice parameters. This leads to different lattice mismatches with the YBa2Cu3O7−x (YBCO superconducting layer on top and with the buffer layers or substrate underneath. This possibility of minimized lattice mismatch should allow the use of one single buffer layer instead of the current complicated buffer architectures such as Ni-(5% W/LZO/LZO/CeO2. Here, single, crack-free LCZO and non-stoichiometric LZO layers with thicknesses of up to 140 nm could be obtained in one single CSD step. The crystallinity and microstructure of these layers were studied by XRD, and SEM and the effective buffer layer action was studied using XPS depth profiling.

  20. The buffering-out effect and phase separation in aqueous solutions of EPPS buffer with 1-propanol, 2-propanol, or 2-methyl-2-propanol at T = 298.15 K

    International Nuclear Information System (INIS)

    Highlights: ► Buffering-out is a new liquid–liquid phase separation containing biological buffer. ► EPPS buffer-induced phase separation of aqueous solutions of aliphatic alcohols. ► Phase diagrams of EPPS + water + 1-propanol/2-propanol/2-methyl-2-propanol are studied. ► EPPS breaks the 1-propanol + water and 2-methyl-2-propanol + water azeotropes. ► The (liquid + liquid) equilibria can be well correlated by the NRTL model. - Abstract: Buffering-out is a new liquid–liquid phase separation phenomenon observed in mixtures containing a buffer as a mass separating agent. The (liquid + liquid) equilibrium (LLE) and (solid + liquid + liquid) equilibrium (SLLE) data were measured for the ternary systems {3-[4-(2-hydroxyethyl)piperazin-1-yl]propanesulfonic acid (EPPS) buffer + 1-propanol, 2-propanol, or 2-methyl-2-propanol + water} at T = 298.15 K under atmospheric pressure. The phase boundary data were fitted to an empirical equation relating to the concentrations of organic solvent and buffer. The effective excluded volume (EEV) values of EPPS were obtained from the phase boundary data. The phase-separation abilities of the investigated aliphatic alcohols were discussed. The reliability of the experimental tie-lines was satisfactorily confirmed by the Othmer–Tobias correlation. The experimental tie-lines data for the ternary systems have been correlated using the NRTL activity coefficient model. The separation of these aliphatic alcohols from their azeotropic aqueous mixtures is of particular interest to industrial process. The addition of the EPPS as an auxiliary agent breaks the (1-propanol + water) and (2-methyl-2-propanol + water) azeotropes. The possibility of using the new phase separation systems in the extraction process is demonstrated by using different dyestuffs.

  1. Strontium Titanate Buffer Layers on Cu/33%Ni Substrates using a Novel Solution Chemistry

    DEFF Research Database (Denmark)

    Pallewatta, Pallewatta G A P; Yue, Zhao; Hui, Tian;

    2013-01-01

    textured Cu/33%Ni substrates using dip-coating in a precursor solution followed by drying and annealing under controlled oxygen partial pressures. The control of the ambient atmosphere during annealing is an important experimental issue in order to achieve thin films with high quality surface texture. We...

  2. Solution processing towards titania buffer layers for dye sensitized solar cells: Electrochemical chatacterization

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav

    Lille: EMRS, 2014. I.17.5. [EMRS. 2014 Spring Meeting. Symposium I. Solution processing and properties of functional oxide thin films and nanoctructures. 26.05.2014-30.05.2014, Lille] R&D Projects: GA ČR GA13-07724S Institutional support: RVO:61388955 Keywords : electrochemistry * TiO2 * dye-sensitized solar cell Subject RIV: CG - Electrochemistry

  3. Effect of Phosphate-Buffered Solution Corrosion on the Ratcheting Fatigue Behavior of a Duplex Mg-Li-Al Alloy

    Science.gov (United States)

    Yuan, Xin; Yu, Dunji; Gao, Li-Lan; Gao, Hong

    2016-05-01

    This work reports the uniaxial ratcheting and fatigue behavior of a duplex Mg-Li-Al alloy under the influence of phosphate-buffered solution corrosion. Microstructural observations reveal pitting and filament corrosion defects, which impair the load-bearing capacity of the alloy and cause stress concentration, thus leading to an accelerated accumulation of ratcheting strain and shortened fatigue life under the same nominal loading conditions. Comparing Smith model, Smith-Watson-Topper model, and Paul-Sivaprasad-Dhar model, a ratcheting fatigue life prediction model based on the Broberg damage rule and the Paul-Sivaprasad-Dhar model was proposed, and the model yielded a superior prediction for the studied magnesium alloy.

  4. Surface characterization of simulated low-level radioactive waste glasses corroded in water and LiOH buffer solution

    International Nuclear Information System (INIS)

    Chemical durability of simulated radioactive low-level waste (LLW) baseline glass, 6-5412, was found to decrease with the addition of either phosphate or sulfate, or chromium oxide. Scanning electron microscopic study of corroded samples suggests that the effect of these components on glass chemical durability may be attributed to cluster formation of: Na-O-P-O or Na-O-S-O, or (O0)3-Cr3+-(O-)3 groups. Preferential corrosion attack was severe on certain corroded sample surface areas that are possibly enriched in these clusters. Durability tests in a solution with LiOH as a buffer suggest that chlorine in the glass slightly improved glass corrosion resistance, while fluorine significantly deteriorated glass corrosion resistance

  5. Effect of Phosphate-Buffered Solution Corrosion on the Ratcheting Fatigue Behavior of a Duplex Mg-Li-Al Alloy

    Science.gov (United States)

    Yuan, Xin; Yu, Dunji; Gao, Li-Lan; Gao, Hong

    2016-04-01

    This work reports the uniaxial ratcheting and fatigue behavior of a duplex Mg-Li-Al alloy under the influence of phosphate-buffered solution corrosion. Microstructural observations reveal pitting and filament corrosion defects, which impair the load-bearing capacity of the alloy and cause stress concentration, thus leading to an accelerated accumulation of ratcheting strain and shortened fatigue life under the same nominal loading conditions. Comparing Smith model, Smith-Watson-Topper model, and Paul-Sivaprasad-Dhar model, a ratcheting fatigue life prediction model based on the Broberg damage rule and the Paul-Sivaprasad-Dhar model was proposed, and the model yielded a superior prediction for the studied magnesium alloy.

  6. A simple ratiometric and colorimetric chemosensor for the selective detection of fluoride in DMSO buffered solution

    Science.gov (United States)

    Niu, Hu; Shu, Qinghai; Jin, Shaohua; Li, Bingjun; Zhu, Jiaping; Li, Lijie; Chen, Shusen

    2016-01-01

    A derivative of squaramide (cyclobuta[b]quinoxaline-1, 2(3H, 8H)-dione) has been synthesized for the ratiometric and colorimetric sensing of F- in aqueous solution in competitive fashion. With F-, probe 1 showed a highly selective naked-eye detectable color change along with a characteristic UV-Vis absorbance over other tested ions, which probably originates from the deprotonation occurred between 1 and F-, as proved by the 1H NMR titration experiments and DFT calculations.

  7. Chemiluminescence flow biosensor for glucose using Mg-Al carbonate layered double hydroxides as catalysts and buffer solutions.

    Science.gov (United States)

    Wang, Zhihua; Liu, Fang; Lu, Chao

    2012-01-01

    In this work, serving as supports in immobilizing luminol reagent, catalysts of luminol chemiluminescence (CL), and buffer solutions for the CL reaction, Mg-Al-CO(3) layered double hydroxides (LDHs) were found to trigger luminol CL in weak acid solutions (pH 5.8). The silica sol-gel with glucose oxidase and horseradish peroxidase was immobilized in the first half of the inside surface of a clear quartz tube, and luminol-hybrid Mg-Al-CO(3) LDHs were packed in the second half. Therefore, a novel CL flow-through biosensor for glucose was constructed in weak acid solutions. The CL intensity was linear with glucose concentration in the range of 0.005-1.0mM, and the detection limit for glucose (S/N=3) was 0.1 μM. The proposed biosensor exhibited excellent stability, high reproducibility and high selectivity for the determination of glucose and has been successfully applied to determine glucose in human plasma samples with satisfactory results. The success of this work has broken the bottleneck of the pH incompatibility between luminol CL and enzyme activity. PMID:22770831

  8. Electron transfer across anodic films formed on tin in carbonate-bicarbonate buffer solution

    International Nuclear Information System (INIS)

    Impedance and steady-state data were recorded in order to study the kinetics of electron transfer between passive tin electrodes and an electrolytic solution containing the K3Fe(CN)6-K4Fe(CN)6 redox couple. Film thickness plays a key role in determining the type of electronic conduction of these oxide covered electrodes. Electron exchange with the oxide takes place with participation of the conduction band in the semiconducting film. A mechanism involving direct electron tunneling through the space charge barrier is the most suitable to interpret the experimental evidence

  9. Aqueous Chemical Solution Deposition of Novel, Thick and Dense Lattice-Matched Single Buffer Layers Suitable for YBCO Coated Conductors: Preparation and Characterization

    OpenAIRE

    Isabel Van Driessche; Petra Lommens; Sigelinde van Steenberge; Vyshnavi Narayanan

    2012-01-01

    In this work we present the preparation and characterization of cerium doped lanthanum zirconate (LCZO) films and non-stoichiometric lanthanum zirconate (LZO) buffer layers on metallic Ni-5% W substrates using chemical solution deposition (CSD), starting from aqueous precursor solutions. La2Zr2O7 films doped with varying percentages of Ce at constant La concentration (La0.5CexZr1−xOy) were prepared as well as non-stoichiometric La0.5+xZr0.5−xOy buffer layers with different percentages of La a...

  10. A Novel Solution for Discriminating Wormhole Attacks in MANETs from Congested Traffic using RTT and Transitory Buffer

    Directory of Open Access Journals (Sweden)

    Maria Sebastian

    2013-06-01

    Full Text Available Nowadays, the computing and communication services are accessed while on the move. Setting up of fixed access points and backbone infrastructure is not always viable. So in order to provide communication where there is lack of infrastructure or inconvenience in using the existing infrastructure, Mobile Adhoc Networks (MANETs are used. This inherent flexibility allows MANETs to be used for a wide range of applications such as rescue operations, military applications, vehicular communication, and business meetings. As there is no apriori trust relationship between the nodes of an ad hoc network and basic network functions like packet forwarding and routing are performed by the available nodes, security is an essential component in MANETs. Various attacks in MANETs are blackhole attack, byzantine attack, resource consumption attack, rushing attack, and wormhole attack. Wormhole attack is a severe threat among the other threats in MANET. Existing solutions to detect wormhole attacks include Packet Leashes, SECTOR, DelPHI, RTT-TC, TTM, etc. These solutions require special hardware or strict synchronized clocks or cause message overhead. Some solutions do not locate the wormhole, and some other may generate false alarms or does not consider network congestion into account. In this paper, wormhole attack detection is proposed based on RTT between successive nodes and congestion detection mechanism. If the RTT between two successive nodes is higher than the threshold value, a wormhole attack is suspected. If a wormhole is suspected, node's transitory buffer is probed to determine whether the long delay between the nodes is due to wormhole or not, as delays can be caused due to congestion or by queuing delays. The proposed method prevents both the hidden and the exposed attack. Advantage of our proposed solution is that it does not require any specialized hardware or synchronized clocks.

  11. Structural point defects in 'Iceland spar' calcite

    International Nuclear Information System (INIS)

    Trace element concentrations by micro-PIXE, cathodoluminescence (CL) emission spectra and electron spin resonance (ESR) spectra of Mn2+ in 'Iceland spar' calcite have been measured. The average rare earth elements (REE) abundances of the Iceland spar calcite revealed a concave shape with positive Eu and Tb anomalies. All samples show comparable average REE abundances compared to average chondrites standard. The REE signal in hydrothermal solution seems to be similar for the different locations and age of formation although the absolute REE concentration in the solution was certainly different. The CL-properties of investigated Iceland spar varied from orange to green. The orange luminescence is based on Mn2+ in Ca-position of calcite while this uncommon green luminescence is most likely attributed to UO22+ complex ions associated with electron-hole centres

  12. Preparation of DNA films for studies under vacuum conditions. The influence of cations in buffer solutions

    Science.gov (United States)

    Śmiałek, M. A.; Balog, R.; Jones, N. C.; Field, D.; Mason, N. J.

    2010-10-01

    Experiments were carried out to determine the optimum conditions required for the preparation of uniform films of supercoiled plasmid DNA to be used in irradiation experiments under high vacuum conditions. Investigations reveal that significant damage to the DNA molecules occurs due to the evacuation process when films were formed from DNA samples in ultra high purity water only. A variety of bases were tested for their possible protective capabilities and sodium hydroxide solution was found to be the most effective in maintaining the supercoiled structure of plasmid DNA during the preparation process. Using a transmission electron microscope we also examined the structure of the DNA films which are formed upon evacuation and how the proposed adducts influence the preparation process. It was found that the addition of bases cause the DNA to aggregate, noting that a base is required for the stability of the DNA molecules. The experimental results presented in this paper show that it may not be possible to perform experiments on so-called pure DNA under vacuum with no stabilizers being added to the sample before the evacuation process.

  13. Ink-jet printing of SrTiO3 buffer layers from aqueous solutions

    International Nuclear Information System (INIS)

    In this work, fully a-axis oriented SrTiO3 thin films were synthesized by ink-jet printing of water-based precursor inks. The developed precursor solution or ‘ink’ was optimized in terms of rheology, leading to the ejection of single droplets showing a maximum contact angle of 12° on (100) oriented single crystal LaAlO3 substrates. By using the appropriate ink-jet deposition parameters and thermal treatment, well-textured and dense SrTiO3 films of 130 nm thickness were obtained. The biaxial texture is maintained up to the surface of the films, leading to the formation of (h00)-oriented terraces. As shown by transmission electron microscopy, excellent texture transfer was achieved from the SrTiO3 film to the YBa2Cu3O7 − δ layer deposited by pulsed laser deposition. Outstanding superconducting properties were obtained with critical current densities up to 3.6 MA cm−2 in self-field at 77 K, demonstrating that these sustainable SrTiO3 films meet the requirements to be used as growing template for high quality superconducting coatings. (paper)

  14. Mechanistic aspects of the calcite precipitation reaction and supercritical fluid movements in calcite lattice: implication for mineral storage of CO2

    International Nuclear Information System (INIS)

    The geologic sequestration of CO2 seems to be one of the most relevant strategy for the long term reduction of the atmospheric releases of this greenhouse gas. Indeed, CO2 can be stored in geologic formations in different ways. The solution which appears as the most stable is to make react fluids rich in CO2 with rocks minerals (or organic matter) of the surrounding geological formations and to produce a new carbonated solid matrix. The kinetics implied in the mineralization of CO2 have been studied. In the first part of this work is described the mechanistic aspects of the precipitation reaction of the calcite by a kinetic approach allowing to precisely obtain the velocities and the kinetic constants of the reactions as well as the data on the reactional mechanisms in making the temperature range between 5 and 70 C, as well as the composition of the solution (sur-saturation degree and inhibitor presence: Mg2+ and SO42-). The results have shown that the temperature role is not limited to a simple catalyst effect but that the kinetic mechanisms changes, that the temperature induces, determine the Mg quantities which can be incorporated into the calcite. By extension to this study, a global empirical law describing the variation of the precipitation rate in terms of the carbonate concentration and of the different physico-chemical parameters influencing the reaction of the calcite formation (PCO2, salinity, temperature, inhibitors, organic matter) has been established. It is appeared that the temperature can make the precipitation rate increase but only in the conditions of important imbalance when PCO2 has an equal influence near and far from the equilibrium in solutions however completely buffered. In the second part, the study has dealt with the movements of supercritical fluids inside a calcitic solid matrix. It has been shown that CO2 supercritical bubbles trapped into fluid inclusions contained in a calcite polycrystalline matrix could circulate until the

  15. Acid neutralizing processes in an alpine watershed front range, Colorado, U.S.A.-1: Buffering capacity of dissolved organic carbon in soil solutions

    Science.gov (United States)

    Iggy, Litaor M.; Thurman, E.M.

    1988-01-01

    Soil interstitial waters in the Green Lakes Valley, Front Range, Colorado were studied to evaluate the capacity of the soil system to buffer acid deposition. In order to determine the contribution of humic substances to the buffering capacity of a given soil, dissolved organic carbon (DOC) and pH of the soil solutions were measured. The concentration of the organic anion, Ai-, derived from DOC at sample pH and the concentration of organic anion, Ax- at the equivalence point were calculated using carboxyl contents from isolated and purified humic material from soil solutions. Subtracting Ax- from Ai- yields the contribution of humic substances to the buffering capacity (Aequiv.-). Using this method, one can evaluate the relative contribution of inorganic and organic constituents to the acid neutralizing capacity (ANC) of the soil solutions. The relative contribution of organic acids to the overall ANC was found to be extremely important in the alpine wetland (52%) and the forest-tundra ecotone (40%), and somewhat less important in the alpine tundra sites (20%). A failure to recognize the importance of organic acids in soil solutions to the ANC will result in erroneous estimates of the buffering capacity in the alpine environment of the Front Range, Colorado. ?? 1988.

  16. Glassy carbon electrode modified by graphene–gold nanocomposite coating for detection of trace lead ions in acetate buffer solution

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Pui Mun [Interdisplinary Graduate School, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Environmental Chemistry and Materials Group (ECMG), Nanyang Environment and Water Research Institute (NEWRI), Nanyang Technological University, 1 Cleantech Loop, Singapore 637141 (Singapore); School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Wang, Zhaomeng [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Liu, Xiaoxu [Heilongjiang University of Science and Technology, Harbin 150027 (China); Chen, Zhong [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Liu, Erjia, E-mail: MEJLiu@ntu.edu.sg [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)

    2015-06-01

    Reduced graphene oxide (RGO) decorated with gold nanoparticles (AuNPs) was electrodeposited on glassy carbon electrode (GCE) using cyclic voltammetric method. The results of Raman spectroscopy confirmed the simultaneous formation of AuNPs and reduction of graphene oxide through the electrodeposition process. Scanning electron microscopic measurements showed a uniform distribution of the AuNPs on the RGO sheets. The RGO-AuNP nanocomposite coated GCE (G–Au/GCE) was used to detect lead ions (Pb{sup 2+}) contained in a 0.1 M acetate buffer solution (pH 5.3) using square wave anodic stripping voltammetry (SWASV). The G–Au/GCE demonstrated higher detection sensitivity and stronger SWASV signals than the bare GCE, with the limit of detection of about 0.8 nM. - Highlights: • Graphene with gold nanoparticles was electrodeposited on glassy carbon electrode. • The prepared electrode was able to detect trace lead ions at nM concentration. • Interference study against copper confirmed the selectivity of the electrode for lead. • The prepared electrode showed a promising recovery tested in tap water samples.

  17. Glassy carbon electrode modified by graphene–gold nanocomposite coating for detection of trace lead ions in acetate buffer solution

    International Nuclear Information System (INIS)

    Reduced graphene oxide (RGO) decorated with gold nanoparticles (AuNPs) was electrodeposited on glassy carbon electrode (GCE) using cyclic voltammetric method. The results of Raman spectroscopy confirmed the simultaneous formation of AuNPs and reduction of graphene oxide through the electrodeposition process. Scanning electron microscopic measurements showed a uniform distribution of the AuNPs on the RGO sheets. The RGO-AuNP nanocomposite coated GCE (G–Au/GCE) was used to detect lead ions (Pb2+) contained in a 0.1 M acetate buffer solution (pH 5.3) using square wave anodic stripping voltammetry (SWASV). The G–Au/GCE demonstrated higher detection sensitivity and stronger SWASV signals than the bare GCE, with the limit of detection of about 0.8 nM. - Highlights: • Graphene with gold nanoparticles was electrodeposited on glassy carbon electrode. • The prepared electrode was able to detect trace lead ions at nM concentration. • Interference study against copper confirmed the selectivity of the electrode for lead. • The prepared electrode showed a promising recovery tested in tap water samples

  18. Repassivation behavior of 316L stainless steel in borate buffer solution: Kinetics analysis of anodic dissolution and film formation

    Science.gov (United States)

    Xu, Haisong; Sun, Dongbai; Yu, Hongying

    2015-12-01

    The repassivation behavior of metals or alloys after oxide film damage determines the development of local corrosion and corrosion resistance. In this work, the repassivation kinetics of 316L stainless steel (316L SS) are investigated in borate buffer solution (pH 9.1) by using the abrading electrode technique. The current densities flowing from bare 316L SS surface are measured by potentiostatic method and analyzed to characterize repassivation kinetics. The initial stages of current decay (t Avrami kinetics. Then the two independent components are analyzed individually. The film formation rate and the thickness of film are compared in different applied potential. It is shown that anodic dissolution dominates the repassivation for a short time during the early times, and a higher applied potential will promote the anodic dissolution of metal. The film growth rate increases slightly with increasing in potential. Correspondingly, increase in applied potential from 0 VSCE to 0.8 VSCE results in thicker monolayer, which covers the whole bare surface at the time of θ = 1. The electric field strengths through the thin passive film could reach 3.97 × 106 V cm-1.

  19. Corrosion Behavior of Ultra-fine Grained 1050 Aluminum Alloy Fabricated by ARB Process in a Buffer Borate Solution

    Science.gov (United States)

    Fattah-alhosseini, A.; Gashti, S. O.

    2015-09-01

    Accumulative roll bonding (ARB) has been used as a severe plastic deformation process for the industrial production of ultra-fine grained (UFG) and nano-crystalline sheets with excellent mechanical properties. In the present study, the effect of the ARB process on the corrosion behavior of UFG and nano-crystalline 1050 aluminum alloy in a buffer borate solution (pH 5.5) has been investigated. The result of microhardness tests revealed that microhardness values increase with an increasing number of ARB cycles. A sharp increase in microhardness is seen after three ARB cycles, whereas moderate additional increases are observed afterward for up to nine cycles. Also, the XRD results showed that the mean crystallite size decreased to about 91 nm after nine cycles. The potentiodynamic plots show that as a result of ARB, the corrosion behavior of the UFG and nano-crystalline specimens improves, compared to the annealed 1050 aluminum alloy. Moreover, electrochemical impedance spectroscopy measurements showed that the polarization resistance increases with an increasing number of ARB cycles.

  20. Do organic ligands affect calcite dissolution rates?

    Science.gov (United States)

    Oelkers, Eric H.; Golubev, Sergey V.; Pokrovsky, Oleg S.; Bénézeth, Pascale

    2011-04-01

    Steady state Iceland-spar calcite dissolution rates were measured at 25 °C in aqueous solutions containing 0.1 M NaCl and up to 0.05 M dissolved bicarbonate at pH from 7.9 to 9.1 in the presence of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those most likely to be present in either (1) aquifers at the conditions pertinent to CO 2 sequestration or (2) soil/early diagenetic environments: acetate, phthalate, citrate, EDTA 4-, succinate, D-glucosaminate, L-glutamate, D-gluconate, 2,4-dihydroxybenzoate, 3,4-dihydroxybenzoate, fumarate, malonate, and gallate. Results show that the presence of extract, humic acid, pectin, and gum xanthan. In no case did the presence of <100 ppm of these organics change calcite dissolution rates by more than a factor of 2.5. Results obtained in this study suggest that the presence of aqueous organic anions negligibly affects calcite forward dissolution rates in most natural environments. Some effect on calcite reactivity may be observed, however, by the presence of organic anions if they change substantially the chemical affinity of the fluid with respect to calcite.

  1. Calcite solubility in simulated geothermal brines

    Energy Technology Data Exchange (ETDEWEB)

    Pool, K.H.; Raney, P.J.; Shannon, D.W.

    1987-02-01

    The deposition of scale on geothermal piping surfaces has been recognized as a cause of increased pressure drop and diminished fluid flow. The two most common scales encountered in the geothermal energy field are silica and calcite. The main purpose of this study was to obtain accurate, reliable calcite solubility data in brines similar to natural geothermal brines over the temperature range of most known exploitable geothermal resources. In addition, geothermal fluid equilibrium modeling efforts and data bases can be refined and fine-turned with respect to the commercially important calcite-geothermal fluid stability problem with these data. The effect of sodium chloride and sodium bicarbonate on the solubility of CaCO/sub 3/ (calcite) in high temperature solutions was measured over the 100 to 300/sup 0/C temperature range. The brines studied contained 0 to 5 wt % NaCl, 0 to 5 mM NaHCO/sub 3/, and 0.003 to 0.1 M CO/sub 2/. The data detailing calcite solubility at various temperatures are presented in tabular, graphical, and regression-equation form for each brine composition tested.

  2. Size Control of 99mTc-tin Colloid Using PVP and Buffer Solution for Sentinel Lymph Node Detection

    OpenAIRE

    Kim, Eun-Mi; Lim, Seok Tae; Sohn, Myung-Hee; Jeong, Hwan-Jeong

    2015-01-01

    Colloidal particle size is an important characteristic that allows mapping sentinel nodes in lymphoscintigraphy. This investigation aimed to introduce different ways of making a 99mTc-tin colloid with a size of tens of nanometers. All agents, tin fluoride, sodium fluoride, poloxamer-188, and polyvinylpyrrolidone (PVP), were mixed and labeled with 99mTc. Either phosphate or sodium bicarbonate buffers were used to adjust the pH levels. When the buffers were added, the size of the colloids incre...

  3. Buffer solutes as stabilizers of 35S-amino acids: A study of volatility, radiochemical purity and biological activity

    International Nuclear Information System (INIS)

    It is well established that volatile radioactive compounds are associated with preparations of 35S-amino acids, but misconceptions still exist. The addition of stabilizers to these preparations has created a false sense of security regarding the evolution of these volatiles from cell culture medium. Experiments presented here show that the commercially used buffers L-lysine, tricine and 3,4-pyridine-dicarboxylic acid all reduced, but did not eliminate, the evolution of 35S volatiles from tissue culture medium. In each case, the rate of release was approximately 12 nCi/mCi/day (or 0.001%), compared to approximately 44 nCi/mCi/day in the buffer's absence. None of six alternative buffers tested are more effective than the commercially used buffers. We found that the release of labeled volatiles is dependent on the nature of the culture medium, but is no greater from crude 35S-amino acid preparations than from purified 35S-methionine. These commercially used buffers are also effective in maintaining radiochemical purity and are compatible with biological activity; however, because these buffers do not entirely eliminate the release of radioactivity into the gas phase, routine safe-handling procedures should be practiced when working with these products

  4. Carbon isotope fractionation in synthetic magnesian calcite

    Science.gov (United States)

    Jimenez-Lopez, Concepción; Romanek, Christopher S.; Caballero, Emilia

    2006-03-01

    Mg-calcite was precipitated at 25 °C in closed system, free-drift experiments, from solutions containing NaHCO 3, CaCl 2 and MgCl 2. The carbon stable isotope composition of bulk solid and solution were analyzed from subsamples collected during time course experiments of 24 h duration. Considering only the Mg-content and δ 13C values for the bulk solid, the carbon isotope fractionation factor for the Mg-calcite-HCO 3(aq)- system (as 103lnα) increased with average mol percentage of Mg (X Mg) in the solid at a rate of (0.024 ± 0.011) per mol% MgCO 3. Extrapolation of this relationship to the pure calcite end member yields a value of 0.82 ± 0.09, which is similar to published values for the calcite-HCO 3(aq)- system. Although 103lnα did not vary for precipitation rates that ranged from 10 3.21 to 10 4.60 μmol m -2 h -1, it was not possible to hold Mg-content of the solid constant, so kinetic effect on 10 3 ln α could not be evaluated from these experiments.

  5. Effects of EDTA on the electronic properties of passive film formed on Fe-20Cr in pH 8.5 buffer solution

    International Nuclear Information System (INIS)

    The electronic properties of the passive film formed on Fe-20Cr ferritic stainless steel in pH 8.5 buffer solution containing 0.05 M EDTA (ethylene diammine tetraacetic acid) were examined by the photocurrent measurements and Mott-Schottky analysis for the film. XPS depth profile for the film demonstrated that Cr content in the outermost layer of the passive film was higher in the solution with EDTA than that in the solution without EDTA, due to selective dissolution of Fe by EDTA. In the solution with EDTA, the passive film showed characteristics of an amorphous or highly disordered n-type semiconductor. The band gap energies of the passive film are estimated to be ∼ 3.0 eV, irrespective of film formation potential from 0 to 700 mVSCE and of presence of EDTA. However, the donor density of the passive film formed in the solution with EDTA is much higher than that formed in the solution without EDTA, due to an increase in oxygen vacancy resulted from the dissolution of Fe-oxide in the outermost layer of the passive film. These results support the proposed model that the passive film formed on Fe-20Cr in pH 8.5 buffer solution mainly consists of Cr-substituted γ-Fe2O3

  6. Influences of Temperature and pH Value on the Corrosion Behaviors of X80 Pipeline Steel in Carbonate/Bicarbonate Buffer Solution

    Institute of Scientific and Technical Information of China (English)

    LI,Jin-Bo; ZUO,Jian-E

    2008-01-01

    The joint effect of temperature and pH value on the corrosion behavior of X80 steel in carbonate/bicarbonate buffer solution was detected by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Mott-Schottky analysis. The results show that an unstable corrosion film will be formed on the X80 steel surface in low pH value solutions, and a better protective corrosion film can be formed on the X80 steel surface in high pH value solutions. On the whole, the corrosion film resistance and transfer resistance increase with the increment of pH value, and decrease with increase of solution temperature, which indicates that the protective effect of the corrosion film on X80 steel is enhanced with increasing pH value and decreasing the solution temperature. The corrosion film formed on X80 steel surface in carbonate/bicarbonate buffer solution has an n-type semi-conductive character, and the donor density decreases with increasing the pH value, and increases with increasing the solution temperature. The flat-band potential and pH value have a linear relationship with a positive slope.

  7. Thermodynamic characteristics of molecular interactions between L-tryptophan and nicotinic acid and uracyl in aqueous buffer solutions at 298 K

    Science.gov (United States)

    Badelin, V. G.; Tyunina, E. Yu.; Mezhevoi, I. N.; Tarasova, G. N.

    2015-12-01

    The interaction between L-tryptophan (Trp) and nicotinic acid (NA) and uracyl (Ur) in aqueous buffer solutions (pH 7.35) at different ratios of reagents is studied via the calorimetry of dissolution. The enthalpies of dissolution of the amino acid in the buffer solutions of the ligands at 298.15 K are obtained. The stoichiometric compositions of the complexes being formed and binding constants have been determined. The values of the thermodynamic characteristics for the complex formation of L-tryptophan with nicotinic acid and uracyl are calculated. It is shown that the formation of molecular complexes with 1 : 2 composition is stabilized by the entropy factor for the Trp-NA system, and by the enthalpy factor for the Trp-Ur system.

  8. Natural dissolved organic matter mobilizes Cd but does not affect the Cd uptake by the green algae Pseudokirchneriella subcapitata (Korschikov) in resin buffered solutions

    Energy Technology Data Exchange (ETDEWEB)

    Verheyen, Liesbeth, E-mail: verheyenliesbeth@gmail.com; Versieren, Liske, E-mail: liske.versieren@ees.kuleuven.be; Smolders, Erik, E-mail: erik.smolders@ees.kuleuven.be

    2014-09-15

    Highlights: • Different DOM samples were added to solutions with a resin buffered Cd{sup 2+} activity. • This increased total dissolved Cd by factors 3–16 due to complexation reactions. • Cd uptake in algae was unaffected or increased maximally 1.6 fold upon addition. • Free Cd{sup 2+} is the main bioavailable form of Cd for algae in well buffered solutions. - Abstract: Natural dissolved organic matter (DOM) can have contrasting effects on metal bioaccumulation in algae because of complexation reactions that reduce free metal ion concentrations and because of DOM adsorption to algal surfaces which promote metal adsorption. This study was set up to reveal the role of different natural DOM samples on cadmium (Cd) uptake by the green algae Pseudokirchneriella subcapitata (Korschikov). Six different DOM samples were collected from natural freshwater systems and isolated by reverse osmosis. In addition, one {sup 13}C enriched DOM sample was isolated from soil to trace DOM adsorption to algae. Algae were exposed to standardized solutions with or without these DOM samples, each exposed at equal DOM concentrations and at equal non-toxic Cd{sup 2+} activity (∼4 nM) that was buffered with a resin. The DOM increased total dissolved Cd by factors 3–16 due to complexation reactions at equal Cd{sup 2+} activity. In contrast, the Cd uptake was unaffected by DOM or increased maximally 1.6 fold ({sup 13}C enriched DOM). The {sup 13}C analysis revealed that maximally 6% of algal C was derived from DOM and that this can explain the small increase in biomass Cd. It is concluded that free Cd{sup 2+} and not DOM-complexed Cd is the main bioavailable form of Cd when solution Cd{sup 2+} is well buffered.

  9. Natural dissolved organic matter mobilizes Cd but does not affect the Cd uptake by the green algae Pseudokirchneriella subcapitata (Korschikov) in resin buffered solutions

    International Nuclear Information System (INIS)

    Highlights: • Different DOM samples were added to solutions with a resin buffered Cd2+ activity. • This increased total dissolved Cd by factors 3–16 due to complexation reactions. • Cd uptake in algae was unaffected or increased maximally 1.6 fold upon addition. • Free Cd2+ is the main bioavailable form of Cd for algae in well buffered solutions. - Abstract: Natural dissolved organic matter (DOM) can have contrasting effects on metal bioaccumulation in algae because of complexation reactions that reduce free metal ion concentrations and because of DOM adsorption to algal surfaces which promote metal adsorption. This study was set up to reveal the role of different natural DOM samples on cadmium (Cd) uptake by the green algae Pseudokirchneriella subcapitata (Korschikov). Six different DOM samples were collected from natural freshwater systems and isolated by reverse osmosis. In addition, one 13C enriched DOM sample was isolated from soil to trace DOM adsorption to algae. Algae were exposed to standardized solutions with or without these DOM samples, each exposed at equal DOM concentrations and at equal non-toxic Cd2+ activity (∼4 nM) that was buffered with a resin. The DOM increased total dissolved Cd by factors 3–16 due to complexation reactions at equal Cd2+ activity. In contrast, the Cd uptake was unaffected by DOM or increased maximally 1.6 fold (13C enriched DOM). The 13C analysis revealed that maximally 6% of algal C was derived from DOM and that this can explain the small increase in biomass Cd. It is concluded that free Cd2+ and not DOM-complexed Cd is the main bioavailable form of Cd when solution Cd2+ is well buffered

  10. Growth of thick La2Zr2O7 buffer layers for coated conductors by polymer-assisted chemical solution deposition

    International Nuclear Information System (INIS)

    Highlights: • We develops a low-cost and high-efficient technology of fabricating LZO buffer layers. • Sufficient thickness LZO buffer layers have been obtained on NiW (2 0 0) alloy substrate. • Highly biaxially textured YBCO thin film has been deposited on LZO/NiW. - Abstract: La2Zr2O7 (LZO) epitaxial films have been deposited on LaAlO3 (LAO) (1 0 0) single-crystal surface and bi-axially textured NiW (2 0 0) alloy substrate by polymer-assisted chemical solution deposition, and afterwards studied with XRD, SEM and AFM approaches. Highly in-plane and out-of-plane oriented, dense, smooth, crack free and with a sufficient thickness (>240 nm) LZO buffer layers have been obtained on LAO (1 0 0) single-crystal surface; The films deposited on NiW (2 0 0) alloy substrate are also found with high degree in-plane and out-of-plane texturing, good density with pin-hole-free, micro-crack-free nature and a thickness of 300 nm. Highly epitaxial 500 nm thick YBa2Cu3O7−x (YBCO) thin film exhibits the self-field critical current density (Jc) reached 1.3 MA/cm2 at 77 K .These results demonstrate the LZO epi-films obtained with current techniques have potential to be a buffer layer for REBCO coated conductors

  11. Evaluation of Chromate as Dezincification Inhibitor for α-brass (Cu/Zn : 64/36) in 3% Chloride Buffer Solutions

    OpenAIRE

    H. H. Rehan; N.A. Al-Moubarak; H.A. Al-Rafai

    2003-01-01

    The inhibition behavior of chromate ions towards corrosion and dezincification of α-brass (Cu/Zn: 64/36) in acetate buffer solutions (pH 2.4, 7.0 and 8.5) containing 3% sodium chloride was studied. Weight loss and solution analysis were used for a long period (four weeks) and electrochemical polarization for a short period (one hour). Chromate accelerated corrosion and dezincification at pH 2.4 by acting as depolarizer but chromate suppressed efficiently the corrosion and dezincification...

  12. 盐酸盐溶液中温度对方解石和白云石溶解度的影响%Influence of temperature on dissolving degrees of calcite and dolomite in hydrochloride solution

    Institute of Scientific and Technical Information of China (English)

    梁冰; 陈楠; 姜利国

    2011-01-01

    为了更好的防止岩溶灾害的发生,研究了不同温度条件下盐酸盐溶液对石灰岩和白云岩侵蚀规律.应用美国地质调查所开发的水化学模拟软件Phreeqc对在不同CO2分压下,不同浓度的NaCl和MgCl2溶液中的方解石和白云石的溶解度和温度的关系进行了水化学模拟并进行了实验验证.研究结果显示,在NaC1溶液中,方解石和白云石溶解度均大于在纯水中的溶解度;方解石在MgCl2溶液中的溶解度大于在同条件下NaCl溶液中的溶解度;无CO2分压的情况下,在同浓度的盐溶液中,方解石和白云石的溶解度随着温度的升高迅速升高;在P∞2=10-4.5MPa时,方解石和白云石溶解度随着温度的升高而降低,然而始终大于在无CO2分压时的溶解度.在岩溶塌陷区,在与大气联系非常小的地下水系统中,温度的升高能够增强对岩体的侵蚀,从而使塌陷的危险增大;在与大气联系非常紧密的地下水系统中,温度降低(大于0℃)能够增强对岩体的侵蚀,从而使塌陷的危险增大.%In order to prevent karst disaster, the paper researched the influence of dissolving degrees of limestone and dolomite caused by temperature in hydrochloride solution. A water chemistry simulation software - phreeqc developed by American Geological Investigation Institute was used, the relation model between temperature and dissolving degrees of calcite and dolomite was simulated under different CO2 pressure and different concentration NaCl and MgCl2 solution,which was tested by experiment. The results indicated that dissolving degrees of calcite and dolomite in NaCl solution is larger than that in pure water; The dissolving degrees of calcite in MgCl2 solution is larger than that in NaCl solution under same condition; without CO2 pressure, in the same concentration salt solution, the dissolving degrees of limestone and dolomite increased rapidly with temperature; While pco2 = 10-4.5 Mpa the reverse

  13. Differences in the immobilization of arsenite and arsenate by calcite

    Science.gov (United States)

    Yokoyama, Yuka; Tanaka, Kazuya; Takahashi, Yoshio

    2012-08-01

    The sorption and coprecipitation experiments of arsenic (As) with calcite coupled with determinations of the chemical state of As both in the reaction fluid and in calcite were conducted to investigate the influence of the As oxidation state on its immobilization into calcite. The oxidation states of As in calcite and water were determined via As K-edge XANES and HPLC-ICP-MS analysis, respectively. The results of the sorption experiments at pH 8.2 show that only As(V) is distributed to calcite regardless of the As oxidation state in the solution. In coprecipitation experiments, As(V) is preferentially incorporated into calcite over a wide range of pH (7-12). On the other hand, the incorporation of As(III) into calcite is not observed at circumneutral pH. This difference between As(III) and As(V) is attributed to the fact that their dissolved species are neutral vs. negatively charged, respectively, at circumneutral pH (arsenite as H3AsO3; arsenate as H2AsO4- or HAsO42-). As the pH increases (>9), up to 33% of As(III)/Astotal ratio is partitioned into calcite or a precursor of calcite (metastable vaterite formed during the early stage of precipitation). The higher interaction of As with calcite at an alkaline pH compared with circumneutral pH is due to the negative charge of As(III) at alkaline pH. However, the As(III)/Astotal ratio decreases as time progresses and only As(V) can be found finally in calcite. The ratio of distribution coefficients of As(III) and As(V) into calcite (KAs(V)/KAs(III)) at pH ˜7 is larger than 2.1 × 103, suggesting that the oxidation state of As is a significant issue in considering the interaction between As and calcite in groundwater. Moreover, low KAs(III) shows that the sequestration of As via coprecipitation with calcite is not an important chemical process under reducing conditions, such as in the groundwaters in Bangladesh and other As-contaminated areas where As(III) is the dominant dissolved species of As. In the system spiked

  14. Activity of the Human Rhinovirus 3C Protease Studied in Various Buffers, Additives and Detergents Solutions for Recombinant Protein Production

    OpenAIRE

    Raheem Ullah; Majid Ali Shah; Soban Tufail; Fouzia Ismat; Muhammad Imran; Mazhar Iqbal; Osman Mirza; Moazur Rhaman

    2016-01-01

    Proteases are widely used to remove affinity and solubility tags from recombinant proteins to avoid potential interference of these tags with the structure and function of the fusion partner. In recent years, great interest has been seen in use of the human rhinovirus 3C protease owing to its stringent sequence specificity and enhanced activity. Like other proteases, activity of the human rhinovirus 3C protease can be affected in part by the buffer components and additives that are generally ...

  15. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

    Chapman, Piers; *Morse, John W. (*/deceased)

    2010-11-15

    1. Objective The general objective of this research was to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, carbon dioxide partial pressure (pCO2), and modest ranges of T and P. This would be done by studying both reaction rates and solubility from changes in solution chemistry. Also, nanoscale observations of calcite surface morphology and composition would be made to provide an understanding of rate controlling mechanisms.

  16. Optimization of the Energy Level Alignment between the Photoactive Layer and the Cathode Contact Utilizing Solution-Processed Hafnium Acetylacetonate as Buffer Layer for Efficient Polymer Solar Cells.

    Science.gov (United States)

    Yu, Lu; Li, Qiuxiang; Shi, Zhenzhen; Liu, Hao; Wang, Yaping; Wang, Fuzhi; Zhang, Bing; Dai, Songyuan; Lin, Jun; Tan, Zhan'ao

    2016-01-13

    The insertion of an appropriate interfacial buffer layer between the photoactive layer and the contact electrodes makes a great impact on the performance of polymer solar cells (PSCs). Ideal interfacial buffer layers could minimize the interfacial traps and the interfacial barriers caused by the incompatibility between the photoactive layer and the electrodes. In this work, we utilized solution-processed hafnium(IV) acetylacetonate (Hf(acac)4) as an effective cathode buffer layer (CBL) in PSCs to optimize the energy level alignment between the photoactive layer and the cathode contact, with the short-circuit current density (Jsc), open-circuit voltage (Voc), and fill factor (FF) all simultaneously improved with Hf(acac)4 CBL, leading to enhanced power conversion efficiencies (PCEs). Ultraviolet photoemission spectroscopy (UPS) and scanning Kelvin probe microscopy (SKPM) were performed to confirm that the interfacial dipoles were formed with the same orientation direction as the built-in potential between the photoactive layer and Hf(acac)4 CBL, benefiting the exciton separation and electron transport/extraction. In addition, the optical characteristics and surface morphology of the Hf(acac)4 CBL were also investigated. PMID:26684416

  17. Corrosion behavior of Mg-3Zn/bioglass (45S5) composite in simulated body fluid (SBF) and phosphate buffered saline (PBS) solution

    Science.gov (United States)

    Ab llah, N.; Jamaludin, S. B.; Daud, Z. C.; Zaludin, M. A. F.; Jamal, Z. A. Z.; Idris, M. S.; Osman, R. A. M.

    2016-07-01

    Magnesium has emerged as promising materials in biomaterials research due to its good mechanical and physical properties closer to human bones. However, magnesium has poor corrosion resistance to chloride ions that exist in human blood plasma thus preventing its application in biomedical. The addition of zinc and bioglass can reduce magnesium corrosion rate. In this work, the effect of different solution media (Simulated Body Fluid and Phosphate Buffered Saline) to the corrosion behavior of Mg-Zn/bioglass (45S5) composites was investigated. The composites of Mg-3Zn added with 5, 10, 15, 20, 15 and 30 wt. % bioglass were fabricated by powder metallurgy. The composites were prepared by mixing at 140 rpm for 1 hour, pressing at 500 MPa and sintering in an argon environment at a temperature of 450°C for 3 hours. Sintered samples were immersed in Simulated Body Fluid (SBF) and Phosphate Buffered Saline (PBS) in order to investigate the corrosion behavior. Samples mass loss was determined after 3 days of immersion. Samples microstructure and corrosion products were analyzed using optical microscope and x-ray diffraction (XRD) respectively. The results revealed that the samples immersed in the Phosphate Buffered Saline (PBS) shows lower mass loss compare to the samples immersed in the Simulated Body Fluid (SBF) for all composition except for Mg-3Zn without bio-glass. The results indicated that the existence of high phosphate ions in PBS has retarded the corrosion rate of composite Mg-3Zn/45S5. The pH value of the PBS solution after immersion showed significant increase between 10.3 and 11.09. Diffraction pattern (XRD) showed the presence of Mg(OH)2 as the major corrosion product for samples immersed in the SBF and PBS solutions. The mass loss of samples decreased with the addition of bio-glass.

  18. Activity of the Human Rhinovirus 3C Protease Studied in Various Buffers, Additives and Detergents Solutions for Recombinant Protein Production

    DEFF Research Database (Denmark)

    Ullah, Raheem; Shah, Majid Ali; Tufail, Soban;

    2016-01-01

    stringent sequence specificity and enhanced activity. Like other proteases, activity of the human rhinovirus 3C protease can be affected in part by the buffer components and additives that are generally employed for purification and stabilization of proteins, hence, necessitate their removal by tedious...... different fusion proteins at 4°C, a temperature of choice for purification of many proteins. The results show that the human rhinovirus 3C protease performs better at 4°C than the frequently used tobacco etch virus protease and its activity was insensitive to most of the experimental conditions tested...

  19. Thermal and Environmental Stability of Semi-Transparent Perovskite Solar Cells for Tandems Enabled by a Solution-Processed Nanoparticle Buffer Layer and Sputtered ITO Electrode.

    Science.gov (United States)

    Bush, Kevin A; Bailie, Colin D; Chen, Ye; Bowring, Andrea R; Wang, Wei; Ma, Wen; Leijtens, Tomas; Moghadam, Farhad; McGehee, Michael D

    2016-05-01

    A sputtered oxide layer enabled by a solution-processed oxide nanoparticle buffer layer to protect underlying layers is used to make semi-transparent perovskite solar cells. Single-junction semi-transparent cells are 12.3% efficient, and mechanically stacked tandems on silicon solar cells are 18.0% efficient. The semi-transparent perovskite solar cell has a T 80 lifetime of 124 h when operated at the maximum power point at 100 °C without additional sealing in ambient atmosphere under visible illumination. PMID:26880196

  20. The dissolution of monosodium urate monohydrate crystals: formulation of a biocompatible buffer solution with potential use in the treatment of gouty arthropathies

    Directory of Open Access Journals (Sweden)

    Gabriella Tamasi

    2013-04-01

    Full Text Available The dissolving abilities (DAs of several aqueous media for microcrystalline monosodium\turate\tmonohydrate\t(MSU, NaC5N4O3H3·H2O have been investigated using UV spectrophotometry for quantitative analytical determinations and X-ray diffraction, scanning electron microscopy and polarized light optical microscopy to assess structural aspects. High DAs were found for a buffer labeled TMT which contains tris(hydroxymethylaminomethane (TRIS, tris(hydroxymethylaminomethane\thydrochloride (TRIS·HCl, D-mannitol (MAN and taurine (TAU and gave DA30=1298(5 mg/L for synthetic MSU after 30 min incubation at 37°C and pH 7.4, most of the dissolution taking place within the first 5-10 min. Semiempirical molecular modelling techniques (ZINDO/1 show a favorable energy balance for the formation of a TRIS-urate-TRIS adduct which might explain the high DA values. Buffers containing linear or dendrimeric polyamines gave DA values which suggest that complex formation toward sodium cations is less important. An ex vivo MSU sample was found to have a significantly lower DA value (DA30=1124(5 mg/L in TMT as well as a lower crystallinity than its synthetic counterpart, possibly related to the presence of a non-crystalline impurity such as endogenous proteins. Cytotoxicity tests based on the MTT assay were used to check the biocompatibility of the TMT buffer and showed only moderate cell mortality after 24 h contact with the buffer solution.

  1. Growth of thick La{sub 2}Zr{sub 2}O{sub 7} buffer layers for coated conductors by polymer-assisted chemical solution deposition

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xin, E-mail: xzhang@my.swjtu.edu.cn [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity and New Energy Center (SNEC), Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); School of Electrical Engineering, Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Zhao, Yong, E-mail: yzhao@swjtu.edu.cn [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity and New Energy Center (SNEC), Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); School of Materials Science and Engineering, University of New South Wales, Sydney, 2052 NSW (Australia); Xia, Yudong [State Key Lab of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of China, Chengdu 610054 (China); Guo, Chunsheng [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity and New Energy Center (SNEC), Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Cheng, C.H. [School of Materials Science and Engineering, University of New South Wales, Sydney, 2052 NSW (Australia); Zhang, Yong [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity and New Energy Center (SNEC), Southwest Jiaotong University, Chengdu, Sichuan 610031 (China); Zhang, Han [Department of Physics, Peking University, Beijing 100871 (China)

    2015-06-15

    Highlights: • We develops a low-cost and high-efficient technology of fabricating LZO buffer layers. • Sufficient thickness LZO buffer layers have been obtained on NiW (2 0 0) alloy substrate. • Highly biaxially textured YBCO thin film has been deposited on LZO/NiW. - Abstract: La{sub 2}Zr{sub 2}O{sub 7} (LZO) epitaxial films have been deposited on LaAlO{sub 3} (LAO) (1 0 0) single-crystal surface and bi-axially textured NiW (2 0 0) alloy substrate by polymer-assisted chemical solution deposition, and afterwards studied with XRD, SEM and AFM approaches. Highly in-plane and out-of-plane oriented, dense, smooth, crack free and with a sufficient thickness (>240 nm) LZO buffer layers have been obtained on LAO (1 0 0) single-crystal surface; The films deposited on NiW (2 0 0) alloy substrate are also found with high degree in-plane and out-of-plane texturing, good density with pin-hole-free, micro-crack-free nature and a thickness of 300 nm. Highly epitaxial 500 nm thick YBa{sub 2}Cu{sub 3}O{sub 7−x} (YBCO) thin film exhibits the self-field critical current density (Jc) reached 1.3 MA/cm{sup 2} at 77 K .These results demonstrate the LZO epi-films obtained with current techniques have potential to be a buffer layer for REBCO coated conductors.

  2. Oxygen isotope fractionation in synthetic magnesian calcite

    Science.gov (United States)

    Jiménez-López, Concepción; Romanek, Christopher S.; Huertas, F. Javier; Ohmoto, Hiroshi; Caballero, Emilia

    2004-08-01

    Mg-bearing calcite was precipitated at 25°C in closed system free-drift experiments from solutions containing NaHCO 3, CaCl 2 and MgCl 2. The chemical and isotope composition of the solution and precipitate were investigated during time course experiments of 24-h duration. Monohydrocalcite and calcite precipitated early in the experiments (95%) thereafter. Solid collected at the end of the experiments displayed compositional zoning from pure calcite in crystal cores to up to 23 mol% MgCO 3 in the rims. Smaller excursions in Mg were superimposed on this chemical record, which is characteristic of oscillatory zoning observed in synthetic and natural solid-solution carbonates of differing solubility. Magnesium also altered the predominant morphology of crystals over time from the {104} to {100} and {110} growth forms. The oxygen isotope fractionation factor for the magnesian-calcite-water system (as 10 3lnα Mg-cl-H 2O ) displayed a strong dependence on the mol% MgCO 3 in the solid phase, but quantification of the relationship was difficult due to the heterogeneous nature of the precipitate. Considering only the Mg-content and δ 18O values for the bulk solid, 10 3lnα Mg-cl-H 2O increased at a rate of 0.17 ± 0.02 per mol% MgCO 3; this value is a factor of three higher than the single previous estimate (Tarutani T., Clayton R.N., and Mayeda T. K. (1969) The effect of polymorphims and magnesium substitution on oxygen isotope fractionation between calcium carbonate and water. Geochim. Cosmochim. Acta 33, 987-996). Nevertheless, extrapolation of our relationship to the pure calcite end member yielded a value of 27.9 ± 0.02, which is similar in magnitude to published values for the calcite-water system. Although no kinetic effect was observed on 10 3lnα Mg-cl-H 2O for precipitation rates that ranged from 10 3.21 to 10 4.60 μmol · m -2 · h -1, it was impossible to disentangle the potential effect(s) of precipitation rate and Mg-content on 10 3lnα Mg-cl-H 2O due to

  3. Activity of the Human Rhinovirus 3C Protease Studied in Various Buffers, Additives and Detergents Solutions for Recombinant Protein Production.

    Directory of Open Access Journals (Sweden)

    Raheem Ullah

    Full Text Available Proteases are widely used to remove affinity and solubility tags from recombinant proteins to avoid potential interference of these tags with the structure and function of the fusion partner. In recent years, great interest has been seen in use of the human rhinovirus 3C protease owing to its stringent sequence specificity and enhanced activity. Like other proteases, activity of the human rhinovirus 3C protease can be affected in part by the buffer components and additives that are generally employed for purification and stabilization of proteins, hence, necessitate their removal by tedious and time-consuming procedures before proteolysis can occur. To address this issue, we examined the effect of elution buffers used for common affinity based purifications, salt ions, stability/solubility and reducing agents, and detergents on the activity of the human rhinovirus 3C protease using three different fusion proteins at 4°C, a temperature of choice for purification of many proteins. The results show that the human rhinovirus 3C protease performs better at 4°C than the frequently used tobacco etch virus protease and its activity was insensitive to most of the experimental conditions tested. Though number of fusion proteins tested is limited, we expect that these finding will facilitate the use of the human rhinovirus 3C protease in recombinant protein production for pharmaceutical and biotechnological applications.

  4. Activity of the Human Rhinovirus 3C Protease Studied in Various Buffers, Additives and Detergents Solutions for Recombinant Protein Production

    Science.gov (United States)

    Tufail, Soban; Ismat, Fouzia; Imran, Muhammad; Iqbal, Mazhar; Mirza, Osman; Rhaman, Moazur

    2016-01-01

    Proteases are widely used to remove affinity and solubility tags from recombinant proteins to avoid potential interference of these tags with the structure and function of the fusion partner. In recent years, great interest has been seen in use of the human rhinovirus 3C protease owing to its stringent sequence specificity and enhanced activity. Like other proteases, activity of the human rhinovirus 3C protease can be affected in part by the buffer components and additives that are generally employed for purification and stabilization of proteins, hence, necessitate their removal by tedious and time-consuming procedures before proteolysis can occur. To address this issue, we examined the effect of elution buffers used for common affinity based purifications, salt ions, stability/solubility and reducing agents, and detergents on the activity of the human rhinovirus 3C protease using three different fusion proteins at 4°C, a temperature of choice for purification of many proteins. The results show that the human rhinovirus 3C protease performs better at 4°C than the frequently used tobacco etch virus protease and its activity was insensitive to most of the experimental conditions tested. Though number of fusion proteins tested is limited, we expect that these finding will facilitate the use of the human rhinovirus 3C protease in recombinant protein production for pharmaceutical and biotechnological applications. PMID:27093053

  5. Calcite crystal growth rate inhibition by polycarboxylic acids

    Science.gov (United States)

    Reddy, M.M.; Hoch, A.R.

    2001-01-01

    Calcite crystal growth rates measured in the presence of several polycarboxyclic acids show that tetrahydrofurantetracarboxylic acid (THFTCA) and cyclopentanetetracarboxylic acid (CPTCA) are effective growth rate inhibitors at low solution concentrations (0.01 to 1 mg/L). In contrast, linear polycarbocylic acids (citric acid and tricarballylic acid) had no inhibiting effect on calcite growth rates at concentrations up to 10 mg/L. Calcite crystal growth rate inhibition by cyclic polycarboxyclic acids appears to involve blockage of crystal growth sites on the mineral surface by several carboxylate groups. Growth morphology varied for growth in the absence and in the presence of both THFTCA and CPTCA. More effective growth rate reduction by CPTCA relative to THFTCA suggests that inhibitor carboxylate stereochemical orientation controls calcite surface interaction with carboxylate inhibitors. ?? 20O1 Academic Press.

  6. in situ Calcite Precipitation for Contaminant Immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Yoshiko Fujita; Robert W. Smith

    2009-08-01

    in situ Calcite Precipitation for Contaminant Immobilization Yoshiko Fujita (Yoshiko.fujita@inl.gov) (Idaho National Laboratory, Idaho Falls, Idaho, USA) Robert W. Smith (University of Idaho-Idaho Falls, Idaho Falls, Idaho, USA) Subsurface radionuclide and trace metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE’s greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent trace ions, such as the short-lived radionuclide strontium-90, is co-precipitation in calcite. Calcite, a common mineral in the arid western U.S., can form solid solutions with trace metals. The rate of trace metal incorporation is susceptible to manipulation using either abiotic or biotic means. We have previously demonstrated that increasing the calcite precipitation rate by stimulating the activity of urea hydrolyzing microorganisms can result in significantly enhanced Sr uptake. Urea hydrolysis causes the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity, and also by liberating the reactive cations from the aquifer matrix via exchange reactions involving the ammonium ion derived from urea: H2NCONH2 + 3H2O ? 2NH4+ + HCO3- + OH- urea hydrolysis >X:2Ca + 2NH4+ ? 2>X:NH4 + Ca2+ ion exchange Ca2+ + HCO3- + OH- ? CaCO3(s) + H2O calcite precipitation where >X: is a cation exchange site on the aquifer matrix. This contaminant immobilization approach has several attractive features. Urea hydrolysis is catalyzed by the urease enzyme, which is produced by many indigenous subsurface microorganisms. Addition of foreign microbes is unnecessary. In turn the involvement of the native microbes and the consequent in situ generation of reactive components in the aqueous phase (e.g., carbonate and Ca or Sr) can allow dissemination of the reaction over a larger volume and/or farther away from an amendment injection point, as compared to direct addition of the reactants at

  7. PVC mixtures’ mechanical properties with the addition of modified calcite as filler

    Directory of Open Access Journals (Sweden)

    Vučinić Dušica R.

    2012-01-01

    Full Text Available In this study mechanical properties of PVC mixtures (PVC, stabilizer, lubricant, filler such as tensile strength, tensile elongation, breaking strength, and breaking elongation were investigated. Unmodified calcite, as well as calcite modified by stearic acid, were used as fillers in wet and dry processes. The PVC mixtures containing the calcite modified by wet procedure have better mechanical properties compared to those with the calcite modified by the dry process. Tensile and breaking strength of the PVC mixture containing the calcite modified with 1.5% stearic acid using wet process, are higher for 2.8% and 5.2%, respectively, compared to the PVC mixture containing the calcite modified with the same amount of acid used in the dry process. The tensile strength difference between the mixtures increases with the increase of the concentration of used stearic acid up to 3%. The strength of PVC mixture with the calcite modified by wet process is 3.1% higher compared to the mixture containing calcite modified by dry process. The results showed that the bonding strength between calcite and the adsorbed organic component affected tensile strength, tensile elongation and breaking strength of the PVC mixtures. The best filler was obtained by wet modification using 1.5% stearic acid solution that provided the formation of a stearate monolayer chemisorbed on calcite. The PVC mixtures containing the calcite modified by wet process using 1.5% stearic acid solution exhibited the best mechanical properties. This calcite was completely hydrophobic with dominant chemically adsorbed surfactant, which means that stearate chemisorbed on calcite provided stronger interaction in the calcite-stearic acid-PVC system.

  8. Real-time HD Exchange Kinetics of Proteins from Buffered Aqueous Solution with Electrothermal Supercharging and Top-Down Tandem Mass Spectrometry

    Science.gov (United States)

    Going, Catherine C.; Xia, Zijie; Williams, Evan R.

    2016-02-01

    Electrothermal supercharging (ETS) with electrospray ionization produces highly charged protein ions from buffered aqueous solutions in which proteins have native folded structures. ETS increases the charge of ribonuclease A by 34%, whereas only a 6% increase in charge occurs for a reduced-alkylated form of this protein, which is unfolded and its structure is ~66% random coil in this solution. These results indicate that protein denaturation that occurs in the ESI droplets is the primary mechanism for ETS. ETS does not affect the extent of solution-phase hydrogen-deuterium exchange (HDX) that occurs for four proteins that have significantly different structures in solution, consistent with a droplet lifetime that is considerably shorter than observable rates of HDX. Rate constants for HDX of ubiquitin are obtained with a spatial resolution of ~1.3 residues with ETS and electron transfer dissociation of the 10+ charge-state using a single capillary containing a few μL of protein solution in which HDX continuously occurs. HDX protection at individual residues with ETS HDX is similar to that with reagent supercharging HDX and with solution-phase NMR, indicating that the high spray potentials required to induce ETS do not lead to HD scrambling.

  9. Real-time HD Exchange Kinetics of Proteins from Buffered Aqueous Solution with Electrothermal Supercharging and Top-Down Tandem Mass Spectrometry

    Science.gov (United States)

    Going, Catherine C.; Xia, Zijie; Williams, Evan R.

    2016-06-01

    Electrothermal supercharging (ETS) with electrospray ionization produces highly charged protein ions from buffered aqueous solutions in which proteins have native folded structures. ETS increases the charge of ribonuclease A by 34%, whereas only a 6% increase in charge occurs for a reduced-alkylated form of this protein, which is unfolded and its structure is ~66% random coil in this solution. These results indicate that protein denaturation that occurs in the ESI droplets is the primary mechanism for ETS. ETS does not affect the extent of solution-phase hydrogen-deuterium exchange (HDX) that occurs for four proteins that have significantly different structures in solution, consistent with a droplet lifetime that is considerably shorter than observable rates of HDX. Rate constants for HDX of ubiquitin are obtained with a spatial resolution of ~1.3 residues with ETS and electron transfer dissociation of the 10+ charge-state using a single capillary containing a few μL of protein solution in which HDX continuously occurs. HDX protection at individual residues with ETS HDX is similar to that with reagent supercharging HDX and with solution-phase NMR, indicating that the high spray potentials required to induce ETS do not lead to HD scrambling.

  10. Real-time HD Exchange Kinetics of Proteins from Buffered Aqueous Solution with Electrothermal Supercharging and Top-Down Tandem Mass Spectrometry.

    Science.gov (United States)

    Going, Catherine C; Xia, Zijie; Williams, Evan R

    2016-06-01

    Electrothermal supercharging (ETS) with electrospray ionization produces highly charged protein ions from buffered aqueous solutions in which proteins have native folded structures. ETS increases the charge of ribonuclease A by 34%, whereas only a 6% increase in charge occurs for a reduced-alkylated form of this protein, which is unfolded and its structure is ~66% random coil in this solution. These results indicate that protein denaturation that occurs in the ESI droplets is the primary mechanism for ETS. ETS does not affect the extent of solution-phase hydrogen-deuterium exchange (HDX) that occurs for four proteins that have significantly different structures in solution, consistent with a droplet lifetime that is considerably shorter than observable rates of HDX. Rate constants for HDX of ubiquitin are obtained with a spatial resolution of ~1.3 residues with ETS and electron transfer dissociation of the 10+ charge-state using a single capillary containing a few μL of protein solution in which HDX continuously occurs. HDX protection at individual residues with ETS HDX is similar to that with reagent supercharging HDX and with solution-phase NMR, indicating that the high spray potentials required to induce ETS do not lead to HD scrambling. Graphical Abstract ᅟ. PMID:26919868

  11. Zinc isotope fractionation during adsorption on calcite

    Science.gov (United States)

    Dong, S.; Wasylenki, L. E.

    2013-12-01

    Zinc is an important element as a nutrient in the marine biosphere. However, our understanding of its biogeochemical cycling in the oceans is relatively limited. The Zn stable isotope system holds the promise of providing novel insights, since published Zn isotopic values for various natural samples reveal significant fractionations in the marine environment. Surface seawater, basalts, shales, deep-sea clay sediments, sediment trap material, bulk plankton and zooplankton samples, and eolian dust fall within a tight range (δ66/64Zn from -0.1 to 0.5‰), but modern ferromanganese crusts (δ66/64Zn from 0.5 to 1.2‰), as well as carbonates (δ66/64Zn from 0.3 to 1.4‰), are notably enriched in heavy Zn isotopes [1-4]. In this study we seek to constrain the mechanism by which carbonates are enriched in heavier isotopes. In particular, we have conducted experiments to quantify isotope fractionation during adsorption of Zn onto the surfaces of calcite crystals that are in equilibrium with solution. The adsorption experiments were carried out in a series of small-volume batch reactions in a clean laboratory environment, using high-purity reagents and calcite seed crystals. The calcite was equilibrated with the solution prior to addition of Zn at atmospheric CO2 pressure (i.e., in air) for 5 days until a stable pH of 8.3 was reached. Later, a small aliquot of dissolved ZnCl2 was added such that the solution remained undersaturated with respect to hydrozincite. Experimental duration varied among the replicates from 6 to 144 hours, and then all solids and solutions were separated by filtration, purified by ion exchange chromatography, and analyzed by MC-ICP-MS. Zn adsorbed on calcite is isotopically heavier than in the co-existing solutions, with Δ68/66Zncalcite-solution of approximately 0.3‰. The variation of Δ68/66Zncalcite-solution beyond 24 hours is insignificant, so we infer that isotopic equilibrium is reached by this time. Previous work strongly suggests that a

  12. Evolution and the Calcite Eye Lens

    CERN Document Server

    Williams, Vernon L

    2013-01-01

    Calcite is a uniaxial, birefringent crystal, which in its optically transparent form, has been used for animal eye lenses, the trilobite being one such animal. Because of the calcite birefringence there is a difficulty in using calcite as a lens. When the propagation direction of incoming light is not exactly on the c-axis, the mages blur. In this paper, calcite blurring is evaluated, and the non-blurring by a crystallin eye lens is compared to a calcite one.

  13. In-Line Desalting of Proteins from Buffer and Synthetic Urine Solution Prior to ESI-MS Analysis via a Capillary-Channeled Polymer Fiber Microcolumn

    Science.gov (United States)

    Burdette, Carolyn Q.; Marcus, R. Kenneth

    2013-06-01

    Presented here is a novel in-line solid phase extraction (SPE) method utilizing a capillary-channeled polymer (C-CP) fiber microcolumn prior to introduction to an electrospray ionization (ESI) source. The high permeability of the microcolumn allows for operation under syringe pump or HPLC driven flow, ultimately providing greater mass spectral clarity and accurate molecular weight determinations for different protein/buffer combinations. Studies presented here focus on the desalting of several target proteins from a standard phosphate buffered saline (PBS) matrix and a synthetic urine solution prior to ESI-MS determinations. In every case, responses for μM-level proteins in PBS improve from the situation of not permitting molecular weight determinations to values that are precise to better than ±10 Da, without internal standards, with relative improvements in the signal-to-background ratios (S/B) on the order of 3,000×. De-salting of a myoglobin-spiked (12 μM) synthetic urine results in equally-improved spectral quality.

  14. Growth of thick La2Zr2O7 buffer layers for coated conductors by polymer-assisted chemical solution deposition

    Science.gov (United States)

    Zhang, Xin; Zhao, Yong; Xia, Yudong; Guo, Chunsheng; Cheng, C. H.; Zhang, Yong; Zhang, Han

    2015-06-01

    La2Zr2O7 (LZO) epitaxial films have been deposited on LaAlO3 (LAO) (1 0 0) single-crystal surface and bi-axially textured NiW (2 0 0) alloy substrate by polymer-assisted chemical solution deposition, and afterwards studied with XRD, SEM and AFM approaches. Highly in-plane and out-of-plane oriented, dense, smooth, crack free and with a sufficient thickness (>240 nm) LZO buffer layers have been obtained on LAO (1 0 0) single-crystal surface; The films deposited on NiW (2 0 0) alloy substrate are also found with high degree in-plane and out-of-plane texturing, good density with pin-hole-free, micro-crack-free nature and a thickness of 300 nm. Highly epitaxial 500 nm thick YBa2Cu3O7-x (YBCO) thin film exhibits the self-field critical current density (Jc) reached 1.3 MA/cm2 at 77 K .These results demonstrate the LZO epi-films obtained with current techniques have potential to be a buffer layer for REBCO coated conductors.

  15. Spectral pH dependence of erythrosin B in sol-gel silica coatings and buffered solutions

    OpenAIRE

    Montero, E. F.; García, M.A.; Villegas Broncano, María Ángeles; LLopis, J.

    2008-01-01

    [EN] Thin coatings optically sensitive against pH are obtained by entrapping erythrosin B molecules in a sol-gel silica matrix. Comparisons between optical spectra of erythrosin B in solutions and those once entrapped in silica coatings are performed for pH ranging from 0.5 to 12.0. Significant differences between both kinds of spectra (solutions and coatings) of erythrosin B are observed. Main changes are displayed in the absorption spectra for neutral to basic pH. Furthermore, the erythrosi...

  16. Action spectrum for the induction of single-strand breaks in DNA buffered aqueous solution in the wavelength range from 150 to 272 nm: dual mechanism

    International Nuclear Information System (INIS)

    The induction of single-strand breaks by vacuum-u.v. and far-u.v. radiations (150 nm - 272 nm) in plasmid Col E1 DNA in buffered aqueous solution was studied by agarose gel electrophoresis. The results indicated that the mechanisms of DNA strand-break induction are different in the two u.v. regions: above 210 nm the direct excitation of DNA seemed to be the main cause; below 180 nm the photolysis of solvent water seemed to be essential. The demonstration of a systematic protection at 160 nm and not at 209 nm by OH scavengers, such as ethyl alcohol, potassium iodide and D-mannitol, supports the involvement of OH radicals in the vacuum-u.v. region. (author)

  17. Buffer capacity of biologics--from buffer salts to buffering by antibodies.

    Science.gov (United States)

    Karow, Anne R; Bahrenburg, Sven; Garidel, Patrick

    2013-01-01

    Controlling pH is essential for a variety of biopharmaceutical process steps. The chemical stability of biologics such as monoclonal antibodies is pH-dependent and slightly acidic conditions are favorable for stability in a number of cases. Since control of pH is widely provided by added buffer salts, the current study summarizes the buffer characteristics of acetate, citrate, histidine, succinate, and phosphate buffers. Experimentally derived values largely coincide with values calculated from a model that had been proposed in 1922 by van Slyke. As high concentrated protein formulations become more and more prevalent for biologics, the self-buffering potential of proteins becomes of relevance. The current study provides information on buffer characteristics for pH ranges down to 4.0 and up to 8.0 and shows that a monoclonal antibody at 50 mg/mL exhibits similar buffer capacity as 6 mM citrate or 14 mM histidine (pH 5.0-6.0). Buffer capacity of antibody solutions scales linearly with protein concentration up to more than 200 mg/mL. At a protein concentration of 220 mg/mL, the buffer capacity resembles the buffer capacity of 30 mM citrate or 50 mM histidine (pH 5.0-6.0). The buffer capacity of monoclonal antibodies is practically identical at the process relevant temperatures 5, 25, and 40°C. Changes in ionic strength of ΔI=0.15, in contrast, can alter the buffer capacity up to 35%. In conclusion, due to efficient self-buffering by antibodies in the pH range of favored chemical stability, conventional buffer excipients could be dispensable for pH stabilization of high concentrated protein solutions. PMID:23296746

  18. The appearance of Ti3+ states in solution-processed TiOx buffer layers in inverted organic photovoltaics

    Science.gov (United States)

    Zhidkov, Ivan S.; McLeod, John A.; Kurmaev, Ernst Z.; Korotin, Michael A.; Kukharenko, Andrey I.; Savva, Achilleas; Choulis, Stelios A.; Korotin, Danila M.; Cholakh, Seif O.

    2016-07-01

    We study the low-temperature solution processed TiOx films and device structures using core level and valence X-ray photoelectron spectroscopy (XPS) and electronic structure calculations. We are able to correlate the fraction of Ti3+ present as obtained from Ti 2p core level XPS with the intensity of the defect states that appear within the band gap as observed with our valence XPS. Constructing an operating inverted organic photovoltaic (OPV) using the TiOx film as an electron selective contact may increase the fraction of Ti3+ present. We provide evidence that the number of charge carriers in TiOx can be significantly varied and this might influence the performance of inverted OPVs.

  19. CdS and Cd-Free Buffer Layers on Solution Phase Grown Cu2ZnSn(SxSe1- x)4 :Band Alignments and Electronic Structure Determined with Femtosecond Ultraviolet Photoemission Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Haight, Richard; Barkhouse, Aaron; Wang, Wei; Yu, Luo; Shao, Xiaoyan; Mitzi, David; Hiroi, Homare; Sugimoto, Hiroki

    2013-12-02

    The heterojunctions formed between solution phase grown Cu2ZnSn(SxSe1- x)4(CZTS,Se) and a number of important buffer materials including CdS, ZnS, ZnO, and In2S3, were studied using femtosecond ultraviolet photoemission spectroscopy (fs-UPS) and photovoltage spectroscopy. With this approach we extract the magnitude and direction of the CZTS,Se band bending, locate the Fermi level within the band gaps of absorber and buffer and measure the absorber/buffer band offsets under flatband conditions. We will also discuss two-color pump/probe experiments in which the band bending in the buffer layer can be independently determined. Finally, studies of the bare CZTS,Se surface will be discussed including our observation of mid-gap Fermi level pinning and its relation to Voc limitations and bulk defects.

  20. On the complex conductivity signatures of calcite precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Yuxin; Hubbard, Susan; Williams, Kenneth Hurst; Ajo-Franklin, Jonathan

    2009-11-01

    Calcite is a mineral phase that frequently precipitates during subsurface remediation or geotechnical engineering processes. This precipitation can lead to changes in the overall behavior of the system, such as flow alternation and soil strengthening. Because induced calcite precipitation is typically quite variable in space and time, monitoring its distribution in the subsurface is a challenge. In this research, we conducted a laboratory column experiment to investigate the potential of complex conductivity as a mean to remotely monitor calcite precipitation. Calcite precipitation was induced in a glass bead (3 mm) packed column through abiotic mixing of CaCl{sub 2} and Na{sub 2}CO{sub 3} solutions. The experiment continued for 12 days with a constant precipitation rate of {approx}0.6 milimole/d. Visual observations and scanning electron microscopy imaging revealed two distinct phases of precipitation: an earlier phase dominated by well distributed, discrete precipitates and a later phase characterized by localized precipitate aggregation and associated pore clogging. Complex conductivity measurements exhibited polarization signals that were characteristic of both phases of calcite precipitation, with the precipitation volume and crystal size controlling the overall polarization magnitude and relaxation time constant. We attribute the observed responses to polarization at the electrical double layer surrounding calcite crystals. Our experiment illustrates the potential of electrical methods for characterizing the distribution and aggregation state of nonconductive minerals like calcite. Advancing our ability to quantify geochemical transformations using such noninvasive methods is expected to facilitate our understanding of complex processes associated with natural subsurface systems as well as processes induced through engineered treatments (such as environmental remediation and carbon sequestration).

  1. Surface tension alteration on calcite, induced by ion substitution

    DEFF Research Database (Denmark)

    Sakuma, Hiroshi; Andersson, Martin Peter; Bechgaard, Klaus;

    2014-01-01

    , where particles are smaller than the smallest droplet? We investigated the energy required to exchange Mg2+ and SO4 2- from aqueous solution into calcite {10.4} surfaces using density functional theory. Mg2+ substitution for Ca2+ is favored but only when SO4 2- is also present and MgSO4 incorporates...... the pore water. Incorporation of MgSO4 into calcite, which is energetically favored, decreases surface tension and releases polar oil compounds. © 2014 American Chemical Society....

  2. Is there a reversible step in 45Ca sorption onto pure calcite?

    International Nuclear Information System (INIS)

    Complete text of publications follows: Metal sorption onto carbonate minerals have been intensively interpreted in literature by two reaction steps: (1) a first one rapid and completed within few hours and (2) a second one slower, eventually irreversible and occurring at a constant rate (Davis et al., 1987; Zachara et al., 1991; Mevellec, 2000). The first step is often attributed to an ion exchange process, but its reversibility is rarely investigated. Consequently, discrimination of the global sorption phenomenon into two different mechanisms is not always justified. Therefore, we have investigate both sorption and desorption of Ca, radio-traced with isotope 45Ca, onto synthetic pure calcite in aqueous solutions saturated with respect to calcite and in equilibrium with the atmospheric CO2. Batch experiments were performed as a function of time and at different pH using anionic chemical buffers having no affinity towards calcite. The distribution coefficient of 45Ca was calculated from radiochemical measurements of the supernatants before and after sorption, and the total Ca aqueous concentration was measured by ion - chromatography. As mentioned by previously cited authors, our results show that whatever the pH, Kd's of 45Ca increase with time without reaching a stationary state within two weeks. Moreover, Kd's calculated with desorption experimental data are systematically higher than those calculated with the sorption ones. In order to test the occurrence of a first reversible ion exchange step, we applied the approach of Badillo-Almaraz and Ly (2003) put forward for the interpretation of Ca sorption onto hydroxyapatite. More specifically, on the basis of isotopic equilibrium principle and from the knowledge of the isotopic ratios (45Ca/Catot), it is possible to calculate 'reversible' Kd's of 45Ca for both sorption and desorption steps. Doing this, we observe that both calculated Kd's values are similar, whatever the time and pH. In these conditions, we are able

  3. Influence of heat treatment on microstructure and passivity of Cu–30Zn–1Sn alloy in buffer solution containing chloride ions

    Indian Academy of Sciences (India)

    U Tabrizi; R Parvizi; A Davoodi; M H Moayed

    2012-02-01

    Tin as an alloying element is of great interest in brasses for dezincification impediment. In this paper, Cu–30Zn–1Sn alloy was submitted to three different heat treatments, viz. A (heating up to 800 °C for 20 h, held at 200 °C for 20 h in salt bath and air cooled), B (heating up to 800 °C for 20 h and water quenched) and C (heating up to 600 °C for 20 h and water quenched). The influence of heat treatment on microstructure was evaluated by OM and SEM–EDS analysis. The corrosion resistance in buffer solution (pH 9), H3BO3/Na2B4O7.10H2O, with various concentrations of chloride ions was evaluated by potentiodynamic polarization curves and compared with multicomponent Pourbaix diagrams. A correlation between the heat treatment, microstructure and passivity of the heat treated samples was observed. The results indicated that all heat treatment procedures led to formation of , and -Sn-rich phases as microstructure constituents with a small fraction of ' phase in A. Sn-rich phase appears in grain boundaries and its morphology was slightly changed due to heat treatment. Beneficial influence of low concentration chloride ions on passivity was associated with the formation of copper oxides/hydroxide and chloride complexes. Deterioration was observed at concentrations higher than 0.05 M NaCl due to accelerated dissolution of copper by formation of CuCl$^{−}_{2}$. As a result of dezincification process, preferential corrosion attack and copper redeposition on phase (matrix) were observed. However, Sn-rich (1) phase in grain boundaries was not attacked due to SnO2 formation. In buffer solution, the higher passivity current density in A was related to the presence of small amount of ' phase. On the other hand, in 1 M NaCl, lower critical current density for passivation in B and A (about two times lower than C) was attributed to the grain size effect.

  4. Thermoluminescence measurement of calcite shells

    International Nuclear Information System (INIS)

    Thermoluminescence (TL) measurements of calcite derived from shells or shell fragments are relevant to the detection of irradiated shellfish for enforcement of food labelling regulations, and to dating of archaeological and fossil materials. The bio-inorganic nature of the material, which is both micro-porous and an intimate mixture of organic and inorganic phases, presents problems for direct TL measurements. This paper discusses the optimal conditions for direct TL measurements on dried, powdered samples from modern shells. (Author)

  5. Transformation of Mg-bearing amorphous calcium carbonate to Mg-calcite - In situ monitoring

    Science.gov (United States)

    Purgstaller, Bettina; Mavromatis, Vasileios; Immenhauser, Adrian; Dietzel, Martin

    2016-02-01

    The formation of Mg-bearing calcite via an amorphous precursor is a poorly understood process that is of relevance for biogenic and abiogenic carbonate precipitation. In order to gain an improved insight on the controls of Mg incorporation in calcite formed via an Mg-rich amorphous calcium carbonate (Mg-ACC) precursor, the precipitation of Mg-ACC and its transformation to Mg-calcite was monitored by in situ Raman spectroscopy. The experiments were performed at 25.0 ± 0.03 °C and pH 8.3 ± 0.1 and revealed two distinct pathways of Mg-calcite formation: (i) At initial aqueous Mg/Ca molar ratios ⩽ 1:6, Mg-calcite formation occurs via direct precipitation from solution. (ii) Conversely, at higher initial Mg/Ca molar ratios, Mg-calcite forms via an intermediate Mg-rich ACC phase. In the latter case, the final product is a calcite with up to 20 mol% Mg. This Mg content is significant higher than that of the Mg-rich ACC precursor phase. Thus, a strong net uptake of Mg ions from the solution into the crystalline precipitate throughout and also subsequent to ACC transformation is postulated. Moreover, the temporal evolution of the geochemical composition of the reactive solution and the Mg-ACC has no significant effect on the obtained "solubility product" of Mg-ACC. The enrichment of Mg in calcite throughout and subsequent to Mg-ACC transformation is likely affected by the high aqueous Mg/Ca ratio and carbonate alkalinity concentrations in the reactive solution. The experimental results have a bearing on the formation mechanism of Mg-rich calcites in marine early diagenetic environments, where high carbonate alkalinity concentrations are the rule rather than the exception, and on the insufficiently investigated inorganic component of biomineralisation pathways in many calcite secreting organisms.

  6. Effect of synovial fluid, phosphate-buffered saline solution, and water on the dissolution and corrosion properties of CoCrMo alloys as used in orthopedic implants.

    Science.gov (United States)

    Lewis, A C; Kilburn, M R; Papageorgiou, I; Allen, G C; Case, C P

    2005-06-15

    The corrosion and dissolution of high- and low-carbon CoCrMo alloys, as used in orthopedic joint replacements, were studied by immersing samples in phosphate-buffered saline (PBS), water, and synovial fluid at 37 degrees C for up to 35 days. Bulk properties were analyzed with a fine ion beam microscope. Surface analyses by X-ray photoelectron spectroscopy and Auger electron spectroscopy showed surprisingly that synovial fluid produced a thin oxide/hydroxide layer. Release of ions into solution from the alloy also followed an unexpected pattern where synovial fluid, of all the samples, had the highest Cr concentration but the lowest Co concentration. The presence of carbide inclusions in the alloy did not affect the corrosion or the dissolution mechanisms, although the carbides were a significant feature on the metal surface. Only one mechanism was recognized as controlling the thickness of the oxide/hydroxide interface. The analysis of the dissolved metal showed two mechanisms at work: (1) a protein film caused ligand-induced dissolution, increasing the Cr concentration in synovial fluid, and was explained by the equilibrium constants; (2) corrosion at the interface increased the Co in PBS. The effect of prepassivating the samples (ASTM F-86-01) did not always have the desired effect of reducing dissolution. The release of Cr into PBS increased after prepassivation. The metal-synovial fluid interface did not contain calcium phosphate as a deposit, typically found where samples are exposed to calcium rich bodily fluids. PMID:15900610

  7. Synthesis, electrochemical, spectrophotometric and potentiometric studies of two azo-compounds derived from 4-amino-2-methylquinoline in ethanolic-aqueous buffered solutions

    Energy Technology Data Exchange (ETDEWEB)

    El-Attar, Mona A.; Ghoneim, Mohamed M. [Analytical Chemistry Research Unit, Chemistry Department, Tanta University (Egypt); Ismail, Iqbal M., E-mail: maema.2011@yahoo.com [Chemistry Department, Faculty of Science, King Abdul Aziz University, Jeddah (Saudi Arabia)

    2012-08-15

    Two azo-compounds, 2-methyl-4-(5-amino-2-hydroxy-phenylazo)-quinoline (2) and 2-methyl-4-(2-hydroxy-5-nitrophenylazo)-quinoline, derived from 4-amino-2-methylquinoline were synthesized. Their chemical structures were characterized and confirmed by means of elemental chemical analysis, infrared (IR) spectroscopy, {sup 1}H nuclear magnetic resonance (NMR) and mass spectrometry (MS). The electrochemical behavior of the starting compound (4-amino-2-methylquinoline) and of the two synthesized azo-derivatives was studied at the mercury electrode in the B-R universal buffer at various pH values (2-11.5) containing 40% (v/v) ethanol using dc-polarography, cyclic voltammetry and controlled-potential coulometry. Their electrode reaction pathways were elucidated and discussed. The dissociation constants (pKa) of the examined compounds, stability constants and stoichiometry of their complexes in solution with some transition metal ions (Co(II), Ni(II), Cu(II), La(III) and UO{sup 2+}{sub 2}) were determined. (author)

  8. Direct nanoscale observations of the coupled dissolution of calcite and dolomite and the precipitation of gypsum.

    Science.gov (United States)

    Offeddu, Francesco Giancarlo; Cama, Jordi; Soler, Josep Maria; Putnis, Christine V

    2014-01-01

    In-situ atomic force microscopy (AFM) experiments were performed to study the overall process of dissolution of common carbonate minerals (calcite and dolomite) and precipitation of gypsum in Na2SO4 and CaSO4 solutions with pH values ranging from 2 to 6 at room temperature (23 ± 1 °C). The dissolution of the carbonate minerals took place at the (104) cleavage surfaces in sulfate-rich solutions undersaturated with respect to gypsum, by the formation of characteristic rhombohedral-shaped etch pits. Rounding of the etch pit corners was observed as solutions approached close-to-equilibrium conditions with respect to calcite. The calculated dissolution rates of calcite at pH 4.8 and 5.6 agreed with the values reported in the literature. When using solutions previously equilibrated with respect to gypsum, gypsum precipitation coupled with calcite dissolution showed short gypsum nucleation induction times. The gypsum precipitate quickly coated the calcite surface, forming arrow-like forms parallel to the crystallographic orientations of the calcite etch pits. Gypsum precipitation coupled with dolomite dissolution was slower than that of calcite, indicating the dissolution rate to be the rate-controlling step. The resulting gypsum coating partially covered the surface during the experimental duration of a few hours. PMID:25161860

  9. Development of a four-zone carousel process packed with metal ion-imprinted polymer for continuous separation of copper ions from manganese ions, cobalt ions, and the constituent metal ions of the buffer solution used as eluent.

    Science.gov (United States)

    Jo, Se-Hee; Park, Chanhun; Yi, Sung Chul; Kim, Dukjoon; Mun, Sungyong

    2011-08-19

    A three-zone carousel process, in which Cu(II)-imprinted polymer (Cu-MIP) and a buffer solution were employed as adsorbent and eluent respectively, has been developed previously for continuous separation of Cu²⁺ (product) from Mn²⁺ and Co²⁺ (impurities). Although this process was reported to be successful in the aforementioned separation task, the way of using a buffer solution as eluent made it inevitable that the product stream included the buffer-related metal ions (i.e., the constituent metal ions of the buffer solution) as well as copper ions. For a more perfect recovery of copper ions, it would be necessary to improve the previous carousel process such that it can remove the buffer-related metal ions from copper ions while maintaining the previous function of separating copper ions from the other 2 impure heavy-metal ions. This improvement was made in this study by proposing a four-zone carousel process based on the following strategy: (1) the addition of one more zone for performing the two-step re-equilibration tasks and (2) the use of water as the eluent of the washing step in the separation zone. The operating conditions of such a proposed process were determined on the basis of the data from a series of single-column experiments. Under the determined operating conditions, 3 runs of carousel experiments were carried out. The results of these experiments revealed that the feed-loading time was a key parameter affecting the performance of the proposed process. Consequently, the continuous separation of copper ions from both the impure heavy-metal ions and the buffer-related metal ions could be achieved with a purity of 91.9% and a yield of 92.8% by using the proposed carousel process based on a properly chosen feed-loading time. PMID:21764065

  10. Experimental study of the replacement of calcite by calcium sulphates

    Science.gov (United States)

    Ruiz-Agudo, E.; Putnis, C. V.; Hövelmann, J.; Álvarez-Lloret, P.; Ibáñez-Velasco, A.; Putnis, A.

    2015-05-01

    Among the most relevant mineral replacement reactions are those involving sulphates and carbonates, which have important geological and technological implications. Here it is shown experimentally that during the interaction of calcite (CaCO3) cleavage surfaces with sulphate-bearing acidic solutions, calcite is ultimately replaced by gypsum (CaSO4 2H2O) and anhydrite (CaSO4), depending on the reaction temperature. Observations suggest that this occurs most likely via an interface-coupled dissolution-precipitation reaction, in which the substrate is replaced pseudomorphically by the product. At 120 and 200 °C gypsum and/or bassanite (CaSO4·0.5H2O) form as precursor phases for the thermodynamically stable anhydrite. Salinity promotes the formation of less hydrated precursor phases during the replacement of calcite by anhydrite. The reaction stops before equilibrium with respect to calcite is reached and during the course of the reaction most of the bulk solutions are undersaturated with respect to the precipitating phase(s). A mechanism consisting of the dissolution of small amounts of solid in a thin layer of fluid at the mineral-fluid interface and the subsequent precipitation of the product phase from this layer is in agreement with these observations. PHREEQC simulations performed in the framework of this mechanism highlight the relevance of transport and surface reaction kinetics on the volume change associated with the CaCO3-CaSO4 replacement. Under our experimental conditions, this reaction occurs with a positive volume change, which ultimately results in passivation of the unreacted substrate before calcite attains equilibrium with respect to the bulk solution.

  11. Thermoluminescence dating of stalagmitic calcite

    International Nuclear Information System (INIS)

    The thermoluminescence (TL) method of dating stalagmitic calcite has been applied to twenty-seven samples from two paleolithic cave sites; Pontnewydd, Wales, and Caune de L'Arago, Tautavel, France. Environmental dose-rates were evaluated mainly by means of CaF2 capsule burials. The ages of the stalagmitic samples were independently determined by means of the uranium series disequilibrium method. In general, good agreement is found between the TL and uranium series dates, which cover a range from approximately 15 000 to 300 000 years B.P. It is estimated that the TL method should extend to the order of a million years in good circumstances. (author)

  12. Magnesium stable isotope fractionation in marine biogenic calcite and aragonite

    Science.gov (United States)

    Wombacher, F.; Eisenhauer, A.; Böhm, F.; Gussone, N.; Regenberg, M.; Dullo, W.-Chr.; Rüggeberg, A.

    2011-10-01

    This survey of magnesium stable isotope compositions in marine biogenic aragonite and calcite includes samples from corals, sclerosponges, benthic porcelaneous and planktonic perforate foraminifera, coccolith oozes, red algae, and an echinoid and brachiopod test. The analyses were carried out using MC-ICP-MS with an external repeatability of ±0.22‰ (2SD for δ 26Mg; n = 37), obtained from a coral reference sample (JCp-1). Magnesium isotope fractionation in calcitic corals and sclerosponges agrees with published data for calcitic speleothems with an average Δ 26Mg calcite-seawater = -2.6 ± 0.3‰ that appears to be weakly related to temperature. With one exception ( Vaceletia spp.), aragonitic corals and sclerosponges also display uniform Mg isotope fractionations relative to seawater with Δ 26Mg biogenic aragonite-seawater = -0.9 ± 0.2. Magnesium isotopes in high-Mg calcites from red algae, echinoids and perhaps some porcelaneous foraminifera as well as in all low-Mg calcites (perforate foraminifera, coccoliths and brachiopods) display significant biological influences. For planktonic foraminifera, the Mg isotope data is consistent with the fixation of Mg by organic material under equilibrium conditions, but appears to be inconsistent with Mg removal from vacuoles. Our preferred model, however, suggests that planktonic foraminifera synthesize biomolecules that increase the energetic barrier for Mg incorporation. In this model, the need to remove large quantities of Mg from vacuole solutions is avoided. For the high-Mg calcites from echinoids, the precipitation of amorphous calcium carbonate may be responsible for their weaker Mg isotope fractionation. Disregarding superimposed biological effects, it appears that cation light isotope enrichments in CaCO 3 principally result from a chemical kinetic isotope effect, related to the incorporation of cations at kink sites. In this model, the systematics of cation isotope fractionations in CaCO 3 relate to the

  13. An all chemical solution deposition approach for the growth of highly textured CeO2 cap layers on La2Zr2O7-buffered long lengths of biaxially textured Ni-W substrates for YBCO-coated conductors

    International Nuclear Information System (INIS)

    A reel-to-reel, dip coating process has been developed to continuously deposit epitaxial La2Zr2O7 (LZO) and CeO2 on 5 m long cube-textured {100} (001)Ni tapes. Recent results for La2Zr2O7 and CeO2 buffer layers deposited on long lengths of Ni substrate for the realization of YBa2Cu3O7-x (YBCO)-coated conductors are presented. The major achievement is the development of a new all chemical solution deposition (CSD) process leading to the formation of highly textured buffer layers at moderate annealing temperatures. Reproducible highly textured, dense and crack-free LZO buffer layers and CeO2 cap layers were obtained for annealing temperatures as low as 900 deg. C in a reducing atmosphere (Ar-5 at.%-H2). The thickness of the LZO buffer layers was determined to be (200 ± 10) nm per single coating; prepared cerium oxide layers showed a thickness of 60 nm ± 10 nm. Pulsed laser deposition (PLD) was used to grow YBCO films on these substrates. A Tc0 of T = 90.5 K and ΔTc = 1.4 K was obtained on PLD-YBCO/CSD-CeO2 /CSD-LZO/Ni-5 at.% W, which shows the outstanding features of this new buffer layer architecture processed by CSD. The large layer thickness combined with low annealing temperatures is the main advantage of this new process for low-cost buffer layer deposition on Ni-RABiTS (rolling-assisted biaxially textured substrates)

  14. Epitaxial growth of YBa2Cu3O7−x films on Ce0.9La0.1O2−y buffered yttria-stabilized zirconia substrates by an all-chemical-solution route

    DEFF Research Database (Denmark)

    Yue, Zhao; Wu, Wei; Tang, Xiao;

    2014-01-01

    In view of high rate fabrication of coated conductors at low-cost, YBa2Cu3O7 (YBCO) films on Ce0.9La0.1O2−y buffered yttria-stabilized zirconia substrates were deposited by means of a novel low-fluorine metal–organic solution route. A high critical current density of 3 MA cm−2 (77 K, self field...

  15. Buffer moisture protection system

    International Nuclear Information System (INIS)

    With the present knowledge, bentonite blocks have to be protected from the air relative humidity and from any moisture leakages in the environment that might cause swelling of the bentonite blocks during the 'open' installation phase before backfilling. The purpose of this work was to design the structural reference solution both for the bottom of the deposition hole and for the buffer moisture protection and dewatering system with their integrated equipment needed in the deposition hole. This report describes the Posiva's reference solution for the buffer moisture protection system and the bottom plate on basis of the demands and functional requirements set by long-term safety. The reference solution with structural details has been developed in research work made 2010-2011. The structural solution of the moisture protection system has not yet been tested in practice. On the bottom of the deposition hole a copper plate which protects the lowest bentonite block from the gathered water is installed straight to machined and even rock surface. The moisture protection sheet made of EPDM rubber is attached to the copper plate with an inflatable seal. The upper part of the moisture protection sheet is fixed to the collar structures of the lid which protects the deposition hole in the disposal tunnel. The main function of the moisture protection sheet is to protect bentonite blocks from the leaking water and from the influence of the air humidity at their installation stage. The leaking water is controlled by the dewatering and alarm system which has been integrated into the moisture protection liner. (orig.)

  16. Buffer moisture protection system

    Energy Technology Data Exchange (ETDEWEB)

    Ritola, J.; Peura, J. [VTT Technical Research Centre of Finland, Espoo (Finland)

    2013-11-15

    With the present knowledge, bentonite blocks have to be protected from the air relative humidity and from any moisture leakages in the environment that might cause swelling of the bentonite blocks during the 'open' installation phase before backfilling. The purpose of this work was to design the structural reference solution both for the bottom of the deposition hole and for the buffer moisture protection and dewatering system with their integrated equipment needed in the deposition hole. This report describes the Posiva's reference solution for the buffer moisture protection system and the bottom plate on basis of the demands and functional requirements set by long-term safety. The reference solution with structural details has been developed in research work made 2010-2011. The structural solution of the moisture protection system has not yet been tested in practice. On the bottom of the deposition hole a copper plate which protects the lowest bentonite block from the gathered water is installed straight to machined and even rock surface. The moisture protection sheet made of EPDM rubber is attached to the copper plate with an inflatable seal. The upper part of the moisture protection sheet is fixed to the collar structures of the lid which protects the deposition hole in the disposal tunnel. The main function of the moisture protection sheet is to protect bentonite blocks from the leaking water and from the influence of the air humidity at their installation stage. The leaking water is controlled by the dewatering and alarm system which has been integrated into the moisture protection liner. (orig.)

  17. Arsenite sorption and co-precipitation with calcite

    CERN Document Server

    Roman-Ross, Gabriela; Turrillas, Xavier; Fernandez-Martinez, Alejandro; Charlet, Laurent

    2008-01-01

    Sorption of As(III) by calcite was investigated as a function of As(III) concentration, time and pH. The sorption isotherm, i.e. the log As(III) vs. log [As(OH)3 degrees / Assat] plot is S-shaped and has been modelled on an extended version of the surface precipitation model. At low concentrations, As(OH)3 degrees is adsorbed by complexation to surface Ca surface sites, as previously described by the X-ray standing wave technique. The inflexion point of the isotherm, where As(OH)3 degrees is limited by the amount of surface sites (ST), yields 6 sites nm-2 in good agreement with crystallographic data. Beyond this value, the amount of sorbed arsenic increases linearly with solution concentration, up to the saturation of arsenic with respect to the precipitation of CaHAsO3(s). The solid solutions formed in this concentration range were examined by X-ray and neutron diffraction. The doped calcite lattice parameters increase with arsenic content while c/a ratio remains constant. Our results made on bulk calcite on...

  18. FORMATION OF CALCITE AND SILICA FROM PERCOLATION IN A HYDROLOGICALLY UNSATURATED SETTING, YUCCA MOUNTAIN, NEVADA

    International Nuclear Information System (INIS)

    Geological, mineralogical, chemical, and isotopic evidence from coatings of calcite and silica on open fractures and lithophysal cavities within welded tuffs at Yucca Mountain indicate an origin from meteoric water percolating through a thick (500 to 700 m) unsaturated zone (UZ) rather than from pulses of ascending ground water. Geologic evidence for a UZ setting includes the presence of coatings in only a small percentage of cavities, the restriction of coatings to fracture footwalls and cavity floors, and an absence of mineral high-water marks indicative of water ponding. Systematic mineral sequences (early calcite, followed by chalcedony with minor quartz and fluorite, and finally calcite with intercalated opal forming the bulk of the coatings) indicate progressive changes in UZ conditions through time, rather than repeated saturation by flooding. Percolation under the influence of gravity also results in mineral textures that vary between steeply dipping sites (thinner coatings of blocky calcite) and shallowly dipping sites (thicker coatings of coarse, commonly bladed calcite, with globules and sheets of opal). Micrometer-scale growth banding in both calcite and opal reflects slow average growth rates (scale of mm/m.y.) over millions of years rather than only a few rapidly deposited growth episodes. Isotopic compositions of C, O, Sr, and U from calcite and opal indicate a percolation-modified meteoric water source, and collectively refute a deeper ground-water source. Chemical and isotopic variations in coatings also indicate long-term evolution of water compositions. Although some compositional changes are related to shifts in climate, growth rates in the deeper UZ are buffered from large changes in meteoric input. Coatings most likely formed from films of water flowing down connected fracture pathways. Mineral precipitation is consistent with water vapor and carbon dioxide loss from films at very slow rates. Data collectively indicate that mineral coatings

  19. In situ AFM crystal growth and dissolution study of calcite in the presence of aqueous fluoride

    Science.gov (United States)

    Vavouraki, A.; Putnis, C. V.; Putnis, A.; Koutsoukos, P. G.

    2009-04-01

    Fluoride is naturally abundant, encountered in rocks, soil and fresh and ocean water. Calcite crystals, during crystal growth may incorporate fluoride ions into their lattice (Okumura et al., 1983). In situ atomic force microscopy (AFM) has been used to study the growth and dissolution of calcite {104} surfaces in aqueous solutions in the presence of fluoride, using a fluid cell in which the supersaturated and the understaturated solutions respectively, flow over a freshly cleaved calcite crystal. For growth experiments, supersaturation index (S.I.) with respect to calcite was equal to 0.89 and the initial solution pH 10.2. The crystal growth rates were measured from the closure of the rhombohedral etch pits along the [010] direction induced by an initial dissolution step using pure water. The spreading rate of 2-dimensional nuclei was also measured along the same direction. In the presence of low fluoride concentrations (≤0.33 mM), the crystal growth rate of calcite was unaffected. At higher concentrations (up to 5 mM) growth rate decreased substantially to 50% of the rate in the absence of fluoride. Potential fluoride sorption over the calcite surface may ascribe the decrease of growth rates. Dissolution experiments were conducted at pH= 7.2 and dissolution rates of calcite were measured from the spreading of rhombohedral etch pits along both [010] and [42] directions. The presence of low concentrations of fluoride (≤1.1 mM) in the undersaturated solutions enhanced the dissolution rate along the [42] direction by 50% in comparison with pure water. The morphology of rhombohedral etch pits changed to hexagonal in the presence of fluoride in the undersaturated solutions. The AFM dissolution experiments suggested that the fluoride ions adsorbed onto the calcite surface. Further increase of fluoride concentrations (up to 1.6 mM) resulted in the decrease of the calcite dissolution rate by 60% in both [010] and [42] directions. Reference: Okumura, M, Kitano, Y

  20. Calcite formation in soft coral sclerites is determined by a single reactive extracellular protein.

    Science.gov (United States)

    Rahman, M Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-09-01

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called "calcite and aragonite seas." Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that -OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature. PMID:21768106

  1. Growth rate controlled barium partitioning in calcite and aragonite

    Science.gov (United States)

    Goetschl, Katja Elisabeth; Mavromatis, Vasileios; Baldermann, Andre; Purgstaller, Bettina; Dietzel, Martin

    2016-04-01

    The barium (Ba) content and the Ba/Ca molar ratios in biogenic and abiotic carbonates have been widely used from the scientific community as a geochemical proxy especially in marine and early diagenetic settings. The Ba content of carbonate minerals has been earlier associated to changes in oceanic circulation that may have been caused by upwelling, changes in weathering regimes and river-runoff as well as melt water discharge. The physicochemical controls of Ba ion incorporation in the two most abundant CaCO3 polymorphs found in Earth's surface environments, i.e. calcite and aragonite, have adequately been studied only for calcite. These earlier studies (i.e. [1]) suggest that at increasing growth rate, Ba partitioning in calcite is increasing as well. In contrast, to date the effect of growth rate on the partitioning of Ba in aragonite remains questionable, despite the fact that this mineral phase is the predominant carbonate-forming polymorph in shallow marine environments. To shed light on the mechanisms controlling Ba ion uptake in carbonates in this study we performed steady-state Ba co-precipitation experiments with calcite and aragonite at 25°C. The obtained results for the partitioning of Ba in calcite are in good agreement with those reported earlier by [1], whereas those for aragonite indicate a reduction of Ba partitioning at elevated aragonite growth rates, with the partitioning coefficient value between solid and fluid to be approaching the unity. This finding is good agreement with the formation of a solid solution in the aragonite-witherite system, owing to the isostructural crystallography of the two mineral phases. Moreover, our data set provides new insights that are required for reconstructing the evolution of the Ba content of pristine marine versus diagenetically altered carbonate minerals commonly occurring in marine subfloor settings, as the thermodynamically less stable aragonite will transform to calcite enriched in Ba, whilst affecting

  2. Interaction of alcohols with the calcite surface

    DEFF Research Database (Denmark)

    Bovet, Nicolas Emile; Yang, Mingjun; Javadi, Meshkat Sadat;

    2015-01-01

    A clearer understanding of calcite interactions with organic molecules would contribute to a range of fields including harnessing the secrets of biomineralisation where organisms produce hard parts, increasing oil production from spent reservoirs, remediating contaminated soils and drinking water...... aquifers and improving manufacturing methods for industrial products such as pigments, soft abrasives, building materials and optical devices. Biomineralisation by some species of blue green algae produces beautifully elaborate platelets of calcite where the individual crystals are of nanometer scale...

  3. Microbially Induced Calcite Precipitation Employing Environmental Isolates

    OpenAIRE

    Gunjo Kim; Heejung Youn

    2016-01-01

    In this study, five microbes were employed to precipitate calcite in cohesionless soils. Four microbes were selected from calcite-precipitating microbes isolated from calcareous sand and limestone cave soils, with Sporosarcina pasteurii ATCC 11859 (standard strain) used as a control. Urease activities of the four microbes were higher than that of S. pasteurii. The microbes and urea–CaCl2 medium were injected at least four times into cohesionless soils of two different relative densities (60% ...

  4. Isotopic tracer evidence for the amorphous calcium carbonate to calcite transformation by dissolution-reprecipitation

    Science.gov (United States)

    Giuffre, Anthony J.; Gagnon, Alexander C.; De Yoreo, James J.; Dove, Patricia M.

    2015-09-01

    Observations that some biogenic and sedimentary calcites grow from amorphous calcium carbonate (ACC) raise the question of how this mineralization process influences composition. However, the detailed pathway and geochemical consequences of the ACC to calcite transformation are not well constrained. This experimental study investigated the formation of calcite from ACC by using magnesium and calcium stable isotope labeling to directly probe the transformation pathway and controls on composition. Four processes were considered: dissolution-reprecipitation, solid state transformation, and combinations of these end-members. To distinguish between these scenarios, ACC was synthesized from natural isotope abundance solutions and subsequently transferred to spiked solutions that were enriched in 43Ca and 25Mg for the transformation to calcite. Isotope measurements by NanoSIMS determined the 43Ca/40Ca, and 25Mg/24Mg ratios of the resulting calcite crystals. Analysis of the data shows the transformation is best explained by a dissolution-reprecipitation process. We find that when a small amount of ACC is transferred, the isotopic signals in the resulting calcite are largely replaced by the composition of the surrounding spiked solution. When larger amounts of ACC are transferred, calcite compositions reflect a mixture between the ACC and initial solution end-member. Comparisons of the measurements to the predictions of a simple mixing model indicate that calcite compositions (1) are sensitive to relative amounts of ACC and the surrounding solution reservoir and (2) are primarily governed by the conditions at the time of ACC transformation rather than the initial ACC formation. Shifts in calcite composition over the duration of the transformation period reflect the progressive evolution of the local solution conditions. This dependence indicates the extent to which there is water available would change the end point composition on the mixing line. While these findings have

  5. Influence of a hyper-alkaline solution on six different bentonites with potential use as buffer barriers for radioactive waste confinement

    International Nuclear Information System (INIS)

    The cementitious material in a nuclear waste repository will act as a source of alkaline fluids modifying the mineralogy, pH and physico-chemical properties of the bentonite barrier. A series of reactivity experiments were proposed to determine and compare the response of MX-80 and other five types of bentonite with potential use as buffer barriers. These materials are the Ca,Na-dominant FEBEX bentonite (considered as the reference buffer material in the Spanish concept of radioactive waste confinement), an homogenized in magnesium FEBEX sample, the Na-activated Bentonil C2 commercial bentonite, a saponite from the Madrid basin designated 'saponite from el Cerro del Aguila', and a montmorillonite- rich Na-bentonite from Chile. This study proves that the use of bentonite with saponitic character could be an alternative to the commonly accepted di-octahedral types of bentonite due to their mineralogical and physico-chemical stability under the alkaline cement influence at long term. The completion of these experiments of interaction between OPC (Ordinary Portland Cement) pore water and different types of bentonite helps to determine possible reaction paths in the early stage of cement leaching at the concrete - bentonite interface. (authors)

  6. Towards a Mechanism-Based Understanding of Vital Effects: Biomolecules Influence Mg/Ca in Calcite

    Science.gov (United States)

    Stephenson, A. E.; Nelson, E. J.; Wu, K. J.; de Yoreo, J. J.; Dove, P. M.

    2006-12-01

    Recent findings from our group suggest that the chemistry of biomolecules present at sites of mineral formation have a strong influence on the structure of water near calcite surfaces (Elhadj et al., CGD, 2006) and exercise predictable controls on the rate of calcite growth (Elhadj et al., submitted). Observing the extent to which biomolecules can mediate growth processes leads us to hypothesize that they also have measurable influence over impurity (Mg, Sr) contents. If true, this could be a significant contributor to the widely documented 'vital effects' that complicate interpretations of paleoenvironments, largely based on chemical signatures found in the skeletal remains of organisms. We use in situ AFM to measure the growth rate of calcite at the nanoscale under controlled solution compositions and at characterized chemical driving force. The relationship between the presence of carboxyl- rich peptides in solution during growth and the magnesium content in the resulting calcite was quantified using time-of-flight SIMS. This new work with tof-SIMS has validated previous compositional maps of Mg distributions collected by electron microprobe, and has yielded new insights into controls on impurity content. We are using similar methods to also determine factors that influence impurity contents of calcites grown in solutions at seawater ionic strength.

  7. Calcite growth-rate inhibition by fulvic acids isolated from Big Soda Lake, Nevada, USA, The Suwannee River, Georgia, USA and by polycarboxylic acids

    Science.gov (United States)

    Reddy, Michael M.; Leenheer, Jerry

    2011-01-01

    Calcite crystallization rates are characterized using a constant solution composition at 25°C, pH=8.5, and calcite supersaturation (Ω) of 4.5 in the absence and presence of fulvic acids isolated from Big Soda Lake, Nevada (BSLFA), and a fulvic acid from the Suwannee River, Georgia (SRFA). Rates are also measured in the presence and absence of low-molar mass, aliphatic-alicyclic polycarboxylic acids (PCA). BSLFA inhibits calcite crystal-growth rates with increasing BSLFA concentration, suggesting that BSLFA adsorbs at growth sites on the calcite crystal surface. Calcite growth morphology in the presence of BSLFA differed from growth in its absence, supporting an adsorption mechanism of calcite-growth inhibition by BSLFA. Calcite growth-rate inhibition by BSLFA is consistent with a model indicating that polycarboxylic acid molecules present in BSLFA adsorb at growth sites on the calcite crystal surface. In contrast to published results for an unfractionated SRFA, there is dramatic calcite growth inhibition (at a concentration of 1 mg/L) by a SRFA fraction eluted by pH 5 solution from XAD-8 resin, indicating that calcite growth-rate inhibition is related to specific SRFA component fractions. A cyclic PCA, 1, 2, 3, 4, 5, 6-cyclohexane hexacarboxylic acid (CHXHCA) is a strong calcite growth-rate inhibitor at concentrations less than 0.1 mg/L. Two other cyclic PCAs, 1, 1 cyclopentanedicarboxylic acid (CPDCA) and 1, 1 cyclobutanedicarboxylic acid (CBDCA) with the carboxylic acid groups attached to the same ring carbon atom, have no effect on calcite growth rates up to concentrations of 10 mg/L. Organic matter ad-sorbed from the air onto the seed crystals has no effect on the measured calcite crystal-growth rates.

  8. Calcite Biohybrids as Microenvironment for Stem Cells

    Directory of Open Access Journals (Sweden)

    Razi Vago

    2012-04-01

    Full Text Available A new type of composite 3D biomaterial that provides extracellular cues that govern the differentiation processes of mesenchymal stem cells (MSCs has been developed. In the present study, we evaluated the chondrogenecity of a biohybrid composed of a calcium carbonate scaffold in its calcite polymorph and hyaluronic acid (HA. The source of the calcite scaffolding is an exoskeleton of a sea barnacle Tetraclita rifotincta (T. rifotincta, Pilsbry (1916. The combination of a calcium carbonate-based bioactive scaffold with a natural polymeric hydrogel is designed to mimic the organic-mineral composite of developing bone by providing a fine-tuned microenvironment. The results indicate that the calcite-HA interface creates a suitable microenvironment for the chondrogenic differentiation of MSCs, and therefore, the biohybrid may provide a tool for tissue-engineered cartilage.

  9. Growing spherulitic calcite grains in saline, hyperalkaline lakes: experimental evaluation of the effects of Mg-clays and organic acids

    Science.gov (United States)

    Mercedes-Martín, R.; Rogerson, M. R.; Brasier, A. T.; Vonhof, H. B.; Prior, T. J.; Fellows, S. M.; Reijmer, J. J. G.; Billing, I.; Pedley, H. M.

    2016-04-01

    The origin of spherical-radial calcite bodies - spherulites - in sublacustrine, hyperalkaline and saline systems is unclear, and therefore their palaeoenvironmental significance as allochems is disputed. Here, we experimentally investigate two hypotheses concerning the origin of spherulites. The first is that spherulites precipitate from solutions super-saturated with respect to magnesium-silicate clays, such as stevensite. The second is that spherulite precipitation happens in the presence of dissolved, organic acid molecules. In both cases, experiments were performed under sterile conditions using large batches of a synthetic and cell-free solution replicating waters found in hyperalkaline, saline lakes (such as Mono Lake, California). Our experimental results show that a highly alkaline and highly saline solution supersaturated with respect to calcite (control solution) will precipitate euhedral to subhedral rhombic and trigonal bladed calcite crystals. The same solution supersaturated with respect to stevensite precipitates sheet-like stevensite crystals rather than a gel, and calcite precipitation is reduced by ~ 50% compared to the control solution, producing a mixture of patchy prismatic subhedral to euhedral, and minor needle-like, calcite crystals. Enhanced magnesium concentration in solution is the likely the cause of decreased volumes of calcite precipitation, as this raised equilibrium ion activity ratio in the solution. On the other hand, when alginic acid was present then the result was widespread development of micron-size calcium carbonate spherulite bodies. With further growth time, but falling supersaturation, these spherules fused into botryoidal-topped crusts made of micron-size fibro-radial calcite crystals. We conclude that the simplest tested mechanism to deposit significant spherical-radial calcite bodies is to begin with a strongly supersaturated solution that contains specific but environmentally-common organic acids. Furthermore, we found

  10. Adsorption and co-precipitation of metals and radionuclides at the calcite-water interface: spectroscopic observations

    International Nuclear Information System (INIS)

    Rapid kinetics of interfacial processes and moderate solubilities strongly coupled with solution properties allow for multiple, complex sorption mechanisms of metals and radionuclides at the surfaces of carbonate minerals. Calcite is the most abundant of the carbonate minerals and forms readily in a wide range of near-surface environments. For near-neutral and basic pH conditions, which are typical of many calcite-containing systems, the presence of significant amounts of dissolved carbonate allows competition between solution and surface-bound carbonate species for dissolved metals. Metal adsorption may dominate at low metal concentrations but overlaps with or gives way to precipitation and/or co-precipitation at higher concentrations. The presence of multiple surface sites and distinct preferences for uptake results in heterogeneous sorption and co-precipitation for many metals and radionuclides of environmental significance. We briefly examine results from in situ spectroscopic characterization of uptake of selected metals in calcite pre-equilibrated suspensions and in calcite-supersaturated systems. As examples, Pb(II) and Zn(II) both show a high affinity for binding at the calcite surface and both readily co-precipitate to form calcite solid solutions. At low metal concentrations in calcite-saturated systems, EXAFS spectroscopy shows that Zn(II) and Pb(II) adsorb as inner-sphere surface complexes at the calcite-water interface. Observed coordination geometries differ from the octahedral coordination of Zn or Pb substituting in a Ca site in the calcite structure. Binding at steps and/or kink sites is favored over terrace sites. At higher metal concentrations, precipitation and adsorption both occur, with the precipitate phase depending on solution conditions. In calcite-supersaturated systems, Zn shows a strong preference for uptake at distinct surface sites in steps on the common growth face of calcite, similar to the preferences observed for Sr and Ba. This

  11. Uranium immobilization by sulfate-reducing biofilms grown on hematite, dolomite, and calcite

    International Nuclear Information System (INIS)

    Biofilms of sulfate-reducing bacteria Desulfovibrio desulfuricans G20 were used to reduce dissolved U(VI)and subsequently immobilize U(IV) in the presence of uranium-complexing carbonates. The biofilms were grown in three identically operated fixed bed reactors, filled with three types of minerals: one noncarbonate-bearing mineral(hematite) and two carbonate-bearing minerals (calcite and dolomite). The source of carbonates in the reactors filled with calcite and dolomite were the minerals, while in the reactor filled with hematite it was a 10 mM carbonate buffer, pH 7.2, which we added to the growth medium. Our five-month study demonstrated that the sulfate-reducing biofilms grown in all reactors were able to immobilize/reduce uranium efficiently, despite the presence of uranium-complexing carbonates

  12. Buffer erosion in dilute groundwater

    International Nuclear Information System (INIS)

    One scenario of interest for repository safety assessment involves the loss of bentonite buffer material in contact with dilute groundwater flowing through a transmissive fracture interface. In order to examine the extrusion/erosion behavior of bentonite buffer material under such circumstances, a series of experiments were performed in a flow-through, 1 mm aperture, artificial fracture system. These experiments covered a range of solution chemistry (salt concentration and composition), material composition (sodium montmorillonite and admixtures with calcium montmorillonite), and flow velocity conditions. No erosion was observed for sodium montmorillonite against solution compositions from 0.5 g/L to 10 g/L NaCl. No erosion was observed for 50/50 calcium/sodium montmorillonite against 0.5 g/L NaCl. Erosion was observed for both sodium montmorillonite and 50/50 calcium/sodium montmorillonite against solution compositions ≤ 0.25 g/L NaCl. The calculated erosion rates for the tests with the highest levels of measured erosion, i.e., the tests run under the most dilute conditions (ionic strength (IS) < ∼1 mM), were well-correlated to flow velocity, whereas the calculated erosion rates for the tests with lower levels of measured erosion, i.e., the tests run under somewhat less dilute conditions (∼1 mM < IS < ∼4 mM), were not similarly correlated indicating that material and solution composition can significantly affect erosion rates. In every experiment, both erosive and non-erosive, emplaced buffer material extruded into the fracture and was observed to be impermeable to water flowing in the fracture effectively forming an extended diffusive barrier around the intersecting fracture/buffer interface. Additionally, a model which was developed previously to predict the rate of erosion of bentonite buffer material in low ionic strength water in rock fracture environments was applied to three different cases: sodium montmorillonite expansion in a vertical tube, a

  13. The Effect of the Oxygen Scavenging System on the pH of Buffered Sample Solutions: in the Context of Single-molecule Fluorescence Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung Eun; Lee, Il Buem; Hong, Seok Cheol [Korea University, Seoul (Korea, Republic of)

    2012-03-15

    In single-molecule fluorescence experiment, the oxygen scavenging system is indispensable for avoiding photo-bleaching of fluorescent dyes. Here we report that the gloxy-based oxygen scavenging system commonly used in single molecule fluorescence experiments can disturb the solution pH considerably. To track in situ pH change, we utilized the pH-sensitive conformational transition of i-motif and examined the transition with ensemble and single-molecule FRET measurements. Based on our results, we also suggested several practical remedies for the stability of the solution pH

  14. The Effect of the Oxygen Scavenging System on the pH of Buffered Sample Solutions: in the Context of Single-molecule Fluorescence Measurements

    International Nuclear Information System (INIS)

    In single-molecule fluorescence experiment, the oxygen scavenging system is indispensable for avoiding photo-bleaching of fluorescent dyes. Here we report that the gloxy-based oxygen scavenging system commonly used in single molecule fluorescence experiments can disturb the solution pH considerably. To track in situ pH change, we utilized the pH-sensitive conformational transition of i-motif and examined the transition with ensemble and single-molecule FRET measurements. Based on our results, we also suggested several practical remedies for the stability of the solution pH

  15. The passive oxide films growth on 316L stainless steel in borate buffer solution measured by real-time spectroscopic ellipsometry

    International Nuclear Information System (INIS)

    Highlights: • The optical properties of passive oxide films on 316L stainless steel were studied. • The thickness of the oxide films (1.5–2.6 nm) increased linearly with the potentials. • The growth of passive film followed high electric field ion conduction model. • Selective solubility of oxide induced compositional change of passive film. - Abstract: Passive film growth on 316L stainless steel was investigated in borate buffer electrolyte (pH = 9.1) by real-time spectroscopic ellipsometry (SE) and the composition was estimated by X-ray photoelectron spectroscopy (XPS). Anodic passivation of 316L SS was carried out in the potential range from 0 VSCE to 0.9 VSCE, after potentiostatic polarization for 1800s, the current density decayed from 10−2 A cm−2 to 10−6 A cm−2. The passive film thickness was simulated from Frenel and Drude reflection equations, the average complex refractive index was assumed to be N = 2.3 − j0.445. The estimated thickness increased linearly with potential from 1.5 nm at 0 V to 2.6 nm at 0.8 V. The growth of passive film followed high electric field ion conduction model. The passive film mainly contained the oxide/hydroxide of iron and chromium. The selective solubility of oxide in passive film explained the change of iron and chromium content at different potentials. Few nickel and molybdenum also contributed to the passive film with a constant content

  16. The passive oxide films growth on 316L stainless steel in borate buffer solution measured by real-time spectroscopic ellipsometry

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Haisong; Wang, Lu; Sun, Dongbai [National Center for Materials Service Safety (NCMS), University of Science and Technology Beijing, Beijing 100083 (China); Yu, Hongying, E-mail: hyyu@ustb.edu.cn [Institute of Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083 (China)

    2015-10-01

    Highlights: • The optical properties of passive oxide films on 316L stainless steel were studied. • The thickness of the oxide films (1.5–2.6 nm) increased linearly with the potentials. • The growth of passive film followed high electric field ion conduction model. • Selective solubility of oxide induced compositional change of passive film. - Abstract: Passive film growth on 316L stainless steel was investigated in borate buffer electrolyte (pH = 9.1) by real-time spectroscopic ellipsometry (SE) and the composition was estimated by X-ray photoelectron spectroscopy (XPS). Anodic passivation of 316L SS was carried out in the potential range from 0 V{sub SCE} to 0.9 V{sub SCE}, after potentiostatic polarization for 1800s, the current density decayed from 10{sup −2} A cm{sup −2} to 10{sup −6} A cm{sup −2}. The passive film thickness was simulated from Frenel and Drude reflection equations, the average complex refractive index was assumed to be N = 2.3 − j0.445. The estimated thickness increased linearly with potential from 1.5 nm at 0 V to 2.6 nm at 0.8 V. The growth of passive film followed high electric field ion conduction model. The passive film mainly contained the oxide/hydroxide of iron and chromium. The selective solubility of oxide in passive film explained the change of iron and chromium content at different potentials. Few nickel and molybdenum also contributed to the passive film with a constant content.

  17. Heterogeneous growth of cadmium and cobalt carbonate phases at the (101¯4) calcite surface

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Man; Ilton, Eugene S.; Engelhard, Mark H.; Qafoku, Odeta; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien N.

    2015-03-01

    The ability of surface precipitates to form heteroepitaxially is an important factor that controls the extent of heterogeneous growth. In this work, the growth of cadmium and cobalt carbonate phases on (10-14) calcite surfaces is compared for a range of initial saturation states with respect to otavite (CdCO3) and sphaerocobaltite (CoCO3), two isostructural metal carbonates that exhibit different lattice misfits with respect to calcite. Calcite single crystals were reacted in static conditions for 16 hours with CdCl2 and CoCl2 aqueous solutions with initial concentrations 0.3 ≤ [Cd2+]0 ≤ 100 μM and 25 ≤ [Co2+]0 ≤ 200 μM. The reacted crystals were imaged in situ with atomic force microscopy (AFM) and analyzed ex situ with X-ray photoelectron spectroscopy (XPS). AFM images of Cd-reacted crystals showed the formation of large islands elongated along the direction, clear evidence of heteroepitaxial growth, whereas surface precipitates on Co-reacted crystals were small round islands. Deformation of calcite etch pits in both cases indicated the incorporation of Cd and Co at step edges. XPS analysis pointed to the formation of a Cd-rich (Ca,Cd)CO3 solid solution coating atop the calcite substrate. In contrast, XPS measurements of the Co-reacted crystals provided evidence for the formation of a mixed hydroxy-carbonate cobalt phase. The combined AFM and XPS results suggest that the lattice misfit between CoCO3 and CaCO3 ( 15% based on surface areas) is too large to allow for heteroepitaxial growth of a pure cobalt carbonate phase on calcite surfaces in aqueous solutions and at ambient conditions. The use of the satellite structure of the Co 2p3/2 photoelectron line as a tool for determining the nature of cobalt surface precipitates is also discussed.

  18. Binding of ethanol on calcite: the role of the OH bond and its relevance to biomineralization

    DEFF Research Database (Denmark)

    Sand, K K; Yang, M; Makovicky, E; Cooke, David; Hassenkam, T; Bechgaard, K; Stipp, S L S

    2010-01-01

    The interaction of OH-containing compounds with calcite, CaCO(3), such as is required for the processes that control biomineralization, has been investigated in a low-water solution. We used ethanol (EtOH) as a simple, model, OH-containing organic compound, and observed the strength of its adsorp...

  19. UV-ozone-treated MoO3 as the hole-collecting buffer layer for high-efficiency solution-processed SQ:PC71BM photovoltaic devices

    International Nuclear Information System (INIS)

    The enhanced performance of a squaraine compound, with 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine as the donor and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as the acceptor, in solution-processed organic photovoltaic devices is obtained by using UV-ozone-treated MoO3 as the hole-collecting buffer layer. The optimized thickness of the MoO3 layer is 8 nm, at which the device shows the best power conversion efficiency (PCE) among all devices, resulting from a balance of optical absorption and charge transport. After being treated by UV-ozone for 10 min, the transmittance of the MoO3 film is almost unchanged. Atomic force microscopy results show that the treated surface morphology is improved. A high PCE of 3.99% under AM 1.5 G illumination (100 mW/cm2) is obtained

  20. Dolomite-magnesian calcite relations at elevated temperatures and CO2 pressures

    Science.gov (United States)

    Graf, D.L.; Goldsmith, J.R.

    1955-01-01

    The equilibrium thermal decomposition curve of dolomite has been determined up to a CO2 pressure of 20,000 lb/in.2, at which pressure dolomite decomposes at 857??C. Equilibrium was approached from both directions, by the breakdown and by the solid-state synthesis of dolomite. At elevated temperatures and pressures, calcites in equilibrium with periclase as well as those in equilibrium with dolomite contain Mg in solid solution. In the former, the Mg content increases with increasing CO2 pressure, and decreases with increasing temperature. In the latter, it is a function of temperature only. The exsolution curve of dolomite and magnesian calcite has been determined between 500?? and 800??C; at 500?? dolomite is in equilibrium with a magnesian calcite containing ~6 mol per cent MgCO2; at 800??, ~22 mol per cent. There appears to be a small but real deviation from the ideal 1 : 1 Ca : Mg ratio of dolomite, in the direction of excess Ca, for material in equilibrium with magnesian calcite at high temperature. The experimental findings indicate that very little Mg is stable in the calcites of sedimentary environments, but that an appreciable amount is stable under higher-temperature metamorphic conditions, if sufficient CO2 pressure is maintained. ?? 1955.

  1. Bioleaching of cobalt and zinc from pyrite ore in relation to calcitic gangue content.

    Science.gov (United States)

    Baldi, F; Bralia, A; Riccobono, F; Sabatini, G

    1991-05-01

    Bioleaching of a pyrite ore containing high concentrations of cobalt (0.1%) and zinc (0.065%) was affected by small amounts of calcitic gangue (from 0.01 to 1.01%). Results from an air-lift percolator and from Erlenmeyer flask experiments show that a small percentage of calcite raises the pH and arrests the growth of the acidophilic bacterium Thiobacillus ferrooxidans. In percolator experiments, when calcite is completely removed by the continuous addition of small quantities of acid, and the pH of the liquor becomes acid, the micro-organism begins to grow and to bio-oxidize the pyrite ore. The growth of T. ferrooxidans shows different lag phase spans (from 13 to 190 days) depending on carbonate dissolution. The metals Fe, Zn and Co are released into the leaching solution together at different rates after a lag-time which depends on calcite concentrations in pyrite gangue. Metal ratios in the mineral bulk are different from those in the liquor, Zn dissolving 5 times more readily than Co. Bioleaching rates for metal removal from pyrite are higher in percolator (for Fe, from 5 to 15 mg/l/h) than in flask experiments (from 0.5 to 2 mg/l/h), but the lag phases are shorter (from 2 to 65 days). The differences between the two systems are related to calcite dissolution and gypsum precipitation. PMID:24425016

  2. 黄芩苷在不同pH值缓冲液中理化常数的测定%Physicochemical properties of baicalin in different pH phosphate buffer solutions

    Institute of Scientific and Technical Information of China (English)

    何琳; 丁沐淦; 卢秀霞; 李志棠; 袁飞; 龙晓英

    2012-01-01

    目的 考察黄芩苷在不同pH值中的平衡溶解度与表观油水分配系数,为制剂研究奠定基础.方法 采用摇瓶-紫外分光光度法测定温度为25和37 ℃时,黄芩苷在不同pH值磷酸盐缓冲溶液中的平衡溶解度及在正辛醇/缓冲液体系中的表观油水分配系数.结果 25 ℃时,黄芩苷在pH=2.0,3.0,4.0,5.0,6.0,6.8,7.4,8.0和9.0缓冲液中的平衡溶解度分别为0.032,0.034,0.119,0.873,3.329,12.96,11.49,4.605和11.87 mg·mL-1,相应条件下表观油水分配系数(P)值分别为0.363,0.244,0.292,0.137,0.057,0.046,0.036,0.028和0.029.37 ℃时,黄芩苷在pH=2.0,3.0,4.0,5.0,6.0,6.8,7.4,8.0和9.0缓冲液中的平衡溶解度分别为0.028,0.048,0.095,0.950,4.881,14.15,26.65,14.48和17.89 mg·mL-1,相应条件下表观油水分配系数(P)值分别为0.234,0.224,0.365,0.103,0.074,0.049,0.034,0.034和0.035.结论 黄芩苷的平衡溶解度在酸性及中性条件下受温度影响很小,在碱性条件下随着温度升高而增加;黄芩苷在酸性条件下的P值比在碱性条件下大,Pmax=0.363(T=25 ℃,pH=2),Pmax=0.365(T=37 ℃,pH=4),随着碱性的增加P值变化不明显,且温度对黄芩苷的P值几乎无影响.%Objective To determine the equilibrium solubility of baicalin in different pH phosphate buffer solutions ,to determine its apparent partition coefficient for the ra-octanol/buffer solution systems in different pH value ,and to lay the foundation for further pharmaceutical research .Method A shake flask-ultraviolet spectrophotometry method was applied to measure the equilibrium solubility and partition coefficient of baicalin with temperature of 25 and 37 ℃ .Result At 25 °C ,the equilibrium solubility of baicalin were 0 .032 ,0 .034,0 .119 ,0 .873 ,3 .329 ,12 .96 ,11 .49 ,4 .605 and 11.87 mg · mL-1 in buffer solutions with pH values of 2 .0 ,3 .0 , 4 .0 ,5 .0 ,6 .0 ,6 .8 ,7 .4,8 .0 and 9 .0 respectively .The oil/water partition coefficient (P) of baicalin were 0 .363 ,0 .244,0 .292 , 0

  3. Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

    Science.gov (United States)

    Reddy, Michael M.

    2012-01-01

    Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10−4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10−4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

  4. Upscaling Calcite Growth Rates From the Mesoscale to the Macroscale

    Energy Technology Data Exchange (ETDEWEB)

    Bracco, Jacquelyn N [ORNL; Stack, Andrew G [ORNL; Steefel, Carl I [Lawrence Berkeley National Laboratory (LBNL)

    2013-01-01

    Quantitative prediction of mineral reaction rates in the subsurface remains a daunting task partly because a key parameter for macroscopic models, the reactive site density, is poorly constrained. Here we report atomic force microscopy (AFM) measurements on the calcite surface of monomolecular step densities, treated as equivalent to the reactive site density, as a function of aqueous calcium-to-carbonate ratio and saturation index. Data for the obtuse step orientation are combined with existing step velocity measurements to generate a model that predicts overall macroscopic calcite growth rates. The model is quantitatively consistent with several published macroscopic rates under a range of alkaline solution conditions, particularly for two of the most comprehensive data sets without the need for additional fit parameters. The model reproduces peak growth rates and its functional form is simple enough to be incorporated into reactive transport or other macroscopic models designed for predictions in porous media. However, it currently cannot model equilibrium, pH effects, and may overestimate rates at high aqueous calcium-to-carbonate ratios. The discrepancies in rates at high calcium-to-carbonate ratios may be due to differences in pre-treatment, such as exposing the seed material to SI 1.0 to generate/develop growth hillocks, or other factors.

  5. Acceleration of calcite kinetics by abalone nacre proteins

    Energy Technology Data Exchange (ETDEWEB)

    Fu, G; Qiu, S R; Orme, C A; Morse, D E; De Yoreo, J J

    2005-06-09

    The fascinating shapes and hierarchical designs of biomineralized structures have long been an inspiration to materials scientists because of the potential they suggest for biomolecular control over synthesis of crystalline materials. One prevailing view is that mineral-associated macromolecules are responsible for initiating and stabilizing non-equilibrium crystal polymorphs and morphologies through interactions between anionic moieties and cations in solution or at mineral surfaces. Indeed, numerous studies have demonstrated that bio-organic additives can dramatically alter crystal shapes and growth-rates in vitro. However, previous molecular-scale studies revealing mechanisms of growth modification focused on small molecules such as amino acids or peptides and always observed growth inhibition. In contrast, studies using full proteins were non-quantitative and underlying sources of growth modification were ill-defined. Here we investigate interactions between proteins isolated from abalone shell nacre and growing surfaces of calcite. We find that these proteins significantly accelerate the molecular-scale kinetics and, though much larger than atomic steps, alter growth morphology through step-specific interactions that lower their free energies. We propose that these proteins act as surfactants to promote ion attachment at calcite surfaces.

  6. The effect of fluid composition, salinity, and acidity on subcritical crack growth in calcite crystals

    Science.gov (United States)

    Bergsaker, Anne Schad; Røyne, Anja; Ougier-Simonin, Audrey; Aubry, Jérôme; Renard, François

    2016-03-01

    Chemically activated processes of subcritical cracking in calcite control the time-dependent strength of this mineral, which is a major constituent of the Earth's brittle upper crust. Here experimental data on subcritical crack growth are acquired with a double torsion apparatus to characterize the influence of fluid pH (range 5-7.5) and ionic strength and species (Na2SO4, NaCl, MgSO4, and MgCl2) on the propagation of microcracks in calcite single crystals. The effect of different ions on crack healing has also been investigated by decreasing the load on the crack for durations up to 30 min and allowing it to relax and close. All solutions were saturated with CaCO3. The crack velocities reached during the experiments are in the range 10-9-10-2 m/s and cover the range of subcritical to close to dynamic rupture propagation velocities. Results show that for calcite saturated solutions, the energy necessary to fracture calcite is independent of pH. As a consequence, the effects of fluid salinity, measured through its ionic strength, or the variation of water activity have stronger effects on subcritical crack propagation in calcite than pH. Consequently, when considering the geological sequestration of CO2 into carbonate reservoirs, the decrease of pH within the range of 5-7.5 due to CO2 dissolution into water should not significantly alter the rate of fracturing of calcite. Increase in salinity caused by drying may lead to further reduction in cracking and consequently a decrease in brittle creep. The healing of cracks is found to vary with the specific ions present.

  7. Magnesian calcite sorbent for carbon dioxide capture

    Energy Technology Data Exchange (ETDEWEB)

    Mabry, J.C.; Mondal, K. [Southern Illinois University, Carbondale, IL (United States)

    2011-07-01

    Magnesian calcite with controlled properties was synthesized for the removal of carbon dioxide. The results from characterization, reactivity and CO{sub 2} capture capacity for different synthesis conditions are reported. The magnesian calcite samples (CaCO{sub 3}:MgCO{sub 3}) were synthesized by the coprecipitation of specific amounts of commercially available CaO and MgO by carbon dioxide. Characterization was done with BET, SEM/EDS, particle size analysis and XRD. The capacity was measured using TGA cycles at 800 {sup o}C and compared for different preparation conditions. The effects of CaO, MgO and surfactant loading on the physical properties and carbonation activity were studied to determine the optimal synthesis condition. A long-term carbonation-calcination cycling test was conducted on the optimal sample. It was observed that the sample maintained its capacity to 86% of its original uptake even after 50 cycles.

  8. Recovery of crystallinity in ground calcite

    Energy Technology Data Exchange (ETDEWEB)

    Gammage, R.B.; Glasson, D.R.

    1976-01-01

    Recovery processes by thermal treatment and recrystallization are examined in a calcite specimen severely disordered by ball milling. As the annealing temperature is increased, restructuring in the bulk lags behind the recovery of crystalline perfection in the surface regions. Surface reordering is significant at temperatures as low as 150 to 175/sup 0/C and is rapidly completed at 400/sup 0/C. Annealing at 600/sup 0/C is required for removal of all lattice strain. Before loss of surface can occur by sintering, the temperature needs to exceed 300/sup 0/C. The corresponding temperature for a high-area precipitated calcite is 400/sup 0/C. Recovery of crystallinity is also promoted by light-etching with aqueous acid when extensive whisker growth occurs. Aging over a period of twelve years has led to loss of the ultrareactive characteristics.

  9. Biogenic calcite granules--are brachiopods different?

    Science.gov (United States)

    Pérez-Huerta, Alberto; Dauphin, Yannicke; Cusack, Maggie

    2013-01-01

    Brachiopods are still one of the least studied groups of organisms in terms of biomineralization despite recent studies indicating the presence of highly complex biomineral structures, particularly in taxa with calcitic shells. Here, we analyze the nanostructure of calcite biominerals, fibers and semi-nacre tablets, in brachiopod shells by high-resolution scanning electron microscopy (SEM) and atomic force microscopy (AFM). We demonstrate that basic mechanisms of carbonate biomineralization are not uniform within the phylum, with semi-nacre tablets composed of spherical aggregates with sub-rounded granules and fibers composed of large, triangular or rod-like particles composed of small sub-rounded granules (40-60 nm). Additionally, proteinaceous envelopes surrounding calcite fibers have been shown for the first time to have a dual function: providing a micro-environment in which granules are produced and acting as the organic template for particle orientation as fiber components. In summary, these new findings in brachiopod shells reveal a complex and distinctive style of biomineralization among carbonate-producing organisms. PMID:23026148

  10. Radiation-induced cathodoluminescent signatures in calcite

    International Nuclear Information System (INIS)

    At ambient temperatures, a permanent change due to neutron irradiation has been identified in the luminescent properties of the common mineral calcite. Calcite is one of many ubiquitous minerals that are known to exhibit luminescence under electron bombardment, a process known as cathodoluminescence (CL). The UV–Visible spectra of individual calcite grains were measured with CL spectroscopy before and after neutron irradiation. Exposure to neutrons causes additional crystal lattice defects (beyond those naturally-occurring) that leave a permanent, readily-measurable CL signature in the 515 nm region of the spectrum. Dose response results following irradiation have been measured and a spectroscopic signature is described that increases proportionately to neutron dose. The CL measurements are complicated by a dependence on the orientation relative to direction of excitation. When taken into account, the total dose to the crystal can be estimated, and possibly even the direction of the neutron source can be determined. This signature could potentially be developed into a nuclear forensics tool to help identify locations where special nuclear materials have been stored.

  11. Sorption of cesium on bentonite: The role of calcite

    International Nuclear Information System (INIS)

    Full text: Since bentonite is investigated for its use in Engineered Barriers Systems as backfill material, many studies of their surfaces properties have been performed in the past years to qualify and quantify adsorption on their surfaces, which can be one of the major processes limiting migration of radionuclides away from a disposal site. Nevertheless, most of these studies concerned simplified systems, such as Na-montmorillonite in mono-electrolyte solution. As ion-exchange processes are of importance in water-clays interactions, adsorption of natural major ions has also to be taken into account for natural systems. The aim of this work is (i) to quantify the sorption of the natural major cations on the montmorillonite surface, (ii) to compare the sorption of cesium, in two different systems, a simple one (Na-montmorillonite in NaNO3 0.05 Mol.L-1) and a complex one (natural bentonite in a synthetic natural water) and then (iii) to assess the influence of the natural major ions on this sorption, and to identify the role of the calcite phase present in bentonite. The methodology used consists in several batch experiments, first considering a very simple solution (NaNO3), then using mixtures of two different electrolytes, and lastly using a synthetic natural water. A surface complexation model, describing the surface of clays as a mixture of ion-exchange and complexation surface sites, is used to provide interpretations and quantifications of the sorption processes. Observed results indicate that affinity for the montmorillonite surface is greatest for Ca, then Mg and then K. The sorption of cesium is strongly affected by the presence in solution of Ca, witch can come from the partial dissolution of calcite. (author)

  12. Sorption of cesium on bentonite: The role of calcite

    International Nuclear Information System (INIS)

    Full text: Since bentonite is investigated for its use in Engineered Barriers Systems as backfill material, many studies of their surfaces properties have been performed in the past years to qualify and quantify adsorption on their surfaces, which can be one of the major processes limiting migration of radionuclides away from a disposal site. Nevertheless, most of these studies concerned simplified systems, such as Na-montmorillonite in mono-electrolyte solution. As ion-exchange processes are of importance in water-clays interactions, adsorption of natural major ions has also to be taken into account for natural systems. The aim of this work is (i) to quantify the sorption of the natural major cations on the montmorillonite surface; (ii) to compare the sorption of cesium, in two different systems, a simple one ( Na-montmorillonite in NaNO3 0.05 Mol.L-1) and a complex one (natural bentonite in a synthetic natural water) and then; (iii) to assess the influence of the natural major ions on this sorption, and to identify the role of the calcite phase present in bentonite. The methodology used consists in several batch experiments, first considering a very simple solution (NaNO3), then using mixtures of two different electrolytes, and lastly using a synthetic natural water. A surface complexation model, describing the surface of clays as a mixture of ion-exchange and complexation surface sites, is used to provide interpretations and quantifications of the sorption processes. Observed results indicate that affinity for the montmorillonite surface is greatest for Ca, then Mg and then K. The sorption of cesium is strongly affected by the presence in solution of Ca, witch can come from the partial dissolution of calcite. This study is one part of a work supported by ANDRA on the retention properties of bentonite materials. (author)

  13. Processes affecting the stable isotope composition of calcite during precipitation on the surface of stalagmites: Laboratory experiments investigating the isotope exchange between DIC in the solution layer on top of a speleothem and the CO2 of the cave atmosphere

    Science.gov (United States)

    Dreybrodt, Wolfgang; Hansen, Maximilian; Scholz, Denis

    2016-02-01

    We present a theoretical derivation of the exchange time, τex, needed to establish isotopic equilibrium between atmospheric CO2 in a cave and HCO3- dissolved in a thin water film covering the surface of a speleothem. The result is τex = τredex · [HCO3-]/ (KH · pCO2 cave) , where τredex depends on the depth, a, of the water film and on temperature. [HCO3-] is the concentration of bicarbonate, pCO2 cave the partial pressure of CO2, and KH is Henry's constant. To test the theory we prepared stagnant or flowing thin films of a NaHCO3 solution and exposed them at 20 °C to an CO2 containing atmosphere of pCO2 500, 12,500, or 25,000 ppmV and defined isotope composition. The δ13C and δ18O values of the DIC in the solution were measured as a function of the exposure time. For stagnant films with depths between 0.06 and 0.2 cm the δ13C values exhibit an exponential approach towards isotope equilibrium with the atmospheric CO2 with exchange time, τex. The δ18O values first evolve towards isotopic equilibrium with atmospheric CO2, reach a minimum value and then drift away from the isotopic equilibrium with atmospheric CO2 approaching a steady state caused by isotopic exchange of oxygen with water. The experimental findings are in satisfactory agreement with the theoretical predictions. To further investigate isotope evolution in cave analogue conditions, a water film containing 5 mmol/L of NaHCO3 with a depth of 0.013 cm flowing down an inclined borosilicate glass plate was exposed to an atmosphere with pCO2 = 500 ppmV at a temperature of 20 °C. The δ13C and δ18O values were measured as a function of flow (exposure) time, t. The isotope compositions in the DIC of the water film decrease linear in time by δDIC (t) =δDIC (0) - (δDIC (0) -δDIC (∞)) · t /τex where δDIC (0) is the initial isotope composition of dissolved inorganic carbon (DIC) in the water film and δDIC (∞) its final value. From these data an exchange time τex of ca. 7000 s was obtained

  14. Analysis of diffusive mass transport in a cracked buffer

    International Nuclear Information System (INIS)

    In the disposal vault design for the Canadian Nuclear Fuel Waste Management Program, cylindrical containers of used nuclear fuel would be placed in vertical boreholes in rock and surrounded with a bentonite-based buffer material. The buffer is expected to absorb and/or retard radionuclides leaching from the fuel after the containers fail. There is some evidence, however, that the buffer may be susceptible to cracking. In this report we investigate numerically the consequences of cracking on uranium diffusion through the buffer. The derivation of the mass-transport equations and the numerical solution method are presented for the solubility-limited diffusion of uranium in a cracked buffer system for both swept-away and semi-impermeable boundary conditions at the rock-buffer interface. The results indicate that for swept-away boundary conditions the total uranium flux through the cracked buffer system is, as expected, greater than through the uncracked buffer. The effect of the cracks is strongly dependent on the ratio D/Deff, where D and Deff are the pore-water and the effective buffer diffusion coefficient, respectively. However, although a decrease in Deff enhances the effect of cracks on the total cumulative flux (relative to the uncracked buffer), it also decreases the total cumulative flux through the cracked buffer system (relative to a cracked buffer with a larger Deff value). Finally, for semi-impermeable boundary conditions, the effect of cracks on the total radionuclide flux is relatively small

  15. Towards Optimal Buffer Size in Wi-Fi Networks

    KAUST Repository

    Showail, Ahmad J.

    2016-01-19

    Buffer sizing is an important network configuration parameter that impacts the quality of data traffic. Falling memory cost and the fallacy that ‘more is better’ lead to over provisioning network devices with large buffers. Over-buffering or the so called ‘bufferbloat’ phenomenon creates excessive end-to-end delay in today’s networks. On the other hand, under-buffering results in frequent packet loss and subsequent under-utilization of network resources. The buffer sizing problem has been studied extensively for wired networks. However, there is little work addressing the unique challenges of wireless environment. In this dissertation, we discuss buffer sizing challenges in wireless networks, classify the state-of-the-art solutions, and propose two novel buffer sizing schemes. The first scheme targets buffer sizing in wireless multi-hop networks where the radio spectral resource is shared among a set of con- tending nodes. Hence, it sizes the buffer collectively and distributes it over a set of interfering devices. The second buffer sizing scheme is designed to cope up with recent Wi-Fi enhancements. It adapts the buffer size based on measured link characteristics and network load. Also, it enforces limits on the buffer size to maximize frame aggregation benefits. Both mechanisms are evaluated using simulation as well as testbed implementation over half-duplex and full-duplex wireless networks. Experimental evaluation shows that our proposal reduces latency by an order of magnitude.

  16. Fabrication of organic FETs based on printing techniques and the improvement of FET properties by the insertion of solution-processable buffer layers

    Science.gov (United States)

    Itoh, Eiji; Kanamori, Akira

    2016-04-01

    In this study, we developed multilayer deposition and patterning processes that can be used to fabricate all-printed, organic field-effect transistors (OFETs) on the basis of vacuum-free, solution-processable soft-lithography techniques. We have used regioregular poly(3-hexylthiophene) (P3HT) as a soluble p-type polymer semiconductor and (6,6)-phenyl C61 butyric acid methyl ester (PCBM) as a soluble n-type semiconductor, and cross-linked poly(vinyl phenol) (CL-PVP) as a low-temperature (polymer gate insulator. We have compared the electrical properties of OFETs with multiwalled carbon nanotubes (MWCNTs), silver nanoparticles (NPs), and their composites (or multilayers) as printed source-drain (S-D) electrodes in order to fabricate vacuum-free, all-printed OFETs. The P3HT-OFETs with MWCNT S-D electrodes exhibited higher hole mobility and on/off ratios than the devices with Ag NP S-D electrodes owing to better contact at the MWCNT/P3HT interface. On the other hand, Ag/molybdenum oxide (MoO3) S-D electrodes considerably enhanced the hole injection and caused the reduction in the on/off ratio and the difficulty in turning off the devices. The PCBM-OFETs with MWCNT S-D electrodes also exhibited higher electron mobility that is almost comparable to that of P3HT-OFETs and lower threshold voltage, which was considered to be due to the enhanced electron injection at the electrode interface.

  17. Buffer design 2012

    International Nuclear Information System (INIS)

    Posiva's spent nuclear fuel disposal is based on the KBS-3V concept and on the characteristics of the Olkiluoto site. In this concept single canisters containing spent nuclear fuel surrounded by a bentonite buffer are emplaced in individual vertical boreholes drilled in the floor of deposition tunnels in bedrock at about 420 m depth below ground level. Disk type bentonite blocks are installed at the bottom of the hole and on the top of the disposal canister. Ring type bentonite blocks surround the canisters. This report describes the detailed design of the buffer for a KBS-3V repository. The report presents the design basis, the reference design, and summarises the performance analyses carried out for the design. This report addresses aspects concerning the manufacture, quality control, mechanical strength, chemical resistance, thermal dimensioning, handling of buffer components and material ageing phenomena including the effect of radiation. Interaction of buffer and other engineered barriers are included in the study. The long-term evolution of the repository and its effective drivers are considered if they have an impact on the buffer performance but operational safety aspects are also included because they may affect long-term safety. (orig.)

  18. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, Brian P [Colorado School of Mines, Golden, CO (United States)

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  19. Rare Earth element (REE) incorporation in natural calcite. Upper limits for actinide uptake in a secondary phase

    Energy Technology Data Exchange (ETDEWEB)

    Stipp, S.L.S.; Christensen, J.T.; Waight, T.E. [Geological Inst., Univ. of Copenhagen (Denmark); Lakshtanov, L.Z. [Geological Inst., Univ. of Copenhagen (Denmark); Inst. of Experimental Mineralogy, Russian Academy of Science, Chernogolovka (Russian Federation); Baker, J.A. [School of Earth Sciences, Victoria Univ. of Wellington (New Zealand)

    2006-07-01

    Secondary minerals have the potential to sequester escaped actinides in the event of a radioactive waste repository failure, but currently, data to define their maximum uptake capacity are generally lacking. To estimate a maximum limit for solid solution in calcite, we took advantage of the behavioural similarities of the 4f-orbital lanthanides with some of the 5f-orbital actinides and used rare Earth element (REE) concentration as an analogue. A suite of 65 calcite samples, mostly pure single crystals, was assembled from a range of geological settings, ages and locations and analysed by isotope dilution MC-ICP-MS (multiple-collector inductively-coupled plasma mass spectroscopy). All samples were shown to contain significant lanthanide concentrations. The highest were in calcite formed from hydrothermal solutions and from carbonatite magma. Maximum total mole fraction of REE was 4.72 x 10{sup -4}, which represents one substituted atom for about 2000 Ca sites. In comparison, synthetic calcite, precipitated at growth rates slow enough to insure solid solution formation, incorporated 7.5 x 10{sup -4} mole fraction Eu(III). For performance assessment, we propose that 7.5 mmole substitution/kg calcite should be considered the upper limit for actinide incorporation in secondary calcite. The largest source of uncertainty in this estimate results from extrapolating lanthanide data to actinides. However, the data offer confidence that for waters in the hydrothermal temperature range, such as in the near-field, or at groundwater temperatures, such as in the far-field, if calcite formation is favoured and actinides are present, those with behaviour like the trivalent lanthanides, especially Am{sup 3+} and Cm{sup 3+}, will be incorporated. REE are abundant and widely distributed, and they have remained in calcite for millions of years. Thus, one can be certain that incorporated actinides will also remain immobilised in calcite formed in fractures and pore spaces, as long as

  20. A parallel buffer tree

    DEFF Research Database (Denmark)

    Sitchinava, Nodar; Zeh, Norbert

    2012-01-01

    We present the parallel buffer tree, a parallel external memory (PEM) data structure for batched search problems. This data structure is a non-trivial extension of Arge's sequential buffer tree to a private-cache multiprocessor environment and reduces the number of I/O operations by the number...... of available processor cores compared to its sequential counterpart, thereby taking full advantage of multicore parallelism. The parallel buffer tree is a search tree data structure that supports the batched parallel processing of a sequence of N insertions, deletions, membership queries, and range queries...... in the optimal OhOf(psortN + K/PB) parallel I/O complexity, where K is the size of the output reported in the process and psortN is the parallel I/O complexity of sorting N elements using P processors....

  1. A calcite permeable reactive barrier for the remediation of Fluoride from spent potliner (SPL) contaminated groundwater

    DEFF Research Database (Denmark)

    Turner, B.D.; Binning, Philip John; Sloan, S.W.

    2008-01-01

    The use of calcite (CaCO3) as a substrate for a permeable reactive barrier (PRB) for removing fluoride from contaminated groundwater is proposed and is illustrated by application to groundwater contaminated by spent potliner leachate (SPL), a waste derived from the aluminium smelting process. The...... paper focuses on two issues in the implementation of calcite permeable reactive barriers for remediating fluoride contaminated water: the impact of the groundwater chemical matrix and CO2 addition on fluoride removal. Column tests comparing pure NaF solutions, synthetic SPL solutions, and actual SPL...... leachate indicate that the complex chemical matrix of the SPL leachate can impact fluoride removal significantly. For SPL contaminant mixtures, fluoride removal is initially less than expected from idealized, pure, solutions. However, with time, the effect of other contaminants on fluoride removal...

  2. Fracture calcites at Olkiluoto. Evidence from quaternary infills for palaeohydrogeology

    Energy Technology Data Exchange (ETDEWEB)

    Gehoer, S.; Kaerki, A.; Taikina-aho, O. [Kivitieto Oy (Finland); Karhu, J. [Helsinki Univ. (Finland); Loefman, J. [VTT Processes, Espoo (Finland); Pitkaenen, P. [VTT Building and Transport, Espoo (Finland); Ruotsalainen, P. [TUKES, Helsinki (Finland)

    2002-02-01

    Recently formed secondary minerals, predominantly calcite, occur in varying amounts as fracture infills, and the calcite types, their chemical compositions and isotope ratios reflect the compositions and physicochemical factors of the groundwater system in which they were formed. Fluid inclusions trapped in calcites give direct evidence of trapping temperatures and past salinities and of the chemical compositions of the palaeo fluids. A wide range of mineralogical and geochemical examinations were carried out within the EQUIP project to examine features of this kind. The fracture calcites at the Olkiluoto site are of various origins and represent several textural types. The exact number of calcite-producing events is unknown, but the duration of the period that was appropriate for the precipitation of low temperature calcite is estimated to have exceeded 1000 Ma. Thus the number of genetically related calcite units is assumed to be considerable. This study was focused on the petrogenesis of calcites crystallized in fractures of high water conductivity during the latest stages of geological evolution. The majority of these late stage calcites form physically homogeneous, scaly layers, and in a few cases thin layers composed of idiomorphic crystals. Chemically these are almost stoichiometric calcites (CaCO{sub 3}). The MnO content may exceed 1%, while the amounts of other elements present are minor, although the trace element concentrations, particularly those of large ionic trace elements, can be used as distinguishing features for the recognition of individual precipitates representing different calcite generations. Evidence from fluid inclusions, or more correctly from the absence of these in the late stage calcites, can be interpreted as an indication of slow rates of crystallization under cool conditions. Many chemical variables, e.g. oxygen isotope ratios, demonstrate an equilibrium between the latest calcites and water similar to the present groundwater. Older

  3. Fracture calcites at Olkiluoto. Evidence from quaternary infills for palaeohydrogeology

    International Nuclear Information System (INIS)

    Recently formed secondary minerals, predominantly calcite, occur in varying amounts as fracture infills, and the calcite types, their chemical compositions and isotope ratios reflect the compositions and physicochemical factors of the groundwater system in which they were formed. Fluid inclusions trapped in calcites give direct evidence of trapping temperatures and past salinities and of the chemical compositions of the palaeo fluids. A wide range of mineralogical and geochemical examinations were carried out within the EQUIP project to examine features of this kind. The fracture calcites at the Olkiluoto site are of various origins and represent several textural types. The exact number of calcite-producing events is unknown, but the duration of the period that was appropriate for the precipitation of low temperature calcite is estimated to have exceeded 1000 Ma. Thus the number of genetically related calcite units is assumed to be considerable. This study was focused on the petrogenesis of calcites crystallized in fractures of high water conductivity during the latest stages of geological evolution. The majority of these late stage calcites form physically homogeneous, scaly layers, and in a few cases thin layers composed of idiomorphic crystals. Chemically these are almost stoichiometric calcites (CaCO3). The MnO content may exceed 1%, while the amounts of other elements present are minor, although the trace element concentrations, particularly those of large ionic trace elements, can be used as distinguishing features for the recognition of individual precipitates representing different calcite generations. Evidence from fluid inclusions, or more correctly from the absence of these in the late stage calcites, can be interpreted as an indication of slow rates of crystallization under cool conditions. Many chemical variables, e.g. oxygen isotope ratios, demonstrate an equilibrium between the latest calcites and water similar to the present groundwater. Older

  4. A simple reactive-transport model of calcite precipitation in soils and other porous media

    Science.gov (United States)

    Kirk, G. J. D.; Versteegen, A.; Ritz, K.; Milodowski, A. E.

    2015-09-01

    Calcite formation in soils and other porous media generally occurs around a localised source of reactants, such as a plant root or soil macro-pore, and the rate depends on the transport of reactants to and from the precipitation zone as well as the kinetics of the precipitation reaction itself. However most studies are made in well mixed systems, in which such transport limitations are largely removed. We developed a mathematical model of calcite precipitation near a source of base in soil, allowing for transport limitations and precipitation kinetics. We tested the model against experimentally-determined rates of calcite precipitation and reactant concentration-distance profiles in columns of soil in contact with a layer of HCO3--saturated exchange resin. The model parameter values were determined independently. The agreement between observed and predicted results was satisfactory given experimental limitations, indicating that the model correctly describes the important processes. A sensitivity analysis showed that all model parameters are important, indicating a simpler treatment would be inadequate. The sensitivity analysis showed that the amount of calcite precipitated and the spread of the precipitation zone were sensitive to parameters controlling rates of reactant transport (soil moisture content, salt content, pH, pH buffer power and CO2 pressure), as well as to the precipitation rate constant. We illustrate practical applications of the model with two examples: pH changes and CaCO3 precipitation in the soil around a plant root, and around a soil macro-pore containing a source of base such as urea.

  5. Identification of biogenetic calcite and aragonite using SEM

    OpenAIRE

    Bermanec, Vladimir; Posilović, Hrvoje; Žigovečki Gobac, Željka

    2009-01-01

    Identification of calcite and aragonite is very important for studying different fossil or recent biomineralized skeletons. Problem occurs when scanning electron microscopy is used for studying calcite and aragonite present in the same part of skeleton. The same chemical composition of these two minerals produces the same contrast on SEM images. There are three possible ways how to distinguish calcite and aragonite in such mixture. (1) It is possible to recognize the crystal habits of the...

  6. Origin of calcite in the glacigenic Virttaankangas complex

    Directory of Open Access Journals (Sweden)

    Nina M. Kortelainen

    2007-01-01

    Full Text Available Groundwaters of the glacigenic Virttaankangas complex in southern Finland are characterized by high pH values ranging up to 9.5. These values are significantly higher than those observed in silicate-rich shallow groundwater formations in crystalline bedrock areas. TheVirttaankangas sediments were discovered to contain small amounts of fine grained, dispersed calcite, which has a high tendency to increase the pH of local groundwaters. The primary goal of this study was to determine the mode of occurrence of calcite and to identifyits sources. The mineralogy of the glacigenic Virttaankangas complex was studied using material from 21 sediment drill cores. Fine-grained calcite is present in trace amounts (<< 1.4 % in the glaciofluvial and glaciolacustrine depositional units of the Virttaankangas complex. The topmost littoral sands were practically devoid of calcite. The isotope records of carbon and oxygen, the angular morphology of the grains and the uniform dispersion of calcite in the complex suggest a clastic origin for calcite, with no evidence for in-situ precipitation. In order to constrain the source of calcite, the isotopic composition of carbon and oxygen in five calcite samples was compared to the isotopic data from five carbonate rock erratics and eight crystalline bedrock samples from the region. Based on carbon and oxygen isotope ratios and chemical compositions, the dispersed calcite grains of the Virttaankangas complex appear to have been derived from the Mesoproterozoic Satakunta Formation, some 30 km NW from the Virttaankangas area. In sandstone, calcite is predominantly present as diagenetic cement in grain interspaces, concretions and interlayers. The source of detrital calcite was unexpected, as prior to this study the Satakunta sandstone hasnot been known to contain calcite.

  7. Evolution of calcite growth morphology in the presence of magnesium: Implications for the dolomite problem

    Science.gov (United States)

    Hong, Mina; Xu, Jie; Teng, Henry H.

    2016-01-01

    The effect of magnesium on calcite growth morphology was known to occur as step rounding in some cases and surface segmentation in others. What remains unknown are the conditions for and the relations between the different effects, suggesting a lack of comprehensive understanding of the fundamental cause. Here we investigated the evolution of spiral hillock morphology on calcite cleavage surfaces in solutions with increasing Ca to Mg ratios and supersaturation levels using in situ atomic force microscopy. We isolated the effects of Mg and saturation by conducting experiments under conditions of constant pH, ionic strength, and Ca2+/CO32-. Our results revealed three types of morphological variations, ranging from step rounding in one direction (type I), to all directions (type II), and finally to a mosaic-like surface segmentation associated with monolayer buckling and step bunching (type III). These results suggest that the effect of magnesium on calcite growth depends upon multiple parameters including the concentration of Mg in solution, the step speed, as well as the extensiveness of Mg for Ca substitution in calcite lattice. We propose that the morphological variation may be understood by a model taken into consideration of (1) the lifespan and flux size of Mg ions at kinks in comparison to step kinetics, and (2) the diffusion and alignment of point defects created by the substitution of Mg for Ca in the crystal lattice. Stress calculations show that the maximum amount of Mg which calcite lattice can sustain before plastic deformation is ∼40%, suggesting that lattice stress due to the mismatch between MgCO3 and CaCO3 is likely the ultimate cause for the difficulty of ambient condition dolomite crystallization.

  8. A Reacidification Model for Acidified Lakes Neutralized With Calcite

    Science.gov (United States)

    Sverdrup, Harald; Warfvinge, Per

    1985-09-01

    In lake liming operations in Sweden, acidified lakes are reclaimed by neutralization with calcite powder. The amount added is intended to neutralize the water column as well as to delay the reacidification. The reacidification of limed lakes is dependent on the dilution of the dissolved calcium carbonate with time and, for a limited period of time, the dissolution of calcite from the lake sediments. Calcite on the lake bottom will, in addition to being covered by sedimentation, become inactivated by precipitates of humus and clay minerals clogging the calcite surfaces. A model has been developed to calculate the reacidification of a limed lake which includes the following mechanisms: (1) the dissolution of calcite and a subsequent neutralization of acid water, (2) owing to the increase inpH value, occurrence of precipitation of humus and dissolved metals onto the calcite surface and inhibition of the dissolution of calcite (3) reversible sorbtion of calcium from the water column by sediments not covered with calcite, and (4) diffusive transport through a boundary bottom layer to the water column. In a first approach the lake was modeled as a continuously stirred tank. The equations were derived from a mass balance and the dissolution kinetics for calcite to describe the long-term development ofpH, alkalinity, and calcium concentration in the lake. The differential equations describing the mechanisms were solved with the help of a computer code. The model accurately describes the reacidification and the mass balances observed in several limed lakes.

  9. Calcite twin morphology : a low-temperature deformation geothermometer

    OpenAIRE

    Ferrill, David A.; Morris, Alan P.; Evans, Mark A; Burkhard, Martin; Groshong Jr., Richard H.; Onasch, Charles M.

    2005-01-01

    Twinning of the e-plane is the dominant crystal–plastic deformation mechanism in calcite deformed below about 400 °C. Calcite in a twin domain has a different crystallographic orientation from the host calcite grain. So-called thin twins appear as thin black lines when viewed parallel to the twin plane at 200–320× magnification under a petrographic microscope. Thick twins viewed in the same way have a microscopically visible width of twinned material between black lines. Calcite e-twin width ...

  10. Synthesis and characterization of spider silk calcite composite

    Directory of Open Access Journals (Sweden)

    Svetlana Dmitrović

    2016-03-01

    Full Text Available Spider silk poses excellent mechanical properties, tenacity and elasticity and it has been used as a template for calcite mineralization to improve load bearing strength of osteoconductive calcite. The samples were obtained by mimicking biomineralization for five days in order to follow formation and growth of calcite on the surface of spider silk. Crystal phase was detected by XRD and FTIR spectroscopy. Microstructure, crystal size and its morphology were studied by means of FESEM. After two days of processing, pure calcite phase was obtained, and a size of the formed crystals increased with prolongation of biomineralization.

  11. Mineralogical sources of the buffer capacity in a granite catchment determined by strontium isotopes

    International Nuclear Information System (INIS)

    The role of different minerals in base cation release and thus the increase of buffering capacity of groundwater against acid deposition is controversially discussed in the literature. The 87Sr/86Sr ratios and base cation concentration were investigated in whole rock leachates, mineral separates, precipitation, soil solution, groundwater and stream water samples in the Lehstenbach catchment (Germany) to identify the weathering sequence of the granite bedrock. Three different approaches were followed in parallel. It was assumed that the contribution of different minerals to base cation supply of the groundwater with increasing weathering intensity would be observed by investigating (1) unweathered rock leachates, deep groundwater and shallow groundwater, (2) groundwater samples from new groundwater wells, reflecting the initial weathering of the drilled bedrock, and groundwater from wells that were drilled in 1988, (3) stream water during baseflow, dominated by deep groundwater, and stream water during high flow, being predominantly shallow groundwater. Whereas the first approach yielded consistent patterns, there was some evidence that groundwater from the new wells initially reflected contamination by the filter gravel rather than cation release in an initial stage of weathering. Time series samples of stream water and groundwater solute concentrations and isotope ratios turned out to reflect varying fractions of soil water and precipitation water at baseflow and high flow conditions rather than varying contributions of different minerals that prevail at different stages of granite weathering. The early phase of weathering was clearly dominated by base cation release from biotite weathering and to a lesser extent by apatite dissolution. Feldspars contributed to base cation release as well, but could not be regarded as endmembers of the mixing diagram. There was no clear evidence for a contribution from calcite. Correspondingly, base cation input by atmospheric

  12. Calcite surface structure and reactivity: molecular dynamics simulations and macroscopic surface modelling of the calcite-water interface

    OpenAIRE

    Wolthers, M.; Di Tommaso, D.; Du, Z; de Leeuw, N. H.

    2012-01-01

    Calcite–water interactions are important not only in carbon sequestration and the global carbon cycle, but also in contaminant behaviour in calcite-bearing host rock and in many industrial applications. Here we quantify the effect of variations in surface structure on calcite surface reactivity. Firstly, we employ classical Molecular Dynamics simulations of calcite surfaces containing an etch pit and a growth terrace, to show that the local environment in water around structurally different s...

  13. Downscaled tests on buffer behaviour

    International Nuclear Information System (INIS)

    Two types of tests, nicknamed X-Boy (bentonite sample diameter 350 mm, sample height 800 mm) and Transu (sample diameter 269 mm, sample height 800 mm), were performed to investigate the early saturation behavior of the buffer at mock-up scale using distinct point inflows at 0.1 L/min across a range of solution salinity from tap water to 35 g/L. Specifically, swelling pressure development, piping and erosion due to groundwater inflow and the extent of the homogenization process from the initial heterogeneous state (i.e., compacted blocks and either an empty or pellet-filled gap between the blocks and test device wall) were followed. For all test formats a set of consistent observations were made. No significant resistance to inlet water pressure was observed for any of the tests, due to developments occurring within the test cylinders, indicating that flow pathways through the buffer system remained open. Effluent solids concentrations above background levels were observed over the course of all of the tests indicating continuous erosion. Relatively low swelling pressures (both axial and radial) were observed during all of the tests. Non-uniform, radial swelling pressure development and saturation (from post-mortem sampling) were observed for all of the tests. (orig.)

  14. Downscaled tests on buffer behaviour

    Energy Technology Data Exchange (ETDEWEB)

    Pintado, X.; Adesola, F.; Turtiainen, M. [B and Tech Oy, Helsinki (Finland)

    2013-10-15

    Two types of tests, nicknamed X-Boy (bentonite sample diameter 350 mm, sample height 800 mm) and Transu (sample diameter 269 mm, sample height 800 mm), were performed to investigate the early saturation behavior of the buffer at mock-up scale using distinct point inflows at 0.1 L/min across a range of solution salinity from tap water to 35 g/L. Specifically, swelling pressure development, piping and erosion due to groundwater inflow and the extent of the homogenization process from the initial heterogeneous state (i.e., compacted blocks and either an empty or pellet-filled gap between the blocks and test device wall) were followed. For all test formats a set of consistent observations were made. No significant resistance to inlet water pressure was observed for any of the tests, due to developments occurring within the test cylinders, indicating that flow pathways through the buffer system remained open. Effluent solids concentrations above background levels were observed over the course of all of the tests indicating continuous erosion. Relatively low swelling pressures (both axial and radial) were observed during all of the tests. Non-uniform, radial swelling pressure development and saturation (from post-mortem sampling) were observed for all of the tests. (orig.)

  15. Competitive adsorption of arsenate and phosphate onto calcite; experimental results and modeling with CCM and CD-MUSIC

    Science.gov (United States)

    Sø, Helle Ugilt; Postma, Dieke; Jakobsen, Rasmus; Larsen, Flemming

    2012-09-01

    The competitive adsorption of arsenate and phosphate onto calcite was studied in batch experiments using calcite-equilibrated solutions. The solutions had circum-neutral pH (7-8.3) and covered a wide span in the activity of Ca2+ and CO32-. The results show that the adsorption of arsenate onto calcite is strongly reduced by the presence of phosphate, whereas phosphate adsorption is only slightly reduced by arsenate addition. Simultaneous and sequential addition (3 h apart) yields the same reduction in adsorption, underlining the high reversibility of the system. The reduction in adsorption of both arsenate and phosphate is most likely due to competition for the same sorption sites at the calcite surface, considering the similarity in sorption edges, pKa's and geometry of the two anions. The strong reduction in arsenate adsorption by competition with phosphate suggests that adsorption of arsenate onto calcite is of minor importance in most groundwater aquifers, as phosphate is often present at concentration levels sufficient to significantly reduce arsenate adsorption. The CD-MUSIC model for calcite was used successfully to model adsorption of arsenate and phosphate separately. By combining the models for single sorbate systems the competitive adsorption of phosphate and arsenate onto calcite in the binary system could be predicted. This is in contrast to the constant capacitance model (CCM) which under-predicted the competition when combining the models for single sorbate systems. This study clearly shows the importance of performing competitive adsorption studies for validation of multi-component models and for estimating the mobility of an ion in the environment.

  16. BUFFER PROPERTIES OF SOIL MINERALS. PART 1. THEORETICAL ASPECTS

    Directory of Open Access Journals (Sweden)

    Povar Igor

    2013-12-01

    Full Text Available The key quantitative characteristics of the theory of buffer action for polycomponent mono- and two-phase systems have been derived. It is shown, that the buffer properties in relation to the solid phase components are amplified with an increase of solubility due to protolytic or complex formation equilibria in saturated solutions.

  17. BUFFER PROPERTIES OF SOIL MINERALS. PART 1. THEORETICAL ASPECTS

    OpenAIRE

    Povar Igor; Spinu Oxana

    2013-01-01

    The key quantitative characteristics of the theory of buffer action for polycomponent mono- and two-phase systems have been derived. It is shown, that the buffer properties in relation to the solid phase components are amplified with an increase of solubility due to protolytic or complex formation equilibria in saturated solutions.

  18. From nanometer aggregates to micrometer crystals: Insight into the coarsening mechanism of calcite

    OpenAIRE

    Schultz L.N., Dideriksen K., Lakshtanov L., Hakim S.S., Müter D., Haußer F., Bechgaard K. and Stipp S.L.S.

    2013-01-01

    Grain size increases when crystals respond to dynamic equilibrium in a saturated solution. The pathway to coarsening is generally thought to be driven by Ostwald ripening, that is, simultaneous dissolution and reprecipitation, but models to describe Ostwald ripening neglect solid−solid interactions and crystal shapes. Grain coarsening of calcite, CaCO3, is relevant for biomineralization and commercial products and is an important process in diagenesis of ...

  19. Buffer Overflow Detection on Binary Code

    Institute of Scientific and Technical Information of China (English)

    ZHENG Yan-fei; LI Hui; CHEN Ke-fei

    2006-01-01

    Most solutions for detecting buffer overflow are based on source code. But the requirement for source code is not always practical especially for business software. A new approach was presented to detect statically the potential buffer overflow vulnerabilities in the binary code of software. The binary code was translated into assembly code without the lose of the information of string operation functions. The feature code abstract graph was constructed to generate more accurate constraint statements, and analyze the assembly code using the method of integer range constraint. After getting the elementary report on suspicious code where buffer overflows possibly happen, the control flow sensitive analysis using program dependence graph was done to decrease the rate of false positive. A prototype was implemented which demonstrates the feasibility and efficiency of the new approach.

  20. Cryogenic and non-cryogenic pool calcites indicating permafrost and non-permafrost periods: a case study from the Herbstlabyrinth-Advent Cave system (Germany

    Directory of Open Access Journals (Sweden)

    D. K. Richter

    2010-11-01

    Full Text Available Weichselian cryogenic calcites collected in what is referred to as the Rätselhalle of the Herbstlabyrinth-Advent Cave system are structurally classified as rhombohedral crystals and spherulitic aggregates. The carbon and oxygen isotopic composition of these precipitates (δ13C = +0.6 to −7.3‰ δ18O = −6.9 to −18.0‰ corresponds to those of known slowly precipitated cryogenic cave calcites under conditions of isotopic equilibrium between water and ice of Central European caves. The carbon and oxygen isotopic composition varies between different caves which is attributed to the effects of cave air ventilation before the freezing started.

    By petrographic and geochemical comparisons of Weichselian cryogenic calcite with recent to sub-recent precipitates as well as Weichselian non-cryogenic calcites of the same locality, a model for the precipitation of these calcites is proposed. While the recent and sub-recent pool-calcites isotopically match the composition of interglacial speleothems (stalagmites, etc., isotope ratios of Weichselian non-cryogenic pool-calcites reflect cooler conditions. Weichselian cryogenic calcites show a trend towards low δ18O values with higher carbon isotope ratios reflecting slow freezing of the precipitating solution. In essence, the isotope geochemistry of the Weichselian calcites reflects the climate history changing from overall initial permafrost conditions to permafrost-free and subsequently to renewed permafrost conditions. Judging from the data compiled here, the last permafrost stage in the Rätselhalle is followed by a warm period (interstadial and/or Holocene. During this warmer period, the cave ice melted and cryogenic and non-cryogenic Weichselian calcite precipitates were deposited on the cave ground or on fallen blocks, respectively.

  1. Equilibrium constraints on buffer erosion based on the chemistry and chemical evolution of glacial meltwaters

    International Nuclear Information System (INIS)

    Document available in extended abstract form only. Colloidal montmorillonite sols could form if the bentonite buffer in a KBS-3 repository for spent nuclear fuel should expand into a fracture and come into contact with dilute glacial meltwaters that have migrated to repository depths from the surface of a warm-based ice sheet. Transport of the sols away from deposition holes in flowing groundwater could conceivably result in significant erosional mass losses of the buffer, thus compromising one or more safety functions assigned to this key engineered barrier. Equilibrium constraints on sol formation were considered in the present study based on observations characterizing the chemistry of sub-glacial meltwaters and the possible chemical evolution of such solutions as they migrate through repository host rocks at Forsmark. Montmorillonite sols are stable under two general limiting conditions: 1) if the concentrations of divalent cations in the colloidal system are below a threshold 'critical coagulation concentration' (CCC) consistent with DLVO theory and the Shulze-Hardy rule, or 2) if monovalent cations occupy a significant fraction of ion-exchange sites. Regarding the first condition, the CCC for Ca2+, the dominant divalent cation in many Swedish groundwaters, is approximately 1 mM. Regarding the second condition, a limited number of experimental studies indicate that montmorillonite sols become unstable, forming gels, if the equivalent fraction, X, of Ca2+ on exchange sites ≥ 0.9. This behaviour results from the effects of ion-ion correlations, which are not accounted for in DLVO theory and which strongly increase the net attraction between colloidal particles having high surface charge and divalent counterions in the electrical double layer. Mass-action constraints for the reaction Ca2+(solution) + 2Na+(montmorillonite) = 2Na+(solution) + Ca2+(montmorillonite) assuming that 1) exchange sites are occupied predominantly by Na+ and/or Ca2+ and 2) the

  2. Calcite solubility in supercritical CO 2H 2O fluids

    Science.gov (United States)

    Fein, Jeremy B.; Walther, John V.

    1987-06-01

    An extraction-quench apparatus was used to measure calcite solubilities in supercritical CO 2H 2O mixtures. Experiments were conducted at 1 kbar and 2 kbar, between 240°C and 620°C and from XCO 2 = .02 toXCO 2 = .15 in order to determine the solubility behavior as a function of pressure, temperature and CO 2 content. The results indicate that calcite solubilities under these conditions behave similarly to previously investigated calcite solubilities at lower pressures and temperatures (SHARP and Kennedy, 1965). At constant XCO 2, the solubility increases with increasing pressure, but it decreases with increasing temperature. When the temperature and pressure are constant, the calcite solubility rises with increasing XCO 2 to a maximum value at XCO 2 between 0.02 and 0.05. For higher CO 2 contents, up to XCO 2 = .15, the calcite solubility decreases, probably due to the decrease of H 2O activities to values significantly below unity. The solubility behavior can be successfully modeled by making the assumption that Ca ++ is the dominant calcium species and that the carbon-bearing species are CO 2(aq) and HCO -3. Since for these dilute H 2OCO 2 fluids, all activity coefficients can be assumed to not differ significantly from unity, ionization constants for the reaction H 2O + CO 2(aq) H + + HCO -3 can be calculated at 1 and 2 kbar between 250°C and 550°C. These calculated values are in good agreement with the low temperature determinations of the ionization constants for this reaction determined by Read (1975). Values of the molal Gibbs free energy of CO 2(aq) obtained in our study exhibit a much greater positive departure from ideality than those calculated with the modified Redlich-Kwong equations of either Flowers (1979) or Kerrick and Jacobs (1981) for dilute CO 2 aqueous solutions.

  3. Ion exchange model for reversible sorption of divalent metals on calcite: implications for natural environments

    International Nuclear Information System (INIS)

    Most of the thermodynamic models available in the literature describing the speciation of the calcite surface do not predict a significant concentration of sorbed Ca(II), whereas previous electrokinetics studies clearly show that Ca2+ is the main cation determining the potential of the calcite surface. This study proposes a new thermodynamic model based on ion-exchange theory that is able to describe the reversible sorption of Ca2+ on calcite. To constrain the model, concentrations of Ca(II) sorbed reversibly on the mineral surface were obtained as a function of pH. Such experimental data were obtained using solutions in equilibrium with both calcite and fixed p(co2(g)) values (from 10-5 to 10-2 atm). The concentration of (de)sorbed Ca(II) is almost constant in the [7-9.5] pH range, having a value of approximately 1.2 * 10-6 ± 0.4 * 10-7 eq.g-1. Such a value agrees with total sorption site densities that were previously calculated by crystallography and is used to obtain a selectivity coefficient between H+ and Ca2+ species by fitting the experimental data. Then, selectivity coefficients between H+ and different metallic cations (Zn2+, Cd2+, Pb2+) that are able to accurately describe previously published data are proposed. Finally, the model is used to predict the contribution of calcite in the overall sorption of Cd(II) on a natural and complex solid (calcareous aquifer sand). (authors)

  4. Temperature buffer test. Hydro-mechanical and chemical/ mineralogical characterizations

    Energy Technology Data Exchange (ETDEWEB)

    Aakesson, Mattias; Olsson, Siv; Dueck, Ann; Nilsson, Ulf; Karnland, Ola [Clay Technology AB, Lund (Sweden); Kiviranta, Leena; Kumpulainen, Sirpa [BandTech Oy, Helsinki (Finland); Linden, Johan [Aabo Akademi, Aabo (Finland)

    2012-01-15

    TEM), iron oxidation state (Moessbauer spectroscopy). The retention tests, the CEC-determinations, the chemical analyses by ICP, and the mineralogical analyses by XRD and FTIR were performed on bulk samples as well as on a Na-converted fine fraction (<0.5 {mu}m). The latter fraction was subjected also to TEM analyses. The hydro-mechanical characterizations of the bentonite resulted in the following observations: i) compared to the reference material no large deviation was seen in the retention curves for the Na converted fine fraction of the material from the innermost positions, and for the bulk material from the same positions a marked deviation was observed for equilibrium with RH = 97%; ii) a reduction in swelling pressure was observed on re-saturated samples from the field experiment, especially on those from the innermost part. Measured hydraulic conductivity values were generally scattered, but displayed a tendency with increased values on re-saturated specimens drilled from the innermost part, and a similar tendency was also observed on ground and re-compacted specimens and specimens prepared from dried material; iii) the triaxial test performed on the one specimen from the inner part demonstrated a brittle behaviour involving high stiffness, high shear strength, and low strain at failure; and iv) the unconfined compression tests demonstrated a reduced strain at failure on all specimens from the field material, and also a reduced maximum deviator stress on the re-saturated specimens from the innermost position. The chemical/mineralogical characterization indicated that: i) sulfate was redistributed under the thermal and hydration gradients that were prevalent during the test. Anhydrite accumulated at some distance from the heater, whereas gypsum was dissolved in the peripheral parts of the buffer where water was supplied; ii) cristobalite was dissolved at the bentonite/heater contact; iii) calcite was dissolved in the warmest parts of the block; iv

  5. Universal buffers for use in biochemistry and biophysical experiments

    Directory of Open Access Journals (Sweden)

    Dewey Brooke

    2015-08-01

    Full Text Available The use of buffers that mimic biological solutions is a foundation of biochemical and biophysical studies. However, buffering agents have both specific and nonspecific interactions with proteins. Buffer molecules can induce changes in conformational equilibria, dynamic behavior, and catalytic properties merely by their presence in solution. This effect is of concern because many of the standard experiments used to investigate protein structure and function involve changing solution conditions such as pH and/or temperature. In experiments in which pH is varied, it is common practice to switch buffering agents so that the pH is within the working range of the weak acid and conjugate base. If multiple buffers are used, it is not always possible to decouple buffer induced change from pH or temperature induced change. We have developed a series of mixed biological buffers for protein analysis that can be used across a broad pH range, are compatible with biologically relevant metal ions, and avoid complications that may arise from changing the small molecule composition of buffers when pH is used as an experimental variable.

  6. A thermodynamic adsorption/entrapment model for selenium(IV) coprecipitation with calcite

    Science.gov (United States)

    Heberling, Frank; Vinograd, Victor L.; Polly, Robert; Gale, Julian D.; Heck, Stephanie; Rothe, Jörg; Bosbach, Dirk; Geckeis, Horst; Winkler, Björn

    2014-06-01

    Selenium is an environmentally relevant trace element, while the radioisotope 79Se is of particular concern in the context of nuclear waste disposal safety. Oxidized selenium species are relatively soluble and show only weak adsorption at common mineral surfaces. However, a possible sorption mechanism for selenium in the geosphere is the structural incorporation of selenium(IV) (selenite, SeO32-) into calcite (CaCO3). In this study we investigate the interactions between selenite and calcite by a series of experimental and computational methods with the aim to quantify selenite incorporation into calcite at standard conditions. We further seek to describe the thermodynamics of selenite-doped calcite, and selenite coprecipitation with calcite. The structure of the incorporated species is investigated using Se K-edge EXAFS (isotropic and polarization dependent) and results are compared to density functional theory (DFT) calculations. These investigations confirm structural incorporation of selenite into calcite by the substitution of carbonate for selenite, leading to the formation of a Ca(SeO3)X(CO3)(1-X) solid solution. Coprecipitation experiments at low supersaturation indicate a linear increase of the selenite to carbonate ratio in the solid with the increase of the selenite to carbonate ratio in the contact solution. This relationship can be described under the assumption of an ideal mixing between calcite and a virtual CaSeO3 endmember, whose standard Gibbs free energy (G0(CaSeO3_exp) = -953 ± 6 kJ/mol, log10(KSP(CaSeO3_exp)) = -6.7 ± 1.0) is defined by linear extrapolation of the excess free energy from the dilute Henry’s law domain to X(CaSeO3) = 1. In contrast to this experimental result, DFT and force field calculations predict the virtual bulk CaSeO3 endmember to be significantly less stable and more soluble: G0(CaSeO3 bulk) = -912 ± 10 kJ/mol and log10(KSP(CaSeO3_bulk)) = 0.5 ± 1.7. To explain this discrepancy we introduce a thermodynamic adsorption

  7. Common Ion Effects In Zeoponic Substrates: Dissolution And Cation Exchange Variations Due to Additions of Calcite, Dolomite and Wollastonite

    Science.gov (United States)

    Beiersdorfer, R. E.; Ming, D. W.; Galindo, C., Jr.

    2003-01-01

    c1inoptilolite-rich tuff-hydroxyapatite mixture (zeoponic substrate) has the potential to serve as a synthetic soil-additive for plant growth. Essential plant macro-nutrients such as calcium, phosphorous, magnesium, ammonium and potassium are released into solution via dissolution of the hydroxyapatite and cation exchange on zeolite charged sites. Plant growth experiments resulting in low yield for wheat have been attributed to a Ca deficiency caused by a high degree of cation exchange by the zeolite. Batch-equilibration experiments were performed in order to determine if the Ca deficiency can be remedied by the addition of a second Ca-bearing, soluble, mineral such as calcite, dolomite or wollastonite. Variations in the amount of calcite, dolomite or wollastonite resulted in systematic changes in the concentrations of Ca and P. The addition of calcite, dolomite or wollastonite to the zeoponic substrate resulted in an exponential decrease in the phosphorous concentration in solution. The exponential rate of decay was greatest for calcite (5.60 wt. % -I), intermediate for wollastonite (2.85 wt.% -I) and least for dolomite (1.58 wt.% -I). Additions of the three minerals resulted in linear increases in the calcium concentration in solution. The rate of increase was greatest for calcite (3.64), intermediate for wollastonite (2.41) and least for dolomite (0.61). The observed changes in P and Ca concentration are consistent with the solubilities of calcite, dolomite and wollastonite and with changes expected from a common ion effect with Ca. Keywords: zeolite, zeoponics, common-ion effect, clinoptilolite, hydroxyapatite

  8. Synthesis of Gold Nanoparticles with Buffer-Dependent Variations of Size and Morphology in Biological Buffers

    Science.gov (United States)

    Ahmed, Syed Rahin; Oh, Sangjin; Baba, Rina; Zhou, Hongjian; Hwang, Sungu; Lee, Jaebeom; Park, Enoch Y.

    2016-02-01

    The demand for biologically compatible and stable noble metal nanoparticles (NPs) has increased in recent years due to their inert nature and unique optical properties. In this article, we present 11 different synthetic methods for obtaining gold nanoparticles (Au NPs) through the use of common biological buffers. The results demonstrate that the sizes, shapes, and monodispersity of the NPs could be varied depending on the type of buffer used, as these buffers acted as both a reducing agent and a stabilizer in each synthesis. Theoretical simulations and electrochemical experiments were performed to understand the buffer-dependent variations of size and morphology exhibited by these Au NPs, which revealed that surface interactions and the electrostatic energy on the (111) surface of Au were the determining factors. The long-term stability of the synthesized NPs in buffer solution was also investigated. Most NPs synthesized using buffers showed a uniquely wide range of pH stability and excellent cell viability without the need for further modifications.

  9. Synthesis of Gold Nanoparticles with Buffer-Dependent Variations of Size and Morphology in Biological Buffers.

    Science.gov (United States)

    Ahmed, Syed Rahin; Oh, Sangjin; Baba, Rina; Zhou, Hongjian; Hwang, Sungu; Lee, Jaebeom; Park, Enoch Y

    2016-12-01

    The demand for biologically compatible and stable noble metal nanoparticles (NPs) has increased in recent years due to their inert nature and unique optical properties. In this article, we present 11 different synthetic methods for obtaining gold nanoparticles (Au NPs) through the use of common biological buffers. The results demonstrate that the sizes, shapes, and monodispersity of the NPs could be varied depending on the type of buffer used, as these buffers acted as both a reducing agent and a stabilizer in each synthesis. Theoretical simulations and electrochemical experiments were performed to understand the buffer-dependent variations of size and morphology exhibited by these Au NPs, which revealed that surface interactions and the electrostatic energy on the (111) surface of Au were the determining factors. The long-term stability of the synthesized NPs in buffer solution was also investigated. Most NPs synthesized using buffers showed a uniquely wide range of pH stability and excellent cell viability without the need for further modifications. PMID:26847691

  10. A field and modeling study of fractured rock permeability reduction using microbially induced calcite precipitation.

    Science.gov (United States)

    Cuthbert, Mark O; McMillan, Lindsay A; Handley-Sidhu, Stephanie; Riley, Michael S; Tobler, Dominique J; Phoenix, Vernon R

    2013-01-01

    Microbially induced calcite precipitation (MICP) offers an attractive alternative to traditional grouting technologies for creating barriers to groundwater flow and containing subsurface contamination, but has only thus far been successfully demonstrated at the laboratory scale and predominantly in porous media. We present results of the first field experiments applying MICP to reduce fractured rock permeability in the subsurface. Initially, the ureolytic bacterium, Sporosarcina pasteurii, was fixed in the fractured rock. Subsequent injection of cementing fluid comprising calcium chloride and urea resulted in precipitation of large quantities (approximately 750 g) of calcite; significant reduction in the transmissivity of a single fracture over an area of several m(2) was achieved in around 17 h of treatment. A novel numerical model is also presented which simulates the field data well by coupling flow and bacterial and solute reactive transport processes including feedback due to aperture reduction via calcite precipitation. The results show that MICP can be successfully manipulated under field conditions to reduce the permeability of fractured rock and suggest that an MICP-based technique, informed by numerical models, may form the basis of viable solutions to aid pollution mitigation. PMID:24147737

  11. Uranyl incorporation into calcite and aragonite: XAFS and luminescence studies

    International Nuclear Information System (INIS)

    X-ray absorption, luminescence, and Raman spectroscopic studies of U(VI)-containing calcite and aragonite show that the UO22+ ion, the dominant and mobile form of dissolved uranium in near-surface waters, has a disordered and apparently less stable coordination environment when incorporated into calcite in comparison to aragonite, both common polymorphs of CaCO3. Their findings suggest that calcite, a widely distributed authigenic mineral in soils and near-surface sediments and a principal weathering product of concrete-based containment structures, is not likely to be a suitable host for the long-term sequestration of U(VI). The more stable coordination provided by aragonite suggests that its long-term retention should be favored in this phase, until it inverts to calcite. Consequently, future remobilization of U(VI) coprecipitated with calcium carbonate minerals should not be ruled out in assessments of contaminated sites. Their observation of a similar equatorial coordination of UO22+ in aragonite and the dominant aqueous species [UO2(CO3)34-] but a different coordination in calcite indicates that a change in UO22+ coordination is required for its incorporation into calcite. This may explain the observed preferential uptake of U(VI) by aragonite relative to calcite

  12. Adsorption of arsenic and phosphate onto the surface of calcite as revealed by batch experiments and surface complexation modelling

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt

    eleven different calcite-equilibrated solutions that varied in pH, PCO2, ionic strength and activity of Ca2+, CO3 2- and HCO3 -. To avoid the precipitation of phosphate or arsenic-containing minerals the experiments were conducted using a short reaction time (generally 3 h) and a low concentration of...... phosphate (≤ 50 μM) and arsenic (≤ 33 μM). The results show that little or no arsenite adsorbs onto calcite within 24 h at initial arsenite concentration of 0.67 μM. In contrast, both arsenate and phosphate adsorbs readily and quickly onto calcite, with arsenate adsorbing faster than phosphate (adsorption...... similarity in sorption edges, pKa’s and geometry of the two anions. The adsorption of arsenate and phosphate in the single sorbate systems was modelled successfully using either the constant capacitance model (CCM) for calcite or the CD-MUSIC model for calcite. Generally the models capture the variation in...

  13. Calcite surface structure and reactivity: molecular dynamics simulations and macroscopic surface modelling of the calcite-water interface.

    Science.gov (United States)

    Wolthers, M; Di Tommaso, D; Du, Z; de Leeuw, N H

    2012-11-21

    Calcite-water interactions are important not only in carbon sequestration and the global carbon cycle, but also in contaminant behaviour in calcite-bearing host rock and in many industrial applications. Here we quantify the effect of variations in surface structure on calcite surface reactivity. Firstly, we employ classical Molecular Dynamics simulations of calcite surfaces containing an etch pit and a growth terrace, to show that the local environment in water around structurally different surface sites is distinct. In addition to observing the expected formation of more calcium-water interactions and hydrogen-bonds at lower-coordinated sites, we also observed subtle differences in hydrogen bonding around acute versus obtuse edges and corners. We subsequently used this information to refine the protonation constants for the calcite surface sites, according to the Charge Distribution MUltiSite Ion Complexation (CD-MUSIC) approach. The subtle differences in hydrogen bonding translate into markedly different charging behaviour versus pH, in particular for acute versus obtuse corner sites. The results show quantitatively that calcite surface reactivity is directly related to surface topography. The information obtained in this study is not only crucial for the improvement of existing macroscopic surface models of the reactivity of calcite towards contaminants, but also improves our atomic-level understanding of mineral-water interactions. PMID:23042085

  14. Variation of power generation at different buffer types and conductivities in single chamber microbial fuel cells

    KAUST Repository

    Nam, Joo-Youn

    2010-01-15

    Microbial fuel cells (MFCs) are operated with solutions containing various chemical species required for the growth of electrochemically active microorganisms including nutrients and vitamins, substrates, and chemical buffers. Many different buffers are used in laboratory media, but the effects of these buffers and their inherent electrolyte conductivities have not been examined relative to current generation in MFCs. We investigated the effect of several common buffers (phosphate, MES, HEPES, and PIPES) on power production in single chambered MFCs compared to a non-buffered control. At the same concentrations the buffers produced different solution conductivities which resulted in different ohmic resistances and power densities. Increasing the solution conductivities to the same values using NaCl produced comparable power densities for all buffers. Very large increases in conductivity resulted in a rapid voltage drop at high current densities. Our results suggest that solution conductivity at a specific pH for each buffer is more important in MFC studies than the buffer itself given relatively constant pH conditions. Based on our analysis of internal resistance and a set neutral pH, phosphate and PIPES are the most useful buffers of those examined here because pH was maintained close to the pKa of the buffer, maximizing the ability of the buffer to contribute to increase current generation at high power densities. © 2009 Elsevier B.V. All rights reserved.

  15. Aluminum elution and precipitation in glass vials: effect of pH and buffer species.

    Science.gov (United States)

    Ogawa, Toru; Miyajima, Makoto; Wakiyama, Naoki; Terada, Katsuhide

    2015-02-01

    Inorganic extractables from glass vials may cause particle formation in the drug solution. In this study, the ability of eluting Al ion from borosilicate glass vials, and tendencies of precipitation containing Al were investigated using various pHs of phosphate, citrate, acetate and histidine buffer. Through heating, all of the buffers showed that Si and Al were eluted from glass vials in ratios almost the same as the composition of borosilicate glass, and the amounts of Al and Si from various buffer solutions at pH 7 were in the following order: citrate > phosphate > acetate > histidine. In addition, during storage after heating, the Al concentration at certain pHs of phosphate and acetate buffer solution decreased, suggesting the formation of particles containing Al. In citrate buffer, Al did not decrease in spite of the high elution amount. Considering that the solubility profile of aluminum oxide and the Al eluting profile of borosilicate glass were different, it is speculated that Al ion may be forced to leach into the buffer solution according to Si elution on the surface of glass vials. When Al ions were added to the buffer solutions, phosphate, acetate and histidine buffer showed a decrease of Al concentration during storage at a neutral range of pHs, indicating the formation of particles containing Al. In conclusion, it is suggested that phosphate buffer solution has higher possibility of forming particles containing Al than other buffer solutions. PMID:24261406

  16. Molecular ordering of ethanol at the calcite surface

    DEFF Research Database (Denmark)

    Pasarín, I. S.; Yang, M.; Bovet, Nicolas Emile;

    2012-01-01

    dynamics (MD) simulations, the structuring on calcite of a layer of the simplest carbon chain molecule that contains an OH group, ethanol (CH 3-CH2-OH). We found evidence that EtOH forms a highly ordered structure at the calcite surface, where the first layer molecules bond with calcite. The ethanol...... molecules stand up perpendicularly at the interface or nearly so. As a consequence, the fatty, CH3 ends form a new surface, about 6 Å from the termination of the bulk calcite, and beyond that, there is a thin gap where ethanol density is low. Following is a more disordered layer that is two to three...... ethanol molecules thick, about 14 Å, where density more resembles that of bulk liquid ethanol. The good agreement between theory and experiment gives confidence that a theoretical approach can offer information about behavior in more complex systems. © 2012 American Chemical Society....

  17. Nuclear anomalies in the buccal cells of calcite factory workers

    OpenAIRE

    Songül Budak Diler; Serap Ergene

    2010-01-01

    The micronucleus (MN) assay on exfoliated buccal cells is a useful and minimally invasive method for monitoring genetic damage in humans. To determine the genotoxic effects of calcite dust that forms during processing, MN assay was carried out in exfoliated buccal cells of 50 (25 smokers and 25 non-smokers) calcite factory workers and 50 (25 smokers and 25 non-smokers) age- and sex-matched control subjects. Frequencies of nuclear abnormalities (NA) other than micronuclei, such as binucleates,...

  18. INVESTIGATION ON THE MORPHOLOGY OF PRECIPITATED CHEMICALS FROM TE BUFFER ON SOLID SUBSTRATES

    OpenAIRE

    HUABIN WANG; LIJUAN ZHANG; FENG ZHANG; HONGJIE AN; SHIMOU CHEN; HAI LI; PENG WANG; XINYANG WANG; YANG WANG; HAIJUN YANG

    2007-01-01

    Buffer is often involved in the biological studies on a surface with the scanning probe microscopy and the remnant of the salts of buffer may affect the correct interpretation of the experimental results. However, the knowledge on the performance of chemicals of buffer on a substrate is still very poor. TE solution (Tris–HCl, NaCl, and ethylene diamine tetraacetic acid (EDTA)) is a widely used buffer in stocking biological molecules. Herein, we report the performance of the precipitated chemi...

  19. Existence and release of fluid inclusions in bornite and its associated quartz and calcite

    Science.gov (United States)

    Deng, Jiu-shuai; Wen, Shu-ming; Wu, Dan-dan; Liu, Jian; Zhang, Xiao-lin; Shen, Hai-ying

    2013-09-01

    The existence and release of fluid inclusions in bornite and its associated minerals, namely, quartz and calcite were investigated and confirmed. The structures, forms, and phases of these large quantities of fluid inclusions were also studied. A mass of fluid inclusions with various sizes, distributions, shapes, and phases exist in bornite and its associated minerals. Their sizes vary from a few micrometers to tens of micrometers, and the forms appear as negative crystals, or elongated, elliptical, and irregular. At room temperature, fluid inclusions were mainly characterized as gas-liquid twophase. However, small amounts of fluid inclusions with pure gas phase and pure liquid single-phase were also observed in quartz and calcite. These fluid inclusions initially broke during the ore crushing and grinding process and then released into the flotation pulp in the flotation process. The quantitative analysis of fluid inclusions in the solution and the comparisons of mineral dissolution show that the amount of copper and iron released by fluid inclusions in the bornite sample is higher than the amount dissolved by the mineral; fluid inclusions in the associated gangue minerals, quartz, and calcite also make contribution.

  20. The calcite/water interface II. Effect of added lattice ions on the charge properties and adsorption of sodium polyacrylate.

    Science.gov (United States)

    Eriksson, Rasmus; Merta, Juha; Rosenholm, Jarl B

    2008-10-15

    The origin of the surface potential of calcium carbonate in aqueous dispersions and the dissolution of calcite in systems containing excess Ca(2+) and CO(3)(2-) have been the subjects of this study. In addition, stabilization of calcite particles with an anionic polyelectrolyte (sodium polyacrylate (NaPA)) and the effect on surface potential and dissolution of calcite have been studied. Preferential dissolution of either Ca(2+) or CO(3)(2-) from the surface, which is governed by the partial pressure of CO(2) in solution and the pH of the solution, mainly determines the surface potential. Both lattice ions (Ca(2+) and CO(3)(2-)) adsorb onto the surface and thus alter the surface potential. NaPA adsorbs strongly onto the calcite surface regardless of background electrolyte concentration, and reverses the surface potential to negative values. Chelation of the surface due to NaPA can be partly prevented by adding Ca(2+) to the dispersion. PMID:18675424

  1. BUFFERS AND VEGETATIVE FILTER STRIPS

    Science.gov (United States)

    Buffers and filter strips are areas of permanent vegetation located within and between agricultural fields and the water courses to which they drain. These buffers are intended to intercept and slow runoff thereby providing water quality benefits. In addition, in many settings they are intended to...

  2. Environmentally acceptable effect of hydrogen peroxide on cave 'lamp-flora', calcite speleothems and limestones

    International Nuclear Information System (INIS)

    Hydrogen peroxide plus limestone fragments allows removal of organisms without corrosion of limestone and speleothem. - Mosses, algae, and cyanobacteria (lamp-flora) colonize illuminated areas in show caves. This biota is commonly removed by a sodium hypochlorite solution. Because chlorine and other deleterious compounds are released into a cave environment during lamp-flora cleansing, hydrogen peroxide was tested as an alternative agent. In a multidisciplinary study conducted in the Katerinska Cave (Moravian Karst, Czech Republic), 12 algae- and cyanobacteria taxons and 19 moss taxons were detected. The threshold hydrogen peroxide concentration for the destruction of this lamp-flora was found to be 15 vol.%. Based on laboratory experiments in stirred batch reactors, the dissolution rates of limestones and calcite speleothems in water were determined as 3.77x10-3 and 1.81x10-3 mol m-2 h-1, respectively. In the 15% peroxide solution, the limestone and speleothem dissolution rates were one order of magnitude higher, 2.00x10-2 and 2.21x10-2 mol m-2 h-1, respectively. So, the peroxide solution was recognised to attack carbonates somewhat more aggressively than karst water. In order to prevent the potential corrosion of limestone and speleothems, the reaching of preliminary peroxide saturation with respect to calcite is recommended, for example, by adding of few limestone fragments into the solution at least 10 h prior to its application

  3. 1,3,5-Tris(phenyl-2-benzimidazole)-benzene cathode buffer layer thickness dependence in solution-processable organic solar cell based on 1,4,8,11,15,18,22,25-octahexylphthalocyanine

    Science.gov (United States)

    De Roméo Banoukepa, Gilles; Fujii, Akihiko; Shimizu, Yo; Ozaki, Masanori

    2015-04-01

    Studies on the insertion effects of a cathode buffer layer on bulk heterojunction organic solar cell based on 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH2) and 1-(3-methoxy-carbonyl)-propyl-1-1-phenyl-(6,6)C61 (PCBM) by using 1,3,5-tris(phenyl-2-benzimidazole)-benzene (TPBi) as a cathode buffer layer material have been carried out. The external quantum efficiency and the short-circuit current markedly increased, resulting in the enhancement of the power conversion efficiency. The solar cell performance has been discussed from the atomic force microscopy, photoelectron yield spectroscopy and X-ray photoelectron spectroscopy measurements.

  4. A Raman spectroscopic comparison of calcite and dolomite.

    Science.gov (United States)

    Sun, Junmin; Wu, Zeguang; Cheng, Hongfei; Zhang, Zhanjun; Frost, Ray L

    2014-01-01

    Raman spectroscopy was used to characterize and differentiate the two minerals calcite and dolomite and the bands related to the mineral structure. The (CO3)(2-) group is characterized by four prominent Raman vibrational modes: (a) the symmetric stretching, (b) the asymmetric deformation, (c) asymmetric stretching and (d) symmetric deformation. These vibrational modes of the calcite and dolomite were observed at 1440, 1088, 715 and 278 cm(-1). The significant differences between the minerals calcite and dolomite are observed by Raman spectroscopy. Calcite shows the typical bands observed at 1361, 1047, 715 and 157 cm(-1), and the special bands at 1393, 1098, 1069, 1019, 299, 258 and 176 cm(-1) for dolomite are observed. The difference is explained on the basis of the structure variation of the two minerals. Calcite has a trigonal structure with two molecules per unit cell, and dolomite has a hexagonal structure. This is more likely to cause the splitting and distorting of the carbonate groups. Another cause for the difference is the cation substituting for Mg in the dolomite mineral. PMID:23988531

  5. Strontium, nickel, cadmium, and lead substitution into calcite, studied by density functional theory

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Sakuma, Hiroshi; Stipp, Susan Louise Svane

    2014-01-01

    -fluid interface, and into the second layer of the solid. This information can be used as an indicator for cation substitution in the bulk phase, such as for the uptake of toxic metals from the environment and the growth of secondary phases. In both the surface and in the second layer, Ni(2+), Cd(2+), and Pb(2...... is favored at the mineral-fluid interface compared with bulk substitution, which also agrees with experimental data. Our results predict that Ni(2+), Cd(2+), and Pb(2+) form a stable solid solution with calcite. Successful prediction of the experimental results gives us confidence in our ability to...

  6. The efficiency of buffer

    Directory of Open Access Journals (Sweden)

    Ahmed Aldammas

    2016-04-01

    This paper proposes an internal router architecture, for on chip communication, implementing flow-control mechanism for congestion avoidance with QoS consideration. It describes the internal functions of this router for optimal output flit scheduling and its capability to apply per-class service for inbound flows. The paper focuses mainly on the description and performance analysis of two proposed schemes for data flow control that can be used with the proposed router architecture. The results shown in this paper prove that the application of these proposed schemes in NoC achieves an interesting enhancement in the measured end to end QoS. We carried out an extensive comparison of the proposed solutions with the existing schemes published in the literature to show that the proposed solution outperforms these, maintaining an interesting tradeoff with the hardware characteristics when designed with 45 nm integration technology.

  7. Study of delta18O calcite-dolomite mixtures

    International Nuclear Information System (INIS)

    Isotope ratio of oxygen in carbonate mixtures has been studied. For the purpose samples of calcite and dolomite with the known values delta18O are mixed in the ratios 9:1, 3:1, 1:1, 1:3, 1:9. Then from the mixtures prepared CO2 gas is separated using the McCrea method, delta18O of the gas is measured using mass-srectrometer. It has been established that to obtain delta18O calcite in the mixtures with calcite excess CO2 gas should be collected in the interval 15-30 min of the reaction duration and for the mixtures with dolomite excess - in the interval 5-15 min. To determine delta18O of dolomite the optimum time of CO2 gas collection for all the mixtures is 4-24 h

  8. Carbon isotopic thermometry calibrated by dolomite-calcite solvus temperatures

    International Nuclear Information System (INIS)

    The temperature dependence of carbon isotopic fractionations between calcite and graphite, and between dolomite and graphite are calibrated by the calcite-dolomite solvus geothermometry using marbles collected from the contact metamorphic aureole in the Kasuga area, central Japan. The carbon isotopic fractionations systematically decrease with increasing metamorphic temperature. The concordant relationships between the fractionations and solvus temperatures which are presented, are approximately linear with T-2 over the temperature range, 400 deg to 680 deg C. They suggest that carbon isotopic equilibria between carbonates and graphite were attained in many cases. The equation for the calcite-graphite system has a slope steeper than Bottinga's (1969) results. It is, however, in good agreement with that of Valley and O'Neil (1981) in the temperature range from 600 deg to 800 deg C. Because of the relatively high sensitivity to temperature, these isotopic geothermometers are useful for determining the temperatures in moderate- to high-grade metamorphosed carbonate rocks. (author)

  9. Monoclinic deformation of calcite crystals at ambient conditions

    Science.gov (United States)

    Przeniosło, R.; Fabrykiewicz, P.; Sosnowska, I.

    2016-09-01

    High resolution synchrotron radiation powder diffraction shows that the average crystal structure of calcite at ambient conditions is described with the trigonal space group R 3 bar c but there is a systematic hkl-dependent Bragg peak broadening. A modelling of this anisotropic peak broadening with the microstrain model from Stephens (1999) [15] is presented. The observed lattice parameters' correlations can be described by assuming a monoclinic-type deformation of calcite crystallites. A quantitative model of this monoclinic deformation observed at ambient conditions is described with the space group C 2 / c . The monoclinic unit cell suggested at ambient conditions is related with the monoclinic unit cell reported in calcite at high pressure (Merrill and Bassett (1975) [10]).

  10. Heat conductivity of buffer materials

    International Nuclear Information System (INIS)

    The report deals with the thermal conductivity of bentonite based buffer materials. An improved technique for measuring the thermal conductivity of buffer materials is described. Measurements of FLAC calculations applying this technique have led to a proposal of how standardized tests should be conducted and evaluated. The thermal conductivity of bentonite with different void ratio and degree of water saturation has been determined in the following different ways: * Theoretically according to three different investigations by other researchers. * Laboratory measurements with the proposed method. * Results from back-calculated field tests. Comparison and evaluation showed that these results agreed very well, when the buffer material was almost water saturated. However, the influence of the degree of saturation was not very well predicted with the theoretical methods. Furthermore, the field tests showed that the average thermal conductivity in situ of buffer material (compacted to blocks) with low degree of water saturation was lower than expected from laboratory tests. 12 refs, 29 figs, 11 tabs

  11. Sulfated Macromolecules as Templates for Calcite Nucleation and Growth

    Science.gov (United States)

    David, M.; Passalacqua, K.; Neira, A. C.; Fernandez, M. S.

    2003-12-01

    Mineralization of egg and seashells is controlled by an intimate association of inorganic materials with organic macromolecules. Among them, particular polyanionic sulfated macromolecules referred to as proteoglycans have been described to be involved in the calcification of these biominerals. The sulfated moieties of the proteoglycans are part of polymer chains constituted of building-blocks of disaccharide units, referred to as sulfated glycosaminoglycans (GAGs), which are covalently attached to a protein core. By using a sitting drop crystallization assay under controlled conditions of time, pH and reactants concentration, we have tested several sulfated and non-sulfated GAGs (i.e.: dermatan and keratan sulfate, hyaluronic acid and heparin), differing in their sulfonate and carboxylate degree and pattern, in their ability to modify calcium carbonate crystal morphology as observed under scanning electron microscopy. Without the addition of GAGs, regular \\{104\\} rhombohedral calcite crystals were obtained. When hyaluronic acid (HA), a non-sulfated but carboxylated GAG, was added, 20 mm long piles of unmodified calcite crystals were observed. When desulfated dermatan, which is an epimeric form of HA but shorter polymer, having their carboxylate groups in an inverted configuration, was added, isolated rhombohedral \\{104\\} calcite crystals showing rounded corners with planes oriented parallel to the c axis were observed. When dermatan sulfated was added, isolated calcite crystals exhibit a columnar morphology as a \\{hk0\\} cylinder with three \\{104\\} faces forming a cap at both ends. Heparin activity depends on the fraction added. Fast-moving heparin fraction (FM), is an undersulfated, low-molecular-weight heterogeneous polymer, while slow-moving heparin fraction (SM) is an high-molecular-weight homogeneous polymer rich in trisulfated-disaccharide units. When FM was added, isolated calcite crystals displayed rhombohedrical \\{104\\} faces but flat corners of

  12. Magnesium incorporation in calcite in the presence of organic ligands

    Science.gov (United States)

    Mavromatis, Vasileios; Baldermann, Andre; Purgstaller, Bettina; Dietzel, Martin

    2015-04-01

    The formation of authigenic Mg-calcites in marine early diagenetic environments is commonly driven by a bio-induced process, the anaerobic oxidation of methane (AOM), which provides inorganic carbon required for the precipitation of such authigenic carbonates. In such settings the availability of major and/or trace divalent metal cations (Me2+) incorporated in calcite and their aqueous speciation are controlled by the presence of aqueous organic molecules that are produced either as (by-)products of biological activity (i.e. exopolymeric substances) or during degradation of allochthonous organic matter in the sediments. Despite the fact that the presence of aqueous organic ligands strongly affects the growth rates and the mineralogy of precipitating CaCO3 polymorphs, till now no study addresses the role of Me2+-ligand aqueous complexes on the extent of Mg and/or other trace element content of Mg-calcites. In order to shed light on this process, relevant to authigenic calcite formation in organic-rich marine sediments and continental soils, we precipitated calcite in the presence of aqueous Mg and a variety of low molecular weight carboxylic- and aminoacids. Our experimental data indicate that the presence of organic ligands augments significantly the saturation state of calcite in the parent fluid during its precipitation. Moreover, they suggest that the higher the ligand concentration, the higher the obtained distribution coefficient of Mg in calcite. The latter is directly proportional to the ratio of Mg2+/Ca2+ aqueous ions for all ligands used. Hydrogeochemical modelling of the aqueous fluids indicate that the observed correlation can be explained by the stronger complexation of Ca2+ with organic ligands compared to Mg2+, which results in higher availability of Mg2+ vs. Ca2+ aqueous ions. Overall the obtained results suggest that the higher the organic ligand aqueous concentration the higher the Mg content of calcite forming from this fluid. These findings are

  13. A Bicriteria Approximation for the Reordering Buffer Problem

    CERN Document Server

    Barman, Siddharth; Umboh, Seeun

    2012-01-01

    In the reordering buffer problem (RBP), a server is asked to process a sequence of requests lying in a metric space. To process a request the server must move to the corresponding point in the metric. The requests can be processed slightly out of order; in particular, the server has a buffer of capacity k which can store up to k requests as it reads in the sequence. The goal is to reorder the requests in such a manner that the buffer constraint is satisfied and the total travel cost of the server is minimized. The RBP arises in many applications that require scheduling with a limited buffer capacity, such as scheduling a disk arm in storage systems, switching colors in paint shops of a car manufacturing plant, and rendering 3D images in computer graphics. We study the offline version of RBP and develop bicriteria approximations. When the underlying metric is a tree, we obtain a solution of cost no more than 9OPT using a buffer of capacity 4k + 1 where OPT is the cost of an optimal solution with buffer capacit...

  14. ENVIRONMENTAL MANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACE METALS IN GROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 AND OTHER DIVALENT METALS AND RADIONUCLIDES AT ARID WESTERN DOE SITES

    International Nuclear Information System (INIS)

    Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) weapons complex. In situ containment and stabilization of these contaminants in vadose zones or groundwater is a cost-effective treatment strategy. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal coprecipitation) by increasing groundwater pH and alkalinity (Fujita et al., 2000; Warren et al., 2001). Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface urea hydrolyzing microorganisms. Because the precipitation processes are irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from groundwater. The rate at which trace metals are incorporated into calcite is a function of calcite precipitation kinetics, adsorption interactions between the calcite surface and the trace metal in solution (Zachara et al., 1991), solid solution properties of the trace metal in calcite (Tesoriero and Pankow, 1996), and also the surfaces upon which the calcite is precipitating. A fundamental understanding of the coupling of calcite precipitation and trace metal partitioning, and how this occurs in aquifers and vadose environments is lacking. This report summarizes work undertaken during the second year of this project

  15. Porosity and hydric behavior of typical calcite microfabrics in stalagmites

    OpenAIRE

    Muñoz García, Mercedes; López Arce, Paula; Fernández Valle, Mª Encarnación; Martín Chivelet, Javier; Fort González, Rafael

    2012-01-01

    Petrophysical techniques commonly used for material characterization are applied for the first time to speleothem samples to investigate the porosity and hydric behavior of calcite stalagmites used in paleoclimatology. These techniques allow the determination of the stalagmites' potential to undergo diagenetic transformations when substantial changes in drip waters occur in the cave environment. The petrophysical techniques include water absorption under vacuum and by capillarity,...

  16. Removal of trace elements from landfill leachate by calcite precipitation

    Czech Academy of Sciences Publication Activity Database

    Ettler, V.; Zelená, O.; Mihaljevič, M.; Šebek, O.; Strnad, L.; Coufal, P.; Bezdička, Petr

    2006-01-01

    Roč. 88, 1-3 (2006), s. 28-31. ISSN 0375-6742 R&D Projects: GA AV ČR(CZ) KJB3111402 Institutional research plan: CEZ:AV0Z40320502 Keywords : landfill leachate * calcite * scavenging Subject RIV: CA - Inorganic Chemistry Impact factor: 0.922, year: 2006

  17. Isolation and identification of Pseudomonas azotoformans for induced calcite precipitation.

    Science.gov (United States)

    Heidari Nonakaran, Siamak; Pazhouhandeh, Maghsoud; Keyvani, Abdullah; Abdollahipour, Fatemeh Zahra; Shirzad, Akbar

    2015-12-01

    Biomineralization is a process by which living organisms produce minerals. The extracellular production of these biominerals by microbes has potential for various bioengineering applications. For example, crack remediation and improvement of durability of concrete is an important goal for engineers and biomineral-producing microbes could be a useful tool in achieving this goal. Here we report the isolation, biochemical characterization and molecular identification of Pseudomonas azotoformans, a microbe that produces calcite and which potentially be used to repair cracks in concrete structures. Initially, 38 bacterial isolates were isolated from soil and cements. As a first test, the isolates were screened using a urease assay followed by biochemical tests for the rate of urea hydrolysis, calcite production and the insolubility of calcite. Molecular amplification and sequencing of a 16S rRNA fragment of selected isolates permitted us to identify P. azotoformans as a good candidate for preparation of biotechnological concrete. This species was isolated from soil and the results show that among the tested isolates it had the highest rate of urea hydrolysis, produced the highest amount of calcite, which, furthermore was the most adhesive and insoluble. This species is thus of interest as an agent with the potential ability to repair cracks in concrete. PMID:26386580

  18. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    DEFF Research Database (Denmark)

    Madsen, Lene; Grahl-Madsen, Laila; Grøn, Christian; Lind, Ida; Engell, John

    1996-01-01

    The wettability of hydrocarbon reservoirs depends on how and to what extent the organic compounds are adsorbed onto the surfaces of calcite, quartz and clay. A model system of synthetic call cite, cyclohexane and the three probe molecules: benzoic acid, benzyl alcohol and benzylamine, have been...

  19. Is bicarbonate stable in and on the calcite surface?

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Rodriguez Blanco, Juan Diego; Stipp, Susan Louise Svane

    2016-01-01

    We have used density functional theory with the COSMO-RS implicit solvent model to predict the pKa for the deprotonation of bicarbonate to carbonate, i.e. HCO3− <=> CO32− + H+, when HCO3− is included in, and adsorbed on, a calcite surface. We have used cluster models (80–100 atoms) to represent t...

  20. Aragonite / Calcite seas and the evolution of biomineralization

    Science.gov (United States)

    Balthasar, Uwe

    2015-04-01

    The vast majority of marine invertebrate skeletons are composed of the CaCO3 polymorphs aragonite and calcite, yet the influence of seawater composition on the evolution of calcareous skeletal composition is poorly understood. The main theoretical framework in which the evolution of CaCO3 shell mineralogy is assessed is the aragonite-calcite sea hypothesis with conventional thinking suggesting that a threshold in the marine Mg:Ca ratio determines CaCO3 polymorph formation. I present data from CaCO3 precipitation experiments to show that the concept of a distinct threshold is misleading because Mg:Ca ratio and temperature combined result in a Phanerozoic continuum of co-existing aragonite-calcite seas with aragonite-facilitating conditions existing throughout the Phanerozoic in shallow warm-water (>20° C) environments. The stable reservoir of aragonite-favouring conditions in shallow warm water environments potentially explains the trend of increasing occurrences of skeletal aragonite throughout the Phanerozoic, particularly in the context of the 'out of the tropics' hypothesis. By contrast, the most prominent fluctuations with respect to aragonite-calcite sea conditions can be expected to have occurred in mid- to high latitudes.

  1. NMR spectroscopic study of organic phosphate esters coprecipitated with calcite

    Science.gov (United States)

    Phillips, Brian L.; Zhang, Zelong; Kubista, Laura; Frisia, Silvia; Borsato, Andrea

    2016-06-01

    Organic phosphorus incorporated in calcite during laboratory precipitation experiments and in natural cave deposits was investigated by solid-state NMR spectroscopy. For calcite precipitated in the presence of organic phosphoesters of varying size and functionality, solid-state 31P{1H} CP/MAS NMR shows that the phosphoesters were incorporated intact into the solid. Systematic changes in the 31P NMR chemical shift of the phosphate group were observed between the solid phosphoester and that incorporated in the solid precipitate, yielding 31P NMR chemical shifts of the coprecipitates in the range of +1.8 to -2.2 ppm. These chemical shifts are distinct from that of similarly prepared calcite coprecipitated with inorganic phosphate, 3.5 ppm. Only minor changes were noted in the phosphoester 31P chemical shift anisotropy (CSA) which suggests no significant change in the local structure of the phosphate group, which is dominated by C-O-P bonding. Close spatial proximity of the organic phosphate group to calcite structural components was revealed by 31P/13C rotational echo double resonance (REDOR) experiments for coprecipitates prepared with 13C-labeled carbonate. All coprecipitates showed significant 31P dephasing effects upon 13C-irradiation, signaling atomic-scale proximity to carbonate carbon. The dephasing rate for smaller organophosphate molecules is similar to that observed for inorganic phosphate, whereas much slower dephasing was observed for larger molecules having long and/or bulky side-chains. This result suggests that small organic molecules can be tightly enclosed within the calcite structure, whereas significant structural disruption required to accommodate the larger organic molecules leads to longer phosphate-carbonate distances. Comparison of 31P NMR spectroscopic data from the synthetic coprecipitates with those from calcite moonmilk speleothems indicates that phosphorus occurs mainly as inorganic orthophosphate in the natural deposits, although small

  2. Flow and transport through a damaged buffer - exploration of the impact of a cemented and an eroded buffer

    International Nuclear Information System (INIS)

    The compacted bentonite buffer that surrounds the canister with spent fuel is designed not to allow water to flow through it in any appreciable quantities. Should the buffer be severely damaged water could flow to the canister and bring with it corrosive agent such as sulphide. This could speed up the rate of copper corrosion. Should the canister have a damage or be corroded so that the spent fuel inside the canister comes in contact with the water radionuclides could dissolve in the water and be carried away. Two modes of canister damage and their consequences for solute transport are explored in this report. In one case the buffer can potentially be eroded by the water seeping in the fractures in the surrounding rock and attain a high hydraulic conductivity allowing water to flow through it, at least locally. In another case it is conjectured that the buffer is cemented and becomes brittle. Then a crack could conceivably form in the cemented buffer allowing water to flow through it directly to the canister surface. Both cases are hypothetical although in the erosion case the erosion rate could possibly be quantified. The cases studied are to be seen as exploratory calculations for 'what if' cases. Some worst case assumptions have been used to explore bounding scenarios. Thus for the erosion case it is assumed that the hydraulic conductivity is so high that the buffer exerts negligible resistance to water flow. This implies that all the water that can flow through the fractures intersecting the deposition hole can reach the canister. Similarly for the cemented buffer case it is assumed that the crack in the buffer directly connects the rock fracture to the canister surface. For these circumstances it is found that the flowrate that can enter the deposition hole will be approximately two times as large as the water flow that would pass a projected area equal to that of the deposition hole. Thus if the flux in the rock some distance from the deposition hole is 1

  3. Impact-Induced Devolatilization or Melting of Calcite? Or Both? Answers from MEMIN Experiments

    Science.gov (United States)

    Hamann, C.; Hecht, L.; Deutsch, A.

    2015-07-01

    Calcite was experimentally shocked in a series of MEMIN hypervelocity impact and laser melting experiments. Evidence for the formation of calcite melts in both types of experiments is presented and discussed.

  4. On the Shock Behavior of Calcite: Recent Results from MEMIN Experiments

    Science.gov (United States)

    Hamann, C.; Hecht, L.; Deutsch, A.

    2015-09-01

    Hypervelocity impact and laser melting experiments, aiming at a better understanding of the shock behavior of calcite, suggest that both melting and decomposition of calcite can occur at P-T conditions commensurate with impact processes.

  5. Thermophysical tests of buffer materials

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, H. [ITC, Tokyo (Japan); Taniguchi, Wataru

    1999-03-01

    Thermodynamic properties of buffer materials were measured for putting in order thermodynamic constants to be used in the near-field thermal analysis. The thermal diffusivity and thermal conductivity were measured as functions of the water content and temperature to deduce the specific heat. The thermal conductivity and specific heat varied significantly as the water content changed. Obtained values of the specific heat agreed well the expected values calculated based on the constituents of the buffer material. Temperature dependence of the thermodynamic constants was found small below 90degC. From the findings, the thermal conductivity and specific heat of the buffer material were formulated as functions of the water content. Thermodynamic study of powdery bentonite was carried out as well with a purpose of use for filling apertures in the artificial barrier. (H. Baba)

  6. The evolution of Carbon isotopes in calcite in the presence of cyanobacteria

    Science.gov (United States)

    Grimm, Christian; Mavromatis, Vasileios; Pokrovsky, Oleg S.; Oelkers, Eric H.

    2016-04-01

    Stable isotopic compositions in carbonates are widely used as indicators of environmental conditions prevailing during mineral formation. This reconstruction is substantially based on the assumption that there is no change in the mineral composition over geological time. However, recent experimental studies have shown that carbon and magnesium isotopes in hydrous Mg-carbonates undergo continuous re-equilibration with the ambient solution even after mineral precipitation stopped ([1] and [2], respectively). To verify whether this holds true for anhydrous Ca-bearing carbonates which readily form at earth's surface environments, a series of batch system calcite precipitation experiments were performed in the presence of actively growing cyanobacteria Synechococcus sp. The bacteria were grown at ambient temperature in a BG11 culture medium (SIGMA C3061) and continuous stirring, air-bubbling and illumination. Calcite precipitation was initiated by the addition of 8.5mM CaCl2 and 0-50 mM NaHCO3 or NaHCO3-Na2CO3 mixtures. The presence of cyanobacteria is on one hand promoting CaCO3 formation due to increasing pH resulting from photosynthesis. On the other hand, actively growing cyanobacteria drastically change carbon isotope signature of the aqueous fluid phase by preferably incorporating the lighter 12C isotope into biomass [1]. This study explores the effect of continuously changing carbon isotope compositions in dissolved inorganic carbon (DIC) on precipitated calcite which is in chemical equilibrium with the ambient fluid phase. [1] Mavromatis et al. (2015). The continuous re-equilibration of carbon isotope compositions of hydrous Mg-carbonates in the presence of cyanobacteria. Chem. Geol. 404, 41-51 [2] Mavromatis et al. (2012). Magnesium isotope fractionation during hydrous magnesium carbonate precipitation with and without cyanobacteria. Geochim. Cosmochim. Acta 76, 161-174

  7. ACETIC ACID AND A BUFFER

    DEFF Research Database (Denmark)

    2009-01-01

    The present invention relates to a composition comprising : a) 0.01-20% wt/wt acetic acid and b) a physiologically tolerable buffer capable of maintaining acetic acid at a pH in the range of 2-7; and use of such a composition as an antimicrobial agent.......The present invention relates to a composition comprising : a) 0.01-20% wt/wt acetic acid and b) a physiologically tolerable buffer capable of maintaining acetic acid at a pH in the range of 2-7; and use of such a composition as an antimicrobial agent....

  8. Experiment Study on the Removal of Phosphorus in Eutrophic Water Bodies by the Utilization of Mineral Calcite

    Science.gov (United States)

    Xu, Hong; Zhang, Jing; Gao, Yiming

    For seeking a new method to solve the problem of eutrophication, we have made the experiments of removing phosphorus in eutropic water by use of mineral calcite. The results indicate that the mineral calcite can remove phosphorus from the solution, and that the initial phosphorus concentration may influence the efficiency of phosphorus removal. The dephosphorization rate is high when the initial phosphorus concentration is 5 mg/L, and phosphorus can be removed by 88.48%; the dephosphorization rate may reach 69.94% when the initial phosphorus concentration is 3 mg/L; at 1.2 mg/L initial concentration only 12.68% phosphorus can be removed. Increasing temperature can also raise the efficiency of phosphorus removal. The result of TEM shows that the Ca-P precipitation is not in crystalline state.

  9. Buffering in cyclic gene networks

    Science.gov (United States)

    Glyzin, S. D.; Kolesov, A. Yu.; Rozov, N. Kh.

    2016-06-01

    We consider cyclic chains of unidirectionally coupled delay differential-difference equations that are mathematical models of artificial oscillating gene networks. We establish that the buffering phenomenon is realized in these system for an appropriate choice of the parameters: any given finite number of stable periodic motions of a special type, the so-called traveling waves, coexist.

  10. ON OPTIMAL LOCAL BUFFER ALLOCATION IN FLEXIBLE MANUFACTURING SYSTEMS

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    An optimal design problem of local buffer allocation in the FMS is discussed in order to maximize a reward earned from processed jobs at all workstations. Structural properties of the optimal design problem are analyzed for the model with two job routing policies. Based on these properties, approaches to optimal solutions are given.

  11. Experimental acidification of two biogeochemically-distinct neotropical streams: Buffering mechanisms and macroinvertebrate drift

    Energy Technology Data Exchange (ETDEWEB)

    Ardón, Marcelo, E-mail: ardonsayaom@ecu.edu [Department of Biology and North Carolina Center for Biodiversity, East Carolina University, Greenville, NC 27858 (United States); Duff, John H. [U.S. Geological Survey, Menlo Park, CA 94025 (United States); Ramírez, Alonso [Department of Environmental Sciences, University of Puerto Rico, San Juan, PR 00931 (Puerto Rico); Small, Gaston E. [Department of Ecology, Evolution, and Behavior, University of Minnesota, St. Paul, MN 55108 (United States); Jackman, Alan P. [University of California, Davis, CA 95616 (United States); Triska, Frank J. [U.S. Geological Survey, Menlo Park, CA 94025 (United States); Pringle, Catherine M. [Odum School of Ecology, University of Georgia, Athens, GA 30602 (United States)

    2013-01-15

    Research into the buffering mechanisms and ecological consequences of acidification in tropical streams is lacking. We have documented seasonal and episodic acidification events in streams draining La Selva Biological Station, Costa Rica. Across this forested landscape, the severity in seasonal and episodic acidification events varies due to interbasin groundwater flow (IGF). Streams that receive IGF have higher concentrations of solutes and more stable pH (∼ 6) than streams that do not receive IGF (pH ∼ 5). To examine the buffering capacity and vulnerability of macroinvertebrates to short-term acidification events, we added hydrochloric acid to acidify a low-solute, poorly buffered (without IGF) and a high-solute, well buffered stream (with IGF). We hypothesized that: 1) protonation of bicarbonate (HCO{sub 3}{sup −}) would neutralize most of the acid added in the high-solute stream, while base cation release from the sediments would be the most important buffering mechanism in the low-solute stream; 2) pH declines would mobilize inorganic aluminum (Ali) from sediments in both streams; and 3) pH declines would increase macroinvertebrate drift in both streams. We found that the high-solute stream neutralized 745 μeq/L (96% of the acid added), while the solute poor stream only neutralized 27.4 μeq/L (40%). Protonation of HCO{sub 3}{sup −} was an important buffering mechanism in both streams. Base cation, Fe{sup 2+}, and Ali release from sediments and protonation of organic acids also provided buffering in the low-solute stream. We measured low concentrations of Ali release in both streams (2-9 μeq/L) in response to acidification, but the low-solute stream released double the amount Ali per 100 μeq of acid added than the high solute stream. Macroinvertebrate drift increased in both streams in response to acidification and was dominated by Ephemeroptera and Chironomidae. Our results elucidate the different buffering mechanisms in tropical streams and

  12. Experimental acidification of two biogeochemically-distinct neotropical streams: Buffering mechanisms and macroinvertebrate drift

    International Nuclear Information System (INIS)

    Research into the buffering mechanisms and ecological consequences of acidification in tropical streams is lacking. We have documented seasonal and episodic acidification events in streams draining La Selva Biological Station, Costa Rica. Across this forested landscape, the severity in seasonal and episodic acidification events varies due to interbasin groundwater flow (IGF). Streams that receive IGF have higher concentrations of solutes and more stable pH (∼ 6) than streams that do not receive IGF (pH ∼ 5). To examine the buffering capacity and vulnerability of macroinvertebrates to short-term acidification events, we added hydrochloric acid to acidify a low-solute, poorly buffered (without IGF) and a high-solute, well buffered stream (with IGF). We hypothesized that: 1) protonation of bicarbonate (HCO3−) would neutralize most of the acid added in the high-solute stream, while base cation release from the sediments would be the most important buffering mechanism in the low-solute stream; 2) pH declines would mobilize inorganic aluminum (Ali) from sediments in both streams; and 3) pH declines would increase macroinvertebrate drift in both streams. We found that the high-solute stream neutralized 745 μeq/L (96% of the acid added), while the solute poor stream only neutralized 27.4 μeq/L (40%). Protonation of HCO3− was an important buffering mechanism in both streams. Base cation, Fe2+, and Ali release from sediments and protonation of organic acids also provided buffering in the low-solute stream. We measured low concentrations of Ali release in both streams (2-9 μeq/L) in response to acidification, but the low-solute stream released double the amount Ali per 100 μeq of acid added than the high solute stream. Macroinvertebrate drift increased in both streams in response to acidification and was dominated by Ephemeroptera and Chironomidae. Our results elucidate the different buffering mechanisms in tropical streams and suggest that low-solute poorly

  13. Thermo-hydro-geochemical modelling of the bentonite buffer. LOT A2 experiment

    Energy Technology Data Exchange (ETDEWEB)

    Sena, Clara; Salas, Joaquin; Arcos, David (Amphos 21 Consulting S.L., Barcelona (Spain))

    2010-12-15

    /condensation process /Karnland et al. 2009/. Once bentonite is water saturated, the transport of solutes is driven by diffusion. Although Donnan equilibrium /Birgersson and Karnland 2009/ and anion exclusion /Muurinen et al. 2004/ are able to influence the mobility of chloride in the bentonite buffer, under the high temperature LOT A2 test conditions, measured data seem to indicate a relatively low influence of these processes on the transport of chloride. For this reason, the transport of chloride has been modelled taking into account advective, dispersive and diffusive fluxes that are believed to have occurred in the LOT A2 test. Numerical results were conducted at fixed thermal gradients for both heated and non-heated bentonite based on the temperatures recorded during the experiment for both heated and non-heated bentonite. The computed evolution of the bentonite saturation indicates that, within approximately one year, the bentonite blocks located at the depth of the heater are completely water saturated which agrees with measured data. The simulated transport of chloride is also in good agreement with data measured at the end of the LOT A2 test for the two cases considered, reflecting the reliability of the conceptual model defined for the LOT A2 test. Based on the geochemical data obtained at end of the LOT A2 test, and on previous modelling exercises /Arcos et al. 2006/, the main geochemical processes that are believed to have developed during the LOT A2 test are: (i) precipitation/dissolution of carbonate, sulphate and silica minerals and, (ii) cation exchange in the montmorillonite interlayer. Numerical results predict the dissolution - precipitation of anhydrite, calcite and silica in the heated bentonite in agreement with data measured at the end of the LOT A2 test

  14. Thermo-hydro-geochemical modelling of the bentonite buffer. LOT A2 experiment

    International Nuclear Information System (INIS)

    /condensation process /Karnland et al. 2009/. Once bentonite is water saturated, the transport of solutes is driven by diffusion. Although Donnan equilibrium /Birgersson and Karnland 2009/ and anion exclusion /Muurinen et al. 2004/ are able to influence the mobility of chloride in the bentonite buffer, under the high temperature LOT A2 test conditions, measured data seem to indicate a relatively low influence of these processes on the transport of chloride. For this reason, the transport of chloride has been modelled taking into account advective, dispersive and diffusive fluxes that are believed to have occurred in the LOT A2 test. Numerical results were conducted at fixed thermal gradients for both heated and non-heated bentonite based on the temperatures recorded during the experiment for both heated and non-heated bentonite. The computed evolution of the bentonite saturation indicates that, within approximately one year, the bentonite blocks located at the depth of the heater are completely water saturated which agrees with measured data. The simulated transport of chloride is also in good agreement with data measured at the end of the LOT A2 test for the two cases considered, reflecting the reliability of the conceptual model defined for the LOT A2 test. Based on the geochemical data obtained at end of the LOT A2 test, and on previous modelling exercises /Arcos et al. 2006/, the main geochemical processes that are believed to have developed during the LOT A2 test are: (i) precipitation/dissolution of carbonate, sulphate and silica minerals and, (ii) cation exchange in the montmorillonite interlayer. Numerical results predict the dissolution - precipitation of anhydrite, calcite and silica in the heated bentonite in agreement with data measured at the end of the LOT A2 test

  15. Biosorption of divalent Pb, Cd and Zn on aragonite and calcite mollusk shells

    Energy Technology Data Exchange (ETDEWEB)

    Du Yang; Lian Fei [Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, Tianjin Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Zhu Lingyan, E-mail: zhuly@nankai.edu.cn [Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, Tianjin Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

    2011-07-15

    The potential of using mollusk shell powder in aragonite (razor clam shells, RCS) and calcite phase (oyster shells, OS) to remove Pb{sup 2+}, Cd{sup 2+} and Zn{sup 2+} from contaminated water was investigated. Both biogenic sorbents displayed very high sorption capacities for the three metals except for Cd on OS. XRD, SEM and XPS results demonstrated that surface precipitation leading to crystal growth took place during sorption. Calcite OS displayed a remarkably higher sorption capacity to Pb than aragonite RCS, while the opposite was observed for Cd. However, both sorbents displayed similar sorption capacities to Zn. These could be due to the different extent of matching in crystal lattice between the metal bearing precipitate and the substrates. The initial pH of the solution, sorbent's dosage and grain size affected the removal efficiency of the heavy meals significantly, while the organic matter in mollusk shells affected the removal efficiency to a lesser extent. - Highlights: > Mollusk shells display high removal efficiency to heavy metals in contaminated water. > Surface precipitation leading to crystal growth takes place during the sorption. > Crystal structure similarity between precipitates and substrates affects the sorption. > pH, sorbent dosage and grain size of adsorbent affects the removal efficiency. > Organic matter in mollusk shells affects the removal efficiency to a less extent. - Mollusk shells display high sorption ability to heavy metals and crystal structure similarity between precipitates and substrates affects the sorption.

  16. Hydroxyapatite coatings for marble protection: Optimization of calcite covering and acid resistance

    Science.gov (United States)

    Graziani, Gabriela; Sassoni, Enrico; Franzoni, Elisa; Scherer, George W.

    2016-04-01

    Hydroxyapatite (HAP) has a much lower dissolution rate and solubility than calcite, especially in an acidic environment, so it has been proposed for the protection of marble against acidic rain corrosion. Promising results were obtained, but further optimization is necessary as the treated layer is often incomplete, cracked and/or porous. In this paper, several parameters were investigated to obtain a coherent, uncracked layer, and to avoid the formation of metastable, soluble phases instead of HAP: the role of the pH of the starting solution; the effect of organic and inorganic additions, and in particular that of ethanol, as it is reported to adsorb on calcite, hence possibly favoring the growth of the HAP layer. Finally, a double application of the treatment was tested. Results were compared to those obtained with ammonium oxalate treatment, widely investigated for marble protection. Results indicate that adding small amounts of ethanol to the formulation remarkably increases the acid resistance of treated samples, and yields better coverage of the surface without crack formation. The effectiveness of the treatment is further enhanced when a second treatment is applied. The efficacy of ethanol-doped DAP mixtures was found to be remarkably higher than that of ammonium oxalate based treatments.

  17. Tuning hardness in calcite by incorporation of amino acids

    Science.gov (United States)

    Kim, Yi-Yeoun; Carloni, Joseph D.; Demarchi, Beatrice; Sparks, David; Reid, David G.; Kunitake, Miki E.; Tang, Chiu C.; Duer, Melinda J.; Freeman, Colin L.; Pokroy, Boaz; Penkman, Kirsty; Harding, John H.; Estroff, Lara A.; Baker, Shefford P.; Meldrum, Fiona C.

    2016-08-01

    Structural biominerals are inorganic/organic composites that exhibit remarkable mechanical properties. However, the structure-property relationships of even the simplest building unit--mineral single crystals containing embedded macromolecules--remain poorly understood. Here, by means of a model biomineral made from calcite single crystals containing glycine (0-7 mol%) or aspartic acid (0-4 mol%), we elucidate the origin of the superior hardness of biogenic calcite. We analysed lattice distortions in these model crystals by using X-ray diffraction and molecular dynamics simulations, and by means of solid-state nuclear magnetic resonance show that the amino acids are incorporated as individual molecules. We also demonstrate that nanoindentation hardness increased with amino acid content, reaching values equivalent to their biogenic counterparts. A dislocation pinning model reveals that the enhanced hardness is determined by the force required to cut covalent bonds in the molecules.

  18. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    DEFF Research Database (Denmark)

    Madsen, Lene; Grahl-Madsen, Laila; Grøn, Christian;

    1996-01-01

    The wettability of hydrocarbon reservoirs depends on how and to what extent the organic compounds are adsorbed onto the surfaces of calcite, quartz and clay. A model system of synthetic call cite, cyclohexane and the three probe molecules: benzoic acid, benzyl alcohol and benzylamine, have been...... studied by adsorption experiments. The results clearly demonstrate the differences in the adsorption behaviour between probes with different functional groups of varying polarity and acidity. The maximum adsorption decreases in the order: benzoic acid, benzyl alcohol and benzylamine. The order of...... magnitude of Delta G degrees for the adsorption process implies the formation of a strong bond between the calcite surface and the adsorbate molecules. Copyright (C) 1996 Elsevier Science Ltd....

  19. Calcite production by coccolithophores in the south east Pacific Ocean

    OpenAIRE

    Beaufort, L.; Couapel, M.; Buchet, N.; H. Claustre; Goyet, C

    2008-01-01

    BIOSOPE cruise covered an oceanographic transect through the centre of the South Pacific Gyre (SPG) from the Marquesas archipelago to the Peru-Chile upwelling (PCU). Water samples from 6 depths in the euphotic zone were collected at 20 stations. The concentrations of suspended calcite particles, coccolithophores cells and detached coccoliths were estimated together with size and weight using an automatic polarizing microscope, a digital camera, and a collection of softwares performing morphom...

  20. Radiation damage in diopside and calcite crystals from uranothorianite inclusions

    OpenAIRE

    A.-M. Seydoux-Guillaume; J.-M. Montel; Richard Wirth; Moine, B.

    2009-01-01

    Combining observation and simulation, radiohalos formed around urano-thorianite (UTh) from the Tranomaro granulitic skarns (SE-Madagascar) were studied. These structures consist of UTh grains surrounded by both aluminous diopside (Cpx) and calcite (Cc1) crystals. Optical microscope and Scanning Electron Microscope (SEM) images revealed (1) the presence of radiating cracks around the UTh probably due to swelling of the metamict UTh, (2) a diffuse optical halo at the Cc1/UTh interface, and (3) ...

  1. The effect of dissolved magnesium on diffusion creep in calcite

    Science.gov (United States)

    Herwegh, Marco; Xiao, Xiaohui; Evans, Brian

    2003-07-01

    We experimentally tested a series of synthetic calcite marbles with varying amounts of dissolved magnesium in a standard triaxial deformation machine at 300 MPa confining pressure, temperatures between 700 and 850°C, stresses between 2 and 100 MPa, and strain rates between 10 -7 and 10 -3 s -1. The samples were fabricated by hot isostatic pressing of a mixture of calcite and dolomite at 850°C and 300 MPa. The fabrication protocol resulted in a homogeneous, fine-grained high-magnesian calcite aggregate with minimal porosity and with magnesium contents between 0.07 and 0.17 mol% MgCO 3. At stresses below 40 MPa the samples deformed with linear viscosity that depended inversely on grain size to the 3.26±0.51 power, suggesting that the mechanisms of deformation were some combination of grain boundary diffusion and grain boundary sliding. Because small grain sizes tended to occur in the high-magnesium calcite, the strength also appeared to vary inversely with magnesium content. However, the strength at constant grain size does not depend on the amount of dissolved magnesium, and thus, the impurity effect seems to be indirect. At stresses higher than 40 MPa, the aggregates become non-linearly viscous, a regime we interpret to be dislocation creep. The transition between the two regimes depends on grain size, as expected. The activation energy for diffusion creep is 200±30 kJ/mol and is quite similar to previous measurements in natural and synthetic marbles deformed at similar conditions with no added magnesium.

  2. Origin of calcite in the glacigenic Virttaankangas complex

    OpenAIRE

    Nina M. Kortelainen; Petri J. Korkeakoski; Karhu, Juha A.

    2007-01-01

    Groundwaters of the glacigenic Virttaankangas complex in southern Finland are characterized by high pH values ranging up to 9.5. These values are significantly higher than those observed in silicate-rich shallow groundwater formations in crystalline bedrock areas. TheVirttaankangas sediments were discovered to contain small amounts of fine grained, dispersed calcite, which has a high tendency to increase the pH of local groundwaters. The primary goal of this study was to determine the mode of...

  3. Biogenic calcite structures in Green Lake, James Ross Island, Antarctica

    Czech Academy of Sciences Publication Activity Database

    Elster, Josef; Nedbalová, Linda; Komárek, Jiří; Vodrážka, R.

    Brno: Masarykova Univerzita, 2009 - (Barták, M.; Hájek, J.; Váczi, P.), s. 38-40 ISBN 978-80-210-4987-1. [Electronic Conference on Interactions between Antarctic Life and Environmental Factors. Brno (CZ), 22.10.2009-23.10.2009] R&D Projects: GA MŠk(CZ) ME 945 Institutional research plan: CEZ:AV0Z60050516 Keywords : Green Lake * James Ross * Biogenic calcite structures Subject RIV: EF - Botanics

  4. Magnetic Separation of Calcite Using Selective Magnetite Coating

    OpenAIRE

    Prakash, S; Das, B.; R. Venugopal

    1999-01-01

    Magnetic separation of naturally occurring calcite (98.2% CaCO3) using selective coating of synthetic colloidal magnetite with sodium oleate has been investigated as a function of pH, concentration of colloidal magnetite, magnetic intensity and particle size. Colloidal magnetite treated with sodium oleate (oleate magnetite) is found to be a better coating agent than the natural magnetite. The mechanism of oleate magnetite coating has been investigated through adsorption and electrokinetics me...

  5. Synthetic Calcite as a Scaffold for Osteoinductive Bone Substitutes.

    Science.gov (United States)

    Chróścicka, Anna; Jaegermann, Zbigniew; Wychowański, Piotr; Ratajska, Anna; Sadło, Jarosław; Hoser, Grażyna; Michałowski, Sławomir; Lewandowska-Szumiel, Malgorzata

    2016-07-01

    Although a wide variety of biomaterials have been already proposed for use in bone tissue engineering, there is still need for man-made materials, which would combine support for osteogenesis with simplicity desirable for upscaling and costs reduction. In this study we have shown that synthetic calcite may serve as a scaffold for human osteoblasts transplantation. A simple dynamic system allows uniform and effective cell distribution. Cell viability and osteogenic phenotype were confirmed by XTT assay, alkaline phosphatase activity and selected osteoblast-specific genes expression. Extracellular matrix deposited by cells improved elasticity and made the whole system similar to the flexible composite material rather than to the brittle ceramic implants. It was revealed in the compression tests and also by the improved samples handling. Subcutaneous implantation of the cell-seeded calcite scaffolds to immunodeficient mice resulted in mineralized bone formation, which was confirmed histologically and by EPR analysis. The latter we propose as a method supplementary to histological analysis, for bone regeneration investigations. It specifically confirms the presence of bone mineral with a unique sensitivity and using bulk samples, which eliminates the risk of missing the material in the preparation. Our study resulted in development of a new osteogenic tissue engineered product based on man-made calcite. PMID:26666226

  6. Dual mode logic buffers for VLSI interconnects

    Directory of Open Access Journals (Sweden)

    A.Ilakkiya

    2015-10-01

    Full Text Available Buffer insertion is a mechanism widely used to increase the performance of VLSI digital circuits. Buffer insertion has a strong impact on reliability in terms of delay and power dissipation of synchronous systems, since the clock distribution system requires reduced or controlled clock skew, being the buffer insertion and buffer sizing becomes an important aspect. Buffer insertion has also been used to reduce the noise generation, especially in heavy loaded nets, since the inclusion of buffer helps to desynchronize signal transitions.

  7. Influence of glyphosate on the copper dissolution in phosphate buffer

    Science.gov (United States)

    Coutinho, C. F. B.; Silva, M. O.; Machado, S. A. S.; Mazo, L. H.

    2007-01-01

    The electrochemical behavior of copper microelectrode in phosphate buffer in the presence of glyphosate was investigated by electrochemical techniques. It was observed that the additions of glyphosate in the phosphate buffer increased the anodic current of copper microelectrode and the electrochemical dissolution was observed. This phenomenon could be associated with the Cu(II) complexation by glyphosate forming a soluble complex. Physical characterization of the surface showed that, in absence of glyphosate, an insoluble layer covered the copper surface; on the other hand, in presence of glyphosate, it was observed a corroded copper surface with the formation of glyphosate complex in solution.

  8. The Uptake of Eu(III) and Th(IV) by Calcite under Hyperalkaline Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Tits, J.; Wieland, E.; Bradbury, M.H.; Eckert, P.; Schaible, A

    2002-10-01

    Calcite is an important component of Valanginian marl, a potential host rock for a low and intermediate level radioactive waste (L/ILW) repository in Switzerland. This mineral also forms an important component of the disturbed zone around a repository, as it remains largely unaffected by the hyperalkaline waters migrating out of the cementitious repository . The sorption behaviour of Eu(III) and Th(IV) on Merck calcite in an artificial cement pore water (ACW) at pH 13.3 has been studied in batch-type sorption experiments. In addition, the effect of {alpha}-isosaccharinic acid (ISA) and gluconic acid (GLU) on the sorption of these two cations has been investigated. In the absence of ISA and GLU, a strong interaction of Eu(III) and Th(IV) with Merck calcite was observed. Eu(III) and Th(IV) sorption kinetics were fast and the isotherms indicated a linear adsorption behaviour over the experimentally accessible concentration range. In the case of Eu(III), a decrease of the R{sub d} value with increasing solid to liquid (S:L) ratio was observed indicating that, along with adsorption, other processes might influence the immobilisation of this cation by Merck calcite under ACW conditions. In the case of Th(IV), however, changes in the S:L ratio had no effect on the sorption behaviour . High ISA and GLU concentrations in solution significantly affected the sorption of both Eu(III) and Th(IV): R{sub d} values for Eu(III) decreased significantly at ISA concentrations higher than 10{sup -5} M and at GLU concentrations higher than 10{sup -7} M. The sorption of Th(IV) was reduced at ISA concentrations above 2.10{sup -5} M and at GLU concentrations above 10{sup -6} M. The effects of ISA and GLU on the immobilisation of Eu(III) and Th(IV) were interpreted in terms of complex formation in solution. In the case of Eu(III) the metal ligand complexes were found to have a 1 : 1 stoichiometry. Complexation constants derived for the aqueous Eu(III)-ISA. and Eu(III)GLU complexes were

  9. The Uptake of Eu(III) and Th(IV) by Calcite under Hyperalkaline Conditions

    International Nuclear Information System (INIS)

    Calcite is an important component of Valanginian marl, a potential host rock for a low and intermediate level radioactive waste (L/ILW) repository in Switzerland. This mineral also forms an important component of the disturbed zone around a repository, as it remains largely unaffected by the hyperalkaline waters migrating out of the cementitious repository . The sorption behaviour of Eu(III) and Th(IV) on Merck calcite in an artificial cement pore water (ACW) at pH 13.3 has been studied in batch-type sorption experiments. In addition, the effect of α-isosaccharinic acid (ISA) and gluconic acid (GLU) on the sorption of these two cations has been investigated. In the absence of ISA and GLU, a strong interaction of Eu(III) and Th(IV) with Merck calcite was observed. Eu(III) and Th(IV) sorption kinetics were fast and the isotherms indicated a linear adsorption behaviour over the experimentally accessible concentration range. In the case of Eu(III), a decrease of the Rd value with increasing solid to liquid (S:L) ratio was observed indicating that, along with adsorption, other processes might influence the immobilisation of this cation by Merck calcite under ACW conditions. In the case of Th(IV), however, changes in the S:L ratio had no effect on the sorption behaviour . High ISA and GLU concentrations in solution significantly affected the sorption of both Eu(III) and Th(IV): Rd values for Eu(III) decreased significantly at ISA concentrations higher than 10-5 M and at GLU concentrations higher than 10-7 M. The sorption of Th(IV) was reduced at ISA concentrations above 2.10-5 M and at GLU concentrations above 10-6 M. The effects of ISA and GLU on the immobilisation of Eu(III) and Th(IV) were interpreted in terms of complex formation in solution. In the case of Eu(III) the metal ligand complexes were found to have a 1 : 1 stoichiometry. Complexation constants derived for the aqueous Eu(III)-ISA. and Eu(III)GLU complexes were determined to be logβ0EulSA = -31.1±O.2 and

  10. A Capital Adequacy Buffer Model

    OpenAIRE

    David Allen; Michael McAleer

    2013-01-01

    In this paper, we develop a new capital adequacy buffer model (CABM) which is sensitive to dynamic economic circumstances. The model, which measures additional bank capital required to compensate for fluctuating credit risk, is a novel combination of the Merton structural model which measures distance to default and the timeless capital asset pricing model (CAPM) which measures additional returns to compensate for additional share price risk.

  11. Static Switching Dynamic Buffer Circuit

    OpenAIRE

    Pandey, A. K.; R. A. Mishra; R. K. Nagaria

    2013-01-01

    We proposed footless domino logic buffer circuit. It minimizes redundant switching at the dynamic and the output nodes. The proposed circuit avoids propagation of precharge pulse to the output node and allows the dynamic node which saves power consumption. Simulation is done using 0.18 µm CMOS technology. We have calculated the power consumption, delay, and power delay product of the proposed circuit and compared the results with the existing circuits for different logic function, loading co...

  12. Microscopic optical buffering in a harmonic potential

    CERN Document Server

    Sumetsky, M

    2015-01-01

    In the early days of quantum mechanics, Schr\\"odinger noticed that oscillations of a wave packet in a one-dimensional harmonic potential well are periodic and, in contrast to those in anharmonic potential wells, do not experience distortion over time. This original idea did not find applications up to now since an exact one-dimensional harmonic resonator does not exist in nature and has not been created artificially. However, an optical pulse propagating in a bottle microresonator (a dielectric cylinder with a nanoscale-high bump of the effective radius) can exactly imitate a quantum wave packet in the harmonic potential. Here, we propose a tuneable microresonator that can trap an optical pulse completely, hold it as long as the material losses permit, and release it without distortion. This result suggests the solution of the long standing problem of creating a microscopic optical buffer, the key element of the future optical signal processing devices.

  13. Buffer-gas effects on dark resonances: Theory and experiment

    Science.gov (United States)

    Erhard, Michael; Helm, Hanspeter

    2001-04-01

    Dark resonances with widths below 30 Hz have been observed in a rubidium cell filled with neon as buffer gas at room temperature. We compare an approximate analytic solution of a Λ system to our data and show that under our experimental conditions the presence of the buffer gas reduces the power broadening of the dark resonances by two orders of magnitude. We also present numerical calculations that take into account the thermal motion and velocity-changing collisions with the buffer-gas atoms. The resulting dark-resonance features exhibit strong Dicke-type narrowing effects and thereby explain the elimination of Doppler shifts and Doppler broadening, leading to observation of a single ultranarrow dark line.

  14. Carbonated hydroxyapatite starting from calcite and different orthophosphates under moderate hydrothermal conditions: Synthesis and surface reactivity in simulated body fluid

    International Nuclear Information System (INIS)

    Highlights: • Carbonated apatite (CAP) could be easily obtained from CaCO3 and orthophosphates. • Highest CaCO3 dissolution and apatitic carbonate content were obtained with H3PO4. • A-B-type CAP was formed. • The synthesized CAP was thermally stable up to 1000 °C. • This CAP showed high biomineralization activity before and after thermal treatment. - Abstract: The one-step synthesis of carbonated hydroxyapatite (CAP) using calcite and different orthophosphates was investigated in a closed batch reactor. Only orthophosphoric acid could lead to the complete decomposition of calcite particles, when the reaction temperature was set at 80 °C. On the other hand, the reaction time and the dilution of the initial calcite suspension had no significant influence on the formation of the solid products. CAP was formed as the main crystalline calcium phosphate with the carbonate content in the range of 4.2–4.6 wt.%. The thermal decarbonation of the synthesized CAP started at 750 °C but it was only significant at 1000 °C under air atmosphere. This thermal decarbonation was total at 1200 °C or above. All CAP samples and products following thermal treatments were found bioactive in the test using simulated body fluid (SBF) solution

  15. Carbonated hydroxyapatite starting from calcite and different orthophosphates under moderate hydrothermal conditions: Synthesis and surface reactivity in simulated body fluid

    Energy Technology Data Exchange (ETDEWEB)

    Pham Minh, Doan, E-mail: doan.phamminh@mines-albi.fr; Nzihou, Ange; Sharrock, Patrick

    2014-12-15

    Highlights: • Carbonated apatite (CAP) could be easily obtained from CaCO{sub 3} and orthophosphates. • Highest CaCO{sub 3} dissolution and apatitic carbonate content were obtained with H{sub 3}PO{sub 4}. • A-B-type CAP was formed. • The synthesized CAP was thermally stable up to 1000 °C. • This CAP showed high biomineralization activity before and after thermal treatment. - Abstract: The one-step synthesis of carbonated hydroxyapatite (CAP) using calcite and different orthophosphates was investigated in a closed batch reactor. Only orthophosphoric acid could lead to the complete decomposition of calcite particles, when the reaction temperature was set at 80 °C. On the other hand, the reaction time and the dilution of the initial calcite suspension had no significant influence on the formation of the solid products. CAP was formed as the main crystalline calcium phosphate with the carbonate content in the range of 4.2–4.6 wt.%. The thermal decarbonation of the synthesized CAP started at 750 °C but it was only significant at 1000 °C under air atmosphere. This thermal decarbonation was total at 1200 °C or above. All CAP samples and products following thermal treatments were found bioactive in the test using simulated body fluid (SBF) solution.

  16. Development of One Meter Long Double-Sided CeO2 Buffered Ni-5at.%W Templates by Reel-to-Reel Chemical Solution Deposition Route

    DEFF Research Database (Denmark)

    Yue, Zhao; Konstantopoulou, K.; Wulff, Anders Christian;

    2013-01-01

    layer are 7.2◦ and 5.8◦ with standard deviation of 0.26◦ and 0.34◦, respectively, being indicative of the high quality epitaxial growth of the films prepared in the continuous manner. An all chemical solution derived YBCOLow−TFA/Ce0.9La0.1O2/Gd2Zr2O7/CeO2 structure is obtained on a short sample...

  17. Buffer-aided multihop wireless communications

    OpenAIRE

    Dong, Chen

    2014-01-01

    In this thesis, we propose a suite of buffer-aided transmission schemes designed for a multihop link or for a three-node network by exploiting the characteristics of buffer-aided transmissions. Our objective is to improve the end-to-end BER, outage probability, throughput and energy dissipation. Specifically, we firstly proposed and studied a buffer-aided multihop link (MHL), where all the relay nodes (RNs) are assumed to have buffers for temporarily storing their received packets. Hence,...

  18. Stable isotope (C, O) and monovalent cation fractionation upon synthesis of carbonate-bearing hydroxyl apatite (CHAP) via calcite transformation

    Science.gov (United States)

    Böttcher, Michael E.; Schmiedinger, Iris; Wacker, Ulrike; Conrad, Anika C.; Grathoff, Georg; Schmidt, Burkhard; Bahlo, Rainer; Gehlken, Peer-L.; Fiebig, Jens

    2016-04-01

    Carbonate-bearing hydroxyl-apatite (CHAP) is of fundamental and applied interest to the (bio)geochemical, paleontological, medical and material science communities, since it forms the basic mineral phase in human and animal teeth and bones. In addition, it is found in non-biogenic phosphate deposits. The stable isotope and foreign element composition of biogenic CHAP is widely used to estimate the formation conditions. This requires careful experimental calibration under well-defined boundary conditions. Within the DFG project EXCALIBOR, synthesis of carbonate-bearing hydroxyapatite was conducted via the transformation of synthetic calcite powder in aqueous solution as a function of time, pH, and temperature using batch-type experiments. The aqueous solution was analyzed for the carbon isotope composition of dissolved inorganic carbonate (gas irmMS), the oxygen isotope composition of water (LCRDS), and the cationic composition. The solid was characterized by powder X-ray diffraction, micro Raman and FTIR spectroscopy, SEM-EDX, elemental analysis (EA, ICP-OES) and gas irmMS. Temperature was found to significantly impact the transformation rate of calcite to CHAP. Upon complete transformation, CHAP was found to contain up to 5% dwt carbonate, depending on the solution composition (e.g., pH), both incorporated on the A and B type position of the crystal lattice. The oxygen isotope fractionation between water and CHAP decreased with increasing temperature with a tentative slope shallower than those reported in the literature for apatite, calcite or aragonite. In addition, the presence of dissolved NH4+, K+ or Na+ in aqueous solution led to partial incorporation into the CHAP lattice. How these distortions of the crystal lattice may impact stable isotope discrimination is subject of future investigations.

  19. Photoinduced synthesis of single-digit micrometer-size spheroidal calcite composites in the presence of partially hydrolyzed poly(vinyl alcohol)

    Science.gov (United States)

    Nishio, Takashi; Naka, Kensuke

    2015-06-01

    Photoinduced crystallization of calcium carbonate (CaCO3), which was based on the photodecarboxylation of ketoprofen (KP, 2-(3-benzoylphyenyl)propionic acid) under alkaline conditions of pH 8.4 and 10 was studied for preparation of CaCO3 composite particles in single-digit micrometer-sizes. In this method, a homogeneous solution comprising KP, calcium chloride, ammonia, and partially hydrolyzed poly(vinyl alcohol) (PVAPS, degree of saponification: 86.5-89.0 mol%) was used as a precursor solution and was exposed to ultraviolet (UV) irradiation for different time periods. After the UV irradiation for 50 min, calcite spheroids in single-digit micrometer-sizes were obtained as major products at pH 8.4. The obtained calcite spheroids contained organic components of about 10 wt%. The comparison of the characteristics of the CaCO3 obtained at pH 8.4 and 10 suggests that the nucleation and crystallization of both vaterite and calcite continuously took place in a moderated supersaturation owing to the CO2 hydration equilibrium as long as the photodecarboxylation of KP continued. Consequently, the aggregation-based crystal growth in the presence of PVAPS seemed to enable the formation of the spheroidal composites of calcite in single-digit micrometer-sizes.

  20. Empirical equations for the temperature dependence of calcite-water oxygen isotope fractionation from 10 to 70°C.

    Science.gov (United States)

    Demény, Attila; Kele, Sándor; Siklósy, Zoltán

    2010-12-30

    Although the temperature dependence of calcite-water oxygen isotope fractionation seems to have been well established by numerous empirical, experimental and theoretical studies, it is still being discussed, especially due to the demand for increased accuracy of paleotemperature calculations. Experimentally determined equations are available and have been verified by theoretical calculations (considered as representative of isotopic equilibrium); however, many natural formations do not seem to follow these relationships implying either that existing fractionation equations should be revised, or that carbonate deposits are seriously affected by kinetic and solution chemistry effects, or late-stage alterations. In order to test if existing fractionation-temperature relationships can be used for natural deposits, we have studied calcite formations precipitated in various environments by means of stable isotope mass spectrometry: travertines (freshwater limestones) precipitating from hot and warm waters in open-air or quasi-closed environments, as well as cave deposits formed in closed systems. Physical and chemical parameters as well as oxygen isotope composition of water were monitored for all the investigated sites. Measuring precipitation temperatures along with oxygen isotope compositions of waters and calcites yielded empirical environment-specific fractionation-temperature equations: [1] 1000 · lnα = 17599/T - 29.64 [for travertines with a temperature range of 30 to 70°C] and [2] 1000 · lnα = 17500/T - 29.89 [for cave deposits for the range 10 to 25°C]. Finally, based on the comparison of literature data and our results, the use of distinct calcite-water oxygen isotopic fractionation relationships and application strategies to obtain the most reliable paleoclimate information are evaluated. PMID:21080503

  1. Evaluations of composition for buffer materials based on genetic algorithms

    International Nuclear Information System (INIS)

    To provide an overall functional evaluations of buffer materials, this study attempted to investigate the relationships among the engineering properties, plastic index (PI), compaction efficiency, hydraulic conductivity(k); sorption properties, distribution ratio(Rd) for some buffer materials composed of quartz sand and bentonite. According to engineering and sorption properties, the optimal composition can be found out with some optimal approaches. However, a genetic algorithm (GA) is a robust method for searching the optimum solution to a complex problem and widely is applied to many different topics. It is a search algorithm based upon mechanics of natural selection, derived from the theory of natural evolution. The study of genetic algorithms (GAS) has developed into powerful optimization approach since 1970, so this study tries to apply GAS to this problem. Under both synthetic groundwater (GW) and seawater (SW) conditions, the composition of quartz sand and bentonite was evaluated by associating engineering and sorption properties. Due to ends of experiments, this study assumes linearly proportional relationship among bentonite content of buffer materials, PI, k, and sorption properties. And GAS was carried out using a population size of 50, a crossover rate of 0,5, and a mutation rate of 0,1. The final results based on genetic algorithms are consistent with consequences of previous tests. From the viewpoints of associated engineering and sorption properties, the buffer materials nearly containing 70% bentonite are probably the most favorable choice. These results will show a determination of more effective buffer material composition. (authors)

  2. Geochemical signatures of fluid paleo-transfer in fracture filling calcite from low permeability rock masses: examples taken from Bure's and Tournemire's site in France and northern Switzerland; Signatures geochimiques de paleocirculations aqueuses dans la calcite de remplissage de fracture de massifs argileux peu permeables et de leurs encaissants: exemples pris sur les sites de Bure, Tournemire et Suisse du nord

    Energy Technology Data Exchange (ETDEWEB)

    Lecocq, D

    2002-12-15

    Fractures in rock masses represent preferential path for fluid transfer and, as such, are the most efficient way for migration of radionuclides at a regional scale. The impact of fracturing on hydrogeological system is a major challenge for underground radioactive waste storage projects. In this context, geochemistry of fracture-filling calcite is used to better understand physical and chemical properties of palaeo-fluids. A new methodology has been developed to analyze Mg, Mn, Fe, Sr and Rare Earth Elements REE (La, Ce, Nd, Sm, Eu, Dy and Yb) in calcite by Secondary Ion Mass Spectrometry. Analyses of calcite crystals have been performed in fractures from Jurassic clays and limestones in France (Bure and Tournemire sites) and northern Switzerland (Mt Terri's tunnel and deep borehole). On each case, several geochemical signatures are observed, according to REE partitioning and Mn and Fe concentrations. In the Bure site, a dependence of calcite geochemistry from fracture host rock has been evidenced. On the other hand, speciation of REE in solution equilibrated with clayey or calcareous rocks at circum-neutral pH (7 to 8) is not significantly influenced by the media: speciation is dominated by carbonate species in both cases and phosphate complexes can modify heavy REE availability in relatively to light REE. These results point out that in fractures in clays, calcite crystallizes at equilibrium with a fluid expulsed during diagenesis from clay minerals, recording the effect of clays and accessory phases. In limestone fractures, calcite records a later event related to the past functioning of the present aquifer, and the fluid has reached equilibrium with the rock minerals. In secondary filling calcite from Toarcian Argilites faults close to Tournemire's tunnel, three successive generations of calcite are observed in an extensive fault, and a fourth in a compressive one. In Aalenian Opalinus Clays veins, comparison between existing isotopic data and Mn, Fe

  3. BUFFER CAPACITY IN HETEROGENEOUS MULTICOMPONENT SYSTEMS. REVIEW

    Directory of Open Access Journals (Sweden)

    Oxana Spinu

    2015-12-01

    Full Text Available The quantitative basis of the theory of buffer properties for two-phase acid-base buffer systems and for multicomponent heterogeneous systems has been derived. The analytical equations with respect to all components for diverse multicomponent systems were deduced. It has been established, that the buffer capacities of components are mutually proportional.

  4. BUFFER CAPACITY IN HETEROGENEOUS MULTICOMPONENT SYSTEMS. REVIEW

    OpenAIRE

    Oxana Spinu; Igor Povar

    2015-01-01

    The quantitative basis of the theory of buffer properties for two-phase acid-base buffer systems and for multicomponent heterogeneous systems has been derived. The analytical equations with respect to all components for diverse multicomponent systems were deduced. It has been established, that the buffer capacities of components are mutually proportional.

  5. Evaluation of Sikora instead of SMP buffer to estimate the potential acidity of brazilian soils

    Directory of Open Access Journals (Sweden)

    Maria Alice Santanna

    2011-10-01

    Full Text Available Despite the efficiency of the Shoemaker, McLean, Pratt (SMP buffer method in estimating soil acidity, the presence of p-nitrophenol and potassium chromate in the solution, both hazardous substances, has caused increasing environmental concerns. The purpose of this study was to test Sikora method (Sikora, 2006 as an alternative to the adapted SMP buffer method, generally used to estimate potential acidity of Southern Brazilian soils. For the test, 21 soils in the South and Cerrado regions of Brazil were sampled. (1 The potential acidity values of these soils range from 35.95 to 4.02 cmol c kg-1 of soil, reflecting a wide acidity variation. The Sikora buffer does not mimic the adapted SMP buffer used in Southern Brazil, since the former has a low ability to distinguish soils with different acidity from each other, probably due to the higher buffer capacity than of the adapted SMP solution.

  6. Calcite production by coccolithophores in the south east Pacific Ocean

    Directory of Open Access Journals (Sweden)

    L. Beaufort

    2008-08-01

    Full Text Available BIOSOPE cruise covered an oceanographic transect through the centre of the South Pacific Gyre (SPG from the Marquesas archipelago to the Peru-Chile upwelling (PCU. Water samples from 6 depths in the euphotic zone were collected at 20 stations. The concentrations of suspended calcite particles, coccolithophores cells and detached coccoliths were estimated together with size and weight using an automatic polarizing microscope, a digital camera, and a collection of softwares performing morphometry and pattern recognition. Some of these softwares are new and described here for the first time. The coccolithophores standing stocks were usually low and reached maxima west of the PCU. The coccoliths of Emiliania huxleyi, Gephyrocapsa spp. and Crenalithus spp. (Order Isochrysidales represented more than 30% of all the suspended calcite particles detected in the size range 0.1–46 μm (22% of PIC in term of calcite weight. These species grew preferentially in the Chlorophyll maximum zone. In the SPG their maximum cell concentrations were recorded between depth of 150 and 200 m, which is unusually deep for these taxa. The weight of coccoliths and coccospheres were correlated to their size. Large and heavy coccoliths and coccospheres were found in regions with relatively high fertility in the Marquises Island and in the PCU. Small and light coccoliths and coccospheres were found west of the PCU. This distribution is strongly related to ocean chemistry in particular to alkalinity and to carbonate ions concentration. The biotic (coccolithophores production influence on calcification is mainly driven at the local scale (depth whereas the abiotic (carbonate chemistry plays its most important role at the regional (horizontal level. Here 94% of the variability of coccolith and coccosphere weight can be explained by a change in 7 environmental variables.

  7. Calcite production by coccolithophores in the south east Pacific Ocean

    Science.gov (United States)

    Beaufort, L.; Couapel, M.; Buchet, N.; Claustre, H.; Goyet, C.

    2008-08-01

    BIOSOPE cruise covered an oceanographic transect through the centre of the South Pacific Gyre (SPG) from the Marquesas archipelago to the Peru-Chile upwelling (PCU). Water samples from 6 depths in the euphotic zone were collected at 20 stations. The concentrations of suspended calcite particles, coccolithophores cells and detached coccoliths were estimated together with size and weight using an automatic polarizing microscope, a digital camera, and a collection of softwares performing morphometry and pattern recognition. Some of these softwares are new and described here for the first time. The coccolithophores standing stocks were usually low and reached maxima west of the PCU. The coccoliths of Emiliania huxleyi, Gephyrocapsa spp. and Crenalithus spp. (Order Isochrysidales) represented more than 30% of all the suspended calcite particles detected in the size range 0.1 46 μm (22% of PIC in term of calcite weight). These species grew preferentially in the Chlorophyll maximum zone. In the SPG their maximum cell concentrations were recorded between depth of 150 and 200 m, which is unusually deep for these taxa. The weight of coccoliths and coccospheres were correlated to their size. Large and heavy coccoliths and coccospheres were found in regions with relatively high fertility in the Marquises Island and in the PCU. Small and light coccoliths and coccospheres were found west of the PCU. This distribution is strongly related to ocean chemistry in particular to alkalinity and to carbonate ions concentration. The biotic (coccolithophores production) influence on calcification is mainly driven at the local scale (depth) whereas the abiotic (carbonate chemistry) plays its most important role at the regional (horizontal) level. Here 94% of the variability of coccolith and coccosphere weight can be explained by a change in 7 environmental variables.

  8. Principles of calcite dissolution in human and artificial otoconia.

    Directory of Open Access Journals (Sweden)

    Leif Erik Walther

    Full Text Available Human otoconia provide mechanical stimuli to deflect hair cells of the vestibular sensory epithelium for purposes of detecting linear acceleration and head tilts. During lifetime, the volume and number of otoconia are gradually reduced. In a process of degeneration morphological changes occur. Structural changes in human otoconia are assumed to cause vertigo and balance disorders such as benign paroxysmal positional vertigo (BPPV. The aim of this study was to investigate the main principles of morphological changes in human otoconia in dissolution experiments by exposure to hydrochloric acid, EDTA, demineralized water and completely purified water respectively. For comparison reasons artificial (biomimetic otoconia (calcite gelatin nanocomposits and natural calcite were used. Morphological changes were detected in time steps by the use of environmental scanning electron microscopy (ESEM. Under in vitro conditions three main dissolution mechanisms were identified as causing characteristic morphological changes of the specimen under consideration: pH drops in the acidic range, complex formation with calcium ions and changes of ion concentrations in the vicinity of otoconia. Shifts in pH cause a more uniform reduction of otoconia size (isotropic dissolution whereas complexation reactions and changes of the ionic concentrations within the surrounding medium bring about preferred attacks at specific areas (anisotropic dissolution of human and artificial otoconia. Owing to successive reduction of material, all the dissolution mechanisms finally produce fragments and remnants of otoconia. It can be assumed that the organic component of otoconia is not significantly attacked under the given conditions. Artificial otoconia serve as a suitable model system mimicking chemical attacks on biogenic specimens. The underlying principles of calcite dissolution under in vitro conditions may play a role in otoconia degeneration processes such as BPPV.

  9. Arsenite sorption and co-precipitation with calcite

    OpenAIRE

    Roman-Ross, Gabriela; Cuello, Gabriel; Turrillas, Xavier; Fernandez-Martinez, Alejandro; Charlet, Laurent

    2008-01-01

    Sorption of As(III) by calcite was investigated as a function of As(III) concentration, time and pH. The sorption isotherm, i.e. the log As(III) vs. log [As(OH)3 degrees / Assat] plot is S-shaped and has been modelled on an extended version of the surface precipitation model. At low concentrations, As(OH)3 degrees is adsorbed by complexation to surface Ca surface sites, as previously described by the X-ray standing wave technique. The inflexion point of the isotherm, where As(OH)3 degrees is ...

  10. Improving Water Quality With Conservation Buffers

    Science.gov (United States)

    Lowrance, R.; Dabney, S.; Schultz, R.

    2003-12-01

    Conservation buffer technologies are new approaches that need wider application. In-field buffer practices work best when used in combination with other buffer types and other conservation practices. Vegetative barriers may be used in combination with edge-of-field buffers to protect and improve their function and longevity by dispersing runoff and encouraging sediment deposition upslope of the buffer. It's important to understand how buffers can be managed to help reduce nutrient transport potential for high loading of nutrients from manure land application sites, A restored riparian wetland buffer retained or removed at least 59 percent of the nitrogen and 66 percent of the phosphorus that entered from an adjacent manure land application site. The Bear Creek National Restoration Demonstration Watershed project in Iowa has been the site of riparian forest buffers and filter strips creation; constructed wetlands to capture tile flow; stream-bank bioengineering; in-stream structures; and controlling livestock grazing. We need field studies that test various widths of buffers of different plant community compositions for their efficacy in trapping surface runoff, reducing nonpoint source pollutants in subsurface waters, and enhancing the aquatic ecosystem. Research is needed to evaluate the impact of different riparian grazing strategies on channel morphology, water quality, and the fate of livestock-associated pathogens and antibiotics. Integrating riparian buffers and other conservation buffers into these models is a key objective in future model development.

  11. Thermoluminescent of induced calcite by gamma and ultraviolet radiation

    International Nuclear Information System (INIS)

    Samples of brazilian calcite, exposed to gamma radiation in laboratory and heated at constant rate of 2.70 C/s, showed three glow peaks at 150, 250 and 350 0C in their thermoluminescent emission curves. The analysis of these peaks, using different models, indicated that they follow a second order kinetics; it has been obtained, for the activation energy, 1.3, 1.5 and 1.7 eV, and, for the pre-exponential factors, 8.1 x 10 14, 6.8 x10 13 and 2.4 x 1012 s-1. Although the total thermoluminescent emission has stayed constant, the relative height of glow peaks has changed with the temperature of annealing in the range of 400 to 700 0C. Exposed samples were also illuminated with ultraviolet light and the resultant curves showed partial or total bleaching or some glow peaks and the growth of peaks at lower temperatures. Samples of virgin calcite, submited to increasing exposures of gamma rays, showed a corresponding enhancement of the optical absorption bands in the range of 25000 to 47000 cm-1 A subsequent illumination of these samples with ultraviolet light produced a decrease of the optical absorption bands at the same range. (author)

  12. Calcite sealing in a fractured geothermal reservoir: Insights from combined EBSD and chemistry mapping

    Science.gov (United States)

    McNamara, David D.; Lister, Aaron; Prior, Dave J.

    2016-09-01

    Fractures play an important role as fluid flow pathways in geothermal resources hosted in indurated greywacke basement of the Taupo Volcanic Zone, New Zealand, including the Kawerau Geothermal Field. Over time, the permeability of such geothermal reservoirs can be degraded by fracture sealing as minerals deposit out of transported geothermal fluids. Calcite is one such fracture sealing mineral. This study, for the first time, utilises combined data from electron backscatter diffraction and chemical mapping to characterise calcite vein fill morphologies, and gain insight into the mechanisms of calcite fracture sealing in the Kawerau Geothermal Field. Two calcite sealing mechanisms are identified 1) asymmetrical syntaxial growth of calcite, inferred by the presence of single, twinned, calcite crystals spanning the entire fracture width, and 2) 3D, interlocking growth of bladed vein calcite into free space as determined from chemical and crystallographic orientation mapping. This study also identifies other potential uses of combined EBSD and chemical mapping to understand geothermal field evolution including, potentially informing on levels of fluid supersaturation from the study of calcite lattice distortion, and providing information on a reservoir's history of stress, strain, and deformation through investigation of calcite crystal deformation and twinning patterns.

  13. Prediction of calcite Cement Distribution in Shallow Marine Sandstone Reservoirs using Seismic Data

    Energy Technology Data Exchange (ETDEWEB)

    Bakke, N.E.

    1996-12-31

    This doctoral thesis investigates how calcite cemented layers can be detected by reflection seismic data and how seismic data combined with other methods can be used to predict lateral variation in calcite cementation in shallow marine sandstone reservoirs. Focus is on the geophysical aspects. Sequence stratigraphy and stochastic modelling aspects are only covered superficially. Possible sources of calcite in shallow marine sandstone are grouped into internal and external sources depending on their location relative to the presently cemented rock. Well data and seismic data from the Troll Field in the Norwegian North Sea have been analysed. Tuning amplitudes from stacks of thin calcite cemented layers are analysed. Tuning effects are constructive or destructive interference of pulses resulting from two or more closely spaced reflectors. The zero-offset tuning amplitude is shown to depend on calcite content in the stack and vertical stack size. The relationship is found by regression analysis based on extensive seismic modelling. The results are used to predict calcite distribution in a synthetic and a real data example. It is found that describing calcite cemented beds in shallow marine sandstone reservoirs is not a deterministic problem. Hence seismic inversion and sequence stratigraphy interpretation of well data have been combined in a probabilistic approach to produce models of calcite cemented barriers constrained by a maximum amount of information. It is concluded that seismic data can provide valuable information on distribution of calcite cemented beds in reservoirs where the background sandstones are relatively homogeneous. 63 refs., 78 figs., 10 tabs.

  14. Buffer clustering policy for sequential production lines with deterministic processing times

    Directory of Open Access Journals (Sweden)

    Francesca Schuler

    2016-09-01

    Full Text Available A sequential production line is defined as a set of sequential operations within a factory or distribution center whereby entities undergo one or more processes to produce a final product. Sequential production lines may gain efficiencies such as increased throughput or reduced work in progress by utilizing specific configurations while maintaining the chronological order of operations. One problem identified by the authors via a case study is that, some of the configurations, such as work cell or U-shaped production lines that have groups of buffers, often increase the space utilization. Therefore, many facilities do not take advantage of the configuration efficiencies that a work cell or U-shaped production line provide. To solve this problem, the authors introduce the concept of a buffer cluster. The production line implemented with one or more buffer clusters maintains the throughput of the line, identical to that with dedicated buffers, but with the clusters reduces the buffer storage space. The paper derives a time based parametric model that determines the sizing of the buffer cluster, provides a reduced time space for which to search for the buffer cluster sizing, and determines an optimal buffer clustering policy that can be applied to any N-server, N+1 buffer sequential line configuration with deterministic processing time. This solution reduces the buffer storage space utilized while ensuring no overflows or underflows occur in the buffer. Furthermore, the paper demonstrates how the buffer clustering policy serves as an input into a facility layout tool that provides the optimal production line layout.

  15. Phosphorus concentrations in soil and subsurface water: a field study among cropland and riparian buffers.

    Science.gov (United States)

    Young, Eric O; Briggs, Russell D

    2008-01-01

    Riparian buffers can be effective at removing phosphorus (P) in overland flow, but their influence on subsurface P loading is not well known. Phosphorus concentrations in the soil, soil solution, and shallow ground water of 16 paired cropland-buffer plots were characterized during 2004 and 2005. The sites were located at two private dairy farms in Central New York on silt and gravelly silt loams (Aeric Endoaqualfs, Fluvaquentic Endoaquepts, Fluvaquentic Eutrudepts, Glossaquic Hapludalfs, and Glossic Hapludalfs). It was hypothesized that P availability (sodium acetate extractable-P) and soil-landscape variability would affect P release to the soil solution and shallow ground water. Results showed that P availability tended to be greater in crop fields relative to paired buffer plots. Soil P was a good indicator of soil solution dissolved ( or =0.45 microm) reactive P (PRP), and dissolved unreactive P (DUP) concentrations in ground water. Soil organic matter and 50-cm depth soil solution DRP in buffers jointly explained 75% of the average buffer ground water DRP variability. Results suggest that buffers were relatively effective at reducing soil solution and shallow ground water DRP concentrations, but their impact on particulate and organic P in ground water was less clear. PMID:18178879

  16. Melatonin: Buffering the Immune System

    Directory of Open Access Journals (Sweden)

    Juan M. Guerrero

    2013-04-01

    Full Text Available Melatonin modulates a wide range of physiological functions with pleiotropic effects on the immune system. Despite the large number of reports implicating melatonin as an immunomodulatory compound, it still remains unclear how melatonin regulates immunity. While some authors argue that melatonin is an immunostimulant, many studies have also described anti-inflammatory properties. The data reviewed in this paper support the idea of melatonin as an immune buffer, acting as a stimulant under basal or immunosuppressive conditions or as an anti-inflammatory compound in the presence of exacerbated immune responses, such as acute inflammation. The clinical relevance of the multiple functions of melatonin under different immune conditions, such as infection, autoimmunity, vaccination and immunosenescence, is also reviewed.

  17. Electroejaculation and semen buffer evaluation in the microbat Carollia perspicillata.

    Science.gov (United States)

    Fasel, Nicolas Jean; Helfenstein, Fabrice; Buff, Samuel; Richner, Heinz

    2015-03-15

    Scientific interests and conservation needs currently stress the necessity to better understanding bat reproductive biology. In this study, we present the first, safe, inexpensive, and reliable method to obtain sperm from a microbat species (Carollia perspicillata) by electroejaculation. This method revealed to be highly efficient (100% success rate). We obtained ejaculates composed of two characteristically different fractions. We compared three buffers and recommend using an Earle's balanced salt solution as a semen extender. Earle's balanced salt solution provided significant repeatable measure of swimming ability (intraclass correlation coefficient: 0.74, P < 0.01) and proportion of motile sperms (intraclass correlation coefficient: 0.08, P = 0.01) and allowed sperm to maintain optimal swimming capacity over time. None of the buffers could dissolve all the coagulated sperm. Although the trypsin buffer freed a larger fraction of spermatozoa in the ejaculate, it impaired swimming ability without improving motility, viability, and stamina. We thus argue that the sperm population analyzed with Earle's balanced salt solution is a representative of the ejaculate. Finally, we found that the mean sperm velocity of C perspicillata (78.8 μm/s) is lower than that predicted by regressing sperm velocity on relative testes mass, a proxy of sperm competition. The question as to whether C perspicillata is an outsider for sperm velocity, or whether bats evolved yet another unique mechanism to cope with sperm competition deserves more investigations. PMID:25541424

  18. Operation voltage behavior of organic light emitting diodes with polymeric buffer layers doped by weak electron acceptor

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Hyeon Soo; Cho, Sang Hee [Department of Information Display and Advanced Display Research Center, Kyung Hee University, Seoul 130-701 (Korea, Republic of); Seo, Jaewon; Park, Yongsup [Department of Physics, Kyung Hee University, Seoul 130-701 (Korea, Republic of); Suh, Min Chul, E-mail: mcsuh@khu.ac.kr [Department of Information Display and Advanced Display Research Center, Kyung Hee University, Seoul 130-701 (Korea, Republic of)

    2013-11-01

    We present polymeric buffer materials based on poly[2,7-(9,9-dioctyl-fluorene)-co-(1,4-phenylene -((4-sec-butylphenyl)imino)-1,4-phenylene)] (TFB) for highly efficient solution processed organic light emitting diodes (OLEDs). Doped TFB with 9,10-dicyanoanthracene, a weak electron acceptor results in significant improvement of current flow and driving voltage. Maximum current- and power-efficiency value of 12.6 cd/A and 18.1 lm/W are demonstrated from phosphorescent red OLEDs with this doped polymeric anode buffer system. - Highlights: • Polymeric buffer materials for organic light emitting diodes (OLEDs). • Method to control hole conductivity of polymeric buffer layer in OLED device. • Enhanced current density of buffer layers upon 9,10-dicyanoanthracene (DCA) doping. • Comparison of OLED devices having polymeric buffer layer with or without DCA. • Effect on operating voltage by doping DCA in the buffer layer.

  19. Operation voltage behavior of organic light emitting diodes with polymeric buffer layers doped by weak electron acceptor

    International Nuclear Information System (INIS)

    We present polymeric buffer materials based on poly[2,7-(9,9-dioctyl-fluorene)-co-(1,4-phenylene -((4-sec-butylphenyl)imino)-1,4-phenylene)] (TFB) for highly efficient solution processed organic light emitting diodes (OLEDs). Doped TFB with 9,10-dicyanoanthracene, a weak electron acceptor results in significant improvement of current flow and driving voltage. Maximum current- and power-efficiency value of 12.6 cd/A and 18.1 lm/W are demonstrated from phosphorescent red OLEDs with this doped polymeric anode buffer system. - Highlights: • Polymeric buffer materials for organic light emitting diodes (OLEDs). • Method to control hole conductivity of polymeric buffer layer in OLED device. • Enhanced current density of buffer layers upon 9,10-dicyanoanthracene (DCA) doping. • Comparison of OLED devices having polymeric buffer layer with or without DCA. • Effect on operating voltage by doping DCA in the buffer layer

  20. Moisture Buffering in the Indoor Environment

    OpenAIRE

    Svennberg, Kaisa

    2006-01-01

    Moisture buffering in the indoor environment is the ability, through absorption and desorption, of surface materials to attenuate the moisture variations of the indoor air. Moisture buffering plays an important role in understanding the risks for biological growth in surface materials in the indoor environment, e.g., mold growth on walls and house dust mites in beds, and thereby also have an impact on the health of the inhabitants. Apart from the health aspects, moisture buffering is also imp...

  1. A Constant Factor Approximation Algorithm for Reordering Buffer Management

    CERN Document Server

    Avigdor-Elgrabli, Noa

    2012-01-01

    In the reordering buffer management problem (RBM) a sequence of $n$ colored items enters a buffer with limited capacity $k$. When the buffer is full, one item is removed to the output sequence, making room for the next input item. This step is repeated until the input sequence is exhausted and the buffer is empty. The objective is to find a sequence of removals that minimizes the total number of color changes in the output sequence. The problem formalizes numerous applications in computer and production systems, and is known to be NP-hard. We give the first constant factor approximation guarantee for RBM. Our algorithm is based on an intricate "rounding" of the solution to an LP relaxation for RBM, so it also establishes a constant upper bound on the integrality gap of this relaxation. Our results improve upon the best previous bound of $O(\\sqrt{\\log k})$ of Adamaszek et al. (STOC 2011) that used different methods and gave an online algorithm. Our constant factor approximation beats the super-constant lower b...

  2. On the origin of fiber calcite crystals in moonmilk deposits.

    Science.gov (United States)

    Cañaveras, Juan Carlos; Cuezva, Soledad; Sanchez-Moral, Sergio; Lario, Javier; Laiz, Leonila; Gonzalez, Juan Miguel; Saiz-Jimenez, Cesareo

    2006-01-01

    In this study, we show that moonmilk subaerial speleothems in Altamira Cave (Spain) consist of a network of fiber calcite crystals and active microbial structures. In Altamira moonmilks, the study of the typology and distribution of fiber crystals, extracellular polymeric substances, and microorganisms allowed us to define the initial stages of fiber crystal formation in recent samples as well as the variations in the microstructural arrangement in more evolved stages. Thus, we have been able to show the existence of a relationship among the different types of fiber crystals and their origins. This allowed us to outline a model that illustrates the different stages of formation of the moonmilk, developed on different substrata, concluding that microbes influence physicochemical precipitation, resulting in a variety of fiber crystal morphologies and sizes. PMID:16240102

  3. Shock-induced effects in calcite from Cactus Crater

    Science.gov (United States)

    Vizgirda, J.; Ahrens, T. J.; Tsay, F.-D.

    1980-01-01

    The paper discusses shock metamorphism of calcite from coralline limestone samples retrieved from a borehole drilled into rocks beneath Cactus Crater, a nuclear explosion crater at Eniwetok Atoll. The metamorphism was detected and quantified using electron spin resonance (ESR); the ESR spectra of Mn(+) present as a trace constituent in the coral samples, show a consistent decrease in hyperfine peak splitting with decreasing depth of sample. It is suggested that the decrease in hyperfine peak splitting reflects a decrease in crystal field splitting, and therefore, small increases on cation-anion distances produced by mechanical energy input during the shock process. Two alternative crater models suggested by the ESR results are a depiction of a steady decay of the shock wave, and a delineation of a breccia lens with a breccia-bedrock interface at 20 plus or minus 5 m.

  4. Development of analytical technique of alteration minerals formed in bentonite by the reaction with alkaline solution

    International Nuclear Information System (INIS)

    Bentonite will be used as a buffer material, according to the TRU waste disposal concept in Japan, to retard radionuclides migration, to restrict seepage of ground water and to filtrate colloids. One of the concern about the buffer material is the long term alteration of bentonite with cementitious material. Long term alteration of bentonite-based materials with alkaline solution has been studied by means of analytical approaches, coupling mass transport and chemical reactions, which suggest changes in various properties of buffer materials. Long term performance assessment of engineered barriers under disposal conditions is important to achieve a reasonable design, eliminating excessive conservatism in the safety assessment. Therefore it is essential for improving the reliance of the performance assessment to verify the analytical results through alteration tests and/or natural analogue. The geochemical analyses indicate that major alteration reactions involve dissolution of portlandite, chalcedony and montmorillonite and formation of C-S-H gel and analcime at the interface between cement and bentonite. However, in the alteration tests assuming interaction between bentonite and cement, secondary minerals due to alteration under the expected condition for geological disposal (equilibrated water with cement at low liquid/solid ratio) had not been observed, though the alteration was observed under accelerated hyper alkaline and high temperatures conditions. The reason is considered that it is difficult to analyze C-S-H gel formed at the interface because of its small quantity. One of examples is the Kunigel V1, a potential buffer material in Japan, which consists of montmorillonite, chalcedony, plagioclase, and calcite. In the XRD analysis of the Kunigel V 1, the locations of the primary peak of the calcite and that of the C-S-H gel overlap, which makes identification of small quantity of C-S-H gel formed as a secondary mineral difficult. Thus development of

  5. Biotic control of skeletal growth by scleractinian corals in aragonite-calcite seas.

    Directory of Open Access Journals (Sweden)

    Tomihiko Higuchi

    Full Text Available Modern scleractinian coral skeletons are commonly composed of aragonite, the orthorhombic form of CaCO3. Under certain conditions, modern corals produce calcite as a secondary precipitate to fill pore space. However, coral construction of primary skeletons from calcite has yet to be demonstrated. We report a calcitic primary skeleton produced by the modern scleractinian coral Acropora tenuis. When uncalcified juveniles were incubated from the larval stage in seawater with low mMg/Ca levels, the juveniles constructed calcitic crystals in parts of the primary skeleton such as the septa; the deposits were observable under Raman microscopy. Using scanning electron microscopy, we observed different crystal morphologies of aragonite and calcite in a single juvenile skeleton. Quantitative analysis using X-ray diffraction showed that the majority of the skeleton was composed of aragonite even though we had exposed the juveniles to manipulated seawater before their initial crystal nucleation and growth processes. Our results indicate that the modern scleractinian coral Acropora mainly produces aragonite skeletons in both aragonite and calcite seas, but also has the ability to use calcite for part of its skeletal growth when incubated in calcite seas.

  6. Carbon and oxygen isotopes in apatite CO2 and co-existing calcite

    International Nuclear Information System (INIS)

    Carbon and oxygen isotopes were analyzed in carbonate apatite CO2 and in co-existing calcite. Both C and O in apatite CO2 are enriched in the respective light isotopes relative to calcite. These results confirm the proposition that carbonate is part of the apatite structure

  7. Biotic Control of Skeletal Growth by Scleractinian Corals in Aragonite–Calcite Seas

    Science.gov (United States)

    Higuchi, Tomihiko; Fujimura, Hiroyuki; Yuyama, Ikuko; Harii, Saki; Agostini, Sylvain; Oomori, Tamotsu

    2014-01-01

    Modern scleractinian coral skeletons are commonly composed of aragonite, the orthorhombic form of CaCO3. Under certain conditions, modern corals produce calcite as a secondary precipitate to fill pore space. However, coral construction of primary skeletons from calcite has yet to be demonstrated. We report a calcitic primary skeleton produced by the modern scleractinian coral Acropora tenuis. When uncalcified juveniles were incubated from the larval stage in seawater with low mMg/Ca levels, the juveniles constructed calcitic crystals in parts of the primary skeleton such as the septa; the deposits were observable under Raman microscopy. Using scanning electron microscopy, we observed different crystal morphologies of aragonite and calcite in a single juvenile skeleton. Quantitative analysis using X-ray diffraction showed that the majority of the skeleton was composed of aragonite even though we had exposed the juveniles to manipulated seawater before their initial crystal nucleation and growth processes. Our results indicate that the modern scleractinian coral Acropora mainly produces aragonite skeletons in both aragonite and calcite seas, but also has the ability to use calcite for part of its skeletal growth when incubated in calcite seas. PMID:24609012

  8. Temperature buffer test. Dismantling operation

    Energy Technology Data Exchange (ETDEWEB)

    Aakesson, Mattias [Clay Technology AB, Lund (Sweden)

    2010-12-15

    The Temperature Buffer Test (TBT) is a joint project between SKB/ANDRA and supported by ENRESA (modelling) and DBE (instrumentation), which aims at improving the understanding and to model the thermo-hydro-mechanical behavior of buffers made of swelling clay submitted to high temperatures (over 100 deg C) during the water saturation process. The test has been carried out in a KBS-3 deposition hole at Aespoe HRL. It was installed during the spring of 2003. Two heaters (3 m long, 0.6 m diameter) and two buffer arrangements have been investigated: the lower heater was surrounded by bentonite in the usual way, whereas the upper heater was surrounded by a ring of sand. The test was dismantled and sampled during a period from the end of October 2009 to the end of April 2010, and this report describes this operation. Different types of samples have been obtained during this operation. A large number of diameter 50 mm bentonite cores have been taken for analysis of water content and density. Large pieces, so-called big sectors, have been taken for hydro-mechanical and chemical characterizations. Finally, there has been an interest to obtain different types of interface samples in which bentonite were in contact with sand, iron or concrete. One goal has been to investigate the retrievability of the upper heater, given the possibility to remove the surrounding sand shield, and a retrieval test has therefore been performed. The sand in the shield was first removed with an industrial vacuum cleaner after loosening the material through mechanical means (with hammer drill and core machine). A front loader was subsequently used for applying a sufficient lifting force to release the heater from the bentonite underneath. The experiment has been documented in different aspects: measurements of the coordinate (height or radius) of different interfaces (between bentonite blocks and between bentonite and sand); verification of sensor positions and retrieval of sensors for subsequent

  9. Low limit of Mn 2+-activated cathodoluminescence of calcite: state of the art

    Science.gov (United States)

    Habermann, Dirk; Neuser, Rolf D.; Richter, Detlev K.

    1998-02-01

    In the literature, the lower limit for Mn 2+-activated cathodoluminescence (CL) of calcite is variously reputed to over a very wide range of values above 10 ppm Mn. Our spectroscopic investigations of the CL response in natural calcite reveal that below 10 ppm manganese content Mn 2+-activation is also present. Using the Quantitative High Resolution Spectral analysis of CL (QHRS-CL) an activation by Mn 2+ in the range of 700 ppb is proved, which cannot be determined visually. So, if not quenched, the minimum Mn 2+ content for Mn 2+-activation is one atom in the irradiated calcite crystal lattice volume. As the intrinsic (background blue) luminescence is used to determine non-altered biogenic calcite, the limit of Mn 2+-activation plays an important role in the interpretation of diagenetic processes. Our results of spectroscopic analyses require a revision of current opinions about the diagenesis of calcite as revealed by CL investigation.

  10. Influence of surface conductivity on the apparent zeta potential of calcite

    CERN Document Server

    Li, Shuai; Heberling, Frank; Devau, Nicolas; Jougnot, Damien; Chiaberge, Christophe

    2016-01-01

    Zeta potential is a physicochemical parameter of particular importance in describing the surface electrical properties of charged porous media. However, the zeta potential of calcite is still poorly known because of the difficulty to interpret streaming potential experiments. The Helmholtz-Smoluchowski (HS) equation is widely used to estimate the apparent zeta potential from these experiments. However, this equation neglects the influence of surface conductivity on streaming potential. We present streaming potential and electrical conductivity measurements on a calcite powder in contact with an aqueous NaCl electrolyte. Our streaming potential model corrects the apparent zeta potential of calcite by accounting for the influence of surface conductivity and flow regime. We show that the HS equation seriously underestimates the zeta potential of calcite, particularly when the electrolyte is diluted (ionic strength < 0.01 M) because of calcite surface conductivity. The basic Stern model successfully predicted ...

  11. Comparison of three buffers used in the formulation of buffered charcoal yeast extract medium.

    OpenAIRE

    Edelstein, P H; Edelstein, M A

    1993-01-01

    Growth of Legionella spp. on buffered charcoal yeast extract medium supplemented with alpha-ketoglutarate and formulated with 3-(n-morpholino)propanesulfonic acid (MOPS), 3-(n-morpholino)-2-hydroxypropanesulfonic acid (MOPSO), or n-(2-acetamido)-2-aminoethanesulfonic acid (ACES) buffer was similar. With three exceptions, growth was no different in buffered yeast extract broth supplemented with alpha-ketoglutarate and formulated with MOPS or ACES buffer.

  12. Study of adsorption behaviors of Cs+ and Yb3+ on calcite, kaolinite, montmorillonite, chlorite and glauconite

    International Nuclear Information System (INIS)

    The adsorption behaviors of Cs+ and Yb3+ on five minerals including calcite, kaolinite, montmorillonite, chlorite and glauconite are simultaneously investigated by the static equilibrium batch experiments with radioactive tracer technique. The experimental results indicate that under same experimental conditions (initial solution acidity, initial ion concentration and liquid-solid phase ratio), the adsorption capacity (Q) in unit of mmol/g of montmorillonite towards Cs+ and/or Yb3+ are stronger than other 4 minerals, which display no evident difference of Q values. The Rd of Cs+ and Yb3+ on the five minerals decrease with increasing of their initial concentrations in solution. The uptakes of Cs+ are ordinary lower than Ya3+ except for the high c0. The adsorption isotherms of Cs+ and Yb3+ are all in fairly agreement with the Freundlich's equation. The adsorption mechanism of Cs+ and Yb3+ in the systems of kaolinite, montmorillonite and chlorite at the experimental pH range is likely attributed to the process of ion exchange

  13. Investigation on the Morphology of Precipitated Chemicals from te Buffer on Solid Substrates

    Science.gov (United States)

    Wang, Huabin; Zhang, Lijuan; Zhang, Feng; An, Hongjie; Chen, Shimou; Li, Hai; Wang, Peng; Wang, Xinyang; Wang, Yang; Yang, Haijun

    Buffer is often involved in the biological studies on a surface with the scanning probe microscopy and the remnant of the salts of buffer may affect the correct interpretation of the experimental results. However, the knowledge on the performance of chemicals of buffer on a substrate is still very poor. TE solution (Tris-HCl, NaCl, and ethylene diamine tetraacetic acid (EDTA)) is a widely used buffer in stocking biological molecules. Herein, we report the performance of the precipitated chemicals from TE solution on two typical substrates with several commonly used sample preparation methods. The results showed that the chemicals in TE solution could self-organize into parallel nanofilaments on hydrophobic highly oriented pyrolitic graphite (HOPG) surface by blotting the shortly incubated solution droplet from the substrate or by drying the diluted solution droplet naturally. In contrast, no such special structures were observed on hydrophilic mica using the same methods. By imaging in TE solutions, no special structures were found on either the HOPG or the mica. Moreover, the effects of the concentration of chemicals of TE buffer on the morphology of precipitated chemicals were also investigated.

  14. 21 CFR 520.1696a - Buffered penicillin powder, penicillin powder with buffered aqueous diluent.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Buffered penicillin powder, penicillin powder with... FORM NEW ANIMAL DRUGS § 520.1696a Buffered penicillin powder, penicillin powder with buffered aqueous diluent. (a) Specifications. When reconstituted, each milliliter contains penicillin G procaine...

  15. Armouring of well cement in H2S–CO2 saturated brine by calcite coating – Experiments and numerical modelling

    International Nuclear Information System (INIS)

    The active acid gas (H2S–CO2 mixture) injection operations in North America provide practical experience for the operators in charge of industrial scale CO2 geological storage sites. Potential leakage via wells and their environmental impacts make well construction durability an issue for efficiency/safety of gas geological storage. In such operations, the well cement is in contact with reservoir brines and the injected gas, meaning that gas–water–solid chemical reactions may change the physical properties of the cement and its ability to confine the gas downhole. The cement-forming Calcium silicate hydrates carbonation (by CO2) and ferrite sulfidation (by H2S) reactions are expected. The main objective of this study is to determine their consequences on cement mineralogy and transfer ability. Fifteen and 60 days duration batch experiments were performed in which well cement bars were immersed in brine itself caped by a H2S–CO2 phase at 500 bar–120 °C. Scanning electron microscopy including observations/analyses and elemental mapping, mineralogical mapping by micro-Raman spectroscopy, X-ray diffraction and water porosimetry were used to characterize the aged cement. Speciation by micro-Raman spectroscopy of brine trapped within synthetic fluid inclusions were also performed. The expected calcium silicate hydrates carbonation and ferrite sulfidation reactions were evidenced. Furthermore, armouring of the cement through the fast creation of a non-porous calcite coating, global porosity decrease of the cement (clogging) and mineral assemblage conservation were demonstrated. The low W/R ratio of the experimental system (allowing the cement to buffer the interstitial and external solution pH at basic values) and mixed species diffusion and chemical reactions are proposed to explain these features. This interpretation is confirmed by reactive transport modelling performed with the HYTEC code. The observed cement armouring, clogging and mineral assemblage

  16. 46 CFR 58.25-45 - Buffers.

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 2 2010-10-01 2010-10-01 false Buffers. 58.25-45 Section 58.25-45 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING MAIN AND AUXILIARY MACHINERY AND RELATED SYSTEMS Steering Gear § 58.25-45 Buffers. For each vessel on an ocean, coastwise, or Great Lakes...

  17. African American College Women's Suicide Buffers.

    Science.gov (United States)

    Marion, Michelle S.; Range, Lillian M.

    2003-01-01

    To examine the relationships buffers may have with suicide ideation, 300 African American female college students completed measures of suicide ideation and buffers. Three variables accounted for a significant and unique portion of the variance in suicide ideation: family support, a view that suicide is unacceptable, and a collaborative religious…

  18. Shock buffer for nuclear control assembly

    International Nuclear Information System (INIS)

    A shock buffer is provided for the gradual deceleration of a rapidly descending control element assembly in a nuclear reactor. The interactive buffer components are associated respectively with the movable control element assembly and part of the upper guide structure independent of and spaced from the fuel assemblies of the reactor

  19. Buffer management in wireless full-duplex systems

    KAUST Repository

    Bouacida, Nader

    2015-10-19

    Wireless full-duplex radios can simultaneously transmit and receive using the same frequency. In theory, this can double the throughput. In fact, there is only little work addressing aspects other than throughput gains in full-duplex systems. Over-buffering in today\\'s networks or the so-called “bufferbloat” phenomenon creates excessive end-to-end delays resulting in network performance degradation. Our analysis shows that full-duplex systems may suffer from high latency caused by bloated buffers. In this paper, we address the problem of buffer management in full-duplex networks by using Wireless Queue Management (WQM), which is an active queue management technique for wireless networks. Our solution is based on Relay Full-Duplex MAC (RFD-MAC), an asynchronous media access control protocol designed for relay full-duplexing. We compare the performance of WQM in full-duplex environment to Drop Tail mechanism over various scenarios. Our solution reduces the end-to-end delay by two orders of magnitude while achieving similar throughput in most of the cases.

  20. Buffer sizing for multi-hop networks

    KAUST Repository

    Shihada, Basem

    2014-01-28

    A cumulative buffer may be defined for an interference domain in a wireless mesh network and distributed among nodes in the network to maintain or improve capacity utilization of network resources in the interference domain without increasing packet queuing delay times. When an interference domain having communications links sharing resources in a network is identified, a cumulative buffer size is calculated. The cumulative buffer may be distributed among buffers in each node of the interference domain according to a simple division or according to a cost function taking into account a distance of the communications link from the source and destination. The network may be monitored and the cumulative buffer size recalculated and redistributed when the network conditions change.

  1. SYSTEM AGGREGATION METHOD FOR FAILURE PRONE PRODUCTION LINES WITH UNRELIABLE LIMITED BUFFERS

    Institute of Scientific and Technical Information of China (English)

    LIU Jun; RUI Zhiyuan; ZHAO Juntian; WEI Yaobing

    2008-01-01

    Different from traditional aggregation method, the unreliable buffers are originally considered and a more general aggregation method is offered, in which not only the unreliable buffers are considered, but also the probabilities of system states are obtained by a discrete model rather than the continuous flow model of unreliable manufacturing systems. The solution technique is offered to get the system sate probabilities. The method advances the traditional system aggregation techniques. Numerical results specify the extended aggregation method and also show that the unreliable limited buffers have a strong impact on the efficiency of the production lines.

  2. Design on Buffer Structure of Traction Running with a Constant Speed

    Directory of Open Access Journals (Sweden)

    Zeng Xianren

    2013-06-01

    Full Text Available This study mainly aims to study buffer structure design on the traction transport system when the traction transport boundary conditions are given. With such conditions as the maximum impact force, traction speed, maximum speed of alluvium, the elasticity coefficient and the mass of buffer structure, a mathematical model was established and the solution of differential equations was solved. At last, a program was compiled with MATLAB language. With this program the elasticity coefficient and the maximum impact force which meet the requirements in impact process can be solved as long as the boundary conditions are input. This provides a quick design basis of buffer structure for most mechanical engineers.

  3. Optimized DPPH assay in a detergent-based buffer system for measuring antioxidant activity of proteins

    OpenAIRE

    Nicklisch, Sascha C.T.; Herbert Waite, J.

    2014-01-01

    © 2014 The Authors. (Graph Presented) The free radical method using 1,1-diphenyl-2-picryl-hydrazyl (DPPH) is a well established assay for the in vitro determination of antioxidant activity in food and biological extracts. The standard DPPH assay uses methanol or ethanol as solvents, or buffered alcoholic solutions in a ratio of 40%/60% (buffer/alcohol, v/v) to keep the hydrophobic hydrazyl radical and phenolic test compounds soluble while offering sufficient buffering capacity at different pH...

  4. STRONTIUM ISOTOPE EVOLUTION OF PORE WATER AND CALCITE IN THE TOPOPAH SPRING TUFF, YUCCA MOUNTAIN, NEVADA

    International Nuclear Information System (INIS)

    Yucca Mountain, a ridge of Miocene volcanic rocks in southwest Nevada, is being characterized as a site for a potential high-level radioactive waste repository. One issue of concern for the future performance of the potential repository is the movement of water in and around the potential repository horizon. Past water movement in this unsaturated zone is indicated by fluid inclusions trapped in calcite coatings on fracture footwall surfaces and in some lithophysal cavities. Some of the fluid inclusions have homogenization temperatures above the present-day geotherm (J.F. Whelan, written communication), so determining the ages of the calcite associated with those fluid inclusions is important in understanding the thermal history of the potential repository site. Calcite ages have been constrained by uranium-lead dating of silica polymorphs (opal and chalcedony) that are present in most coatings. The opal and chalcedony ages indicate that deposition of the calcite and opal coatings in the welded part of the Topopah Spring Tuff (TSw hydrogeologic unit) spanned nearly the entire history of the 12.8-million-year-old rock mass at fairly uniform overall long-term rates of deposition (within a factor of five). Constraining the age of a layer of calcite associated with specific fluid inclusions is complicated. Calcite is commonly bladed with complex textural relations, and datable opal or chalcedony may be millions of years older or younger than the calcite layer or may be absent from the coating entirely. Therefore, a more direct method of dating the calcite is presented in this paper by developing a model for strontium evolution in pore water in the TSw as recorded by the strontium coprecipitated with calcium in the calcite. Although the water that precipitated the calcite in fractures and cavities may not have been in local isotopic equilibrium with the pore water, the strontium isotope composition of all water in the TSw is primarily controlled by water

  5. Temperature buffer test. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Aakesson, Mattias [Clay Technology AB, Lund (Sweden)

    2012-04-15

    The Temperature Buffer Test (TBT) is a joint project between SKB/ANDRA and supported by ENRESA (modelling) and DBE (instrumentation), which aims at improving the understanding and to model the thermo-hydro-mechanical behavior of buffers made of swelling clay submitted to high temperatures (over 100 deg C) during the water saturation process. The test has been carried out in a KBS-3 deposition hole at Aspo HRL. It was installed during the spring of 2003. Two steel heaters (3 m long, 0.6 m diameter) and two buffer arrangements have been investigated: the lower heater was surrounded by rings of compacted Wyoming bentonite only, whereas the upper heater was surrounded by a composite barrier, with a sand shield between the heater and the bentonite. The test was dismantled and sampled during the winter of 2009/2010. This report is the final report and a summary of all work performed within the TBT project. The design and the installation of the different components are summarized: the depositions hole, the heating system, the bentonite blocks with emphasis on the initial density and water content in these, the filling of slots with sand or pellets, the retaining construction with the plug, lid and nine anchor cables, the artificial saturation system, and finally the instrumentation. An overview of the operational conditions is presented: the power output from heaters, which was 1,500 W (and also 1,600 W) from each heater during the first {approx}1,700 days, and then changed to 1,000 and 2,000 W, for the upper and lower heater respectively, during the last {approx}600 days. From the start, the bentonite was hydrated with a groundwater from a nearby bore-hole, but this groundwater was replaced with de-ionized water from day {approx}1,500, due to the high flow resistance of the injections points in the filter, which implied that a high filter pressure couldn't be sustained. The sand shield around the upper heater was hydrated from day {approx}1,500 to day {approx}1

  6. Temperature buffer test. Final report

    International Nuclear Information System (INIS)

    The Temperature Buffer Test (TBT) is a joint project between SKB/ANDRA and supported by ENRESA (modelling) and DBE (instrumentation), which aims at improving the understanding and to model the thermo-hydro-mechanical behavior of buffers made of swelling clay submitted to high temperatures (over 100 deg C) during the water saturation process. The test has been carried out in a KBS-3 deposition hole at Aspo HRL. It was installed during the spring of 2003. Two steel heaters (3 m long, 0.6 m diameter) and two buffer arrangements have been investigated: the lower heater was surrounded by rings of compacted Wyoming bentonite only, whereas the upper heater was surrounded by a composite barrier, with a sand shield between the heater and the bentonite. The test was dismantled and sampled during the winter of 2009/2010. This report is the final report and a summary of all work performed within the TBT project. The design and the installation of the different components are summarized: the depositions hole, the heating system, the bentonite blocks with emphasis on the initial density and water content in these, the filling of slots with sand or pellets, the retaining construction with the plug, lid and nine anchor cables, the artificial saturation system, and finally the instrumentation. An overview of the operational conditions is presented: the power output from heaters, which was 1,500 W (and also 1,600 W) from each heater during the first ∼1,700 days, and then changed to 1,000 and 2,000 W, for the upper and lower heater respectively, during the last ∼600 days. From the start, the bentonite was hydrated with a groundwater from a nearby bore-hole, but this groundwater was replaced with de-ionized water from day ∼1,500, due to the high flow resistance of the injections points in the filter, which implied that a high filter pressure couldn't be sustained. The sand shield around the upper heater was hydrated from day ∼1,500 to day ∼1,800. The sensors data concerning

  7. Uranium isotope fractionation during coprecipitation with aragonite and calcite

    Science.gov (United States)

    Chen, Xinming; Romaniello, Stephen J.; Herrmann, Achim D.; Wasylenki, Laura E.; Anbar, Ariel D.

    2016-09-01

    Natural variations in 238U/235U of marine calcium carbonates might provide a useful way of constraining redox conditions of ancient environments. In order to evaluate the reliability of this proxy, we conducted aragonite and calcite coprecipitation experiments at pH ∼7.5 and ∼8.5 to study possible U isotope fractionation during incorporation into these minerals. Small but significant U isotope fractionation was observed in aragonite experiments at pH ∼8.5, with heavier U isotopes preferentially enriched in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007 + 0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ∼7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3(aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism. These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2 , Ca2+, or Mg2+ concentrations. In general, these effects are likely to be small (<0.13‰), but are nevertheless potentially significant because of the small natural range of

  8. U-Th dating of calcitic corals from the Red Sea

    Science.gov (United States)

    Stein, M.; Yehudai, M.; Kohn, N.; Shaked, Y.; Agnon, A.; Lazar, B.

    2013-12-01

    Pristine aragonite skeletons of reef building corals can be rapidly recrystallized to calcite by the interaction of the corals with freshwater in coastal aquifers. The aragonite/calcite transformation is accompanied by opening the coral's U-Th isotope system in which uranium is partly lost while Th remains adsorbed and reincorporates into the newly formed calcite. Depending on the geological setting of the reef, the corals may incorporate secondary aragonite with higher U and 234U/238U isotope ratio, while still submerged, before the recrystallization process. Recrystallization to calcite occurs during sea level drop or coast tectonic uplift and later may follow a subaerial closed system decay scheme. In this study we examine the behavior of the U and Th in calcitic corals from the last interglacial reefs at the northern Gulf of Aqaba. We analyzed several subsamples from selected reef coral skeletons in an attempt to follow the recrystallization scheme of the corals and find a reliable method to estimate the age of these heavily altered corals. The main assumptions were that all subsamples from the same coral have identical deposition age and the sub-samples Th (and hence 230Th) was fully preserved during recrystallization to calcite (increasing the 230Th/238U isotope ratio). Diagenesis to calcite occurred several thousand years after the initial precipitation of the aragonitic skeleton. This calls for wetter (than present) conditions during the last interglacial in the currently hyperarid northern Red Sea.

  9. Analyses IR quantitatives des sédiments. Exemple du dosage du quartz et de la calcite Quantitative Ir Analysis of Sediments. Example of Quartz and Calcite Determination

    Directory of Open Access Journals (Sweden)

    Pichard C.

    2006-11-01

    Full Text Available Plus généralement utilisée pour l'étude des phases fluides, la spectrophotométrie d'absorption infrarouge a trouvé un important champ d'application dans l'analyse minéralogique quantitative globale des roches sédimentaires. En s'appuyant sur deux exemples précis de constituants importants des sédiments (quartz et calcite, on montre ici les différentes possibilités analytiques avec échantillon seul, compensation du diluant pur, compensation d'un minéral pur et compensation d'un minéral en mélange artificiel et naturel (roche sédimentaire. On décrit les modifications subies par les spectres et des courbes d'étalonnages sont dressées dans chaque cas. Les données recueillies permettent de vérifier l'utilisation légitime de la loi d'absorption pour ces analyses infrarouges de phases solides impliquant une compensation, et donc un traitement des spectres originaux, l'erreur relative maximale expérimentale ne dépassant pas quelques pourcents dans les cas les plus défavorables. Dans les limites du dosage de minéraux à composition chimique et structure cristalline fixes, l'analyse d'un minéral par sa compensation partielle peut être d'un grand intérêt pour des constituants majeurs de roches, car autorisant l'analyse là où une concentration trop élevée l'aurait interdite. Cette méthode de compensation est plus délicate, voire impossible, pour les solutions solides ou tout minéral à formule chimique variable. D'une manière générale, les principaux constituants des roches sédimentaires peuvent être ainsi quantifiés sur un seul spectre par l'analyse IR qui offre donc la possibilité d'une définition numérique des faciès. Although it is more generally used for analyzing fluid phases, infrared absorption spectrophotometry has found an important area of application in the bulk quantitative mineralogical analysis of sedimentary rocks. On the basis of two specific examples of important constituents of sediments

  10. Electrophoretic mobilities of erythrocytes in various buffers

    Science.gov (United States)

    Plank, L. D.; Kunze, M. E.; Todd, P. W.

    1985-01-01

    The calibration of space flight equipment depends on a source of standard test particles, this test particle of choice is the fixed erythrocyte. Erythrocytes from different species have different electrophoretic mobilities. Electrophoretic mobility depends upon zeta potential, which, in turn depends upon ionic strength. Zeta potential decreases with increasing ionic strength, so cells have high electrophoretic mobility in space electrophoresis buffers than in typical physiological buffers. The electrophoretic mobilities of fixed human, rat, and rabbit erythrocytes in 0.145 M salt and buffers of varying ionic strength, temperature, and composition, to assess the effects of some of the unique combinations used in space buffers were characterized. Several effects were assessed: glycerol or DMSO (dimethylsulfoxide) were considered for use as cryoprotectants. The effect of these substances on erythrocyte electrophoretic mobility was examined. The choice of buffer depended upon cell mobility. Primary experiments with kidney cells established the choice of buffer and cryoprotectant. A nonstandard temperature of EPM in the suitable buffer was determined. A loss of ionic strength control occurs in the course of preparing columns for flight, the effects of small increases in ionic strength over the expected low values need to be evaluated.

  11. Constraints on quaternary unsaturated- and saturated-zone hydrology from geochronological and isotopic studies of calcite and silica, Yucca Mountain, Nevada, USA

    International Nuclear Information System (INIS)

    Both unsaturated- and saturated-zone aqueous solutions are capable of precipitating secondary mineral deposits that document the history and origins of past water flux. Calcite and opal occur as thin coatings on open fractures and cavity floors within the thick unsaturated zone at Yucca Mountain. Outermost surfaces of calcite have 14C ages of between 44,000 and 16,000 radiocarbon years; however, the same surfaces have 230Th/U ages from 28 ka to more than 500 ka. This discordance, along with negative covariance between conventionally calculated 230Th/U ages and initial 234U/238U is best explained by very slow rates of mineral growth where discrete depositional layers are too fine to separate and measure individually. Therefore, isotopic analyses and resulting ages represent mixtures between the deepest and shallowest layers incorporated within a given sub-sample. (author)

  12. The potential for phosphorus pollution remediation by calcite precipitation in UK freshwaters

    Directory of Open Access Journals (Sweden)

    C. Neal

    2001-01-01

    Full Text Available This paper examines the potential for calcium carbonate to reduce phosphate pollution in freshwaters by co-precipitation, a process known as a "self cleansing mechanism". Calcium carbonate saturation levels and phosphate concentrations (SRP - soluble reactive phosphate across the major eastern UK river basins are examined to test for solubility controls. The study shows that calcite saturation varies for each catchment as a function of flow and biological activity rather than by direct regulation by SRP. Indeed, there is no evidence, for any of the rivers studied, that calcite solubility controls hold. However, for groundwater and groundwater-fed springs in the Chalk of the Thames basin, calcite saturation is observed with associated low SRP levels. A self-cleansing mechanism may well be operative within the Chalk due to two factors. Firstly, there is a high potential for nucleation on the calcite micro-crystals in the aquifer. Secondly, there are within aquifer reactions that remove the calcite nucleating inhibitors (SRP and dissolved organic carbon, DOC to levels lower than those occurring within the rivers do. These inhibitors enter the catchment at very high concentrations in association with agricultural pollution (fertilizer application and animal slurry and household contamination (e.g. sewage sources from septic tanks. Under low flow conditions, when the saturation index for calcite is at its highest, so too is the concentration of the nucleation inhibitor SRP. Companion work shows that calcite precipitation can occur at the water-sediment interface of the river and this may involve SRP removal. The data, as a whole, define an apparent bound for calcite solubility control where in the presence of nucleating centres, SRP must be less than 4 mM-P l-1 and DOC must be less than 150 mM-C l-1: a condition that does not seem to pertain within most UK rivers. Keywords: calcite, calcium carbonate, phosphate, soluble reactive phosphate, dissolved

  13. Low-magnesium uranium-calcite with high degree of crystallinity and gigantic luminescence emission

    Energy Technology Data Exchange (ETDEWEB)

    Valle-Fuentes, Francisco-Jose [Instituto de Ceramica y Vidrio, CSIC. Cantoblanco, 28049 Madrid (Spain); Garcia-Guinea, Javier [Museo Nacional Ciencias Naturales, CSIC, 28006 Madrid (Spain)]. E-mail: guinea@mncn.csic.es; Cremades, Ana [Departmento Fisica de Materiales, Facultad de Fisicas, University Complutense de Madrid, 28040 Madrid (Spain); Correcher, Virgilio [CIEMAT, Laboratory Dosimetria de Radiaciones, 28040 Madrid (Spain); Sanchez-Moral, Sergio [Museo Nacional Ciencias Naturales, CSIC, 28006 Madrid (Spain); Gonzalez-Martin, Rafael [Museo Nacional Ciencias Naturales, CSIC, 28006 Madrid (Spain); Sanchez-Munoz, Luis [CIEMAT, Laboratory Dosimetria de Radiaciones, 28040 Madrid (Spain); Lopez-Arce, Paula [Getty Conservation Institute, 1200 Getty Center Drive, Suite 700, Los Angeles, CA 90049 (United States)

    2007-01-15

    Cabrera (Madrid) low-Mg calcites exhibit: (i) an unusual twofold elevation in X-ray diffraction pattern intensity; (ii) a 60-fold elevation of luminescence emission, compared to six common natural calcites selected for comparison purposes; (iii) a natural relatively high radiation level of circa 200 nSv h{sup -1} not detected in 1300 other calcites from the Natural History Museum of Madrid. Calcites were analysed by the X-ray diffraction powder method (XRD), cathodo-luminescence spectroscopy in scanning electron microscopy (CL-SEM), thermoluminescence (TL), differential thermal analysis (DTA), X-ray fluorescence spectrometry (XRF) and particle size distribution (PSD). The Cabrera calcite study shows: (i) helicoidally distributed steps along the (0 0 0 1) orientation; (ii) protuberance defects onto the (0 0 0 1) surface, observed by SEM; (iii) XRF chemical contents of 0.03% MgO, 0.013% of Y{sub 2}O{sub 3}, and 0.022% of U{sub 3}O{sub 8}, with accessory amounts of rare earth elements (REE); (iv) DTA dissociation temperature of 879 {sup o}C; (v) TL maxima peaks at 233 and 297 {sup o}C whose areas are 60 times compared to other calcites; (vi) spectra CL-SEM bands at 2.0 and 3.4 eV in the classic structure of Mn{sup 2+} activators; (vii) a twofold XRD pattern explained given that sample is a low-Mg calcite. The huge TL and CL emissions of the Cabrera calcite sample must be linked with the uranyl group presence. This intense XRD pattern in low-Mg calcites could bring into being analytical errors.

  14. Investigation of Strontium Incorporation into Biotically and Abiotically Precipitated-Calcium Calcite Using Secondary Ion Mass Spectrometry

    Science.gov (United States)

    Ingram, J.; Fujita, Y.

    2001-12-01

    Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) complex. A possible approach to their remediation is in situ immobilization by co-precipitation of these elements in authigenic calcite and calcite overgrowths. Microorganisms are known to facilitate the precipitation of calicite; hence the stimulation of biogenic calcite production may offer a means to accelerate co-precipitation of contaminant metals. Strontium is well-known to substitute for Ca in calcium carbonate minerals, and consequently , the uranium fission product 90Sr is a prime candidate for this type of remediation approach. In order to predict the extent and stability of Sr incorporation into calcite precipitated under this bioremediation strategy, it is necessary to understand how much Sr is being incorporated. In these studies, secondary ion mass spectrometry (SIMS) was utilized to characterize the surface chemistry of carbonates generated by bacterial activity in synthetic groundwater containing Ca and Sr. SIMS with sputter depth profiling allows the determination of changes in Sr to Ca ratios with depth in particulate carbonate samples. The sputter depth profiling results can be compared with analysis of the bulk composition by inductively coupled plasma atomic emission spectroscopy (ICP-AES). Results of analyses on carbonates generated by B. pasteurii in synthetic groundwater with initial Ca and Sr concentrations of 80 ppm and 10 ppm, respectively, showed that SIMS could successfully measure ion ratios on the surface and within these particles. ICP-AES data indicated a bulk Sr:Ca ratio of 0.11, and sputtering SIMS data approached this value with increasing depth into the particle. The Sr:Ca ratio however, contrary to what would be expected from precipitation under batch conditions, was lower at the surface of the particles (ca. 0.05) and increased with depth. One possible reason for this phenomenon is re

  15. Buffer protection in the installation phase

    International Nuclear Information System (INIS)

    The research and development of the design and construction of the SKB's repository for final disposal of spent reactor fuel is conducted along several paths ('lines'). Issues concerning the bedrock are dealt with in the 'rock line' and those related to buffer and backfill in deposition holes and tunnels are considered in the 'buffer line' and 'backfill line', respectively. These lines also deal with sub-activities that are coupled to several other lines. One of them includes development of techniques for protecting buffer blocks from moisture and water in the installation phase. Techniques and methods for placement and removal of the 'buffer protection sheet' are dealt with in the 'buffer line'. The removal is, however, considered as being part of the backfilling sequence. Since the performance of the sheet is of fundamental importance to the placement and function of the buffer it deserves particular attention. Thus, the removal of the rubber sheet that serves to protect the buffer blocks in the installation phase may be difficult and can cause significant problems that may require retrieval of already placed canister, buffer and backfill. These matters are in focus in the present report. Arrangements for protecting already placed buffer blocks from moist air and water have been tested in earlier large-scale experiments, i.e. the Prototype Repository project at Aespoe but the experience from them has called for more effective protection of the clay blocks as described in the present report. Focus is on the construction of foundation components at the bottom of the deposition holes required for establishing a tight seal between rock and buffer blocks, and on the protection sheet and arrangements for limiting water pressure on it. Special attention is paid to the drainage of the space between rock and protection sheet that is necessary for avoiding failure of the sheet and to systems for achieving this and for providing alarm signals if the allowed pressure is

  16. Surface Water Protection by Productive Buffers

    DEFF Research Database (Denmark)

    Christen, Benjamin

    Vegetated riparian buffer zones are a widely recommended best management practice in agriculture for protecting surface and coastal waters from diffuse nutrient pollution. On the background of the EU funded research project NitroEurope (NEU; www.NitroEurope.eu), this study concentrates...... on the mitigation of nitrogen pollution in surface and groundwater, using riparian buffer zones for biomass production. The objectives are to map suitable areas for buffer implementation across the six NEU study landscapes, model tentative N-loss mitigation, calculate biomass production potential and economic...... designed for local conditions could be a way of protecting water quality attractive to many stakeholders....

  17. Paleohydrogeological implications from fracture calcites in fissures of low transmissivity. A report of investigations in 2011

    International Nuclear Information System (INIS)

    Samples of fracture fillings were collected from 26 bedrock fractures at Olkiluoto. Special attention was paid to fractures having low transmissivities of <1E-8 m2/s. The chemical composition and the C and O isotopic composition of the fracture filling calcite were analysed. In addition, fluid inclusions were studied and microthermometric measurements conducted on fracture filling calcite. The most common minor element in calcite fillings was Mn, having concentrations up to 3.4 wt-%. The δ13C values had a wide range, from -13.0 to 14.5 per mille, and the δ18O values a narrower range, from -13.4 to -7.3 per mille. The δ18O values of late-stage calcite appear to be independent of the transmissivity of the fractures, ranging from -11.2 to -7.3 per mille over a T range from 3E-6 to 1.6E-11 m2/s. The δ13C values of late-stage calcite appear to have more variation at high transmissivities of >1E-8 m2/s. Unusually low and high δ13C values in late-stage calcite fillings occur in the upper ∼ 400 m of the bedrock and are probably related to microbial reduction processes, at near surface (<60 m) conditions to oxidation of organic matter resulting in low δ13C values and at ∼ 55-400 m to methanogenesis, causing high δ 13C values. A relatively low spread in the δ 13C values of late-stage calcite precipitates in low transmissivity (<1E-8 m2/s) fractures is most likely caused by stable conditions in the areas of low conductivity in the bedrock, reflecting slow dissolution/reprecipitation of older carbonate fillings. Fluid inclusion data indicate variation in fracture water types from high temperature, ∼ 200 deg C, low salinity fluid with < 4 wt-% of NaCleq to low temperature, <100 deg C, high salinity fluid with 17-29 wt-% of NaCleq. The high temperature fluid is associated with Group 5 calcite fillings and the low temperature fluid with Group 3 calcite. The composition of fluids related to Group 4 calcite falls roughly between the compositions representing Group 5

  18. Comparison of galvanic displacement and electroless methods for deposition of gold nanoparticles on synthetic calcite

    Indian Academy of Sciences (India)

    Chamarthi K Srikanth; P Jeevanandam

    2012-11-01

    Gold nanoparticles have been deposited on synthetic calcite substrate by galvanic displacement reaction and electroless deposition methods. A comparative study has shown that electroless deposition is superior compared to galvanic displacement reaction for uniform deposition of gold nanoparticles on calcite. Characterization of the samples, prepared by two different deposition methods, was carried out by X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy (FE–SEM) and diffuse reflectance spectroscopy (DRS) measurements. FE–SEM studies prove that smaller nanoparticles of gold are deposited uniformly on calcite if electroless deposition method was employed and DRS measurements show the characteristic surface plasmon resonance of gold nanoparticles.

  19. Paleohydrogeological implications from fracture calcites in fissures of low transmissivity. A report of investigations in 2011

    Energy Technology Data Exchange (ETDEWEB)

    Sahlstedt, E.; Karhu, J. [Univ. of Helsinki (Finland)

    2014-07-15

    Samples of fracture fillings were collected from 26 bedrock fractures at Olkiluoto. Special attention was paid to fractures having low transmissivities of <1E-8 m{sup 2}/s. The chemical composition and the C and O isotopic composition of the fracture filling calcite were analysed. In addition, fluid inclusions were studied and microthermometric measurements conducted on fracture filling calcite. The most common minor element in calcite fillings was Mn, having concentrations up to 3.4 wt-%. The δ13C values had a wide range, from -13.0 to 14.5 per mille, and the δ18O values a narrower range, from -13.4 to -7.3 per mille. The δ18O values of late-stage calcite appear to be independent of the transmissivity of the fractures, ranging from -11.2 to -7.3 per mille over a T range from 3E{sup -6} to 1.6E{sup -1}1 m{sup 2}/s. The δ13C values of late-stage calcite appear to have more variation at high transmissivities of >1E-8 m{sup 2}/s. Unusually low and high δ13C values in late-stage calcite fillings occur in the upper ∼ 400 m of the bedrock and are probably related to microbial reduction processes, at near surface (<60 m) conditions to oxidation of organic matter resulting in low δ13C values and at ∼ 55-400 m to methanogenesis, causing high δ 13C values. A relatively low spread in the δ 13C values of late-stage calcite precipitates in low transmissivity (<1E-8 m{sup 2}/s) fractures is most likely caused by stable conditions in the areas of low conductivity in the bedrock, reflecting slow dissolution/reprecipitation of older carbonate fillings. Fluid inclusion data indicate variation in fracture water types from high temperature, ∼ 200 deg C, low salinity fluid with < 4 wt-% of NaCl{sub eq} to low temperature, <100 deg C, high salinity fluid with 17-29 wt-% of NaCl{sub eq}. The high temperature fluid is associated with Group 5 calcite fillings and the low temperature fluid with Group 3 calcite. The composition of fluids related to Group 4 calcite falls roughly

  20. Distribution of Minor Elements in Calcite From the Unsaturated Zone at Yucca Mountain, Nevada

    Science.gov (United States)

    Marshall, B. D.; Whelan, J. F.

    2001-12-01

    Calcite is sporadically distributed in fractures and cavities in the volcanic rocks that form the 500- to 700-m-thick unsaturated zone at Yucca Mountain. Previous work has shown that the calcite precipitated from water moving downward through the unsaturated zone since the volcanic rocks were emplaced approximately 13 Ma. Calcite thus serves as a proxy for the chemistry and amounts of past percolation, two parameters that are important in predictions of the future behavior of the potential radioactive waste repository at Yucca Mountain. Latest calcite, which began forming between approximately 5 and 2 Ma, typically displays fine-scale growth zoning defined by distributions of Mn (inferred from cathodoluminescence), Mg, and Sr. Electron microprobe (EPMA) mapping of outermost calcite reveals Mg growth zoning1 and higher overall concentrations of Mg in late calcite than in older calcite. Micro X-ray fluorescence (micro-XRF) maps were obtained by slow rastering of the samples over a 100-watt X-ray source collimated through a final aperture of 100 μ m. Although the spatial resolution of the micro-XRF mapping is much less than that of EPMA, this technique reveals distributions of some elements to which EPMA is less sensitive. Micro-XRF maps show that Sr is spatially correlated with Mg; Sr concentrations range to 500 μ g/g at the resolution of the 100-μ m collimator. Because both Mg and Sr have similar calcite-water distribution coefficients much less than one, the Mg/Sr in calcite reflects the Mg/Sr of the water that precipitated the calcite. The distribution coefficient for Mn is greater than one and variations in Mn are not correlated with Mg and Sr. Covariation of Mg and Sr in the percolating water may be explained by reactions that affect the rate of uptake of chemical constituents from the overlying rock and soil, and/or evaporation. Late calcite has lower δ 13C values, probably due to a regional change from wetter to drier climate conditions. The higher Mg and

  1. Alkaline flocculation of Phaeodactylum tricornutum induced by brucite and calcite.

    Science.gov (United States)

    Vandamme, Dries; Pohl, Philip I; Beuckels, Annelies; Foubert, Imogen; Brady, Patrick V; Hewson, John C; Muylaert, Koenraad

    2015-11-01

    Alkaline flocculation holds great potential as a low-cost harvesting method for marine microalgae biomass production. Alkaline flocculation is induced by an increase in pH and is related to precipitation of calcium and magnesium salts. In this study, we used the diatom Phaeodactylum tricornutum as model organism to study alkaline flocculation of marine microalgae cultured in seawater medium. Flocculation started when pH was increased to 10 and flocculation efficiency reached 90% when pH was 10.5, which was consistent with precipitation modeling for brucite or Mg(OH)2. Compared to freshwater species, more magnesium is needed to achieve flocculation (>7.5mM). Zeta potential measurements suggest that brucite precipitation caused flocculation by charge neutralization. When calcium concentration was 12.5mM, flocculation was also observed at a pH of 10. Zeta potential remained negative up to pH 11.5, suggesting that precipitated calcite caused flocculation by a sweeping coagulation mechanism. PMID:26310384

  2. Stress remagnetization in pyrrhotite-calcite synthetic aggregates

    Science.gov (United States)

    Robion, Philippe; Borradaile, Graham J.

    2001-01-01

    Stress-induced remagnetization has been applied to multidomain pyrrhotite-calcite synthetic aggregates in a triaxial rig. Experimental deformation used 150MPa confining pressure, a constant strain rate of 10-5 s-1 and applied differential stresses of up to 70MPa. New components of magnetization, parallel to the direction of the pressure vessel field, were added to the pre-deformational magnetization. The intensity of remagnetization (M'-M0) increases with the intensity of the applied differential stress and affects the coercivity fraction below 15mT. Bulk shortening is less than 8 per cent, thus grain rotation cannot explain selective remagnetization of the low-coercivity fraction. Remagnetization is thus attributed to deformational viscous remanent magnetization (DVRM). It is observed that high-coercivity (>15mT) grains do not remagnetize. There is, however, slight progressive rotation of pre-deformational magnetization with increasing strain up to 8 per cent of bulk shortening. The lack of piezoremanent magnetization in the high-coercivity range may be due to defects introduced in pyrrhotite during sample preparation. Experiments using synthetic pyrrhotite, expected to show low dislocation densities, would be necessary to test this effect.

  3. Microbiologically Induced Calcite Precipitation Mediated by Sporosarcina pasteurii.

    Science.gov (United States)

    Bhaduri, Swayamdipta; Debnath, Nandini; Mitra, Sushanta; Liu, Yang; Kumar, Aloke

    2016-01-01

    The particular bacterium under investigation here (S. pasteurii) is unique in its ability, under the right conditions, to induce the hydrolysis of urea (ureolysis) in naturally occurring environments through secretion of an enzyme urease. This process of ureolysis, through a chain of chemical reactions, leads to the formation of calcium carbonate precipitates. This is known as Microbiologically Induced Calcite Precipitation (MICP). The proper culture protocols for MICP are detailed here. Finally, visualization experiments under different modes of microscopy were performed to understand various aspects of the precipitation process. Techniques like optical microscopy, Scanning Electron Microscopy (SEM) and X-Ray Photo-electron Spectroscopy (XPS) were employed to chemically characterize the end-product. Further, the ability of these precipitates to clog pores inside a natural porous medium was demonstrated through a qualitative experiment where sponge bars were used to mimic a pore-network with a range of length scales. A sponge bar dipped in the culture medium containing the bacterial cells hardens due to the clogging of its pores resulting from the continuous process of chemical precipitation. This hardened sponge bar exhibits superior strength when compared to a control sponge bar which becomes compressed and squeezed under the action of an applied external load, while the hardened bar is able to support the same weight with little deformation. PMID:27167458

  4. Moisture Buffer Value of Building Materials

    DEFF Research Database (Denmark)

    Rode, Carsten; Peuhkuri, Ruut; Time, Berit;

    2007-01-01

    When building materials are in contact with indoor air they have some effect to moderate the variations of indoor humidity in occupied buildings. But so far there has been a lack of a standardized quantity to characterize the moisture buffering capability of materials. It has been the objective of...... a recent Nordic project to define such a quantity, and to declare it in the form of a NORDTEST method. The Moisture Buffer Value is the figure that has been developed in the project as a way to appraise the moisture buffer effect of materials, and the value is described in the paper. Also explained...... is a test protocol which expresses how materials should be tested for determination of their Moisture Buffer Value. Finally, the paper presents some of the results of a Round Robin Test on various typical building materials that has been carried out in the project....

  5. Study on buffering characteristics of hydraulic absorber

    International Nuclear Information System (INIS)

    Control rod hydraulic drive mechanism (CRHDM) is a new type of in-vessel control rod drive technology. Hydraulic absorber is one of the key parts of control rod hydraulic drive line. It is used to buffer control rod when the rod scrams to prevent the cross-blades of control rod from deformation and damage. Based on the working process of the hydraulic absorber, a theoretical model of the buffering process was established. Calculation results of the theoretical model agree well with the experiment results. The trend of pressure change in absorber cylinder, the displacement and velocity of the piston and buffering force during the buffering process were obtained from the calculation results of the theoretical model. Then influence parameters about cushioning characteristics were analyzed, which laid foundation for optimal design of the hydraulic absorber. (authors)

  6. Marriage a Buffer Against Drinking Problems?

    Science.gov (United States)

    ... page: https://medlineplus.gov/news/fullstory_158887.html Marriage a Buffer Against Drinking Problems? Study found protective ... aware of the potentially important protective effects of marriage on alcohol problems, our study puts this observation ...

  7. ARC Filters with Diamond Transistors and Buffers

    OpenAIRE

    T. Dostal

    1998-01-01

    Active RC first and second order filters using diamond transistors (voltage controlled current sources) and voltage diamond buffers (voltage controlled voltage sources) are given in this paper. Circuits are simulated and experimentally compared.

  8. How Might New Neurons Buffer Against Stress?

    Science.gov (United States)

    ... 99 items) How Might New Neurons Buffer Against Stress? Clues Emerging from Studies in New Porter Neuroscience ... role in the action of antidepressants , resilience to stress , the benefits of exercise and enriched environments , and ...

  9. Moisture buffer capacity of different insulation materials

    DEFF Research Database (Denmark)

    Peuhkuri, Ruut Hannele; Rode, Carsten; Hansen, Kurt Kielsgaard

    2004-01-01

    lead to more durable constructions. In this paper, a large range of very different thermal insulation materials have been tested in specially constructed laboratory facilities to determine their moisture buffer capacity. Both isothermal and nonisothermal experimental set-ups have been used...... are discussed, and different ways are presented how to determine the moisture buffer capacity of the materials using partly standard material parameters and partly parameters determined from the actual measurements. The results so far show that the determination of moisture buffer capacity is very sensitive...... to the used analysis method and therefore great care has to be taken when comparing results of different experiments. This paper discusses this issue and will come with a recommendation of a simple and consistent way to present the moisture buffer capacity of the materials in contact with the indoor air...

  10. A generalised chemical precipitation modelling approach in wastewater treatment applied to calcite.

    Science.gov (United States)

    Mbamba, Christian Kazadi; Batstone, Damien J; Flores-Alsina, Xavier; Tait, Stephan

    2015-01-01

    Process simulation models used across the wastewater industry have inherent limitations due to over-simplistic descriptions of important physico–chemical reactions, especially for mineral solids precipitation. As part of the efforts towards a larger Generalized Physicochemical Modelling Framework, the present study aims to identify a broadly applicable precipitation modelling approach. The study uses two experimental platforms applied to calcite precipitating from synthetic aqueous solutions to identify and validate the model approach. Firstly, dynamic pH titration tests are performed to define the baseline model approach. Constant Composition Method (CCM) experiments are then used to examine influence of environmental factors on the baseline approach. Results show that the baseline model should include precipitation kinetics (not be quasi-equilibrium), should include a 1st order effect of the mineral particulate state (Xcryst) and, for calcite, have a 2nd order dependency (exponent n = 2.05 ± 0.29) on thermodynamic supersaturation (σ). Parameter analysis indicated that the model was more tolerant to a fast kinetic coefficient (kcryst) and so, in general, it is recommended that a large kcryst value be nominally selected where insufficient process data is available. Zero seed (self nucleating) conditions were effectively represented by including arbitrarily small amounts of mineral phase in the initial conditions. Both of these aspects are important for wastewater modelling, where knowledge of kinetic coefficients is usually not available, and it is typically uncertain which precipitates are actually present. The CCM experiments confirmed the baseline model, particularly the dependency on supersaturation. Temperature was also identified as an influential factor that should be corrected for via an Arrhenius-style correction of kcryst. The influence of magnesium (a common and representative added impurity) on kcryst was found to be significant but was considered

  11. Buffer layer for thin film structures

    Energy Technology Data Exchange (ETDEWEB)

    Foltyn, Stephen R.; Jia, Quanxi; Arendt, Paul N.; Wang, Haiyan

    2010-06-15

    A composite structure including a base substrate and a layer of a mixture of strontium titanate and strontium ruthenate is provided. A superconducting article can include a composite structure including an outermost layer of magnesium oxide, a buffer layer of strontium titanate or a mixture of strontium titanate and strontium ruthenate and a top-layer of a superconducting material such as YBCO upon the buffer layer.

  12. Buffer layer for thin film structures

    Energy Technology Data Exchange (ETDEWEB)

    Foltyn, Stephen R.; Jia, Quanxi; Arendt, Paul N.; Wang, Haiyan

    2006-10-31

    A composite structure including a base substrate and a layer of a mixture of strontium titanate and strontium ruthenate is provided. A superconducting article can include a composite structure including an outermost layer of magnesium oxide, a buffer layer of strontium titanate or a mixture of strontium titanate and strontium ruthenate and a top-layer of a superconducting material such as YBCO upon the buffer layer.

  13. Lucas Heights buffer zone: plan of management

    International Nuclear Information System (INIS)

    This plan is being used by the Commission as a guide for its management of the Lucas Heights buffer zone, which is essentially a circular area having a 1-6 km radius around the HIFAR reactor. Aspects covered by this plan include past uses, current use, objectives for buffer zone land management, emergency evacuation, resource conservation, archaeology, fire, access, rehabilitation of disturbed areas, resource management and plan implementation

  14. The Determinants of Capital Buffers in CEECs

    OpenAIRE

    D'Arack, Francesco; Levasseur, Sandrine

    2007-01-01

    Banking capital ratios show a steadily decline in almost Central and Eastern European Countries (CEECs) since 2001, despite unchanged capital adequacy rules. Using a dynamic panel-analysis based on country-level data for CEECs, we empirically assess the determinants of capital buffers. Main results are as follows. First, there are large and significant adjustment costs in raising capital. Second, banks behave pro-cyclically, depleting their buffers in upturns to benefit from unanticipated inv...

  15. Required buffer capacities in assembly systems

    Directory of Open Access Journals (Sweden)

    D. Krenczyk

    2007-07-01

    Full Text Available Purpose: The aim of the realised analysis is the determination of the set of conditions. The fulfilment of those conditions enables the synchronisation of the assembly system work into the steady state. It is necessary to specify the rules controlling the assembly system work. Rhythmic concurrent production with wide assortment in the considered assembly system is realised.Design/methodology/approach: The theoretical roots of the considerations presented in that paper include theory of constraints. The presented approach is consistent with the authority method called Requirements and Possibilities Balance Method (RPBMFindings: Two kinds of system buffers: the entrance buffers and the inter-resources buffers are considered in that paper. The number of buffers elements needed for production during first steady state of the given system has been determined. Mathematical formulas specifying the minimal capacity of the buffers allocated in the assembly system have been outworked.Research limitations/implications: The formulas specifying the minimal buffer capacity constitute the first step towards formulation of the automatic method. That method is designed for the automatic construction of rules controlling the system work during transient phases between two different steady states. The process enables automation of the introduction filling of the system buffers.Practical implications: The presented formulas can become an integrated part of existing authority software. The developed computer system aids the decision-making process connected with production planning and ensures effective utilisation of production resources. Moreover, the formulas correctness during computer simulations has been verified.Originality/value: To develop the formulas specifying the minimal capacity of the system buffers is the main achievement of the given paper. The presented approach permits to solve the problem concerning the synchronisation of the assembly system work

  16. Capacitive Deionization: Performance Improvement Using Multistep Buffered Arrangement and Ordered Mesoporous Carbon Electrodes

    Science.gov (United States)

    Salamat, Yasamin; Rios Perez, Carlos; Gurijala, Anvesh; Erb, Randall; Hidrovo, Carlos

    2015-11-01

    Capacitive deionization (CDI) is an emerging novel technology for water treatment which uses an electrical field to adsorb ions to oppositely charged high porous media. The most distinguished feature of CDI is its ability to retrieve a fraction of the energy consumed for desalination during the regeneration cycle. Here, we propose a new architecture aiming to improve the overall performance of CDI. In this method, an array of CDI cells are connected in series with solution buffers in between them. The buffer solution homogenizes the outlet concentration of the preceding cell and supplies a constant concentration reservoir for the next cell. The performance of the proposed CDI system with two CDI cells and one solution buffer was compared with a two-cascaded-cells array with no solution buffer. The obtained results demonstrated the superiority of the proposed buffered system, in terms of desalination percentage. In addition, a new method for fabricating ordered mesoporous carbon electrodes was introduced aimed at reducing the electrical resistance of the system and enhancing its adsorption capacity. Performance of the electrodes was evaluated using Electrochemical Impedance Spectroscopy (EIS) and Cyclic Voltammetry (CV). The proposed methods provide great potentials for CDI to be implemented in larger scales and industrial applications. The author would like to thank Jabulani Barber for all his help and support on manufacturing the carbon films.

  17. Chromatographic transport of alkaline buffers through reservoir rock

    International Nuclear Information System (INIS)

    Use of relatively low-pH alkaline buffers, such as sodium carbonate or sodium silicate, is explored as a means for overcoming sodium/hydrogen ion-exchange delay in alkaline waterflooding. A local-equilibrium chromatographic model is outlined to describe the concentration velocities for injection of alkaline buffers into a linear porous medium that exhibits reversible sodium/hydrogen exchange. The theory predicts a buffer ion-exchange wave that is substantially faster than that for equivalent-pH sodium hydroxide solutions. New experimental displacement data are presented for NaOH over a pH range from 11 to 13 and for 0.1, 0.5, and 1.0 wt% Na/sub 2/CO/sub 3/ flowing through a 1 wt% NaCl brine saturated Berea sandstone core at 500C [1220F]. To permit a complete description of the system, column effluent concentrations are measured for sodium ions, hydroxide ions, H/sup 3/-tagged water, and /sup 14/C-tagged carbonate. The experiments confirm that Na/sub 2/CO/sub 3/ propagates through the Berea sand at a higher rate than NaOH. For example, at pH=11.4, Na/sub 2/CO/sub 3/ migrates with a velocity that is 3.5 times faster than NaOH. Comparison of experiment with the ion-exchange chromatography theory shows good agreement. The authors successfully model the concentration histories of tritium-labeled water, total carbon, sodium, and hydroxide, all with no adjustable parameters. This work establishes with both theory and experiment that buffered alkali significantly increases the propagation speed of hydroxide in reservoir sands in comparison with unbuffered alkali at equivalent sodium and hydroxide concentrations. Because lower-pH buffered alkali can also protect against rock dissolution loss, the validated reduction of buffer ion-exchange lag considerably improves the promise of the alkaline flooding process for field application

  18. Impacts of cave air ventilation and in-cave prior calcite precipitation on Golgotha Cave dripwater chemistry, southwest Australia

    Science.gov (United States)

    Treble, Pauline C.; Fairchild, Ian J.; Griffiths, Alan; Baker, Andy; Meredith, Karina T.; Wood, Anne; McGuire, Elizabeth

    2015-11-01

    Speleothem trace element chemistry is an important component of multi-proxy records of environmental change but a thorough understanding of hydrochemical processes is essential for its interpretation. We present a dripwater chemistry dataset (PCO2, alkalinity, Ca, SIcc, Mg and Sr) from an eight-year monitoring study from Golgotha Cave, building on a previous study of hydrology and dripwater oxygen isotopes (Treble et al., 2013). Golgotha Cave is developed in Quaternary aeolianite and located in a forested catchment in the Mediterranean-type climate of southwest Western Australia. All dripwaters from each of the five monitored sites become supersaturated with respect to calcite during most of the year when cave ventilation lowers PCO2 in cave air. In this winter ventilation mode, prior calcite precipitation (PCP) signals of increased Mg/Ca and Sr/Ca in dripwater are attributed to stalactite deposition. A fast-dripping site displays less-evolved carbonate chemistry, implying minimal stalactite growth, phenomena which are attributed to minimal degassing because of the short drip interval (30 s). We employ hydrochemical mass-balance modelling techniques to quantitatively investigate the impact of PCP and CO2 degassing on our dripwater. Initially, we reverse-modelled dripwater solutions to demonstrate that PCP is dominating the dripwater chemistry at our low-flow site and predict that PCP becomes enhanced in underlying stalagmites. Secondly, we forward-modelled the ranges of solution Mg/Ca variation that potentially can be caused by degassing and calcite precipitation to serve as a guide to interpreting the resulting stalagmite chemistry. We predict that stalagmite trace element data from our high-flow sites will reflect trends in original dripwater solutes, preserving information on biogeochemical fluxes within our system. By contrast, stalagmites from our low-flow sites will be dominated by PCP effects driven by cave ventilation. Our poorly karstified system allows us

  19. Probabilistic Analysis of Buffer Starvation in Markovian Queues

    CERN Document Server

    Xu, Yuedong; El-Azouzi, Rachid; Haddad, Majed; Elayoubi, Salaheddine; Jimenez, Tania

    2011-01-01

    Our purpose in this paper is to obtain the exact distribution of the number of buffer starvations within a sequence of $N$ consecutive packet arrivals. The buffer is modeled as an M/M/1 queue, plus the consideration of bursty arrivals characterized by an interrupted Poisson process. When the buffer is empty, the service restarts after a certain amount of packets are prefetched. With this goal, we propose two approaches, one of which is based on Ballot theorem, and the other uses recursive equations. The Ballot theorem approach gives an explicit solution, but at the cost of the high complexity order in certain circumstances. The recursive approach, though not offering an explicit result, needs fewer computations. We further propose a fluid analysis of starvation probability on the file level, given the distribution of file size and the traffic intensity. The starvation probabilities of this paper have many potential applications. We apply them to optimize the quality of experience (QoE) of media streaming serv...

  20. Differential early diagenetic low-Mg calcite cementation and rhythmic hardground development in Campanian-Maastrichtian chalk

    DEFF Research Database (Denmark)

    Molenaar, Nicolaas; J.J.P., Zijlstra

    1997-01-01

    and differences in the degree of early diagenesis. Cemented layers and hardgrounds are the result of differential early marine calcite cementation. In these limestones early calcite cementation cannot be explained by the supply of cementing materials from saturated seawater, An alternative model for...... early marine calcite cementation is proposed, in which early calcite cementation occurred within the sediment at some distance below the seafloor as a result of organic matter degradation and internal redistribution of bioclastic carbonate. Bacterial organic matter degradation caused dissolution of...... relatively unstable high-Mg calcite (and/or aragonite) in the oxic zone followed by precipitation of calcite cement as a consequence of bacterial iron reduction. During periods with a lower sedimentation rate, any significant early cementation and replacement of high-Mg calcite occurred when younger oxic...

  1. Buffer regulation of calcium puff sequences

    International Nuclear Information System (INIS)

    Puffs are localized Ca2+ signals that arise in oocytes in response to inositol 1,4,5-trisphosphate (IP3). They are the result of the liberation of Ca2+ from the endoplasmic reticulum through the coordinated opening of IP3 receptor/channels clustered at a functional release site. The presence of buffers that trap Ca2+ provides a mechanism that enriches the spatio–temporal dynamics of cytosolic calcium. The expression of different types of buffers along the cell's life provides a tool with which Ca2+ signals and their responses can be modulated. In this paper we extend the stochastic model of a cluster of IP3R-Ca2+ channels introduced previously to elucidate the effect of buffers on sequences of puffs at the same release site. We obtain analytically the probability laws of the interpuff time and of the number of channels that participate of the puffs. Furthermore, we show that under typical experimental conditions the effect of buffers can be accounted for in terms of a simple inhibiting function. Hence, by exploring different inhibiting functions we are able to study the effect of a variety of buffers on the puff size and interpuff time distributions. We find the somewhat counter-intuitive result that the addition of a fast Ca2+ buffer can increase the average number of channels that participate of a puff. (paper)

  2. Buffer material applying method and device

    International Nuclear Information System (INIS)

    A powdery buffer material which can be solidified under pressure is charged into a disposing hole, an expandable/shrinkable hydraulic bag is inserted to the powdery buffer material, and then highly pressurized water is injected to expand the hydraulic bag and the powdery buffer material is urged to the inner wall surface of the disposing hole by expansion pressure to solidify and form a solid buffer material. Namely, a movable truck main body comprises a means for elevating an elevating plate so as to open/close an opening, an expandable/shrinkable hydraulic bag disposed to the lower surface of the elevating plate and a highly pressurized water-injection means for injecting highly pressurized water into the hydraulic bag. The buffer material is thus manufactured and applied simultaneously by transporting the heavy weighted buffer material in the form of a powder to a site and press-molding it in the disposing hole thereby capable of reducing the time, labor and cost required for transporting operation remarkably. (N.H.)

  3. Calcium sulfoaluminate (Ye'elimite) hydration in the presence of gypsum, calcite, and vaterite

    International Nuclear Information System (INIS)

    Six calcium sulfoaluminate-based cementitious systems composed of calcium sulfoaluminate, calcite, vaterite, and gypsum were cured as pastes and mortars for 1, 7, 28 and 84 days. Pastes were analyzed with X-ray diffraction, thermogravimetric and differential thermal analyses. Mortars were tested for compressive strength, dimensional stability and setting time. Furthermore, pastes with a water/cementitious material mass ratio of 0.80 were tested for heat evolution during the first 48 h by means of isothermal conduction calorimetry. It has been found that: (1) both calcite and vaterite reacted with monosulfoaluminate to give monocarboaluminate and ettringite, with vaterite being more reactive; (2) gypsum lowered the reactivity of both carbonates; (3) expansion was reduced by calcite and vaterite, irrespective of the presence of gypsum; and (4) both carbonates increased compressive strength in the absence of gypsum and decreased compressive strength less in the presence of gypsum, with vaterite's action more effective than that of calcite

  4. Calcium sulfoaluminate (Ye'elimite) hydration in the presence of gypsum, calcite, and vaterite

    Energy Technology Data Exchange (ETDEWEB)

    Hargis, Craig W. [Department of Civil and Environmental Engineering, University of California, Berkeley, CA (United States); Telesca, Antonio [School of Engineering, University of Basilicata, Potenza (Italy); Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu [Department of Civil and Environmental Engineering, University of California, Berkeley, CA (United States)

    2014-11-15

    Six calcium sulfoaluminate-based cementitious systems composed of calcium sulfoaluminate, calcite, vaterite, and gypsum were cured as pastes and mortars for 1, 7, 28 and 84 days. Pastes were analyzed with X-ray diffraction, thermogravimetric and differential thermal analyses. Mortars were tested for compressive strength, dimensional stability and setting time. Furthermore, pastes with a water/cementitious material mass ratio of 0.80 were tested for heat evolution during the first 48 h by means of isothermal conduction calorimetry. It has been found that: (1) both calcite and vaterite reacted with monosulfoaluminate to give monocarboaluminate and ettringite, with vaterite being more reactive; (2) gypsum lowered the reactivity of both carbonates; (3) expansion was reduced by calcite and vaterite, irrespective of the presence of gypsum; and (4) both carbonates increased compressive strength in the absence of gypsum and decreased compressive strength less in the presence of gypsum, with vaterite's action more effective than that of calcite.

  5. Controlled Chemical Doping of Semiconductor Nanocrystals Using Redox Buffers

    Energy Technology Data Exchange (ETDEWEB)

    Engel, Jesse H. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Surendranath, Yogesh [Univ. of California, Berkeley, CA (United States); Alivisatos, Paul [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2013-07-20

    Semiconductor nanocrystal solids are attractive materials for active layers in next-generation optoelectronic devices; however, their efficient implementation has been impeded by the lack of precise control over dopant concentrations. Herein we demonstrate a chemical strategy for the controlled doping of nanocrystal solids under equilibrium conditions. Exposing lead selenide nanocrystal thin films to solutions containing varying proportions of decamethylferrocene and decamethylferrocenium incrementally and reversibly increased the carrier concentration in the solid by 2 orders of magnitude from their native values. This application of redox buffers for controlled doping provides a new method for the precise control of the majority carrier concentration in porous semiconductor thin films.

  6. (U-Th)/He dating and He diffusion in calcite from veins and breccia

    Science.gov (United States)

    Gautheron, C.; Cros, A.; Pagel, M.; Berthet, P.; Tassan-Got, L.; Douville, E.; Pinna-Jamme, R.; Sarda, P.

    2013-12-01

    Knowledge of He retention in crystalline calcite is mandatory to estimate the possibility of (U-Th)/He dating of calcite. To this aim, fault-filling calcite crystals from the Eocene/Oligocene Gondrecourt graben, Paris Basin, Eastern France, have been sampled, based on their relatively old, Eocene-Oligocene, precipitation age and cold thermal history (agreement with the He-retentive character of calcite as determined by Copeland et al. (2007), and these ages were obtained for the most recently precipitated crystals. To better understand the large He-age scatter and why calcites precipitated earlier show younger ages, He diffusion experiments have been conducted on 10 Gondrecourt calcite fragments from 3 samples with He ages of 0.2 to 6 Ma. In addition, a crystallographic investigation by X-Ray Diffraction (XRD) performed on similar samples reveals that the crystal structure evolves with increasing temperature, showing with micro-cracks and cleavage opening. These XRD results indicate that, in fault-filling calcite, He retention is controlled by multiple diffusion domains (MDD, Lovera et al., 1991) with various sizes, and therefore, evolves through time with strong consequences on (U-Th)/He age. We thus interpret the Gondrecourt calcite (U-Th)/He age scatter of older samples as a consequence of cleavage opening due to a succession of calcite crystallization phases related to the deformation history. Finally, we propose that the crystallization age of a calcite crystal with a known thermal history can nevertheless be retrieved by the (U-Th)/He method provided the He diffusion pattern can be measured by careful step-heating degassing analysis. Copeland, P., Watson, E.B., Urizar, S.C., Patterson, D., Lapen, T.J., 2007. Alpha thermochronology of carbonates. Geochim. Cosmochim. Acta, 71: 4488-4511. Cros, A. Gautheron, C., Pagel, M., Berthet, P., Tassan-Got, L., Douville, E., Pinna-Jamme, R., Sarda, P., submitted GCA, He behavior in calcite filling viewed by (U

  7. Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes?

    Directory of Open Access Journals (Sweden)

    S. Bindschedler

    2014-01-01

    Full Text Available Calcitic nanofibres are ubiquitous habits of secondary calcium carbonate (CaCO3 accumulations observed in calcareous vadose environments. Despite their widespread occurrence, the origin of these nanofeatures remains enigmatic. Three possible mechanisms fuel the debate: (i purely physicochemical processes, (ii mineralization of rod-shaped bacteria, and (iii crystal precipitation on organic templates. Nanofibres can be either mineral (calcitic or organic in nature. They are very often observed in association with Needle Fibre Calcite (NFC, another typical secondary CaCO3 habit in terrestrial environments. This association has contributed to some confusion between both habits, however they are truly two distinct calcitic features and their recurrent association is likely to be an important fact to help understanding the origin of nanofibres. In this manuscript the different hypotheses that currently exist to explain the origin of calcitic nanofibres are critically reviewed. In addition to this, a new hypothesis for the origin of nanofibres is proposed based on the fact that current knowledge attributes a fungal origin to NFC. As this feature and nanofibres are recurrently observed together, a possible fungal origin for nanofibres which are associated with NFC is investigated. Sequential enzymatic digestion of the fungal cell wall of selected fungal species demonstrates that the fungal cell wall can be a source of organic nanofibres. The obtained organic nanofibres show a striking morphological resemblance when compared to their natural counterparts, emphasizing a fungal origin for part of the organic nanofibres observed in association with NFC. It is further hypothesized that these organic nanofibres may act as templates for calcite nucleation in a biologically-influenced mineralization process, generating calcitic nanofibres. This highlights the possible involvement of Fungi in CaCO3 biomineralization processes, a role still poorly documented at

  8. Microstratigraphic logging of calcite fabrics in speleothems as tool for palaeoclimate studies

    OpenAIRE

    Silvia Frisia

    2015-01-01

    The systematic documentation of calcite fabrics in stalagmites and flowstones provides robustness to palaeoclimate interpretation based on geochemical proxies, but it has been neglected because it is difficult to transform crystal morphologies into numerical values, and construct fabric time series. Here, general criteria that allow for coding fabrics of calcite composing stalagmites and flowstones is provided. Being based on known models of fabric development, the coding ascribes sequential ...

  9. The potential for phosphorus pollution remediation by calcite precipitation in UK freshwaters

    Science.gov (United States)

    Neal, Colin

    This paper examines the potential for calcium carbonate to reduce phosphate pollution in freshwaters by co-precipitation, a process known as a "self cleansing mechanism". Calcium carbonate saturation levels and phosphate concentrations (SRP - soluble reactive phosphate) across the major eastern UK river basins are examined to test for solubility controls. The study shows that calcite saturation varies for each catchment as a function of flow and biological activity rather than by direct regulation by SRP. Indeed, there is no evidence, for any of the rivers studied, that calcite solubility controls hold. However, for groundwater and groundwater-fed springs in the Chalk of the Thames basin, calcite saturation is observed with associated low SRP levels. A self-cleansing mechanism may well be operative within the Chalk due to two factors. Firstly, there is a high potential for nucleation on the calcite micro-crystals in the aquifer. Secondly, there are within aquifer reactions that remove the calcite nucleating inhibitors (SRP and dissolved organic carbon, DOC) to levels lower than those occurring within the rivers do. These inhibitors enter the catchment at very high concentrations in association with agricultural pollution (fertilizer application and animal slurry) and household contamination (e.g. sewage sources from septic tanks). Under low flow conditions, when the saturation index for calcite is at its highest, so too is the concentration of the nucleation inhibitor SRP. Companion work shows that calcite precipitation can occur at the water-sediment interface of the river and this may involve SRP removal. The data, as a whole, define an apparent bound for calcite solubility control where in the presence of nucleating centres, SRP must be less than 4 mM-P l-1 and DOC must be less than 150 mM-C l-1: a condition that does not seem to pertain within most UK rivers.

  10. Accurate measurement of the main refractive indices and thermo-optical coefficients of the calcite crystal

    Institute of Scientific and Technical Information of China (English)

    Shuang Zhao; Fuquan Wu; Haifeng Wang; Weigang Zhong; Xiuzhen Li; Hengjing Tang; Meng Shi; Hongyan Deng

    2007-01-01

    The main refractive indices of calcite crystal are measured by the means of auto-collimation, and the thermo-optical coefficients are calculated. The coefficient expression of Sellmeier equation is obtained by solving Sellmeier equation strictly and the refractive indices of different wavelengths are calculated, which accord with experimental esultsery well. The measured main refractive indices of calcite at 488-nm wavelength are identical with the values obtained by Sellmeier equation.

  11. Precipitation of Calcite during the Deposition of Paleogene Sangkarewang Oil Shale, Ombilin Basin, West Sumatra, Indonesia

    Directory of Open Access Journals (Sweden)

    Agus Haris Widayat

    2015-12-01

    Full Text Available Geochemical and petrographical analyses were carried out to investigate the occurrence of calcite in theformer Ombilin lacustrine lake. The study involves eight samples taken from a 56 m long drill core of Sangkarewangoil shale. Geochemical investigation showed that the samples consist of varied terrigenous input represented by Si, Al, K, and Ti, and autochthonous input represented by S, total organic carbon (TOC, and d13C of bulk organic matter. Along the drill core profile the abundance of autochthonous input decreases upwards, while that of terrigenous input oppositely increases upwards. Petrographical analysis revealed that calcite is a major mineral in the samples. In this study, the abundance of calcite could be represented by the abundance of Ca, as calcite is the only significant Ca containing mineral. Ca is abundant in the samples (8.4% in average and its concentration varies similarly with those of S, TOC, and d13C, suggesting that the element as well as calcite incorporates the autochthonous input. Thevariation of calcite abundance in the drill core profile is considered to be related with primary productivity changes during the development of the former lake. Higher primary productivity represented by more positive of d13C value(-24.8‰ during the deposition of the lower part of the drill core profile promoted the higher amount of deposited organic matter. In such environment, the supersaturation of carbonate ion in lake water was also reached and significant precipitation of authigenic calcite occurred. As the lake developed, the primary productivity decreased as indicated by more negative of d13C value (eventually -26.8‰. This condition led to the decreases of deposited organic matterand calcite in the lake sediments.

  12. Molecular dynamics simulation of adsorption of an oil-water-surfactant mixture on calcite surface

    Institute of Scientific and Technical Information of China (English)

    Lu Guiwu; Zhang Xuefen; Shao Changjin; Yang Hong

    2009-01-01

    An interface super molecular structure model for oil-water-surfactant mixture and calcite was established. By using a molecular dynamics method, the effects of rhamnolipid, sodium dodecyl benzene sulfonate and sodium hexadecyl sulfonate on the interface adsorption behavior of oil molecules were investigated. It was found that these three surfactants could reduce oil-calcite interface binding energy, and play a role of oil-displacing agent.

  13. Origin of sulfate in barite and calcite cements in the Jebel Madar salt dome (Oman)

    Science.gov (United States)

    Vandeginste, V.; John, C. M.; Gilhooly, W. P.

    2012-12-01

    Jebel Madar is a 500-m high mountain rising in the desert at the Oman Foothills. The Jebel consists of Triassic to Cretaceous carbonate host rocks forming the carapace of a salt dome. Halokinesis caused major fracturing and faulting at Jebel Madar, and the resulting structures acted as the main pathways for fluids that generated diagenetic cements composed of both barite and calcite. The spatial distribution of calcite and barite occurrences shows that calcite is formed in large abundance along the three main faults, whereas barite is more concentrated along faults further away from the three main ones. The stable carbon and oxygen isotope composition of calcite and fluid inclusion data from both calcite and barite show a distinct evolution of the fluid with a highly saline component towards more mixing with meteoric water. This is in agreement with clumped isotopes data on calcite cements indicating an evolution towards lower temperatures, consistent with doming of the Jebel and greater input of lower-temperature descending meteoric fluids. Here, we present sulphur and oxygen isotopic data on barite that suggest a link between the barite formation and the Precambrian salt underlying Jebel Madar. The average δ34S measured in barite is 33‰ CDT (1σ = 5‰; n = 33), which falls at the lower end of the δ34S range reported for the Ara Group anhydrite. The average δ18O in the same barite samples is 23‰ VSMOW (1σ = 2‰; n = 33). Data from the barite will be compared with sulphur isotopes from the carbonate-associate sulfate in the calcite cements. The overall goal of our research is to gain a better insight in the formation process of barite and calcite in Jebel Madar and its link with salt tectonics. We would like to acknowledge the financial support of QCCSRC (funded jointly by Qatar Petroleum, Shell and the Qatar Science & Technology Park) and the GSA Laubach fund for this study.

  14. Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein*

    OpenAIRE

    Rahman, M. Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-01-01

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called “calcite and aragonite seas.” Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, so...

  15. Low-Temperature Plasticity of Naturally Deformed Calcite Rocks

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Optical, cathodoluminescence and transmission electron microscope (TEM) analyses were conducted onfour groups of calcite fault rocks, a cataclastic limestone, cataclastic coarse-grained marbles from two fault zones, and afractured mylonite. These fault rocks show similar microstructural characteristics and give clues to similar processes ofrock deformation. They are characterized by the structural contrast between macroscopic cataclastic (brittle) andmicroscopic mylonitic (ductile) microstructures. Intragranular deformation microstructures (i.e. deformation twins, kinkbands and microfractures) are well preserved in the deformed grains in clasts or in primary rocks. The matrix materials areof extremely fine grains with diffusive features. Dislocation microstructures for co-existing brittle deformation andcrystalline plasticity were revealed using TEM. Tangled dislocations are often preserved at the cores of highly deformedclasts, while dislocation walls form in the transitions to the fine-grained matrix materials and free dislocations, dislocationloops and dislocation dipoles are observed both in the deformed clasts and in the fine-grained matrix materials. Dynamicrecrystallization grains from subgrain rotation recrystallization and subsequent grain boundary migration constitute themajor parts of the matrix materials. Statistical measurements of densities of free dislocations, grain sizes of subgrains anddynamically recrystallized grains suggest an unsteady state of the rock deformation. Microstructural andcathodoluminescence analyses prove that fluid activity is one of the major parts of faulting processes. Low-temperatureplasticity, and thereby induced co-existence of macroscopic brittle and microscopic ductile microstmctures are attributedto hydrolytic weakening due to the involvement of fluid phases in deformation and subsequent variation of rock rheology.During hydrolytic weakening, fluid phases, e.g. water, enhance the rate of dislocation slip and climb, and

  16. Low noise buffer amplifiers and buffered phase comparators for precise time and frequency measurement and distribution

    Science.gov (United States)

    Eichinger, R. A.; Dachel, P.; Miller, W. H.; Ingold, J. S.

    1982-01-01

    Extremely low noise, high performance, wideband buffer amplifiers and buffered phase comparators were developed. These buffer amplifiers are designed to distribute reference frequencies from 30 KHz to 45 MHz from a hydrogen maser without degrading the hydrogen maser's performance. The buffered phase comparators are designed to intercompare the phase of state of the art hydrogen masers without adding any significant measurement system noise. These devices have a 27 femtosecond phase stability floor and are stable to better than one picosecond for long periods of time. Their temperature coefficient is less than one picosecond per degree C, and they have shown virtually no voltage coefficients.

  17. Ion beam modifications of defect sub-structure of calcite cleavages

    Indian Academy of Sciences (India)

    E Venkateshwar Rao; M Ramakrishna Murthy

    2008-04-01

    Experimental investigations on the defect sub-structure and surface modifications, brought about by He+ ion-bombardment of calcite cleavages (100), have been carried out. Optical and scanning electron microscopic investigations revealed drastic modifications on the surface morphology, local symmetry and defect concentration. Additional structural defects on ion-bombardment of calcite surfaces also have been observed. Changes in shape and form of chemical etch pits are found to be a function of ion-beam energy, as studied by optical microscopy. Radiation damage in calcite has been attributed mainly due to desorption of CO$^{-2}_{3}$ ions from the calcite surfaces, on irradiation. Measurements of surface conductivity on irradiated calcite surfaces have been made employing a four-probe technique. Enhancement of surface conductivity has been considered to be due to an increase in concentration of CO$^{-2}_{3}$ ions formed, on ion irradiation and subsequent thermal stimulation. Planar plastic anisotropy has been studied on irradiated calcite cleavages by measurement of microhardness.

  18. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    Energy Technology Data Exchange (ETDEWEB)

    Bevilaqua, Rochele C. A.; Miranda, Caetano R. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Rigo, Vagner A. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Universidade Tecnológica Federal do Paraná, UTFPR, Cornélio Procópio, PR (Brazil); Veríssimo-Alves, Marcos [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Departamento de Física, ICEx, Universidade Federal Fluminense, UFF, Volta Redonda, RJ (Brazil)

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca{sup 2+}. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO{sub 3} (101{sup ¯}4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for {sup 43}Ca, {sup 13}C, and {sup 17}O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  19. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    International Nuclear Information System (INIS)

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca2+. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for 43Ca, 13C, and 17O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated

  20. Static mechanical properties of buffer material

    International Nuclear Information System (INIS)

    The buffer material is expected to maintain its low water permeability, self-sealing properties, radionuclides adsorption and retardation properties, thermal conductivity, chemical buffering properties, overpack supporting properties, stress buffering properties, etc. over a long period of time. Natural clay is mentioned as a material that can relatively satisfy above. Among the kinds of natural clay, bentonite when compacted is superior because (i) it has exceptionally low water permeability and properties to control the movement of water in buffer, (ii) it fills void spaces in the buffer and fractures in the host rock as it swells upon water uptake, (iii) it has the ability to exchange cations and to adsorb cationic radioelements. In order to confirm these functions for the purpose of safety assessment, it is necessary to evaluate buffer properties through laboratory tests and engineering-scale tests, and to make assessments based on the ranges in the data obtained. This report describes the procedures, test conditions, results and examinations on the buffer material of unconfined compression tests, one-dimensional consolidation tests, consolidated-undrained triaxial compression tests and consolidated-undrained triaxial creep tests that aim at getting hold of static mechanical properties. We can get hold of the relationship between the dry density and tensile stress etc. by Brazilian tests, between the dry density and unconfined compressive strength etc. by unconfined compression tests, between the consolidation stress and void ratio etc. by one-dimensional consolidation tests, the stress pass of each effective confining pressure etc. by consolidated-undrained triaxial compression tests and the axial strain rate with time of each axial stress etc. by consolidated-undrained triaxial creep tests. (author)

  1. Redox buffered hydrofluoric acid etchant for the reduction of galvanic attack during release etching of MEMS devices having noble material films

    Science.gov (United States)

    Hankins, Matthew G.

    2009-10-06

    Etchant solutions comprising a redox buffer can be used during the release etch step to reduce damage to the structural layers of a MEMS device that has noble material films. A preferred redox buffer comprises a soluble thiophosphoric acid, ester, or salt that maintains the electrochemical potential of the etchant solution at a level that prevents oxidation of the structural material. Therefore, the redox buffer preferentially oxidizes in place of the structural material. The sacrificial redox buffer thereby protects the exposed structural layers while permitting the dissolution of sacrificial oxide layers during the release etch.

  2. CRACK2. Modelling calcium carbonate deposition from bicarbonate solutions in cracks in concrete

    OpenAIRE

    Brodersen, Knud Erik

    2003-01-01

    The numerical CRACK2 model simulates precipitation of calcite from calcium bicarbonate solution (e.g. groundwater) passing through cracks in concrete or other cementitious materials. A summary of experimental work is followed by a detailed description ofthe model. Hydroxyl ions are transported by diffusion in pore systems in columns of cementitious materials. The hydroxyl is precipitating calcite from a flow of bicarbonate solution in a crack connecting the ends of a row of such columns. Thec...

  3. Influence of pH-buffer action on desorption behavior of 60Co adsorbed on sand

    International Nuclear Information System (INIS)

    In order to clarify influence of pH-buffer action of soil on desorption behavior of radionuclides absorbed on a soil, a batch type desorption experiment, in which a coastal sand adsorbed 60Co was contacted with an aqueous solution of 4, 7 or 10 in pH, was performed. When pH of the solution became higher, the desorption ratio of 60Co from the sand to the solution decreased, while the abundance ratio of non-cationic 60Co species increased. Relationship between the pH of solution and the desorption ratio of 60Co could been explained by a pH dependency of negative charge density on the sand surface. It was found that the non-cationic 60Co species in the solution was colloidal {60Co (OH)2}n, which was formed by hydrolysis of 60Co2+ at buffered pH. (author)

  4. Undergraduate Chemistry Students' Perceptions of and Misconceptions about Buffers and Buffer Problems

    Science.gov (United States)

    Orgill, MaryKay; Sutherland, Aynsley

    2008-01-01

    Both upper- and lower-level chemistry students struggle with understanding the concept of buffers and with solving corresponding buffer problems. While it might be reasonable to expect general chemistry students to struggle with this abstract concept, it is surprising that upper-level students in analytical chemistry and biochemistry continue to…

  5. Buffer construction technique using granular bentonite

    International Nuclear Information System (INIS)

    Buffer construction using bentonite pellets as filling material is a promising technology for enhancing the ease of repository operation. In this study, a test of such technology was conducted in a full-scale simulated disposal drift, using a filling system which utilizes a screw conveyor system. The simulated drift, which contained two dummy overpacks, was configured as a half-cross-section model with a height of 2.22 m and a length of 6.0 m. The average dry density of the buffer obtained in the test was 1.29 Mg/m3, with an angle of repose of 35 to 40 degrees. These test results indicate that buffer construction using a screw conveyor system for pellet emplacement in a waste disposal drift is a promising technology for repositories for high level radioactive wastes. (author)

  6. Buffer management optimization strategy for satellite ATM

    Institute of Scientific and Technical Information of China (English)

    Lu Rong; Cao Zhigang

    2006-01-01

    ECTD (erroneous cell tail drop), a buffer management optimization strategy is suggested which can improve the utilization of buffer resources in satellite ATM (asynchronous transfer mode) networks. The strategy, in which erroneous cells caused by satellite channel and the following cells that belong to the same PDU (protocol data Unit) are discarded, concerns non-real-time data services that use higher layer protocol for retransmission. Based on EPD (early packet drop) policy, mathematical models are established with and without ECTD. The numerical results show that ECTD would optimize buffer management and improve effective throughput (goodput), and the increment of goodput is relative to the CER (cell error ratio) and the PDU length. The higher their values are, the greater the increment. For example,when the average PDU length values are 30 and 90, the improvement of goodput are respectively about 4% and 10%.

  7. Tropical Silurian Paleotemperatures from Clumped Isotope Analysis of Coexisting Dolomite and Calcite

    Science.gov (United States)

    Winkelstern, I. Z.; Lohmann, K. C.

    2013-12-01

    In many instances, pervasive diagenetic alteration of original material prevents the use of quantitative climate proxies on Paleozoic or older rocks. As an inherently diagenetic phase, dolomite may provide a more resilient paleotemperature resource. The Δ47 carbonate clumped isotope thermometer has been shown to be an accurate paleothermometer and, in a limited way, has been shown to be applicable to dolomites. The shallow water carbonates of the Pipe Creek Jr. Reef in central Indiana offer an opportunity to test the viability of the technique in ancient dolomite. After formation in the late Silurian, a sea level drop resulted in a diagenetic sequence of meteoric phreatic alteration of marine cement and biotic components, which included precipitation of dolomite cements inter-grown within the meteoric phreatic calcite cement. This was post-dated by a coarse void filling calcite spar formed at burial temperatures of ~100°C (based on fluid inclusion analysis). Preliminary analyses of coexisting dolomite and calcite suggest that near-surface temperatures are preserved in dolomites despite having experienced elevated thermal diagenetic effects.. In contrast, co-existing early-formed calcites exhibit resetting of earth surface temperatures to elevated values. Δ47 measurements in dolomites yield temperatures around 30°C using the Guo et al., (2009) theoretical calibration. This contrasts with analyses of early (original) and late (hydrothermal) calcites, which record temperatures greater than ~80°C using the Δ47-calcite calibration of Dennis and Schrag (2010). These data support the hypothesis that dolomite can be a more resilient paleotemperature proxy relative to calcite in deep-time studies. Temperatures from dolomites compare reasonably with other late Silurian paleoclimate studies, and offer insight into regional-scale paleoclimate.

  8. Temperature Buffer Test. Final THM modelling

    International Nuclear Information System (INIS)

    The Temperature Buffer Test (TBT) is a joint project between SKB/ANDRA and supported by ENRESA (modelling) and DBE (instrumentation), which aims at improving the understanding and to model the thermo-hydro-mechanical behavior of buffers made of swelling clay submitted to high temperatures (over 100 deg C) during the water saturation process. The test has been carried out in a KBS-3 deposition hole at Aespoe HRL. It was installed during the spring of 2003. Two heaters (3 m long, 0.6 m diameter) and two buffer arrangements have been investigated: the lower heater was surrounded by bentonite only, whereas the upper heater was surrounded by a composite barrier, with a sand shield between the heater and the bentonite. The test was dismantled and sampled during the winter of 2009/2010. This report presents the final THM modelling which was resumed subsequent to the dismantling operation. The main part of this work has been numerical modelling of the field test. Three different modelling teams have presented several model cases for different geometries and different degree of process complexity. Two different numerical codes, CodeBright and Abaqus, have been used. The modelling performed by UPC-Cimne using CodeBright, has been divided in three subtasks: i) analysis of the response observed in the lower part of the test, by inclusion of a number of considerations: (a) the use of the Barcelona Expansive Model for MX-80 bentonite; (b) updated parameters in the vapour diffusive flow term; (c) the use of a non-conventional water retention curve for MX-80 at high temperature; ii) assessment of a possible relation between the cracks observed in the bentonite blocks in the upper part of TBT, and the cycles of suction and stresses registered in that zone at the start of the experiment; and iii) analysis of the performance, observations and interpretation of the entire test. It was however not possible to carry out a full THM analysis until the end of the test due to convergence

  9. Temperature Buffer Test. Final THM modelling

    Energy Technology Data Exchange (ETDEWEB)

    Aakesson, Mattias; Malmberg, Daniel; Boergesson, Lennart; Hernelind, Jan [Clay Technology AB, Lund (Sweden); Ledesma, Alberto; Jacinto, Abel [UPC, Universitat Politecnica de Catalunya, Barcelona (Spain)

    2012-01-15

    The Temperature Buffer Test (TBT) is a joint project between SKB/ANDRA and supported by ENRESA (modelling) and DBE (instrumentation), which aims at improving the understanding and to model the thermo-hydro-mechanical behavior of buffers made of swelling clay submitted to high temperatures (over 100 deg C) during the water saturation process. The test has been carried out in a KBS-3 deposition hole at Aespoe HRL. It was installed during the spring of 2003. Two heaters (3 m long, 0.6 m diameter) and two buffer arrangements have been investigated: the lower heater was surrounded by bentonite only, whereas the upper heater was surrounded by a composite barrier, with a sand shield between the heater and the bentonite. The test was dismantled and sampled during the winter of 2009/2010. This report presents the final THM modelling which was resumed subsequent to the dismantling operation. The main part of this work has been numerical modelling of the field test. Three different modelling teams have presented several model cases for different geometries and different degree of process complexity. Two different numerical codes, Code{sub B}right and Abaqus, have been used. The modelling performed by UPC-Cimne using Code{sub B}right, has been divided in three subtasks: i) analysis of the response observed in the lower part of the test, by inclusion of a number of considerations: (a) the use of the Barcelona Expansive Model for MX-80 bentonite; (b) updated parameters in the vapour diffusive flow term; (c) the use of a non-conventional water retention curve for MX-80 at high temperature; ii) assessment of a possible relation between the cracks observed in the bentonite blocks in the upper part of TBT, and the cycles of suction and stresses registered in that zone at the start of the experiment; and iii) analysis of the performance, observations and interpretation of the entire test. It was however not possible to carry out a full THM analysis until the end of the test due to

  10. Buffer modification in determination of fluoride using selective ion electrode

    International Nuclear Information System (INIS)

    Determination of Fluoride in the Lanonorm 1 as Standard Reference material for urine OOSA 52/53 was done by Fluoride Ion selective Electrode Preparation of TISB (Total Ionic Strength Adjustor Buffer) was modified with Sodium and Potassium Chloride Salt at the pH 5,3. Standard Solution had been made 2 ppb until 9.10 exp. 4 ppb F from NaF and KF salt. The pH of TISB was made 5.3 ISE Fluoride and Double junction Reference 3,5 M KCl in outer compartment had been Installed within Metrohm 654 Potentiometer for investigating potential. Best result sample with error 3,6 % was found by TISB Natrium which use KF as calibration standard solution. (author)

  11. The buffer effect in neutral electrolyte supercapacitors

    DEFF Research Database (Denmark)

    Thrane Vindt, Steffen; Skou, Eivind M.

    2016-01-01

    The observation that double-layer capacitors based on neutral aqueous electrolytes can have significantly wider usable potential windows than those based on acidic or alkaline electrolytes is studied. This effect is explained by a local pH change taking place at the electrode surfaces, leading to a...... of addition of a buffer to such systems. It is shown that a 56 % higher dynamic storage capacity may be achieved, simply by controlling the buffer capacity of the electrolyte. The model system used, is based on a well-known commercial activated carbon (NORIT™ A SUPRA) as the electrode material...

  12. Buffer of Events as a Markovian Process

    International Nuclear Information System (INIS)

    In Particle and Asro-Particle Physics experiments, the events which get trough the detectors are read and processes on-line before they are stored for a more detailed processing and future Physics analysis. Since the events are read and, usually, processed sequentially, the time involved in these operations can lead to a significant lose of events which is, to some extent, reduced by using buffers. We present an estimate of the optimum buffer size and the fraction of events lost for a simple experimental condition which serves as an introductory example to the use of Markow Chains.(Author)

  13. Emplacement of small and large buffer blocks

    International Nuclear Information System (INIS)

    The report describes emplacement of a buffer structure encircling a spent fuel canister to be deposited in a vertical hole. The report deals with installability of various size blocks and with an emplacement gear, as well as evaluates the achieved quality of emplacement and the time needed for installing the buffer. Two block assembly of unequal size were chosen for examination. A first option involved small blocks, the use of which resulted in a buffer structure consisting of small sector blocks 200 mm in height. A second option involved large blocks, resulting in a buffer structure which consists of eight blocks. In these tests, the material chosen for both block options was concrete instead of bentonite. The emplacement test was a three-phase process. A first phase included stacking a two meter high buffer structure with small blocks for ensuring the operation of test equipment and blocks. A second phase included installing buffer structures with both block options to a height matching that of a canister-encircling cylindrical component. A third phase included testing also the installability of blocks to be placed above the canister by using small blocks. In emplacement tests, special attention was paid to the installability of blocks as well as to the time required for emplacement. Lifters for both blocks worked well. Due to the mass to be lifted, the lifter for large blocks had a more heavy-duty frame structure (and other lifting gear). The employed lifters were suspended in the tests on a single steel wire rope. Stacking was managed with both block sizes at adequate precision and stacked-up towers were steady. The stacking of large blocks was considerably faster. Therefore it is probably that the overall handling of the large blocks will be more convenient at a final disposal site. From the standpoint of reliability in lifting, the small blocks were safer to install above the canister. In large blocks, there are strict shape-related requirements which are

  14. The influence of final repository relevant electrolyte on the interaction of trivalent lanthanides and actinides with calcite; Der Einfluss endlagerrelevanter Elektrolyte auf die Wechselwirkung dreiwertiger Lanthanide und Actinide mit Calcit

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, Sascha

    2015-10-21

    Calcite, a naturally occurring and very abundant mineral, is considered a potential retentive geochemical barrier regarding nuclear waste disposal. In this work, the reactivity of calcite towards trivalent Ln and An has been determined by spectroscopic, microscopic and X-ray scattering techniques. This, in connection with the use of luminescent probes Eu(III) and Cm(III), allowed for the understanding of electrolyte influences on the retention potential of calcite.

  15. On the Complexity of Buffer Allocation in Message Passing Systems

    OpenAIRE

    Brodsky, Alex; Pedersen, Jan B.; Wagner, Alan

    2003-01-01

    Message passing programs commonly use buffers to avoid unnecessary synchronizations and to improve performance by overlapping communication with computation. Unfortunately, using buffers makes the program no longer portable, potentially unable to complete on systems without a sufficient number of buffers. Effective buffer use entails that the minimum number needed for a safe execution be allocated. We explore a variety of problems related to buffer allocation for safe and efficient execution ...

  16. Aqueous solution dispersement of carbon nanotubes

    Science.gov (United States)

    Kim, Jae-Woo (Inventor); Park, Cheol (Inventor); Choi, Sang H. (Inventor); Lillehei, Peter T. (Inventor); Harrison, Joycelyn S. (Inventor)

    2011-01-01

    Carbon nanotubes (CNTs) are dispersed in an aqueous buffer solution consisting of at least 50 weight percent water and a remainder weight percent that includes a buffer material. The buffer material has a molecular structure defined by a first end, a second end, and a middle disposed between the first and second ends. The first end is a cyclic ring with nitrogen and oxygen heteroatomes, the middle is a hydrophobic alkyl chain, and the second end is a charged group.

  17. Mechanism of Calcite Co-Orientation in the Sea Urchin Tooth

    Energy Technology Data Exchange (ETDEWEB)

    Killian, Christopher; Metzler, Rebecca; Gong, Y. U. T.; Olson, Ian; Aizenberg, Joanna; Politi, Yael; Wilt, Fred; Scholl, Andreas; Young, Anthony; Doran, Andrew; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan; Gilbert, P. U. P. A.

    2009-12-01

    Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO{sub 3}) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin (Strongylocentrotus purpuratus), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction ({mu}XRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO{sub 3} is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.

  18. Low-magnesium calcite produced by coralline algae in seawater of Late Cretaceous composition.

    Science.gov (United States)

    Stanley, Steven M; Ries, Justin B; Hardie, Lawrence A

    2002-11-26

    Shifts in the MgCa ratio of seawater driven by changes in midocean ridge spreading rates have produced oscillations in the mineralogy of nonskeletal carbonate precipitates from seawater on time scales of 10(8) years. Since Cambrian time, skeletal mineralogies of anatomically simple organisms functioning as major reef builders or producers of shallow marine limestones have generally corresponded in mineral composition to nonskeletal precipitates. Here we report on experiments showing that the ambient MgCa ratio actually governs the skeletal mineralogy of some simple organisms. In modern seas, coralline algae produce skeletons of high-Mg calcite (>4 mol % MgCO(3)). We grew three species of these algae in artificial seawaters having three different MgCa ratios. All of the species incorporated amounts of Mg into their skeletons in proportion to the ambient MgCa ratio, mimicking the pattern for nonskeletal precipitation. Thus, the algae calcified as if they were simply inducing precipitation from seawater through their consumption of CO(2) for photosynthesis; presumably organic templates specify the calcite crystal structure of their skeletons. In artificial seawater with the low MgCa ratio of Late Cretaceous seas, the algae in our experiments produced low-Mg calcite (MgCO(3)), the carbonate mineral formed by nonskeletal precipitation in those ancient seas. Our results suggest that many taxa that produce high-Mg calcite today produced low-Mg calcite in Late Cretaceous seas. PMID:12399549

  19. Vorticity analysis in calcite tectonites: An example from the Attico-Cycladic massif (Attica, Greece)

    Science.gov (United States)

    Spanos, D.; Xypolias, P.; Koukouvelas, I.

    2015-11-01

    Although calcite tectonites are widespread in nature their use to quantify flow vorticity is limited. We use new (micro-)structural, petrofabric and vorticity data to analyse the kinematics of flow in outcrop-scale calcite mylonite zones. These zones are genetically related to a crustal-scale NE-directed ductile thrust (Basal Thrust) that emplaced the Blueschist over the Basal unit during the exhumation of the Attico-Cycladic Massif. Calcite microstructures reveal that the last stage of deformation occurred at temperatures 200-300 °C achieved by mild heating, which is possibly related with the reburial of the Basal Thrust's footwall. Vorticity analyses were based on the degree of asymmetry of calcite c-axis fabrics as well as on the assumption that the orientation of the long axes of calcite neoblasts within an oblique foliation delineates the direction of instantaneous stretching axis. Both methodological approaches provide consistent estimates with a simple shear component between 55% and 82% (Wn = 0.76-0.96). The use of the stress axis (σ1) orientation recorded by twin-c-axis-pairs to quantify vorticity generally gives significantly lower simple shear component. Comparison of our vorticity estimates with previous estimates inferred from quartz fabrics and rigid porphyroclasts reveals that exhumation-related deformation in the nappe pile was steady state.

  20. Model study of initial adsorption of SO2 on calcite and dolomite

    International Nuclear Information System (INIS)

    The rate of calcareous stone degradation is to a significant extent controlled by their surface chemistry with SO2. Initial surface sulphite is converted to a harmful gypsum upon, e.g. NO2 catalysed oxidation. However, it has been observed by scanning electron microscopy that the lateral distributions of gypsum crystals differ between calcitic and dolomitic marbles. The first-principles density functional theory is employed to understand the origin of these fundamentally different morphologies. Here, the stability differences of surface sulphite at calcite CaCO3 (s) and dolomite CaxMg1-xCO3 (s) are determined. A qualitative difference in surface sulphite stability, favouring the former, is reported. This is taken to imply that calcitic micro-crystals embedded in a dolomitic matrix act as sinks in the surface sulphation process, controlled by SO2 diffusion. The subsequent formation of gypsum under such conditions will not require SO42- (aq) ion transport. This explains the homogeneous distribution of gypsum observed on the calcitic micro-crystals in dolomite. In contrast, sulphation on purely calcitic marbles never reaches such high SO2 coverage. Rather, upon oxidation, SO42- (aq) transport to nucleation centres, such as grain boundaries, is required for the growth of gypsum crystals

  1. The influence of final repository relevant electrolyte on the interaction of trivalent lanthanides and actinides with calcite

    International Nuclear Information System (INIS)

    Calcite, a naturally occurring and very abundant mineral, is considered a potential retentive geochemical barrier regarding nuclear waste disposal. In this work, the reactivity of calcite towards trivalent Ln and An has been determined by spectroscopic, microscopic and X-ray scattering techniques. This, in connection with the use of luminescent probes Eu(III) and Cm(III), allowed for the understanding of electrolyte influences on the retention potential of calcite.

  2. Engineered barrier experiments and analytical studies on coupled thermal - hydraulic - chemical processes in bentonite buffer material

    International Nuclear Information System (INIS)

    It is anticipated that thermal - hydraulic - mechanical - chemical (THMC) processes will be coupled in the bentonite buffer material of a high-level radioactive waste repository. The main contributors to these processes are heat arising from the radioactive decay of the vitrified waste, infiltration of groundwater from the host rock and/or leachate from the cementitious component of the repository, and the consequent increase in swelling pressure and chemical reactions. In order to evaluate these coupled processes in the bentonite buffer material, it is necessary to take steps towards the development of a credible and robust THMC model. The current paper describes the measured data of an engineering-scale coupled THC process experiment and the calculated results of a THC model undergoing development. The coupled experiment used an electric heater, bentonite blocks and a mortar block, subjected to infiltrating water to simulate a high-alkaline porewater derived from the concrete tunnel support seeping into the bentonite buffer material under a thermal gradient provided by the vitrified waste. Temperature and water content of the bentonite buffer material were measured by several sensors continuously for several months. After this time, the buffer material was sampled. The results of mineral analysis of the samples suggested that the precipitate of amorphous hydrate with silica was found in the buffer material in contact with the mortar. The developing THC model simulated C-S-H gel precipitation as a secondary mineral in the exact same locality because of the solution being saturated with respect to portlandite and chalcedony, thereby providing some confidence in the chemical feature of the developing THC model. Some important issues in the future development of the model were also identified, including the concentration of porewater being influenced by vapor movement in the bentonite buffer material due to heating from the vitrified waste and geochemical reactions

  3. The buffer effect in neutral electrolyte supercapacitors

    Science.gov (United States)

    Vindt, Steffen T.; Skou, Eivind M.

    2016-02-01

    The observation that double-layer capacitors based on neutral aqueous electrolytes can have significantly wider usable potential windows than those based on acidic or alkaline electrolytes is studied. This effect is explained by a local pH change taking place at the electrode surfaces, leading to a change in the redox potential of water in opposite directions on the two electrodes, resulting in the wider stability window. The magnitude of this effect is suggested to be dependent on the buffer capacity, rather than the intrinsic pH value of the electrolyte. This is confirmed by studying the impact of addition of a buffer to such systems. It is shown that a 56 % higher dynamic storage capacity may be achieved, simply by controlling the buffer capacity of the electrolyte. The model system used, is based on a well-known commercial activated carbon (NORIT™ A SUPRA) as the electrode material, aqueous potassium nitrate as the electrolyte and potassium phosphates as the buffer system.

  4. A Discovery Chemistry Experiment on Buffers

    Science.gov (United States)

    Kulevich, Suzanne E.; Herrick, Richard S.; Mills, Kenneth V.

    2014-01-01

    The Holy Cross Chemistry Department has designed and implemented an experiment on buffers as part of our Discovery Chemistry curriculum. The pedagogical philosophy of Discovery Chemistry is to make the laboratory the focal point of learning for students in their first two years of undergraduate instruction. We first pose questions in prelaboratory…

  5. Buffer gas cooling of ion beams

    International Nuclear Information System (INIS)

    The cooling action of a buffer gas on ions contained within it can be used to cool an ion beam, thereby greatly improving its emittance and energy spread. It can also be used to greatly enhance the collection of an ion beam in an electromagnetic trap. The basic principles will be introduced in the context of a prototype system for such a beam cooler

  6. Analysis and Study of Buffer Overflow

    Institute of Scientific and Technical Information of China (English)

    Liu Sidong; Zen TaoYu; Yongquan

    2009-01-01

    Buffer overflow attack is one of the most threatening attack types and it jeopardizes security a lot. According to the principle of the attack, this paper demonstrates how it works, and emphasizes the importance of writing code that does not permit such attacks.

  7. Regulatory fit buffers against disidentification from groups

    NARCIS (Netherlands)

    Hamstra, Melvyn R.W.; Sassenberg, Kai; Van Yperen, Nico W.; Wisse, Barbara; Rietzschel, Eric F.

    2015-01-01

    Disidentification refers to people’s active psychological distancing from a group due to a negative self-defining affiliation with the group. Because disidentification can threaten group survival and group functioning, it is important to gain insight into factors that potentially buffer its occurren

  8. Biochar contribution to soil pH buffer capacity

    Science.gov (United States)

    Tonutare, Tonu; Krebstein, Kadri; Utso, Maarius; Rodima, Ako; Kolli, Raimo; Shanskiy, Merrit

    2014-05-01

    Biochar as ecologically clean and stable form of carbon has complex of physical and chemical properties which make it a potentially powerful soil amendment (Mutezo, 2013). Therefore during the last decade the biochar application as soil amendment has been a matter for a great number of investigations. For the ecological viewpoint the trend of decreasing of soil organic matter in European agricultural land is a major problem. Society is faced with the task to find possibilities to stabilize or increase soil organic matter content in soil and quality. The availability of different functional groups (e.g. carboxylic, phenolic, acidic, alcoholic, amine, amide) allows soil organic matter to buffer over a wide range of soil pH values (Krull et al. 2004). Therefore the loss of soil organic matter also reduces cation exchange capacity resulting in lower nutrient retention (Kimetu et al. 2008). Biochar can retain elements in soil directly through the negative charge that develops on its surfaces, and this negative charge can buffer acidity in the soil. There are lack of investigations about the effect of biochar to soil pH buffering properties, The aim of our investigation was to investigate the changes in soil pH buffer capacity in a result of addition of carbonizated material to temperate region soils. In the experiment different kind of softwood biochars, activated carbon and different soil types with various organic matter and pH were used. The study soils were Albeluvisols, Leptosols, Cambisols, Regosols and Histosols . In the experiment the series of the soil: biochar mixtures with the biochar content 0 to 100% were used. The times of equiliberation between solid and liquid phase were from 1 to 168 hours. The suspension of soil: biochar mixtures was titrated with HCl solution. The titration curves were established and pH buffer capacities were calculated for the pH interval from 3.0 to 10.0. The results demonstrate the dependence of pH buffer capacity from soil type

  9. Using 3H and 14C to constrain the degree of closed-system dissolution of calcite in groundwater

    International Nuclear Information System (INIS)

    Highlights: ► δ13C and 87Sr/86Sr in Ovens groundwater imply substantial carbonate dissolution. ► 3H vs. 14C imply negligible closed-system calcite dissolution. ► Calcite dissolution largely open-system process. ► Recognising open-system calcite dissolution important for dating deeper groundwater. - Abstract: This study uses 3H concentrations, 14C activities (a14C), 87Sr/86Sr ratios, and δ13C values to constrain calcite dissolution in groundwater from the Ovens catchment SE Australia. Taken in isolation, the δ13C values of dissolved organic C (DIC) and 87Sr/86Sr ratios in the Ovens groundwater imply that there has been significant calcite dissolution. However, the covariance of 3H and 14C and the calculated initial 14C activities (a014C) imply that most groundwater cannot have dissolved more than 20% of 14C-free calcite under closed-system conditions. Rather, calcite dissolution must have been partially an open-system process allowing 13C and 14C to re-equilibrate with CO2 in the unsaturated zone. Recognising that open-system calcite dissolution has occurred is important for dating deeper groundwater that is removed from its recharge area in this and other basins. The study is one of the first to use 14C and 3H to constrain the degree of calcite dissolution and illustrates that it is a valuable tool for assessing geochemical processes in recharge areas

  10. Improving performance of inverted organic solar cells using ZTO nanoparticles as cathode buffer layer

    Science.gov (United States)

    Tsai, Meng-Yen; Cheng, Wen-Hui; Jeng, Jiann-Shing; Chen, Jen-Sue

    2016-06-01

    In this study, a low-temperature solution-processed zinc tin oxide (ZTO) films are successfully utilized as the cathode buffer layer in the inverted organic P3HT:PCBM bulk heterojunction solar cells. ZTO film cathode buffer layer with an appropriate Sn-doping concentration outperforms the zinc oxide (ZnO) film with an improved power conversion efficiency (1.96% (ZTO film) vs. 1.56% (ZnO film)). Furthermore, ZTO nanoparticles (NPs) are also synthesized via low-temperature solution route and the device with ZTO NPs buffer layer exhibits a significant improvement in device performance to reach a PCE of 2.60%. The crystallinity of the cathode buffer layer plays an influential factor in the performance. From impedance spectroscopy analysis, a correlation between short circuit current (Jsc), carrier life time (τavg) and, thus, PCE is observed. The interplay between composition and crystallinity of the cathode buffer layers is discussed to find their influences on the solar cell performance.

  11. Reactive-Transport Model of Buffer Cementation

    Energy Technology Data Exchange (ETDEWEB)

    Arthur, Randy; Wei Zhou [Monitor Scientific LLC, Denver, CO (United States)

    2005-10-15

    Thermal gradients during the early, non-isothermal period of near-field evolution in a KBS-3 repository for spent nuclear fuel could alter the mineralogy of the bentonite buffer and cause the constituent clay particles to become cemented together by mineral precipitates. Cementation is a potential concern because it could alter the ductility, mechanical strength and swelling pressure of the buffer, thereby possibly adversely affecting the primary performance function of this key barrier to provide a stable diffusional transport pathway between the canister and rock. The present study uses the TOUGHREACT computer program to simulate reactive-transport processes that are thought to control buffer cementation. TOUGHREACT is generally applicable to problems involving non-isothermal, multiphase reactive transport in variably saturated media. For cementation problems, the modeling approach must account specifically for the temperature dependence of equilibrium and kinetic constraints on dissolution/precipitation reactions involving the primary smectite clays and accessory phases in bentonite, and for diffusive transport of aqueous reactants and products along concentration gradients that are aligned with, or in opposition to, the direction of decreasing temperatures across the near field. The modeling approach was evaluated in two stages. A conceptual model of buffer cementation was first calibrated using observations from field tests carried out at the Stripa mine and Aespoe HRL (LOT pilot experiments). The calibrated model was then used to simulate the geochemical evolution of the KBS-3 buffer during the non-isothermal period of repository evolution. This model accounts for the imbibition of groundwater from a granitic host rock into initially unsaturated buffer materials under capillary and hydraulic pressure gradients, and uses realistic time-temperature constraints on the thermal evolution of the near-field. Preliminary results suggest that the total extent of

  12. Reactive-Transport Model of Buffer Cementation

    International Nuclear Information System (INIS)

    Thermal gradients during the early, non-isothermal period of near-field evolution in a KBS-3 repository for spent nuclear fuel could alter the mineralogy of the bentonite buffer and cause the constituent clay particles to become cemented together by mineral precipitates. Cementation is a potential concern because it could alter the ductility, mechanical strength and swelling pressure of the buffer, thereby possibly adversely affecting the primary performance function of this key barrier to provide a stable diffusional transport pathway between the canister and rock. The present study uses the TOUGHREACT computer program to simulate reactive-transport processes that are thought to control buffer cementation. TOUGHREACT is generally applicable to problems involving non-isothermal, multiphase reactive transport in variably saturated media. For cementation problems, the modeling approach must account specifically for the temperature dependence of equilibrium and kinetic constraints on dissolution/precipitation reactions involving the primary smectite clays and accessory phases in bentonite, and for diffusive transport of aqueous reactants and products along concentration gradients that are aligned with, or in opposition to, the direction of decreasing temperatures across the near field. The modeling approach was evaluated in two stages. A conceptual model of buffer cementation was first calibrated using observations from field tests carried out at the Stripa mine and Aespoe HRL (LOT pilot experiments). The calibrated model was then used to simulate the geochemical evolution of the KBS-3 buffer during the non-isothermal period of repository evolution. This model accounts for the imbibition of groundwater from a granitic host rock into initially unsaturated buffer materials under capillary and hydraulic pressure gradients, and uses realistic time-temperature constraints on the thermal evolution of the near-field. Preliminary results suggest that the total extent of

  13. Strontium isotope evolution of pore water and calcite in the Topopah Spring Tuff, Yucca Mountain, Nevada

    International Nuclear Information System (INIS)

    Pore water in the Topopah Spring Tuff has a narrow range of (delta)87Sr values that can be calculated from the (delta)87Sr values of the rock considering advection through and reaction with the overlying nonwelded tuffs of the PTn. This model can be extended to estimate the variation of (delta)87Sr in the pore water through time; this approximates the variation of (delta)87Sr measured in calcite fracture coatings. In samples of calcite where no silica can be dated by other methods, strontium isotope data may be the only method to determine ages. In addition, other Sr-bearing minerals in the calcite and opal coatings, such as fluorite, may be dated using the same model

  14. Origin of platy calcite crystals in hot-spring deposits in the Kenya Rift Valley

    Energy Technology Data Exchange (ETDEWEB)

    Jones, B. [Univ. of Alberta, Edmonton, Alberta (Canada). Dept. of Earth and Atmospheric Sciences; Renault, R.W. [Univ. of Saskatchewan, Saskatoon, Saskatchewan (Canada). Dept. of Geological Sciences

    1998-09-01

    Platy calcite crystals, which have their c axis parallel to their shortest length axis, are common components of travertine deposits found around some hot springs in the Kenya Rift Valley. They are composite crystals formed of numerous paper-thin subcrystals. Individual plates allowed to grow without obstruction develop a hexagonal motif. The Kenyan crystals typically form in hot (>75 C) waters that have a low Ca content (<10 mg/l), a high CO{sub 2} content, and a high rate of CO{sub 2} degassing. At Chemurkeu, aggregates of numerous small platy crystals collectively form lattice crystals that superficially resemble ray crystals. The walls of the lattice crystals are formed of large platy crystals that have their long and intermediate length axes aligned parallel to the plane of the long axis of the lattice crystal. Internally, the lattice crystals are formed of small platy calcite crystals arranged in a boxlike pattern that creates the appearance of a lattice when viewed in thin section. Lattice crystals are highly porous, with each pore being enclosed by platy crystals. At Lorusio, travertines are mainly formed of pseudodentrites that are constructed by numerous small platy crystals attached to a main stem which is a large platy crystal that commonly curves along its long axis. The pseudodentrites are the main construction blocks in ledges and lilypads that form in the vent pool and spring outflow channels, where the water is too hot for microbes other than hyperthermophiles. The platy calcite crystals in the Kenyan travertines are morphologically similar to platy calcite crystals that form as scale in pipes in the geothermal fields of New Zealand and hydrothermal angel wing calcite from the La Fe mine in Mexico. Comparison of the Kenyan and New Zealand crystals indicates that platy calcite crystals form from waters with a low Ca{sup 2+} content and a high CO{sub 3}/Ca ratio due to rapid rates of CO{sub 2} degassing.

  15. Characteristics of a calcite "limestone"-marble from Macedonia, used as flux material

    Directory of Open Access Journals (Sweden)

    Hristova E.

    2003-01-01

    Full Text Available The phase characteristics of calcite "limestone"-marble from Banjany area village (near Skopje, Macedonia were examined by means of XRD, SEM microscope in polarizing and reflected lights, chemical, DT/TG-analyses. It was concluded as follows: - calcite (CaCO3 is a major mineral component (cca 80-90 % prevailing in the marble over the other minerals - dolomite is generally of minor importance (cca 10-20 % in the rock - quartz, micas graphite, pyrite represent typical accessories. As result of the mentioned phase characteristics, this raw materials was for a long time (more than 30 years used as flux in the iron and steel metallurgy in Macedonia.

  16. U and Sr Isotopes in ground water and calcite, Yucca Mountain, Nevada: Evidence against upwelling water

    Science.gov (United States)

    Stuckless, J.S.; Peterman, Z.E.; Muhs, D.R.

    1991-01-01

    Hydrogenic calcite and opaline silica deposits in fault zones at Yucca Mountain, Nevada, have created considerable public and scientific controversy because of the possible development of a high-level nuclear waste repository at this location. Strontium and uranium isotopic compositions of hydrogenic materials were used to test whether the veins could have formed by upwelling of deep-seated waters. The vein deposits are isotopically distinct from ground water in the two aquifers that underlie Yucca Mountain, indicating that the calcite could not have precipitated from ground water. The data are consistent with a surficial origin for the hydrogenic deposits.

  17. Kinetic study of the thermal decomposition process of calcite particles in air and CO2 atmosphere

    OpenAIRE

    Escardino Benlloch, Agustín; García Ten, Francisco Javier; Feliu Mingarro, Carlos; Saburit Llaudis, Alejandro; Cantavella Soler, Vicente

    2013-01-01

    The thermal decomposition process of calcite particles (0.45–3.60 mm average diameter), made up of porous agglomerates of very small CaCO3 microcrystals, was studied in the 975–1216 K temperature range. The experiments were carried out under isothermal conditions in air atmosphere, in CO2 atmosphere, as well as in a gas stream comprising different concentrations of air and CO2. An equation is proposed that relates the calcite conversion degree to both reaction time and operating condition...

  18. Contribution to the interpretation of flotability characteristics of the calcite/apatite system

    International Nuclear Information System (INIS)

    Studies of morfology and determinations of chemical composition of apatite and calcite samples from Jacupiranga, (SP), Brazil, and Itataia (CE), Brazil, were compared with results of microflotation tests. The microflotation tests were carried out with pure and mixture samples. The ores samples were characterized by X ray diffraction. The behavior of the same ores from other deposits was different of these same ores during microflotation. The flotability of calcite depends on its morphology; the MgO content is a less important variable. (Author)

  19. Smaller Calcite Lattice Deformation Caused by Occluded Organic Material in Coccoliths than in Mollusk Shell

    DEFF Research Database (Denmark)

    Froelich, Simon; Sørensen, H.O.; Hakim, S.S.;

    2015-01-01

    The growth and nucleation of biominerals are directed and affected by associated biological molecules. In this paper, we investigate the influence of occluded biomolecules on biogenic calcite from the coccolithophorid Pleurochrysis carterae and from chalk, a rock composed predominantly of fossil...... suggests that the interaction between biomolecules and calcite is not as tight in the coccoliths as in the shell. Although the shape of chalk has been preserved over millions of years, no major influence on the crystal lattice was observed in the chalk samples....

  20. Thickness and structure of the water film deposited from vapour on calcite surfaces

    DEFF Research Database (Denmark)

    Bohr, Jakob; Wogelius, Roy A.; Morris, Peter M.; Stipp, Susan L.S.

    2010-01-01

    Synchrotron X-ray reflectivity (SXR) was used to measure the thickness of the water film that adsorbs on a {10¯14} cleavage surface of calcite (CaCO3) in a sample chamber where relative humidity could be controlled within the range from......Synchrotron X-ray reflectivity (SXR) was used to measure the thickness of the water film that adsorbs on a {10¯14} cleavage surface of calcite (CaCO3) in a sample chamber where relative humidity could be controlled within the range from...

  1. Not all calcite ballast is created equal: differing effects of foraminiferan and coccolith calcite on the formation and sinking of aggregates

    Directory of Open Access Journals (Sweden)

    K. Schmidt

    2013-09-01

    Full Text Available Correlation between particulate organic carbon (POC and calcium carbonate sinking through the deep ocean has led to the idea that ballast provided by calcium carbonate is important for the export of POC from the surface ocean. While this idea is certainly to some extent true, it is worth considering in more nuance, for example, examining the different effects on the aggregation and sinking of POC of small, non-sinking calcite particles like coccoliths and large, rapidly sinking calcite like planktonic foraminiferan tests. We have done that here in a simple experiment carried out in roller tanks that allow particles to sink continuously without being impeded by container walls. Coccoliths were efficiently incorporated into aggregates that formed during the experiment, increasing their sinking speed compared to similarly sized aggregates lacking added calcite ballast. The foraminiferan tests, which sank as fast as 700 m d−1, became associated with only very minor amounts of POC. In addition, when they collided with other, larger, foraminferan-less aggregates, they fragmented them into two smaller, more slowly sinking aggregates. While these effects were certainly exaggerated within the confines of the roller tanks, they clearly demonstrate that calcium carbonate ballast is not just calcium carbonate ballast- different forms of calcium carbonate ballast have notably different effects on POC aggregation, sinking, and export.

  2. Buffer and spectral characteristics of exyhemoglobin modified by guanidine hydrochloride and by long wave ultra violet radiation

    International Nuclear Information System (INIS)

    Studied are the buffer and spectral characteristics of oxyhemoglobin solutions, subjected to the action of guanidine hydrochloride and long wave ultra-violet radiation. The alkali buffer volume of protein is shown to increase at the action of 1-6 M guanidine, acidic buffer volume being decreased in the presence of 1 M guanidine. A conclusion is made that the quantity and states of ''binding centres'' of (H+) acid and (OH-) alkali and chromophore groups in oxyhemoglobin molecules in the result of modification by guanidine. Studied is the photosensitivity of conformative states of oxyhemoglobin arising under the guanidine effect

  3. Thermo-hydro-mechanical tests of buffer material

    International Nuclear Information System (INIS)

    MX-80 bentonite is the reference clay material for the buffer component planned to be used in the deep geological repository for the disposal of spent nuclear fuel in Finland. The buffer presents complex thermo-hydro-mechanical behavior which is modeled with different constitutive models for heat flow, water flow and stress-strain evolution in the buffer. Thermo, hydro and mechanical models need parameters to evaluate the THM-behavior. These modeling parameters were determined by performing series of laboratory experiments as follows: Water retention curve tests were performed on compacted bentonite samples, encompassing a range of initial dry density values from 1397 to 1718 kg/m3 as the initial water content was around of 5-8 %. The water retention curve was determined by imposing different suctions to the samples and the suctions were then checked using capacitive hygrometer and chilled mirror psychrometer. Oedometer tests were performed on compacted bentonite samples, encompassing a range of initial dry density values from 1590 to 1750 kg/m3 as the initial water content was around of 6 %. Samples were saturated with tap water, 35 or 70 g/L salt solutions. Infiltration tests were performed on compacted unsaturated bentonite samples, encompassing a range of initial dry density values from 1400 to 1720 kg/m3 as the initial water content was approximately between 4-7 %. Samples were saturated with tap water, 0.87, 35 or 70 g/L salt solutions. Tortuosity tests were performed on bentonite samples, encompassing a range of dry density values from 1460 to 1750 kg/m3 and the degree of saturation varied between 33-93 %. Thermal conductivity tests were performed on compacted bentonite samples, encompassing a range of dry density values from 1545 to 1715 kg/m3 and the degree of saturation varied between 31-88 %. The measurement was performed using a thermal needle probe. The general trend of all analyzed parameters was as expected when dry density, water content, and

  4. Intra-skeletal calcite in a live-collected Porites sp.: Impact on environmental proxies and potential formation process

    Science.gov (United States)

    Lazareth, Claire E.; Soares-Pereira, Caroline; Douville, Eric; Brahmi, Chloé; Dissard, Delphine; Le Cornec, Florence; Thil, François; Gonzalez-Roubaud, Cécile; Caquineau, Sandrine; Cabioch, Guy

    2016-03-01

    Geochemical proxies measured in the carbonate skeleton of tropical coral Porites sp. have commonly been used to reconstruct sea surface temperature (SST) and more recently seawater pH. Nevertheless, both reconstructed SST and pH depend on the preservation state of the skeleton, here made of aragonite; i.e., diagenetic processes and its related effects should be limited. In this study, we report on the impact of the presence of intra-skeletal calcite on the skeleton geochemistry of a live-collected Porites sp. The Porites skeleton preservation state was analyzed using X-ray diffraction and scanning electron microscopy. Sr/Ca, Mg/Ca, U/Ca, Ba/Ca, Li/Mg, and B/Ca ratios were measured at a monthly and yearly resolution using quadrupole ICP-MS and multi-collector ICP-MS. The δ11B signatures and the calcite percentages were acquired at a yearly timescale. The coral colony presents two parts, one with less than 3% calcite (referred to as "no-calcite" skeleton), the other one, corresponding to the skeleton formed during the last 4 years of growth, with calcite percentages varying from 13% to 32% (referred to as "with calcite" skeleton). This intra-skeletal calcite replaces partly or completely numerous centers of calcification (COCs). All investigated geochemical tracers are significantly impacted by the presence of calcite. The reconstructed SST decreases by about 0.1 °C per calcite-percent as inferred from the Sr/Ca ratio. Such impact reaches up to 0.26 °C per calcite-percent for temperature deduced from the Li/Mg ratio. So, less than 5% of such intra-skeletal calcite does not prevent SST reconstructions using Sr/Ca ratio, but the percentage and type of calcite have to be determined before fine SST interpretation. Seawater pH reconstruction inferred from boron isotopes drop by about -0.011 pH-unit per calcite-percent. Such sensitivity to calcite presence is particularly dramatic for fine paleo-pH reconstructions. Here we suggest that after being brought to shallow

  5. Power-Gating Technique for Network-on-Chip Buffers

    OpenAIRE

    Zamboni, Maurizio; Yadav, Manoj Kumar; Casu, Mario Roberto

    2013-01-01

    A new approach to reducing leakage power in network-on-chip buffers is presented. The non-uniformity of buffer utilisation is leveraged across the network and power-gating is applied to scarcely utilised buffers. Instead of turning-off the buffers completely, a buffer portion is kept turned-on. This design choice has a significant performance benefit because the buffer is always able to receive network packets. Design aspects and trade-offs in a 45 nm CMOS technology are discussed and results...

  6. HEAVY TRAFFIC LIMIT THEOREMS IN FLUID BUFFER MODELS

    Institute of Scientific and Technical Information of China (English)

    YIN Gang; ZHANG Hanqin

    2004-01-01

    A fluid buffer model with Markov modulated input-output rates is considered.When traffic intensity is near its critical value, the system is known as in heavy traffic.It is shown that a suitably scaled sequence of the equilibrium buffer contents has a weakor distributional limit under heavy traffic conditionsThis weak limit is a functional of adiffusion process determined by the Markov chain modulating the input and output rates.The first passage time of the reflected process is examinedIt is shown that the mean firstpassage time can be obtained via a solution of a Dirichlet problemThen the transitiondensity of the reflected process is derived by solving the Kolmogorov forward equation witha Neumann boundary conditionFurthermore, when the fast changing part of the generatorof the Markov chain is a constant matrix, the representation of the probability distributionof the reflected process is derivedUpper and lower bounds of the probability distributionare also obtained by means of asymptotic expansions of standard normal distribution.

  7. Observations on the Solubility of Skeletal Carbonates in Aqueous Solutions.

    Science.gov (United States)

    Chave, K E; Deffeyes, K S; Weyl, P K; Garrels, R M; Thompson, M E

    1962-07-01

    Carbonate skeletal materials of marine organisms exhibit a wide range of solubilities in aqueous solutions. In most cases, the dissolution of the carbonate mineral is irreversible and therefore the material can have no true equilibrium solubility. Relative solubilities have been measured in distilled water and in sea water. The least soluble mineral appears to be calcite with low magnesium content; the most soluble is calcite containing 20 to 30 percent MgCO(3) in solid solution. Aragonite has an intermediate solubility. PMID:17774123

  8. Development of all chemical solution derived Ce0.9La0.1O2 − y/Gd2Zr2O7 buffer layer stack for coated conductors: influence of the post-annealing process on surface crystallinity

    DEFF Research Database (Denmark)

    Yue, Zhao; Li, Xiaofen; Khoryushin, Alexey;

    2012-01-01

    Preparation and characterization of a biaxially textured Gd2Zr2O7 and Ce0.9La0.1O2 − y (CLO, cap)/Gd2Zr2O7 (GZO, barrier) buffer layer stack by the metal–organic deposition route are reported. YBa2Cu3O7 − d (YBCO) superconductor films were deposited by the pulsed-laser deposition (PLD) technique to...

  9. Isostatic compression of buffer blocks. Middle scale

    Energy Technology Data Exchange (ETDEWEB)

    Ritola, J.; Pyy, E. [VTT Technical Research Centre of Finland, Espoo (Finland)

    2012-01-15

    Manufacturing of buffer components using isostatic compression method has been studied in small scale in 2008 (Laaksonen 2010). These tests included manufacturing of buffer blocks using different bentonite materials and different compression pressures. Isostatic mould technology was also tested, along with different methods to fill the mould, such as vibration and partial vacuum, as well as a stepwise compression of the blocks. The development of manufacturing techniques has continued with small-scale (30 %) blocks (diameter 600 mm) in 2009. This was done in a separate project: Isostatic compression, manufacturing and testing of small scale (D = 600 mm) buffer blocks. The research on the isostatic compression method continued in 2010 in a project aimed to test and examine the isostatic manufacturing process of buffer blocks at 70 % scale (block diameter 1200 to 1300 mm), and the aim was to continue in 2011 with full-scale blocks (diameter 1700 mm). A total of nine bentonite blocks were manufactured at 70 % scale, of which four were ring-shaped and the rest were cylindrical. It is currently not possible to manufacture full-scale blocks, because there is no sufficiently large isostatic press available. However, such a compression unit is expected to be possible to use in the near future. The test results of bentonite blocks, produced with an isostatic pressing method at different presses and at different sizes, suggest that the technical characteristics, for example bulk density and strength values, are somewhat independent of the size of the block, and that the blocks have fairly homogenous characteristics. Water content and compression pressure are the two most important properties determining the characteristics of the compressed blocks. By adjusting these two properties it is fairly easy to produce blocks at a desired density. The commonly used compression pressure in the manufacturing of bentonite blocks is 100 MPa, which compresses bentonite to approximately

  10. Isostatic compression of buffer blocks. Middle scale

    International Nuclear Information System (INIS)

    Manufacturing of buffer components using isostatic compression method has been studied in small scale in 2008 (Laaksonen 2010). These tests included manufacturing of buffer blocks using different bentonite materials and different compression pressures. Isostatic mould technology was also tested, along with different methods to fill the mould, such as vibration and partial vacuum, as well as a stepwise compression of the blocks. The development of manufacturing techniques has continued with small-scale (30 %) blocks (diameter 600 mm) in 2009. This was done in a separate project: Isostatic compression, manufacturing and testing of small scale (D = 600 mm) buffer blocks. The research on the isostatic compression method continued in 2010 in a project aimed to test and examine the isostatic manufacturing process of buffer blocks at 70 % scale (block diameter 1200 to 1300 mm), and the aim was to continue in 2011 with full-scale blocks (diameter 1700 mm). A total of nine bentonite blocks were manufactured at 70 % scale, of which four were ring-shaped and the rest were cylindrical. It is currently not possible to manufacture full-scale blocks, because there is no sufficiently large isostatic press available. However, such a compression unit is expected to be possible to use in the near future. The test results of bentonite blocks, produced with an isostatic pressing method at different presses and at different sizes, suggest that the technical characteristics, for example bulk density and strength values, are somewhat independent of the size of the block, and that the blocks have fairly homogenous characteristics. Water content and compression pressure are the two most important properties determining the characteristics of the compressed blocks. By adjusting these two properties it is fairly easy to produce blocks at a desired density. The commonly used compression pressure in the manufacturing of bentonite blocks is 100 MPa, which compresses bentonite to approximately

  11. Microbial activity in bentonite buffers. Literature study

    Energy Technology Data Exchange (ETDEWEB)

    Ratto, M.; Itavaara, M.

    2012-07-01

    The proposed disposal concept for high-level radioactive wastes involves storing the wastes underground in copper-iron containers embedded in buffer material of compacted bentonite. Hydrogen sulphide production by sulphate-reducing prokaryotes is a potential mechanism that could cause corrosion of waste containers in repository conditions. The prevailing conditions in compacted bentonite buffer will be harsh. The swelling pressure is 7-8 MPa, the amount of free water is low and the average pore and pore throat diameters are small. This literature study aims to assess the potential of microbial activity in bentonite buffers. Literature on the environmental limits of microbial life in extreme conditions and the occurrence of sulphatereducing prokaryotes in extreme environments is reviewed briefly and the results of published studies characterizing microbes and microbial processes in repository conditions or in relevant subsurface environments are presented. The presence of bacteria, including SRBs, has been confirmed in deep groundwater and bentonite-based materials. Sulphate reducers have been detected in various high-pressure environments, and sulphate-reduction based on hydrogen as an energy source is considered a major microbial process in deep subsurface environments. In bentonite, microbial activity is strongly suppressed, mainly due to the low amount of free water and small pores, which limit the transport of microbes and nutrients. Spore-forming bacteria have been shown to survive in compacted bentonite as dormant spores, and they are able to resume a metabolically active state after decompaction. Thus, microbial sulphide production may increase in repository conditions if the dry density of the bentonite buffer is locally reduced. (orig.)

  12. Social buffering: relief from stress and anxiety

    OpenAIRE

    Kikusui, Takefumi; Winslow, James T.; Mori, Yuji

    2006-01-01

    Communication is essential to members of a society not only for the expression of personal information, but also for the protection from environmental threats. Highly social mammals have a distinct characteristic: when conspecific animals are together, they show a better recovery from experiences of distress. This phenomenon, termed ‘social buffering’, has been found in rodents, birds, non-human primates and also in humans. This paper reviews classical findings on social buffering and focuses...

  13. Microbial activity in bentonite buffers. Literature study

    International Nuclear Information System (INIS)

    The proposed disposal concept for high-level radioactive wastes involves storing the wastes underground in copper-iron containers embedded in buffer material of compacted bentonite. Hydrogen sulphide production by sulphate-reducing prokaryotes is a potential mechanism that could cause corrosion of waste containers in repository conditions. The prevailing conditions in compacted bentonite buffer will be harsh. The swelling pressure is 7-8 MPa, the amount of free water is low and the average pore and pore throat diameters are small. This literature study aims to assess the potential of microbial activity in bentonite buffers. Literature on the environmental limits of microbial life in extreme conditions and the occurrence of sulphatereducing prokaryotes in extreme environments is reviewed briefly and the results of published studies characterizing microbes and microbial processes in repository conditions or in relevant subsurface environments are presented. The presence of bacteria, including SRBs, has been confirmed in deep groundwater and bentonite-based materials. Sulphate reducers have been detected in various high-pressure environments, and sulphate-reduction based on hydrogen as an energy source is considered a major microbial process in deep subsurface environments. In bentonite, microbial activity is strongly suppressed, mainly due to the low amount of free water and small pores, which limit the transport of microbes and nutrients. Spore-forming bacteria have been shown to survive in compacted bentonite as dormant spores, and they are able to resume a metabolically active state after decompaction. Thus, microbial sulphide production may increase in repository conditions if the dry density of the bentonite buffer is locally reduced. (orig.)

  14. Competitive adsorption of arsenate and phosphate onto calcite; experimental results and modeling with CCM and CD-MUSIC

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt; Postma, Dieke; Jakobsen, Rasmus;

    2012-01-01

    adsorption of arsenate onto calcite is of minor importance in most groundwater aquifers, as phosphate is often present at concentration levels sufficient to significantly reduce arsenate adsorption. The CD-MUSIC model for calcite was used successfully to model adsorption of arsenate and phosphate separately...

  15. Throughput maximization for buffer-aided hybrid half-/full-duplex relaying with self-interference

    KAUST Repository

    Khafagy, Mohammad Galal

    2015-06-01

    In this work, we consider a two-hop cooperative setting where a source communicates with a destination through an intermediate relay node with a buffer. Unlike the existing body of work on buffer-aided half-duplex relaying, we consider a hybrid half-/full-duplex relaying scenario with loopback interference in the full-duplex mode. Depending on the channel outage and buffer states that are assumed available at the transmitters, the source and relay may either transmit simultaneously or revert to orthogonal transmission. Specifically, a joint source/relay scheduling and relaying mode selection mechanism is proposed to maximize the end-to-end throughput. The throughput maximization problem is converted to a linear program where the exact global optimal solution is efficiently obtained via standard convex/linear numerical optimization tools. Finally, the theoretical findings are corroborated with event-based simulations to provide the necessary performance validation.

  16. Origin of zoning within dedolomite and calcitized gypsum of the Mississippian Arroyo Penasco Group

    Energy Technology Data Exchange (ETDEWEB)

    Ulmer, D.S.

    1985-01-01

    The Mississippian Arroyo Penasco Group carbonates are the oldest Paleozoic rocks present in north-central New Mexico. These supratidal to shallow,subtidal sediments exhibit complex diagenetic fabrics produced by periods of pre-Pennsylvanian subaerial exposure. Both extensive recrystallization of the Espiritu Santo carbonates and brecciation of the overlying Macho Member of the Tererro Formation resulted from an extended period of Mississippian subaerial exposure of broad, low-relief tidal flats. Cathodoluminescent petrography indicates that the recrystallized limestones consist of calcite pseudomorphs of dolomite and gypsum. Dedolomite and calcitized gypsum crystals, with /sup 13/C//sup 12/C ratios of -2 to +1.5% PDB, range from highly zoned to uniformly luminescent. Electron microprobe analyses reveals variable Mn and Fe contents across the pseudomorphs which are responsible for differences in observed luminosity. These features are interpreted to reflect a period of subaerial exposure after deposition of Macho Member sediments, which caused dissolution of gypsum and dolomite by sulfate and Mg depleted meteoric fluids and produced the collapse breccia. Preservation of zoning within some pseudomorphs required simultaneous dissolution of gypsum and dolomite and precipitation of calcite. C-isotope data indicates a meteoric to mixed phreatic origin for pore fluids which precipitated calcite; repetitive zoning within dolomite and gypsum pseudomorphs is indicative of interactions between marine and meteoric phreatic fluids in the intertidal environment.

  17. Unusual biogenic calcite structures in two shallow lakes, James Ross Island, Antarctica

    Science.gov (United States)

    Elster, J.; Nedbalová, L.; Vodrážka, R.; Láska, K.; Haloda, J.; Komárek, J.

    2016-01-01

    The floors of two shallow endorheic lakes, located on volcanic surfaces on James Ross Island, are covered with calcareous organosedimentary structures. Their biological and chemical composition, lake water characteristics, and seasonal variability of the thermal regime are introduced. The lakes are frozen down to the bottom for 8-9 months a year and their water chemistry is characterised by low conductivity and neutral to slightly alkaline pH. The photosynthetic microbial mat is composed of filamentous cyanobacteria and microalgae that are considered to be Antarctic endemic species. The mucilaginous black biofilm is covered by green spots formed by a green microalga and the macroscopic structures are packed together with fine material. Thin sections consist of rock substrate, soft biofilm, calcite spicules and mineral grains originating from different sources. The morphology of the spicules is typical of calcium carbonate monocrystals having a layered structure and specific surface texture, which reflect growth and degradation processes. The spicules' chemical composition and structure correspond to pure calcite. The lakes' age, altitude, morphometry, geomorphological and hydrological stability, including low sedimentation rates, together with thermal regime predispose the existence of this community. We hypothesise that the precipitation of calcite is connected with the photosynthetic activity of the green microalgae that were not recorded in any other lake in the region. This study has shown that the unique community producing biogenic calcite spicules is quite different to any yet described.

  18. Microstratigraphic logging of calcite fabrics in speleothems as tool for palaeoclimate studies

    Directory of Open Access Journals (Sweden)

    Silvia Frisia

    2015-01-01

    Full Text Available The systematic documentation of calcite fabrics in stalagmites and flowstones provides robustness to palaeoclimate interpretation based on geochemical proxies, but it has been neglected because it is difficult to transform crystal morphologies into numerical values, and construct fabric time series. Here, general criteria that allow for coding fabrics of calcite composing stalagmites and flowstones is provided. Being based on known models of fabric development, the coding ascribes sequential numbers to each fabric, which reflect climate-related parameters, such as changes in drip rate variability, bio-mediation or diagenetic modifications. Acronyms are proposed for Columnar types, Dendritic, Micrite, Microsparite and Mosaic fabrics, whose use could then render possible comparison of calcite fabrics in stalagmites and flowstones from diverse latitudinal and altitudinal settings. The climatic and environmental significance of similarities in the geochemical signals and trends analysed in coeval stalagmites and flowstones (or differences in the signals and trends will be more robust when compared with fabric time series. This is particularly true where, such as in the Holocene, changes in geochemical values may be subtle, yet fabrics may show changes related to variations in supersaturation, drip rate or input of detrital particles or organic compounds. The proposed microstratigraphic logging allows recognition of changes in stable isotope ratio or trace element values that can be ascribed to hydrology and diagenesis, with considerable improvement of reconstructions based on the chemical proxies of stalagmites and flowstones composed of calcite.

  19. DC CONDUCTIVITY OF CERAMICS WITH CALCITE WASTE IN THE TEMPERATURE RANGE 20 - 1050C

    Directory of Open Access Journals (Sweden)

    Jan Ondruska

    2015-06-01

    Full Text Available The temperature dependences of the electrical DC conductivity of calcite waste, kaolinite and illite based ceramics were measured in the temperature range of 20 - 1050oC. The ceramic mass that was used was a mixture of 60 wt. % kaolinitic-illitic clay, 20 - 40 wt. % of this clay was fired at 1000oC for 90 min and 0, 10 and 20 wt. % of calcite waste. During heating, several processes take place - the release of the physically bound water, the burning of organic impurities, the dehydroxylation of kaolinite and illite, the decomposition of calcite, and the creation of anorthite and mullite. All of these processes were checked by means of differential thermal analysis (DTA, derivative thermogravimetry (DTG and thermodilatometry (TDA. At low temperatures (20 - 200oC, due to the release and decomposition of physically bound water, H+ and OH- are dominant charge carriers. After completion of release of physically bound water, up to the start of dehydroxylation at the temperature of ~ 450oC, the DC conductivity is dominated by a transport of Na+, K+, and Ca2+ ions. During dehydroxylation, H+ and OH- ions, which are released from kaolinite and illite lattices, contribute to the DC conductivity. Decomposition of calcite runs between ~ 700oC and 900oC. The glassy phase has a dominant influence on the DC conductivity in the fired ceramics. Its high conductivity is determined by the high mobility of Na+, K+, and Ca2+ ions.

  20. Modelling how incorporation of divalent cations affects calcite wettability-implications for biomineralisation and oil recovery.

    Science.gov (United States)

    Andersson, M P; Dideriksen, K; Sakuma, H; Stipp, S L S

    2016-01-01

    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase. PMID:27352933

  1. Modelling how incorporation of divalent cations affects calcite wettability–implications for biomineralisation and oil recovery

    Science.gov (United States)

    Andersson, M. P.; Dideriksen, K.; Sakuma, H.; Stipp, S. L. S.

    2016-01-01

    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase. PMID:27352933

  2. Calcite fracture fillings as indicators of paleohydrology at the Aspo Hard Rock Laboratory, Sweden

    International Nuclear Information System (INIS)

    Isotopic compositions of carbon (δ13C), oxygen (δ16O) strontium (δ87Sr) in calcite fracture fillings are being used to reconstruct the source and evolution of the groundwater at Aespoe and Laxemar, at the Aespoe Hard Rock Laboratory (AEHRL), south-eastern Sweden. These calcites precipitated from groundwater in the fractured crystalline rocks at some time in the past, and δ13C, δ18O and δ87Sr values of the calcites reflect those of the source waters. The fracture fillings mark the pathways of past fluid movement so an understanding of their genesis is particularly important for understanding the paleohydrology in the area. The utility in applying the multiple-isotope approach to groundwater and fracture minerals derives from the fact that the different systems represent different processes. Studies of the groundwater chemistry suggest a very complicated history, however, the isotope data demonstrate that it is possible to postulate mixing of different groundwater members to explain the isotopic systematics of the calcite fracture fillings at Aespoe and Laxemar

  3. Adsorption of pesticides onto quartz, calcite, kaolinite, and α-alumina

    DEFF Research Database (Denmark)

    Clausen, Liselotte; Fabricius, Ida Lykke; Madsen, L.

    2001-01-01

    adsorption characteristics of selected pesticides. Investigated mineral phases included quartz, calcite, kaolinite, and alpha -alumina. Selected pesticides comprised atrazine (6-chloro-N-2-ethyl-N-4-isopropyl-1,3,5-triazine-2,4-diamine isoproturon [3-(4-isopropyl-phenyl)-1,1-dimethylurea)], mecoprop [(RS)-2...

  4. Carbon export and transfer to depth across the Southern Ocean Great Calcite Belt

    Science.gov (United States)

    Rosengard, S. Z.; Lam, P. J.; Balch, W. M.; Auro, M. E.; Pike, S.; Drapeau, D.; Bowler, B.

    2015-07-01

    Sequestration of carbon by the marine biological pump depends on the processes that alter, remineralize, and preserve particulate organic carbon (POC) during transit to the deep ocean. Here, we present data collected from the Great Calcite Belt, a calcite-rich band across the Southern Ocean surface, to compare the transformation of POC in the euphotic and mesopelagic zones of the water column. The 234Th-derived export fluxes and size-fractionated concentrations of POC, particulate inorganic carbon (PIC), and biogenic silica (BSi) were measured from the upper 1000 m of 27 stations across the Atlantic and Indian sectors of the Great Calcite Belt. POC export out of the euphotic zone was correlated with BSi export. PIC export was not, but did correlate positively with POC flux transfer efficiency. Moreover, regions of high BSi concentrations, which corresponded to regions with proportionally larger particles, exhibited higher attenuation of > 51 μm POC concentrations in the mesopelagic zone. The interplay among POC size partitioning, mineral composition, and POC attenuation suggests a more fundamental driver of POC transfer through both depth regimes in the Great Calcite Belt. In particular, we argue that diatom-rich communities produce large and labile POC aggregates, which not only generate high export fluxes but also drive more remineralization in the mesopelagic zone. We observe the opposite in communities with smaller calcifying phytoplankton, such as coccolithophores. We hypothesize that these differences are influenced by inherent differences in the lability of POC exported by different phytoplankton communities.

  5. Mechanics, microstructure and AMS evolution of a synthetic porphyritic calcite aggregate deformed in torsion

    Czech Academy of Sciences Publication Activity Database

    Marques, F. O.; Machek, Matěj; Roxerová, Zuzana; Burg, J.-P.; Almqvist, B. S. G.

    2015-01-01

    Roč. 655, August (2015), s. 41-57. ISSN 0040-1951 Institutional support: RVO:67985530 Keywords : experimental rock deformation * porphyritic calcite aggregate * EBSD and plastic deformation Subject RIV: DB - Geology ; Mineralogy Impact factor: 2.872, year: 2014

  6. Interaction of ethanol and water with the {1014} surface of calcite

    DEFF Research Database (Denmark)

    Cooke, David; Gray, R J; Sand, K K;

    2010-01-01

    the starting configuration consists of a complete monolayer of water at the surface. The computational results are in good agreement with the results from atomic force microscopy experiments where it is observed that a layer of ethanol remains attached to the calcite surface, decreasing its ability to...

  7. Effect of Tris-HCl buffer on DNA adsorption by a variety of soil constituents.

    Science.gov (United States)

    Saeki, Kazutoshi; Kunito, Takashi; Sakai, Masao

    2011-01-01

    We investigated the effect of tris(hydroxymethyl)aminomethane hydrochloride (Tris-HCl) buffer (pH 7.0) as a bulk solution on the adsorption of DNA by gibbsite, goethite, montmorillonite, kaolinite, synthetic and natural allophanes, two humic acids and two andosols. The natural allophane, gibbsite, kaolinite and an andosol adsorbed significantly more DNA in a 0.1 M Tris-HCl buffer than in a 0.1 M NaCl solution (t-test, P<0.005). In contrast, montmorillonite adsorbed significantly less DNA in the Tris-HCl than NaCl solution (P<0.05). Care should be taken when using Tris-HCl in studies on the adsorption of extracellular DNA molecules by soil particles. PMID:21487209

  8. Bus Implementation Using New Low Power PFSCL Tristate Buffers

    OpenAIRE

    Neeta Pandey; Bharat Choudhary; Kirti Gupta; Ankit Mittal

    2016-01-01

    This paper proposes new positive feedback source coupled logic (PFSCL) tristate buffers suited to bus applications. The proposed buffers use switch to attain high impedance state and modify the load or the current source section. An interesting consequence of this is overall reduction in the power consumption. The proposed tristate buffers consume half the power compared to the available switch based counterpart. The issues with available PFSCL tristate buffers based bus implementation are id...

  9. Exchangeability of bentonite buffer and backfill materials

    International Nuclear Information System (INIS)

    Clay-based buffer and tunnel backfill materials are important barriers in the KBS-3 repository concept for final disposal of spent nuclear fuel in Finland. One issue that is relevant to material properties is the degree to which different bentonite compositions can be regarded as interchangeable. In Posiva's current repository design, the reference bentonite composition is MX-80, a sodium montmorillonite dominated clay. Posiva would like to be able to use bentonite with Ca-montmorillonite as the dominant clay mineral. However, at this stage, it is not clear what supporting data need to be acquired/defined to be able to place the state of knowledge of Ca-bentonite at the same level as that of Na-bentonite. In this report, the concept of bentonite exchangeability has been evaluated through consideration of how bentonite behaviour may be affected in six key performance-relevant properties, namely (1) mineralogical composition and availability of materials, (2) hydraulic conductivity, (3) mechanical and rheological properties, (4) long-term alteration, (5) colloidal properties, and (6) swelling pressure. The report evaluates implications for both buffer and backfill. Summary conclusions are drawn from these sections to suggest how bentonite exchangeability may be addressed in regulatory assessments of engineered barrier design for a future geological repository for spent fuel in Finland. Some important conclusions are: (a) There are some fundamental differences between Ca- and Na-bentonites such as colloidal behaviour, pore structure and long-term alteration that could affect the exchangeability of these materials as buffer or backfill materials and which should be further evaluated; (b) Additional experimental data are desirable for some issues such as long-term alteration, hydraulic properties and swelling behaviour, (c) The minor mineral content of bentonites is very variable, both between different bentonites and within the same bentonite type, it is not clear

  10. Effect of Magnesium as Substitute Material in Enzyme-Mediated Calcite Precipitation for Soil-Improvement Technique

    Science.gov (United States)

    Putra, Heriansyah; Yasuhara, Hideaki; Kinoshita, Naoki; Neupane, Debendra; Lu, Chih-Wei

    2016-01-01

    The optimization of enzyme-mediated calcite precipitation was evaluated as a soil-improvement technique. In our previous works, purified urease was utilized to bio-catalyze the hydrolysis of urea, which causes the supplied Ca2+ to precipitate with CO32− as calcium carbonate. In the present work, magnesium chloride was newly added to the injecting solutions to delay the reaction rate and to enhance the amount of carbonate precipitation. Soil specimens were prepared in PVC cylinders and treated with concentration-controlled solutions composed of urea, urease, calcium, and magnesium chloride. The mechanical properties of the treated soil specimens were examined through unconfined compressive strength (UCS) tests. A precipitation ratio of the carbonate up to 90% of the maximum theoretical precipitation was achieved by adding a small amount of magnesium chloride. Adding magnesium chloride as a delaying agent was indeed found to reduce the reaction rate of the precipitation, which may increase the volume of the treated soil if used in real fields because of the slower precipitation rate and the resulting higher injectivity. A mineralogical analysis revealed that magnesium chloride decreases the crystal size of the precipitated materials and that another carbonate of aragonite is newly formed. Mechanical test results indicated that carbonate precipitates within the soils and brings about a significant improvement in strength. A maximum UCS of 0.6 MPa was obtained from the treated samples. PMID:27200343

  11. Dissolution of Kaolinite Induced by Citric Acids, Oxalic Acids and Malic Acids in HAC-NH4AC Buffer Solution%醋酸-醋酸铵缓冲体系中柠檬酸、草酸和苹果酸对高岭石的溶解特征

    Institute of Scientific and Technical Information of China (English)

    胡华锋; 王兴祥; 介晓磊; 李清曼

    2013-01-01

    采用间歇法(batch method)模拟研究醋酸-醋酸铵缓冲体系中柠檬酸、草酸和苹果酸三种低分子量有机酸对高岭石的溶解特征.结果表明:柠檬酸、草酸和苹果酸三种有机酸均能显著促进高岭石的溶解,溶解能力都是随其浓度和酸度的升高而增强;当有机酸浓度为1 mmol/L,pH3.5时,草酸>柠檬酸>苹果酸;pH5.5和pH4.5时,柠檬酸>草酸>苹果酸;而当有机酸浓度≥5 mmol/L时,草酸>柠檬酸>苹果酸,且对高岭石的溶解能力都大于无机酸.当柠檬酸、草酸和苹果酸浓度为1mmol/L时,反应级数(nHL)分别为0.09、0.27和0.18,速率常数(kHL)分别为4.03×10-13、2.62×10-12和4.73×10-13;当其浓度为5mmol/L时,其反应级数(nHL)分别为0.16、0.37和0.16,速率常数(kHL)分别为1.38×10-12、2.32×10-11和4.97×10-13;其浓度为10 mmol/L时,反应级数(nHL)分别为0.18、0.34和0.16,速率常数(kHL)分别为2.17×10-12、2.60×10-11和6.05×10-13.对于柠檬酸和草酸而言,在促进高岭石溶解的作用上,相对于质子,配体的贡献是主要的;而对于苹果酸而言,配体的贡献是次要的.配体促进溶解速率(RL)可以用配体浓度的指数形式来表示.对柠檬酸、草酸和苹果酸而言,pH5.5时,分别为RL=10-13.01[配体]0.23、RL=10-13.28[配体]0.70和RL=10-13.72[配体]0.38;pH4.5时,分别为RL=10-13.00[配体]0.51、RL=10-13.03[配体]1.05和RL=10-14.07[配体]0.77;pH3.5时,分别为RL=10-12.99[配体]0.64、RL=10-12.72[配体]0.89和RL=10-14.61[配体]1.69.%Experiments were conducted to investigate the dissolution characteristics of kaolinite induced by three kinds of lowmolecular-weight organic acids (LOAs) (citric acids,oxalic acids and malic acids) with the batch method in HAC-NH4AC buffer solution.The results showed that LOAs enhanced significantly the solubility of kaolinite,The solubility of kaolinite was enhanced with an increase in the concentration and acidity of citric acids

  12. Factors controlling the growth rate, carbon and oxygen isotope variation in modern calcite precipitation in a subtropical cave, Southwest China

    Science.gov (United States)

    Pu, Junbing; Wang, Aoyu; Shen, Licheng; Yin, Jianjun; Yuan, Daoxian; Zhao, Heping

    2016-04-01

    A prerequisite for using cave speleothems to reconstruct palaeoenvironmental conditions is an accurate understanding of specific factors controlling calcite growth, in particular the isotopic partitioning of oxygen (δ18O) and carbon (δ13C) which are the most commonly used proxies. An in situ monitoring study from April 2008 to September 2009 at Xueyu Cave, Chongqing, SW China, provides insight into the controls on calcite growth rates, drip water composition, cave air parameters and δ18O and δ13C isotopic values of modern calcite precipitation. Both cave air PCO2 and drip water hydrochemical characteristics show obvious seasonality driven by seasonal changes in the external environment. Calcite growth rates also display clear intra-annual variation, with the lowest values occurring during wet season and peak values during the dry season. Seasonal variations of calcite growth rate are primarily controlled by variations of cave air PCO2 and drip water rate. Seasonal δ18O-VPDB and δ13C-VPDB in modern calcite precipitates vary, with more negative values in the wet season than in the dry season. Strong positive correlation of δ18O-VPDB vs. δ13C-VPDB is due to simultaneous enrichment of both isotopes in the calcite. This correlation indicates that kinetic fractionation occurs between parent drip water and depositing calcite, likely caused by the variations of cave air PCO2 and drip rate influenced by seasonal cave ventilation. Kinetic fractionation amplifies the equilibrium fractionation value of calcite δ18O (by ∼1.5‰) and δ13C (by ∼1.7‰), which quantitatively reflects surface conditions during the cave ventilation season. These results indicate that the cave monitoring of growth rate and δ18O and δ13C of modern calcite precipitation are necessary in order to use a speleothem to reconstruct palaeoenvironment.

  13. Ca-Mg inter-diffusion in synthetic polycrystalline dolomite-calcite aggregate at elevated temperatures and pressure

    Science.gov (United States)

    Huang, Wuu-Liang; Liu, Teh-Ching; Shen, Pouyan; Hsu, Allen

    2009-03-01

    This study measures the reaction rate of dolomite and aragonite (calcite) into Mg-calcite at 800, 850, and 900°C and 1.6 GPa. The dry synthetic dolomite-aragonite aggregate transformed very rapidly into dolomite-calcite polycrystalline aggregate while Mg-calcites formed at a relatively slow rate, becoming progressively richer in Mg with run time. We modeled the reaction progress semi-empirically by the first-order rate law. The temperature dependence of the overall transport rate of MgCO3 into calcite can be described by the kinetic parameters ( E = 231.7 kJ/mol and A o = 22.69 h-1). Extrapolation using the Arrhenius equation to the conditions during exhumation of UHPM rocks indicates that the reaction of dolomite with aragonite into Mg-saturated calcite can be completed as the P-T path enters the Mg-calcite stability field in a geologically short time period (340°C and >10 My). SEM-EDS analysis of individual calcite grains shows compositional gradients of Mg in the calcite grains. The Mg-Ca inter-diffusion coefficient at 850°C is around 1.68 × 10-14 m2/sec if diffusion is the major control of the reaction. The calculated closure temperatures for Ca-Mg inter-diffusion as a function of cooling rate and grain size reveal that Ca/Mg resetting in calcite in a dry polycrystalline carbonate aggregate (with grain size around 1 mm) may not occur at temperatures below 480°C at a geological cooling rate around 10°C/My, unless other processes, such as short-circuit interdiffusion along grain boundaries and dislocations, are involved.

  14. Patterns of sediment and phosphorus accumulation in a riparian buffer

    Science.gov (United States)

    Riparian buffers prevent sediment and phosphorus (P) from reaching streams, but their accumulation in buffers is seldom measured. This study's objectives were to determine accumulations of sediment and P in a multi-species riparian buffer, and characterize spatial-temporal patterns of P in soil wate...

  15. Visualizing Organophosphate Precipitation at the Calcite-Water Interface by in Situ Atomic-Force Microscopy.

    Science.gov (United States)

    Wang, Lijun; Qin, Lihong; Putnis, Christine V; Ruiz-Agudo, Encarnación; King, Helen E; Putnis, Andrew

    2016-01-01

    Esters of phosphoric acid constitute a large fraction of the total organic phosphorus (OP) in the soil environment and, thus, play an important role in the global phosphorus cycle. These esters, such as glucose-6-phosphate (G6P), exhibit unusual reactivity toward various mineral particles in soils, especially those containing calcite. Many important processes of OP transformation, including adsorption, hydrolysis, and precipitation, occur primarily at mineral-fluid interfaces, which ultimately governs the fate of organophosphates in the environment. However, little is known about the kinetics of specific mineral-surface-induced adsorption and precipitation of organophosphates. Here, by using in situ atomic-force microscopy (AFM) to visualize the dissolution of calcite (1014) faces, we show that the presence of G6P results in morphology changes of etch pits from the typical rhombohedral to a fan-shaped form. This can be explained by a site-selective mechanism of G6P-calcite surface interactions that stabilize the energetically unfavorable (0001) or (0112) faces through step-specific adsorption of G6P. Continuous dissolution at calcite (1014)-water interfaces caused a boundary layer at the calcite-water interface to become supersaturated with respect to a G6P-Ca phase that then drives the nucleation and growth of a G6P-Ca precipitate. Furthermore, after the introduction of the enzyme alkaline phosphatase (AP), the precipitates were observed to contain a mixture of components associated with G6P-Ca, amorphous calcium phosphate (ACP)-hydroxyapatite (HAP) and dicalcium phosphate dihydrate (DCPD). These direct dynamic observations of the transformation of adsorption- and complexation-surface precipitation and enzyme-mediated pathways may improve the mechanistic understanding of the mineral-interface-induced organophosphate sequestration in the soil environment. PMID:26636475

  16. The relationship between chemistry, texture and anisotropy of magnetic susceptibility for a set of calcite mylonites

    International Nuclear Information System (INIS)

    Complete text of publication follows. Magnetic susceptibility and its anisotropy (AMS) are sensitive indicators for trace amounts of paramagnetic impurities and second-phase minerals in rocks that display diamagnetic bulk susceptibility. To illustrate this relationship a set of highly strained calcite mylonites has been collected from the overturned limb (shear zone) of the Morcles Nappe (Helvetic Alps, southwestern Switzerland). The sample set consists of white and gray fine-grained calcite mylonites (Upper and Lower Urgonian) with less than 10 vol% of secondary phase content and varying amounts of paramagnetic Fe and Mn impurities. The AMS of these specimens are studied using a combination of low- and high-field magnetic susceptibility measurements. In addition, high-field AMS measurements are performed at 77 K. The use of these methods illustrates a strong relationship between the magnetic susceptibility, the development of crystallographic preferred orientation (CPO) of calcite and the Fe plus Mn impurity content. The bulk magnetic susceptibility and AMS varies systematically according to the amount of Fe and Mn. At room-temperature the AMS results from a combination of the diamagnetic and paramagnetic sub-fabrics, whereas at 77 K the paramagnetic sub-fabric is dominant. The k1 and k3 axes invert positions when comparing the AMS at room temperature and 77 K. The degree of anisotropy is shown to be related to bulk susceptibility, which in itself is directly dependent on the amount of Fe incorporated into the calcite's lattice, and the strength of the calcite's CPO. Our results indicate that AMS can be used as a sensitive tool for studying the relationship between trace element chemistry and deformation.

  17. Impact of trace metals on the water structure at the calcite surface

    Science.gov (United States)

    Wolthers, Mariette; Di Tommaso, Devis; De Leeuw, Nora

    2014-05-01

    Carbonate minerals play an important role in regulating the chemistry of aquatic environments, including the oceans, aquifers, hydrothermal systems, soils and sediments. Through mineral surface processes such as dissolution, precipitation and sorption, carbonate minerals affect the biogeochemical cycles of not only the constituent elements of carbonates, such as Ca, Mg, Fe and C, but also H, P and trace elements. Surface charging of the calcite mineral-water interface, and its reactivity towards foreign ions can be quantified using a surface structural model that includes, among others, the water structure at the interface (i.e. hydrogen bridging) [1,2] in accordance with the CD-MUSIC formalism [3]. Here we will show the impact of foreign metals such as Mg and Sr on the water structure around different surface sites present in etch pits and on growth terraces at the calcite (10-14) surface. We have performed Molecular Dynamics simulations of metal-doped calcite surfaces, using different interatomic water potentials. Results show that the local environment around the structurally distinct sites differs depending on metal presence, suggesting that metal substitutions in calcite affect its reactivity. The information obtained in this study will help in improving existing macroscopic surface model for the reactivity of calcite [2] and give more general insight in mineral surface reactivity in relation to crystal composition. [1] Wolthers, Charlet, & Van Cappellen (2008). Am. J. Sci., 308, 905-941. [2] Wolthers, Di Tommaso, Du, & de Leeuw (2012). Phys. Chem. Chem. Phys. 14, 15145-15157. [3] Hiemstra and Van Riemsdijk (1996) J. Colloid Interf. Sci. 179, 488-508.

  18. Studies on cyanobacterial extracellular polymeric substances: functional groups, calcite biomineralization and formation of capsular polymeric substances

    Science.gov (United States)

    Dittrich, M.; Sibler, S.; Matsko, N.

    2006-12-01

    Extracellular polymeric substances (EPS) of microbial origin are an important class of polymeric materials which have been involved in different processes such as biofilm development or mineral precipitation. Cyanobacteria have been known as potential EPS producers for a long time. Despite their ubiquitous distribution, there is still a great lack of knowledge concerning the diversity of EPS binding sites of different picocyanobacterial strains on the one hand and the specific components of EPS which are responsible for calcite precipitation and crystal morphology on the other hand. It is generally accepted that capsular extracellular polymeric substances are the main components of biofilm matrixes. In this context, it is important to understand under which conditions cyanobacteria produce surface polysaccharides. In a recent study, we characterized the binding sites of EPS of three unicellular autotrophic picocyanobacterial strains of the Synechococcus-type. Potentiometric titrations were conducted to determine different types of functional groups present at the various sites. Precipitation experiments with EPS of different strains allowed for estimating the potential of EPS to precipitate calcium carbonate and the impact of functional groups composition on crystal morphology. In order to clarify the conditions under which cyanobacteria formed capsular EPS, we performed growth experiments in nutrients medium with different phosphorus concentrations (0.4, 4.1, 8.2 and 41 mgP/l). Cyanobacterial cells produced capsular EPS under phosphorus concentrations of 0.4, 4.1 and 8.2 mgP/l, while no capsular EPS were observed for the highest P concentration (41 mgP/l). At this concentration, however, calcium rich storage products were detected in the cells. The results thus suggest that both extracellular and intracellular products are regulated through phosphorus concentrations in growth solutions. Titrations reveal five or six distinct sites on surfaces of picocyanobacterial

  19. Chemical buffering in natural and engineered barrier systems: Thermodynamic constraints and performance assessment consequences

    International Nuclear Information System (INIS)

    Thermodynamic and kinetic constraints on the chemical buffering properties of natural and engineered-barrier systems are derived in this study from theoretical descriptions, incorporated in the reaction-path model, of reversible and irreversible mass transfer in multicomponent, multiphase systems. The buffering properties of such systems are conditional properties because they refer to a specific aqueous species in a system that is open with respect to a specific reactant. The solution to a mathematical statement of this concept requires evaluation of the dependence of the activity of the buffered species on incremental changes in the overall reaction-progress variable. This dependence can be represented by a truncated Taylor's series expansion, where the values of associated derivatives are calculated using finite-difference techniques and mass-balance, charge-balance and mass-action constraints. Kinetic constraints on buffering behavior can also be described if the relation between reactant flux and reaction rate is well defined. This relation is explicit for the important case of advective groundwater flow and water-rock interaction. We apply the theoretical basis of the chemical buffering concept to processes that could affect the performance of a deep geologic repository for nuclear waste. Specifically, we focus on the likelihood that an inverse relation must exist between the buffer intensity and the migration velocity of reaction fronts in systems involving advective or diffusive mass transport. A quantitative understanding of this relation would provide the basis for evaluating the potential role of chemical buffering in achieving the isolation and retardation functions, of the EBS and geosphere in a KBS-3 repository. Our preliminary evaluation of this role considers the effects of chemical buffering on the propagation velocity of a pH front in both the near- and far field. We use a geochemical modeling technique compatible with the reaction-path model to

  20. Environmental controls for the precipitation of different fibrous calcite cement fabrics

    Science.gov (United States)

    Ritter, Ann-Christine; Wiethoff, Felix; Neuser, Rolf D.; Richter, Detlev K.; Immenhauser, Adrian

    2016-04-01

    Abiogenic calcite cements are widely used as climate archives. They can yield information on environmental change and climate dynamics at the time when the sediment was lithified in a (marine) diagenetic environment. Radiaxial-fibrous (RFC) and fascicular-optic fibrous (FOFC) calcite cements are two very common and similar pore-filling cement fabrics in Palaeozoic and Mesozoic carbonate rocks (Richter et al., 2011) and in Holocene Mg-calcitic speleothems (Richter et al., 2015). Both fabrics are characterised by distinct crystallographic properties. Current research has shown that these fabrics are often underexplored and that a careful combination of conservative and innovative proxies allows for a better applicability of these carbonate archives to paleoenvironmental reconstructions (Ritter et al., 2015). A main uncertainty in this context is that it is still poorly understood which parameters lead to the formation of either RFC or FOFC and if differential crystallographic parameters affect proxy data from these fabrics. This study aims at a better understanding of the environmental factors that may control either RFC or FOFC precipitation. Therefore, suitable samples (a stalagmite and a Triassic marine cement succession), each with clearly differentiable layers of RFC and FOFC, were identified and analysed in high detail using a multi-proxy approach. Detailed thin section and cathodoluminescence analysis of the samples allowed for a precise identification of layers consisting solely of either RFC or FOFC. Isotopic (δ13C, δ18O) as well as trace elemental compositions have been determined and the comparison of data obtained from these different carbonate archives sheds light on changes in environmental parameters during RFC or FOFC precipitation. References: Richter, D.K., et al., 2011. Radiaxial-fibrous calcites: A new look at an old problem. Sedimentary Geology, 239, 26-36 Richter, D.K., et al., 2015. Radiaxial-fibrous and fascicular-optic Mg-calcitic cave

  1. A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock.

    Science.gov (United States)

    Xu, Tianfu; Sonnenthal, Eric; Bodvarsson, Gudmundur

    2003-06-01

    The percolation flux in the unsaturated zone (UZ) is an important parameter addressed in site characterization and flow and transport modeling of the potential nuclear-waste repository at Yucca Mountain, NV, USA. The US Geological Survey (USGS) has documented hydrogenic calcite abundances in fractures and lithophysal cavities at Yucca Mountain to provide constraints on percolation fluxes in the UZ. The purpose of this study was to investigate the relationship between percolation flux and measured calcite abundances using reactive transport modeling. Our model considers the following essential factors affecting calcite precipitation: (1) infiltration, (2) the ambient geothermal gradient, (3) gaseous CO(2) diffusive transport and partitioning in liquid and gas phases, (4) fracture-matrix interaction for water flow and chemical constituents, and (5) water-rock interaction. Over a bounding range of 2-20 mm/year infiltration rate, the simulated calcite distributions capture the trend in calcite abundances measured in a deep borehole (WT-24) by the USGS. The calcite is found predominantly in fractures in the welded tuffs, which is also captured by the model simulations. Simulations showed that from about 2 to 6 mm/year, the amount of calcite precipitated in the welded Topopah Spring tuff is sensitive to the infiltration rate. This dependence decreases at higher infiltration rates owing to a modification of the geothermal gradient from the increased percolation flux. The model also confirms the conceptual model for higher percolation fluxes in the fractures compared to the matrix in the welded units, and the significant contribution of Ca from water-rock interaction. This study indicates that reactive transport modeling of calcite deposition can yield important constraints on the unsaturated zone infiltration-percolation flux and provide useful insight into processes such as fracture-matrix interaction as well as conditions and parameters controlling calcite deposition

  2. Calibration of the calcite-water oxygen-isotope geothermometer at Devils Hole, Nevada, a natural laboratory

    Science.gov (United States)

    Coplen, T.B.

    2007-01-01

    The ??18O of ground water (-13.54 ?? 0.05 ???) and inorganically precipitated Holocene vein calcite (+14.56 ?? 0.03 ???) from Devils Hole cave #2 in southcentral Nevada yield an oxygen isotopic fractionation factor between calcite and water at 33.7 ??C of 1.02849 ?? 0.00013 (1000 ln ??calcite-water = 28.09 ?? 0.13). Using the commonly accepted value of ???(??calcite-water)/???T of -0.00020 K-1, this corresponds to a 1000 ln ??calcite-water value at 25 ??C of 29.80, which differs substantially from the current accepted value of 28.3. Use of previously published oxygen isotopic fractionation factors would yield a calcite precipitation temperature in Devils Hole that is 8 ??C lower than the measured ground water temperature. Alternatively, previously published fractionation factors would yield a ??18O of water, from which the calcite precipitated, that is too negative by 1.5 ??? using a temperature of 33.7 ??C. Several lines of evidence indicate that the geochemical environment of Devils Hole has been remarkably constant for at least 10 ka. Accordingly, a re-evaluation of calcite-water oxygen isotopic fractionation factor may be in order. Assuming the Devils Hole oxygen isotopic value of ??calcite-water represents thermodynamic equilibrium, many marine carbonates are precipitated with a ??18O value that is too low, apparently due to a kinetic isotopic fractionation that preferentially enriches 16O in the solid carbonate over 18O, feigning oxygen isotopic equilibrium.

  3. Clad buffer rod sensors for liquid metals

    International Nuclear Information System (INIS)

    Clad buffer rods, consisting of a core and a cladding, have been developed for ultrasonic monitoring of liquid metal processing. The cores of these rods are made of low ultrasonic-loss materials and the claddings are fabricated by thermal spray techniques. The clad geometry ensures proper ultrasonic guidance. The lengths of these rods ranges from tens of centimeters to 1m. On-line ultrasonic level measurements in liquid metals such as magnesium at 700 deg C and aluminum at 960 deg C are presented to demonstrate their operation at high temperature and their high ultrasonic performance. A spherical concave lens is machined at the rod end for improving the spatial resolution. High quality ultrasonic images have been obtained in the liquid zinc at 600 deg C. High spatial resolution is needed for the detection of inclusions in liquid metals during processing. We also show that the elastic properties such as density, longitudinal and shear wave velocities of liquid metals can be measured using a transducer which generates and receives both longitudinal and shear waves and is mounted at the end of a clad buffer rod. (author)

  4. Competitive Buffer Management with Class Segregation

    CERN Document Server

    Al-Bawani, Kamal

    2011-01-01

    We introduce a new model for buffer management of network switches with Quality of Service (QoS) requirements and give a tight analysis. Specifically, each network packet is associated with a numerical value, called Class of Service (CoS), which represents its priority. We are furthermore given a network switch with $m$ queues that have individual capacities. Each queue stores packets of a certain CoS, only. A stream of packets arrives over time at the switch and an online algorithm has to decide on the admission and transmission of packets. The objective is to maximize the total CoS-value of the transmitted packets. Our main contribution is a natural online $\\GREEDY$ algorithm, which accepts any arriving packet, if the corresponding CoS-queue is not full. It always sends a buffered packet with highest value. We show that this algorithm is 2-competitive. This result is essentially best-possible since we also show a lower bound of $2 - v_m / (\\sum_{i=1}^m v_i)$ on the competitiveness of any deterministic onlin...

  5. Experimental Research on Microscopic Indicators of Temperature's Returning-to-Zero in Deformation of Calcite and Discussions of Correlation Problem

    Institute of Scientific and Technical Information of China (English)

    Yao Daquan; Zhai Hongtao

    2005-01-01

    In order to determine the degree of returning-to-zero of temperatures of deformed calcite, a series of rock-breaking experiments were designed to test calcite-rich limestone samples under fixed confining pressures and different temperatures. The consolidated deformed samples in their initial state were observed under a microscope and the microscopic indicators in different zero-returning states were put forward, thus providing a microscopic foundation for evaluation of reliability of dating values of deformation in calcite. At last, the correction of dating values of deformation for samples whose temperature has not yet returned to zero is discussed.

  6. Infrared spectroscopy and density functional theory investigation of calcite, chalk, and coccoliths-do we observe the mineral surface?

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Hem, Caroline Piper; Schultz, Logan Nicholas;

    2014-01-01

    broadening from macroscopic dielectric effects. We detect water adsorbed on the high surface area synthetic calcite, which permits observation of the chemistry of thin liquid films on calcite using transmission infrared spectroscopy. The combination of infrared spectroscopy and density functional theory also...... asymmetric for the coccoliths and the synthetic calcite prepared using the carbonation method. It can be very well fitted by two peaks: a narrow Lorenzian at lower frequency and a broader Gaussian at higher frequency. These two samples both have a high specific surface area. Density functional theory for...

  7. CRACK2 - Modelling calcium carbonate deposition from bicarbonate solution in cracks in concrete

    International Nuclear Information System (INIS)

    The numerical CRACK2 model simulates precipitation of calcite from calcium bicarbonate solution (e.g. groundwater) passing through cracks in concrete or other cementitious materials. A summary of experimental work is followed by a detailed description of the model. Hydroxyl ions are transported by diffusion in pore systems in columns of cementitious materials. The hydroxyl is precipitating calcite from a flow of bicarbonate solution in a crack connecting the ends of a row of such columns. The cementitious material is simulated as calcium hydroxide mixed with inert material but with sodium hydroxide dissolved in the pore solution. Diffusive migration of cesium as radioactive isotope is also considered. Electrical interaction of the migrating ions is taken into account. Example calculations demonstrate effects of parameter variations on distribution of precipitated calcite in the crack and on the composition of the outflowing solution, which can be compared directly with experimental results. Leaching behavior of sodium can be used to tune the model to experimental observations. The calcite is mostly precipitated on top of the original crack surface and may under certain circumstances fill the crack. The produced thin layers of low porosity calcite act as a diffusion barrier limiting contact between cement and solution. Pore closure mechanisms in such layers are discussed. Implications for safety assessment of radioactive waste disposal are shortly mentioned. The model is also relevant for conventional uses of concrete. (au)

  8. CRACK2 - Modelling calcium carbonate deposition from bicarbonate solution in cracks in concrete

    Energy Technology Data Exchange (ETDEWEB)

    Brodersen, K

    2003-03-01

    The numerical CRACK2 model simulates precipitation of calcite from calcium bicarbonate solution (e.g. groundwater) passing through cracks in concrete or other cementitious materials. A summary of experimental work is followed by a detailed description of the model. Hydroxyl ions are transported by diffusion in pore systems in columns of cementitious materials. The hydroxyl is precipitating calcite from a flow of bicarbonate solution in a crack connecting the ends of a row of such columns. The cementitious material is simulated as calcium hydroxide mixed with inert material but with sodium hydroxide dissolved in the pore solution. Diffusive migration of cesium as radioactive isotope is also considered. Electrical interaction of the migrating ions is taken into account. Example calculations demonstrate effects of parameter variations on distribution of precipitated calcite in the crack and on the composition of the outflowing solution, which can be compared directly with experimental results. Leaching behavior of sodium can be used to tune the model to experimental observations. The calcite is mostly precipitated on top of the original crack surface and may under certain circumstances fill the crack. The produced thin layers of low porosity calcite act as a diffusion barrier limiting contact between cement and solution. Pore closure mechanisms in such layers are discussed. Implications for safety assessment of radioactive waste disposal are shortly mentioned. The model is also relevant for conventional uses of concrete. (au)

  9. Calcite and dolomite in intrusive carbonatites. II. Trace-element variations

    Science.gov (United States)

    Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Couëslan, Christopher; Yang, Panseok

    2016-04-01

    The composition of calcite and dolomite from several carbonatite complexes (including a large set of petrographically diverse samples from the Aley complex in Canada) was studied by electron-microprobe analysis and laser-ablation inductively-coupled-plasma mass-spectrometry to identify the extent of substitution of rare-earth and other trace elements in these minerals and the effects of different igneous and postmagmatic processes on their composition. Analysis of the newly acquired and published data shows that the contents of rare-earth elements (REE) and certain REE ratios in magmatic calcite and dolomite are controlled by crystal fractionation of fluorapatite, monazite and, possibly, other minerals. Enrichment in REE observed in some samples (up to ~2000 ppm in calcite) cannot be accounted for by coupled substitutions involving Na, P or As. At Aley, the REE abundances and chondrite-normalized (La/Yb)cn ratios in carbonates decrease with progressive fractionation. Sequestration of heavy REE from carbonatitic magma by calcic garnet may be responsible for a steeply sloping "exponential" pattern and lowered Ce/Ce* ratios of calcite from Magnet Cove (USA) and other localities. Alternatively, the low levels of Ce and Mn in these samples could result from preferential removal of these elements by Ce4+- and Mn3+-bearing minerals (such as cerianite and spinels) at increasing f(O2) in the magma. The distribution of large-ion lithophile elements (LILE = Sr, Ba and Pb) in rock-forming carbonates also shows trends indicative of crystal fractionation effects (e.g., concomitant depletion in Ba + Pb at Aley, or Sr + Ba at Kerimasi), although the phases responsible for these variations cannot be identified unambiguously at present. Overall, element ratios sensitive to the redox state of the magma and its complexing characteristics (Eu/Eu*, Ce/Ce* and Y/Ho) are least variable and in both primary calcite and dolomite, approach the average chondritic values. In consanguineous

  10. Arsenic uptake by gypsum and calcite: Modeling and probing by neutron and x-ray scattering

    CERN Document Server

    Fernandez-Martinez, Alejandro; Roman-Ross, Gabriela; Johnson, Mark R; Bardelli, Fabrizio; Turrillas, Xavier; Charlet, Laurent

    2006-01-01

    Here we report on two structural studies performed on As-doped gypsum (CaSO4 2H2O) and calcite (CaCO3), using neutron (D20-ILL) and x-ray (ID11-ESRF) diffraction data and EXAFS (BM8-ESRF). The aim of this study is to determine whether As gets into the bulk of gypsum and calcite structures or is simply adsorbed on the surface. Different mechanisms of substitution are used as hypotheses. The combined Rietveld analysis of neutron and x-ray diffraction data shows an expansion of the unit cell volume proportional to the As concentration within the samples. DFT-based simulations confirm the increase of the unit cell volume proportional to the amount of carbonate or sulphate groups substituted. Interpolation of the experimental Rietveld data allows us to distinguish As substituted within the structure from that adsorbed on the surface of both minerals.

  11. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

    Science.gov (United States)

    Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; Kim, Yi-Yeoun; Schenk, Anna S.; Kulak, Alexander N.; Comyn, Timothy P.; Chammas, Oliver; Harder, Ross J.; Duffy, Dorothy M.; Robinson, Ian K.; Meldrum, Fiona C.

    2016-06-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates.

  12. Modelling the in situ performance of bentonite-sand buffer

    International Nuclear Information System (INIS)

    In the Canadian nuclear fuel waste management concept, a number of engineered barriers, such as the bentonite-sand buffer which surrounds the waste container in the emplacement boreholes, are used to inhibit the transport of radionuclides. The buffer material is also required to effectively conduct heat from the fuel-waste containers to the surrounding rock. To a large extent, in situ buffer performance will depend on the degree of moisture within the buffer. The moisture content will in turn depend on temperature, temperature gradients, and buffer initial and moisture flux boundary conditions. Modelling of coupled heat and moisture transport in the buffer before resaturation is necessary to assess in situ buffer performance. This paper describes the results of a parametric study using the Philip and de Vries coupled heat and moisture transport model to assess the effects of variations in the moisture diffusivity parameters and the boundary conditions on buffer performance. The results show that the thermal performance of the buffer is affected by heat-induced moisture movement. In particular, the thermal vapor diffusivity, DTvap, has the most significant effect on thermal drying in a closed system. Work is currently underway to improve capability to model coupled heat and moisture transport in buffer. Laboratory experiments are in progress to more accurately define the moisture diffusivity parameters and the model is being modified to include the effects of boundary moisture fluxes and pressure potentials so that the resaturation process may be modelled

  13. Buffer Sizing in 802.11 Wireless Mesh Networks

    KAUST Repository

    Jamshaid, Kamran

    2011-10-01

    We analyze the problem of buffer sizing for TCP flows in 802.11-based Wireless Mesh Networks. Our objective is to maintain high network utilization while providing low queueing delays. The problem is complicated by the time-varying capacity of the wireless channel as well as the random access mechanism of 802.11 MAC protocol. While arbitrarily large buffers can maintain high network utilization, this results in large queueing delays. Such delays may affect TCP stability characteristics, and also increase queueing delays for other flows (including real-time flows) sharing the buffer. In this paper we propose sizing link buffers collectively for a set of nodes within mutual interference range called the \\'collision domain\\'. We aim to provide a buffer just large enough to saturate the available capacity of the bottleneck collision domain that limits the carrying capacity of the network. This neighborhood buffer is distributed over multiple nodes that constitute the network bottleneck; a transmission by any of these nodes fully utilizes the available spectral resource for the duration of the transmission. We show that sizing routing buffers collectively for this bottleneck allows us to have small buffers (as low as 2 - 3 packets) at individual nodes without any significant loss in network utilization. We propose heuristics to determine these buffer sizes in WMNs. Our results show that we can reduce the end-to-end delays by 6× to 10× at the cost of losing roughly 5% of the network capacity achievable with large buffers.

  14. A bio-chemo-hydro-mechanical model for microbially induced calcite precipitation in soils

    OpenAIRE

    Fauriel, Suzanne; Laloui, Lyesse

    2012-01-01

    Microbial Induced Calcite Precipitation (MICP) is an innovative technique for soil grouting involving a bacterial reactive grout. A comprehensive research work is carried out to better understand and consequently describe the phenomenon of multispecies reactive biogrout transport in saturated, deformable soil. A unique predictive model of behavior of the porous media during biogrout injection taking into account flow, transport, sorption, bacterial decay and chemical reaction, as well as cons...

  15. Coccolithophore responses to environmental variability in the South China Sea: species composition and calcite content

    OpenAIRE

    Jin, X. B.; C. L. Liu; Poulton, A. J.; M. H. Dai; X.H. Guo

    2016-01-01

    Coccolithophore contributions to the global marine carbon cycle are regulated by the calcite content of their scales (coccoliths), and the relative cellular levels of photosynthesis and calcification. All three of these factors vary between coccolithophore species, and with response to the growth environment. Here, water samples were collected in the northern basin of the South China Sea (SCS) during summer 2014 in order to examine how environmental variability influenced species composition ...

  16. Quantitative laboratory measurements of biogeochemical processes controlling biogenic calcite carbon sequestration.

    Energy Technology Data Exchange (ETDEWEB)

    Zendejas, Frank; Lane, Todd W.; Lane, Pamela D.

    2011-01-01

    The purpose of this LDRD was to generate data that could be used to populate and thereby reduce the uncertainty in global carbon cycle models. These efforts were focused on developing a system for determining the dissolution rate of biogenic calcite under oceanic pressure and temperature conditions and on carrying out a digital transcriptomic analysis of gene expression in response to changes in pCO2, and the consequent acidification of the growth medium.

  17. Rapid changes in water hardness and alkalinity: Calcite formation is lethal to Daphnia magna.

    Science.gov (United States)

    Bogart, Sarah J; Woodman, Samuel; Steinkey, Dylan; Meays, Cindy; Pyle, Greg G

    2016-07-15

    There is growing concern that freshwater ecosystems may be negatively affected by ever-increasing anthropogenic inputs of extremely hard, highly alkaline effluent containing large quantities of Ca(2+), Mg(2+), CO3(2-), and HCO3(-) ions. In this study, the toxicity of rapid and extreme shifts in water hardness (38-600mg/L as CaCO3) and alkalinity (30-420mg/L as CaCO3) to Daphnia magna was tested, both independently and in combination. Within these ranges, where no precipitation event occurred, shifts in water hardness and/or alkalinity were not toxic to D. magna. In contrast, 98-100% of D. magna died within 96h after exposure to 600mg/L as CaCO3 water hardness and 420mg/L as CaCO3 alkalinity (LT50 of 60h with a 95% CI of 54.2-66.0h). In this treatment, a CaCO3 (calcite) precipitate formed in the water column which was ingested by and thoroughly coated the D. magna. Calcite collected from a mining impacted stream contained embedded organisms, suggesting field streams may also experience similar conditions and possibly increased mortality as observed in the lab tests. Although further investigation is required to determine the exact fate of aquatic organisms exposed to rapid calcite precipitation in the field, we caution that negative effects may occur more quickly or at lower concentrations of water hardness and alkalinity in which we observed effects in D. magna, because some species, such as aquatic insects, are more sensitive than cladocerans to changes in ionic strength. Our results provide evidence that both calcite precipitation and the major ion balance of waters should be managed in industrially affected ecosystems and we support the development of a hardness+alkalinity guideline for the protection of aquatic life. PMID:27060657

  18. Morphological tranformation of calcite crystal growth by prismatic "acidic" polypeptide sequences.

    Energy Technology Data Exchange (ETDEWEB)

    Kim, I; Giocondi, J L; Orme, C A; Collino, J; Evans, J S

    2007-02-13

    Many of the interesting mechanical and materials properties of the mollusk shell are thought to stem from the prismatic calcite crystal assemblies within this composite structure. It is now evident that proteins play a major role in the formation of these assemblies. Recently, a superfamily of 7 conserved prismatic layer-specific mollusk shell proteins, Asprich, were sequenced, and the 42 AA C-terminal sequence region of this protein superfamily was found to introduce surface voids or porosities on calcite crystals in vitro. Using AFM imaging techniques, we further investigate the effect that this 42 AA domain (Fragment-2) and its constituent subdomains, DEAD-17 and Acidic-2, have on the morphology and growth kinetics of calcite dislocation hillocks. We find that Fragment-2 adsorbs on terrace surfaces and pins acute steps, accelerates then decelerates the growth of obtuse steps, forms clusters and voids on terrace surfaces, and transforms calcite hillock morphology from a rhombohedral form to a rounded one. These results mirror yet are distinct from some of the earlier findings obtained for nacreous polypeptides. The subdomains Acidic-2 and DEAD-17 were found to accelerate then decelerate obtuse steps and induce oval rather than rounded hillock morphologies. Unlike DEAD-17, Acidic-2 does form clusters on terrace surfaces and exhibits stronger obtuse velocity inhibition effects than either DEAD-17 or Fragment-2. Interestingly, a 1:1 mixture of both subdomains induces an irregular polygonal morphology to hillocks, and exhibits the highest degree of acute step pinning and obtuse step velocity inhibition. This suggests that there is some interplay between subdomains within an intra (Fragment-2) or intermolecular (1:1 mixture) context, and sequence interplay phenomena may be employed by biomineralization proteins to exert net effects on crystal growth and morphology.

  19. Textural properties of synthetic nano-calcite produced by hydrothermal carbonation of calcium hydroxide

    Science.gov (United States)

    Montes-Hernandez, G.; Fernández-Martínez, A.; Charlet, L.; Tisserand, D.; Renard, F.

    2008-05-01

    The hydrothermal carbonation of calcium hydroxide (Ca(OH) 2) at high pressure of CO 2 (initial P=55 bar) and moderate to high temperature (30 and 90 °C) was used to synthesize fine particles of calcite. This method allows a high carbonation efficiency (about 95% of Ca(OH) 2-CaCO 3 conversion), a significant production rate (48 kg/m 3 h) and high purity of product (about 96%). However, the various initial physicochemical conditions have a strong influence on the crystal size and surface area of the synthesized calcite crystals. The present study is focused on the estimation of the textural properties of synthesized calcite (morphology, specific surface area, average particle size, particle size distribution and particle size evolution with reaction time), using Rietveld refinements of X-ray diffraction (XRD) spectra, Brunauer-Emmett-Teller (BET) measurements, and scanning electron microscope (SEM) and transmission electron microscope (TEM) observations. This study demonstrate that the pressure, the temperature and the dissolved quantity of CO 2 have a significant effect on the average particle size, specific surface area, initial rate of precipitation, and on the morphology of calcium carbonate crystals. In contrast, these PT x conditions used herein have an insignificant effect on the carbonation efficiency of Ca(OH) 2. Finally, the results presented here demonstrate that nano-calcite crystals with high specific surface area ( SBET=6-10 m 2/g) can be produced, with a high potential for industrial applications such as adsorbents and/or filler in papermaking industry.

  20. Effects of surface conductivity on the apparent zeta potential at the calcite-water interface

    OpenAIRE

    Li, Shuai; Leroy, Philippe; Devau, Nicolas

    2015-01-01

    International audience Carbonates are very reactive minerals that are used in many engineering applications like substance remediation and CO2 geological storage. Surface complexation reactions on calcite have significant effects on transport processes in carbonates. Zeta potential is a critical parameter to characterize the mineral surface electrochemical properties. The zeta potential is defined as the electrical potential at the shear plane between quasi immobile and mobile water at the...