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Sample records for calcite surfaces implications

  1. Interaction of alcohols with the calcite surface

    DEFF Research Database (Denmark)

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

    2015-01-01

    . Controlling their growth requires complex polysaccharides. Polysaccharide activity depends on the functionality of OH groups, so to simplify the system in order to get closer to a molecular level understanding, we investigated the interaction of OH from a suite of alcohols with clean, freshly cleaved calcite......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...... with the calcite surface through the OH group, with their carbon chains sticking away in a standing-up orientation. Alcohol molecules are closely packed and form a well-ordered monolayer on the surface....

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

    NARCIS (Netherlands)

    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. Fir

  3. Atomistic simulations of calcium uranyl(VI) carbonate adsorption on calcite and stepped-calcite surfaces.

    Science.gov (United States)

    Doudou, Slimane; Vaughan, David J; Livens, Francis R; Burton, Neil A

    2012-07-17

    Adsorption of actinyl ions onto mineral surfaces is one of the main mechanisms that control the migration of these ions in environmental systems. Here, we present computational classical molecular dynamics (MD) simulations to investigate the behavior of U(VI) in contact with different calcite surfaces. The calcium-uranyl-carbonate [Ca(2)UO(2)(CO(3))(3)] species is shown to display both inner- and outer-sphere adsorption to the flat {101̅4} and the stepped {314̅8} and {31̅2̅16} planes of calcite. Free energy calculations, using the umbrella sampling method, are employed to simulate adsorption paths of the same uranyl species on the different calcite surfaces under aqueous condition. Outer-sphere adsorption is found to dominate over inner-sphere adsorption because of the high free energy barrier of removing a uranyl-carbonate interaction and replacing it with a new uranyl-surface interaction. An important binding mode is proposed involving a single vicinal water monolayer between the surface and the sorbed complex. From the free energy profiles of the different calcite surfaces, the uranyl complex was also found to adsorb preferentially on the acute-stepped {314̅8} face of calcite, in agreement with experiment.

  4. Molecular ordering of ethanol at the calcite surface

    DEFF Research Database (Denmark)

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

    2012-01-01

    -743 ] and molecular dynamics (MD) modeling [ Yang, M., Stipp, S. L. S., and Harding, J. H.Cryst. Growth Des. 2008, 8 (11), 4066-4074 ], have suggested that OH functional groups control polysaccharide attachment. The purpose of this work was to characterize, using X-ray reflectivity (XR) combined with molecular...... 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...

  5. 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...... the flat {10.4} surface, acute steps, obtuse steps, two types of kinks on the acute step and two types of kinks on the obtuse steps. Based on the predicted pKa values, which range from −6.0 to 2.4 depending on the surface site, we conclude that bicarbonate deprotonates to carbonate when it is in calcite...... even when pH in solution is very low. This is true for all surface sites, even for solutions where 2.4 calcite, the predicted pKa for deprotonation is 7.5, which is ∼3 pH units lower than in aqueous solution...

  6. 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

    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......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...

  7. 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 ...

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

    Science.gov (United States)

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

    2016-04-15

    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 the corrected zeta potential by assuming that the zeta potential is located at the outer Helmholtz plane, i.e. without considering a stagnant diffuse layer at the calcite-water interface. The surface conductivity of calcite crystals was inferred from electrical conductivity measurements and computed using our basic Stern model. Surface conductivity was also successfully predicted by our surface complexation model.

  9. Interactions of arsenic with calcite surfaces revealed by in-situ nanoscale imaging

    Science.gov (United States)

    Renard, Francois; Putnis, Christine; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hövelmann, Jörn; Sarret, Géraldine

    2015-04-01

    Arsenic dissolved in water represents a key environmental and health challenge because several million people are under the threat of contamination. In calcareous environments calcite may play an important role in arsenic solubility and transfer in water. Arsenic-calcite interactions remain controversial, especially for As(III) which was proposed to be either incorporated as such, or as As(V) after oxidation. Here, we provide the first time-lapse in-situ study of calcite dissolution and growth in the presence of solutions with various amounts of As(III) or As(V). This was performed at room temperature and pH range 6-9 using a flow through cell connected to an atomic force microscope (AFM), to study the evolution of the (10-14) calcite cleavage surface morphology. Reaction products were then characterized by Raman spectroscopy. In parallel, co-precipitation experiments with either As(III) or As(V) were performed in batch reactors, and the speciation of arsenic in the resulting solids was studied by X-ray absorption spectroscopy (XAS). For As(V), AFM results showed that it interacts strongly with the calcite surface, and XAS results showed that As(V) was mostly incorporated in the calcite structure. For As(III), AFM results showed much less impact on calcite growth and dissolution and less incorporation was observed. This was confirmed by XAS results that indicate that As(III) was partly oxidized into As(V) before being incorporated into calcite and the resulting calcite contained 36% As(III) and 64% As(V). All these experimental results confirm that As(V) has a much stronger interaction with calcite than As(III) and that calcite may represent an important reservoir for arsenic in various geological environments.

  10. Interactions of arsenic with calcite surfaces revealed by in situ nanoscale imaging

    Science.gov (United States)

    Renard, François; Putnis, Christine V.; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hovelmann, Jörn; Sarret, Géraldine

    2015-06-01

    Arsenic dissolved in water represents a key environmental and health challenge because several million people are under the threat of contamination. In calcareous environments calcite may play an important role in arsenic solubility and transfer in water. Arsenic-calcite interactions remain controversial, especially for As(III) which was proposed to be either incorporated as such, or as As(V) after oxidation. Here, we provide the first time-lapse in situ study of the evolution of the (10-14) calcite cleavage surface morphology during dissolution and growth in the presence of solutions with various amounts of As(III) or As(V) at room temperature and pH range 6-11 using a flow-through cell connected to an atomic force microscope (AFM). Reaction products were then characterized by Raman spectroscopy. In parallel, co-precipitation experiments with either As(III) or As(V) were performed in batch reactors, and the speciation of arsenic in the resulting solids was studied by X-ray absorption spectroscopy (XAS). For As(V), AFM results showed that it interacts strongly with the calcite surface, and XAS results showed that As(V) was mostly incorporated in the calcite structure. For As(III), AFM results showed much less impact on calcite growth and dissolution and less incorporation was observed. This was confirmed by XAS results that indicate that As(III) was partly oxidized into As(V) before being incorporated into calcite and the resulting calcite contained 36% As(III) and 64% As(V). All these experimental results confirm that As(V) has a much stronger interaction with calcite than As(III) and that calcite may represent an important reservoir for arsenic in various geological environments.

  11. 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.

  12. 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.

    2016-06-01

    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.

  13. Ethanol adsorption on the {10(1)over-bar4} calcite surface

    DEFF Research Database (Denmark)

    Sand, Karina Krarup; Stipp, Susan Louise Svane; Hassenkam, Tue

    2008-01-01

    Preliminary atomic force microscopy investigations of the {10 (1) over bar4} calcite Surface cleaved in ethanol indicate a different surface behaviour than that of the {10 (1) over bar4} surface cleaved in air. The results are consistent with recent theoretical studies and suggest strong ordering...

  14. Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality

    Science.gov (United States)

    Hazen, R. M.; Filley, T. R.; Goodfriend, G. A.

    2001-01-01

    The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO(3)), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

  15. 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.

  16. 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.

    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...

  17. Adsorption and migration of single metal atoms on the calcite (10.4) surface

    Science.gov (United States)

    Pinto, H.; Haapasilta, V.; Lokhandwala, M.; Öberg, S.; Foster, Adam S.

    2017-04-01

    Transition metal atoms are one of the key ingredients in the formation of functional 2D metal organic coordination networks. Additionally, the co-deposition of metal atoms can play an important role in anchoring the molecular structures to the surface at room temperature. To gain control of such processes requires the understanding of adsorption and diffusion properties of the different transition metals on the target surface. Here, we used density functional theory to investigate the adsorption of 3d (Ti, Cr, Fe, Ni, Cu), 4d (Zr, Nb, Mo, Pd, Ag) and 5d (Hf, W, Ir, Pt, Au) transition metal adatoms on the insulating calcite (10.4) surface. We identified the most stable adsorption sites and calculated binding energies and corresponding ground state structures. We find that the preferential adsorption sites are the Ca–Ca bridge sites. Apart from the Cr, Mo, Cu, Ag and Au all the studied metals bind strongly to the calcite surface. The calculated migration barriers for the representative Ag and Fe atoms indicates that the metal adatoms are mobile on the calcite surface at room temperature. Bader analysis suggests that there is no significant charge transfer between the metal adatoms and the calcite surface.

  18. Crystalline order of a water/glycine film coadsorbed on the (104) calcite surface.

    Science.gov (United States)

    Magdans, Uta; Torrelles, Xavier; Angermund, Klaus; Gies, Hermann; Rius, Jordi

    2007-04-24

    For biomineralization processes, the interaction of the surface of calcite crystals with organic molecules is of particular importance. Especially, biologically controlled biomineralization as in exoskeletons of mollusks and echinoderms, e.g., sea urchin with single-crystal-like spines and shells,1-3 requires molecular control of seed formation and growth process. So far, experiments showing the obvious influence of organic molecules on the morphology and habit of calcite crystals have demonstrated the molecular dimension of the interaction.4-7 Details of the kinetics of growth and dissolution of mineral surfaces influenced by additives are available,8,9 but other experimental data about the structure of the organic/inorganic interface on the atomic scale are rare. On the other hand, complicated organic macromolecules which are involved in biomineralization are numerous, with only a small fraction solved in structure and function so far.10-13 Therefore, model systems have to be designed to provide a basic understanding for the interaction process.14 Using grazing incidence X-ray diffraction combined with molecular modeling techniques, we show that glycine molecules order periodically on the calcite (104) face in competition with the solvent water when exposed to an aqueous solution of the most simple amino acid. In contrast to the general concept of the charge-matching fit of organic molecules on mineral surfaces,4,14 glycine is not attached to the calcite surface directly but substitutes for water molecules in the second hydration layer.

  19. Sorption of trace metals on calcite: Applicability of the surface precipitation model

    NARCIS (Netherlands)

    Comans, R.N.J.; Middelburg, J.J.

    1987-01-01

    Published Sorption isotherm data of Cd2+, Mn2+, Zn2+, and Co2+ on calcite are adequately described by the surface precipitation model which was originally developed by FArley et al. (1985) for the sorption of cations on metal oxides. In addition to monolayer adsorption, the model accounts for the fo

  20. Kinetics and Mechanisms of Cadmium Carbonate Heteroepitaxial Growth at the Calcite (101¯4) Surface

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Man; Kovarik, Libor; Arey, Bruce W.; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien N.

    2014-06-01

    Elucidating the kinetics and mechanisms of heteroepitaxial nucleation and growth at mineral-water interfaces is essential to understanding surface reactivity in geochemical systems. In the present work, the formation of heteroepitaxial cadmium carbonate coatings at calcite-water interfaces was investigated by exposing calcite (10-14) surfaces to Cd-bearing aqueous solutions. In situ atomic force microscopy (AFM) was employed as the primary technique. The AFM results indicate that the heteroepitaxial growth of cadmium carbonate proceeds via three different mechanisms depending on the initial supersaturation of the aqueous solution: advancement of existing steps, nucleation and growth of three-dimensional (3D) islands, and nucleation and spread of two-dimensional (2D) nuclei. The 3D islands and 2D nuclei exhibit different morphologies and growth kinetics. The effects of supersaturation on heteroepitaxial growth mechanisms can be interpreted in terms of the free energy barrier for nucleation. At low initial supersaturation, where 3D nucleation dominates, it is hypothesized, from the growth rate and morphology of the 3D islands observed with AFM, that the crystallization of the overgrowth follows a non-classical pathway involving the formation of a surface precursor that is not fully crystalline, whereas high supersaturation favors the formation of crystalline 2D nuclei whose morphology is based on the atomic structure of the calcite substrate. Cross-sectional transmission electron microscopy (TEM) images reveal that the atomic structure of the interface between the cadmium carbonate coating and calcite shows perfect, dislocation-free epitaxy.

  1. Kinetics and mechanisms of cadmium carbonate heteroepitaxial growth at the calcite (10 1bar 4) surface

    Science.gov (United States)

    Xu, Man; Kovarik, Libor; Arey, Bruce W.; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien

    2014-06-01

    Elucidating the kinetics and mechanisms of heteroepitaxial nucleation and growth at mineral-water interfaces is essential to understanding surface reactivity in geochemical systems. In the present work, the formation of heteroepitaxial cadmium carbonate coatings at calcite-water interfaces was investigated by exposing calcite (10 1bar 4) surfaces to Cd-bearing aqueous solutions. In situ atomic force microscopy (AFM) was employed as the primary technique. The AFM results indicate that the heteroepitaxial growth of cadmium carbonate proceeds via three different mechanisms depending on the initial supersaturation of the aqueous solution: advancement of existing steps, nucleation and growth of three-dimensional (3D) islands, and nucleation and spread of two-dimensional (2D) nuclei. The 3D islands and 2D nuclei exhibit different morphologies and growth kinetics. The effects of supersaturation on heteroepitaxial growth mechanisms can be interpreted in terms of the free energy barrier for nucleation. At low initial supersaturation, where 3D nucleation dominates, it is hypothesized, from the growth rate and morphology of the 3D islands observed with AFM, that the crystallization of the overgrowth follows a non-classical pathway involving the formation of a surface precursor that is not fully crystalline, whereas high supersaturation favors the formation of crystalline 2D nuclei whose morphology is based on the atomic structure of the calcite substrate. Cross-sectional transmission electron microscopy (TEM) images reveal that the atomic structure of the interface between the cadmium carbonate coating and calcite shows perfect, dislocation-free epitaxy.

  2. 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

    Molecular dynamics simulations have been used to model the interaction between ethanol, water, and the {1014} surface of calcite. Our results demonstrate that a single ethanol molecule is able to form two interactions with the mineral surface (both Ca-O and O-H), resulting in a highly ordered......, stable adsorption layer. In contrast, a single water molecule can only form one or other of these interactions and is thus less well bound, resulting in a more unstable adsorption layer. Consequently, when competitive adsorption is considered, ethanol dominates the adsorption layer that forms even when...... 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 interact...

  3. The Effect of the Ca2+:CO32- Activity Ratio on Spiral Growth at the Calcite {1014} Surface

    DEFF Research Database (Denmark)

    Larsen, Kirsten Kolbjørn; Bechgaard, Klaus; Stipp, Susan Louise Svane

    2010-01-01

    Variation in the Ca2+ to CO 2¿ activity ratio of natural waters is rarely considered in models intended to describe calcite 3 growth. Atomic force microscopy (AFM) and differential interference contrast (DIC) microscopy were used to examine spiral growth on calcite f10¿14g surfaces from solutions...

  4. Comparison of Dissolution and Surface Reactions Between Calcite and Aragonite in L-Glutamic and L-Aspartic Acid Solutions

    Directory of Open Access Journals (Sweden)

    Kwangsuk You

    2010-01-01

    Full Text Available We have investigated dissolution and surface reaction of calcite and aragonite in amino acid solutions of L-glutamic (L-glu and L-aspartic acid (L-asp at weak acidity of above pH 3. The surface reactions of calcite and aragonite were related with the dissolution. Calcite was dissolved in both solutions but the dissolution was limited by an adsorption of Ca-carboxylate salt. Aragonite was neither dissolved nor reacted in amino acid solutions because the crystal surface consisted of a hard to dissolve structure.

  5. Nanobacteria-like calcite single crystals at the surface of the Tataouine meteorite.

    Science.gov (United States)

    Benzerara, Karim; Menguy, Nicolas; Guyot, Francois; Dominici, Christian; Gillet, Philippe

    2003-06-24

    Nanobacteria-like objects evidenced at the surface of the orthopyroxenes of the Tataouine meteorite in South Tunisia have been studied by scanning and transmission electron microscopies. A method of micromanipulation has been developed to ensure that exactly the same objects were studied by both methods. We have shown that the nanobacteria-like objects are spatially correlated with filaments of microorganisms that colonized the surface of the meteoritic pyroxene during its 70 years of residence in the aridic Tataouine soil. Depressions of a few micrometers in depth are observed in the pyroxene below the carbonates, indicating preferential dissolution of the pyroxene and calcite precipitation at these locations. The nanobacteria-like small rods that constitute calcium carbonate rosettes are well crystallized calcite single crystals surrounded by a thin amorphous layer of carbonate composition that smoothes the crystal edges and induces rounded shapes. Those morphologies are unusual for calcite single crystals observed in natural samples. A survey of recent literature suggests that the intervention of organic compounds derived from biological activity is likely in their formation.

  6. Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

    Science.gov (United States)

    Ylikantola, A.; Linnanto, J.; Knuutinen, J.; Oravilahti, A.; Toivakka, M.

    2013-07-01

    The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree-Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree-Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree-Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

  7. Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

    Energy Technology Data Exchange (ETDEWEB)

    Ylikantola, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Linnanto, J., E-mail: juha.m.linnanto@gmail.com [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); University of Tartu, Institute of Physics, Riia 142, EE-51014 Tartu (Estonia); Knuutinen, J.; Oravilahti, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Toivakka, M. [Åbo Akademi University, Laboratory of Paper Coating and Converting and Center for Functional Materials, FI-20500 Turku/Åbo (Finland)

    2013-07-01

    The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree–Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree–Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree–Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

  8. Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation

    Energy Technology Data Exchange (ETDEWEB)

    Branson, Oscar; Bonnin, Elisa A.; Perea, Daniel E.; Spero, Howard J.; Zhu, Zihua; Winters, Maria; Hönisch, Bärbel; Russell, Ann D.; Fehrenbacher, Jennifer S.; Gagnon, Alexander C.

    2016-10-28

    Biomineralizing organisms exhibit exquisite control over skeletal morphology and composition. The promise of understanding and harnessing this feat of natural engineering has motivated an intense search for the mechanisms that direct in vivo mineral self-assembly. We used atom probe tomography, a sub-nanometer 3D chemical mapping technique, to examine the chemistry of a buried organic-mineral interface in biomineral calcite from a marine foraminifer. The chemical patterns at this interface capture the processes of early biomineralization, when the shape, mineralogy, and orientation of skeletal growth are initially established. Sodium is enriched by a factor of nine on the organic side of the interface. Based on this pattern, we suggest that sodium plays an integral role in early biomineralization, potentially altering interfacial energy to promote crystal nucleation, and that interactions between organic surfaces and electrolytes other than calcium or carbonate could be a crucial aspect of CaCO3 biomineralization.

  9. 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...... allowed us to quantify the amount of polysaccharides associated with the coccoliths. The amount of polysaccharides left in chalk, demonstrated to be present in other work, is below the IR detection limit, which is 0.5% by mass....

  10. Structure and dynamics of microbe-exuded polymers and their interactions with calcite surfaces.

    Energy Technology Data Exchange (ETDEWEB)

    Cygan, Randall Timothy; Mitchell, Ralph (Harvard University, Cambridge, MA); Perry, Thomas D. (Harvard University, Cambridge, MA)

    2005-12-01

    Cation binding by polysaccharides is observed in many environments and is important for predictive environmental modeling, and numerous industrial and food technology applications. The complexities of these organo-cation interactions are well suited to predictive molecular modeling studies for investigating the roles of conformation and configuration of polysaccharides on cation binding. In this study, alginic acid was chosen as a model polymer and representative disaccharide and polysaccharide subunits were modeled. The ability of disaccharide subunits to bind calcium and to associate with the surface of calcite was investigated. The findings were extended to modeling polymer interactions with calcium ions.

  11. Dissolution and Sorption Processes on the Surface of Calcite in the Presence of High Co2+ Concentration

    Directory of Open Access Journals (Sweden)

    Jorge González-López

    2017-02-01

    Full Text Available The interaction of the calcite surface with Co2+-rich aqueous solutions ([Co2+aq]initial = 1000 ppm, i.e., ca. 17 mM was investigated by means of macroscopic experiments and surface spectroscopic techniques. In the case of the macroscopic experiments, calcite powder and monocrystals were immersed into solutions for different time periods (from 1 min to one month. The Ca concentrations in the filtrates was measured by means of atomic absorption spectrometry (AAS while the interacted solids were studied using a combination of X-ray photoelectron spectroscopy (XPS and 12C-rutherford backscattering spectrometry (12C-RBS. The macroscopic data showed a characteristic surface dissolution process, in parallel to the surface sorption processes. Adsorption and co-precipitation were seen for almost the entire immersion period for both calcite powder and monocrystals. The surface study by XPS (analyzed at a depth of approximately 12 nm suggested that adsorption takes place in the first hour of the interaction, followed by incorporation of Co2+ into calcite surface layers, leading to the formation of a Co2+-bearing surface (coprecipitate, which occurs over a period of hours and days. The 12C-RBS measurements on calcite { 10 1 ¯ 4 } indicated that the thickness of this surface co-precipitate was 270 nm after one day and then stabilized at 320 nm after more than a week.

  12. Sorption and catalytic oxidation of Fe(II) at the surface of calcite

    NARCIS (Netherlands)

    Mettler, S.; Wolthers, M.; Charlet, L.; Von Gunten, U.

    2009-01-01

    The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a

  13. Stability of Basalt plus Anhydrite plus Calcite at HP-HT: Implications for Venus, the Earth and Mars

    Science.gov (United States)

    Martin, A. M.; Righter, K.; Treiman, A. H.

    2010-01-01

    "Canali" observed at Venus surface by Magellan are evidence for very long melt flows, but their composition and origin remain uncertain. The hypothesis of water-rich flow is not reasonable regarding the temperature at Venus surface. The length of these channels could not be explained by a silicate melt composition but more likely, by a carbonate-sulfate melt which has a much lower viscosity (Kargel et al 1994). One hypothesis is that calcite CaCO3 and anhydrite CaSO4 which are alteration products of basalts melted during meteorite impacts. A famous example recorded on the Earth (Chicxulub) produced melt and gas rich in carbon and sulfur. Calcite and sulfate evaporites are also present on Mars surface, associated with basalts. An impact on these materials might release C- and S-rich melt or fluid. Another type of planetary phenomenon (affecting only the Earth) might provoke a high pressure destabilization of basalt+anhydrite+calcite. Very high contents of C and S are measured in some Earth s magmas, either dissolved or in the form of crystals (Luhr 2008). As shown by the high H content and high fO2 of primary igneous anhydrite-bearing lavas, the high S content in their source may be explained by subduction of an anhydrite-bearing oceanic crust, either directly (by melting followed by eruption) or indirectly (by release of S-rich melt or fluid that metasomatize the mantle) . Calcite is a major product of oceanic sedimentation and alteration of the crust. Therefore, sulfate- and calcite-rich material may be subducted to high pressures and high temperatures (HP-HT) and release S- and C-rich melts or fluids which could influence the composition of subduction zone lavas or gases. Both phenomena - meteorite impact and subduction - imply HP-HT conditions - although the P-T-time paths are different. Some HP experimental/theoretical studies have been performed on basalt/eclogite, calcite and anhydrite separately or on a combination of two. In this study we performed piston

  14. The surface reactivity of chalk (biogenic calcite) with hydrophilic and hydrophobic functional groups

    Science.gov (United States)

    Okhrimenko, D. V.; Dalby, K. N.; Skovbjerg, L. L.; Bovet, N.; Christensen, J. H.; Stipp, S. L. S.

    2014-03-01

    The surface properties of calcium carbonate minerals play an important role in a number of industrial and biological processes. Properties such as wettability and adsorption control liquid-solid interface behaviour and thus have a strong influence on processes such as biomineralisation, remediation of aquifers and oil recovery. We investigated how two model molecules of different polarity, namely water and ethanol, interact with reservoir and outcrop chalk samples and we compared their behaviour with that of pure, inorganically precipitated calcite. Thermodynamic quantities, such as the work of wetting, surface energy and isosteric adsorption enthalpy, were determined from vapour adsorption isotherms. The chalks were studied fresh and after extraction of organic residues that were originally present in these samples. The work of wetting correlates with the amount of organic matter present in the chalk samples but we observed a fundamental difference between the adsorption properties of chalk and pure, inorganically precipitated calcite toward the less polar, ethanol molecule. Further analysis of the chemical composition of the organic matter extracted from the chalk samples was made by gas chromatography (GC-MS). Monitoring surface composition by X-ray photoelectron spectroscopy (XPS) before and after extraction of the organic material, and with atomic force microscopy (AFM), showed that nanometer sized clay crystals observed on the chalk particle surfaces could be an important part of the reason for the differences. Removal of the extractable portion of the hydrocarbons liberates adsorption sites that have different wetting properties than the rest of the chalk and these have an energy distribution that is similar to clays. Thus, the results exemplify the complexity of biogenic calcite adsorption behaviour and demonstrate that chalk wetting in drinking water aquifers as well as oil reservoirs is controlled partly by the nanoparticles of clay that have grown on the

  15. Surface Kinetic Model for the Fractionation of Trace Elements and Isotopes in Calcite Precipitated from Aqueous Solution

    Science.gov (United States)

    Depaolo, D. J.; Ryerson, F. J.; Watkins, J. M.; Bourg, I. C.; Yang, W.; Nielsen, L. C.; Druhan, J. L.

    2010-12-01

    The isotopic and trace element concentrations in calcite and other carbonate minerals form the basis for several paleoceanographic and paleoenvironmental indicators. The chemical and isotopic composition of natural calcites is determined by a combination of equilibrium partitioning and kinetic fractionations. Currently there is no general model that describes when equilibrium applies and how kinetic effects depend on the circumstances and rates of mineral growth. A useful approach is to separate the growth of calcite from aqueous solutions into forward (f) and backward (b) reactions, and to consider the mechanisms and fractionations that may be associated with each. We are evaluating a model where the net precipitation rate of calcite (Rp) is expressed as the difference between a forward rate (Rf) and a backward (dissolution) rate (Rb). Dissolution is approached only as Rp/Rb->0. Much natural calcite, including biogenic, forms under conditions where Rp ≫ Rb, hence the isotopic and trace element partitioning is strongly influenced by the kinetics of the forward reaction. Assuming that there are kinetic fractionations associated with the forward and backward reactions, a simple model can be developed for the dependence of calcite composition on precipitation rate. This model can explain most available experimental data on Ca and O isotopes, as well as Sr/Ca and Mn/Ca in calcite, and can be used to infer the behavior of other trace and minor elements. The critical parameter in applying the model is the value of Rb which to first order can be estimated from mineral dissolution rates, but apparently is not a constant, but instead varies with solution chemistry, especially at saturation conditions close to equilibrium. The surface kinetic model requires three parameters that are measureable experimentally and potentially also predictable from molecular dynamics simulation approaches. In this way it differs from the surface entrapment model of Watson (2004) which

  16. 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.

  17. Variations in calcite growth kinetics with surface topography: molecular dynamics simulations and process-based growth kinetics modelling

    NARCIS (Netherlands)

    Wolthers, M.; Di Tommaso, D.; Du, Zhimei; de Leeuw, Nora H.

    2013-01-01

    It is generally accepted that cation dehydration is the rate-limiting step to crystal growth from aqueous solution. Here we employ classical molecular dynamics simulations to show that the water exchange frequency at structurally distinct calcium sites in the calcite surface varies by about two orde

  18. Sorption of phosphate onto calcite; results from batch experiments and surface complexation modeling

    DEFF Research Database (Denmark)

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

    2011-01-01

    The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3h) and low concentrations of phosphate (⩽50μM). Sorption of phosphate on calcite...... was studied in 11 different calcite-equilibrated solutions that varied in pH, PCO2, ionic strength and activity of Ca2+, CO32- and HCO3-. Our results show strong sorption of phosphate onto calcite. The kinetics of phosphate sorption onto calcite are fast; adsorption is complete within 2–3h while desorption...... of a high degree of super-saturation with respect to hydroxyapatite (SIHAP⩽7.83). The amount of phosphate adsorbed varied with the solution composition, in particular, adsorption increases as the CO32- activity decreases (at constant pH) and as pH increases (at constant CO32- activity). The primary effect...

  19. Study of wettability of calcite surfaces using oil-brine-enzyme systems for enhanced oil recovery applications

    DEFF Research Database (Denmark)

    Khusainova, Alsu; Nielsen, Sidsel Marie; Pedersen, Hanne Høst;

    2015-01-01

    Enzymes have recently been considered as possible agents for enhanced oil recovery (EOR) acting at the liquid-solid interface. One way to assess this is via measuring the wettability of calcite surfaces, important for EOR methods in carbonaceous reservoirs. In the present work, we have experiment......Enzymes have recently been considered as possible agents for enhanced oil recovery (EOR) acting at the liquid-solid interface. One way to assess this is via measuring the wettability of calcite surfaces, important for EOR methods in carbonaceous reservoirs. In the present work, we have...... experimentally investigated the effect of enzymes on the wettability of calcite mineral surfaces with oil-brine systems. The action of various enzymes, including esterases/lipases, carbohydrases, proteases and oxidoreductases (along with two commercial mixtures) was studied by contact angle measurements.......1% of the enzyme product (corresponding to 0.002-0.005% protein). Likewise, proteases could also improve wettability, although the effect was not consistent and was dependent on impurities. Other enzymes had no effect on the wettability of calcite at the concentration studied. The main mechanism of enzymatic...

  20. 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.

  1. Understanding 2D atomic resolution imaging of the calcite surface in water by frequency modulation atomic force microscopy

    Science.gov (United States)

    Tracey, John; Miyazawa, Keisuke; Spijker, Peter; Miyata, Kazuki; Reischl, Bernhard; Federici Canova, Filippo; Rohl, Andrew L.; Fukuma, Takeshi; Foster, Adam S.

    2016-10-01

    Frequency modulation atomic force microscopy (FM-AFM) experiments were performed on the calcite (10\\bar{1}4) surface in pure water, and a detailed analysis was made of the 2D images at a variety of frequency setpoints. We observed eight different contrast patterns that reproducibly appeared in different experiments and with different measurement parameters. We then performed systematic free energy calculations of the same system using atomistic molecular dynamics to obtain an effective force field for the tip-surface interaction. By using this force field in a virtual AFM simulation we found that each experimental contrast could be reproduced in our simulations by changing the setpoint, regardless of the experimental parameters. This approach offers a generic method for understanding the wide variety of contrast patterns seen on the calcite surface in water, and is generally applicable to AFM imaging in liquids.

  2. 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

    The adsorption of phosphate, arsenate (As(V)) and arsenite (As(III)) onto synthetic calcite was studied in a series of batch experiments. The adsorption of the three ions was studied separately followed by studies of the competition between arsenate and phosphate. The experimental data was utilized...... is complete after 1 and 2-3 hours, respectively). Also desorption is fast and complete for both ions within 0.5 h. The reversibility of the sorption process indicates that neither arsenate nor phosphate is readily incorporated into the calcite crystal lattice under our experimental conditions. The phosphate....... This clearly shows the importance of competition studies in validating multicomponent models. Extrapolation of the experimental results to calcite bearing aquifers suggests a large variability in the mobility of arsenic. Under reduced conditions, arsenite, which does not adsorb onto calcite, will dominate and...

  3. Nanoscale observations of the effect of citrate on calcium oxalate precipitation on calcite surfaces.

    Science.gov (United States)

    Burgos-Cara, Alejandro; Ruiz-Agudo, Encarnacion; Putnis, Christine V.

    2016-04-01

    Calcium oxalate (CaC2O4ṡxH2O) minerals are naturally occurring minerals found in fossils, plants, kidney stones and is a by-product in some processes such as paper, food and beverage production [1,2]. In particular, calcium oxalate monohydrate phase (COM) also known as whewellite (CaC2O4ṡH2O), is the most frequently reported mineral phase found in urinary and kidney stones together with phosphates. Organic additives are well known to play a key role in the formation of minerals in both biotic and abiotic systems, either facilitating their precipitation or hindering it. In this regard, recent studies have provided direct evidence demonstrating that citrate species could enhance dissolution of COM and inhibit their precipitation. [3,4] The present work aims at evauate the influence of pH, citrate and oxalic acid concentrations in calcium oxalate precipitation on calcite surfaces (Island Spar, Chihuahua, Mexico) through in-situ nanoscale observation using in situ atomic force microscopy (AFM, Multimode, Bruker) in flow-through experiments. Changes in calcium oxalate morphologies and precipitated phases were observed, as well as the inhibitory effect of citrate on calcium oxalate precipitation, which also lead to stabilization an the amorphous calcium oxalate phase. [1] K.D. Demadis, M. Öner, Inhibitory effects of "green"additives on the crystal growth of sparingly soluble salts, in: J.T. Pearlman (Ed.), Green Chemistry Research Trends, Nova Science Publishers Inc., New York, 2009, pp. 265-287. [2] M. Masár, M. Zuborová, D. Kaniansky, B. Stanislawski, Determination of oxalate in beer by zone electrophoresis on a chip with conductivity detection, J. Sep. Sci. 26 (2003) 647-652. [3] Chutipongtanate S, Chaiyarit S, Thongboonkerd V. Citrate, not phosphate, can dissolve calcium oxalate monohydrate crystals and detach these crystals from renal tubular cells. Eur J Pharmacol 2012;689:219-25. [4] Weaver ML, Qiu SR, Hoyer JR, Casey WH, Nancollas GH, De Yoreo JJ

  4. A 250,000-year climatic record from great basin vein calcite: implications for milankovitch theory.

    Science.gov (United States)

    Winograd, I J; Coplen, T B; Szabo, B J; Riggs, A C

    1988-12-02

    A continuous record of oxygen-18 (delta(18)O) variations in the continental hydrosphere during the middle-to-late Pleistocene has been obtained from a uranium-series dated calcitic vein in the southern Great Basin. The vein was deposited from ground water that moved through Devils Hole-an open fault zone at Ash Meadows, Nevada-between 50 and 310 ka (thousand years ago). The configuration of the delta(18)O versus time curve closely resembles the marine and Antarctic ice core (Vostok) delta(18)O curves; however, the U-Th dates indicate that the last interglacial stage (marine oxygen isotope stage 5) began before 147 +/- 3 ka, at least 17,000 years earlier than indicated by the marine delta(18)O record and 7,000 years earlier than indicated by the less well dated Antarctic delta(18)O record. This discrepancy and other differences in the timing of key climatic events suggest that the indirectly dated marine delta(18)O chronology may need revision and that orbital forcing may not be the principal cause of the Pleistocene ice ages.

  5. A 250,000-year climatic record from great basin vein calcite: Implications for Milankovitch theory

    Science.gov (United States)

    Winograd, I.J.; Szabo, B. J.; Coplen, T.B.; Riggs, A.C.

    1988-01-01

    A continuous record of oxygen-18 (??18O) variations in the continental hydrosphere during the middle-to-late Pleistocene has been obtained from a uranium-series dated calcitic vein in the southern Great Basin. The vein was deposited from ground water that moved through Devils Hole - an open fault zone at Ash Meadows, Nevada - between 50 and 310 ka (thousand years ago). The configuration of the ??18O versus time curve closely resembles the marine and Antarctic ice core (Vostok) ??18O curves; however, the U-Th dates indicate that the last interglacial stage (marine oxygen isotope stage 5) began before 147 ?? 3 ka, at least 17,000 years earlier than indicated by the marine ??18O record and 7,000 years earlier than indicated by the less well dated Antarctic ??18O record. This discrepancy and other differences in the timing of key climatic events suggest that the indirectly dated marine ??18O chronology may need revision and that orbital forcing may not be the principal cause of the Pleistocene ice ages.

  6. Grain coarsening of calcite: Fundamental mechanisms and biogenic inhibition

    DEFF Research Database (Denmark)

    Schultz, Logan Nicholas

    In a saturated solution, submicrometer calcite (CaCO3) crystals recrystallize and coarsen to minimize surface area. The thermodynamic driving force is described by the Gibbs-Thomson equation, but the rates and mechanism are poorly understood. Calcite grain coarsening has many implications...... in industry and nature, but the specific focus of this research project was to understand how small, biogenic calcite particles in chalk have resisted grain coarsening for over 60 million years in saturated reservoir fluids. A new method was developed to produce pure calcite powder that has submicrometer...... coarsening – small grains coarsen by aggregation at high temperatures, followed by Ostwald ripening. Alginate, a model for the acidic polysaccharides produced by coccolithiphores, inhibited coarsening at a steady rate. A Pseudomonas aeruginosa biofilm preserved particles for at least 60 days before...

  7. Mineral Chemistry of Melanite from Calcitic Ijolite, the Oka Carbonatite Complex, Canada:Implications for Multi-Pulse Magma Mixing

    Institute of Scientific and Technical Information of China (English)

    Wei Chen; Weiqi Zhang; Antonio Simonetti; Shaoyong Jiang

    2016-01-01

    Ti-rich garnet is found within calcitic ijolite from the Oka carbonatite complex in Can-ada, which is characterized by 58%–73% andradite component (2.12 wt.%–4.18 wt.% TiO2) and classi-fied as melanite. The garnet displays complex zoning and contains abundant high field strength ele-ments (HFSEs) and rare earth elements (REEs). Three groups (I, II, III) have been identified based on their petrographic nature. Compared to groups II and III, Group I garnet cores contain higher TiO2, MgO, HFSE, and REE and lower SiO2 abundances. The distinct chemical and petrographic signatures of the investigated garnets cannot be attributed to simple closed system crystallization, but they are consistent with the multi-pulse magma mixing. Combined with previously reported U-Pb ages for apa-tite from the calcitic ijolite, at least three stages of magma evolution and subsequent mixing have been involved in the generation of calcitic ijolite at Oka. The early-formed melt that generated Group I gar-net core was later mixed with at least two small-volume, more evolved melts. The intermediate stage melt formed the remaining garnet along with some pyroxene, calcite, nepheline, and apatite at 127±3.6 Ma. The youngest, most evolved melt generated the majority of pyroxene, calcite, nepheline, and apatite within the calcitic ijolite at 115±3.1 Ma.

  8. Kinetics of calcium phosphate nucleation and growth on calcite: implications for predicting the fate of dissolved phosphate species in alkaline soils.

    Science.gov (United States)

    Wang, Lijun; Ruiz-Agudo, Encarnación; Putnis, Christine V; Menneken, Martina; Putnis, Andrew

    2012-01-17

    Unraveling the kinetics of calcium orthophosphate (Ca-P) precipitation and dissolution is important for our understanding of the transformation and mobility of dissolved phosphate species in soils. Here we use an in situ atomic force microscopy (AFM) coupled with a fluid reaction cell to study the interaction of phosphate-bearing solutions with calcite surfaces. We observe that the mineral surface-induced formation of Ca-P phases is initiated with the aggregation of clusters leading to the nucleation and subsequent growth of Ca-P phases on calcite, at various pH values and ionic strengths relevant to soil solution conditions. A significant decrease in the dissolved phosphate concentration occurs due to the promoted nucleation of Ca-P phases on calcite surfaces at elevated phosphate concentrations and more significantly at high salt concentrations. Also, kinetic data analyses show that low concentrations of citrate caused an increase in the nucleation rate of Ca-P phases. However, at higher concentrations of citrate, nucleation acceleration was reversed with much longer induction times to form Ca-P nuclei. These results demonstrate that the nucleation-modifying properties of small organic molecules may be scaled up to analyze Ca-P dissolution-precipitation processes that are mediated by a more complex soil environment. This in situ observation, albeit preliminary, may contribute to an improved understanding of the fate of dissolved phosphate species in diverse soil systems.

  9. Chemical Compositions of Calcites in Carbonatites from Panxi Region Implications for Genesis of Carbonatites and Associated REE Deposits

    Institute of Scientific and Technical Information of China (English)

    XU Cheng; HUANG Zhi-long

    2008-01-01

    @@ The Panxi region is important REE mineralization belt in China. Chemical compositions of calcites in carbon-atites from Daluxiang and Maoniuping REE deposits are analyzed by LA-ICPMS. At Maoniuping the reserve of REE2O3 is estimated to be more than 1.45 million tons.

  10. Early diagenetic high-magnesium calcite and dolomite indicate that coal balls formed in marine or brackish water: Stratigraphic and paleoclimatic implications

    Science.gov (United States)

    Raymond, Anne

    2016-04-01

    Coal balls are carbonate and pyrite permineralizations of peat that contain three-dimensional plant fossils preserved at the cellular level. Coal balls, which occur in Pennsylvanian and earliest Permian equatorial coals, provide a detailed record of terrestrial ecology and tropical climate during the Late Paleozoic Ice Age; yet their depositional environment remains controversial. The exquisite preservation of some coal-ball fossils, e.g. pollen with pollen tubes and leaves with mesophyll, indicates rapid formation. The presence of abundant, cement-filled, void spaces within and between the plant debris in most coal balls indicates that they formed in uncompacted peat, near the surface of the mire. Botanical, taphonomic and isotopic evidence point to a freshwater origin for coal balls. The nearest living relatives of coal ball plants (modern lycopsids, sphenopsids, marratialean ferns and conifers) grow in fresh water. Coal-ball peat contains a high percentage of aerial debris, similar to modern freshwater peat. The stable oxygen isotopes of coal-ball carbonate (δ18O = 16 to 3 per mil) suggest a freshwater origin. However, the widespread occurrence of marine invertebrates and early diagenetic framboidal pyrite in coal balls suggests that many formed in close proximity to marine water. Indeed, carbonate petrology points to a marine or brackish water origin for the first-formed carbonate cements in coal balls. Petrographic and geochemical (microprobe) analysis of coal-ball carbonates in Pennsylvanian coals from the midcontinent of North America (Western Interior Basin, West Pangaea) and the Ruhr and Donets Basins (East Pangaea) indicate that the first formed carbonate is either radaxial, nonstochiometric dolomite or high magnesium calcite (9 - 17 mol % MgCO3, indicating precipitation in marine or brackish water. Although both primary dolomite and high magnesium calcite can form in lacustrine settings, the lakes in which these minerals form occur in carbonate terranes

  11. PAM微球表面方解石晶体的制备与表征%Synthesis and characterization of calcite crystal on surface of PAM microgel

    Institute of Scientific and Technical Information of China (English)

    李红; 阮美茹

    2013-01-01

    The synthesis of calcium carbonate crystals (calcite) from aqueous solutions containing polyacrylamide(PAM) microgels was performed by the method of dipping of the solution of CaCl2 and Na2CO3 by turns.The formation of calcite in several laboratory experiments was discussed.The PAM-CaCO3 composite spheres were characterized by SEM,FFIR,EDX,TAG.It was demonstrated that rhombohedral calcite is produced on the surface of microgels.Increasing the concentration of dipping solution,reaction speed quickens,meanwhile rhombohedral calcite begins to cluster.But delaying alternation time and increasing microgels quantity,size of calcite particles and clusters change smaller.%将聚丙烯酰胺(PAM)微凝胶在CaCl2和Na2CO3溶液中交替浸渍,其表面发生碳酸钙沉积反应,研究不同实验条件对所形成碳酸钙晶体(方解石)形貌的影响.利用SEM、FFIR、EDX、TAG等分析手段对制备的PAM-CaCO3复合微球进行表征.结果表明,在PAM微凝胶表面形成了由菱形层状簇集的方解石形貌;随着浸渍的溶液浓度增大,反应速度加快,层数增加,堆积成串状;但浸渍交替时间的延长和PAM微凝胶量的加大,均会使所形成的方解石颗粒变大,簇集层数减少.

  12. The influence of rigid second phases on the mechanical evolution of calcite rocks, with implications for strain localization

    Science.gov (United States)

    Austin, N.; Evans, B.; Dresen, G.; Rybaki, E.

    2007-12-01

    Interactions between rheologically distinct phases may strongly influence both the microstructure and mechanical properties of shear zones, thus playing a key role in the development or inhibition of localized deformation. However, experimental, theoretical, and field observations have produced conflicting suggestions that either A) rigid phases may pin the grain-size of a dominant weak phase, driving deformation into the diffusion creep regime, and promoting weakening, or B) rigid phases may be load supporting, thus increasing the strength of the aggregate. To investigate the influence of chemically inert, rigid second phases on the strength, microstructural evolution, and dominant deformation mechanism of calcite rocks, we have performed conventional triaxial experiments (MIT), and high strain torsion experiments (GFZ-Potsdam) on synthetic calcite aggregates with no second phases added, 1% (by vol.) 4 μm carbon spheres, 10% (by vol.) 4 μm carbon spheres, and 10% (by vol.) 5 μm carbon splinters. Glassy carbon spheres and splinters were chosen as they are chemically inert under the experimental conditions, are mechanically strong compared to the calcite, and can be obtained with a narrow grain size distribution. Prior to deformation, samples were hot isostatically pressed (HIPed) at 1023K and 300 MPa, to control the starting grain-size. The presence of carbon spheres or splinters has a dramatic influence on the grain-size after HIPing: samples with 10% spheres or splinters have an initial grain-size that is a factor of three finer than pure samples after 2.25 hrs while samples with 1% spheres are ~1.5 times finer than pure samples, again after 2.25 hrs. Deformation experiments were performed at 1023K, at a confining pressure of 300 MPa (trixial) or 400 MPa (torsion), at constant equivalent strain rates between 5e-6 s-1 and 1e-3 s-1. In both triaxial compression and torsion experiments, samples containing 10% splinters are stronger than pure samples and those

  13. Relation between etch-pit morphology and step retreat velocity on a calcite surface in aspartic acid solution

    Science.gov (United States)

    Yoshino, Toru; Kagi, Hiroyuki; Kamiya, Natsumi; Kokawa, Ryohei

    2010-04-01

    Effects of L-aspartic acid ( L-Asp) on dissolution of calcite were investigated. The step retreat velocity and dissolution rate of calcite were measured simultaneously using an AFM flow-through system. The etch-pit morphology of calcite was observed using confocal laser scanning microscopy. Results show that the etch-pit morphologies changed drastically depending on the L-Asp concentration ([ L-Asp]) in the order of rhomboidal, pentagonal, and triangular (not perfectly, but retaining an extra step). The change in obtuse step directions and appearance of the [0 1 0] step triggered these morphological changes. Addition of L-Asp accelerated all step retreats at [ L-Asp]0.01 M, L-Asp inhibited the retreats of obtuse steps and [0 1 0] step, although the retreat velocities of acute steps were constant irrespective of [ L-Asp]. These results suggest that the directional changes and the inhibition of retreat velocities of obtuse steps were attributed to the generation of [ 4 1 1] and [4 5 1] steps caused by L-Asp. Moreover, we confirmed the preferential effects of L-Asp on the [4 8 1] + to [ 4 4 1] ± step edge, and proposed the preferential effects of L-Asp on the [ 4 1 1] to [4 5 1] step edge.

  14. Intracrystalline deformation of calcite

    NARCIS (Netherlands)

    de Bresser, Hans

    1991-01-01

    It is well established from observations on natural calcite tectonites that intracrystalline plastic mechanisms are important during the deformation of calcite rocks in nature. In this thesis, new data are presented on fundamental aspects of deformation behaviour of calcite under conditions where 'd

  15. Experimental evidence for the global acidification of surface ocean at the Cretaceous-Palaeogene boundary: the biogenic calcite-poor spherule layers

    Science.gov (United States)

    Premović, Pavle I.

    2009-07-01

    The massive amount of impact-generated atmospheric CO2 at the Cretaceous-Palaeogene boundary (KPB) would have accumulated globally in the surface ocean, leading to acidification and CaCO3 undersaturation. These chemical changes would have caused a crisis of biocalcification of calcareous plankton and enhanced dissolution of their shells; these factors together may have played a crucial role in forming the biogenic calcite-poor KPB spherule layers observed at numerous oceanic sites and marine (now on land) sites in Europe and Africa. Experimental data and observations indicate that the deposition spherule layer probably lasted only a few decades at most.

  16. Effect of melt composition on crustal carbonate assimilation: Implications for the transition from calcite consumption to skarnification and associated CO2 degassing

    Science.gov (United States)

    Carter, Laura B.; Dasgupta, Rajdeep

    2016-10-01

    Skarns are residue of relatively low-temperature magma-induced decarbonation in the crust largely associated with silicic plutons. Mafic magmatic intrusions are also capable of releasing excess CO2 due to carbonate assimilation. However, the effect of mafic to silicic melt evolution on the decarbonation processes, in addition to temperature controls on carbonate-intrusive magmatic systems, particularly at continental arcs, remains unclear. In this study, experiments performed in a piston cylinder apparatus at midcrustal depth (0.5 GPa) at supersolidus temperatures (900-1200°C) document calcite interaction with andesite and dacite melts at equilibrium under closed-system conditions at calcite saturation in a 1:1 melt-calcite ratio by weight. With increasing silica content in the starting melt, at similar melt fractions and identical pressure, assimilation decreases drastically (≤65% andesite-calcite to ≤18% dacite-calcite). In conjunction, the CaO/SiO2 ratio in melts resulting from calcite assimilation in andesitic starting material is >1, but ≤0.3 in those formed from dacite-calcite interaction. With increasing silica-content in the starting melt skarn mineralogy, particularly wollastonite, increases in modal abundance while diopsidic clinopyroxene decreases slightly. More CO2 is released with andesite-calcite reaction (≤2.9 × 1011 g/y) than with more skarn-like dacite-calcite interaction (≤8.1 × 1010 g/y, at one volcano assuming respective calcite-free-superliquidus conditions and a magma flux of 1012 g/y). Our experimental results thus suggest that calcite assimilation in more mafic magmas may have first degassed a significant amount of crustal carbon before the melt evolves to more silicic compositions, producing skarn. Crustal decarbonation in long-lived magmatic systems may hence deliver significant albeit diminishing amounts of carbon to the atmosphere and contribute to long-term climate change.

  17. A Non-Electrostatic Surface Complexation Approach to Modeling Radionuclide Migration at the Nevada Test Site: I. Iron Oxides and Calcite

    Energy Technology Data Exchange (ETDEWEB)

    Zavarin, M; Bruton, C J

    2004-12-17

    Reliable quantitative prediction of contaminant transport in subsurface environments is critical to evaluating the risks associated with radionuclide migration. As part of the Underground Test Area (UGTA) project, radionuclide transport away from various underground nuclear tests conducted in the saturated zone at the Nevada Test Site (NTS) is being examined. In the near-field environment, reactive transport simulations must account for changes in water chemistry and mineralogy as a function of time and their effect on radionuclide migration. Unlike the K{sub d} approach, surface complexation (SC) reactions, in conjunction with ion exchange and precipitation, can be used to describe radionuclide reactive transport as a function of changing environmental conditions. They provide a more robust basis for describing radionuclide retardation in geochemically dynamic environments. The interaction between several radionuclides considered relevant to the UGTA project and iron oxides and calcite are examined in this report. The interaction between these same radionuclides and aluminosilicate minerals is examined in a companion report (Zavarin and Bruton, 2004). Selection criteria for radionuclides were based on abundance, half-life, toxicity to human and environmental health, and potential mobility at NTS (Tompson et al., 1999). Both iron oxide and calcite minerals are known to be present at NTS in various locations and are likely to affect radionuclide migration from the near-field. Modeling the interaction between radionuclides and these minerals was based on surface complexation. The effectiveness of the most simplified SC model, the one-site Non-Electrostatic Model (NEM), to describe sorption under various solution conditions is evaluated in this report. NEM reactions were fit to radionuclide sorption data available in the literature, as well as sorption data recently collected for the UGTA project, and a NEM database was developed. For radionuclide-iron oxide sorption

  18. Total individual ion activity coefficients of calcium and carbonate in seawater at 25°C and 35%. salinity, and implications to the agreement between apparent and thermodynamic constants of calcite and aragonite

    Science.gov (United States)

    Plummer, L. Neil; Sundquist, Eric T.

    1982-01-01

    We have calculated the total individual ion activity coefficients of carbonate and calcium,  and , in seawater. Using the ratios of stoichiometric and thermodynamic constants of carbonic acid dissociation and total mean activity coefficient data measured in seawater, we have obtained values which differ significantly from those widely accepted in the literature. In seawater at 25°C and 35%. salinity the (molal) values of  and  are 0.038 ± 0.002 and 0.173 ± 0.010, respectively. These values of  and  are independent of liquid junction errors and internally consistent with the value . By defining  and  on a common scale (), the product  is independent of the assigned value of  and may be determined directly from thermodynamic measurements in seawater. Using the value  and new thermodynamic equilibrium constants for calcite and aragonite, we show that the apparent constants of calcite and aragonite are consistent with the thermodynamic equilibrium constants at 25°C and 35%. salinity. The demonstrated consistency between thermodynamic and apparent constants of calcite and aragonite does not support a hypothesis of stable Mg-calcite coatings on calcite or aragonite surfaces in seawater, and suggests that the calcite critical carbonate ion curve of Broecker and Takahashi (1978,Deep-Sea Research25, 65–95) defines the calcite equilibrium boundary in the oceans, within the uncertainty of the data.

  19. 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

    2011-01-01

    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, 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

  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

    2011-09-09

    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.

  1. Calcite Twinning in the Ordovician Martinsburg Formation, Delaware Water Gap, New Jersey, USA: Implications for Cleavage Formation and Tectonic Shortening in the Appalachian Piedmont Province

    Directory of Open Access Journals (Sweden)

    John P. Craddock

    2016-02-01

    Full Text Available A traverse across the Stone Church syncline in the Ordovician Martinsburg turbidites reveals an axial planar cleavage (N40°E, SE dips in regional thrust-related folds (N40°E, shallow plunges and five phases of sparry calcite. Calcite fillings are bedding-parallel, cleavage-parallel, and one vein set cross-cuts both earlier phases; the youngest calcite filling is a bedding-parallel fault gouge that crosscuts the cleavage and preserves top-down-to-the-southeast normal fault kinematics. Calcite veins unique to disharmonically-folded calcareous siltstones (Maxwell, 1962 were also analyzed. Stable isotopic analysis (O, C of all of the calcite phases indicates a uniform fluid source (δ13C −2.0, δ18O −13.3 VPDB and, potentially, a similar precipitation and mechanical twinning age. The twinning strains (n = 1341; average Δσ = −32 MPa; average ε1 = −2.9% in the calcite suite are consistent with SE-NW thrust shortening, and sub-horizontal shortening perpendicular to evolving axial planar cleavage planes in the Stone Church syncline. Calcareous siltstone layers within the Martinsburg Fm. turbidites share concordant bedding planes and are unique, chemically (XRF, but folded and cleaved differently than the surrounding clay-rich Martinsburg turbidites. Neither sediment type yielded detrital zircons. Electron backscatter X-ray diffraction (EBSD and calcite twinning results in a folded calcareous siltstone layer preserving a layer-normal SE-NW shortening strain and Lattice Preferred Orientation (LPO. Shortening axes for the five-phase calcite suite trends ~N40°W, consistent with tectonic transport associated with crystalline nappe emplacement of the Reading Prong within the Piedmont province.

  2. Differences in the rheological properties of calcitic and dolomitic lime slurries: influence of particle characteristics and practical implications in lime-based mortar manufacturing

    Directory of Open Access Journals (Sweden)

    Arizzi, A.

    2012-06-01

    Full Text Available The study of the rheological properties of lime suspensions is a useful means to evaluate the workability of lime mortars. In this work, we studied the flow behaviour of two industrial hydrated limes, one of calcitic and the other of dolomitic composition, by means of two types of rheometer with different geometry and setup mode. The obtained results were interpreted taking into account the differences in microstructure and surface properties of the suspended particles. Calcitic lime dry particles are formed by angular and polydisperse clusters and, once dispersed in water, they behave like thixotropic materials. On the other hand, the dolomitic lime is formed by nanoparticles and small round cluster and it shows a pronounced plastic behaviour in suspension. This fundamental difference between the two materials explains the traditional preference for dolomitic lime mortars for plastering and rendering applications.

    El estudio de las propiedades reológicas de suspensiones de cal es una herramienta muy útil para evaluar la trabajabilidad de morteros de cal. En este trabajo se ha estudiado el comportamiento en suspensión de dos cales hidratadas, de composición calcítica y dolomítica, mediante dos tipos de reómetros con geometría y modalidades distintas de medida. Los resultados obtenidos se han interpretado teniendo en cuenta las diferencias en la microestructura y las propiedades de superficie de las partículas en suspensión. Las partículas de cal calcítica están formadas por aglomerados angulares y polidispersos y, una vez dispersadas en agua, presentan un comportamiento tixotrópico. Por su parte, la cal dolomítica está formada por nanopartículas y pequeños agregados redondeados y muestra en suspensión un pronunciado comportamiento plástico. Esta importante diferencia entre las dos cales explica la preferencia tradicional de morteros de cal dolomítica para aplicaciones en revocos.

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

    Science.gov (United States)

    Reddy, Michael M.

    2012-08-01

    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.

  5. Influence of Changing Hydrology on Pedogenic Calcite Precipitation in Vertisols, Dance Bayou, Brazoria County, Tx: Implications for Estimating Paleoatmospheric PCO2

    Science.gov (United States)

    Mintz, J. S.; Driese, S. G.; Ludvigson, G. A.; Breecker, D. O.

    2010-12-01

    Pedogenic (soil formed) calcites preserved in the sedimentary record enable estimation of paleoatmospheric pCO2 using the calcite paleobarometer. A fundamental assumption for applying this paleobarometer is that the calcite precipitated while the soil was in communication with the atmosphere so that atmospheric CO2 concentrations had a direct influence on the calcite δ13C value. Here we address the timing of calcite precipitation in relation to the soil saturation state and atmosphere connectivity in a modern Vertisol (smectitic, clay-rich soil, seasonally saturated) in Brazoria County, Texas. Luminescent phases of calcite growth have more negative δ13C values (avg. δ13C = -11.1 ‰ PDB) than the non-luminescent phases (avg. δ13C = -2.8 ‰ PDB). The luminescent phase formed during the water-saturated portion of the year limiting the soil connectivity with the atmosphere, minimizing the incorporation of atmospheric CO2 and negating its use for pCO2 estimations. The non-luminescent phase formed during the well-drained portion of the year when atmospheric CO2 mixed with soil-respired CO2 and is therefore useful for pCO2 estimation. From these results we present a model to independently test the saturation state of a paleosol at the time of pedogenic carbonate precipitation. Finally we calculate soil respiration rates that are an order of magnitude lower than those that are typically assumed in the paleobarometer equation. Many of the pCO2 estimates through the Phanerozoic are based on carbonate in paleo-Vertisols and may therefore be overestimated or potentially invalid. A) Comparisons of typical morphotype isotope values with interpreted soil conditions at the time of calcite precipitation. B) Model of carbonate precipitation of non-luminescent calcite nodules (dark circles) in the well-drained portion of the season (top) and luminescent calcite nodules (light circles) in the saturated portion of the season (bottom), in a Vertisol at Dance Bayou, Brazoria Co

  6. Modeling the evolution of complex conductivity during calcite precipitation on glass beads

    Science.gov (United States)

    Leroy, Philippe; Li, Shuai; Jougnot, Damien; Revil, André; Wu, Yuxin

    2017-01-01

    SUMMARYWhen pH and alkalinity increase, calcite frequently precipitates and hence modifies the petrophysical properties of porous media. The complex conductivity method can be used to directly monitor calcite precipitation in porous media because it is sensitive to the evolution of the mineralogy, pore structure and its connectivity. We have developed a mechanistic grain polarization model considering the electrochemical polarization of the Stern and diffuse layer surrounding calcite particles. Our complex conductivity model depends on the surface charge density of the Stern layer and on the electrical potential at the onset of the diffuse layer, which are computed using a basic Stern model of the calcite/water interface. The complex conductivity measurements of Wu et al. (2010) on a column packed with glass beads where calcite precipitation occurs are reproduced by our surface complexation and complex conductivity models. The evolution of the size and shape of calcite particles during the calcite precipitation experiment is estimated by our complex conductivity model. At the early stage of the calcite precipitation experiment, modeled particles sizes increase and calcite particles flatten with time because calcite crystals nucleate at the surface of glass beads and grow into larger calcite grains around glass beads. At the later stage of the calcite precipitation experiment, modeled sizes and cementation exponents of calcite particles decrease with time because large calcite grains aggregate over multiple glass beads, a percolation threshold is achieved, and small and discrete calcite crystals polarize.

  7. Phosphorus speciation in calcite speleothems determined from solid-state NMR spectroscopy

    Science.gov (United States)

    Mason, Harris E.; Frisia, Silvia; Tang, Yuanzhi; Reeder, Richard J.; Phillips, Brian L.

    2007-02-01

    Variations in speleothem P concentration show cyclic patterns that have important implications for high resolution palaeoclimate and palaeoenvironmental reconstructions. However, little is known about the speciation of P in calcite speleothems. Here we employ solid-state 31P and 1H magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopic techniques as a non-destructive method for analyzing the distribution of P in speleothems. The 31P MAS NMR results show three peaks indicating the presence of three primary types of phosphate species in samples from the Grotta di Ernesto (northeastern Italy): a broad peak at a chemical shift δP-31 = 3.1 to 3.7 ppm from individual phosphate ions incorporated within calcite, a narrow set of peaks near δP-31 = - 0.9 ppm from crystalline monetite and a narrow peak at δP-31 = 2.9 ppm from an unidentified crystalline phosphate phase. Essentially identical results were obtained for a synthetic calcite/phosphate coprecipitate. Spectra collected for a sample from Grotte de Clamouse (southern France) show only a broad peak near 3.5 ppm suggesting a possible limit for phosphate incorporation into the calcite structure. These data suggest that P in this system can interact to form calcium phosphate surface precipitates during infiltration events and are subsequently enclosed during calcite growth.

  8. Structural incorporation of Neptunyl(V) into Calcite: Interfacial Reactions and Kinetics

    OpenAIRE

    Heberling, Frank

    2010-01-01

    In this experimental work the calcite-water interface is characterized by means of zetapotential and surface diffraction measurements. Based on the experimental results a new Basic Stern Surface Complexation model for calcite is developed. Neptunyl(V) adsorption at the calcite surface and incorporation into the calcite structure is studied by batch type adsorption- and mixed flow reactor experiments. Adsorption and incorporation species of Neptunyl are investigated by EXAFS spectroscopy.

  9. Defects in Calcite.

    Science.gov (United States)

    1991-05-13

    Interatomic Distances in Halides and Chalcogenides" Acta. Cryst. 32 (19-76) 751. 3 8 S.A. Marshall, J.A. McMillan, and R.A. Serway . "Electron Spin... Serway RA (1967) Electron Spin Resonance Absorption Spectrum of Y3 -Stabilized C0 3- Molecular-Ion in Single- Crystal Calcite. J. Chem. Phys. 48:5131-5137

  10. The origin of carbon isotope vital effects in coccolith calcite

    Science.gov (United States)

    McClelland, H. L. O.; Bruggeman, J.; Hermoso, M.; Rickaby, R. E. M.

    2017-01-01

    Calcite microfossils are widely used to study climate and oceanography in Earth's geological past. Coccoliths, readily preserved calcite plates produced by a group of single-celled surface-ocean dwelling algae called coccolithophores, have formed a significant fraction of marine sediments since the Late Triassic. However, unlike the shells of foraminifera, their zooplankton counterparts, coccoliths remain underused in palaeo-reconstructions. Precipitated in an intracellular chemical and isotopic microenvironment, coccolith calcite exhibits large and enigmatic departures from the isotopic composition of abiogenic calcite, known as vital effects. Here we show that the calcification to carbon fixation ratio determines whether coccolith calcite is isotopically heavier or lighter than abiogenic calcite, and that the size of the deviation is determined by the degree of carbon utilization. We discuss the theoretical potential for, and current limitations of, coccolith-based CO2 paleobarometry, that may eventually facilitate use of the ubiquitous and geologically extensive sedimentary archive. PMID:28262764

  11. 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.

  12. Elastic constants of calcite

    Science.gov (United States)

    Peselnick, L.; Robie, R.A.

    1962-01-01

    The recent measurements of the elastic constants of calcite by Reddy and Subrahmanyam (1960) disagree with the values obtained independently by Voigt (1910) and Bhimasenachar (1945). The present authors, using an ultrasonic pulse technique at 3 Mc and 25??C, determined the elastic constants of calcite using the exact equations governing the wave velocities in the single crystal. The results are C11=13.7, C33=8.11, C44=3.50, C12=4.82, C13=5.68, and C14=-2.00, in units of 1011 dyncm2. Independent checks of several of the elastic constants were made employing other directions and polarizations of the wave velocities. With the exception of C13, these values substantially agree with the data of Voigt and Bhimasenachar. ?? 1962 The American Institute of Physics.

  13. Biogenic and synthetic high magnesium calcite - a review.

    Science.gov (United States)

    Long, Xia; Ma, Yurong; Qi, Limin

    2014-01-01

    Systematic studies on the Mg distributions, the crystal orientations, the formation mechanisms and the mechanical properties of biogenic high-Mg calcites in different marine organisms were summarized in detail in this review. The high-Mg calcites in the hard tissues of marine organisms mentioned generally own a few common features as follows. Firstly, the Mg distribution is not uniform in most of the minerals. Secondly, high-Mg calcite biominerals are usually composed of nanoparticles that own almost the same crystallographic orientations and thus they behave like single crystals or mesocrystals. Thirdly, the formation of thermodynamically unstable high-Mg calcites in marine organisms under mild conditions is affected by three key factors, that is, the formation of amorphous calcium (magnesium) carbonate precursor, the control of polymorph via biomolecules and the high Mg/Ca ratios in modern sea. Lastly, the existence of Mg ions in the Mg-containing calcite may improve the mechanical properties of biogenic minerals. Furthermore, the key progress in the synthesis of high-Mg calcites in the laboratory based on the formation mechanisms of the biogenic high-Mg calcites was reviewed. Many researchers have realized the synthesis of high-Mg calcites in the laboratory under ambient conditions with the help of intermediate amorphous phase, mixed solvents, organic/inorganic surfaces and soluble additives. Studies on the structural analysis and formation mechanisms of thermodynamically unstable biogenic high-Mg calcite minerals may shed light on the preparation of functional materials with enhanced mechanical properties.

  14. Thermal and Evolved Gas Analysis of Calcite Under Reduced Operating Pressures: Implications for the 2011 MSL Sample Analysis at Mars (SAM) Instrument

    Science.gov (United States)

    Lauer, H. V. Jr.; Ming, D. W.; Sutter, B.; Mahaffy, P. R.

    2010-01-01

    The Mars Science Laboratory (MSL) is scheduled for launch in 2011. The science objectives for MSL are to assess the past or present biological potential, to characterize the geology, and to investigate other planetary processes that influence habitability at the landing site. The Sample Analysis at Mars (SAM) is a key instrument on the MSL payload that will explore the potential habitability at the landing site [1]. In addition to searching for organic compounds, SAM will have the capability to characterized evolved gases as a function of increasing temperature and provide information on the mineralogy of volatile-bearing phases such as carbonates, sulfates, phyllosilicates, and Fe-oxyhydroxides. The operating conditions in SAM ovens will be maintained at 30 mb pressure with a He carrier gas flowing at 1 sccm. We have previously characterized the thermal and evolved gas behaviors of volatile-bearing species under reduced pressure conditions that simulated operating conditions of the Thermal and Evolved Gas Analyzer (TEGA) that was onboard the 2007 Mars Phoenix Scout Mission [e.g., 2-8]. TEGA ovens operated at 12 mb pressure with a N2 carrier gas flowing at 0.04 sccm. Another key difference between SAM and TEGA is that TEGA was able to perform differential scanning calorimetry whereas SAM only has a pyrolysis oven. The operating conditions for TEGA and SAM have several key parameter differences including operating pressure (12 vs 30 mb), carrier gas (N2 vs. He), and carrier gas flow rate (0.04 vs 1 sccm). The objectives of this study are to characterize the thermal and evolved gas analysis of calcite under SAM operating conditions and then compare it to calcite thermal and evolved gas analysis under TEGA operating conditions.

  15. 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.

  16. Interactions between cadmium and calcite

    OpenAIRE

    Van der Weijden, R.D.

    1995-01-01

    The thesis is composed of five chapters, some of which have been published or have been accepted for publication. The contents in some of the chapters may therefore slightly overlap, also because the subjects are closely related. The first two chapters focus mostly on the sorption of Cd on calcite, whereas the next two chapters are devoted to calcite growth and Cd incorporation during growth. In the fifth and final chapter, Cd sorption and incorporation is studied in an environment where calc...

  17. Meteoric calcitization of magnesite in Miocene lacustrine deposits (Calatayud basin, NE Spain)

    Science.gov (United States)

    Cañaveras, J. C.; Sánchez-Moral, S.; Sanz-Rubio, E.; Hoyos, M.

    1998-08-01

    Sedimentary magnesite deposits are commonly present in evaporite successions in the Tertiary Calatayud basin (NE Spain). Outcropping evaporite sequences, mainly composed of secondary gypsum after anhydrite-glauberite, show centimetre-thick layers of magnesite passing laterally into calcite pseudospar. Petrographic and stable isotope data indicate that calcite pseudospar formed via late-stage calcitization of magnesite under near-surface conditions. Calcitization occurred by the interaction between magnesite and Ca-enriched waters derived from the dissolution of gypsum and/or glauberite. The geochemical simulation of this process, petrographic evidence, and the correlation between the magnesite/calcite ratio and the δ18O values of both magnesite and calcite samples across the reaction front are in agreement with the existence of neoformed 18O-depleted magnesite during the waning stages of the calcitization process.

  18. Magnesium-Calcite Crystal Formation Mediated by the Thermophilic Bacterium Geobacillus thermoglucosidasius Requires Calcium and Endospores.

    Science.gov (United States)

    Murai, Rie; Yoshida, Naoto

    2016-11-01

    Fresh Geobacillus thermoglucosidasius cells grown on soybean-casein digest nutrient agar were inoculated as a parent colony 1 cm in diameter on the surface of an agar gel containing acetate and calcium ions (calcite-promoting hydrogel) and incubated at 60 °C for 4 days, after which magnesium-calcite single crystals of 50-130 µm in size formed within the parent colony. Addition of EDTA, polyacrylic acid or N,N-dicyclohexylcarbodiimide to the calcite-forming hydrogel inhibited the parent colony from forming magnesium-calcite crystals. Inoculation of G. thermoglucosidasius on calcite-forming hydrogel containing 5 µM cadmium and 20 µM zinc resulted in a decrease in the sporulation rate from 55 to 7-8 %. Magnesium-calcite synthesis decreased relative to the sporulation rate. G. thermoglucosidasius exhibited higher adsorption/absorbance of calcium than other Geobacillus sp. that do not mediate calcite formation and higher levels of magnesium accumulation. Calcium ions contained in the calcite-promoting hydrogel and magnesium ions concentrated in G. thermoglucosidasius cells serve as the elements for magnesium-calcite synthesis. The observed decreases in sporulation rate and magnesium-calcite formation support the hypothesis that endospores act as nuclei for the synthesis of magnesium-calcite single crystals.

  19. 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.

  20. An AFM study of calcite dissolution in concentrated electrolyte solutions

    Science.gov (United States)

    Ruiz Agudo, E.; Putnis, C. V.; Putnis, A.; Rodriguez-Navarro, C.

    2009-04-01

    Calcite-solution interactions are of a paramount importance in a range of processes such as the removal of heavy metals, carbon dioxide sequestration, landscape modeling, weathering of building stone and biomineralization. Water in contact with minerals often carries significant amounts of solutes; additionally, their concentration may vary due to evaporation and condensation. It is well known that calcite dissolution is affected dramatically by the presence of such solutes. Here we present investigations on the dissolution of calcite in the presence of different electrolytes. Both bulk (batch reactors) experiments and nanoscale (in situ AFM) techniques are used to study the dissolution of calcite in a range of solutions containing alkaly cations balanced by halide anions. Previous works have indicated that the ionic strength has little influence in calcite dissolution rates measured from bulk experiments (Pokrovsky et al. 2005; Glendhill and Morse, 2004). Contrary to these results, our quantitative analyses of AFM observations show an enhancement of the calcite dissolution rate with increasing electrolyte concentration. Such an effect is concentration-dependent and it is most evident in concentrated solutions. AFM experiments have been carried out in a fluid cell using calcite cleavage surfaces in contact with solutions of simple salts of the alkaly metals and halides at different undersaturations with respect to calcite to try to specify the effect of the ionic strength on etch pit spreading rate and calcite dissolution rate. These results show that the presence of soluble salts may critically affect the weathering of carbonate rocks in nature as well as the decay of carbonate stone in built cultural heritage. References: Pokrosky, O.S.; Golubev, S.V.; Schott, J. Dissolution kinetics of calcite, dolomite and magnesite at 25°C and 0 to 50 atm pCO2. Chemical Geology, 2005, 217 (3-4) 239-255. Glendhill, D.K.; Morse, J.W. Dissolution kinetics of calcite in Na

  1. Interactions between cadmium and calcite

    NARCIS (Netherlands)

    van der Weijden, R.D.

    1995-01-01

    The thesis is composed of five chapters, some of which have been published or have been accepted for publication. The contents in some of the chapters may therefore slightly overlap, also because the subjects are closely related. The first two chapters focus mostly on the sorption of Cd on calcite,

  2. The Effect of the CO32- to Ca2+ Ion activity ratio on calcite precipitation kinetics and Sr2+ partitioning

    Directory of Open Access Journals (Sweden)

    Gebrehiwet Tsigabu A

    2012-01-01

    Full Text Available Abstract Background A proposed strategy for immobilizing trace metals in the subsurface is to stimulate calcium carbonate precipitation and incorporate contaminants by co-precipitation. Such an approach will require injecting chemical amendments into the subsurface to generate supersaturated conditions that promote mineral precipitation. However, the formation of reactant mixing zones will create gradients in both the saturation state and ion activity ratios (i.e., aCO32-/aCa2+. To better understand the effect of ion activity ratios on CaCO3 precipitation kinetics and Sr2+ co-precipitation, experiments were conducted under constant composition conditions where the supersaturation state (Ω for calcite was held constant at 9.4, but the ion activity ratio (r=aCO32-/aCa2+ was varied between 0.0032 and 4.15. Results Calcite was the only phase observed, by XRD, at the end of the experiments. Precipitation rates increased from 41.3 ± 3.4 μmol m-2 min-1 at r = 0.0315 to a maximum rate of 74.5 ± 4.8 μmol m-2 min-1 at r = 0.306 followed by a decrease to 46.3 ± 9.6 μmol m-2 min-1 at r = 1.822. The trend was simulated using a simple mass transfer model for solute uptake at the calcite surface. However, precipitation rates at fixed saturation states also evolved with time. Precipitation rates accelerated for low r values but slowed for high r values. These trends may be related to changes in effective reactive surface area. The aCO32-/aCa2+ ratios did not affect the distribution coefficient for Sr in calcite (DPSr2+, apart from the indirect effect associated with the established positive correlation between DPSr2+ and calcite precipitation rate. Conclusion At a constant supersaturation state (Ω = 9.4, varying the ion activity ratio affects the calcite precipitation rate. This behavior is not predicted by affinity-based rate models. Furthermore, at the highest ion ratio tested, no precipitation was observed, while at the lowest ion ratio precipitation

  3. A ubiquitous hydrothermal episode recorded in the sheet-crack cements of a Marinoan cap dolostone of South China: Implication for the origin of the extremely 13C-depleted calcite cement

    Science.gov (United States)

    Zhou, Guanghong; Luo, Taiyi; Zhou, Mingzhong; Xing, Lecai; Gan, Tian

    2017-02-01

    Sheet-crack - primarily filled with chalcedony, quartz and calcite - is a type of significant sedimentary structure in almost all documented cap carbonates in platform-to-slope settings, which sharply overlie the global Marinoan (∼635 Ma) glacial tillite. The Jiulongwan section, located in the Yangtze Gorges areas, South China, is significant for the first discovery of extremely 13C-depleted (δ13C down to -41‰) calcite cements in sheet-crack structure (Jiang et al., 2003a), which provides direct evidence for the methane seep hypothesis (Kennedy et al., 2001). Focusing on the calcite cements in the same section, Bristow et al. (2011) proposed a hydrothermal origin based on high temperatures (378 °C) determined by carbonate clumped isotope thermometry (CCIT). In this study, we provide evidence for the hydrothermal model using fluid inclusion technology (FIT) to quartz cements in the Jiulongwan section. The widespread sheet-crack structures in South China have uniform mineral paragenetic assemblages, which apparently reflect three stages of a hydrothermal fluid activity, including dolomitization at the early stage, silicification comprising chalcedony and quartz at the middle stage, and calcitization characterized by carbonaceous calcite filling preexisting voids at the late stage. Primary aqueous fluid inclusions from quartz crystals have homogenization temperatures of approximately 160-220 °C (mean, 192 °C, n = 31), while the salinity histogram contains two peaks at low salinity (6.3-8.3 wt.% NaCl equiv.) and high salinity (18.0-20.8 wt.% NaCl equiv.), reflecting precipitation caused by mixing of high- and low-salinity fluids. A modified and detailed hydrothermal model is proposed indicating that the sheet-crack structure resulted from successive thermal fluid activity after karstic dissolution due to postglacial isostatic rebound. This model is compatible with the unified sequence of glacio-eustatic events after the termination of Marinoan glaciation (Zhou

  4. Hydrochemical controls on aragonite versus calcite precipitation in cave dripwaters

    Science.gov (United States)

    Rossi, Carlos; Lozano, Rafael P.

    2016-11-01

    Despite the paleoclimatic relevance of primary calcite to aragonite transitions in stalagmites, the relative role of fluid Mg/Ca ratio, supersaturation and CO32- concentration in controlling such transitions is still incompletely understood. Accordingly, we have monitored the hydrochemistry of 50 drips and 8 pools that are currently precipitating calcite and/or aragonite in El Soplao and Torca Ancha Caves (N. Spain), investigating the mineralogy and geochemistry of the CaCO3 precipitates on the corresponding natural speleothem surfaces. The data reveal that, apart from possible substrate effects, dripwater Mg/Ca is the only obvious control on CaCO3 polymorphism in the studied stalagmites and pools, where calcite- and aragonite-precipitating dripwaters are separated by an initial (i.e. at stalactite tips) Mg/Ca threshold at ≈1.1 mol/mol. Within the analyzed ranges of pH (8.2-8.6), CO32- concentration (1-6 mg/L), supersaturation (SIaragonite: 0.08-1.08; SIcalcite: 0.23-1.24), drip rate (0.2-81 drops/min) and dissolved Zn (6-90 μg/L), we observe no unequivocal influence of these parameters on CaCO3 mineralogy. Despite the almost complete overlapping supersaturations of calcite- and aragonite-precipitating waters, the latter are on average less supersaturated because the waters having Mg/Ca above ∼1.1 have mostly achieved such high ratios by previously precipitating calcite. Both calcite and aragonite precipitated at or near oxygen isotopic equilibrium, and Mg incorporation into calcite was consistent with literature-based predictions, indicating that in the studied cases CaCO3 precipitation was not significantly influenced by strong kinetic effects. In the studied cases, the calcites that precipitate at ∼11 °C from dripwaters with initial Mg/Ca approaching ∼1.1 incorporate ∼5 mol% MgCO3, close to the published value above which calcite solubility exceeds aragonite solubility, suggesting that aragonite precipitation in high-relative-humidity caves is

  5. Catalytic peptide hydrolysis by mineral surface: Implications for prebiotic chemistry

    Science.gov (United States)

    Marshall-Bowman, Karina; Ohara, Shohei; Sverjensky, Dimitri A.; Hazen, Robert M.; Cleaves, H. James

    2010-10-01

    The abiotic polymerization of amino acids may have been important for the origin of life, as peptides may have been components of the first self-replicating systems. Though amino acid concentrations in the primitive oceans may have been too dilute for significant oligomerization to occur, mineral surface adsorption may have provided a concentration mechanism. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied mainly the reverse reaction of polymer degradation to measure the impact of mineral surface catalysis on peptide bonds. Aqueous glycine (G), diglycine (GG), diketopiperazine (DKP), and triglycine (GGG) were reacted with minerals (calcite, hematite, montmorillonite, pyrite, rutile, or amorphous silica) in the presence of 0.05 M, pH 8.1, KHCO 3 buffer and 0.1 M NaCl as background electrolyte in a thermostatted oven at 25, 50 or 70 °C. Below 70 °C, reaction kinetics were too sluggish to detect catalytic activity over amenable laboratory time-scales. Minerals were not found to have measurable effects on the degradation or elongation of G, GG or DKP at 70 °C in solution. At 70 °C pyrite was the most catalytic mineral with detectible effects on the degradation of GGG, although several others also displayed catalytic behavior. GGG degraded ˜1.5-4 times faster in the presence of pyrite than in control reactions, depending on the ratio of solution concentration to mineral surface area. The rate of pyrite catalysis of GGG hydrolysis was found to be saturable, suggesting the presence of discrete catalytic sites on the mineral surface. The mineral-catalyzed degradation of GGG appears to occur via a GGG → DKP + G mechanism, rather than via GGG → GG + G, as in solution-phase reactions. These results are compatible with many previous findings and suggest that minerals may have assisted in peptide synthesis in certain geological settings, specifically by speeding the approach to equilibrium

  6. Surface history of Mercury - Implications for terrestrial planets

    Science.gov (United States)

    Murray, B. C.; Strom, R. G.; Trask, N. J.; Gault, D. E.

    1975-01-01

    A plausible surface history of Mercury is presented which is suggested by Mariner 10 television pictures. Five periods are postulated which are delineated by successive variations in the modification of the surface by external and internal processes: accretion and differentiation, terminal heavy bombardment, formation of the Caloris basin, flooding of that basin and other areas, and light cratering accumulated on the smooth plains. Each period is described in detail; the overall history is compared with the surface histories of Venus, Mars, and the moon; and the implications of this history for earth are discussed. It is tentatively concluded that: Mercury is a differentiated planet most likely composed of a large iron core enclosed by a relatively thin silicate layer; heavy surface bombardment occurred about four billion years ago, which probably affected all the inner planets, and was followed by a period of volcanic activity; no surface modifications caused by tectonic, volcanic, or atmospheric processes took place after the volcanic period.

  7. Shock-induced devolatilization of calcite

    Science.gov (United States)

    Boslough, M. B.; Ahrens, T. J.; Vizgirda, J.; Becker, R. H.; Epstein, S.

    1982-01-01

    Experimental measurements of the release adiabats by Vizgirda (1981) indicate that substantial vaporization takes place upon release from shock pressures of 37 GPa for calcite and 14 GPa for aragonite. The present investigation includes the first controlled partial vaporization experiments on calcite. The experiments were conducted to test the predictions of the release adiabat experiments. The quantities of the gaseous species produced from shocked calcite and their carbon and oxygen isotopic compositions were determined, and the shock-induced effect on the Mn(2+) electron spin resonance spectrum in the shock-recovered calcite was observed. On the basis of the obtained results, it is concluded that shock stresses at the 17-18 GPa level give rise to volatilization of 0.03-0.3 (mole) percent of calcite to CO2 and CO. The devolatilization of calcite occurs at low pressure at significantly lower entropy densities than predicted on the basis of thermodynamic continuum models.

  8. The radiation of surface wave energy: Implications for volcanic tremor

    Science.gov (United States)

    Haney, M. M.; Denolle, M.; Lyons, J. J.; Nakahara, H.

    2015-12-01

    The seismic energy radiated by active volcanism is one common measurement of eruption size. For example, the magnitudes of individual earthquakes in volcano-tectonic (VT) swarms can be summed and expressed in terms of cumulative magnitude, energy, or moment release. However, discrepancies exist in current practice when treating the radiated energy of volcano seismicity dominated by surface waves. This has implications for volcanic tremor, since eruption tremor typically originates at shallow depth and is made up of surface waves. In the absence of a method to compute surface wave energy, estimates of eruption energy partitioning between acoustic and seismic waves typically assume seismic energy is composed of body waves. Furthermore, without the proper treatment of surface wave energy, it is unclear how much volcanic tremor contributes to the overall seismic energy budget during volcanic unrest. To address this issue, we derive, from first principles, the expression of surface wave radiated energy. In contrast with body waves, the surface wave energy equation is naturally expressed in the frequency domain instead of the time domain. We validate our result by reproducing an analytical solution for the radiated power of a vertical force source acting on a free surface. We further show that the surface wave energy equation leads to an explicit relationship between energy and the imaginary part of the surface wave Green's tensor at the source location, a fundamental property recognized within the field of seismic interferometry. With the new surface wave energy equation, we make clear connections to reduced displacement and propose an improved formula for the calculation of surface wave reduced displacement involving integration over the frequency band of tremor. As an alternative to reduced displacement, we show that reduced particle velocity squared is also a valid physical measure of tremor size, one based on seismic energy rate instead of seismic moment rate. These

  9. 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.

  10. 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.

  11. Incorporation of Eu(III) into Calcite under Recrystallization conditions.

    Science.gov (United States)

    Hellebrandt, S E; Hofmann, S; Jordan, N; Barkleit, A; Schmidt, M

    2016-09-13

    The interaction of calcite with trivalent europium under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). We conducted batch studies with a reaction time from seven days up to three years with three calcite powders, which differed in their specific surface area, recrystallization rates and impurities content. With increase of the recrystallization rate incorporation of Eu(3+) occurs faster and its speciation comes to be dominated by one species with its excitation maximum at 578.8 nm, so far not identified during previous investigations of this process under growth and phase transformation conditions. A long lifetime of 3750 μs demonstrates complete loss of hydration, consequently Eu must have been incorporated into the bulk crystal. The results show a strong dependence of the incorporation kinetics on the recrystallization rate of the different calcites. Furthermore the investigation of the effect of different background electrolytes (NaCl and KCl) demonstrate that the incorporation process under recrystallization conditions strongly depends on the availability of Na(+). These findings emphasize the different retention potential of calcite as a primary and secondary mineral e.g. in a nuclear waste disposal site.

  12. Incorporation of Eu(III) into Calcite under Recrystallization conditions

    Science.gov (United States)

    Hellebrandt, S. E.; Hofmann, S.; Jordan, N.; Barkleit, A.; Schmidt, M.

    2016-09-01

    The interaction of calcite with trivalent europium under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). We conducted batch studies with a reaction time from seven days up to three years with three calcite powders, which differed in their specific surface area, recrystallization rates and impurities content. With increase of the recrystallization rate incorporation of Eu3+ occurs faster and its speciation comes to be dominated by one species with its excitation maximum at 578.8 nm, so far not identified during previous investigations of this process under growth and phase transformation conditions. A long lifetime of 3750 μs demonstrates complete loss of hydration, consequently Eu must have been incorporated into the bulk crystal. The results show a strong dependence of the incorporation kinetics on the recrystallization rate of the different calcites. Furthermore the investigation of the effect of different background electrolytes (NaCl and KCl) demonstrate that the incorporation process under recrystallization conditions strongly depends on the availability of Na+. These findings emphasize the different retention potential of calcite as a primary and secondary mineral e.g. in a nuclear waste disposal site.

  13. 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...

  14. Fracture-aperture alteration induced by calcite precipitation

    Science.gov (United States)

    Jones, T.; Detwiler, R. L.

    2013-12-01

    Mineral precipitation significantly alters the transport properties of fractured rock. Chemical solubility gradients that favor precipitation induce mineral growth, which decreases the local aperture and alters preferential flow paths. Understanding the resulting development of spatial heterogeneities is necessary to predict the evolution of transport properties in the subsurface. We present experimental results that quantify the relationship between mineral precipitation and aperture alteration in a transparent analog fracture, 7.62cm x 7.62cm, with a uniform aperture of ~200 μm. Prior to flow experiments, a pump circulated a super-saturated calcite solution over the bottom glass, coating the glass surface with calcite. This method of seeding resulted in clusters of calcite crystals with large reactive surface area and provided micro-scale variability in the aperture field. A continuous flow syringe pump injected a reactive fluid into the fracture at 0.5 ml/min. The fluid was a mixture of sodium bicarbonate (NaHCO3, 0.02M) and calcium chloride (CaCl2 0.0004M) with a saturation index, Ω, of 8.51 with respect to calcite. A strobed LED panel backlit the fracture and a high-resolution CCD camera monitored changes in transmitted light intensity. Light transmission techniques provided a quantitative measurement of fracture aperture over the flow field. Results from these preliminary experiments showed growth near the inlet of the fracture, with decreasing precipitation rates in the flow direction. Over a period of two weeks, the fracture aperture decreased by 17% within the first 4mm of the inlet. Newly precipitated calcite bridged individual crystal clusters and smoothed the reacting surface. This observation is an interesting contradiction to the expectation of surface roughening induced by mineral growth. Additionally, the aperture decreased uniformly across the width of the fracture due to the initial aperture distribution. Future experiments of precipitation

  15. 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.

  16. 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;

    2010-01-01

    adsorption on calcite relative to OH from water and the consequences of the differences in interaction on crystal growth and dissolution. A combination of atomic force microscopy (AFM) and molecular dynamics (MD) simulations showed that EtOH attachment on calcite is stronger than HOH binding...... to the surface. The strong influence of calcite in structuring ethanol extends further into the liquid than expected from electrical double-layer theory. This suggests that in fluids where water activity is low, such as in biological systems optimized for biomineralization, organic molecules can control ion...

  17. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    DEFF Research Database (Denmark)

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

    1996-01-01

    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....

  18. Calcite biomineralization in coccoliths: Evidence from atomic force microscopy (AFM)

    DEFF Research Database (Denmark)

    Henriksen, Karen; Stipp, S.L.S.

    2002-01-01

    geochemistry, crystal orientation, coccolith function, biomineralization, biological calcite, atomic force microscopy......geochemistry, crystal orientation, coccolith function, biomineralization, biological calcite, atomic force microscopy...

  19. Fabrication of porous calcite using chopped nylon fiber and its evaluation using rats.

    Science.gov (United States)

    Ishikawa, Kunio; Tram, Nguyen Xuan Thanh; Tsuru, Kanji; Toita, Riki

    2015-02-01

    Although porous calcite has attracted attention as bone substitutes, limited studies have been made so far. In the present study, porous calcite block was fabricated by introducing chopped nylon fiber as porogen. Ca(OH)2 powder containing 10 wt% chopped nylon fiber was compacted at 150 MPa, and sintered to burn out the fiber and to carbonate the Ca(OH)2 under stream of 1:2 O2-CO2. Sintering of Ca(OH)2 at 750 °C or lower temperature resulted in incomplete burning out of the fiber whereas sintering at 800 °C or higher temperature resulted in the formation of CaO due to the thermal decomposition of Ca(OH)2. However, sintering at 770 °C resulted in complete burning out of the fiber and complete carbonation of Ca(OH)2 to calcite without forming CaO. Macro- and micro-porosities of the porous calcite were approximately 23 and 16%, respectively. Diameter of the macropores was approximately 100 μm which is suitable for bone tissue penetration. Porous calcite block fabricated by this method exhibited good tissue response when implanted in the bone defect in femur of 12-weeks-old rat. Four weeks after implantation, bone bonded on the surface of calcite. Furthermore, bone tissue penetrated interior to the macropore at 8 weeks. These results demonstrated the good potential value of porous calcite as artificial bone substitutes.

  20. Aragonite-calcite transformation in fossil snail shells of loess sequences in Loess Plateau, Central China

    Institute of Scientific and Technical Information of China (English)

    SHENG Xuefen; CHEN Jun; CAI Yuanfeng; CHEN Yang; JI Junfeng

    2005-01-01

    The methods of X-ray diffraction (XRD) and ICP-AES are applied to analyzing the mineral composition of modern and fossil snail shells in Luochuan section and Xifeng section. The results show that the mineral phase of calcium carbonate in modern snail shells is aragonite, but for some fossil snail shells in certain layers of loess sequences, a part of aragonite is transformed into calcite. In Luochuan and Xifeng sections, the stratigraphic borderline of aragonite-calcite transformation appearing obviously is between L5 and L6. Under the earth surface condition, the aragonite-calcite transformation is influenced by the factor of temperature only in a long time scale. It seems that the pressure is not the factor influencing the aragonite-calcite transformation. The results also show that existing age of snail shells is possibly the dominant and principal factor for the aragonite-calcite transformation. To a certain extent, the degree of aragonite-calcite transformation in snail shell is controlled by the content of trace element, such as Mg2+. The trace element can improve the stability of snail shell aragonite and impede the process of aragonite transforming into calcite.

  1. Formation Process and Thermodynamic Poperties of Calcite

    Institute of Scientific and Technical Information of China (English)

    NAN,Zhao-Dong; SHI,Zuo-Yi; QIN,Mei; HOU,Wan-Guo; TAN,Zhi-Cheng

    2007-01-01

    The fast mixing of aqueous solutions of calcium chloride and sodium carbonate resulted in crystalline forms of vaterite and calcite under vigorous stirring. Then, the vaterite was transformed to pure calcite within about 180 min.The crystalline forms all grew with experimental time increase. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction spectroscopy (XRD) techniques were employed to characterize the as-prepared samples. The heat capacity of the stable as-synthesized calcite was determined by means of an adiabatic calorimeter from 80 to 390 K. The thermodynamic functions of the calcite were derived based on the relationships among the thermodynamic functions and the function of the measured heat capacity with respect to temperature.

  2. Interactions of salicylic acid derivatives with calcite crystals.

    Science.gov (United States)

    Ukrainczyk, Marko; Gredičak, Matija; Jerić, Ivanka; Kralj, Damir

    2012-01-01

    Investigation of basic interactions between the active pharmaceutical compounds and calcium carbonates is of great importance because of the possibility to use the carbonates as a mineral carrier in drug delivery systems. In this study the mode and extent of interactions of salicylic acid and its amino acid derivates, chosen as pharmaceutically relevant model compounds, with calcite crystals are described. Therefore, the crystal growth kinetics of well defined rhombohedral calcite seed crystals in the systems containing salicylic acid (SA), 5-amino salicylic acid (5-ASA), N-salicyloil-l-aspartic acid (N-Sal-Asp) or N-salicyloil-l-glutamic acid (N-Sal-Glu), were investigated. The precipitation systems were of relatively low initial supersaturation and of apparently neutral pH. The data on the crystal growth rate reductions in the presence of the applied salicylate molecules were analyzed by means of Cabrera & Vermileya's, and Kubota & Mullin's models of interactions of the dissolved additives and crystal surfaces. The crystal growth kinetic experiments were additionally supported with the appropriate electrokinetic, spectroscopic and adsorption measurements. The Langmuir adsorption constants were determined and they were found to be in a good correlation with values obtained from crystal growth kinetic analyses. The results indicated that salicylate molecules preferentially adsorb along the steps on the growing calcite surfaces. The values of average spacing between the adjacent salicylate adsorption active sites and the average distance between the neighboring adsorbed salicylate molecules were also estimated.

  3. Diffusion of Ca and Mg in Calcite

    Energy Technology Data Exchange (ETDEWEB)

    Cygan, R.T.; Fisler, D.K.

    1999-02-10

    The self-diffusion of Ca and the tracer diffusion of Mg in calcite have been experimentally measured using isotopic tracers of {sup 25}Mg and {sup 44}Ca. Natural single crystals of calcite were coated with a thermally-sputtered oxide thin film and then annealed in a CO{sub 2} gas at one atmosphere total pressure and temperatures from 550 to 800 C. Diffusion coefficient values were derived from the depth profiles obtained by ion microprobe analysis. The resultant activation energies for Mg tracer diffusion and Ca self-diffusion are respectively: E{sub a}(Mg) = 284 {+-} 74 kJ/mol and E{sub a}(Ca) = 271 {+-} 80 kJ/mol. For the temperature ranges in these experiments, the diffusion of Mg is faster than Ca. The results are generally consistent in magnitude with divalent cation diffusion rates obtained in previous studies and provide a means of interpreting the thermal histories of carbonate minerals, the mechanism of dolomitization, and other diffusion-controlled processes. The results indicate that cation diffusion in calcite is relatively slow and cations are the rate-limiting diffusing species for the deformation of calcite and carbonate rocks. Application of the calcite-dolomite geothermometer to metamorphic assemblages will be constrained by cation diffusion and cooling rates. The direct measurement of Mg tracer diffusion in calcite indicates that dolomitization is unlikely to be accomplished by Mg diffusion in the solid state but by a recrystallization process.

  4. Interactions between glycine derivatives and mineral surfaces: Implications for the origins of life on planetary surfaces

    Science.gov (United States)

    Marshall-Bowman, K. J.; Cleaves, H. J.; Sverjensky, D. A.; Hazen, R. M.

    2009-12-01

    Various mechanisms could have delivered amino acids to the prebiotic Earth (Miller and Orgel 1974). The polymerization of amino acids may have been important for the origin of life, as peptides may have been components for the first self-replicating systems (Kauffman 1971; Yao et al 1998). Though amino acid concentrations in the primitive oceans were likely too dilute for significant oligomerization to occur (Cleaves et al 2009), mineral surface adsorption may have concentrated these biomolecules (Bernal 1951; Lambert 2008). Few studies have examined the catalytic effects of mineral surfaces on aqueous peptide oligomerization or degradation. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied the reverse reaction of polymer degradation to measure potential mineral catalysis. Glycine (G) derivatives glycylglycine (GG), diketopiperazine (DKP), and glycylglycylglycine (GGG) were reacted with different minerals (calcite, hematite, montmorillonite, rutile, amorphous silica, and pyrite) in the presence of 0.05 M pH 8.1 KHCO3 buffer and 0.1 M NaCl as background electrolyte. Experiments were performed by reacting the aqueous amino acid derivative-mineral mixtures in a thermostatted oven (modified to accommodate a mechanical rotator) at 25°, 50° or 70°C. Samples were removed after 30, 60, 90, and 140 hours. Samples were then analyzed using high performance liquid chromatography to quantify the products. Besides mineral catalysis, it was determined that degradation of GGG proceeds principally via a GGG → DKP + G mechanism, rather than via GGG → GG + G. Below 70°C kinetics were generally too sluggish to detect catalytic activity over reasonable laboratory time-scales at this pH. At 70°C, pyrite was the only mineral with detectible catalytic effects on the degradation of GGG. GGG degraded ~ 1.5 - 4 x faster in the presence of pyrite than in control reactions, depending on the ratio of solution

  5. 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.

  6. Fingerprinting stress: Stylolite and calcite twinning paleopiezometry revealing the complexity of progressive stress patterns during folding—The case of the Monte Nero anticline in the Apennines, Italy

    Science.gov (United States)

    Beaudoin, Nicolas; Koehn, Daniel; Lacombe, Olivier; Lecouty, Alexandre; Billi, Andrea; Aharonov, Einat; Parlangeau, Camille

    2016-07-01

    In this study we show for the first time how quantitative stress estimates can be derived by combining calcite twinning and stylolite roughness stress fingerprinting techniques in a fold-and-thrust belt. First, we present a new method that gives access to stress inversion using tectonic stylolites without access to the stylolite surface and compare results with calcite twin inversion. Second, we use our new approach to present a high-resolution deformation and stress history that affected Meso-Cenozoic limestone strata in the Monte Nero Anticline during its late Miocene-Pliocene growth in the Umbria-Marche Arcuate Ridge (northern Apennines, Italy). In this area an extensive stylolite-joint/vein network developed during layer-parallel shortening (LPS), as well as during and after folding. Stress fingerprinting illustrates how stress in the sedimentary strata did build up prior to folding during LPS. The stress regime oscillated between strike slip and compressional during LPS before ultimately becoming strike slip again during late stage fold tightening. Our case study shows that high-resolution stress fingerprinting is possible and that this novel method can be used to unravel temporal relationships that relate to local variations of regional orogenic stresses. Beyond regional implications, this study validates our approach as a new powerful toolbox to high-resolution stress fingerprinting in basins and orogens combining joint and vein analysis with sedimentary and tectonic stylolite and calcite twin inversion techniques.

  7. Effect of airborne particle on SO 2-calcite reaction

    Science.gov (United States)

    Böke, Hasan; Göktürk, E. Hale; Caner-Saltık, Emine N.; Demirci, Şahinde

    1999-02-01

    In modern urban atmosphere, sulphur dioxide (SO 2) attacks calcite (CaCO 3) in calcareous stone-producing gypsum (CaSO 4·2H 2O) which forms crust at rain sheltered surfaces and accelerates erosion at areas exposed to rain. The airborne particles collected on stone surfaces have always been considered to enhance the gypsum crust formation and thus it is believed that they should be removed from the surface to decrease the effects of SO 2. In this study, our aim was to investigate this event by carrying out a series of experiments in laboratory using pure calcium carbonate powder to represent calcareous stone. Sodium montmorillonite, activated carbon, ferric oxide, vanadium pentoxide and cupric chloride were mixed in the pure calcium carbonate powder as substitutes of the airborne particles in the polluted atmosphere. The samples have been exposed at nearly 10 ppmv SO 2 concentrations at 90% relative humidity conditions in a reaction chamber for several days. The mineralogical composition of the exposed samples were determined by X-ray diffraction (XRD) analysis and infrared spectrometer (IR). Sulphation reaction products, calcium sulphite hemihydrate, gypsum and unreacted calcite, were determined quantitatively using IR. Exposed samples have also been investigated morphologically using a scanning electron microscope (SEM). Experimental results reveal that calcium sulphite hemihydrate is the main reaction product of the SO 2-calcite reaction. It turns out that airborne particles play an important catalytic role in the oxidation of calcium sulphite hemihydrate into gypsum, although their presence does not very significantly affect the extent of sulphation reaction. This behaviour of airborne particles is explained by the presence of liquid film on the calcium carbonate surface where a series of reactions in the gas-liquid-solid interfaces takes place.

  8. Selective Separation of Fluorite, Barite and Calcite with Valonea Extract and Sodium Fluosilicate as Depressants

    Directory of Open Access Journals (Sweden)

    Zijie Ren

    2017-02-01

    Full Text Available Fluorite, barite and calcite are important industry minerals. However, they often co-exist, presenting difficulty in selectively separating them due to their similar surface properties. In this study, valonea extract and sodium fluosilicate were used as depressants to selectively separate them by flotation, with sodium oleate as the collector. The single mineral flotation results showed that valonea extract displayed the strongest depression on calcite, while sodium fluosilicate displayed the strongest depression on barite. These two depressants allowed selective separation of the three minerals through sequential flotation. The flotation of mixed minerals showed that 94% of the calcite was successfully depressed by the valonea extract, and 95% recovery of the fluorite was achieved in the subsequent flotation with sodium fluosilicate depressing barite. The different depressant–mineral interactions were investigated via electro-kinetic studies and molecular dynamics (MD simulations using the Materials Studio 6.0 program. The valonea extract exhibited the strongest adsorption on the calcite surface, and sodium fluosilicate exhibited the strongest adsorption on the barite surface, which prevented oleate species from reacting with Ca2+ or Ba2+ surface sites. This study provides useful guidance for how to process fluorite, barite and calcite resources.

  9. 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.

  10. Geochemical characterization of surface water and spring water in SE Kashmir Valley, western Himalaya: Implications to water–rock interaction

    Indian Academy of Sciences (India)

    Gh Jeelani; Nadeem A Bhat; K Shivanna; M Y Bhat

    2011-10-01

    Water samples from precipitation, glacier melt, snow melt, glacial lake, streams and karst springs were collected across SE of Kashmir Valley, to understand the hydrogeochemical processes governing the evolution of the water in a natural and non-industrial area of western Himalayas. The time series data on solute chemistry suggest that the hydrochemical processes controlling the chemistry of spring waters is more complex than the surface water. This is attributed to more time available for infiltrating water to interact with the diverse host lithology. Total dissolved solids (TDS), in general, increases with decrease in altitude. However, high TDS of some streams at higher altitudes and low TDS of some springs at lower altitudes indicated contribution of high TDS waters from glacial lakes and low TDS waters from streams, respectively. The results show that some karst springs are recharged by surface water; Achabalnag by the Bringi stream and Andernag and Martandnag by the Liddar stream. Calcite dissolution, dedolomitization and silicate weathering were found to be the main processes controlling the chemistry of the spring waters and calcite dissolution as the dominant process in controlling the chemistry of the surface waters. The spring waters were undersaturated with respect to calcite and dolomite in most of the seasons except in November, which is attributed to the replenishment of the CO2 by recharging waters during most of the seasons.

  11. 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.

  12. Hydrothermal replacement of calcite by Mg-carbonates

    Science.gov (United States)

    Jonas, Laura; Mueller, Thomas; Dohmen, Ralf

    2014-05-01

    The transport of heat and mass through the Earth's crust is coupled to mineral reactions and the exchange of isotopes and elements between different phases. Carbonate minerals are a major constituent of the Earth's crust and play an important role in different physical, chemical and even biological processes. In this experimental study, the element exchange reaction between calcite (CaCO3) and a Mg-rich fluid phase is investigated under hydrothermal conditions. Single crystals of calcite (2x2x2 mm) react with 1 ml of a 1 M MgCl2 solution at 200° C in a Teflon-lined steel autoclave for different times between one day and four weeks. The reaction leads to the formation of a porous reaction front and the pseudomorphic replacement of calcite by dolomite [CaMg(CO3)2] and magnesite (MgCO3). Scanning electron microscopy revealed that the reaction rim consists of small Mg-carbonate rhombs closely attached to each other, suggesting that the replacement reaction takes place by a dissolution-precipitation mechanism. Typically, the observed reaction front can be divided into two different domains. The outer part of the reaction rim, i.e. from the mineral surface in contact to the fluid inwards, consists of magnesite, whereas the inner part of the rim surrounding the unreacted calcite core consists of Ca-rich dolomite. The formation of a porous microstructure that varies in different parts of the reaction rim is a direct result of the large molar volume change induced by the replacement of calcite by magnesite and dolomite. The developing porosity therefore creates fluid pathways that promote the progress of the reaction front towards the unreacted core of the single crystal. Compositional profiles measured perpendicular to the mineral surface across the reactions rims using electron microprobe (EMPA) further revealed a compositional gradient within the reaction rim with regard to the structure-forming elements Mg and Ca. Here, the amount of Mg incorporated in both product

  13. Effects of L-Aspartic acid on the step retreat kinetics of calcite

    Science.gov (United States)

    Yoshino, Toru; Kagi, Hiroyuki

    2012-01-01

    Effects of L-Aspartic acid (L-Asp) on step retreat kinetics in the dissolution of calcite were investigated. The step retreat velocities under surface-controlled kinetics were determined from in-situ atomic force microscopic observations using an improved flow-through system. Comparison of the present results with those obtained under a mixed kinetics condition revealed that the addition of L-Asp promotes the transport process in the calcite dissolution through acid-base and/or complex forming reactions in the diffusion boundary layer. Additionally, promotion of the acute and obtuse step retreats by the L-Asp additive was observed under surface-controlled kinetics. This report is the first to clarify that L-Asp promotes surface processes in the dissolution of calcite.

  14. Cigarette smoke toxins deposited on surfaces: implications for human health.

    Directory of Open Access Journals (Sweden)

    Manuela Martins-Green

    Full Text Available Cigarette smoking remains a significant health threat for smokers and nonsmokers alike. Secondhand smoke (SHS is intrinsically more toxic than directly inhaled smoke. Recently, a new threat has been discovered - Thirdhand smoke (THS - the accumulation of SHS on surfaces that ages with time, becoming progressively more toxic. THS is a potential health threat to children, spouses of smokers and workers in environments where smoking is or has been allowed. The goal of this study is to investigate the effects of THS on liver, lung, skin healing, and behavior, using an animal model exposed to THS under conditions that mimic exposure of humans. THS-exposed mice show alterations in multiple organ systems and excrete levels of NNAL (a tobacco-specific carcinogen biomarker similar to those found in children exposed to SHS (and consequently to THS. In liver, THS leads to increased lipid levels and non-alcoholic fatty liver disease, a precursor to cirrhosis and cancer and a potential contributor to cardiovascular disease. In lung, THS stimulates excess collagen production and high levels of inflammatory cytokines, suggesting propensity for fibrosis with implications for inflammation-induced diseases such as chronic obstructive pulmonary disease and asthma. In wounded skin, healing in THS-exposed mice has many characteristics of the poor healing of surgical incisions observed in human smokers. Lastly, behavioral tests show that THS-exposed mice become hyperactive. The latter data, combined with emerging associated behavioral problems in children exposed to SHS/THS, suggest that, with prolonged exposure, they may be at significant risk for developing more severe neurological disorders. These results provide a basis for studies on the toxic effects of THS in humans and inform potential regulatory policies to prevent involuntary exposure to THS.

  15. Trace concentration - Huge impact: Nitrate in the calcite/Eu(III) system

    Science.gov (United States)

    Hofmann, Sascha; Voïtchovsky, Kislon; Schmidt, Moritz; Stumpf, Thorsten

    2014-01-01

    The interactions of trivalent lanthanides and actinides with secondary mineral phases such as calcite is of high importance for the safety assessment of deep geological repositories for high level nuclear waste (HLW). Due to similar ionic radii, calcium-bearing mineral phases are suitable host minerals for Ln(III) and An(III) ions. Especially calcite has been proven to retain these metal ions effectively by both surface complexation and bulk incorporation. Since anionic ligands (e.g., nitrate) are omnipresent in the geological environment and due to their coordinating properties, their influence on retentive processes should not be underestimated. Nitrate is a common contaminant in most HLW forms as a result of using nitric acid in fuel reprocessing. It is also formed by microbial activity under aerobic conditions. In this study, atomic force microscopy investigations revealed a major influence of nitrate upon the surface of calcite crystals. NaNO3 causes serious modifications even in trace amounts (surface layer of low crystallinity on top of the calcite crystal. Time-resolved laser fluorescence spectroscopy of Eu(III) showed that, within this layer, Eu(III) ions are incorporated, while losing most of their hydration shell. The results show that solid solution modelling for actinides in calcite must take into account the presence of nitrate in pore and ground waters.

  16. Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

    Science.gov (United States)

    Wilkinson, Bruce H.

    1982-01-01

    Discusses causes of cyclicity in cratonic carbonate sequences and evidence for and potential significance of postulated primary calcite sediment components in past Paleozoic seas, outlining problems, focusing on models explaining existing data, and identifying background. Future sedimentary geologists will need to address these and related areas…

  17. 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.

  18. Simulating Succinate-Promoted Dissolution at Calcite {104} Steps

    Science.gov (United States)

    Mkhonto, D.; Sahai, N.

    2008-12-01

    Organic molecules of a wide range of molecular weights from small organic acids, amino-acids, acidic peptides and acidic proteins to humic and fulvic acids play a key role in modulating nucleation, crystal growth and dissolution of calcium carbonate polymorphs. In general, these acidic molecules inhibit calcite growth and, promote dissolution preferentially along specific crystallographic directions, in the process, regulating crystal shape and size, and even whether a metastable polymorph (e.g., vaterite or aragonite) is nucleated first. For example, chiral faces of calcite are selected by chiral amino-acids and the unusual {hk0} faces are expressed in the presence of amino-acids [Orme et al., 2001], and unusual heptagonal dissolution etch-pit are seen in the presence of succinate compared to the normal rhombohedral pits in water alone [Teng et al., 2006]. Thus, the presence of unusual crystal morphologies may indicate organic-mediated growth, thus serving as a biosignature. We have conducted the Molecular Dynamics (MD) simulations using the Consistent Valence Force Field (CVFF) as implemented in the FORCITE© module of the Materials Studio © software package (Accelrys, Inc. TM) to model the adsorption of succinate, a dicarboxylic acid, and charge- balancing Na+ ions on dry and hydrated steps in different directions on the {104} cleavage face of calcite [Mkhonto and Sahai, in prep.]. At the site of succinate adsorption, we find elongation of the interatomic distances (Ca-OCO3,i) between surface Ca2+ cation and the oxygen of the underlying inorganic CO32- anion the first surface layer of calcite, compared to the corresponding distances in the presence of water alone, suggesting greater ease of surface Ca2+ detachment. This result is consistent with the empirically observed increase in overall dissolution rate with succinate [Teng et al., 2006]. Furthermore, succinate adsorption lowers the step energies, which explains the appearance of steps in the unsusual [42

  19. Interaction of europium and nickel with calcite studied by Rutherford Backscattering Spectrometry and Time-Resolved Laser Fluorescence Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sabau, A. [Agence Nationale pour la gestion des Déchets RAdioactifs, 1-7 rue J. Monnet, Parc de la Croix Blanche, 92298 Châtenay-Malabry Cedex (France); Université de Nice Sophia Antipolis, Ecosystèmes Côtiers Marins et Réponses aux Stress (ECOMERS), 28 avenue Valrose, 06108 Nice Cedex 2 (France); Pipon, Y., E-mail: pipon@ipnl.in2p3.fr [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); Institut Universitaire de Technologie (IUT) Lyon-1, Université Claude Bernard Lyon 1, 69 622 Villeurbanne Cedex (France); Toulhoat, N. [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); CEA/DEN, Saclay, 91191 Gif sur Yvette (France); Lomenech, C. [Université de Nice Sophia Antipolis, Ecosystèmes Côtiers Marins et Réponses aux Stress (ECOMERS), 28 avenue Valrose, 06108 Nice Cedex 2 (France); Jordan, N. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (IRE) (Germany); Moncoffre, N. [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); Barkleit, A. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (IRE) (Germany); and others

    2014-08-01

    This study aims at elucidating the mechanisms regulating the interaction of Eu and Ni with calcite (CaCO{sub 3}). Calcite powders or single crystals (some mm sized) were put into contact with Eu or Ni solutions at concentrations ranging from 10{sup −3} to 10{sup −5} mol L{sup −1} for Eu and 10{sup −3} mol L{sup −1} for Ni. The sorption durations ranged from 1 week to 1 month. Rutherford Backscattering Spectrometry (RBS) well adapted to discriminate incorporation processes such as: (i) adsorption or co precipitation at the mineral surfaces or, (ii) incorporation into the mineral structure (through diffusion for instance), has been carried out. Moreover, using the fluorescence properties of europium, the results have been compared to those obtained by Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) on calcite powders. For the single crystals, complementary SEM observations of the mineral surfaces at low voltage were also performed. Results showed that Ni accumulates at the calcite surface whereas Eu is also incorporated at a greater depth. Eu seems therefore to be incorporated into two different states in calcite: (i) heterogeneous surface accumulation and (ii) incorporation at depth greater than 160 nm after 1 month of sorption. Ni was found to accumulate at the surface of calcite without incorporation.

  20. Simulating speleothem growth in the laboratory: Determination of stable isotope fractionation factors during precipitation of speleothem calcite

    Science.gov (United States)

    Hansen, Maximilian; Schöne, Bernd R.; Spötl, Christoph; Scholz, Denis

    2016-04-01

    temperature-dependent oxygen isotope fractionation between the precipitated CaCO3 and the water was in good agreement with previously reported values[3]. [1] Dreybrodt, W., M. Hansen, and D. Scholz, 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. Geochimica et Cosmochimica Acta, 2016. 174: p. 247-262. [2] Hansen, M., W. Dreybrodt, and D. Scholz, Chemical evolution of dissolved inorganic carbon species flowing in thin water films and its implications for (rapid) degassing of CO2 during speleothem growth. Geochimica et Cosmochimica Acta, 2013. 107: p. 242-251. [3] Tremaine, D.M., P.N. Froelich, and Y. Wang, Speleothem calcite farmed in situ: Modern calibration of δ18O and δ13C paleoclimate proxies in a continuously-monitored natural cave system. Geochimica et Cosmochimica Acta, 2011. 75: p. 4929-4950.

  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. High-Magnesian Calcite Mesocrystals : A Coordination Chemistry Approach

    NARCIS (Netherlands)

    Lenders, Jos J. M.; Dey, Archan; Bomans, Paul H. H.; Spielmann, Jan; Hendrix, Marco M. R. M.; de With, Gijsbertus; Meldrum, Fiona C.; Harder, Sjoerd; Sommerdijk, Nico A. J. M.

    2012-01-01

    While biogenic calcites frequently contain appreciable levels of magnesium, the pathways leading to such high concentrations remain unclear. The production of high-magnesian calcites in vitro is highly challenging, because Mg-free aragonite, rather than calcite, is the favored product in the presenc

  3. 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

  4. Isotopic analysis for degradation diagnosis of calcite matrix in mortar.

    Science.gov (United States)

    Dotsika, E; Psomiadis, D; Poutoukis, D; Raco, B; Gamaletsos, P

    2009-12-01

    Mortar that was used in building as well as in conservation and restoration works of wall paintings have been analysed isotopically (delta(13)C and delta(18)O) in order to evaluate the setting environments and secondary processes, to distinguish the structural components used and to determine the exact causes that incurred the degradation phenomena. The material undergoes weathering and decay on a large proportion of its surface and in depth, due to the infiltration of water through the structural blocks. Mineralogical analysis indicated signs of sulphation and dissolution/recrystallisation processes taking place on the material, whereas stable isotopes provided information relative to the origin of the CO(2) and water during calcite formation and degradation processes. Isotopic change of the initial delta(13)C and delta(18)O in carbonate matrix was caused by alteration of the primary source of CO(2) and H(2)O in mortar over time, particularly by recrystallisation of calcite with porewater, evaporated or re-condensed water, and CO(2) from various sources of atmospheric and biogenic origin. Human influence (surface treatment) and biological growth (e.g. fungus) are major exogenic processes which may alter delta(18)O and delta(13)C in lime mortar.

  5. 3D Mapping of calcite and a demonstration of its relevance to permeability evolution in reactive fractures

    Science.gov (United States)

    Ellis, Brian R.; Peters, Catherine A.

    2016-09-01

    There is a need to better understand reaction-induced changes in fluid transport in fractured shales, caprocks and reservoirs, especially in the context of emerging energy technologies, including geologic carbon sequestration, unconventional natural gas, and enhanced geothermal systems. We developed a method for 3D calcite mapping in rock specimens. Such information is critical in reactive transport modeling, which relies on information about the locations and accessible surface area of reactive minerals. We focused on calcite because it is a mineral whose dissolution could lead to substantial pathway alteration because of its high solubility, fast reactivity, and abundance in sedimentary rocks. Our approach combines X-ray computed tomography (XCT) and scanning electron microscopy. The method was developed and demonstrated for a fractured limestone core containing about 50% calcite, which was 2.5 cm in diameter and 3.5 cm in length and had been scanned using XCT. The core was subsequently sectioned and energy dispersive X-ray spectroscopy was used to determine elemental signatures for mineral identification and mapping. Back-scattered electron microscopy was used to identify features for co-location. Finally, image analysis resulted in characteristic grayscale intensities of X-ray attenuation that identify calcite. This attenuation mapping ultimately produced a binary segmented 3D image of the spatial distribution of calcite in the entire core. To demonstrate the value of this information, permeability changes were investigated for hypothetical fractures created by eroding calcite from 2D rock surfaces. Fluid flow was simulated using a 2D steady state model. The resulting increases in permeability were profoundly influenced by the degree to which calcite is contiguous along the flow path. If there are bands of less reactive minerals perpendicular to the direction of flow, fracture permeability may be an order of magnitude smaller than when calcite is contiguous

  6. Mineralogical study of surface sediments in the western Arctic Ocean and their implications for material sources

    Institute of Scientific and Technical Information of China (English)

    DONG Linsen; SHI Xuefa; LIU Yanguang; FANG Xisheng; CHEN Zhihua; WANG Chunjuan; ZOU Jianjun; HUANG Yuanhui

    2014-01-01

    Mineralogical analysis was performed on bulk sediments of 79 surface samples using X-ray diffraction. The analytical results, combined with data on ocean currents and the regional geological background, were used to investigate the mineral sources. Mineral assemblages in sediments and their distribution in the study area indicate that the material sources are complex. (1) Feldspar is abundant in the sediments of the middle Chukchi Sea near the Bering Strait, originating from sediments in the Anadyr River carried by the Anadyr Current. Sediments deposited on the western side of the Chukchi Sea are rich in feldspar. Compared with other areas, sediments in this region are rich in hornblende transported from volcanic and sedimentary rocks in Siberia by the Anadyr Stream and the Siberian Coastal Current. Sediments in the eastern Chukchi Sea are rich in quartz sourced from sediments of the Yukon and Kuskokwim rivers carried by the Alaska Coastal Current. Sediments in the northern Chukchi Sea are rich in quartz and carbonates from the Mackenzie River sediments. (2) Sediments of the southern and central Canada Basin contain little calcite and dolomite, mainly due to the small impact of the Beaufort Gyre carrying carbonates from the Canadian Arctic Islands. Compared with other areas, the mica content in the region is high, implying that the Laptev Sea is the main sediment source for the southern and central Canada Basin. In the other deep sea areas, calcite and dolomite levels are high caused by the input of large amounts of sediment carried by the Beaufort Gyre from the Canadian Arctic Islands (Banks and Victoria). The Siberian Laptev Sea also provides small amounts of sediment for this region. Furthermore, the Atlantic mid-water contributes some fine-grained material to the entire deep western Arctic Ocean.

  7. The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite.

    Science.gov (United States)

    Rodriguez-Blanco, Juan Diego; Shaw, Samuel; Benning, Liane G

    2011-01-01

    The kinetics and mechanisms of nanoparticulate amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite, were studied at a range of environmentally relevant temperatures (7.5-25 °C) using synchrotron-based in situ time-resolved Energy Dispersive X-ray Diffraction (ED-XRD) in conjunction with high-resolution electron microscopy, ex situ X-ray diffraction and infrared spectroscopy. The crystallization process occurs in two stages; firstly, the particles of ACC rapidly dehydrate and crystallize to form individual particles of vaterite; secondly, the vaterite transforms to calcite via a dissolution and reprecipitation mechanism with the reaction rate controlled by the surface area of calcite. The second stage of the reaction is approximately 10 times slower than the first. Activation energies of calcite nucleation and crystallization are 73±10 and 66±2 kJ mol(-1), respectively. A model to calculate the degree of calcite crystallization from ACC at environmentally relevant temperatures (7.5-40 °C) is also presented.

  8. Removal of organic magnesium in coccolithophore calcite

    Science.gov (United States)

    Blanco-Ameijeiras, S.; Lebrato, M.; Stoll, H. M.; Iglesias-Rodriguez, M. D.; Méndez-Vicente, A.; Sett, S.; Müller, M. N.; Oschlies, A.; Schulz, K. G.

    2012-07-01

    Coccolithophore calcite refers to the plates of calcium carbonate (CaCO3) produced by the calcifying phytoplankton, coccolithophores. The empirical study of the elemental composition has a great potential in the development of paleoproxies. However, the difficulties to separate coccolithophore carbonates from organic phases hamper the investigation of coccoliths magnesium to calcium ratios (Mg/Ca) in biogeochemical studies. Magnesium (Mg) is found in organic molecules in the cells at concentrations up to 400 times higher than in inorganically precipitated calcite in present-day seawater. The aim of this study was to optimize a reliable procedure for organic Mg removal from coccolithophore samples to ensure reproducibility in measurements of inorganic Mg in calcite. Two baseline methods comprising organic matter oxidations with (1) bleach and (2) hydrogen peroxide (H2O2) were tested on synthetic pellets, prepared by mixing reagent grade CaCO3 with organic matter from the non-calcifying marine algae Chlorella autotrophica and measured with an ICP-AES (inductively coupled plasma-atomic emission spectrometer). Our results show that treatments with a reductive solution [using hydroxylamine-hydrochloride (NH2OH·HCl + NH4OH)] followed by three consecutive oxidations (using H2O2) yielded the best cleaning efficiencies, removing >99% of organic Mg in 24 h. P/Ca and Fe/Ca were used as indicators for organic contamination in the treated material. The optimized protocol was tested in dried coccolithophore pellets from batch cultures of Emiliania huxleyi, Calcidiscus leptoporus and Gephyrocapsa oceanica. Mg/Ca of treated coccolithophores were 0.151 ± 0.018, 0.220 ± 0.040, and 0.064 ± 0.023 mmol/mol, respectively. Comparison with Mg/Ca literature coccolith values, suggests a tight dependence on modern seawater Mg/Ca, which changes as a consequence of different seawater origins (protocol applicable to field and laboratory studies of trace elemental composition in

  9. Curvature-dependent surface energy and implications for nanostructures

    Science.gov (United States)

    Chhapadia, P.; Mohammadi, P.; Sharma, P.

    2011-10-01

    At small length scales, several size-effects in both physical phenomena and properties can be rationalized by invoking the concept of surface energy. Conventional theoretical frameworks of surface energy, in both the mechanics and physics communities, assume curvature independence. In this work we adopt a simplified and linearized version of a theory proposed by Steigmann-Ogden to capture curvature-dependence of surface energy. Connecting the theory to atomistic calculations and the solution to an illustrative paradigmatical problem of a bent cantilever beam, we catalog the influence of curvature-dependence of surface energy on the effective elastic modulus of nanostructures. The observation in atomistic calculations that the elastic modulus of bent nanostructures is dramatically different than under tension - sometimes softer, sometimes stiffer - has been a source of puzzlement to the scientific community. We show that the corrected surface mechanics framework provides a resolution to this issue. Finally, we propose an unambiguous definition of the thickness of a crystalline surface.

  10. Environmental controls on the Emiliania huxleyi calcite mass

    Science.gov (United States)

    Horigome, M. T.; Ziveri, P.; Grelaud, M.; Baumann, K.-H.; Marino, G.; Mortyn, P. G.

    2013-06-01

    Although ocean acidification is expected to impact (bio)calcification by decreasing the seawater carbonate ion concentration, [CO32-], there exists evidence of non-uniform response of marine calcifying plankton to low seawater [CO32-]. This raises questions on the role of environmental factors other than acidification and on the complex physiological responses behind calcification. Here we investigate the synergistic effect of multiple environmental parameters, including temperature, nutrient (nitrate and phosphate) availability, and seawater carbonate chemistry on the coccolith calcite mass of the cosmopolitan coccolithophore Emiliania huxleyi, the most abundant species in the world ocean. We use a suite of surface (late Holocene) sediment samples from the South Atlantic and southwestern Indian Ocean taken from depths lying well above the modern lysocline. The coccolith calcite mass in our results presents a latitudinal distribution pattern that mimics the main oceanographic features, thereby pointing to the potential importance of phosphorus and temperature in determining coccolith mass by affecting primary calcification and possibly driving the E. huxleyi morphotype distribution. This evidence does not necessarily argue against the potentially important role of the rapidly changing seawater carbonate chemistry in the future, when unabated fossil fuel burning will likely perturb ocean chemistry beyond a critical point. Rather our study highlights the importance of evaluating the combined effect of several environmental stressors on calcifying organisms to project their physiological response(s) in a high CO2 world and improve interpretation of paleorecords.

  11. Surface activity, lipid profiles and their implications in cervical cancer.

    Directory of Open Access Journals (Sweden)

    Preetha A

    2005-01-01

    Full Text Available Background: The profiles of lipids in normal and cancerous tissues may differ revealing information about cancer development and progression. Lipids being surface active, changes in lipid profiles can manifest as altered surface activity profiles. Langmuir monolayers offer a convenient model for evaluating surface activity of biological membranes. Aims: The aims of this study were to quantify phospholipids and their effects on surface activity of normal and cancerous human cervical tissues as well as to evaluate the role of phosphatidylcholine (PC and sphingomyelin (SM in cervical cancer using Langmuir monolayers. Methods and Materials: Lipid quantification was done using thin layer chromatography and phosphorus assay. Surface activity was evaluated using Langmuir monolayers. Monolayers were formed on the surface of deionized water by spreading tissue organic phase corresponding to 1 mg of tissue and studying their surface pressure-area isotherms at body temperature. The PC and SM contents of cancerous human cervical tissues were higher than those of the normal human cervical tissues. Role of PC and SM were evaluated by adding varying amounts of these lipids to normal cervical pooled organic phase. Statistical analysis: Student′s t-test (p < 0.05 and one-way analysis of variance (ANOVA was used. Results: Our results reveals that the phosphatidylglycerol level in cancerous cervical tissue was nearly five folds higher than that in normal cervical tissue. Also PC and sphingomyelin SM were found to be the major phospholipid components in cancerous and normal cervical tissues respectively. The addition of either 1.5 µg DPPC or 0.5 µg SM /mg of tissue to the normal organic phase changed its surface activity profile to that of the cancerous tissues. Statistically significant surface activity parameters showed that PC and SM have remarkable roles in shifting the normal cervical lipophilic surface activity towards that of cancerous lipophilic

  12. The role of background electrolytes on the kinetics and mechanism of calcite dissolution

    Science.gov (United States)

    Ruiz-Agudo, E.; Kowacz, M.; Putnis, C. V.; Putnis, A.

    2010-02-01

    The influence of background electrolytes on the mechanism and kinetics of calcite dissolution was investigated using in situ Atomic Force Microscopy (AFM). Experiments were carried out far from equilibrium by passing alkali halide salt (NaCl, NaF, NaI, KCl and LiCl) solutions over calcite cleavage surfaces. This AFM study shows that all the electrolytes tested enhance the calcite dissolution rate. The effect and its magnitude is determined by the nature and concentration of the electrolyte solution. Changes in morphology of dissolution etch pits and dissolution rates are interpreted in terms of modification in water structure dynamics (i.e. in the activation energy barrier of breaking water-water interactions), as well as solute and surface hydration induced by the presence of different ions in solution. At low ionic strength, stabilization of water hydration shells of calcium ions by non-paired electrolytes leads to a reduction in the calcite dissolution rate compared to pure water. At high ionic strength, salts with a common anion yield similar dissolution rates, increasing in the order Cl - salts with a common cation due to an increasing mobility of water around the calcium ion. Changes in etch pit morphology observed in the presence of F - and Li + are explained by stabilization of etch pit edges bonded by like-charged ions and ion incorporation, respectively. As previously reported and confirmed here for the case of F -, highly hydrated ions increased the etch pit nucleation density on calcite surfaces compared to pure water. This may be related to a reduction in the energy barrier for etch pit nucleation due to disruption of the surface hydration layer.

  13. Coccolithophore responses to environmental variability in the South China Sea: species composition and calcite content

    Science.gov (United States)

    Jin, Xiaobo; Liu, Chuanlian; Poulton, Alex J.; Dai, Minhan; Guo, Xianghui

    2016-08-01

    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 rates. 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 and cellular levels of calcite content. Average coccolithophore abundance and their calcite concentration in the water column were 11.82 cells mL-1 and 1508.3 pg C mL-1, respectively, during the cruise. Water samples can be divided into three floral groups according to their distinct coccolithophore communities. The vertical structure of the coccolithophore community in the water column was controlled by the trophic conditions, which were regulated by mesoscale eddies across the SCS basin. The evaluation of coccolithophore-based calcite in the surface ocean also showed that three key species in the SCS (Emiliania huxleyi, Gephyrocapsa oceanica, Florisphaera profunda) and other larger, numerically rare species made almost equal contributions to total coccolith-based calcite in the water column. For Emiliania huxleyi biometry measurements, coccolith size positively correlated with nutrients (nitrate, phosphate), and it is suggested that coccolith length is influenced by light and nutrients through the regulation of growth rates. Larger-sized coccoliths were also linked statistically to low pH and calcite saturation states; however, it is not a simple cause and effect relationship, as carbonate chemistry was strongly co-correlated with the other key environmental factors (nutrients, light).

  14. 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

  15. Machining of Additively Manufactured Parts: Implications for Surface Integrity

    OpenAIRE

    Oyelola, O.; Crawforth, P.; M'Saoubi, R.; Clare, A.T.

    2016-01-01

    Additive manufacturing methods continue to move towards production ready technologies with the widely extolled virtues of rapid transition from design to part and enhanced design freedoms. However, due to fundamental limitations of laser based processes for metal additive manufacturing, there is a significant ongoing need for these parts to be subject to additional machining operations. This paper reports on a study to investigate the machining behavior and surface integrity of Ti-6Al-4 V com...

  16. Stigmatic surface in the Vochysiaceae: reproductive and taxonomic implications

    OpenAIRE

    Carmo-Oliveira, Renata; Morretes,Berta Lange de

    2009-01-01

    The Vochysiaceae are Neotropical trees and shrubs, common in the savanna areas in Central Brazil (Cerrados). The family has been traditionally divided into two tribes: Erismeae, with three genera, and Vochysieae, with five genera. We investigated the stigmatic surface of six Vochysiaceae species, belonging to four genera of Vochysieae: Vochysia, Salvertia, Callisthene and Qualea. Flowers and buds at different developmental stages were collected. Morphological features were observed on fresh m...

  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. Constraints on surface evapotranspiration: implications for modeling and observations

    Science.gov (United States)

    Gentine, P.

    2015-12-01

    The continental hydrological cycle and especially evapotranspiration are constrained by additional factors such as the energy availability and the carbon cycle. As a results trying to understand and predict the surface hydrologic cycle in isolation might be highly unreliable. We present two examples were constraints induced by 1) radiation control through cloud albedo feedback and 2) carbon control on the surface water use efficiency are essential to correctly predict the seasonal hydrologic cycle. In the first example we show that correctly modeling diurnal and seasonal convection and the associated cloud-albedo feedback (through land-atmosphere and convection-large-scale circulation feedbacks) is essential to correctly model the surface hydrologic cycle in the Amazon, and to correct biases observed in all general circulation models. This calls for improved modeling of convection to correctly predict the tropical continental hydrologic cycle.In the second example we show that typical drought index based only on energy want water availability misses vegetation physiological and carbon feedback and cannot correctly represent the seasonal cycle of soil moisture stress. The typical Palmer Drought Stress Index is shown to be incapable of rejecting water stress in the future. This calls for new drought assessment metrics that may include vegetation and carbon feedback.

  19. 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.

  20. An explanation for the 18O excess in Noelaerhabdaceae coccolith calcite

    OpenAIRE

    2016-01-01

    Coccoliths have dominated the sedimentary archive in the pelagic environment since the Jurassic. The biominerals produced by the coccolithophores are ideally placed to infer sea surface temperatures from their oxygen isotopic composition, as calcification in this photosynthetic algal group only occurs in the sunlit surface waters. In the present study, we dissect the isotopic mechanisms contributing to the "vital effect”, which overprints the oceanic temperatures recorded in coccolith calcite...

  1. Drainage pits in cohesionless materials: implications for surface of Phobos.

    Science.gov (United States)

    Horstman, K C; Melosh, H J

    1989-09-10

    Viking orbiter images show grooves and chains of pits crossing the surface of Phobos, many of which converge toward the large crater Stickney or its antipode. Although it has been proposed that the pits and grooves are chains of secondary craters, their morphology and geometric relations suggest that they are the surface traces of fractures in the underlying solid body of Phobos. Several models have been proposed to explain the pits, of which the most plausible are gas venting and drainage of regolith into open fractures. the latter mechanism is best supported by the image data and is the mechanism studied in this investigation. Drainage pits and fissures are modeled experimentally by using two rigid substrate plates placed edge to edge and covered by uniform thicknesses of dry fragmental debris (simulated regolith). Fracture extension is simulated by drawing the plates apart, allowing drainage of regolith into the newly created void. A typical drainage experiment begins with a shallow depression on the surface of the regolith, above the open fissure. Increased drainage causes local drainage pits to form; continued drainage causes the pits to coalesce, forming a cuspate groove. The resulting experimental patterns of pits and grooves have pronounced similarities to those observed on Phobos. Characteristics such as lack of raised rims, linearity of grooves and chains of pits, uniform spacing of pits, and progression from discrete pits to cuspate grooves are the same in the experiments and on Phobos. In contrast, gas-venting pits occur in irregular chains and have raised rims. These experiments thus indicate that the Phobos grooves and pits formed as drainage structures. The pit spacing in an experiment is measured at the time that the maximum number of pits forms, prior to groove development. The average pit spacing is compared to the regolith thickness for each material. Regression line fits indicate that the average spacing of drainage pits in unconsolidated

  2. Search for past life on Mars: Physical and chemical characterization of minerals of biotic and abiotic origin: part 1 - Calcite

    Science.gov (United States)

    Stalport, Fabien; Coll, Patrice; Cabane, Michel; Person, Alain; González, Rafael Navarro; Raulin, Francois; Vaulay, Marie Jo; Ausset, Patrick; McKay, Chris P.; Szopa, Cyril; Zarnecki, John

    2005-12-01

    Several lines of evidence suggest that early Mars once had liquid water on its surface, a denser atmosphere and a mild climate. Similar environmental conditions led to the origin of life on the Earth more than 3.5 billion years ago; consequently, life might also have originated on Mars. The Viking landers searched for evidence of organic molecules on the surface of Mars, and found that the Martian soil is depleted in organics at ppb levels at the landing sites. We contend that inorganic compounds could give us interesting clues as to the existence of possible biological activity in future astrobiological missions to Mars. Consequently, we have investigated the physical and chemical properties of calcite, which could be expected on Mars because liquid water was certainly present on the surface of early Mars and carbon dioxide was abundant in its atmosphere. Calcite is interesting because on Earth this mineral is produced by abiotic processes as well as by biological activity. One may suppose that crystalline defects and trace element in the crystal lattice and the growth speed of biotic calcites must indicate a difference between them and pure abiotic calcites. We investigated twelve different terrestrial calcite samples from various origins: biotic, diagenetic and abiotic. The minerals were studied by X-ray diffraction and electron scanning microscopy to determine their mineralogical and chemical composition, and differential thermal analysis coupled to thermogravimetric analysis (DTA-TG) to determine their thermal behavior. Our results show that the thermal degradation of abiotic calcite starts at a temperature at least 40°C higher than the degradation temperature of any biotic calcite investigated. Consequently, in the case of a Martian in-situ study or in a sample return mission, the analysis of Martian minerals by DTA-TG represents a promising approach to detect evidence of past biological activity on Mars.

  3. A global deglacial negative carbon isotope excursion in speleothem calcite

    Science.gov (United States)

    Breecker, D.

    2015-12-01

    δ13C values of speleothem calcite decreased globally during the last deglaciation defining a carbon isotope excursion (CIE) despite relatively constant δ13C values of carbon in the ocean-atmosphere system. The magnitude of the CIE varied with latitude, increasing poleward from ~2‰ in the tropics to as much as 7‰ at high latitudes. This recent CIE provides an interesting comparison with CIEs observed in deep time. A substantial portion of this CIE can be explained by the increase in atmospheric pCO2 that accompanied deglaciation. The dependence of C3 plant δ13C values on atmospheric pCO2 predicts a 2‰ δ13C decrease driven by the deglacial pCO2 increase. I propose that this signal was transferred to caves and thus explains nearly 100% of the CIE magnitude observed in the tropics and no less than 30% at the highest latitudes in the compilation. An atmospheric pCO2 control on speleothem δ13C values, if real, will need to be corrected for using ice core data before δ13C records can be interpreted in a paleoclimate context. The decrease in the magnitude of the equilibrium calcite-CO2 carbon isotope fractionation factor explains a maximum of 1‰ of the CIE at the highest northern latitude in the compilation, which experienced the largest deglacial warming. Much of the residual extratropical CIE was likely driven by increasing belowground respiration rates, which were presumably pronounced at high latitudes as glacial retreat exposed fresh surfaces and/or vegetation density increased. The largest increases in belowground respiration would have therefore occurred at the highest latitudes, explaining the meridional trend. This work supports the notion that increases in atmospheric pCO2 and belowground respiration rates can result in large CIEs recorded in terrestrial carbonates, which, as previously suggested, may explain the magnitude of the PETM CIE as recorded by paleosol carbonates.

  4. Microstructural Characterization of Calcite-Based Powder Materials Prepared by Planetary Ball Milling

    Directory of Open Access Journals (Sweden)

    Wen-Tien Tsai

    2013-08-01

    Full Text Available In this work, a planetary ball milling was used to modify the surface properties of calcite-based material from waste oyster shell under the rotational speed of 200–600 rpm, grinding time of 5–180 min and sample mass of 1–10 g. The milling significantly changed the microstructural properties of the calcite-based minerals (i.e., surface area, pore volume, true density, and porosity. The surface characterization of the resulting powder should be macroporous and/or nonporous based on the nitrogen adsorption/desorption isotherms. Under the optimal conditions at the rotational speed of 400 rpm, grinding time of 30 min and sample mass of 5 g, the resulting calcite-based powder had larger specific surface area (i.e., 10.64 m2·g−1 than the starting material (i.e., 4.05 m2·g−1. This finding was also consistent with the measurement of laser-diffraction (i.e., 9.7 vs. 15.0 μm of mean diameter. In addition, the results from the scanning electron microscope (SEM observation indicated that surface roughness can be enhanced as particle size decreases as a result of particle-particle attrition. Thus, grinding the aquacultural bioresource by a high-energy ball milling can create the fine materials, which may be applied in the fields of inorganic minerals like aggregate and construction material.

  5. 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...

  6. 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...

  7. Emission polarization study on quartz and calcite.

    Science.gov (United States)

    Vincent, R. K.

    1972-01-01

    Calculation of the spectral emission polarization of quartz and calcite polished plates for observation angles of 20 and 70 deg by the substitution of complex index of refraction values for each mineral into Fresnel's equations. The emission polarization is shown to be quite wavelength-dependent, demonstrating that selected narrow or medium-width spectral bands exhibit a significantly higher percentage of polarization than a broad spectral band for these two minerals. Field measurements with a broadband infrared radiometer yield polarizations on the order of 2% for a coarse-grained granite rock and beach sand (both quartz-rich). This implies that a more sensitive detector with a selected medium-width filter may be capable of measuring emission polarization accurately enough to make this parameter useful as a remote sensing tool for discrimination among rocks on the basis of texture.

  8. Search For Past Life On Mars: Physical And Chemical Characterization Of Calcite Minerals Of Biotic And Abiotic Origin

    Science.gov (United States)

    Stalport, Fabien; Coll, P.; Cabane, M.; Person, A.; Navarro-Gonzales, R.; Raulin, F.; Valay, M.; Ausset, P.; Szopa, C.; McKay, C. P.

    2006-09-01

    Several lines of evidence suggest that early Mars once had liquid water on its surface, a denser atmosphere and a mild climate. Similar environmental conditions led to the origin of life on the Earth more than 3.5 billion years ago; consequently, life might also have originated on Mars. We contend that inorganic compounds could give us interesting clues as to the existence of possible biological activity in future astrobiological missions to Mars. Consequently, we have investigated the physical and chemical properties of calcite, which could be expected on Mars because liquid water was certainly present on the surface of early Mars and carbon dioxide was abundant in its atmosphere. Calcite is interesting because on Earth this mineral is produced by abiotic processes as well as by biological activity. One may suppose that crystalline defects and trace element in the crystal lattice and the growth speed of biotic calcites must indicate a difference between them and pure abiotic calcites. We investigated twelve different terrestrial calcite samples from various origins: biotic, diagenetic and abiotic. The minerals were studied by X-ray diffraction and electron scanning microscopy to determine their mineralogical and chemical composition, and differential thermal analysis coupled to thermogravimetric analysis (DTA-TG) to determine their thermal behavior. Our results show that the thermal degradation of abiotic calcite starts at a temperature at least 40°C higher than the degradation temperature of any biotic calcite investigated. Consequently, in the case of a Martian in-situ study or in a sample return mission, the analysis of Martian minerals by DTA-TG represents a promising approach to detect evidence of past biological activity on Mars.

  9. Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field, Tarim Basin, China

    Institute of Scientific and Technical Information of China (English)

    YU BingSong; DONG HaiLiang; RUAN Zhuang

    2008-01-01

    This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are collected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chemistry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are inversely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a systematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630-3695 m), and to the CaCl2 type at the greater depth (3728-3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2+ concentration, the total inorganic carbon concentration (∑CO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2]-[Ca2+]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermediate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and

  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. 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.

  12. Role of specific amine surface configurations for grafted surfaces: implications for nanostructured CO2 adsorbents.

    Science.gov (United States)

    Shimizu, Steven; Song, Changsik; Strano, Michael

    2011-03-15

    Amine-grafted porous materials that capture CO2 from emission streams have been considered to be potential alternatives to the more energy-intensive liquid amine systems currently employed. An underappreciated fact in the uptake mechanism of these materials is that under dry, anhydrous conditions each CO2 molecule must react with two adjacent amine groups to adsorb onto the surface, which makes the configuration of amine groups on the surface critically important. Using this chemical mechanism, we developed a semiempirical adsorption isotherm equation that allows straightforward computation of the adsorption isotherm from an arbitrary surface configuration of grafted amines for honeycomb, square, and triangular lattices. The model makes use of the fact that the distribution of amines with respect to the number of nearest neighbors, referred to as the z-histogram, along with the amine loading and equilibrium constant, uniquely determine the adsorption characteristics to a very good approximation. This model was used to predict the range of uptakes possible just through surface configuration, and it was used to fit experimental data in the literature to give a meaningful equilibrium constant and show how efficiently amines were utilized. We also demonstrate how the model can be utilized to design more efficient nanostructured adsorbents and polymer-based adsorbents. Recommendations for exploiting the role of surface configuration include the use of linear instead of branched polyamines, higher amine grafting densities, the use of flexible, less bulky, long, and rotationally free amine groups, and increased silanol densities.

  13. Physical and stable-isotope evidence for formation of secondary calcite and silica in the unsaturated zone, Yucca Mountain, Nevada

    Science.gov (United States)

    Whelan, J.F.; Paces, J.B.; Peterman, Z.E.

    2002-01-01

    Calcite and silica form coatings on fracture footwalls and cavity floors in the welded tuffs at Yucca Mountain, the potential site of a high-level radioactive waste repository. These secondary mineral deposits are heterogeneously distributed in the unsaturated zone (UZ) with fewer than 10% of possible depositional sites mineralized. The paragenetic sequence, compiled from deposits throughout the UZ, consists of an early-stage assemblage of calcite??fluorite??zeolites that is frequently capped by chalcedony??quartz. Intermediate- and late-stage deposits consist largely of calcite, commonly with opal on buried growth layers or outermost crystal faces of the calcite. Coatings on steep-dipping fractures usually are thin (??? 3 mm) with low-relief outer surfaces whereas shallow-dipping fractures and lithophysal cavities typically contain thicker, more coarsely crystalline deposits characterized by unusual thin, tabular calcite blades up to several cms in length. These blades may be capped with knobby or corniced overgrowths of late-stage calcite intergrown with opal. The observed textures in the fracture and cavity deposits are consistent with deposition from films of water fingering down fracture footwalls or drawn up faces of growing crystals by surface tension and evaporated at the crystal tips. Fluid inclusion studies have shown that most early-stage and some intermediate-stage calcite formed at temperatures of 35 to 85??C. Calcite deposition during the past several million years appears to have been at temperatures < 30??C. The elevated temperatures indicated by the fluid inclusions are consistent with temperatures estimated from calcite ??18O values. Although others have interpreted the elevated temperatures as evidence of hydrothermal activity and flooding of the tuffs of the potential repository, the authors conclude that the temperatures and fluid-inclusion assemblages are consistent with deposition in a UZ environment that experienced prolonged heat input from

  14. An assessment of calcite crystal growth mechanisms based on crystal size distributions

    Science.gov (United States)

    Kile, D.E.; Eberl, D.D.; Hoch, A.R.; Reddy, M.M.

    2000-01-01

    Calcite crystal growth experiments were undertaken to test a recently proposed model that relates crystal growth mechanisms to the shapes of crystal size distributions (CSDs). According to this approach, CSDs for minerals have three basic shapes: (1) asymptotic, which is related to a crystal growth mechanism having constant-rate nucleation accompanied by surface-controlled growth; (2) lognormal, which results from decaying-rate nucleation accompanied by surface-controlled growth; and (3) a theoretical, universal, steady-state curve attributed to Ostwald ripening. In addition, there is a fourth crystal growth mechanism that does not have a specific CSD shape, but which preserves the relative shapes of previously formed CSDs. This mechanism is attributed to supply-controlled growth. All three shapes were produced experimentally in the calcite growth experiments by modifying nucleation conditions and solution concentrations. The asymptotic CSD formed when additional reactants were added stepwise to the surface of solutions that were supersaturated with respect to calcite (initial Ω = 20, where Ω = 1 represents saturation), thereby leading to the continuous nucleation and growth of calcite crystals. Lognormal CSDs resulted when reactants were added continuously below the solution surface, via a submerged tube, to similarly supersaturated solutions (initial Ω = 22 to 41), thereby leading to a single nucleation event followed by surface-controlled growth. The Ostwald CSD resulted when concentrated reactants were rapidly mixed, leading initially to high levels of supersaturation (Ω >100), and to the formation and subsequent dissolution of very small nuclei, thereby yielding CSDs having small crystal size variances. The three CSD shapes likely were produced early in the crystallization process, in the nanometer crystal size range, and preserved during subsequent growth. Preservation of the relative shapes of the CSDs indicates that a supply-controlled growth mechanism

  15. Inducing Changes in Surface Topography of Copper Thin Films: Implications for Chemical Mechanical Polishing

    Science.gov (United States)

    Smith, C. L.; Mitchell, E. J. R.; Koeck, D. C.; Galloway, H. C.

    2000-10-01

    We have investigated the effects of pH and corrosion inhibitors on the surface of Cu films when exposed and polished in H_2O2 based slurries. Acetic Acid was used to buffer H_2O2 into the acidic range necessary to keep the corrosion inhibitor, benzotriazole (BTA) in solution. Surface characteristics were examined using atomic force microscopy and profilometry. Some conditions cause dramatic changes in the surface topography of the Cu films. The original small "grains" that give the film a uniform roughness, disappear and leave large crystalline appearing structures with terrace widths of up to 600 Åand heights of 200-1000 ÅWe believe these changes have strong implications for Chemical Mechanical Polishing processes used to manufacture integrated circuits and will discuss how these changes in surface topography may be occurring.

  16. Surface Reactivity in Tropical Highly Weathered Soils and Implications for Rational Soil Management

    Institute of Scientific and Technical Information of China (English)

    R. MOREAU; J. PETARD

    2004-01-01

    Highly weathered soils are distributed in the humid and wet-dry tropics, as well as in the humid subtropics. As a result of strong weathering, these soils are characterized by low activity clays, which develop variable surface charge and related specific properties. Surface reactions regarding base exchange and soil acidification, heavy metal sorption and mobility, and phosphorus sorption and availability of the tropical highly weathered soils are reviewed in this paper.Factors controlling surface reactivity towards cations and anions, including ion exchange and specific adsorption processes, are discussed with consideration on practical implications for rational management of these soils. Organic matter content and pH value are major basic factors that should be controlled through appropriate agricultural practices, in order to optimise favorable effects of colloid surface properties on soil fertility and environmental quality.

  17. Microstructural analysis of calcite-filled fractures inherited from basement structures, southern Ontario, Canada: long term instability of the craton?

    Science.gov (United States)

    Spalding, Jennifer; Schneider, David

    2016-04-01

    Intra-cratonic regions are generally characterized by tectonic stability and low seismicity. In southern Ontario, Canada, moderate levels of seismicity have been recorded over the last few decades reaching magnitudes of 5 MN, indicating that the geosphere is not as stable as predicted. The stratigraphy of the region consists of Ordovician limestone with a thickness of ~200 m that unconformably overlays the Mesoproterozoic crystalline Grenville Province. Subsequent tectonism including repeated Paleozoic orogenies and rifting along the east coast of North America has reactivated Proterozoic structures that have propagated into the overlying carbonate platform forming mesoscopic-scale brittle structures. Exposed along the shores of Lake Ontario are decameter-scale fracture zones, with a fracture spacing of 0.5 to 10 meters. The dominant fracture set trends E-W, and often forms conjugate sets with less prominent NNE-oriented fractures. More locally, an older NW-oriented fracture set is cross cut by the E-W and NNE oriented fractures. Regionally, there have been six directions of maximum horizontal stress in southern Ontario since the Precambrian, with the current orientation of maximum stress oriented ENE as a consequence of far field Atlantic ridge-push forces generated at distant plate boundaries. Calcite mineralization along fractured surfaces locally form sub-horizontal slickenside fabrics which are covered by a layer of euhedral calcite crystals, suggesting that fracture dilation (and fluid flow) occurred after fracture slip to allow the growth of calcite crystals. Due to the proximity of the carbonate units to the crystalline basement, we expect the calcitic veins to be enriched in rare earth elements and are presently conducting geochemical analyses. The calcite veins and surfaces vary from 2.5 cm to 1 mm thicknesses, often with larger calcite crystals in the center of the vein and smaller crystals at the vein boundaries, likely representing nucleation on small

  18. Chemical interactions between the present-day Martian atmosphere and surface minerals: Implications for sample return

    Science.gov (United States)

    Prinn, Ronald; Fegley, Bruce

    1988-01-01

    Thermochemical and photochemical reactions between surface minerals and present-day atmospheric constituents are predicted to produce microscopic effects on the surface of mineral grains. Relevant reactions hypothesized in the literature include conversions of silicates and volcanic glasses to clay minerals, conversion of ferrous to ferric compounds, and formation of carbonates, nitrates, and sulfates. These types of surface-atmosphere weathering of minerals, biological potential of the surface environment, and atmospheric stability in both present and past Martian epochs. It is emphasized that the product of these reactions will be observable and interpretable on the microscopic surface layers of Martian surface rocks using modern techniques with obvious implications for sample return from Mars. Macroscopic products of chemical weathering reactions in past Martian epochs are also expected in Martian surface materials. These products are expected not only as a result of reactions similar to those proceeding today but also due to aqueous reactions in past epochs in which liquid water was putatively present. It may prove very difficult or impossible, however, to determine definitively from the relic macroscopic product alone either the exact weathering process which led to its formation of the identity of its weathering parent mineral. The enormous advantages of studying the Martian chemical weathering by investigating the microscopic products of present-day chemical reactions on sample surfaces are very apparent.

  19. Fluid inclusion studies of calcite veins from Yucca Mountain, Nevada, Tuffs: Environment of formation

    Energy Technology Data Exchange (ETDEWEB)

    Roedder, E. [Harvard Univ., Cambridge, MA (United States); Whelan, J.F. [Geological Survey, Denver, CO (United States); Vaniman, D.T. [Los Alamos National Lab., NM (United States)

    1994-12-31

    Calcite vein and vug fillings at four depths (130-314m), all above the present water table in USW G-1 bore hole at Yucca Mountain, Nevada, contain primary fluid inclusions with variable vapor/liquid raitos: Most of these inclusions are either full of liquid or full of vapor. The liquid-filled inclusions show that most of the host calcite crystallized from fluids at <100{degrees}C. The vapor-filled inclusions provide evidence that a separate vapor phase was present in the fluid during crystallization. Studies of these vapor-filled inclusions on the microscope crushing stage were interpreted in an earlier paper as indicating trapping of an air-water-CO{sub 2} vapor phase at ``<100{degrees}C``. Our new studies reveal the additional presence of major methane in the vapor-filled inclusion, indicating even lower temperatures of trapping, perhaps at near-surface temperatures. They also show that the host calcite crystals grew from a flowing film of water on the walls of fractures open to the atmosphere, the vapor-filled inclusions representing bubbles that exsolved from this film onto the crystal surface.

  20. Inhibition mechanism of sodium hexametaphosphate on calcite%六偏磷酸钠对方解石的抑制机理

    Institute of Scientific and Technical Information of China (English)

    冯其明; 周清波; 张国范; 卢毅屏; 杨少燕

    2011-01-01

    The effect of sodium hexametaphosphate on the flotation of calcite and its surface properties was investigated by flotation test, IR spectroscopy, adsorptive capacity and ζ potential.The flotation result shows that the inhibition of calcite is remarkable when the sodium hexametaphosphate is used.The mechanism tests indicate that hexametaphosphate is not adsorbed too much on the surface of calcite, and the active points of adsorption on the calcite are decreased for Ca2+ on the surface of calcite taken from solid phase to liquid phase under the action of hexametaphosphate, thus calcite is inhibited.%通过浮选试验、红外光谱分析、吸附量测试、动电位测试等研究六偏磷酸钠对方解石浮选行为与表面性质的影响.浮选试验结果表明,六偏磷酸钠很好地抑制方解石的上浮.机理测试则表明,六偏磷酸钠未大量吸附在方解石表面,而是在其作用下,方解石表面的金属离子Ca2+从固相转入液相,减少方解石表面捕收剂吸附的活性点,从而实现方解石的浮选抑制.

  1. Thermoluminescence glow curve of {gamma}-irradiated calcite

    Energy Technology Data Exchange (ETDEWEB)

    Singh, S.D.; Ingotombi, S. [Manipur Univ. (India). Dept. of Physics

    1995-07-14

    The trapping parameters, namely the activation energy E, frequency factor s and b order of kinetics of the thermoluminescence (TL) peaks of calcites (brown and colourless varieties) irradiated with 4.08 kGy of {gamma}-rays, are determined using the least-squares curve-fitting technique. The electron lifetime {tau} of the peaks of calcite are calculated in order to estimate the upper limit of their utility in TL dating. (author).

  2. Selective Flotation of Calcite from Fluorite: A Novel Reagent Schedule

    Directory of Open Access Journals (Sweden)

    Zhiyong Gao

    2016-10-01

    Full Text Available Fluorite is an important strategic mineral. In general, fluorite ores will contain a certain amount of calcite gangue mineral. Thus, they need to be separated from each other. For an economic separation, a reverse flotation process is used to float calcite gangue from fluorite. However, little information on the separation is available. In this study, a novel reagent schedule using citric acid (CA as the depressant, sodium fluoride (NaF as the regulator and sulfoleic acid (SOA as the collector, was developed to separate calcite from fluorite. The results demonstrated a high selectivity for the flotation of calcite from fluorite using this new reagent schedule. The best selective separation for a single mineral and mixed binary minerals was obtained when 200 mg/L of NaF, 50 mg/L of CA, and 6 mg/L of SOA were used at pH 9. In addition, a batch flotation experiment was carried out using a run-of-mine feed material. Selective separation was achieved with 85.18% calcite removal while only 11.2% of fluorite was lost. An attempt was made to understand the effect of the new reagent schedule on the flotation of calcite. The results from both microflotation and bench scale flotation demonstrated a great potential for industrial application using this novel reagent schedule to upgrade fluorite ore.

  3. Calcite Farming at Hollow Ridge Cave: Calibrating Net Rainfall and Cave Microclimate to Dripwater and Calcite Chemical Variability

    Science.gov (United States)

    Tremaine, D. M.; Kilgore, B. P.; Froelich, P. N.

    2012-04-01

    Stable isotope (δ18O and δ13C) and trace element records in cave speleothems are often interpreted as climate changes in rainfall amount or source, cave air temperature, overlying vegetation and atmospheric pCO2. However, these records are difficult to verify without in situ calibration of changes in cave microclimate (e.g., net rainfall, interior ventilation changes) to contemporaneous variations in dripwater and speleothem chemistry. In this study at Hollow Ridge Cave (HRC) in Marianna, Florida (USA), cave dripwater, bedrock, and modern calcite (farmed in situ) were collected in conjunction with continuous cave air pCO2, temperature, barometric pressure, relative humidity, radon-222 activity, airflow velocity and direction, rainfall amount, and drip rate data [1]. We analyzed rain and dripwater δD and δ18O, dripwater Ca2+, pH, δ13C and TCO2, cave air pCO2 and δ13C, and farmed calcite δ18O and δ13C to examine the relationships among rainwater isotopic composition, cave air ventilation, cave air temperature, calcite growth rate and seasonal timing, and calcite isotopic composition. Farmed calcite δ13C decreases linearly with distance from the front entrance to the interior of the cave during all seasons, with a maximum entrance-to-interior gradient of Δδ13C = -7‰ . A whole-cave "Hendy test" at distributed contemporaneous farming sites reveals that ventilation induces a +1.9 ± 0.96‰ δ13C offset between calcite precipitated in a ventilation flow path and out of flow paths. Farmed calcite δ18O exhibits a +0.82 ± 0.24‰ offset from values predicted by both theoretical calcite-water calculations and by laboratory-grown calcite [2]. Unlike calcite δ13C, oxygen isotopes show no ventilation effects and are a function only of temperature. Combining our data with other speleothem studies, we find a new empirical relationship for cave-specific water-calcite oxygen isotope fractionation across a range of temperatures and cave environments: 1000 ln α = 16

  4. In-situ growth of calcite at Devils Hole, Nevada: Comparison of field and laboratory rates to a 500,000 year record of near-equilibrium calcite growth

    Science.gov (United States)

    Plummer, L.N.; Busenberg, E.; Riggs, A.C.

    2000-01-01

    Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7??C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34??C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of P(CO)(2), decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.

  5. Transformation of amorphous calcium carbonate to rod-like single crystal calcite via "copying" collagen template.

    Science.gov (United States)

    Xue, Zhonghui; Hu, Binbin; Dai, Shuxi; Du, Zuliang

    2015-10-01

    Collagen Langmuir films were prepared by spreading the solution of collagen over deionized water, CaCl2 solution and Ca(HCO3)2 solution. Resultant collagen Langmuir monolayers were then compressed to a lateral pressure of 10 mN/m and held there for different duration, allowing the crystallization of CaCO3. The effect of crystallization time on the phase composition and microstructure of CaCO3 was investigated. It was found that amorphous calcium carbonate (ACC) was obtained at a crystallization time of 6 h. The amorphous CaCO3 was transformed to rod-like single crystal calcite crystals at an extended crystallization time of 12 h and 24 h, via "copying" the symmetry and dimensionalities of collagen fibers. Resultant calcite crystallites were well oriented along the longitudinal axis of collagen fibers. The ordered surface structure of collagen fibers and electrostatic interactions played key roles in tuning the oriented nucleation and growth of the calcite crystallites. The mineralized collagen possessing both desired mechanical properties of collagen fiber and good biocompatibility of calcium carbonate may be assembled into an ideal biomaterial for bone implants.

  6. Nickel adsorption on chalk and calcite

    DEFF Research Database (Denmark)

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

    2014-01-01

    and chalk and pH ranging from 7.7 to 8.8, explored the influence of initial concentration and the amount and type of sorbent on Ni uptake. Adsorption increases with increased surface area and pH. A surface complexation model describes the data well. Stability constants for the Ni surface complex are log KNi...

  7. Defluoridation of drinking water by boiling with brushite and calcite.

    Science.gov (United States)

    Larsen, M J; Pearce, E I F

    2002-01-01

    Existing methods for defluoridating drinking water involve expensive high technology or are slow, inefficient and/or unhygienic. A new method is now suggested, encompassing brushite and calcite suspension followed by boiling. Our aim was to examine the efficiency of the method and the chemical reactions involved. Brushite, 0.3-0.5 g, and an equal weight of calcite were suspended in 1 litre water containing 5-20 ppm fluoride. The suspensions were boiled in an electric kettle, left to cool and the calcium salts to sediment. Solution ion concentrations were determined and sediments were examined by X-ray diffraction. In distilled water initially containing 5, 10 and 20 ppm fluoride the concentration was reduced to 0.06, 0.4 and 5.9 ppm, respectively. Using Aarhus tap water which contained 2.6 mmol/l calcium the final concentrations were 1.2, 2.5 and 7.7 ppm, respectively, and runs without calcite gave results similar to those with calcite. Without boiling the fluoride concentration remained unaltered, as did the brushite and calcite salts, despite occasional agitation by hand. All solutions were supersaturated with respect to fluorapatite and hydroxyapatite and close to saturation with respect to brushite. Boiling produced well-crystallised apatite and traces of calcite, while boiling of brushite alone left a poorly crystallised apatite. We conclude that boiling a brushite/calcite suspension rapidly converts the two salts to apatite which incorporates fluoride if present in solution, and that this process may be exploited to defluoridate drinking water.

  8. A Raman spectroscopic comparison of calcite and dolomite.

    Science.gov (United States)

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

    2014-01-03

    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.

  9. Modeling Np and Pu transport with a surface complexation model and spatially variant sorption capacities: Implications for reactive transport modeling and performance assessments of nuclear waste disposal sites

    Science.gov (United States)

    Glynn, P.D.

    2003-01-01

    One-dimensional (1D) geochemical transport modeling is used to demonstrate the effects of speciation and sorption reactions on the ground-water transport of Np and Pu, two redox-sensitive elements. Earlier 1D simulations (Reardon, 1981) considered the kinetically limited dissolution of calcite and its effect on ion-exchange reactions (involving 90Sr, Ca, Na, Mg and K), and documented the spatial variation of a 90Sr partition coefficient under both transient and steady-state chemical conditions. In contrast, the simulations presented here assume local equilibrium for all reactions, and consider sorption on constant potential, rather than constant charge, surfaces. Reardon's (1981) seminal findings on the spatial and temporal variability of partitioning (of 90Sr) are reexamined and found partially caused by his assumption of a kinetically limited reaction. In the present work, sorption is assumed the predominant retardation process controlling Pu and Np transport, and is simulated using a diffuse-double-layer-surface-complexation (DDLSC) model. Transport simulations consider the infiltration of Np- and Pu-contaminated waters into an initially uncontaminated environment, followed by the cleanup of the resultant contamination with uncontaminated water. Simulations are conducted using different spatial distributions of sorption capacities (with the same total potential sorption capacity, but with different variances and spatial correlation structures). Results obtained differ markedly from those that would be obtained in transport simulations using constant Kd, Langmuir or Freundlich sorption models. When possible, simulation results (breakthrough curves) are fitted to a constant K d advection-dispersion transport model and compared. Functional differences often are great enough that they prevent a meaningful fit of the simulation results with a constant K d (or even a Langmuir or Freundlich) model, even in the case of Np, a weakly sorbed radionuclide under the

  10. Influence of isotopic re-equilibration on speleothem and fluid inclusion isotope ratios after primary calcite precipitation

    Science.gov (United States)

    Kluge, Tobias; Haderlein, Astrid; Weißbach, Therese

    2016-04-01

    quantitative estimates of oxygen isotope exchange rates and to infer the dimension of the actively participating molecular layer at the surface of the calcite mineral. References: Mavromatis, V., Bundeleva, I.A., Shirokova, L.S., Millo, C., Pokrovsky, P.S., Benezeth, P., Ader, M., Oelkers, E.H., 2015. The continuous re-equilibration of carbon isotope compositions of hydrous Mg carbonates in the presence of cyanobacteria. Chem Geol., 404, 41-51. Oelkers, E. H., Berning, U.-N., Rinder, T., Mavromatis, V., Perez-Fernandez, A., Pogge von Strandmann, P., 2015. Rapid isotopic fractionation among minerals and fluids during dissolution, precipitation, and at equilibrium. Goldschmidt abstracts, 2318.

  11. 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]).

  12. Shell microstructure and its inheritance in the calcitic helcionellid Mackinnonia

    Directory of Open Access Journals (Sweden)

    Michael J. Vendrasco

    2015-02-01

    Full Text Available Mackinnonia davidi from the Cambrian (Series 2 of Australia has a prismatic outer shell layer and, as newly described here, a calcitic semi-nacre inner layer. The pattern is the same as in stenothecids such as Mellopegma, providing more evidence for a strong phylogenetic signal in the shell microstructure of Cambrian molluscs. In addition, calcite now appears to have been common in helcionellids and other molluscs during the early and middle Cambrian, with many species exhibiting foliated calcite. This is surprising given the dominance of aragonite in molluscs, both modern and from post-Cambrian fossil deposits with exceptional shell microstructure preservation, including localities from the Ordovician of the Cincinnati region, USA.

  13. Small scale shear zone in calcite: AMS and microstructure

    Science.gov (United States)

    Roxerová, Zuzana; Machek, Matěj; Kusbach, Vladimír; Racek, Martin; Silva, Pedro F.

    2016-04-01

    Two structural profiles across thin shear zone in calcite from quarry in Estremoz (Portugal) were studied to find a relationship between AMS and strain in natural rocks. The mesoscopic fabric is characterized by the change from the subhorizontal coarse-grained foliation towards the ~2cm-wide shear zone center with subvertical fine-grained foliation. In microstructure, the shear zone records dynamic recrystallization of calcite aggregate which resulted in development of porphyroclastic microstructure with increasing proportion of fine-grained recrystallized matrix towards the shear zone center. Two distinct crystallographic preferred orientations of calcite were recorded. One related with porphyroclasts, characterized by subvertical orientation of calcite axes and another associated with recrystallized matrix showing subhorizontal calcite axes orientation. The magnetic susceptibility ranges from -8e-6SI to 9e-6SI, with the average -4e-6SI. The majority of the rock mass is diamagnetic, corresponding well with the thermomagnetic curves, with local paramagnetic accumulations in form of thin bands. The AMS of the both profiles exhibits stable subvertical foliation bearing vertical lineation which is locally alternated by the medium-angle foliation. We interpret the AMS fabric pattern which is perpendicular to the mineral one as a type of inverse AMS fabric, due to high iron content in major part of calcite grains The magnetic and microstructural description of the shear zone is accompanied by numerical modeling of AMS based on CPO and different proportion of porphyroclasts, matrix and mica for purposes of deciphering the influence of present microstructural features on AMS.

  14. Isotopic and elemental proxies in mollusc and brachiopod calcite

    DEFF Research Database (Denmark)

    Ullmann, Clemens Vinzenz

    This thesis summarizes the findings of studies conducted at the University of Copenhagen from September 2010 to September 2013, aiming at a better understanding of the geochemical signatures in marine, biogenic calcite. Throughout the history of the Earth, the climatic conditions and the chemical...... for a meaningful interpretation of isotopic and elemental ratios in shell materials. Without this knowledge the correct interpretation of the shell composition in terms of past environments is impossible. Calcite shells of brachiopods, bivalves and belemnites were analyzed here for shell ultra...

  15. Diagenetic alteration in low-Mg calcite from macrofossils

    DEFF Research Database (Denmark)

    Ullmann, Clemens Vinzenz; Korte, Christoph

    2015-01-01

    microscopy) and chemical (trace element abundances, isotopic ratios) screening techniques used to assess the alteration degree of low-Mg calcite macrofossils and summarize the findings on diagenetic trends observed for elemental and isotopic systems in such materials. For a robust evaluation...... of the preservation state of biogenic calcite, it is advisable to combine a set of complementary techniques. Absolute limiting values of element and isotope ratios for discarding diagenetically altered materials cannot be universally applied, but should rather be evaluated on a case to case basis. The evaluation can...

  16. Rapid high temperature field test method for evaluation of geothermal calcite scale inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Asperger, R.G.

    1982-08-01

    A test method is described which allows the rapid field testing of calcite scale inhibitors in high- temperature geothermal brines. Five commercial formulations, chosen on the basis of laboratory screening tests, were tested in brines with low total dissolved solids at ca 500 F. Four were found to be effective; of these, 2 were found to be capable of removing recently deposited scale. One chemical was tested in the full-flow brine line for 6 wks. It was shown to stop a severe surface scaling problem at the well's control valve, thus proving the viability of the rapid test method. (12 refs.)

  17. Understanding global cycling of atmosphere-surface exchangeable pollutants and its implications

    Science.gov (United States)

    Selin, N. E.; Giang, A.; Song, S.; Pike-thackray, C.; Friedman, C. L.

    2014-12-01

    We combine modeling approaches with data analysis to provide quantitative constraints on the global biogeochemical cycling of pollutants such as mercury (Hg) and persistent organic pollutants (POPs). These pollutants, released by human activities, continue to cycle between land, ocean, and atmosphere surfaces, extending their effective lifetimes in the environment. Measurement data are limited for all of these substances, providing few constraints on the magnitude of surface-atmosphere fluxes and thus the timescales of their cycling. This limits our ability to trace emissions to impacts for these substances, particularly in the context of both ongoing policies and climate change. We present a suite of modeling and analysis tools, including uncertainty analysis, that can provide quantitative constraints on cycling for these data-limited problems, and we illustrate their applicability through examples of Hg and selected POPs. Specifically, we summarize recent insights from inverse modeling of mercury, polynomial chaos-based methods for PAHs. Finally, we assess how uncertainty in timescales affects the entire emissions-to-impacts pathway for atmosphere-surface exchangeable pollutants. We discuss the implications of this analysis for policies under the Stockholm and Minamata Conventions.

  18. New and revised 14C dates for Hawaiian surface lava flows: Paleomagnetic and geomagnetic implications

    Science.gov (United States)

    Pressline, N.; Trusdell, F.A.; Gubbins, David

    2009-01-01

    Radiocarbon dates have been obtained for 30 charcoal samples corresponding to 27 surface lava flows from the Mauna Loa and Kilauea volcanoes on the Island of Hawaii. The submitted charcoal was a mixture of fresh and archived material. Preparation and analysis was undertaken at the NERC Radiocarbon Laboratory in Glasgow, Scotland, and the associated SUERC Accelerator Mass Spectrometry facility. The resulting dates range from 390 years B.P. to 12,910 years B.P. with corresponding error bars an order of magnitude smaller than previously obtained using the gas-counting method. The new and revised 14C data set can aid hazard and risk assessment on the island. The data presented here also have implications for geomagnetic modelling, which at present is limited by large dating errors. Copyright 2009 by the American Geophysical Union.

  19. Surface-enhanced Raman spectroscopy at single-molecule scale and its implications in biology.

    Science.gov (United States)

    Wang, Yuling; Irudayaraj, Joseph

    2013-02-05

    Single-molecule (SM) spectroscopy has been an exciting area of research offering significant promise and hope in the field of sensor development to detect targets at ultra-low levels down to SM resolution. To the experts and developers in the field of surface-enhanced Raman spectroscopy (SERS), this has often been a challenge and a significant opportunity for exploration. Needless to say, the opportunities and excitement of this multidisciplinary area impacts span the fields of physics, chemistry and engineering, along with a significant thrust in applications constituting areas in medicine, biology, environment and agriculture among others. In this review, we will attempt to provide a quick snapshot of the basics of SM-SERS, nanostructures and devices that can enable SM Raman measurement. We will conclude with a discussion on SERS implications in biomedical sciences.

  20. Adsorption of pesticides onto quartz, calcite, kaolinite, and α-alumina

    DEFF Research Database (Denmark)

    Clausen, Liselotte; Fabricius, Ida Lykke; Madsen, L.

    2001-01-01

    The fate of pesticides in aquifers is influenced by the small but not insignificant adsorption of pesticides to mineral surfaces. Batch experiments with five pesticides and four minerals were conducted to quantify the contributions to adsorption from different mineral surfaces and compare...... 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-chloro-2-methyl phenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2-dioxide]. Specific surface area and mineral surface charge proved to be important for the adsorption of these pesticides. Detectable adsorption...

  1. An explanation for the 18O excess in Noelaerhabdaceae coccolith calcite

    Science.gov (United States)

    Hermoso, M.; Minoletti, F.; Aloisi, G.; Bonifacie, M.; McClelland, H. L. O.; Labourdette, N.; Renforth, P.; Chaduteau, C.; Rickaby, R. E. M.

    2016-09-01

    Coccoliths have dominated the sedimentary archive in the pelagic environment since the Jurassic. The biominerals produced by the coccolithophores are ideally placed to infer sea surface temperatures from their oxygen isotopic composition, as calcification in this photosynthetic algal group only occurs in the sunlit surface waters. In the present study, we dissect the isotopic mechanisms contributing to the "vital effect", which overprints the oceanic temperatures recorded in coccolith calcite. Applying the passive diffusion model of carbon acquisition by the marine phytoplankton widely used in biogeochemical and palaeoceanographic studies, our results suggest that the oxygen isotope offsets from inorganic calcite in fast dividing species Emiliania huxleyi and Gephyrocapsa oceanica originates from the legacy of assimilated 18O-rich CO2 that induces transient isotopic disequilibrium to the internal dissolved inorganic carbon (DIC) pool. The extent to which this intracellular isotopic disequilibrium is recorded in coccolith calcite (1.5 to +3‰ over a 10 to 25 °C temperature range) is set by the degree of isotopic re-equilibration between CO2 and water molecules before intracellular mineralisation. We show that the extent of re-equilibration is, in turn, set by temperature through both physiological (dynamics of the utilisation of the DIC pool) and thermodynamic (completeness of the re-equilibration of the relative 18O-rich CO2 influx) processes. At the highest temperature, less ambient aqueous CO2 is present for algal growth, and the consequence of carbon limitation is exacerbation of the oxygen isotope vital effect, obliterating the temperature signal. This culture dataset further demonstrates that the vital effect is variable for a given species/morphotype, and depends on the intricate relationship between the environment and the physiology of biomineralising algae.

  2. 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

    Energy Technology Data Exchange (ETDEWEB)

    Ferris, F. Grant; Fujita, Yoshiko; Smith, Robert W.

    2004-06-15

    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.

  3. ENVIRONMENTALMANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACEMETALS INGROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 ANDOTHER DIVALENT METALS AND RADIONUCLIDES AT ARIDWESTERN DOE SITES

    Energy Technology Data Exchange (ETDEWEB)

    Ferris, F. Grant; Fujita, Yoshiko; Smith, Robert W.; Cosgrove, Donna M.; Colwell, F. S.

    2004-06-15

    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.

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

    OpenAIRE

    Vučinić Dušica R.; Jovanović Vladimir D.; Kolonja Božo M.; Sekulić Živko T.; Mihajlović Slavica R.

    2012-01-01

    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 breaki...

  5. Mechanical properties of polyvinyl chloride mixtures with the addition of modified calcite as filler

    OpenAIRE

    Mihajlović, Slavica R.; Sekulić, Živko T.; Vučinić, Dušica R.; Jovanović, Vladimir D.; Kolonja, Božo M.

    2012-01-01

    In this study, mechanical properties of PVC mixtures (PVC, stabilizer, lubricant and 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 had better mechanical properties compared to those with the calcite modified by the dry process. Tensile and breaking s...

  6. Visualization of droplet departure on a superhydrophobic surface and implications to heat transfer enhancement during dropwise condensation

    Science.gov (United States)

    Dietz, C.; Rykaczewski, K.; Fedorov, A. G.; Joshi, Y.

    2010-07-01

    Droplet departure frequency is investigated using environmental scanning electron microscopy with implications to enhancing the rate of dropwise condensation on superhydrophobic surfaces. Superhydrophobic surfaces, formed by cupric hydroxide nanostructures, allow the condensate to depart from a surface with a tilt angle of 30° from the horizontal. The resulting decrease in drop departure size shifts the drop size distribution to smaller radii, which may enhance the heat transfer rate during dropwise condensation. The heat transfer enhancement is estimated by modifying the Rose and Le Fevre drop distribution function to account for a smaller maximum droplet size on a superhydrophobic surface.

  7. Reconstructing Cambro-Ordovician Seawater Composition using Clumped Isotope Paleothermometry on Calcitic and Phosphatic Brachiopods

    Science.gov (United States)

    Bergmann, K.; Robles, M.; Finnegan, S.; Hughes, N. C.; Eiler, J. M.; Fischer, W. W.

    2012-12-01

    A secular increase in δ18O values of marine fossils through early Phanerozoic time raises questions about the evolution of climate and the water cycle. This pattern suggests two end-member hypotheses 1) surface temperatures during early Paleozoic time were very warm, in excess of 40°C (tropical MAT), or 2) the isotopic composition of seawater increased by up to 7-8‰. It has been difficult to evaluate these hypotheses because the δ18O composition of fossils depends on both temperature and the δ18O of water. Furthermore, primary isotopic signatures can be overprinted by diagenetic processes that modify geological materials. This too could explain the decrease in δ18O values of marine fossils with age. Carbonate clumped isotope thermometry can constrain this problem by providing an independent measure of crystallization temperature and, when paired with classical δ18O paleothermometry, can determine the isotopic composition of the fluid the mineral last equilibrated with. Combined with traditional tools, this method has the potential to untangle primary isotopic signatures from diagenetic signals. We measured the isotopic ordering of CO3 groups (Δ47) substituted into the phosphate lattice of phosphatic brachiopods in Cambrian strata. Phosphatic fossils are generally less soluble than carbonates in surface and diagenetic environments, and so are hypothesized to provide a more robust record of primary growth conditions. They also provide an archive prior to the rise of thick shelled calcitic fossils during the Ordovician Radiation. Additionally, measurements of the δ18O of the CO3 groups can be compared with the δ18O of PO4 groups to test whether their mutual fractionation is consistent with primary growth and the apparent temperature recorded by carbonate clumped isotope measurements. We are constructing a phosphatic brachiopod calibration for carbonate clumped isotope thermometry, and Δ47 values of CO2 extracted from modern phosphatic brachiopods suggest

  8. 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.

  9. Climate proxies from Sr/Ca of coccolith calcite: calibrations from continuous culture of Emiliania huxleyi

    Science.gov (United States)

    Stoll, Heather M.; Rosenthal, Yair; Falkowski, Paul

    2002-03-01

    Continuous culture of the coccolithophorid Emiliania huxleyi reveals that coccolith Sr/Ca ratios depend on temperature and growth rate. At a constant temperature of 18°C, coccolith Sr/Ca ratios increased nearly 15% as growth rate increased from 0.1 to 1.5 divisions per day and calcification rate increased from 1.5 to 50 pg calcite per cell per day. When temperature increased from 7 to 26°C, Sr/Ca ratios increased by more than 25% (i.e., 1%/1°C), although the range in growth and calcification rates was the same as for experiments at constant temperature. The temperature dependence of Sr/Ca ratios in coccoliths is consistent with that observed in planktonic foraminifera and abiogenic calcites, suggesting that it is controlled by thermodynamic processes. However, the positive correlation of coccolith Sr/Ca with temperature contrasts with field studies in the equatorial Pacific, where Sr/Ca ratios are highest at the locus of maximum upwelling and productivity despite depressed temperatures. This paradox may reflect different calcification rate effects between E. huxleyi and the other species dominating assemblages in the equatorial Pacific sediments, which may be resolved by new techniques for separation of monospecific coccolith samples from sediments. Models of crystal growth indicate that kinetic effects on Sr partitioning in calcite due to surface enrichment could explain the Sr/Ca variations observed in constant temperature experiments but not the larger amplitude calcification rate effects observed in equatorial Pacific sediments. Despite the dual influence of temperature and growth rate on coccolith Sr/Ca, coccolith Sr/Ca correlates with "b," the slope of the dependence of carbon isotope fractionation in biomarkers (ɛ p) on CO 2(aq) at a range of growth rates and temperatures. Consequently, using coccolith Sr/Ca in combination with alkenone ɛ p may improve paleo-CO 2 determinations.

  10. 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

  11. Calcite/opal deposits at Yucca Mountain, Nevada: Pedogenic or hypogene?

    Energy Technology Data Exchange (ETDEWEB)

    Hill, C.A.; Schluter, C.M.; Harmon, R.S. [and others

    1994-01-01

    This study is part of the research program of the Yucca Mountain Project intended to provide the State of Nevada with a detailed assessment of the geology and geochemistry of Yucca Mountain and adjacent regions. The purpose of this paper is to consider all of the geological and geochemical data available for the calcite/opal deposits at Yucca Mountain and to ascertain whether this data favors a pedogenic or hyogene origin for these deposits. Far from being of esoteric concern, this subject is of paramount importance to the debate which rages around the suitability of Yucca Mountain as a high-level radioactive waste repository site. It is also the purpose of this paper to serve as a foundation for a lengthy feature article to be submitted for publication in 1994. In addition, a stand has been taken by the National Research Council of the National Academy of Sciences against the upwelling-water model (a vote of 17 to 0 against), and this same panel report has concluded that {open_quotes}there is no compelling evidence for the repetitive flooding of the environment by expulsion of groundwater{close_quotes} and that {open_quotes}instead, the evidence strongly supports the idea that the near-surface mineral deposits resulted from percolating rainwater, which carried soil minerals down into rock fractures{close_quotes}. Based on such information the Department of Energy has stated that it {open_quotes}finds no basis to continue to study the origin of these specific deposits{close_quotes}. This study, based upon many different independent lines of evidence, reaches the opposite conclusion and instead favors a hypogene spring-travertine origin for the controversial calcite/opal deposits at Yucca Mountain. This study recognizes a pedogenic carbonate component at Yucca Mountain, but argues that this component is distinct from, and sometimes intermixed with, the calcite/opal deposits.

  12. The evolution of 13C and 18O isotope composition of DIC in a calcite depositing film of water with isotope exchange between the DIC and a CO2 containing atmosphere, and simultaneous evaporation of the water. Implication to climate proxies from stalagmites: A theoretical model

    Science.gov (United States)

    Dreybrodt, Wolfgang; Romanov, Douchko

    2016-12-01

    The most widely applied climate proxies in speleothems are the isotope compositions of carbon and oxygen expressed by δ13C and δ18O values. However, mechanisms, which are not related to climate changes, overlay the climate signal. One is the temporal increase of both, δ13C and δ18O values by kinetic processes during precipitation of calcite. Isotope exchange between DIC in the water and the CO2 in the surrounding cave atmosphere can also change isotope composition. Here we present a theoretical model of the temporal isotope evolution of DIC in a thin water layer during precipitation of calcite and simultaneous isotope exchange with the cave atmosphere, and simultaneous evaporation of water. The exchange of oxygen isotopes in the DIC with those in the water is also considered. For drip times for Tdrip calcite, the second stems from isotope exchange with the CO2 of the cave atmosphere, and the third results from isotope exchange between oxygen in the DIC and the oxygen in the water. λ, ε are kinetic parameters, τ is the time scale of precipitation, (δeqatm -δ0) and (δeqwater -δ0) are the differences between the corresponding initial δ-value δ0 and the value δeqatm,water if DIC were in isotope equilibrium with the atmosphere or in the case of oxygen with the water, respectively. τinatm and τwater are the time scales of approach to isotope equilibrium by the exchange reactions. Ceq is the concentration of DIC in chemical equilibrium with the CO2 in the cave atmosphere and C0 is the initial concentration, when the water drips to the stalagmite. Tev is the time needed for complete evaporation of the water layer. εW is the fractionation between water vapor and fluid water. For times Tdrip > 0.2τ we find a further increase of ΔDIC(Tdrip) until a maximum is passed and a final value is reached. If (δeqatm -δ0) and (δeqwater -δ0) are both zero, exchange has no influence on the isotope composition for drip times Tdrip < 0.2τB. For carbon it is likely

  13. Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2+ concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2+]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth

  14. Constitutive Response of Microbial Induced Calcite Precipitation Cemented Sands

    Science.gov (United States)

    Feng, Kai

    In the last decade, microbial induced calcite precipitation (MICP) emerged as a novel technique for implementing soil improvement in an environmentally-friendly and economically beneficial manner. However, the mechanical behavior and constitutive response of these materials are still not fully explored by researchers. In this dissertation, the characteristics of MICP cemented sands are investigated through numerical modelling and experimental tests, including macro and micro tests under both static and dynamic loading. In the first part, the mechanical behavior of MICP cemented sands were probed using monotonic load testing and the existence of calcite precipitation was verified by scanning electron microscopy, with this behavior compared to traditionally cemented soil and naturally cemented soil. Both MICP cementation and traditional cementation were verified to be effective in the increase of stiffness and strength, and unique characteristic of MICP cemented soil was highlighted.

  15. 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.

  16. The effects of steam on the surface properties of palygorskite: Implications for palygorskite-water interactions

    Science.gov (United States)

    Kadakia, Abhy

    decreased by 40-50% after steam treatment. The reduced affinity for water and EGME may represent a reduced affinity for polar molecules in general. These results, particularly the XPS spectra and the observed large changes in rheological properties, suggest that steam altered the H + ion environment and/or concentration on palygorskite's surface. Exposing palygorskite to steam may have significant implications for its industrial applications, adversely affecting some applications and enhancing others.

  17. Inversion of calcite twin data for stress (2) : EBSD as a tool for data measurements

    Science.gov (United States)

    Parlangeau, Camille; Lacombe, Olivier; Brisset, Francois; Kohler, Eric; Daniel, Jean-Marc; Schueller, Sylvie

    2015-04-01

    Inversion of calcite twin data are known to be a powerful tool to reconstruct the past state(s) of stress in carbonate rocks of the crust, especially in fold-and-thrust belts and sedimentary basins. Twin data measurements have been for long carried out optically using a Universal-Stage. This data collection is time-consuming and suffers from limitations and bias related to measurements of twin planes oblique at low angle or parallel to the thin section, or the unambiguous evaluation of the twinned/untwinned character of collected twin data. EBSD (electron backscatter diffraction) is a well-known technique applied to characterize textures and microstructures of metals or deformed fine-grained rocks. The challenge is to define a strategy for measuring calcite-twin orientations that should be fast, without any loss of information, and which must reconcile (1) the need for a large amount of calcite twin data (3 mutually perpendicular thin sections and at least 30 crystals per thin section), (2) the spacing between EBSD spots, that should take into account (3) the small width of twin lamellae within grains deformed at low pressure and temperature and (4) the large size (usually several hundreds of microns) of twinned calcite grains used for stress analysis. To date, these multiple requirements preclude any (classical) automatic twin data acquisition but instead imply a preliminary definition of the areas of the thin section to be scanned by the EBSD spots, including grain boundaries, because the stress inversion technique requires to know for each grain the orientations of the C axis and of the 3 potential e twin planes. In order to reconcile a perfectly polished surface as required by EBSD and the recognition of grain boundaries, we adopted the double etching technique (Herwegh, 2000) to first reveal grain and twin boundaries. Then, with a SEM and a very fine coating sample, the section is scanned using secondary electrons bin; each spot of interest is visually defined

  18. Rate of radiocarbon retention onto calcite by isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Lempinen, Janne; Lehto, Jukka [Helsinki Univ. (Finland). Lab. of Radiochemistry

    2016-11-01

    Radiocarbon ({sup 14}C) is a top priority class radionuclide associated with the long-term safety of spent nuclear fuel disposal. Dissolved inorganic radiocarbon can be retained in bedrock via isotope exchange with calcite (CaCO{sub 3}) at solubility equilibrium with groundwater. In the present study, the rate of the isotope exchange process was investigated on synthetic calcite using batch experiments. Experiments were performed in solutions with a calcium concentration of 0.0002-0.1 M, including two synthetic reference groundwaters. The radiocarbon activity in the solutions decreased exponentially as a function of time, thus following first-order kinetics. The rate of isotope exchange was quantified from an exponential fit to the activity data over time. The rate of radiocarbon retention increased as a function of the calcium activity. The isotope exchange half-life was only 4.3 days at calcium ion activities over 0.01. This half-life is very much shorter than the half-life of {sup 14}C or the time scale of groundwater movements; consequently calcite can effectively retain radiocarbon from brackish and saline groundwaters.

  19. Diverse policy implications for future ozone and surface UV in a changing climate

    Science.gov (United States)

    Butler, A. H.; Daniel, J. S.; Portmann, R. W.; Ravishankara, A. R.; Young, P. J.; Fahey, D. W.; Rosenlof, K. H.

    2016-06-01

    Due to the success of the Montreal Protocol in limiting emissions of ozone-depleting substances, concentrations of atmospheric carbon dioxide, nitrous oxide, and methane will control the evolution of total column and stratospheric ozone by the latter half of the 21st century. As the world proceeds down the path of reducing climate forcing set forth by the 2015 Conference of the Parties to the United Nations Framework Convention on Climate Change (COP 21), a broad range of ozone changes are possible depending on future policies enacted. While decreases in tropical stratospheric ozone will likely persist regardless of the future emissions scenario, extratropical ozone could either remain weakly depleted or even increase well above historical levels, with diverse implication for ultraviolet (UV) radiation. The ozone layer’s dependence on future emissions of these gases creates a complex policy decision space for protecting humans and ecosystems, which includes unexpected options such as accepting nitrous oxide emissions in order to maintain historical column ozone and surface UV levels.

  20. 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.

  1. Pyrite Formation in Organic-rich Clay, Calcitic and Coal-Forming Environments

    Institute of Scientific and Technical Information of China (English)

    Gordana DEVI(C); Petar PFENDT; Branimir JOVAN(C)I(C)EVI(C); Zoran POPOVIC

    2006-01-01

    The early diagenetic characteristics of pyrite formation processes in a Miocene freshwater sequence of mixed sediments (coal fragments in clays, sandstones or shales) alternating with continuous brown coal layers was investigated. Based on abundant minerals, the following main sedimentary environments were distinguished: the illite-montmorillonitic (I-M), calcitic (Ct) and coal-forming environment (CL). For these hydrogeochemically differing environments the effects of limiting factors on the pyrite formation process (availability of sulphate and Fe, amount of organic matter and participation of organic sulphur) were assessed by correlation analysis. Significant differences in the effects of these limiting factors in the particular environments were observed. These differences were explained taking in account the different oxidative activity, Fe-complex and surface complex forming properties of hnmic substances in dependence of pH of environment and the abundance of sorptionally active clay minerals. In environments having a relatively low pH and containing clay minerals (I-Mand CL-environments) the oxidative activity of humic substances (Hs) on pyrite precursors was greatly prevented however pyrite formation depended on reactive Fe availability as the consequence of complex formation. On the contrary, in environments with a relatively high pH, as it was the calcitic,the oxidative activity of Hs was greatly enhanced, thus oxidizing the sulfur precursors of pyrite. The oxidation degree of organic matter was probably also a consequence of the differing activity of the humic electron-acceptors.

  2. Tuning calcite morphology and growth acceleration by a rational design of highly stable protein-mimetics

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Chunlong; Qi, Jiahui; Tao, Jinhui; Zuckermann, Ronald; De Yoreo, James J.

    2014-09-05

    In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic interactions (EI) and hydrophobic interactions (HI), with HI playing the dominant role. While either strong EI or HI inhibit growth and suppress (104) face expression, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate EI allow peptoids to weakly adsorb while moderate HI cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of (104) faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications.

  3. Tuning calcite morphology and growth acceleration by a rational design of highly stable protein-mimetics

    Science.gov (United States)

    Chen, Chun-Long; Qi, Jiahui; Tao, Jinhui; Zuckermann, Ronald N.; Deyoreo, James J.

    2014-09-01

    In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic and hydrophobic interactions, with hydrophobic interactions playing the dominant role. While either strong electrostatic or hydrophobic interactions inhibit growth and reduces expression of the {104} faces, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate electrostatic interactions allow peptoids to weakly adsorb while moderate hydrophobic interactions cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of the {104} faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications.

  4. Calcite biomineralization by bacterial isolates from the recently discovered pristine karstic herrenberg cave.

    Science.gov (United States)

    Rusznyák, Anna; Akob, Denise M; Nietzsche, Sándor; Eusterhues, Karin; Totsche, Kai Uwe; Neu, Thomas R; Frosch, Torsten; Popp, Jürgen; Keiner, Robert; Geletneky, Jörn; Katzschmann, Lutz; Schulze, Ernst-Detlef; Küsel, Kirsten

    2012-02-01

    Karstic caves represent one of the most important subterranean carbon storages on Earth and provide windows into the subsurface. The recent discovery of the Herrenberg Cave, Germany, gave us the opportunity to investigate the diversity and potential role of bacteria in carbonate mineral formation. Calcite was the only mineral observed by Raman spectroscopy to precipitate as stalactites from seepage water. Bacterial cells were found on the surface and interior of stalactites by confocal laser scanning microscopy. Proteobacteria dominated the microbial communities inhabiting stalactites, representing more than 70% of total 16S rRNA gene clones. Proteobacteria formed 22 to 34% of the detected communities in fluvial sediments, and a large fraction of these bacteria were also metabolically active. A total of 9 isolates, belonging to the genera Arthrobacter, Flavobacterium, Pseudomonas, Rhodococcus, Serratia, and Stenotrophomonas, grew on alkaline carbonate-precipitating medium. Two cultures with the most intense precipitate formation, Arthrobacter sulfonivorans and Rhodococcus globerulus, grew as aggregates, produced extracellular polymeric substances (EPS), and formed mixtures of calcite, vaterite, and monohydrocalcite. R. globerulus formed idiomorphous crystals with rhombohedral morphology, whereas A. sulfonivorans formed xenomorphous globular crystals, evidence for taxon-specific crystal morphologies. The results of this study highlighted the importance of combining various techniques in order to understand the geomicrobiology of karstic caves, but further studies are needed to determine whether the mineralogical biosignatures found in nutrient-rich media can also be found in oligotrophic caves.

  5. Biomimetic mineralization of CaCO3 on a phospholipid monolayer: from an amorphous calcium carbonate precursor to calcite via vaterite.

    Science.gov (United States)

    Xiao, Junwu; Wang, Zhining; Tang, Yecang; Yang, Shihe

    2010-04-06

    A phospholipid monolayer, approximately half the bilayer structure of a biological membrane, can be regarded as an ideal model for investigating biomineralization on biological membranes. In this work on the biomimetic mineralization of CaCO(3) under a phospholipid monolayer, we show the initial heterogeneous nucleation of amorphous calcium carbonate precursor (ACC) nanoparticles at the air-water interface, their subsequent transformation into the metastable vaterite phase instead of the most thermodynamically stable calcite phase, and the ultimate phase transformation to calcite. Furthermore, the spontaneity of the transformation from vaterite to calcite was found to be closely related to the surface tension; high surface pressure could inhibit the process, highlighting the determinant of surface energy. To understand better the mechanisms for ACC formation and the transformation from ACC to vaterite and to calcite, in situ Brewster angle microscopy (BAM), ex situ scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray diffraction analysis were employed. This work has clarified the crystallization process of calcium carbonate under phospholipid monolayers and therefore may further our understanding of the biomineralization processes induced by cellular membranes.

  6. Accessory neurovascular foramina on the lingual surface of mandible: Incidence, topography, and clinical implications

    Directory of Open Access Journals (Sweden)

    B V Murlimanju

    2012-01-01

    Full Text Available Context: It was suggested that the accessory neurovascular foramina of the mandible might be of significance in relation to the effectiveness of local anesthesia following the routine inferior alveolar nerve block. Aims: To investigate the incidence of neurovascular foramina over the lingual surface of the mandible in South Indian population. Settings and Design: The study was conducted at the department of anatomy. Materials and Methods: The study included 67 human adult dry mandibles, the exact ages and sexes of which were not known. The location and number of neurovascular foramina were topographically analyzed. Statistical Analysis Used: Descriptive statistics. Results: The foramina were observed in 64 mandibles (95.5% and were often multiple in most of the cases. They were located between the two medial incisors in 8 mandibles (1.9%, between the medial and lateral incisor in 34 mandibles (50.7%; 25-bilateral; 7-right; 2-left, between the lateral incisor and canine in 7 mandibles (10.4%; 2-bilateral; 3-right; 2-left, between the canine and first premolar in 6 cases (8.9%; 3 on each side. Foramina were also present around the genial tubercle in 56 mandibles (83.6%. Among them, 52 mandibles showed a single foramen just above the genial tubercle, 34 mandibles had foramina below the tubercles, 13 mandibles had foramina on the right side of genial tubercle and 17 were having on the left side. Conclusion: Since the anatomical details of these foramina are important to various fields of dentistry and oncology, the present investigation was undertaken. The clinical significance and implications are emphasized.

  7. The bounding-surfaces record of a barrier spit from Huangqihai Lake, North China: implications for coastal barrier boundary hierarchy

    Science.gov (United States)

    Shan, Xin; Yu, Xinghe; Clift, Peter D.; Wang, Tianyi; Tan, Chengpeng; Jin, Lina

    2016-09-01

    Ground-penetrating radar and trenching studies of a barrier spit on the north shore of Huangqihai Lake were made, that reveal important implications for the coastal washover barrier boundary hierarchy and interpretations of this depositional record. A four-fold hierarchy bounding-surface model, representing different levels of impact and genesis, is defined. Each level of the hierarchy is enclosed by a distinct kind of surface characterized by different ground-penetrating radar reflection features, sedimentary characteristics (color, grain size, sorting, rounding and sedimentary structures) and origin. We suggest that this hierarchical model can be applied to any coastal washover barrier deposits.

  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. The sensitized luminescence of manganese-activated calcite

    Science.gov (United States)

    Schulman, J.H.; Evans, L.W.; Ginther, R.J.; Murata, K.J.

    1947-01-01

    Synthetic manganese-activated calcites are shown to be practically inert to ultraviolet excitation in the range 2000-3500A, while they are luminescent under cathode-ray excitation. The incorporation of small amounts of an auxiliary impurity along with the manganese produces the strong response to ultraviolet radiation hitherto ascribed to CaCO3:Mn itself. Three such impurities have been studied: lead, thallium, and cerium. The first two induce excitation in the neighborhood of the mercury resonance line, while the cerium introduces a response principally to longer wave ultraviolet. The strong response to 2537A excitation shown by some natural calcites is likewise found to be due to the presence of lead along with the manganese, rather than to the manganese alone. The data do not warrant ascribing the longer wave-length ultraviolet-excited luminescence of all natural calcites to the action of an auxiliary impurity. The essential identity of the cathode-ray excited luminescence spectra of CaCO 3:Mn, CaCO3: (Pb+Mn), CaCO3:(Tl+Mn), and CaCO3:(Ce+Mn) with the 2537A-excited spectra of the latter three is evidence that the luminescent center in all cases is the manganese ion or the MnO6 group. It is shown that a "cascade" mechanism for the action of the auxiliary impurities, lead, thallium, and cerium, is incorrect; and that the phenomenon must be considered as a case of sensitized luminescence. Owing to the nature of cathode-ray excitation, the manganese activator can be excited by this agent even in the absence of a second impurity. For optical excitation, however, an absorption band for the ultraviolet must be established by building into the CaCO3:Mn a second impurity or "sensitizer.".

  10. Meteoric calcite cementation: diagenetic response to relative fall in sea-level and effect on porosity and permeability, Las Negras area, southeastern Spain

    Science.gov (United States)

    Li, Zhaoqi; Goldstein, Robert H.; Franseen, Evan K.

    2017-03-01

    A dolomitized Upper Miocene carbonate system in southeast Spain contains extensive upper and lower zones of calcite cementation that cut across the stratigraphy. Cement textures including isopachous and circumgranular, which are consistent with phreatic-zone cementation. Cements in the upper cemented zone are non-luminescent, whereas those in the lower cemented zone exhibit multiple bands of luminescent and non-luminescent cements. In the upper cemented zone, isotopic data show two meteoric calcite lines (MCL) with mean δ18O at - 5.1‰ and - 5.8‰ VPDB, whereas no clear MCL is defined in the lower cemented zone where mean δ18O for calcite cement is at - 6.7‰ VPDB. δ13C values in both cement zones are predominantly negative, ranging from - 10 to + 2‰ VPDB, suggestive of carbon from soil gas or decayed organics. Measurements of Tm ice in primary fluid inclusions yield a mode of 0.0 °C in both zones, indicating calcite cementation from fresh water. These two zones define the positions of two different paleo-water tables that formed during a relative sea-level fall and erosional downcutting during the Plio-Pleistocene. The upper cemented zone pre-dated the lower cemented zone on the basis of known relative sea-level history. Meteoric calcite cementation reduced porosity and permeability, but measured values are inconsistent with simple filling of open pore space. Each texture, boundstone, grainstone, packstone, wackestone, produces a different relationship between percent calcite cement and porosity/permeability. Distribution of cements may be predictable on the basis of known sea-level history, and the effect of the cementation can be incorporated into subsurface geomodels by defining surfaces of rock boundaries that separate cemented zones from uncemented zones, and applying texture-specific relationships among cementation, porosity and permeability.

  11. Study of Biomass Calcite as Fine Aggregate of Concrete

    Institute of Scientific and Technical Information of China (English)

    WANG Jian; YU Yan

    2012-01-01

    The possibility of using crushed oyster shell to partly replace the fine aggregate of concrete was evaluated. The compressive strength and slump of concrete mixture with different amount of crushed oyster shell were tested and thus the appropriate dosage was determined. Additionally, the compatibility with super plasticizer and the stability in NazSO4 solution were also discussed to prove the feasibility of oyster shell as fine aggregate of concrete. The microstructure of concrete was observed with XRD and SEM techniques. This research provides the basis for the application of waste biomass calcite.

  12. Calcite Precipitation at an Arctic Geothermal Spring Leads to Endolith Colonization and Ecological Succession

    Science.gov (United States)

    Starke, V.; Fogel, M. L.; Steele, A.

    2012-12-01

    increase with decreasing temperature across the aquatic samples, and all decrease with decreasing water content across the terrestrial samples. We attribute the trends in evenness to the balance of competition, with evenness limited in the most calcite-free environments by competition with photosynthetic eukaryotes, and in the driest endolith by competition for water and possibly nutrients. We suggest that the trends in richness result from the availability of physical niches, with availability first increasing as calcite grain surfaces become available for colonization, and later decreasing as pore volume becomes scares and potentially limiting. We suggest that microbial community structure at Troll can be understood as a consequence of ecological succession. It begins at the spring source with a few dominant phylotypes, progressing as conditions change into a more stable and even community. The succession is characterized by gradual changes in environmental parameters that produce a sequence of small, incremental and cumulative environmental disturbances. Disturbances change resource availability, and alter diversity by affecting growth, reproduction and competition, leading to successional transitions.

  13. Constraints on the vital effect in coccolithophore and dinoflagellate calcite by oxygen isotopic modification of seawater

    Science.gov (United States)

    Hermoso, Michaël; Horner, Tristan J.; Minoletti, Fabrice; Rickaby, Rosalind E. M.

    2014-09-01

    dinoflagellate Thoracosphaera heimii exhibits different behaviour for both isotopic systems, in particular with respect to its very negative carbon isotope composition, owing to coeval intra and extracellular biomineralisation in this group. In this study, we also investigate the sensitivity of 18O/16O fractionation to varying ambient oxygen isotope composition of the medium for inorganic, coccolithophore, and dinoflagellate calcite precipitated under controlled laboratory conditions. The varying responses of different taxa to increased oxygen isotope composition of the growth medium may point to a potential bias in sea surface temperature reconstructions that are based on the oxygen isotopic compositions of sedimentary calcite, especially during times of changing seawater oxygen isotopic composition. Overall, this study represents an important step towards establishing a mechanistic understanding of the “vital effect” in coccolith and dinoflagellate calcite, and provides valuable information for interpreting the geochemistry of the calcareous nannofossils in the sedimentary record, at both monospecific and interspecies levels.

  14. Unusual calcite stromatolites and pisoids from a landfill leachate collection system

    Science.gov (United States)

    Maliva, Robert G.; Missimer, Thomas M.; Leo, Kevin C.; Statom, Richard A.; Dupraz, Christophe; Lynn, Matthew; Dickson, J. A. D.

    2000-10-01

    Low-magnesium calcite stromatolites and pisoids were found to have precipitated within the leachate collection system piping of a Palm Beach County, Florida, landfill. The stromatolites and pisoids formed in an aphotic and anoxic environment that was at times greatly supersaturated with calcite. The stromatolites are composed of branching cylindrical bundles of concentrically laminated radial fibrous crystals. The pisoids consist of concentric layers of radial fibrous and microcrystalline calcite. Bacteria, likely sulfate reducing, appear to have acted as catalysts for calcite crystal nucleation, and thus the formation of the stromatolites and pisoids. The leachate system stromatolites provide a recent example of stromatolites that formed largely by cement precipitation. By acting as catalysts for calcite nucleation, bacteria may cause more rapid cementation than would have occurred under purely abiotic conditions. Rapid calcite precipitation catalyzed by bacteria has interfered with the operation of the Palm Beach County landfill leachate collection by obstructing pipes and may be an unrecognized problem at other landfill sites.

  15. Nucleation and Epitaxy-Mediated Phase Transformation of a Precursor Cadmium Carbonate Phase at the Calcite/Water Interface

    Energy Technology Data Exchange (ETDEWEB)

    Riechers, Shawn L.; Rosso, Kevin M.; Kerisit, Sebastien N.

    2017-02-24

    Mineral nucleation can be catalyzed by the presence of mineral substrates; however, the mechanisms of heterogeneous nucleation remain poorly understood. A combination of in situ time-sequenced measurements and nano-manipulation experiments were performed using atomic force microscopy (AFM) to probe the mechanisms of heteroepitaxial nucleation of otavite (CdCO3) on calcite (CaCO3) single crystals that exposed the (10-14) surface. Otavite and calcite are isostructural carbonates that display a 4% lattice mismatch, based on their (10-14) surface areas. AFM observations revealed a two-stage process in the nucleation of cadmium carbonate surface precipitates. As evidenced by changes in height, shape, growth behavior, and friction signal of the precipitates, a precursor phase was observed to initially form on the surface and subsequently undergo an epitaxy-mediated phase transformation to otavite, which then grew epitaxially. Nano-manipulation experiments, in which the applied force was increased progressively until precipitates were removed from the surface, showed that adhesion of the precursor phase to the substrate was distinctively weaker than that of the epitaxial phase, consistent with that of an amorphous phase. These findings demonstrate for the first time that heterogeneous mineral nucleation can follow a non-classical pathway like that found in homogenous aqueous conditions.

  16. 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.

  17. 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.

  18. Molecular simulation of oligomer inhibitors for calcite scale

    Institute of Scientific and Technical Information of China (English)

    Qiuyu Zhang; Hua Ren; Wenwen Wang; Junping Zhang; Hepeng Zhang

    2012-01-01

    Molecular simulation was performed to study the interaction between CaCO3 crystal and several oligomer inhibitors,by using the equilibrium morphology method to calculate the growth morphology of CaCO3 without inhibitors.The calculated morphology agreed well with SEM photographs.Then,a double-layer model was built to investigate the interaction between calcite crystal and oligomer inhibitors containing maleic anhydride (MA) and acrylic acid (AA).Interaction energy per gram of an oligomer inhibitor was introduced as a scale of inhibition efficiency of different monomers.The results indicated that,for calcite scale inhibition,acrylamide (AM) and vinyl phosphonic acid (VPA) were the most efficient monomers,while allylsulfonic acid (AS) was the poorest.Increasing proportion of AM in dimer inhibitor molecule would improve the inhibition efficiency of MA,though,for a trimer,such as MA-AA-AM,certain sequence of monomers in the inhibitor molecule was necessary besides higher proportion of AM.

  19. Quantitative roughness characterization of geological surfaces and implications for radar signature analysis

    DEFF Research Database (Denmark)

    Dierking, Wolfgang

    1999-01-01

    Stochastic surface models are useful for analyzing in situ roughness profiles and synthetic aperture radar (SAR) images of geological terrain. In this paper, two different surface models are discussed: surfaces with a stationary random roughness (conventional model) and surfaces with a power...

  20. Lithofacies palaeogeography and sedimentology Beef and cone-in-cone calcite fibrous cements associated with the end-Permian and end-Triassic mass extinctions:Reassessment of processes of formation

    Institute of Scientific and Technical Information of China (English)

    Stephen Kershaw; Li Guo

    2016-01-01

    -Eocene Thermal Maximum (PETM) event; (2) isotope signatures suggest B-CIC calcite formed under high pressure in burial at 70-120 ºC, incompatible with interpretation of formation of B-CIC calcite at the redox boundary below the ocean floor; and (3) B-CIC calcite reported in P/T boundary microbialites in one site in Iran is the only occurrence known despite extensive published studies of similar shallow marine settings, demon-strating its formation is localized to the Iran site. Based on the above evidence, our opinion is that B-CIC calcite is best explained as a later diagenetic feature unrelated to rapid Earth-surface environmental change associated with mass extinctions;thus a novel carbonate factory is highly unlikely.

  1. Implications of Surface and Bulk Properties of Abutment Implants and Their Degradation in the Health of Periodontal Tissue

    Directory of Open Access Journals (Sweden)

    Erica Dorigatti de Avila

    2013-12-01

    Full Text Available The aim of the current review was to investigate the implications of the surface and bulk properties of abutment implants and their degradation in relation to periodontal health. The success of dental implants is no longer a challenge for dentistry. The scientific literature presents several types of implants that are specific for each case. However, in cases of prosthetics components, such as abutments, further research is needed to improve the materials used to avoid bacterial adhesion and enhance contact with epithelial cells. The implanted surfaces of the abutments are composed of chemical elements that may degrade under different temperatures or be damaged by the forces applied onto them. This study showed that the resulting release of such chemical elements could cause inflammation in the periodontal tissue. At the same time, the surface characteristics can be altered, thus favoring biofilm development and further increasing the inflammation. Finally, if not treated, this inflammation can cause the loss of the implant.

  2. Yeast expressing hepatitis B virus surface antigen determinants on its surface: Implications for a possible oral vaccine

    NARCIS (Netherlands)

    Schreuder, M.P.; Deen, C.; Boersma, W.J.A.; Pouwels, P.H.; Klis, F.M.

    1996-01-01

    The two major hydrophilic regions of the hepatitis B virus surface antigen (HBsAg) have been expressed in the outer mannoprotein layer of the cell wall of 'Bakers Yeast', Saccharomyces cerevisiae, by fusing them between the yeast invertase signal sequence and the yeast α-agglutinin carboxyterminal c

  3. Making the Surface Fleet Green: The DOTMLPF, Policy, and Cost Implications of Using Biofuel in Surface Ships

    Science.gov (United States)

    2012-12-01

    1 1. A Brief History of Biofuel....................................................................1 2. Classifying Biofuels...use in the Surface Fleet. B. BACKGROUND 1. A Brief History of Biofuel Biological materials, including wood, crops, and vegetables, have been used...diatoms, green algae, golden-brown algae, prymnesiophytes, eustigmatophytes, and cyanobacteria (Department of Defense, Opportunities for DoD, 2010

  4. Effects of DNP on the cell surface properties of marine bacteria and its implication for adhesion to surfaces

    Digital Repository Service at National Institute of Oceanography (India)

    Jain, A.; Nishad, K.K.; Bhosle, N.B.

    was evaluated. Interestingly, after DNP treatment there was a significant decrease in the hydrophobicity of both hydrophobic (p = 0.01) and hydrophilic (p = 0.05) cultures, whereas no significant change was observed in the cell surface charge and EPS production...

  5. Reactive uptake of ozone at simulated leaf surfaces: Implications for 'non-stomatal' ozone flux

    Science.gov (United States)

    Cape, J. Neil; Hamilton, Richard; Heal, Mathew R.

    The reaction of ozone (O 3) with α-pinene has been studied as a function of temperature and relative humidity and in the presence of wax surfaces that simulate a leaf surface. The objective was to determine whether the presence of a wax surface, in which α-pinene could dissolve and form a high surface concentration, would lead to enhanced reaction with O 3. The reaction of O 3 itself with the empty stainless steel reactor and with aluminium and wax surfaces demonstrated an apparent activation energy of around 30 kJ mol -1 for all the surfaces, similar to that observed in long-term field measurements of O 3 fluxes to vegetation. However, the absolute reaction rate was 14 times greater for aluminium foil and saturated hydrocarbon wax surfaces than for stainless steel, and a further 5 times greater for beeswax than hydrocarbon wax. There was no systematic dependence on either relative or absolute humidity for these surface reactions over the range studied (20-100% RH). Reaction of O 3 with α-pinene occurred at rates close to those predicted for the homogeneous gas-phase reaction, and was similar for both the empty reactor and in the presence of wax surfaces. The hypothesis of enhanced reaction at leaf surfaces caused by enhanced surface concentrations of α-pinene was therefore rejected. Comparison of surface decomposition reactions on different surfaces as reported in the literature with the results obtained here demonstrates that the loss of ozone at the earth's surface by decomposition to molecular oxygen (i.e. without oxidative reaction with a substrate) can account for measured 'non-stomatal' deposition velocities of a few mm s -1. In order to quantify such removal, the effective molecular surface area of the vegetation/soil canopy must be known. Such knowledge, combined with the observed temperature-dependence, provides necessary input to global-scale models of O 3 removal from the troposphere at the earth's surface.

  6. Surface-attached cells, biofilms and biocide susceptibility: implications for hospital cleaning and disinfection.

    Science.gov (United States)

    Otter, J A; Vickery, K; Walker, J T; deLancey Pulcini, E; Stoodley, P; Goldenberg, S D; Salkeld, J A G; Chewins, J; Yezli, S; Edgeworth, J D

    2015-01-01

    Microbes tend to attach to available surfaces and readily form biofilms, which is problematic in healthcare settings. Biofilms are traditionally associated with wet or damp surfaces such as indwelling medical devices and tubing on medical equipment. However, microbes can survive for extended periods in a desiccated state on dry hospital surfaces, and biofilms have recently been discovered on dry hospital surfaces. Microbes attached to surfaces and in biofilms are less susceptible to biocides, antibiotics and physical stress. Thus, surface attachment and/or biofilm formation may explain how vegetative bacteria can survive on surfaces for weeks to months (or more), interfere with attempts to recover microbes through environmental sampling, and provide a mixed bacterial population for the horizontal transfer of resistance genes. The capacity of existing detergent formulations and disinfectants to disrupt biofilms may have an important and previously unrecognized role in determining their effectiveness in the field, which should be reflected in testing standards. There is a need for further research to elucidate the nature and physiology of microbes on dry hospital surfaces, specifically the prevalence and composition of biofilms. This will inform new approaches to hospital cleaning and disinfection, including novel surfaces that reduce microbial attachment and improve microbial detachment, and methods to augment the activity of biocides against surface-attached microbes such as bacteriophages and antimicrobial peptides. Future strategies to address environmental contamination on hospital surfaces should consider the presence of microbes attached to surfaces, including biofilms.

  7. Reactive uptake of ozone at simulated leaf surfaces: implications for ‘non-stomatal’ ozone deposition.

    OpenAIRE

    Cape, J. Neil; Hamilton, Richard; Heal, Mathew R

    2009-01-01

    The reaction of ozone (O3) with alpha-pinene has been studied as a function of temperature and relative humidity and in the presence of wax surfaces that simulate a leaf surface. The objective was to determine whether the presence of a wax surface, in which alpha-pinene could dissolve and form a high surface concentration, would lead to enhanced reaction with O3. The reaction of O3 itself with the empty stainless steel reactor and with aluminium and wax surfaces demonstrated an apparent activ...

  8. 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.

  9. Incorporation of water vapor transfer in the JULES land surface model: Implications for key soil variables and land surface fluxes

    Science.gov (United States)

    Garcia Gonzalez, Raquel; Verhoef, Anne; Luigi Vidale, Pier; Braud, Isabelle

    2012-05-01

    This study focuses on the mechanisms underlying water and heat transfer in upper soil layers, and their effects on soil physical prognostic variables and the individual components of the energy balance. The skill of the JULES (Joint UK Environment Simulator) land surface model (LSM) to simulate key soil variables, such as soil moisture content and surface temperature, and fluxes such as evaporation, is investigated. The Richards equation for soil water transfer, as used in most LSMs, was updated by incorporating isothermal and thermal water vapor transfer. The model was tested for three sites representative of semiarid and temperate arid climates: the Jornada site (New Mexico, USA), Griffith site (Australia), and Audubon site (Arizona, USA). Water vapor flux was found to contribute significantly to the water and heat transfer in the upper soil layers. This was mainly due to isothermal vapor diffusion; thermal vapor flux also played a role at the Jornada site just after rainfall events. Inclusion of water vapor flux had an effect on the diurnal evolution of evaporation, soil moisture content, and surface temperature. The incorporation of additional processes, such as water vapor flux among others, into LSMs may improve the coupling between the upper soil layers and the atmosphere, which in turn could increase the reliability of weather and climate predictions.

  10. 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.

  11. Unusual micrometric calcite-aragonite interface in the abalone shell Haliotis (Mollusca, Gastropoda).

    Science.gov (United States)

    Dauphin, Yannicke; Cuif, Jean-Pierre; Castillo-Michel, Hiram; Chevallard, Corinne; Farre, Bastien; Meibom, Anders

    2014-02-01

    Species of Haliotis (abalone) show high variety in structure and mineralogy of the shell. One of the European species (Haliotis tuberculata) in particular has an unusual shell structure in which calcite and aragonite coexist at a microscale with small patches of aragonite embedded in larger calcitic zones. A detailed examination of the boundary between calcite and aragonite using analytical microscopies shows that the organic contents of calcite and aragonite differ. Moreover, changes in the chemical composition of the two minerals seem to be gradual and define a micrometric zone of transition between the two main layers. A similar transition zone has been observed between the layers in more classical and regularly structured mollusk shells. The imbrication of microscopic patches of aragonite within a calcitic zone suggests the occurrence of very fast physiological changes in these taxa.

  12. Absorption mechanism study of benzoic acid on calcite. Influence on the wettability; Etude du mecanisme d`absorption de l`acide benzoique sur la calcite. Incidence sur la mouillabilite

    Energy Technology Data Exchange (ETDEWEB)

    Legens, Ch.

    1997-12-03

    A pure carbonate rock is strongly water-wet whereas oil accumulations study shows that most of carbonate reservoirs are oil-wet or of mixed-wettability. This is one of the main difficulties to extract crude oil. This change of behavior is due to the adsorption of some crude oil compounds on the mineral surface. We have mainly studied the interactions between acid molecules by adsorption on a calcite powder in an organic phase (benzoic acid and lauric acid) and in an aqueous phase (benzoic acid and lauric sodium salt). The technics which enabled us to define and characterize adsorption are thermogravimetry infrared diffuse reflection and thermal analysis with controlled kinetic linked to a mass spectrometer. Molecular modelling calculations have completed these analysis. It has been showed that when crude oil fills the biggest pores of the reservoir rock, the aqueous film is unstable and acids adsorb via ionic bonds on mineral calcium ions. Wettability is evaluated thanks to contact angle measurements of a water droplet deposited on a compacted powder pellet. Calcite wettability changes were all the greater as hydro-carbonated chains were longer, as it confers molecule hydrophobia. It has been also investigated acid molecules diffusion from the organic to the aqueous phase which saturates the smallest pores. Molecules which are able to diffuse from the first to the second medium do not adsorb on the surface. As a consequence, carbonate rock wettability changes require a direct contact between crude oil and mineral that involves aqueous film instability. (author) 128 refs.

  13. AATSR Land Surface Temperature Product Validation Using Ground Measurements in China and Implications for SLSTR

    Science.gov (United States)

    Zhou, Ji; Zmuda, Andy; Desnos, Yves-Louis; Ma, Jin

    2016-08-01

    Land surface temperature (LST) is one of the most important parameters at the interface between the earth's surface and the atmosphere. It acts as a sensitive indicator of climate change and is an essential input parameter for land surface models. Because of the intense variability at different spatial and temporal scales, satellite remote sensing provides the sole opportunity to acquire LSTs over large regions. Validation of the LST products is an necessary step before their applications conducted by scientific community and it is essential for the developers to improve the LST products.

  14. Novel use of trypan blue in ocular surface staining: redefining implications for this vital dye

    Directory of Open Access Journals (Sweden)

    Renato Ambrósio Jr.

    2011-12-01

    Full Text Available Different applications of trypan blue (TB for intraocular surgery have been reported, with very high levels of safety and efficacy. We describe the use of TB as an alternative vital dye for staining the ocular surface to assess the integrity of superficial cell layers of the cornea and the surface environment. This facilitates the diagnosis of various ocular surface disorders, including screening for dry eye disease (DED among refractive and cataract patients. TB staining properties are different from fluorescein and both are stable in a solution, so that a double staining technique is introduced.

  15. The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

    Science.gov (United States)

    Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

    1993-01-01

    Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

  16. 7Be and 210Pb radioactivity and implications on sources of surface ozone at Mt. Waliguan

    Institute of Scientific and Technical Information of China (English)

    ZHENG Xiangdong; WANG Guojiang; TANG Jie; ZHANG Xiaochun; YANG Wei; H. N. Lee; WANG Changsheng

    2005-01-01

    Beryllium-7 (7Be) and lead-210 (210Pb) radioac- tivity in aerosols collected, from October 2002 to January 2004 at Mt. Waliguan, by the Global Atmospheric Watch (GAW) Station, Qinghai Province is presented. The data were analyzed together with simultaneously measured surface ozone concentrations. We found that short time variations of 7Be and 210Pb were linked to alternations of synoptic weather around the Mt. Waliguan region. 210Pb showed the lowest concentration in summer while 7Be showed no obvious sea- sonal changes. Relatively high 7Be and 210Pb radioactivity was observed at Mt. Waliguan when compared with the ob- servations at other mountain sites in other parts of the world. Surface ozone and 7Be showed a consistent seasonal variation. Surface ozone correlated fairly well with 7Be/210Pb ratio. This suggested that vertical transport from higher altitudes of the atmosphere has predominant effects on the budget of surface ozone at Mt. Waliguan.

  17. Adhesion energy between mica surfaces: Implications for the frictional coefficient under dry and wet conditions

    Science.gov (United States)

    Sakuma, Hiroshi

    2013-12-01

    frictional strength of faults is a critical factor that contributes to continuous fault slip and earthquake occurrence. Frictional strength can be reduced by the presence of sheet-structured clay minerals. In this study, two important factors influencing the frictional coefficient of minerals were quantitatively analyzed by a newly developed computational method based on a combination of first-principles study and thermodynamics. One factor that helps reduce the frictional coefficient is the low adhesion energy between the layers under dry conditions. Potassium ions on mica surfaces are easily exchanged with sodium ions when brought into contact with highly concentrated sodium-halide solutions. We found that the surface ion exchange with sodium ions reduces the adhesion energy, indicating that the frictional coefficient can be reduced under dry conditions. Another factor is the lubrication caused by adsorbed water films on mineral surfaces under wet conditions. Potassium and sodium ions on mica surfaces have a strong affinity for water molecules. In order to remove the adsorbed water molecules confined between mica surfaces, a differential compressive stress of the order of tens of gigapascals was necessary at room temperature. These water molecules inhibit direct contact between mineral surfaces and reduce the frictional coefficient. Our results imply that the frictional coefficient can be modified through contact with fluids depending on their salt composition. The low adhesion energy between fault-forming minerals and the presence of an adsorbed water film is a possible reason for the low frictional coefficient observed at continuous fault slip zones.

  18. Implications of Adhesion Studies for Dust Mitigation on Thermal Control Surfaces

    Science.gov (United States)

    Gaier, James R.; Berkebile, Stephen P.

    2012-01-01

    Experiments measuring the adhesion forces under ultrahigh vacuum conditions (10 (exp -10) torr) between a synthetic volcanic glass and commonly used space exploration materials have recently been described. The glass has a chemistry and surface structure typical of the lunar regolith. It was found that Van der Waals forces between the glass and common spacecraft materials was negligible. Charge transfer between the materials was induced by mechanically striking the spacecraft material pin against the glass plate. No measurable adhesion occurred when striking the highly conducting materials, however, on striking insulating dielectric materials the adhesion increased dramatically. This indicates that electrostatic forces dominate over Van der Waals forces under these conditions. The presence of small amounts of surface contaminants was found to lower adhesive forces by at least two orders of magnitude, and perhaps more. Both particle and space exploration material surfaces will be cleaned by the interaction with the solar wind and other energetic processes and stay clean because of the extremely high vacuum (10 (exp -12) torr) so the atomically clean adhesion values are probably the relevant ones for the lunar surface environment. These results are used to interpret the results of dust mitigation technology experiments utilizing textured surfaces, work function matching surfaces and brushing. They have also been used to reinterpret the results of the Apollo 14 Thermal Degradation Samples experiment.

  19. 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

  20. Variability of the temporal bone surface's topography: implications for otologic surgery

    Science.gov (United States)

    Lecoeur, Jérémy; Noble, Jack H.; Balachandran, Ramya; Labadie, Robert F.; Dawant, Benoit M.

    2012-02-01

    Otologic surgery is performed for a variety of reasons including treatment of recurrent ear infections, alleviation of dizziness, and restoration of hearing loss. A typical ear surgery consists of a tympanomastoidectomy in which both the middle ear is explored via a tympanic membrane flap and the bone behind the ear is removed via mastoidectomy to treat disease and/or provide additional access. The mastoid dissection is performed using a high-speed drill to excavate bone based on a pre-operative CT scan. Intraoperatively, the surface of the mastoid component of the temporal bone provides visual feedback allowing the surgeon to guide their dissection. Dissection begins in "safe areas" which, based on surface topography, are believed to be correlated with greatest distance from surface to vital anatomy thus decreasing the chance of injury to the brain, large blood vessels (e.g. the internal jugular vein and internal carotid artery), the inner ear, and the facial nerve. "Safe areas" have been identified based on surgical experience with no identifiable studies showing correlation of the surface with subsurface anatomy. The purpose of our study was to investigate whether such a correlation exists. Through a three-step registration process, we defined a correspondence between each of twenty five clinically-applicable temporal bone CT scans of patients and an atlas and explored displacement and angular differences of surface topography and depth of critical structures from the surface of the skull. The results of this study reflect current knowledge of osteogenesis and anatomy. Based on two features (distance and angular difference), two regions (suprahelical and posterior) of the temporal bone show the least variability between surface and subsurface anatomy.

  1. Biological implications of the hydrodynamics of swimming at or near the surface and in shallow water

    Energy Technology Data Exchange (ETDEWEB)

    Blake, R W [Department of Zoology, University of British Columbia, Vancouver, British Columbia V6T 1Z4 (Canada)], E-mail: blake@zoology.ubc.ca

    2009-03-01

    The origins and effects of wave drag at and near the surface and in shallow water are discussed in terms of the dispersive waves generated by streamlined technical bodies of revolution and by semi-aquatic and aquatic animals with a view to bearing on issues regarding the design and function of autonomous surface and underwater vehicles. A simple two-dimensional model based on energy flux, allowing assessment of drag and its associated wave amplitude, is applied to surface swimming in Lesser Scaup ducks and is in good agreement with measured values. It is argued that hydrodynamic limitations to swimming at speeds associated with the critical Froude number ({approx}0.5) and hull speed do not necessarily set biological limitations as most behaviours occur well below the hull speed. From a comparative standpoint, the need for studies on the hull displacement of different forms is emphasized. For forms in surface proximity, drag is a function of both Froude and Reynolds numbers. Whilst the depth dependence of wave drag is not particularly sensitive to Reynolds number, its magnitude is, with smaller and slower forms subject to relatively less drag augmentation than larger, faster forms that generate additional resistance due to ventilation and spray. A quasi-steady approach to the hydrodynamics of swimming in shallow water identifies substantial drag increases relative to the deeply submerged case at Froude numbers of about 0.9 that could limit the performance of semi-aquatic and aquatic animals and autonomous vehicles. A comparative assessment of fast-starting trout and upside down catfish shows that the energy losses of fast-starting fish are likely to be less for fish in surface proximity in deep water than for those in shallow water. Further work on unsteady swimming in both circumstances is encouraged. Finally, perspectives are offered as to how autonomous surface and underwater vehicles in surface proximity and shallow water could function to avoid prohibitive

  2. 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

  3. Transmission windows in Titan's lower troposphere: Implications for IR spectrometers aboard future aerial and surface missions

    Science.gov (United States)

    McDonald, George D.; Corlies, Paul M.; Wray, James J.; Hofgartner, Jason D.; Hörst, Sarah M.; Hayes, Alexander G.; Liuzzo, Lucas R.; Buffo, Jacob J.

    2015-11-01

    Titan's thick atmosphere contains a 1.5 - 5.7% methane mole fraction. Methane's possession of fundamental, overtone, and combination bands across much of the near and mid IR results in significant absorption in the atmosphere across this spectral region. The consequence is spectral windowing, such that Titan's surface can only be observed at a handful of methane transmission windows. The narrow width of these windows for observations from the top of the atmosphere (ToA) make only multispectral imaging of the surface possible. This limits the information that can be gleaned about the surface composition, which remains largely unknown. From ToA, there is effectively zero transmission at most wavelengths between the windows, so that improvements to the detectors or telescopes of IR spectrometers aboard orbital or flyby missions would not result in any appreciable widening of the windows. Only decreasing the methane column through which observations are made, with a future mission operating near or on the surface, would result in any widening of the windows. We present a new line-by-line radiative transfer model to quantify the window widths for an IR spectrometer aboard an aerial or surface mission to Titan. We take spectral line parameters from the HITRAN database (Rothmann et al. 2013) for methane and six trace gases, include N2-N2 and N2-H2 collision-induced absorptions as measured by McKellar 1989, and the haze extinction measured in situ by Huygens DISR. The number of vertical layers in the model is chosen to correspond with the high cadence of measurements of the physical conditions of Titan's atmosphere by Huygens HASI. We find that the transmission windows do not widen appreciably for an aerial mission operating at altitudes on the order of kilometers above the surface. For surface missions observing at distances of order 10 m, the windows widen considerably to encompass regions where absorptions from hydrated minerals, sulfates, and pentane and higher order

  4. Recurrent Pure Calcite Urolithiasis Confirmed by Endoscopic Removal and Infrared Spectroscopy in a Malnourished Anorectic Female

    Science.gov (United States)

    Andreassen, Kim Hovgaard; Sloth Osther, Palle Jörn

    2016-01-01

    Abstract Often when calcite is found as a component of urinary calculi, they are considered false calculi or artifacts. We present a case of true calcite urolithiasis. The stone material was removed percutaneously from a severely malnourished anorectic woman and analyzed by infrared spectroscopy (IRS). In addition, calcite urolithiasis was confirmed in several recurrent stone events by IRS. Laxative abuse with magnesium oxide was believed to be the underlying cause of stone formation, and ammonium chloride given as one weekly dose turned out to be effective for stone prevention. PMID:27579419

  5. Surface emission from neutron stars and implications for the physics of their interiors.

    Science.gov (United States)

    Ozel, Feryal

    2013-01-01

    Neutron stars are associated with diverse physical phenomena that take place in conditions characterized by ultrahigh densities as well as intense gravitational, magnetic and radiation fields. Understanding the properties and interactions of matter in these regimes remains one of the challenges in compact object astrophysics. Photons emitted from the surfaces of neutron stars provide direct probes of their structure, composition and magnetic fields. In this review, I discuss in detail the physics that governs the properties of emission from the surfaces of neutron stars and their various observational manifestations. I present the constraints on neutron star radii, core and crust composition, and magnetic field strength and topology obtained from studies of their broadband spectra, evolution of thermal luminosity, and the profiles of pulsations that originate on their surfaces.

  6. Subsurface Emission Effects in AMSR-E Measurements: Implications for Land Surface Microwave Emissivity Retrieval

    Science.gov (United States)

    Galantowicz, John F.; Moncet, Jean-Luc; Liang, Pan; Lipton, Alan E.; Uymin, Gennady; Prigent, Catherine; Grassotti, Christopher

    2011-01-01

    An analysis of land surface microwave emission time series shows that the characteristic diurnal signature associated with subsurface emission in sandy deserts carry over to arid and semi-arid region worldwide. Prior work found that diurnal variation of Special Sensor Microwave/Imager (SSM/I) brightness temperatures in deserts was small relative to International Satellite Cloud Climatology Project land surface temperature (LST) variation and that the difference varied with surface type and was largest in sand sea regions. Here we find more widespread subsurface emission effects in Advanced Microwave Scanning Radiometer-EOS (AMSR-E) measurements. The AMSR-E orbit has equator crossing times near 01:30 and 13 :30 local time, resulting in sampling when near-surface temperature gradients are likely to be large and amplifying the influence of emission depth on effective emitting temperature relative to other factors. AMSR-E measurements are also temporally coincident with Moderate Resolution Imaging Spectroradiometer (MODIS) LST measurements, eliminating time lag as a source of LST uncertainty and reducing LST errors due to undetected clouds. This paper presents monthly global emissivity and emission depth index retrievals for 2003 at 11, 19, 37, and 89 GHz from AMSR-E, MODIS, and SSM/I time series data. Retrieval model fit error, stability, self-consistency, and land surface modeling results provide evidence for the validity of the subsurface emission hypothesis and the retrieval approach. An analysis of emission depth index, emissivity, precipitation, and vegetation index seasonal trends in northern and southern Africa suggests that changes in the emission depth index may be tied to changes in land surface moisture and vegetation conditions

  7. A much warmer Earth surface for most of geologic time: implications to biotic weathering

    Science.gov (United States)

    Schwartzman, D. W.; McMenamin, M.

    1993-01-01

    The authors present two scenarios for the temperature history of Earth. One scenario is conventional, the other relies on a warmer history. Both scenarios include surface cooling determined by the evolution of the biosphere and are similar until the Proterozoic period. The warmer scenario requires a higher plant/lichen terrestrial biota to increase weathering intensity. Justification for a warmer surface includes period temperatures from the oxygen isotope record of coexisting phosphates and cherts, an upper limit of 58 degrees C from primary gypsum precipitation, and the lack of fractionation of sulfur isotopes between sulfide and sulfates in Archean sediments.

  8. Evidence for a basalt-free surface on Mercury and implications for internal heat.

    Science.gov (United States)

    Jeanloz, R; Mitchell, D L; Sprague, A L; de Pater, I

    1995-06-01

    Microwave and mid-infrared observations reveal that Mercury's surface contains less FeO + TiO2 and at least as much feldspar as the lunar highlands. The results are compatible with the high albedo (brightness) of Mercury's surface at visible wavelengths in suggesting a rock and soil composition that is devoid of basalt, the primary differentiate of terrestrial mantles. The occurrence of a basalt-free, highly differentiated crust is in accord with recent models of the planet's thermal evolution and suggests that Mercury has retained a hot interior as a result of a combination of inefficient mantle convection and minimal volcanic heat loss.

  9. Ultrasonic Observation of the Calcite-Aragonite Transition

    Science.gov (United States)

    Ahrens, T. J.; Katz, S.

    1963-01-01

    Elastic-wave velocities were measured as a function of pressure by ultrasonic pulse Interferometry in Solenhofen and Manilus limestone specimens to pressures of 27 and 38 kb. Longitudinal velocities decrease sharply from 5.3 km/sec at a mean pressure of 4 kb to a minimum of 4.8 km/sec at 8 kb. Transverse velocities decrease from 3.1 to 2.9 km/sec. At the minimum bulk and rigidity moduli are 25 and 20 per cent below their 4-kb values. A density increase of 1.7 per cent is associated with this minimum. The observed effects are attributed to the calcite-aragonite transition, and they may be due to an inherent property of the material, a component of which undergoes a polymorphic transition, the low- and high-pressure phases coexisting over a considerable pressure range. This may be an additional mechanism to account for low-velocity zones in the earth?s interior.

  10. Microbiologically Induced Calcite Precipitation Mediated by Sporosarcina pasteurii.

    Science.gov (United States)

    Bhaduri, Swayamdipta; Debnath, Nandini; Mitra, Sushanta; Liu, Yang; Kumar, Aloke

    2016-04-16

    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.

  11. 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.

  12. Calcite-forming bacteria for compressive strength improvement in mortar.

    Science.gov (United States)

    Park, Sung-Jin; Park, Yu-Mi; Chun, Woo-Young; Kim, Wha-Jung; Ghim, Sa-Youl

    2010-04-01

    Microbiological calcium carbonate precipitation (MCP) has been investigated for its ability to improve the compressive strength of concrete mortar. However, very few studies have been conducted on the use of calcite-forming bacteria (CFB) to improve compressive strength. In this study, we discovered new bacterial genera that are capable of improving the compressive strength of concrete mortar. We isolated 4 CFB from 7 environmental concrete structures. Using sequence analysis of the 16S rRNA genes, the CFB could be partially identified as Sporosarcina soli KNUC401, Bacillus massiliensis KNUC402, Arthrobacter crystallopoietes KNUC403, and Lysinibacillus fusiformis KNUC404. Crystal aggregates were apparent in the bacterial colonies grown on an agar medium. Stereomicroscopy, scanning electron microscopy, and x-ray diffraction analyses illustrated both the crystal growth and the crystalline structure of the CaCO3 crystals. We used the isolates to improve the compressive strength of concrete mortar cubes and found that KNUC403 offered the best improvement in compressive strength.

  13. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    Energy Technology Data Exchange (ETDEWEB)

    Morrison, Glenn Charles [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    In this dissertation, results are presented of laboratory investigations and mathematical modeling efforts designed to better understand the interactions of ozone with surfaces. In the laboratory, carpet and duct materials were exposed to ozone and measured ozone uptake kinetics and the ozone induced emissions of volatile organic compounds. To understand the results of the experiments, mathematical methods were developed to describe dynamic indoor aldehyde concentrations, mass transport of reactive species to smooth surfaces, the equivalent reaction probability of whole carpet due to the surface reactivity of fibers and carpet backing, and ozone aging of surfaces. Carpets, separated carpet fibers, and separated carpet backing all tended to release aldehydes when exposed to ozone. Secondary emissions were mostly n-nonanal and several other smaller aldehydes. The pattern of emissions suggested that vegetable oils may be precursors for these oxidized emissions. Several possible precursors and experiments in which linseed and tung oils were tested for their secondary emission potential were discussed. Dynamic emission rates of 2-nonenal from a residential carpet may indicate that intermediate species in the oxidation of conjugated olefins can significantly delay aldehyde emissions and act as reservoir for these compounds. The ozone induced emission rate of 2-nonenal, a very odorous compound, can result in odorous indoor concentrations for several years. Surface ozone reactivity is a key parameter in determining the flux of ozone to a surface, is parameterized by the reaction probability, which is simply the probability that an ozone molecule will be irreversibly consumed when it strikes a surface. In laboratory studies of two residential and two commercial carpets, the ozone reaction probability for carpet fibers, carpet backing and the equivalent reaction probability for whole carpet were determined. Typically reaction probability values for these materials were 10

  14. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    Energy Technology Data Exchange (ETDEWEB)

    Morrison, Glenn C.

    1999-12-01

    In this dissertation, results are presented of laboratory investigations and mathematical modeling efforts designed to better understand the interactions of ozone with surfaces. In the laboratory, carpet and duct materials were exposed to ozone and measured ozone uptake kinetics and the ozone induced emissions of volatile organic compounds. To understand the results of the experiments, mathematical methods were developed to describe dynamic indoor aldehyde concentrations, mass transport of reactive species to smooth surfaces, the equivalent reaction probability of whole carpet due to the surface reactivity of fibers and carpet backing, and ozone aging of surfaces. Carpets, separated carpet fibers, and separated carpet backing all tended to release aldehydes when exposed to ozone. Secondary emissions were mostly n-nonanal and several other smaller aldehydes. The pattern of emissions suggested that vegetable oils may be precursors for these oxidized emissions. Several possible precursors and experiments in which linseed and tung oils were tested for their secondary emission potential were discussed. Dynamic emission rates of 2-nonenal from a residential carpet may indicate that intermediate species in the oxidation of conjugated olefins can significantly delay aldehyde emissions and act as reservoir for these compounds. The ozone induced emission rate of 2-nonenal, a very odorous compound, can result in odorous indoor concentrations for several years. Surface ozone reactivity is a key parameter in determining the flux of ozone to a surface, is parameterized by the reaction probability, which is simply the probability that an ozone molecule will be irreversibly consumed when it strikes a surface. In laboratory studies of two residential and two commercial carpets, the ozone reaction probability for carpet fibers, carpet backing and the equivalent reaction probability for whole carpet were determined. Typically reaction probability values for these materials were 10

  15. Range and geophysical corrections in coastal regions: and implications for mean sea surface determination

    DEFF Research Database (Denmark)

    Andersen, Ole Baltazar; Scharroo, Remko

    2011-01-01

    The determination of sea surface height from the altimeter range measurement involves a number of corrections: those expressing the behavior of the radar pulse through the atmosphere, and those correcting for sea state and other geophysical signals. A number of these corrections need special...

  16. THE TULLY-FISHER RELATION FOR LOW SURFACE BRIGHTNESS GALAXIES - IMPLICATIONS FOR GALAXY EVOLUTION

    NARCIS (Netherlands)

    Zwaan, M.A.; VAN DER HULST, JM; DE BLOK, WJG; MCGAUGH, SS

    1995-01-01

    We present the B-band Tully-Fisher relation for low surface brightness (LSB) galaxies. These LSB galaxies follow the same Tully-Fisher relation as normal spiral galaxies. This implies that the mass-to-light ratio (M/L) of LSB galaxies is typically a factor of 2 larger than that of normal galaxies of

  17. The impact of synoptic weather on UK surface ozone and implications for premature mortality

    Science.gov (United States)

    Pope, R. J.; Butt, E. W.; Chipperfield, M. P.; Doherty, R. M.; Fenech, S.; Schmidt, A.; Arnold, S. R.; Savage, N. H.

    2016-12-01

    Air pollutants, such as ozone, have adverse impacts on human health and cause, for example, respiratory and cardiovascular problems. In the United Kingdom (UK), peak surface ozone concentrations typically occur in the spring and summer and are controlled by emission of precursor gases, tropospheric chemistry and local meteorology which can be influenced by large-scale synoptic weather regimes. In this study we composite surface and satellite observations of summer-time (April to September) ozone under different UK atmospheric circulation patterns, as defined by the Lamb weather types. Anticyclonic conditions and easterly flows are shown to significantly enhance ozone concentrations over the UK relative to summer-time average values. Anticyclonic stability and light winds aid the trapping of ozone and its precursor gases near the surface. Easterly flows (NE, E, SE) transport ozone and precursor gases from polluted regions in continental Europe (e.g. the Benelux region) to the UK. Cyclonic conditions and westerly flows, associated with unstable weather, transport ozone from the UK mainland, replacing it with clean maritime (North Atlantic) air masses. Increased cloud cover also likely decrease ozone production rates. We show that the UK Met Office regional air quality model successfully reproduces UK summer-time ozone concentrations and ozone enhancements under anticyclonic and south-easterly conditions for the summer of 2006. By using established ozone exposure-health burden metrics, anticyclonic and easterly condition enhanced surface ozone concentrations pose the greatest public health risk.

  18. Characterizing heavy metal build-up on urban road surfaces: Implication for stormwater reuse

    Energy Technology Data Exchange (ETDEWEB)

    Liu, An [Research Centre of Environmental Engineering and Management, Graduate School at Shenzhen, Tsinghua University, 518055 Shenzhen (China); Cooperative Research and Education Centre for Environmental Technology, Kyoto University–Tsinghua University, 518055 Shenzhen (China); Liu, Liang; Li, Dunzhu [Research Centre of Environmental Engineering and Management, Graduate School at Shenzhen, Tsinghua University, 518055 Shenzhen (China); Guan, Yuntao, E-mail: guanyt@tsinghua.edu.cn [Research Centre of Environmental Engineering and Management, Graduate School at Shenzhen, Tsinghua University, 518055 Shenzhen (China); School of Environment, Tsinghua University, Beijing 100084 (China)

    2015-05-15

    Stormwater reuse is increasingly popular in the worldwide. In terms of urban road stormwater, it commonly contains toxic pollutants such as heavy metals, which could undermine the reuse safety. The research study investigated heavy metal build-up characteristics on urban roads in a typical megacity of South China. The research outcomes show the high variability in heavy metal build-up loads among different urban road sites. The degree of traffic congestion and road surface roughness was found to exert a more significant influence on heavy metal build-up rather than traffic volume. Due to relatively higher heavy metal loads, stormwater from roads with more congested traffic conditions or rougher surfaces might be suitable for low-water-quality required activities while the stormwater from by-pass road sections could be appropriate for relatively high-water-quality required purposes since the stormwater could be relatively less polluted. Based on the research outcomes, a decision-making process for heavy metals based urban road stormwater reuse was proposed. The new finding highlights the importance to undertaking a “fit-for-purpose” road stormwater reuse strategy. Additionally, the research results can also contribute to enhancing stormwater reuse safety. - Highlights: • Heavy metal (HM) build-up varies with traffic and road surface conditions. • Traffic congestion and surface roughness exert a higher impact on HM build-up. • A “fit-for-purpose” strategy could suit urban road stormwater reuse.

  19. Multiscale controls on water surface roughness and implications for remote sensing of rivers

    Science.gov (United States)

    Overstreet, B. T.; Legleiter, C. J.; Harrison, L.; Pitcher, L. H.; Ryan, J.; Rennermalm, A. K.; Smith, L. C.

    2015-12-01

    Remote sensing has emerged as a viable and efficient tool for studying river systems and facilitating their rehabilitation. While many remote sensing applications utilize spectral information from the substrate and water column, light reflected from the water surface is often a significant component of the total at-sensor radiance. As water surface roughness (WSR) increases, a greater proportion of surface facets become oriented so as to reflect, rather than transmit, light. As a result, WSR exerts a primary control on the amount of surface reflected light measured by a remote sensor. WSR in rivers is a function of flow hydraulics, channel form, slope, bed roughness, and wind. While the relative influence of each of these components on WSR changes with scale, understanding these relationships could lead to methods for obtaining hydraulic information from image-derived metrics of WSR (i.e., surface reflectance). We collected field data on flow depth and velocity using an acoustic Doppler current profiler and simultaneously measured WSR using a custom built ultrasonic distance sensor on a diverse set of rivers ranging from a 15 m wide supraglacial river on the Greenland Ice Sheet to 100 m wide gravel-bed rivers in Wyoming and Oregon. Simultaneous multi- and hyperspectral image data sets indicate that image-derived surface reflectance is strongly correlated with WSR. Temporally distributed point measurements of flow depth, velocity, and WSR on the supraglacial river capture a threefold range in discharge (6 m3/s to 17 m3/s) and indicate that flow velocity is a primary control on WSR in smaller channels, even in the absence of sediment-induced bed roughness. Spatially distributed field measurements from large gravel-bed rivers suggests that spatial variability of WSR in the thalweg corresponds with geomorphic facies while WSR along the channel margins is more significantly influenced by grain size, relative submergence, and bank geometry. These findings suggest that

  20. Adhesion of Model Molecules to Metallic Surfaces, the Implications for Corrosion Protection

    Energy Technology Data Exchange (ETDEWEB)

    De Wit, J. H. W.; Van den Brand, J.; De Wit, F. M.; Mol, J. M. C. [Delf University of Technology and Netherlaands Institute for Metals Research, Delf (Netherlands)

    2008-02-15

    The majority of the described experimental results deal with relatively pure aluminium. Variations were made in the pretreatment of the aluminum substrates and an investigation was performed on the resulting changes in oxide layer composition and chemistry. Subsequently, the bonding behavior of the surfaces was investigated by using model adhesion molecules. These molecules were chosen to represent the bonding functionality of an organic polymer. They were applied onto the pretreated surfaces as a monolayer and the bonding behavior was studied using infrared reflection absorption spectroscopy. A direct and clear relation was found between the hydroxyl fraction on the oxide surfaces and the amount of molecules that subsequently bonded to the surface. Moreover, it was found that most bonds between the oxide surface and organic functional groups are not stable in the presence of water. The best performance was obtained using molecules, which are capable of chemisorption with the oxide surface. Finally, it was found that freshly prepared relatively pure aluminum substrates, which are left in air, rapidly lose their bonding capacity towards organic functional groups. This can be attributed to the adsorption of contamination and water to the oxide surface. in addition the adhesion of a typical epoxy-coated aluminum system was investigated during exposure to water at different temperatures. The coating was found to quite rapidly lose its adhesion upon exposure to water. This rapid loss of adhesion corresponds well with the data where it was demonstrated that the studied epoxy coating only bonds through physisorptive hydrogen bonding, these bonds not being stable in the presence of water. After the initial loss the adhesion of the coating was however found to recover again and even exceeded the adhesion prior to exposure. The improvement could be ascribed to the growth of a thin oxyhydroxide layer on the aluminum substrate, which forms a new, water-stable and stronger bond

  1. Ecological filtering and plant traits variation across quarry geomorphological surfaces: implication for restoration.

    Science.gov (United States)

    Gilardelli, Federica; Sgorbati, Sergio; Armiraglio, Stefano; Citterio, Sandra; Gentili, Rodolfo

    2015-05-01

    Revegetation patterns after quarry abandonment have been widely studied from several ecological points of view, but a trait-based approach is still lacking. The aim of this study was to characterise the plant species assemblages and the associated functional traits filtered on different geomorphological surfaces in abandoned limestone quarry areas: artificial cliffs, embankments, and platforms. We then verified if species with certain traits were better able to overcome the dispersal and environmental filters necessary for establishment. To this aim, we analyzed 113 vegetation plots and collected data on 25 morphological, ecological, and dispersal traits to detect species adaptaions across these man-made environments. As a case study, we investigated the extraction basin of Botticino (Lombardy, Italy), the second largest in Italy. The results obtained by SIMPER and CCA analyses showed that rockiness, stoniness, slope, elevation, and time of surfaces are the main filters that varied across quarries and affected plant assemblages at the macro-scale level. Across the three geomorphological surfaces (meso-scale) of quarries, more specific abiotic filters selecting species were found. In turn, traits differentiation according to the three main geomorphological surfaces of quarry emphasized that further filters acting at the micro-scale imply differences in dispersal mechanisms and resource availability. This work highlighted the utility to study species assemblages and environmental filters to address quarry restoration according to the type of geomorphological surface. The investigation of some traits (chorological form, life forms, seed dispersal,s and plant height) can furnish some interesting indications for practice individuating further abiotic filters acting at the micro-scale.

  2. Nickel Alloy Primary Water Bulk Surface and SCC Corrosion Film Analytical Characterization and SCC Mechanistic Implications

    Energy Technology Data Exchange (ETDEWEB)

    Morton, D.; Lewis, N.; Hanson, M.; Rice, S.; Sanders, P.

    2007-04-18

    Alloy 600 corrosion coupon tests were performed: (1) to quantify the temperature dependency of general corrosion and (2) to characterize the composition and structure of bulk surface corrosion films for comparison with ongoing primary water SCC (PWSCC) crack tip corrosion film analyses. Results suggest that the thermal activation energy of Alloy 600 corrosion is consistent with the thermal activation energy of nickel alloy PWSCC. Analytical investigations of the structure and composition of Alloy 600 bulk surface corrosion oxides revealed a duplex (inner and outer) oxide layer structure. The outer layer is discontinuous and comprised of relatively large (1 to 3 {micro}m) nickel ferrite crystals and smaller ({approx}0.1 {micro}m) chromium containing nickel ferrite crystals. The inner layer consists of a relatively continuous chromite spinel (major phase) and chromia (Cr{sub 2}O{sub 3} minor phase) which formed through non-selective oxidation. Chromia and dealloyed Alloy 600 (highly Ni enriched metal) were only observed at 337 C (640 F) and only along the boundaries of deformation induced fine grains and subcells. Specimens having deformation free surfaces exhibited continuous uniform inner chromite spinel oxide layers. Specimens with machining induced surface deformation produced non-uniform inner layer oxides (chromite spinel, Cr{sub 2}O{sub 3} and unoxidized material). PWSCC crack tip oxides, in contrast, were fine grain (no duplex structure) and consisted of both chromium rich spinels and ''NiO'' structure oxides. Generally, nickel rich oxides were more abundant under more oxidized conditions (reduced coolant hydrogen) and spinel rich crack tip oxides were favored under more reducing conditions (increased coolant hydrogen). Bulk surface corrosion film thickness did not correlate with observed SCC growth rates. These results suggest that corrosion is not the rate controlling step of PWSCC but rather that PWSCC and corrosion have a common rate

  3. Ecological Filtering and Plant Traits Variation Across Quarry Geomorphological Surfaces: Implication for Restoration

    Science.gov (United States)

    Gilardelli, Federica; Sgorbati, Sergio; Armiraglio, Stefano; Citterio, Sandra; Gentili, Rodolfo

    2015-05-01

    Revegetation patterns after quarry abandonment have been widely studied from several ecological points of view, but a trait-based approach is still lacking. The aim of this study was to characterise the plant species assemblages and the associated functional traits filtered on different geomorphological surfaces in abandoned limestone quarry areas: artificial cliffs, embankments, and platforms. We then verified if species with certain traits were better able to overcome the dispersal and environmental filters necessary for establishment. To this aim, we analyzed 113 vegetation plots and collected data on 25 morphological, ecological, and dispersal traits to detect species adaptaions across these man-made environments. As a case study, we investigated the extraction basin of Botticino (Lombardy, Italy), the second largest in Italy. The results obtained by SIMPER and CCA analyses showed that rockiness, stoniness, slope, elevation, and time of surfaces are the main filters that varied across quarries and affected plant assemblages at the macro-scale level. Across the three geomorphological surfaces (meso-scale) of quarries, more specific abiotic filters selecting species were found. In turn, traits differentiation according to the three main geomorphological surfaces of quarry emphasized that further filters acting at the micro-scale imply differences in dispersal mechanisms and resource availability. This work highlighted the utility to study species assemblages and environmental filters to address quarry restoration according to the type of geomorphological surface. The investigation of some traits (chorological form, life forms, seed dispersal,s and plant height) can furnish some interesting indications for practice individuating further abiotic filters acting at the micro-scale.

  4. Saturn's Titan: Surface change, ammonia, and implications for atmospheric and tectonic activity

    Science.gov (United States)

    Nelson, R. M.; Kamp, L. W.; Matson, D. L.; Irwin, P. G. J.; Baines, K. H.; Boryta, M. D.; Leader, F. E.; Jaumann, R.; Smythe, W. D.; Sotin, C.; Clark, R. N.; Cruikshank, D. P.; Drossart, P.; Pearl, J. C.; Hapke, B. W.; Lunine, J.; Combes, M.; Bellucci, G.; Bibring, J.-P.; Capaccioni, F.; Cerroni, P.; Coradini, A.; Formisano, V.; Filacchione, G.; Langevin, R. Y.; McCord, T. B.; Mennella, V.; Nicholson, P. D.; Sicardy, B.

    2009-02-01

    Titan is known to have a young surface. Here we present evidence from the Cassini Visual and Infrared Mapping Spectrometer that it is currently geologically active. We report that changes in the near-infrared reflectance of a 73,000 km 2 area on Titan (latitude 26° S, longitude 78° W) occurred between July 2004 and March of 2006. The reflectance of the area increased by a factor of two between July 2004 and March-April 2005; it then returned to the July 2004 level by November 2005. By late December 2005 the reflectance had surged upward again, establishing a new maximum. Thereafter, it trended downward for the next three months. Detailed spectrophotometric analyses suggest these changes happen at or very near the surface. The spectral differences between the region and its surroundings rule out changes in the distribution of the ices of reasonably expected materials such as H 2O, CO 2, and CH 4 as possible causes. Remarkably, the change is spectrally consistent with the deposition and removal of NH 3 frost over a water ice substrate. NH 3 has been proposed as a constituent of Titan's interior and has never been reported on the surface. The detection of NH 3 frost on the surface might possibly be explained by episodic effusive events occur which bring juvenile ammonia from the interior to the surface. If so, its decomposition would feed nitrogen to the atmosphere now and in the future. The lateral extent of the region exceeds that of active areas on the Earth (Hawaii) or Io (Loki).

  5. Can environmental conditions trigger cyanobacterial surfaces and following carbonate formation: implication for biomineralization and biotechnology

    Science.gov (United States)

    Paulo, C.; Dittrich, M.; Zhu, T.

    2015-12-01

    In this presentation we will give an overview what kind of the factors may trigger carbonate formations at the cell surfaces under a variety of environmental conditions. As examples, we will present the results from our recent studies on formation of calcium carbonates, dolomites and bio-cements. The extracellular polymeric substances (EPS) in the Synechococcuscell envelope are recognized key players in the nucleation of carbonates in marine and freshwater environments. Yet, little is known about a nutrient contents control over the molecular composition of Synechococcus cell envelope, and consequently, biomineralization. In the first study, we investigated how a variation of the phosphorus (P) in the growth media can lead to changes in the surface reactivity of the cells and impact their ability to form carbonates. The objective of the second study is to gain insights into the spatial distribution of cyanobacterial EPS and dolomite from different sediment layers of Khor Al-Adaid sabkha (Qatar). Here, we characterized microbial mats on molecular level in respect of organic and inorganic components using in-situ 2D Raman spectroscopy and Atomic Force Microscopy (AFM) were used. Additionally, 2D chemical maps of sediment layers documented spectral characterizations of minerals and organic matter of microbial origins at high spatial resolution. Finally, we will show the results from the experiments with auto-phototrophic cyanobacteria Gloeocapsa PCC73106, which habitat on the monument surfaces, towards its application for bio-concrete, a product of microbial carbonate precipitation. We studied the biomineralization in biofilm forming Gloeocapsa PCC73106 on the concrete surface as a pre-requirement for microbial carbonate precipitation. Biomineralization on the concrete surface by live cells and killed cells were compared with that under the abiotic condition. Our experiments allow us to conclude that environmental conditions play a significant role in the control of

  6. Soil Surface Sealing Effect on Soil Moisture at a Semiarid Hillslope: Implications for Remote Sensing Estimation

    Directory of Open Access Journals (Sweden)

    Shai Sela

    2014-08-01

    Full Text Available Robust estimation of soil moisture using microwave remote sensing depends on extensive ground sampling for calibration and validation of the data. Soil surface sealing is a frequent phenomenon in dry environments. It modulates soil moisture close to the soil surface and, thus, has the potential to affect the retrieval of soil moisture from microwave remote sensing and the validation of these data based on ground observations. We addressed this issue using a physically-based modeling approach that accounts explicitly for surface sealing at the hillslope scale. Simulated mean soil moisture at the respective layers corresponding to both the ground validation probe and the radar beam’s typical effective penetration depth were considered. A cyclic pattern was found in which, as compared to an unsealed profile, the seal layer intensifies the bias in validation during rainfall events and substantially reduces it during subsequent drying periods. The analysis of this cyclic pattern showed that, accounting for soil moisture dynamics at the soil surface, the optimal time for soil sampling following a rainfall event is a few hours in the case of an unsealed system and a few days in the case of a sealed one. Surface sealing was found to increase the temporal stability of soil moisture. In both sealed and unsealed systems, the greatest temporal stability was observed at positions with moderate slope inclination. Soil porosity was the best predictor of soil moisture temporal stability, indicating that prior knowledge regarding the soil texture distribution is crucial for the application of remote sensing validation schemes.

  7. Modelling interstellar physics and chemistry: implications for surface and solid-state processes.

    Science.gov (United States)

    Williams, David; Viti, Serena

    2013-07-13

    We discuss several types of regions in the interstellar medium of the Milky Way and other galaxies in which the chemistry appears to be influenced or dominated by surface and solid-state processes occurring on or in interstellar dust grains. For some of these processes, for example, the formation of H₂ molecules, detailed experimental and theoretical approaches have provided excellent fundamental data for incorporation into astrochemical models. In other cases, there is an astrochemical requirement for much more laboratory and computational study, and we highlight these needs in our description. Nevertheless, in spite of the limitations of the data, it is possible to infer from astrochemical modelling that surface and solid-state processes play a crucial role in astronomical chemistry from early epochs of the Universe up to the present day.

  8. Crystal fractionation in the SNC meteorites: Implications for surface units on Mars

    Science.gov (United States)

    Treiman, Allan H.

    1987-01-01

    Almost all rock types in the SNC meteorites are cumulates, products of magma differentiation by crystal fractionation (addition or removal of crystals). If the SNC meteorites are from the surface of Mars or near sub-surface, then most of the igneous units on Mars are differentiated. Basaltic units probably experienced minor to moderate differentiation, but ultrabasic units probably experienced extreme differentiation. Products of this differentiation may include Fe-rich gabbro, pyroxenite, peridotite (and thus serpentine), and possibly massive sulfides. The SNC meteorites include ten lithologies (three in EETA79001), eight of which are crystal cumulates. The other lithologies, EETA79001 A and B are subophitic basalts. The cumulate lithologies ALHA77005 and EETA79001 C were not fully described or discussed.

  9. Surface-enhanced Raman spectroscopy at single-molecule scale and its implications in biology

    OpenAIRE

    Wang, Yuling; Irudayaraj, Joseph

    2013-01-01

    Single-molecule (SM) spectroscopy has been an exciting area of research offering significant promise and hope in the field of sensor development to detect targets at ultra-low levels down to SM resolution. To the experts and developers in the field of surface-enhanced Raman spectroscopy (SERS), this has often been a challenge and a significant opportunity for exploration. Needless to say, the opportunities and excitement of this multidisciplinary area impacts span the fields of physics, chemi...

  10. Solar Wind Sputtering of Lunar Surface Materials: Role and Some Possible Implications of Potential Sputtering

    Science.gov (United States)

    Barghouty, A. F.; Adams, J. H., Jr.; Meyer, F.; Reinhold, c.

    2010-01-01

    Solar-wind induced sputtering of the lunar surface includes, in principle, both kinetic and potential sputtering. The role of the latter mechanism, however, in many focused studies has not been properly ascertained due partly to lack of data but can also be attributed to the assertion that the contribution of solar-wind heavy ions to the total sputtering is quite low due to their low number density compared to solar-wind protons. Limited laboratory measurements show marked enhancements in the sputter yields of slow-moving, highly-charged ions impacting oxides. Lunar surface sputtering yields are important as they affect, e.g., estimates of the compositional changes in the lunar surface, its erosion rate, as well as its contribution to the exosphere as well as estimates of hydrogen and water contents. Since the typical range of solar-wind ions at 1 keV/amu is comparable to the thickness of the amorphous rim found on lunar soil grains, i.e. few 10s nm, lunar simulant samples JSC-1A AGGL are specifically enhanced to have such rims in addition to the other known characteristics of the actual lunar soil particles. However, most, if not all laboratory studies of potential sputtering were carried out in single crystal targets, quite different from the rim s amorphous structure. The effect of this structural difference on the extent of potential sputtering has not, to our knowledge, been investigated to date.

  11. High School Forum: "Invitations to Enquiry": The Calcite/Acid Reaction.

    Science.gov (United States)

    Herron, J. Dudley, Ed.; Driscoll, D. R.

    1979-01-01

    Describes a high school chemistry experiment which involves the reaction between calcite and hydrochloric and sulfuric acids. This reaction can be carried out as a projected demonstration and on an individual basis. (HM)

  12. Morphological changes of calcite single crystals induced by graphene-biomolecule adducts

    Science.gov (United States)

    Calvaresi, Matteo; Di Giosia, Matteo; Ianiro, Alessandro; Valle, Francesco; Fermani, Simona; Polishchuk, Iryna; Pokroy, Boaz; Falini, Giuseppe

    2017-01-01

    Calcite has the capability to interact with a wide variety of molecules. This usually induces changes in shape and morphology of crystals. Here, this process was investigated using sheets of graphene-biomolecule adducts. They were prepared and made dispersible in water through the exfoliation of graphite by tip sonication in the presence tryptophan or N-acetyl-D-glucosamine. The crystallization of calcium carbonate in the presence of these additives was obtained by the vapor diffusion method and only calcite formed. The analysis of the microscopic observations showed that the graphene-biomolecule adducts affected shape and morphology of rhombohedral {10.4} faced calcite crystals, due to their stabilization of additional {hk.0} faces. The only presence of the biomolecule affected minimally shape and morphology of calcite crystals, highlighting the key role of the graphene sheets as 2D support for the adsorption of the biomolecules.

  13. 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.

  14. Enhancing mechanical properties of calcite by Mg substitutions: An ab initio study

    Science.gov (United States)

    Elstnerova, Pavlina; Friak, Martin; Hickel, Tilmann; Fabritius, Helge Otto; Lymperakis, Liverios; Petrov, Michal; Raabe, Dierk; Neugebauer, Joerg; Nikolov, Svetoslav; Zigler, Andreas; Hild, Sabine

    2011-03-01

    Arthropoda representing a majority of all known animal species are protected by an exoskeleton formed by their cuticle. The cuticle represents a hierarchically structured multifunctional bio-composite based on chitin and proteins. Some groups like Crustacea reinforce the load-bearing parts of their cuticle with calcite. As the calcite sometimes contains Mg it was speculated that Mg may have a stiffening impact on the mechanical properties of the cuticle. We present a theoretical parameter-free quantum-mechanical study of thermodynamic, structural and elastic properties of Mg-substituted calcite. Our results show that substituting Ca by Mg causes an almost linear decrease in the crystal volume with Mg concentration and of substituted crystals. As a consequence the calcite crystals become stiffer giving rise e.g. to substantially increased bulk moduli.

  15. Calcite dissolution along a transect in the western tropical Indian Ocean: A multiproxy approach

    Digital Repository Service at National Institute of Oceanography (India)

    Naik, S.S.; Naidu, P.D.

    Three paleocarbonate ion proxies, size index, planktonic foraminifera shell weight, and calcite crystallinity, have been employed here to a set of core top samples from the western tropical Indian Ocean in the water depth ranges from 1086 to 4730 m...

  16. The Effect of Global Change on Surface Ozone and Reactive Nitrogen Concentrations: Implications for the Biosphere

    Science.gov (United States)

    Hess, P. G.; Murazaki, K.; Emmons, L.; Lamarque, J.

    2005-12-01

    We simulated two ten year periods using the global chemical transport model MOZART-2 (Model of Ozone and Related chemical Tracers version 2): 1990-2000 and 2090-2100. In each case MOZART-2 is driven by meteorology from the National Center for Atmospheric Research (NCAR) coupled Climate Systems Model (CSM) 1.0 forced with the (SRES) A1 scenario. Profound future changes in the summertime climate over the U.S. are found including changes in temperature, water vapor and clouds and the frequency of synoptic venting of the boundary layer. Even allowing for no changes in emissions in the future, the changes in climate alone drive a significant increase in the ozone concentration over the eastern U.S. (up to 5 ppbv on average) and an increase in the persistence of pollution events. Implications of these changes on the biosphere are assessed with and without allowing for the impact of climate on biogenic emissions. Furthermore the changes in climate alone cause large changes in the partitioning of NOy, decreasing PAN by over 20% over the U.S. Coupled with changes in precipitation; this induces significant changes in the deposition of nitrogen species to the biosphere in a future climate.

  17. Geomorphic adjustment to hydrologic modifications along a meandering river: Implications for surface flooding on a floodplain

    Science.gov (United States)

    Edwards, Brandon L.; Keim, Richard F.; Johnson, Erin L.; Hupp, Cliff R.; Marre, Saraline; King, Sammy L.

    2016-09-01

    Responses of large regulated rivers to contemporary changes in base level are not well understood. We used field measurements and historical analysis of air photos and topographic maps to identify geomorphic trends of the lower White River, Arkansas, USA, in the 70 years following base-level lowering at its confluence with the Mississippi River and concurrent with flood control by dams. Incision was identified below a knickpoint area upstream of St. Charles, AR, and increases over the lowermost ~90 km of the study site to ~2 m near the confluence with the Mississippi River. Mean bankfull width increased by 30 m (21%) from 1930 to 2010. Bank widening appears to be the result of flow regulation above the incision knickpoint and concomitant with incision below the knickpoint. Hydraulic modeling indicated that geomorphic adjustments likely reduced flooding by 58% during frequent floods in the incised, lowermost floodplain affected by backwater flooding from the Mississippi River and by 22% above the knickpoint area. Dominance of backwater flooding in the incised reach indicates that incision is more important than flood control on the lower White River in altering flooding and also suggests that the Mississippi River may be the dominant control in shaping the lower floodplain. Overall, results highlight the complex geomorphic adjustment in large river-floodplain systems in response to anthropogenic modifications and their implications, including reduced river-floodplain connectivity.

  18. Conjunctive Surface and Groundwater Management in Utah. Implications for Oil Shale and Oil Sands Development

    Energy Technology Data Exchange (ETDEWEB)

    Keiter, Robert [Univ. of Utah, Salt Lake City, UT (United States); Ruple, John [Univ. of Utah, Salt Lake City, UT (United States); Tanana, Heather [Univ. of Utah, Salt Lake City, UT (United States); Holt, Rebecca [Univ. of Utah, Salt Lake City, UT (United States)

    2011-12-01

    Unconventional fuel development will require scarce water resources. In an environment characterized by scarcity, and where most water resources are fully allocated, prospective development will require minimizing water use and seeking to use water resources in the most efficient manner. Conjunctive use of surface and groundwater provides just such an opportunity. Conjunctive use includes two main practices: First, integrating surface water diversions and groundwater withdrawals to maximize efficiency and minimize impacts on other resource users and ecological processes. Second, conjunctive use includes capturing surplus or unused surface water and injecting or infiltrating that water into groundwater aquifers in order to increase recharge rates. Conjunctive management holds promise as a means of addressing some of the West's most intractable problems. Conjunctive management can firm up water supplies by more effectively capturing spring runoff and surplus water, and by integrating its use with groundwater withdrawals; surface and groundwater use can be further integrated with managed aquifer recharge projects. Such integration can maximize water storage and availability, while simultaneously minimizing evaporative loss, reservoir sedimentation, and surface use impacts. Any of these impacts, if left unresolved, could derail commercial-scale unconventional fuel development. Unconventional fuel developers could therefore benefit from incorporating conjunctive use into their development plans. Despite its advantages, conjunctive use is not a panacea. Conjunctive use means using resources in harmony to maximize and stabilize long-term supplies it does not mean maximizing the use of two separate but interrelated resources for unsustainable short-term gains and it cannot resolve all problems or provide water where no unappropriated water exists. Moreover, conjunctive use may pose risks to ecological values forgone when water that would otherwise remain in a stream

  19. The Influence of Exotic Calcite on the Mechanical Behavior of Quartz Bearing Fault Gouge

    Science.gov (United States)

    Carpenter, B. M.; Di Stefano, G.; Collettini, C.

    2014-12-01

    The interseismic recovery of frictional strength is a fundamental part of the seismic cycle. This restrengthening, and related phenomena, plays a key role in determining the stability and mode of tectonic faulting. Recent experimental data has shown that gouge mineralogy has a strong influence on the rate of frictional healing, with calcite-dominated gouges showing the highest rates. Combining these data with widespread observations of calcite as cement or veins in non-carbonate hosted faults, indicates that the presence of calcite within a fault gouge could play an important role in shallow- and mid-crustal earthquakes. We report on laboratory experiments designed to explore the mechanical behavior of quartz/calcite mixtures as a means to better understand the evolution of fault behavior in faults where carbonate materials are present. We sheared mixtures of powdered Carrara marble (>98% CaCO3) and disaggregated Ottawa sand (99.8% SiO2) at constant normal stress of 5 MPa under saturated conditions at room temperature. We performed slide-hold-slide tests, 1-3,000 seconds, and velocity stepping tests, 0.1-1000 μm/s, to measure the amount of frictional healing and velocity dependence of friction respectively. Small subsets of experiments were conducted at different boundary conditions. Preliminary results show that the presence of calcite in quartz-based fault gouge has a hardening effect, both in overall frictional strength, where the strength of our mixtures increases with increasing calcite content, and in single experiments, where mixtures with low percentages of calcite show a consistent strain-hardening trend. We also observe that the rates of frictional healing and creep relaxation increase with increasing calcite content. Finally, our results show that the addition of as little as 2.5% calcite within a fault gouge results in a 30% increase in the rate of frictional healing, with further increases in calcite content resulting in larger increases in the rate

  20. 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.

  1. 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.

  2. 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

  3. The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

    Science.gov (United States)

    Perrin, J.; Rivard, C.; Vielzeuf, D.; Laporte, D.; Fonquernie, C.; Ricolleau, A.; Cotte, M.; Floquet, N.

    2017-01-01

    Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42-) as a predominant species and a small contribution of sulfite (SO32-), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42- (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S-S), thioether (R-S-CH3), sulfoxide (SO2), sulfonate (SO2O-) and sulfate (SO42-). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

  4. The mechanical and microstructural behaviour of calcite-dolomite composites: An experimental investigation

    OpenAIRE

    Kushnir, Alexandra R. l.; Kennedy, L. A.; Misra, Santanu; Benson, Philip; White, J C

    2015-01-01

    The styles and mechanisms of deformation associated with many variably dolomitized limestone shear systems are strongly controlled by strain partitioning between dolomite and calcite. Here, we present experimental results from the deformation of four composite materials designed to address the role of dolomite on the strength of limestone. Composites were synthesized by hot isostatic pressing mixtures of dolomite (Dm) and calcite powders (% Dm: 25%-Dm, 35%-Dm, 51%-Dm, and 75%-Dm). In all comp...

  5. Sturgeon and paddlefish (Acipenseridae) sagittal otoliths are composed of the calcium carbonate polymorphs vaterite and calcite.

    Science.gov (United States)

    Pracheil, B M; Chakoumakos, B C; Feygenson, M; Whitledge, G W; Koenigs, R P; Bruch, R M

    2017-02-01

    This study sought to resolve whether sturgeon (Acipenseridae) sagittae (otoliths) contain a non-vaterite fraction and to quantify how large a non-vaterite fraction is using neutron diffraction analysis. This study found that all otoliths examined had a calcite fraction that ranged from 18 ± 6 to 36 ± 3% by mass. This calcite fraction is most probably due to biological variation during otolith formation rather than an artefact of polymorph transformation during preparation.

  6. Holocene record of precipitation seasonality from lake calcite δ18O in the central Rocky Mountains, United States

    Science.gov (United States)

    Anderson, Lesleigh

    2011-01-01

    A context for recent hydroclimatic extremes and variability is provided by a ~10 k.y. sediment carbonate oxygen isotope (??18O) record at 5-100 yr resolution from Bison Lake, 3255 m above sea level, in northwestern Colorado (United States). Winter precipitation is the primary water source for the alpine headwater lake in the Upper Colorado River Basin and lake water ??18O measurements reflect seasonal variations in precipitation ??18O. Holocene lake water ??18O variations are inferred from endogenic sedimentary calcite ??18O based on comparisons with historic watershed discharge records and tree-ring reconstructions. Drought periods (i.e., drier winters and/or a more rain-dominated seasonal precipitation balance) generally correspond with higher calcite ??18O values, and vice-versa. Early to middle Holocene ??18O values are higher, implying a rain-dominated seasonal precipitation balance. Lower, more variable ??18O values after ca. 3500 yr ago indicate a snow-dominated but more seasonally variable precipitation balance. The middle to late Holocene ??18O record corresponds with records of El Ni??o Southern Oscillation intensification that supports a teleconnection between Rocky Mountain climate and North Pacific sea-surface temperatures at decade to century time scales. ?? 2011 Geological Society of America.

  7. The grinding tip of the sea urchin tooth exhibits exquisite control over calcite crystal orientation and Mg distribution.

    Science.gov (United States)

    Ma, Yurong; Aichmayer, Barbara; Paris, Oskar; Fratzl, Peter; Meibom, Anders; Metzler, Rebecca A; Politi, Yael; Addadi, Lia; Gilbert, P U P A; Weiner, Steve

    2009-04-14

    The sea urchin tooth is a remarkable grinding tool. Even though the tooth is composed almost entirely of calcite, it is used to grind holes into a rocky substrate itself often composed of calcite. Here, we use 3 complementary high-resolution tools to probe aspects of the structure of the grinding tip: X-ray photoelectron emission spectromicroscopy (X-PEEM), X-ray microdiffraction, and NanoSIMS. We confirm that the needles and plates are aligned and show here that even the high Mg polycrystalline matrix constituents are aligned with the other 2 structural elements when imaged at 20-nm resolution. Furthermore, we show that the entire tooth is composed of 2 cooriented polycrystalline blocks that differ in their orientations by only a few degrees. A unique feature of the grinding tip is that the structural elements from each coaligned block interdigitate. This interdigitation may influence the fracture process by creating a corrugated grinding surface. We also show that the overall Mg content of the tooth structural elements increases toward the grinding tip. This probably contributes to the increasing hardness of the tooth from the periphery to the tip. Clearly the formation of the tooth, and the tooth tip in particular, is amazingly well controlled. The improved understanding of these structural features could lead to the design of better mechanical grinding and cutting tools.

  8. Implications of atmospheric conditions for analysis of surface temperature variability derived from landscape-scale thermography

    Science.gov (United States)

    Hammerle, Albin; Meier, Fred; Heinl, Michael; Egger, Angelika; Leitinger, Georg

    2016-08-01

    Thermal infrared (TIR) cameras perfectly bridge the gap between (i) on-site measurements of land surface temperature (LST) providing high temporal resolution at the cost of low spatial coverage and (ii) remotely sensed data from satellites that provide high spatial coverage at relatively low spatio-temporal resolution. While LST data from satellite (LSTsat) and airborne platforms are routinely corrected for atmospheric effects, such corrections are barely applied for LST from ground-based TIR imagery (using TIR cameras; LSTcam). We show the consequences of neglecting atmospheric effects on LSTcam of different vegetated surfaces at landscape scale. We compare LST measured from different platforms, focusing on the comparison of LST data from on-site radiometry (LSTosr) and LSTcam using a commercially available TIR camera in the region of Bozen/Bolzano (Italy). Given a digital elevation model and measured vertical air temperature profiles, we developed a multiple linear regression model to correct LSTcam data for atmospheric influences. We could show the distinct effect of atmospheric conditions and related radiative processes along the measurement path on LSTcam, proving the necessity to correct LSTcam data on landscape scale, despite their relatively low measurement distances compared to remotely sensed data. Corrected LSTcam data revealed the dampening effect of the atmosphere, especially at high temperature differences between the atmosphere and the vegetated surface. Not correcting for these effects leads to erroneous LST estimates, in particular to an underestimation of the heterogeneity in LST, both in time and space. In the most pronounced case, we found a temperature range extension of almost 10 K.

  9. Energy Crops and their Implications on Soil Carbon Sequestration, Surface Energy and Water Balance

    Science.gov (United States)

    Song, Y.; Barman, R.; Jain, A. K.

    2011-12-01

    The quest to meet growing energy demand with low greenhouse gas emissions has increased attention on the potential of existing and advanced biomass energy crops. Potential energy crops include row crops such as corn, and perennial grasses such as switchgrass. However, a massive expansion of bioenergy crops raises many questions such as: how and where to grow energy crops; and what will be the impacts of growing large scale biofuel crops on the terrestrial hydrological cycle, the surface energy budget, soil carbon sequestration and the concurrent effects on the climate system. An integrated modeling system is being developed with in the framework of a land surface model, the Integrated Science Assessment Model (ISAM), and being applied to address these questions.This framework accounts for the biophysical, physiological and biogeochemical systems governing important processes that regulate crop growth including water, energy and nutrient cycles within the soil-plant-atmosphere system. One row crop (Corn) and two energy crops (Switchgrass and Miscanthus) are studied in current framework. Dynamic phenology processes and parameters for simulating each crop have been developed using observed data from a north to south gradient of field trial sites. This study will specifically focus on the agricultural regions in the US and in Europe. The potential productivity of these three crops will be assessed in terms of carbon sequestration, surface energy and water balance and their spatial variability. This study will help to quantify the importance of various environmental aspects towards modeling bioenergy crops and to better understand the spatial and temporal dynamics of bioenergy crop yields.

  10. Implications of atmospheric conditions for analysis of surface temperature variability derived from landscape-scale thermography.

    Science.gov (United States)

    Hammerle, Albin; Meier, Fred; Heinl, Michael; Egger, Angelika; Leitinger, Georg

    2017-04-01

    Thermal infrared (TIR) cameras perfectly bridge the gap between (i) on-site measurements of land surface temperature (LST) providing high temporal resolution at the cost of low spatial coverage and (ii) remotely sensed data from satellites that provide high spatial coverage at relatively low spatio-temporal resolution. While LST data from satellite (LSTsat) and airborne platforms are routinely corrected for atmospheric effects, such corrections are barely applied for LST from ground-based TIR imagery (using TIR cameras; LSTcam). We show the consequences of neglecting atmospheric effects on LSTcam of different vegetated surfaces at landscape scale. We compare LST measured from different platforms, focusing on the comparison of LST data from on-site radiometry (LSTosr) and LSTcam using a commercially available TIR camera in the region of Bozen/Bolzano (Italy). Given a digital elevation model and measured vertical air temperature profiles, we developed a multiple linear regression model to correct LSTcam data for atmospheric influences. We could show the distinct effect of atmospheric conditions and related radiative processes along the measurement path on LSTcam, proving the necessity to correct LSTcam data on landscape scale, despite their relatively low measurement distances compared to remotely sensed data. Corrected LSTcam data revealed the dampening effect of the atmosphere, especially at high temperature differences between the atmosphere and the vegetated surface. Not correcting for these effects leads to erroneous LST estimates, in particular to an underestimation of the heterogeneity in LST, both in time and space. In the most pronounced case, we found a temperature range extension of almost 10 K.

  11. Photoluminescence Imaging of Polyfluorene Surface Structures on Semiconducting Carbon Nanotubes: Implications for Thin Film Exciton Transport.

    Science.gov (United States)

    Hartmann, Nicolai F; Pramanik, Rajib; Dowgiallo, Anne-Marie; Ihly, Rachelle; Blackburn, Jeffrey L; Doorn, Stephen K

    2016-12-27

    Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. Here, we present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. Pump-probe measurements suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. The open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.

  12. Photoluminescence Imaging of Polyfluorene Surface Structures on Semiconducting Carbon Nanotubes: Implications for Thin Film Exciton Transport

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, Nicolai F.; Pramanik, Rajib; Dowgiallo, Anne-Marie; Ihly, Rachelle; Blackburn, Jeffrey L.; Doorn, Stephen K.

    2016-12-27

    Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. Here, we present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. Pump-probe measurements suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. The open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.

  13. Spatiotemporal dynamics of surface water networks across a global biodiversity hotspot—implications for conservation

    Science.gov (United States)

    Tulbure, Mirela G.; Kininmonth, Stuart; Broich, Mark

    2014-11-01

    The concept of habitat networks represents an important tool for landscape conservation and management at regional scales. Previous studies simulated degradation of temporally fixed networks but few quantified the change in network connectivity from disintegration of key features that undergo naturally occurring spatiotemporal dynamics. This is particularly of concern for aquatic systems, which typically show high natural spatiotemporal variability. Here we focused on the Swan Coastal Plain, a bioregion that encompasses a global biodiversity hotspot in Australia with over 1500 water bodies of high biodiversity. Using graph theory, we conducted a temporal analysis of water body connectivity over 13 years of variable climate. We derived large networks of surface water bodies using Landsat data (1999-2011). We generated an ensemble of 278 potential networks at three dispersal distances approximating the maximum dispersal distance of different water dependent organisms. We assessed network connectivity through several network topology metrics and quantified the resilience of the network topology during wet and dry phases. We identified ‘stepping stone’ water bodies across time and compared our networks with theoretical network models with known properties. Results showed a highly dynamic seasonal pattern of variability in network topology metrics. A decline in connectivity over the 13 years was noted with potential negative consequences for species with limited dispersal capacity. The networks described here resemble theoretical scale-free models, also known as ‘rich get richer’ algorithm. The ‘stepping stone’ water bodies are located in the area around the Peel-Harvey Estuary, a Ramsar listed site, and some are located in a national park. Our results describe a powerful approach that can be implemented when assessing the connectivity for a particular organism with known dispersal distance. The approach of identifying the surface water bodies that act as

  14. Plot-scale field experiment of surface hydrologic processes with EOS implications

    Science.gov (United States)

    Laymon, Charles A.; Macari, Emir J.; Costes, Nicholas C.

    1992-01-01

    Plot-scale hydrologic field studies were initiated at NASA Marshall Space Flight Center to a) investigate the spatial and temporal variability of surface and subsurface hydrologic processes, particularly as affected by vegetation, and b) develop experimental techniques and associated instrumentation methodology to study hydrologic processes at increasingly large spatial scales. About 150 instruments, most of which are remotely operated, have been installed at the field site to monitor ground atmospheric conditions, precipitation, interception, soil-water status, and energy flux. This paper describes the nature of the field experiment, instrumentation and sampling rationale, and presents preliminary findings.

  15. Importance of initial buoyancy field on evolution of mantle thermal structure: Implications of surface boundary conditions

    Directory of Open Access Journals (Sweden)

    Petar Glišović

    2015-01-01

    Full Text Available Although there has been significant progress in the seismic imaging of mantle heterogeneity, the outstanding issue that remains to be resolved is the unknown distribution of mantle temperature anomalies in the distant geological past that give rise to the present-day anomalies inferred by global tomography models. To address this question, we present 3-D convection models in compressible and self-gravitating mantle initialised by different hypothetical temperature patterns. A notable feature of our forward convection modelling is the use of self-consistent coupling of the motion of surface tectonic plates to the underlying mantle flow, without imposing prescribed surface velocities (i.e., plate-like boundary condition. As an approximation for the surface mechanical conditions before plate tectonics began to operate we employ the no-slip (rigid boundary condition. A rigid boundary condition demonstrates that the initial thermally-dominated structure is preserved, and its geographical location is fixed during the evolution of mantle flow. Considering the impact of different assumed surface boundary conditions (rigid and plate-like on the evolution of thermal heterogeneity in the mantle we suggest that the intrinsic buoyancy of seven superplumes is most-likely resolved in the tomographic images of present-day mantle thermal structure. Our convection simulations with a plate-like boundary condition reveal that the evolution of an initial cold anomaly beneath the Java-Indonesian trench system yields a long-term, stable pattern of thermal heterogeneity in the lowermost mantle that resembles the present-day Large Low Shear Velocity Provinces (LLSVPs, especially below the Pacific. The evolution of subduction zones may be, however, influenced by the mantle-wide flow driven by deeply-rooted and long-lived superplumes since Archean times. These convection models also detect the intrinsic buoyancy of the Perm Anomaly that has been identified as a unique

  16. Reaction-induced fracturing in a hot pressed calcite-periclase aggregate

    Science.gov (United States)

    Kuleci, H.; Ulven, O. I.; Rybacki, E.; Wunder, B.; Abart, R.

    2017-01-01

    The chemo-mechanical feedbacks associated with hydration of periclase immersed in a calcite matrix were investigated experimentally. Dense calcite-periclase aggregates with calcite to periclase ratio of 90/10 and 95/5 by volume were prepared by hot isostatic pressing. Subsequent hydration experiments were performed in a hydrothermal apparatus at temperatures of 580-610 °C and a pressure of 200 MPa for run durations of 5-60 min. The rate of the periclase to brucite transformation was primarily controlled by the access of fluid. Where fluid was present, the reaction was too fast for the associated positive volume increase of the solids of about 100% to be accommodated by creep of the calcite matrix, and fracturing was induced. The newly formed cracks greatly enhanced the access of fluid leading to a positive feedback between hydration and fracturing. Mostly the newly formed cracks follow pre-existing grain boundaries in the calcite matrix. Comparison of experimental results with numerical 2D discrete element modelling (DEM) of crack formation revealed that the geometry of the crack pattern around a reacting particle depends on the shape of the original periclase particle, on the mechanical strength of the particle-matrix interface and on the mechanical strength and arrangement of grain boundaries in the calcite matrix in the immediate vicinity of the swelling particle.

  17. Sea urchin tooth mineralization: calcite present early in the aboral plumula.

    Science.gov (United States)

    Stock, Stuart R; Veis, Arthur; Xiao, Xianghui; Almer, Jonathan D; Dorvee, Jason R

    2012-11-01

    In both vertebrate bone, containing carbonated hydroxyapatite as the mineral phase, and in invertebrate hard tissue comprised of calcium carbonate, a popular view is that the mineral phase develops from a long-lived amorphous precursor which later transforms into crystal form. Important questions linked to this popular view are: when and where is the crystallized material formed, and is amorphous solid added subsequently to the crystalline substrate? Sea urchin teeth, in which the earliest mineral forms within isolated compartments, in a time and position dependent manner, allow direct investigation of the timing of crystallization of the calcite primary plates. Living teeth of the sea urchin Lytechinus variegatus, in their native coelomic fluid, were examined by high-energy synchrotron X-ray diffraction. The diffraction data show that calcite is present in the most aboral portions of the plumula, representing the very earliest stages of mineralization, and that this calcite has the same crystal orientation as in the more mature adoral portions of the same tooth. Raman spectroscopy of the aboral plumula confirms the initial primary plate mineral material is calcite and does not detect amorphous calcium carbonate; in the more mature adoral incisal flange, it does detect a broader calcite peak, consistent with two or more magnesium compositions. We hypothesize that some portion of each syncytial membrane in the plumula provides the information for nucleation of identically oriented calcite crystals that subsequently develop to form the complex geometry of the single crystal sea urchin tooth.

  18. The calcite → aragonite transformation in low-Mg marble: Equilibrium relations, transformations mechanisms, and rates

    Science.gov (United States)

    Hacker, Bradley R.; Rubie, David C.; Kirby, Stephen H.; Bohlen, Steven R.

    2005-01-01

    Experimental transformation of a rather pure natural calcite marble to aragonite marble did not proceed via the expected straightforward polymorphic replacement. Instead, the small amount of Mg in the starting material (0.36 wt %) was excluded from the growing aragonite and diffused preferentially into the remaining calcite grains, producing Mg-rich calcite rods that persisted as relicts. Nucleation of aragonite occurred exclusively on grain boundaries, with aragonite [001] oriented subparallel to calcite [0001]. The aragonite crystals preferentially consumed the calcite crystal on which they nucleated, and the reaction fronts developed preferentially along the {010} and {110} planes of aragonite. Each aragonite neoblast that grew was nearly free of Mg (typically growth rates are approximately linear and range from ∼3 × 10−11 m s−1 at 600°C to ∼9 × 10−9 m s−1 at 850°C, with an apparent activation enthalpy of 166 ± 91 kJ mol−1. This reaction mechanism and the resultant texture are akin to cellular precipitation reactions in metals. Similar transformation textures have been reported from high-Mg marbles in Japan and China that disproportionated to low-Mg calcite and dolomite.

  19. 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

  20. Surface Crystallization of Cloud Droplets: Implications for Climate Change and Ozone Depletion

    Science.gov (United States)

    Tabazadeh, A.; Djikaev, Y. S.; Reiss, H.; Gore, Warren J. (Technical Monitor)

    2002-01-01

    The process of supercooled liquid water crystallization into ice is still not well understood. Current experimental data on homogeneous freezing rates of ice nucleation in supercooled water droplets show considerable scatter. For example, at -33 C, the reported freezing nucleation rates vary by as much as 5 orders of magnitude, which is well outside the range of measurement uncertainties. Until now, experimental data on the freezing of supercooled water has been analyzed under the assumption that nucleation of ice took place in the interior volume of a water droplet. Here, the same data is reanalyzed assuming that the nucleation occurred "pseudoheterogeneously" at the air (or oil)-liquid water interface of the droplet. Our analysis suggest that the scatter in the nucleation data can be explained by two main factors. First, the current assumption that nucleation occurs solely inside the volume of a water droplet is incorrect. Second, because the nucleation process most likely occurs on the surface, the rates of nuclei formation could differ vastly when oil or air interfaces are involved. Our results suggest that ice freezing in clouds may initiate on droplet surfaces and such a process can allow for low amounts of liquid water (approx. 0.002 g per cubic meters) to remain supercooled down to -40 C as observed in the atmosphere.

  1. Surface temperatures of the Mid-Pliocene North Atlantic Ocean: Implications for future climate

    Science.gov (United States)

    Dowsett, H.J.; Chandler, M.A.; Robinson, M.M.

    2009-01-01

    The Mid-Pliocene is the most recent interval in the Earth's history to have experienced warming of the magnitude predicted for the second half of the twenty-first century and is, therefore, a possible analogue for future climate conditions. With continents basically in their current positions and atmospheric CO2 similar to early twenty-first century values, the cause of Mid-Pliocene warmth remains elusive. Understanding the behaviour of the North Atlantic Ocean during the Mid-Pliocene is integral to evaluating future climate scenarios owing to its role in deep water formation and its sensitivity to climate change. Under the framework of the Pliocene Research, Interpretation and Synoptic Mapping (PRISM) sea surface reconstruction, we synthesize Mid-Pliocene North Atlantic studies by PRISM members and others, describing each region of the North Atlantic in terms of palaeoceanography. We then relate Mid-Pliocene sea surface conditions to expectations of future warming. The results of the data and climate model comparisons suggest that the North Atlantic is more sensitive to climate change than is suggested by climate model simulations, raising the concern that estimates of future climate change are conservative. ?? 2008 The Royal Society.

  2. Surface energetics and protein-protein interactions: analysis and mechanistic implications

    Science.gov (United States)

    Peri, Claudio; Morra, Giulia; Colombo, Giorgio

    2016-04-01

    Understanding protein-protein interactions (PPI) at the molecular level is a fundamental task in the design of new drugs, the prediction of protein function and the clarification of the mechanisms of (dis)regulation of biochemical pathways. In this study, we use a novel computational approach to investigate the energetics of aminoacid networks located on the surface of proteins, isolated and in complex with their respective partners. Interestingly, the analysis of individual proteins identifies patches of surface residues that, when mapped on the structure of their respective complexes, reveal regions of residue-pair couplings that extend across the binding interfaces, forming continuous motifs. An enhanced effect is visible across the proteins of the dataset forming larger quaternary assemblies. The method indicates the presence of energetic signatures in the isolated proteins that are retained in the bound form, which we hypothesize to determine binding orientation upon complex formation. We propose our method, BLUEPRINT, as a complement to different approaches ranging from the ab-initio characterization of PPIs, to protein-protein docking algorithms, for the physico-chemical and functional investigation of protein-protein interactions.

  3. Surface temperatures of the Mid-Pliocene North Atlantic Ocean: Implications for future climate

    Science.gov (United States)

    Dowsett, Harry J.; Chandler, Mark A.; Robinson, Marci M.

    2009-01-01

    The Mid-Pliocene is the most recent interval in the Earth's history to have experienced warming of the magnitude predicted for the second half of the twenty-first century and is, therefore, a possible analogue for future climate conditions. With continents basically in their current positions and atmospheric CO2 similar to early twenty-first century values, the cause of Mid-Pliocene warmth remains elusive. Understanding the behaviour of the North Atlantic Ocean during the Mid-Pliocene is integral to evaluating future climate scenarios owing to its role in deep water formation and its sensitivity to climate change. Under the framework of the Pliocene Research, Interpretation and Synoptic Mapping (PRISM) sea surface reconstruction, we synthesize Mid-Pliocene North Atlantic studies by PRISM members and others, describing each region of the North Atlantic in terms of palaeoceanography. We then relate Mid-Pliocene sea surface conditions to expectations of future warming. The results of the data and climate model comparisons suggest that the North Atlantic is more sensitive to climate change than is suggested by climate model simulations, raising the concern that estimates of future climate change are conservative.

  4. Chemical functionalization of ceramic tile surfaces by silane coupling agents: polymer modified mortar adhesion mechanism implications

    Directory of Open Access Journals (Sweden)

    Alexandra Ancelmo Piscitelli Mansur

    2008-09-01

    Full Text Available Adhesion between tiles and mortars are crucial to the stability of ceramic tile systems. From the chemical point of view, weak forces such as van der Waals forces and hydrophilic interactions are expected to be developed preferably at the tiles and polymer modified Portland cement mortar interface. The main goal of this paper was to use organosilanes as primers to modify ceramic tile hydrophilic properties to improve adhesion between ceramic tiles and polymer modified mortars. Glass tile surfaces were treated with several silane derivatives bearing specific functionalities. Contact angle measurements and Fourier Transform Infrared Spectroscopy (FTIR were used for evaluating the chemical changes on the tile surface. In addition, pull-off tests were conducted to assess the effect on adhesion properties between tile and poly(ethylene-co-vinyl acetate, EVA, modified mortar. The bond strength results have clearly shown the improvement of adherence at the tile-polymer modified mortar interface, reflecting the overall balance of silane, cement and polymer interactions.

  5. Factors regulating the Great Calcite Belt in the Southern Ocean and its biogeochemical significance

    Science.gov (United States)

    Balch, William M.; Bates, Nicholas R.; Lam, Phoebe J.; Twining, Benjamin S.; Rosengard, Sarah Z.; Bowler, Bruce C.; Drapeau, Dave T.; Garley, Rebecca; Lubelczyk, Laura C.; Mitchell, Catherine; Rauschenberg, Sara

    2016-08-01

    The Great Calcite Belt (GCB) is a region of elevated surface reflectance in the Southern Ocean (SO) covering 16% of the global ocean and is thought to result from elevated, seasonal concentrations of coccolithophores. Here we describe field observations and experiments from two cruises that crossed the GCB in the Atlantic and Indian sectors of the SO. We confirm the presence of coccolithophores, their coccoliths, and associated optical scattering, located primarily in the region of the subtropical, Agulhas, and Subantarctic frontal regions. Coccolithophore-rich regions were typically associated with high-velocity frontal regions with higher seawater partial pressures of CO2 (pCO2) than the atmosphere, sufficient to reverse the direction of gas exchange to a CO2 source. There was no calcium carbonate (CaCO3) enhancement of particulate organic carbon (POC) export, but there were increased POC transfer efficiencies in high-flux particulate inorganic carbon regions. Contemporaneous observations are synthesized with results of trace-metal incubation experiments, 234Th-based flux estimates, and remotely sensed observations to generate a mandala that summarizes our understanding about the factors that regulate the location of the GCB.

  6. Assessing the impact of diagenesis on δ11B, δ13C, δ18O, Sr/Ca and B/Ca values in fossil planktic foraminiferal calcite

    Science.gov (United States)

    Edgar, Kirsty M.; Anagnostou, Eleni; Pearson, Paul N.; Foster, Gavin L.

    2015-10-01

    The geochemical composition of foraminiferal tests is a valuable archive for the reconstruction of paleo-climatic, -oceanographic and -ecological changes. However, dissolution of biogenic calcite and precipitation of inorganic calcite (overgrowth and recrystallization) at the seafloor and in the sediment column can potentially alter the original geochemical composition of the foraminiferal test, biasing any resulting paleoenvironmental reconstruction. The δ11B of planktic foraminiferal calcite is a promising ocean pH-proxy but the effect of diagenesis is still poorly known. Here we present new δ11B, δ13C, δ18O, Sr/Ca and B/Ca data from multiple species of planktic foraminifera from time-equivalent samples for two low latitude sites: clay-rich Tanzanian Drilling Project (TDP) Site 18 from the Indian Ocean containing well-preserved ('glassy') foraminifera and carbonate-rich Ocean Drilling Program (ODP) Site 865 from the central Pacific Ocean hosting recrystallized ('frosty') foraminifera. Our approach makes the assumption that environmental conditions were initially similar at both sites so most chemical differences are attributable to diagenesis. Planktic foraminiferal δ18O and δ13C records show offsets in both relative and absolute values between the two sites consistent with earlier findings that these isotopic ratios are strongly influenced by diagenetic alteration. Sr/Ca and B/Ca ratios in planktic foraminiferal calcite are also offset between the two sites but there is little change in the relative difference between surface and deep dwelling taxa. In contrast, δ11B values indicate no large differences between well-preserved and recrystallized foraminifera suggesting that despite extensive diagenetic alteration the δ11B of biogenic calcite appears robust, potentially indicative of a lack of free exchange of boron between pore fluids and the recrystallizing CaCO3. Our finding may remove one potential source of uncertainty in δ11B based p

  7. Surface and Groundwater Quality in Some Oil Field Communities in the Niger Delta: Implications for Domestic Use and Building Construction

    Directory of Open Access Journals (Sweden)

    E.R. Daka

    2014-02-01

    Full Text Available The aim of this study was to determine surface and groundwater quality in some communities in the Niger Delta and to evaluate the implications for domestic use and building construction. Surface water samples were collected along the Nun River and Taylor creek in the greater Gbaran area; groundwater samples were collected from seven communities in that Gbarain and Ekpetiama kingdoms of Bayelsa State, Nigeria. The surface water turbidity values (24.18 to 130.42 NTU were above the Nigerian drinking water limits. TDS values were low (27-32 mg/L; pH (7.0 to 7.5, conductivity (54.00 to 63.00 &muS/cm, nitrate (0.09-0.61 mg/L. The measured values of conductivity, pH and TDS and nitrate fell within the NIS limits for drinking water in Nigeria. About 50% of the surface water samples had values of iron higher than the Nigerian standard for drinking water. Most of the samples gave values of chromium within the limit for drinking, with a few exceptions. pH of groundwater (6.3-7.8 mostly fell within the Nigerian drinking water limits (6.5-8.5. Mean electrical conductivity values of groundwater was 129.67 µS/cm, the TDS values (51.00 to 81.00 mg/L. The turbidity values ranged from <0.01 NTU to 38.11 NTU. Heavy metals concentrations were generally low; copper values ranged from <0.001 to 0.407 mg/L, chromium (0.020-0.059 mg/L, iron (0. 162 to 0.558 mg/L. The measured physicochemical variables of surface water and groundwater from the study area showed water quality values that were generally within the Nigerian standards for drinking water, apart from turbidity, iron and chromium in both surface and groundwater. However, all the measured parameters showed valued that are within acceptable limits for construction.

  8. Long-term sea surface temperature baselines - time series, spatial covariation and implications for biological processes

    DEFF Research Database (Denmark)

    MacKenzie, Brian; Schiedek, D.

    2007-01-01

    questions at large spatial scales, such as the response of species distributions and phenologies to climate change. In this study we investigate the spatial synchrony of long-term sea surface temperatures in the North Sea-Baltic Sea region as measured daily at four coastal sites (Marsdiep, Netherlands...... and is consistent with the known correlation radius of atmospheric fluctuations (ca. 1000 km). Differences (e. g, long-term trends, amplitude of seasonal variations) between coastal temperatures and those measured in adjacent offshore areas varied nonrandomly over time and were often significantly autocorrelated up...... to 2 years. These differences suggest that spatial variations in physical oceanographic phenomena and sampling heterogeneities associated with opportunistic sampling could affect perceptions of biological responses to temperature fluctuations. The documentation that the coastally measured temperatures...

  9. Earthing: Health Implications of Reconnecting the Human Body to the Earth's Surface Electrons

    Directory of Open Access Journals (Sweden)

    Gaétan Chevalier

    2012-01-01

    Full Text Available Environmental medicine generally addresses environmental factors with a negative impact on human health. However, emerging scientific research has revealed a surprisingly positive and overlooked environmental factor on health: direct physical contact with the vast supply of electrons on the surface of the Earth. Modern lifestyle separates humans from such contact. The research suggests that this disconnect may be a major contributor to physiological dysfunction and unwellness. Reconnection with the Earth's electrons has been found to promote intriguing physiological changes and subjective reports of well-being. Earthing (or grounding refers to the discovery of benefits—including better sleep and reduced pain—from walking barefoot outside or sitting, working, or sleeping indoors connected to conductive systems that transfer the Earth's electrons from the ground into the body. This paper reviews the earthing research and the potential of earthing as a simple and easily accessed global modality of significant clinical importance.

  10. Radioactive elements on Mercury's surface from MESSENGER: implications for the planet's formation and evolution.

    Science.gov (United States)

    Peplowski, Patrick N; Evans, Larry G; Hauck, Steven A; McCoy, Timothy J; Boynton, William V; Gillis-Davis, Jeffery J; Ebel, Denton S; Goldsten, John O; Hamara, David K; Lawrence, David J; McNutt, Ralph L; Nittler, Larry R; Solomon, Sean C; Rhodes, Edgar A; Sprague, Ann L; Starr, Richard D; Stockstill-Cahill, Karen R

    2011-09-30

    The MESSENGER Gamma-Ray Spectrometer measured the average surface abundances of the radioactive elements potassium (K, 1150 ± 220 parts per million), thorium (Th, 220 ± 60 parts per billion), and uranium (U, 90 ± 20 parts per billion) in Mercury's northern hemisphere. The abundance of the moderately volatile element K, relative to Th and U, is inconsistent with physical models for the formation of Mercury requiring extreme heating of the planet or its precursor materials, and supports formation from volatile-containing material comparable to chondritic meteorites. Abundances of K, Th, and U indicate that internal heat production has declined substantially since Mercury's formation, consistent with widespread volcanism shortly after the end of late heavy bombardment 3.8 billion years ago and limited, isolated volcanic activity since.

  11. Contrasting optical properties of surface waters across the Fram Strait and its potential biological implications

    DEFF Research Database (Denmark)

    Pavlov, Alexey K.; Granskog, Mats A.; Stedmon, Colin A.

    2015-01-01

    Spitsbergen Current (WSC) differ with regards to temperature, salinity and optical properties. We present data on absorption properties of CDOM and particles across the Fram Strait (along 79° N), comparing Polar and Atlantic surface waters in September 2009 and 2010. CDOM absorption of Polar water in the EGC...... radiation (PAR, 400-700nm), but does result in notable differences in ultraviolet (UV) light penetration, with higher attenuation in the EGC. Future changes in the Arctic Ocean system will likely affect EGC through diminishing sea-ice cover and potentially increasing CDOM export due to increase in river...... runoff into the Arctic Ocean. Role of attenuation of light by CDOM in determining underwater light regime will become more important, with a potential for future increase in marine productivity in the area of EGC due to elevated PAR and lowered UV light exposures....

  12. Global climate impacts of bioenergy from forests: implications from biogenic CO2 fluxes and surface albedo

    Science.gov (United States)

    Cherubini, Francesco; Bright, Ryan; Strømman, Anders

    2013-04-01

    Production of biomass for bioenergy can alter biogeochemical and biogeophysical mechanisms, thus affecting local and global climate. Recent scientific developments mainly embraced impacts from land use changes resulting from area-expanded biomass production, with several extensive insights available. Comparably less attention, however, is given to the assessment of direct land surface-atmosphere climate impacts of bioenergy systems under rotation such as in plantations and forested ecosystems, whereby land use disturbances are only temporary. In this work, we assess bioenergy systems representative of various biomass species (spruce, pine, aspen, etc.) and climatic regions (US, Canada, Norway, etc.), for both stationary and vehicle applications. In addition to conventional greenhouse gas (GHG) emissions through life cycle activities (harvest, transport, processing, etc.), we evaluate the contributions to global warming of temporary effects resulting from the perturbation in atmospheric carbon dioxide (CO2) concentration caused by the timing of biogenic CO2 fluxes and in surface reflectivity (albedo). Biogenic CO2 fluxes on site after harvest are directly measured through Net Ecosystem Productivity (NEP) chronosequences from flux towers established at the interface between the forest canopy and the atmosphere and are inclusive of all CO2 exchanges occurring in the forest (e.g., sequestration of CO2 in growing trees, emissions from soil respiration and decomposition of dead organic materials). These primary data based on empirical measurements provide an accurate representation of the forest carbon sink behavior over time, and they are used in the elaboration of high-resolution IRFs for biogenic CO2 emissions. Chronosequence of albedo values from clear-cut to pre-harvest levels are gathered from satellite data (MODIS black-sky shortwave broadband, Collection 5, MCD43A). Following the cause-effect chain from emissions to damages, through radiative forcing and changes

  13. Advection and diffusion in random media implications for sea surface temperature anomalies

    CERN Document Server

    Piterbarg, Leonid I

    1997-01-01

    The book presents the foundations of the theory of turbulent transport within the context of stochastic partial differential equations. It serves to establish a firm connection between rigorous and non-rigorous results concerning turbulent diffusion. Mathematically all of the issues addressed in this book are concentrated around a single linear equation: stochastic advection-diffusion (transport) equation. There is no attempt made to derive universal statistics for turbulent flow. Instead emphasis is placed on a statistical description of a passive scalar (tracer) under given velocity statistics. An application concerning transport of sea surface temperature anomalies reconciles the developed theory and a highly practical issue of modern physical oceanography by using the newly designed inversion techniques which take advantage of powerful maximum likelihood and autoregressive estimators. Audience: Graduate students and researchers in mathematics, fluid dynamics, and physical oceanography.

  14. Climatic driven variability of surface water energy potential and implications for future hydroelectricity

    Science.gov (United States)

    Worman, A. L. E.; Lindstrom, G.

    2014-12-01

    An average year the production in Norway and Sweden is around 190 TWh and these two countries stand for about 70% of the hydropower energy stored in the available reservoirs of Europe. There are large challenges for the future use of this regulatory capacity with regard to balancing the electricity production in Europe under climate variability, compliance to water management plans under the Water Framework Directive and to the shifts to more renewable, but intermittent, energy sources required by the Renewable Energy Directive. A main aim of this project is to describe the variation over time of hydrological fluxes across Scandinavia in terms of their energy properties and to link that information to climatic factors and the regulation of hydroelectricty. Along these lines we explored daily data of digitalized hydro-climatological data from 1961, which were used to calibrate the HBV-model for 1001 watersheds in Sweden and the energy potential has been estimated as an average for that period (Figure below). These tentative results show that the surface water energy potential constitutes about one per mille of the latent heat flux due to evapotranspiration and it is, therefore, very sensitive to any fluctuation in the energy quantities of the hydrometeorological system. Tentative analysis suggests that the energy availability of surface water in Sweden exhibits significant decadal long fluctuations from 115 TWh/year up to 180 TWh/year, which follow several different time scales and periodicities, ranging from century-long trends to fluctuations occurring on time scales of a decade and shorter. In addition, recent investigations show that land-use changes and hydropower regulation has caused significant changes in the annual runoff periodicity in Swedish rivers during the 20th century. Those changes in the annual periodicities are caused by structural alterations in river basins affected by intense agriculture and hydropower regulation.

  15. The relation between glauconitization and calcite cementation with the relative sea level changes in the mixed silisiclastic- carbonate sediments of Aitamir Formation (Mid-Cretaceous, Kopet-Dagh basin

    Directory of Open Access Journals (Sweden)

    M., Sharafi,

    2012-01-01

    Full Text Available Two diagenetic processes of glauconitization and calcite cementation and relation those to sea level changes in the siliciclastic-carbonate sediments of the Aitamir Formation (Albian-Cenomanian in Kopet-Dagh basin have studied. The lower sandstone unit consists of mainly sandstone intercalated with shale and limestone and the upper shale units are two major sediments of this formation. The sandstone of the lower unit based on composition and their relations with sea level change subdivided into two transgressive and regressive facies and in this relation, show different pathways of the diagenesis. In the transgressive facies display by high content of the shell remains, with development in diagenesis shows extensive cementation and a little compaction during burial stage. In the regressive sandstone, characterized by little skeletal elements, display little calcite cements and high burial compaction. The glauconitic grains and calcite cementation in the Aitamir Formation concentrated in the transgressive facies and especially in the maximum flooding surface and transgresive surface. Whereas, in the regressive facies the glauconitic grains and calcite cementation is principally low. Moreover, the transgressive system tract and maximum flooding surface is characterized by mature and high mature glauconitic grains.

  16. Surface Elevation Changes in West Antarctica from Satellite Altimetry: Mass Balance Implications

    Science.gov (United States)

    Zwally, H. Jay; Brenner, Anita C.; Cornejo, Helen; Koblinsky, Chester J. (Technical Monitor)

    2001-01-01

    Time-series of surface elevation change, which are constructed from 7-years (1992-1999) of ERS-1 and 2 satellite radar altimeter data of Antarctica, show significant seasonal, inter-annual, and long-term changes. Elevation time-series are created from altimeter crossovers among 90-day data periods on a 50 km grid to 81.5 degrees S and fit with a multivariate linear/sinusoidal function to give the average rate of elevation change (dH/dt) and account for seasonal changes. On the major Ronne, Filchner, and Ronne ice shelves, the dH/dt are small or near zero. In contrast, the ice shelves of the Antarctic Peninsula and along the West Antarctic coast appear to be thinning significantly, with a 23 +/- 3 cm a(exp -1) surface elevation decrease on the Larsen ice shelf and a 65 +/- 4 cm a(exp -1) decrease on the Dotson ice shelf. Significant elevation decreases are obtained over most of the drainage basins of the Pine Island and Thwaites glaciers. Significant increases are obtained over most of the other grounded ice in Marie Byrd Land, the Antarctic Peninsula, and Coates Land. Over the sector from 85 degrees W to 115 degrees W, which includes the Pine Island and Thwaites basins, the average elevation is significantly decreasing by 8.1 cm a(exp -1). The corresponding ice thickness change is about -11 cm a(exp -1), with a corresponding mass loss of 82 Gt a(exp -1), and a 0.22 mm a(exp -1) contribution to global sea level rise. In terms of elevation change, the decrease in the Pine Island-Thwaites sector is largely balanced by the increase in the Marie Byrd Land, but only balanced by about 1/4 in terms of ice thickness change and contribution to sea level rise. The overall average elevation change for the grounded ice is + 1.2 cm a(exp -1). Using an average bedrock uplift of 2.5 cm a(exp -1), implies an average ice thickness decrease of 1.3 cm a(exp -1), a mass loss of 22 Gt a(exp -1), and a 0.06 mm a(exp -1) contribution to global sea level rise.

  17. P Isotope Data of SNC Meteorites and Implications on the Age of the Martian Surface

    Science.gov (United States)

    Jagoutz, E.; Jotter, R.; Kubny, A.; Zartman, R.

    SNC meteorites might originate from the Martian surface. However, these meteorites have experienced a relative young metamorphosis which obscures their origin. Pb isotopes seem to be the best way to look through these young disturbances. A major fraction of the U and Th in the SNCs is not a primary constituent but was introduced at the time of disturbance and resides in the phosphates. By contrast, the Pb in the silicate minerals seems to have remained essentially in isotopic equilibration with the U and Th in the mineral since the time of original crystallization. The main cause of any scatter in the determined initial composition is probably due to the addition of terrestrial Pb, although some minor in situ isotopic disturbance cannot be ruled out. Our best values for the initial isotopic ratios of Shergotty, Zagami, and Los Angeles will be shown. The parent body formed and differentiated at 4.55 Ga, and the various meteorite source lithologies evolved isotopically undisturbed until 0.45 Ga (Los Angeles with a µ =238 U/204 Pb of ˜4, Zagami with a µ of ˜4.5, and Shergotty with a µ of ˜5). At ˜0.45 Ga the "young event" affected each of these meteorites and the initial Pb ratios, after being corrected for subsequent in situ growth of radiogenic Pb, are scattering on a fossilized 0.45 Ga geochron. Additional insight is gained from isotopic data for the Nakhlites, including several that have been newly found and analyzed. All Nakhlites appear to have been derived from an isotopic uniform reservoir, and share a well-defined "young event" age of 1.25 Ga. Of particular note is the fact that their initial Pb isotopic composition does not plot on the modern geochron, but instead to the right of it. If experiencing only a single stage evolution prior to 1.25 Ga, its initial Pb should actually plot on a fossilized 1.25 Ga geochron considerably to the left of the modern geochron. Only a relatively recent increase of the U/Pb ratio in the Nakhlite reservoir could

  18. Plasmonic Purcell factor and coupling efficiency to surface plasmons. Implications for addressing and controlling optical nanosources

    Science.gov (United States)

    Colas des Francs, G.; Barthes, J.; Bouhelier, A.; Weeber, J. C.; Dereux, A.; Cuche, A.; Girard, C.

    2016-09-01

    The Purcell factor F p is a key quantity in cavity quantum electrodynamics (cQED) that quantifies the coupling rate between a dipolar emitter and a cavity mode. Its simple form {F}{{p}}\\propto Q/V unravels the possible strategies to enhance and control light-matter interaction. Practically, efficient light-matter interaction is achieved thanks to either (i) high quality factor Q at the basis of cQED or (ii) low modal volume V at the basis of nanophotonics and plasmonics. In the last decade, strong efforts have been done to derive a plasmonic Purcell factor in order to transpose cQED concepts to the nanocale, in a scale-law approach. In this work, we discuss the plasmonic Purcell factor for both delocalized (SPP) and localized (LSP) surface-plasmon-polaritons and briefly summarize the expected applications for nanophotonics. On the basis of the SPP resonance shape (Lorentzian or Fano profile), we derive closed form expression for the coupling rate to delocalized plasmons. The quality factor factor and modal confinement of both SPP and LSP are quantified, demonstrating their strongly subwavelength behavior.

  19. The relative merits of dolomitic and calcitic limestone in detoxifying and revegetating acidic, nickel- and copper-contaminated soils in the Sudbury mining and smelting region of Canada

    Energy Technology Data Exchange (ETDEWEB)

    McHale, D.; Winterhalder, K. [Laurentian Univ., Sudbury, Ontario (Canada)

    1996-12-31

    Soils in the Sudbury mining and smelting region have been rendered phytotoxic and barren by acidification and Particulate metal contamination, but can be detoxified revegetated by the surface application of an growth is better on soil treated ground limestone. On certain barren sites, plant growth is better on soil treated with dolomitic limestone than with calcitic limestone and greenhouse experiments using mung beans (Vigna radiata) have shown superior root and shoot growth on certain contaminated soils when the limestone is dolomitic rather than calcitic. Results of experiments with species used in revegetation (Agrostis gigantea and Lotus corniculatus) suggest that leguminous species are more sensitive to Ca:Mg ratio than grasses, that the plant response to this ratio is greater at lowering liming levels, and that the response is more marked on more toxic soils. The effects of calcium:magnesium ratio of the limestone used in revegetating acidic, metal-contaminated soils are clearly complex, interactive and difficult to interpret. Further studies are needed, but meanwhile it is recommended that the practice of using dolomitic limestone to detoxify barren Sudbury soils be continued, since there is a risk of induced magnesium deficiency at certain sites when calcitic limestone is used.

  20. Seismic imaging of the upper mantle beneath the northern Central Andean Plateau: Implications for surface topography

    Science.gov (United States)

    Ward, K. M.; Zandt, G.; Beck, S. L.; Wagner, L. S.

    2015-12-01

    Extending over 1,800 km along the active South American Cordilleran margin, the Central Andean Plateau (CAP) as defined by the 3 km elevation contour is second only to the Tibetan Plateau in geographic extent. The uplift history of the 4 km high Plateau remains uncertain with paleoelevation studies along the CAP suggesting a complex, non-uniform uplift history. As part of the Central Andean Uplift and the Geodynamics of High Topography (CAUGHT) project, we use surface waves measured from ambient noise and two-plane wave tomography to image the S-wave velocity structure of the crust and upper mantle to investigate the upper mantle component of plateau uplift. We observe three main features in our S-wave velocity model including (1), a high velocity slab (2), a low velocity anomaly above the slab where the slab changes dip from near horizontal to a normal dip, and (3), a high-velocity feature in the mantle above the slab that extends along the length of the Altiplano from the base of the Moho to a depth of ~120 km with the highest velocities observed under Lake Titicaca. A strong spatial correlation exists between the lateral extent of this high-velocity feature beneath the Altiplano and the lower elevations of the Altiplano basin suggesting a potential relationship. Non-uniqueness in our seismic models preclude uniquely constraining this feature as an uppermost mantle feature bellow the Moho or as a connected eastward dipping feature extending up to 300 km in the mantle as seen in deeper mantle tomography studies. Determining if the high velocity feature represents a small lithospheric root or a delaminating lithospheric root extending ~300 km into the mantle requires more integration of observations, but either interpretation shows a strong geodynamic connection with the uppermost mantle and the current topography of the northern CAP.

  1. The Evolution and Development of the Lunar Regolith and Implications for Lunar Surface Operations and Construction

    Science.gov (United States)

    McKay, David

    2009-01-01

    The lunar regolith consists of about 90% submillimeter particles traditionally termed lunar soil. The remainder consists of larger particles ranging up to boulder size rocks. At the lower size end, soil particles in the 10s of nanometer sizes are present in all soil samples. Lunar regolith overlies bedrock which consists of either lava flows in mare regions or impact-produced megaregolith in highland regions. Lunar regolith has been produced over billions of years by a combination of breaking and communition of bedrock by meteorite bombardment coupled with a variety of complex space weathering processes including solar wind implantation, solar flare and cosmic ray bombardment with attendant radiation damage, melting, vaporization, and vapor condensation driven by impact, and gardening and turnover of the resultant soil. Lunar regolith is poorly sorted compared to most terrestrial soils, and has interesting engineering properties including strong grain adhesion, over-compacted soil density, an abundance of agglutinates with sharp corners, and a variety of properties related to soil maturity. The NASA program has supported a variety of engineering test research projects, the production of bricks by solar or microwave sintering, the production of concrete, the in situ sintering and glazing of regolith by microwave, and the extraction of useful resources such as oxygen, hydrogen, iron, aluminum, silicon and other products. Future requirements for a lunar surface base or outpost will include construction of protective berms, construction of paved roadways, construction of shelters, movement and emplacement of regolith for radiation shielding and thermal control, and extraction of useful products. One early need is for light weight but powerful digging, trenching, and regolith-moving equipment.

  2. Thermal and Evolved Gas Behavior of Calcite Under Mars Phoenix TEGA Operating Conditions

    Science.gov (United States)

    Ming, D.W.; Niles, P.B.; Morris, R.V.; Boynton, W.V.; Golden, D.C.; Lauer, H.V.; Sutter, B.

    2009-01-01

    The Mars Phoenix Scout Mission with its diverse instrument suite successfully examined several soils on the Northern plains of Mars. The Thermal and Evolved Gas Analyzer (TEGA) was employed to detect organic and inorganic materials by coupling a differential scanning calorimeter (DSC) with a magnetic-sector mass spectrometer (MS). Martian soil was heated up to 1000 C in the DSC ovens and evolved gases from mineral decomposition products were examined with the MS. TEGA s DSC has the capability to detect endothermic and exothermic reactions during heating that are characteristic of minerals present in the Martian soil. Initial TEGA results indicated the presence of endothermic peaks with onset temperatures that ranged from 675 C to 750 C with corresponding CO2 release. This result suggests the presence of calcite (CaCO3. CaO + CO2). Organic combustion to CO2 is not likely since this mostly occurs at temperatures below 550 C. Fe-carbonate and Mg-carbonate are not likely because their decomposition temperatures are less than 600 C. TEGA enthalpy determinations suggest that calcite, may occur in the Martian soil in concentrations of approx.1 to 5 wt. %. The detection of calcite could be questioned based on previous results that suggest Mars soils are mostly acidic. However, the Phoenix landing site soil pH was measured at pH 8.3 0.5, which is typical of terrestrial soils where pH is controlled by calcite solubility. The range of onset temperatures and calcite concentration as calculated by TEGA is poorly con-strained in part because of limited thermal data of cal-cite at reduced pressures. TEGA operates at calcite literature thermal data was obtained at 1000 mbar or higher pressures.

  3. Effect of Mg on the Grain Growth and Dislocation Creep of Calcite

    Science.gov (United States)

    Xu, L.

    2004-12-01

    We tested the effect of variations in the amount of the solute impurity (Mg) on grain growth and strength of calcite aggregate. Synthetic marbles were produced by hot isostatic pressing mixtures of powders of calcite and dolomite at 850° C and 300 MPa confining pressure for different intervals (2 to 30 hrs). The HIP treatment resulted in homogeneous aggregates of calcite with Mg content from 0.5 to 17 mol%. Stress stepping tests and constant strain rate tests were used to examine the effect of Mg content on the dislocation creep of calcite. The grain growth rate under static conditions was decreased with Mg content from 7 to 17 mol%, indicating perhaps that grain boundary mobility is suppressed by the solute drag effect. In the diffusion creep at stresses below 40 Mpa, the strength of calcite decreases with increasing Mg content owing to the difference in grain size at 800° C and 300 MPa confining pressure. The contribution of dislocation creep increases with increasing stress, and the transition between diffusion and dislocation creep occurs at higher stresses for the samples with higher magnesium content and smaller grain size. The creep data were fit assuming a composite flow law consisting of a linear combination of diffusion and dislocation creep and a single-valued grain size. The best agreement was obtained by using a dislocation creep law with exponential dependence of strain rate on stress (e.g. Peierls law). More evidence from microstructure is needed to identify the dominant deformation mechanism conclusively. Most of the samples were compressed up to strains of 0.25; small recrystallized grains are formed resulting in a bimodal grain size distribution in some of the deformed samples. Preliminary data shows that the recrystallized grain sizes are smaller for Mg-calcite compared with that of pure calcite. This study will help to understand the effect of impurities on grain-growth kinetics and strain weakening in localized shear zones.

  4. 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.

  5. The UV Surface Environment on Young Planets: Implications for Prebiotic Chemistry & Life on Other Worlds

    Science.gov (United States)

    Ranjan, Sukrit; Simons Collaboration on the Origin of Life, Harvard Origins of Life Initiative

    2017-01-01

    Understanding the origin of life (abiogenesis) on Earth is key to understanding how it might start elsewhere. Recent laboratory studies suggest UV light may have played a critical role in the synthesis of molecules relevant to abiogenesis (prebiotic chemistry), such as RNA. I show that UV light interacts with prebiotic chemistry in ways that may be sensitive to the spectral shape and overall amplitude of irradiation. I use radiative transfer models to constrain the UV environment on early Earth (3.9 Ga). I find that the surface UV is insensitive to much of the considerable uncertainty in the atmospheric state, enabling me to constrain the UV environment for prebiotic chemistry on early Earth. Some authors have suggested Mars as a venue for prebiotic chemistry. Therefore, I explore plausible UV spectral fluences on Mars at 3.9 Ga. I find that the early Martian UV environment is comparable to Earth’s under conventional assumptions about the atmosphere. However, if the atmosphere was dusty or SO2 levels were high, UV fluence would have been strongly suppressed. Intriguingly, despite overall attenuation of UV fluence, SO2 preferentially attenuates destructive FUV radiation over prebiotically-useful NUV radiation, meaning high-SO2 epochs may have been more clement for the origin of life. Better measurements of the spectral dependence of prebiotic photoprocesses are required to constrain this hypothesis. Finally, I calculate the UV fluence on planets orbiting M-dwarfs. I find that UV irradiation on such planets is low compared to Earth. Laboratory studies are required to understand whether prebiotic photoprocesses that worked on Earth can function on low-UV M-dwarf planets. My work 1) provides initial conditions for laboratory studies of prebiotic chemistry, 2) constrains the inhabitability of Mars and planets orbiting M-dwarfs, and 3) demonstrates the need for laboratory studies to characterize the impact of variations in irradiating intensity and spectral shape on

  6. Cratering and penetration experiments in aluminum and teflon: Implications for space-exposed surfaces

    Science.gov (United States)

    Hörz, Friedrich

    2012-04-01

    of either crater diameter or penetration-hole size in Al1100 and TeflonFEP targets of arbitrary thickness. We also placed witness plates behind penetrated targets to intercept the down-range debris plume, which is generally a mixture of both target and impactor fragments and melts. These witness plates also reveal that the debris plume systematically and diagnostically depends on D*. Thick targets shed spall debris only, and target thickness must be less than crater depth (Tc) to allow projectile material on the witness plate. Concentric plume patterns, accented by characteristic "hole saw" rings, characterize penetrated Al-targets at D* = 1-10, but they give way to distinctly radial geometries at D* = 10-20. Most of the target debris occupies the periphery of the plume, while the projectile fragments or melts reside in its central parts. The periphery of the plume is also typically more fine-grained than its center. At D* > 50, the exit plume is dominated by solid projectile fragments that progressively coagulate and overlap with each other, giving rise to compound craters. The latter have irregular crater interiors on account of the heterogeneous mass distribution of a collisionally produced, aggregate impactor. Similarly, complex craters are observed on LDEF and Stardust and they are produced by aggregate cosmic-dust particles containing large, dense components within a relatively low-density, fine-grained matrix. The witness-plate observations can also be used to address the enigmatic clustering of impact sites observed on Stardust's aerogel and aluminum surfaces. We suggest that this clustering is difficult to produce by the collision of particles from comet Wild 2 with the Stardust spacecraft, and that it is more likely due to particle disaggregation in the comet's coma.

  7. A framework model for investigating the export of phosphorus to surface waters in forested watersheds: Implications to management.

    Science.gov (United States)

    Santos, R M B; Sanches Fernandes, L F; Pereira, M G; Cortes, R M V; Pacheco, F A L

    2015-12-01

    The present study was developed in four sub-basins of rivers Cávado and Douro, located in the North of mainland Portugal. The goal was to identify main stressors as well as driving and attenuating processes responsible for the presence of phosphorus in masses of surface water in those catchments. To accomplish the goal, the basins were selected where a quality station was present at the outlet, the forest occupation was greater than 75% and the phosphorus concentrations have repeatedly exceeded the threshold for the good ecological status in the period 2000-2006. Further, in two basins the quality station was installed in a lotic (free-flow water) environment whereas in the other two was placed in a lentic (dammed water) environment. The ArcMap GIS-based software package was used for the spatial analysis of stressors and processes. The yields of phosphorus vary widely across the studied basins, from 0.2-30 kg·ha(-1)·yr(-1). The results point to post-fire soil erosion and hardwood clear cuttings as leading factors of phosphorus exports across the watersheds, with precipitation intensity being the key variable of erosion. However, yields can be attenuated by sediment deposition along the pathway from burned or managed areas to water masses. The observed high yields and concentrations of phosphorus in surface water encompass serious implications for water resources management in the basins, amplified in the lentic cases by potential release of phosphorus from lake sediments especially during the summer season. Therefore, a number of measures were proposed as regards wildfire combat, reduction of phosphorus exports after tree cuts, attenuation of soil erosion and improvement of riparian buffers, all with the purpose of preventing phosphorus concentrations to go beyond the regulatory good ecological status.

  8. Magnetic Susceptibility in Surface Sediments in the Southern South China Sea and Its Implication for Sub-sea Methane Venting

    Institute of Scientific and Technical Information of China (English)

    Chen Zhong; Yan Wen; Tang Xianzan; Liu Jianguo; Chen Muhong; Yang Huaping

    2009-01-01

    In order to understand the characteristics of magnetic variability and their possible implication for sub-sea methane venting,magnetic susceptibility (MS) of 145 surface sediment samples from the southern South China Sea (SCS) was investigated.Magnetic particles extracted from 20 representative samples were also examined for their mineral,chemical compositions and micromorphology.Results indicate that MS values range between -7.73×10-8 and 45.06x10-8 m3/kg.The high MS zones occur at some hydrecarbon-bearing basins and along main tectonic zones,and low ones are distributed mainly within the river delta or along continental shelves.Iron concretions and manganese concretions are not main contributors for high MS values in sediments,while authigenic iron sulphide minerals are possibly responsible for the MS enhancement.This phenomenon is suspected to be produced by the reducing environment where the high upward venting methane beneath the seafloor reacts with seawater sulfate,resulting in seep precipitation of highly susceptible intermediate mineral pyrrhotite,greigite and paramagnetic pyrite.It suggests that MS variability is possibly one of the geochemical indicators for mapping sub-sea zones of methane venting in the southern SCS.

  9. 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.

  10. 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

    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 View the MathML source. The results show that the adsorption...... 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...

  11. 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

    Full Text Available Introduction Several valuable calcite deposits are located in Ghare-Gheshlagh, south basin of Urmia Lake, NW Iran. Ghare-Gheshlagh area is situated in the northern part of tectono-sedimentary unit, forming NW part of Tertiary Sanandaj-Sirjan geological belt (Stocklin and Nabavi, 1972. The predominant rock types of the area include light color limestones (Qom Formation and Quaternary alluviums and underlined dolomite in depth (Eftekharnejhad, 1973. The thickness of these units varies between 10 cm and 6 meters and up to some hundred meters in length. In the present study, the effect of geochemical parameters responsible for precipitating calcite from the carbonate aqueous fluids is interpreted by the TOPSIS method to find the most preferable sampling sites and geochemical data. Materials and Methods A total of 20 samples were taken from a NE-SW trending profile including 15 calcites of fresh surface outcrops (5 samples per each colored calcite units in order to determine the nature of the rocks. The mineral assemblages were analyzed by optical methods in combination with XRD powder diffraction analysis. Major elements were determined by X-Ray Fluorescence Spectrometry (XRF, trace and rare earth elements were determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS in Geological Survey of Iran. Results The abundances of trace elements were normalized to the continental crust values (Taylor and McLennan, 1981. The green calcite revealed enrichment in Rb and Sr, while green and white calcite were enriched in U. The U enrichment in the green calcite indicates the reduction condition of deposition. Incompatible elements such as Ba, Th, Nb and P depleted in all calcites. Varying the Sr/Ba value between 3.18 and 5.21% indicates the continental deposition environment and non-magmatic waters as well (Cheng et al., 2013. The Sr2+ content of calcites varies from 123 to 427 ppm, indicates suitable condition for calcite precipitation. Eu anomalies

  12. Smaller calcite lattice deformation caused by occluded organic material in coccoliths than in mollusk shell

    DEFF Research Database (Denmark)

    Frølich, Simon; Sørensen, Henning Osholm; Hakim, Sepideh Sadat

    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....... Two heating cycles allow us to differentiate the effects of thermal agitation and organic molecules. Single peak analysis and Rietveld refinement were combined to show significant differences resulting from the occluded biomolecules on the mineral phase in biogenic calcite in the mollusk shell....... This 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....

  13. 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...... results show that approximately 99% of 2300 mg/L fluoride can be removed when CO2 is injected directly into the barrier. This can be compared to approximately 30-50% removal when the influent solution is equilibrated with atmospheric CO2 before contact with calcite....

  14. Ca and S K-edge XANES studies of calcite-acid mine water interactions

    Energy Technology Data Exchange (ETDEWEB)

    Myneni, S.C.B.; Perera, R.C.C. [Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    Heavy metal-rich acidic waters (SO{sub 4}{sup 2{minus}}, AsO{sub 4}{sup 3{minus}}, SeO{sub 4}{sup 2{minus}}, Fe{sup 2+}, Fe{sup 3+}, Al{sup 3+}, Cu{sup 2+}, Zn{sup 2+}, Cd{sup 2+}) and related ochreous coatings are common around abandoned sulfide and coal mine sites. This is mainly caused by the natural weathering of pyrite (FeS{sub 2}), arsenopyrite (FeAsS), and other metal sulfide containing shales. Acid generation in the case of pyrite can be explained by a general reaction: FeS{sub 2} + 3.5 O{sub 2} + H{sub 2}O {leftrightarrow} Fe{sup 2+} + SO{sub 4}{sup 2{minus}} + 2H{sup +}. Also, these low pH waters interact with the soils, and mobilize their soluble elements. One of the common remediation strategies is to allow these acid waters to react with limestone (CaCO{sub 3}-rich rock) and neutralize the pH and precipitate out soluble metals. Yet, the associated problem is the precipitation of Fe and Al oxides and hydroxy sulfate coatings on limestone surfaces, which block calcite reactive sites, and make them ineffective a few hours after initiation of treatment. The main objectives of this research are to examine: (1) the chemistry of limestone surface coatings, and (2) their toxic metal uptake and the conditions that inhibit their formation. Previous molecular studies using X-ray diffraction, and vibrational spectroscopy on limestone surface coatings (sampled from Athens, OH) indicate that the surface-most layer (the layer in contact with water) is composed of schwertmannite (Fe(III)-hydroxy sulfate) like phases. However, white, X-ray amorphous; Al-, sulfate- and carbonate-rich; and Ca-poor phases appeared at the interface between the limestone and the iron oxide coatings. The structure, morphology, and coordination chemistry of component major and trace elements of these white precipitate phases have not previously been examined.

  15. A generalised chemical precipitation modelling approach in wastewater treatment applied to calcite

    DEFF Research Database (Denmark)

    Mbamba, Christian Kazadi; Batstone, Damien J.; Flores Alsina, Xavier

    2015-01-01

    , 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...... of the mineral particulate state (Xcryst) and, for calcite, have a 2nd order dependency (exponent n ¼ 2.05 ± 0.29) on thermodynamic supersaturation (s). 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...

  16. 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.

  17. Birefringence measurements in single crystal sapphire and calcite shocked along the a axis

    Science.gov (United States)

    Tear, Gareth R.; Chapman, David J.; Eakins, Daniel E.; Proud, William G.

    2017-01-01

    Calcite and sapphire were shock compressed along the direction (a axis) in a plate impact configuration. Polarimetery and Photonic Doppler Velocimetery (PDV) were used to measure the change in birefringence with particle velocity in the shock direction. Results for sapphire agree well with linear photoelastic theory and current literature showing a linear relationship between birefringence and particle velocity up to 310 m s-1. A maximum change in birefringence of 5% was observed. Calcite however showed anomolous behaviour with no detectable change in birefringence (less than 0.1%) over the range of particle velocities studied (up to 75 m s-1).

  18. Study on vibrational modes by group theory and infrared spectra by D FT for calcite crystal

    Institute of Scientific and Technical Information of China (English)

    Danhua Lou; Fengjiu Sun; Lijuan Li

    2007-01-01

    The factor group symmetry analysis (FSA) method and position symmetry analysis (PSA) method are used to analyze the vibrational modes of calcite (CaCO3) crystal, respectively. With the activated results of infrared and Raman spectra presented, strong points of each method are concluded. The infrared spectra are studied by using dynamics calculations based on density-functional theory (DFT) with the supercell model of calcite crystal. The frequencies of 27 normal modes are achieved, which are consistent with that by the group symmetry analysis very well, and fit with the experimental results better than the lattice dynamical methods.

  19. Galacturonomannan and Golgi-derived membrane linked to growth and shaping of biogenic calcite

    Science.gov (United States)

    Marsh, M. E.; Ridall, A. L.; Azadi, P.; Duke, P. J.

    2002-01-01

    The coccolithophores are valuable models for the design and synthesis of composite materials, because the cellular machinery controlling the nucleation, growth, and patterning of their calcitic scales (coccoliths) can be examined genetically. The coccoliths are formed within the Golgi complex and are the major CaCO(3) component in limestone sediments-particularly those of the Cretaceous period. In this study, we describe mutants lacking a sulfated galacturonomannan and show that this polysaccharide in conjunction with the Golgi-derived membrane is directly linked to the growth and shaping of coccolith calcite but not to the initial orientated nucleation of the mineral phase.

  20. Cryogenic and non-cryogenic pool calcites reflect alternating permafrost and interglacial periods (Breitscheid-Erdbach Cave, Germany

    Directory of Open Access Journals (Sweden)

    D. K. Richter

    2010-07-01

    Full Text Available Weichselian cryogenic calcites collected in what is referred to as the "Rätselhalle" of the Breitscheid-Erdbach Cave were structurally classified as rhombohedral crystal and spherulitic crystal sinters. The carbon and oxygen isotopic composition of these precipitates corresponds to those of known cryogenic calcites of slow genesis of Central European caves (δ13C=+0.6 and −7.3‰; δ18O=−6.9 to −18.0‰. The variant carbon and oxygen isotope pattern differing between different caves is attributed to cave specific ventilation. Particularly, Breitscheid cryogenic calcites reflect mean levels of cave ventilation. 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 geochemistry of interglacial speleothems (stalagmites, etc., isotope ratios of Weichselian non-cryogenic pool-calcites reflect cooler conditions. Weichselian cryogenic calcites show a trend towards 18O-depleted 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 (glacial conditions to an interglacial and subsequently to renewed permafrost conditions. The last stage then grades into the present-day warm period. Judging from the data compiled here, the last permafrost stage is followed by only one interglacial. During this interglacial, the cave ice melted and non-cryogenic Weichselian calcite precipitates were deposited on the cave ground or on fallen blocks, respectively.

  1. Detrital Thermochronology of the Indus-Yarlung suture zone and implications for the tectonic and surface evolution of southern Tibet

    Science.gov (United States)

    Carrapa, B.; Hassim, F.; Kapp, P. A.

    2015-12-01

    Detrital thermochronology has the unique potential to resolve the timing of source cooling associated with magmatic, tectonic and surface processes. Correct interpretation of the detrital signature requires a multi-dating approach involving chronometers sensitive to different temperatures and processes. A multi-dating study of modern river sands from southern Tibet reveals distinct cooling signals that provide significant information about tectonic and erosional evolution of the Indus-Yarlung suture (IYS) after the India-Asia collision with implications for the Cenozoic topographic evolution of the Tibetan Plateau. Modern sands from tributaries of the Yarlung River provide an opportunity to broadly sample source rocks exposed within the suture zone, including the Gangdese batholith, Xigaze forearc, Cenozoic basins, and Tethyan Himalayan rocks, and to investigate their regional geochemical signatures. Samples from rivers along the IYS in southern Tibet, between Xigaze and Mt. Kailas, were analyzed for detrital geochronology and low-temperature thermochronology. Comparison between ages recorded in the source and the detrital signature indicates that both the ages and their proportions directly reflect the ages and relative areas of source rocks in the catchment basins. Apatite fission track ages show two main cooling signals at 22-18 Ma and 12 Ma, which are consistent with accelerated exhumation of the Gangdese batholith and Oligo-Miocene Kailas basin and indicate significant regional exhumation of the IYS during the Miocene. Regional exhumation recorded throughout the IYS is likely the combined product of active Miocene tectonics and erosion of a paleo-Yarlung River. Efficient incision and evacuation of material from the IYS zone by a paleo-Yarlung River during the Miocene suggests a significantly different paleoenvironment than that which exists today. Miocene capture of the Yarlung River by the Brahmaputra River may have enhanced erosion in the IYS zone.

  2. Quantifying small-scale temporal surface change on glaciers and salt pans using terrestrial laser scanning: implications for modelling ablation and dust emission

    Science.gov (United States)

    Nield, J. M.; Wiggs, G. F. S.; Leyland, J.; Darby, S. E.; King, J.; Eckardt, F. D.; Chiverrell, R. C.; Vircavs, L. H.; Jacobs, B.

    2012-04-01

    Physical surface roughness is important in glacial and desert environments as it influences aerodynamic roughness, which in turn determines the ability of the wind to contribute to the turbulent heat flux component of the energy balance for glacial ice ablation or the likelihood of a surface emitting dust. Surface microtopography has traditionally been quantified by single 2D transects, but little is known about how these surfaces vary over time and the feedback between surface properties and other geomorphic processes. Terrestrial laser scanning (TLS) is the perfect tool to examine geomorphic microtopography over large spatial areas relatively quickly with the opportunity for repeat temporal measurements. Here we present examples of daily and weekly surface change measured on the Sua Pan, Botswana and the Svínafellsjökull, Iceland with mm accuracy using TLS. For the first time it is possible to quantify salt crust plucking and extrusion events and elucidate links between surface and wind shear interactions, as well as possible changes in aerodynamic roughness over time as surfaces evolve. Clear patterning is evident, with crust expansion limited to topographic highs. Likewise, we illustrate examples of measured daily ablation rates and patterns, and allude to implications for energy balance modelling by improving estimates of aerodynamic roughness. Specific ice patterning includes melt water eroding channels, the unique interactions of surface debris (volcanic ash from the 21 - 30 May 2011 eruption of Grímsvötn) melting out from the glacier and surface water forming a diverse microtopography of debris cones, cryoconite holes and perched blocks. However, whilst TLS represents a step-change in our ability to move from small transect derived roughness measurements to complete 3D surface change, detecting change on mobile surfaces through time is challenging, and linking surface properties to other point-based process measurements can be problematic.

  3. Influence of the atmosphere on the evaluation of the geopotential from global models on the surface of the Earth: implications for the realization of a World Height System

    Science.gov (United States)

    Mäkinen, Jaakko

    2016-04-01

    Outside the atmosphere, the potential of a standard atmosphere can with high accuracy be approximated with the potential of a surface layer with the same mass, independently of the scale height of the atmosphere. Not so when the potential is evaluated on the surface of the Earth. In a spherically symmetric approximation and assuming a scale height of 7.6 km, the potential at zero height is in a back-of-the-envelope calculation 0.12 percent less than the potential of the surface laýer. This corresponds to a difference of -1.2 ppb in the total geopotential evaluated on the surface of the Earth, the equivalent of a difference of +8 mm in height. Using a realistic atmospheric and Earth model, the difference is not constant. This has obvious implications for the geopotential values associated with a World Height System. The question has in fact already been extensively analyzed in the context of geoid determination.

  4. 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

    The Campanian-Maastrichtian limestones in the south of the Netherlands are well-sorted fine-grained mudstones and silt- to fine sand-sized bioclastic grainstones. These limestones show a distinct lithological cyclicity manifested by fining-upward grain-size cycles with calcite-cemented layers...... 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...

  5. 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.

  6. Assembly Synthesis of Sheet-like Calcite Array and Stable-Vaterite by Supported Liquid Membrane

    Institute of Scientific and Technical Information of China (English)

    SUN,Dong-Mei(孙冬梅); WU,Qing-Sheng(吴庆生)

    2004-01-01

    Sheet-like calcite array and stable vaterite were synthesized by bio-mimetic supported liquid membrane system under different reaction conditions. Both of the FTIR spectra of products showed narrower peak at 1418 cm-1 than that of bulk CaCO3, and that of vaterite has a split in this peak.

  7. Higher Order Elastic Constants, Gruneisen Parameters and Lattice Thermal Expansion of Trigonal Calcite

    Directory of Open Access Journals (Sweden)

    Thresiamma Phlip

    2005-01-01

    Full Text Available The second- and third-order elastic constants of trigonal calcite have been obtained using the deformation theory. The strain energy density derived using the deformation theory is compared with the strain dependent lattice energy obtained from the elastic continuum model approximation to get the expressions for the second- and third-order elastic constants. Higher order elastic constants are a measure of the anharmonicity of a crystal lattice. The seven second-order elastic constants and the fourteen non-vanishing third-order elastic constants of trigonal calcite are obtained. The second-order elastic constants C11, which corresponds to the elastic stiffness along the basal plane of the crystal is greater than C33, which corresponds to the elastic stiffness tensor component along the c-axis of the crystal. First order pressure derivatives of the second-order elastic constants of calcite are evaluated. The higher order elastic constants are used to find the generalized Gruneisen parameters of the elastic waves propagating in different directions in calcite. The Brugger gammas are evaluated and the low temperature limit of the Gruneisen gamma is obtained. The results are compared with available reported values.

  8. EPR OF Mn2+ IMPURITIES IN CALCITE: A DETAILED STUDY PERTINENT TO MARBLE PROVENANCE DETERMINATION

    DEFF Research Database (Denmark)

    Weihe, H.; Piligkos, S.; Barra, A.L.;

    2009-01-01

    We demonstrate that the electron paramagnetic resonance spectrum of Mn2+ impurities in calcite, and therefore also in marble, may be accurately reproduced by a traditional spin Hamiltonian formalism. The success of such a treatment, however, very much depends on the spin Hamiltonian parameters ha...

  9. Epr of Mn2+ Impurities in Calcite: A Detailed Study Pertinent to Marble Provenance Determination

    DEFF Research Database (Denmark)

    Weihe, H.; Piligkos, S.; Barra, A.L.;

    2009-01-01

    We demonstrate that the electron paramagnetic resonance spectrum of Mn2+ impurities in calcite, and therefore also in marble, may be accurately reproduced by a traditional spin Hamiltonian formalism. The success of such a treatment, however, very much depends on the spin Hamiltonian parameters ha...

  10. 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.

  11. Elasticity and yielding of a calcite paste: scaling laws in a dense colloidal suspension.

    Science.gov (United States)

    Liberto, Teresa; Le Merrer, Marie; Barentin, Catherine; Bellotto, Maurizio; Colombani, Jean

    2017-03-08

    We address the mechanical characterization of a calcite paste as a model system to investigate the relation between the microstructure and macroscopic behavior of colloidal suspensions. The ultimate goal is to achieve control of the elastic and yielding properties of calcite which will prove valuable in several domains, from paper coating to paint manufacture and eventually in the comprehension and control of the mechanical properties of carbonate rocks. Rheological measurements have been performed on calcite suspensions over a wide range of particle concentrations. The calcite paste exhibits a typical colloidal gel behavior, with an elastic regime and a clear yield strain above which it enters a plastic regime. The yield strain shows a minimum when increasing the solid concentration, connected to a change in the power law scaling of the storage modulus. In the framework of the classical fractal elasticity model for colloidal suspensions proposed by Shih et al. [Phys. Rev. A, 1990, 42, 4772], we interpret this behavior as a switch with the concentration from the strong-link regime to the weak-link regime, which had never been observed so far in one well-defined system without external or chemical forcing.

  12. 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.

  13. Morphological and mechanical characterization of composite calcite/SWCNT-COOH single crystals.

    Science.gov (United States)

    Calvaresi, Matteo; Falini, Giuseppe; Pasquini, Luca; Reggi, Michela; Fermani, Simona; Gazzadi, Gian Carlo; Frabboni, Stefano; Zerbetto, Francesco

    2013-08-01

    A growing number of classes of organic (macro)molecular materials have been trapped into inorganic crystalline hosts, such as calcite single crystals, without significantly disrupting their crystalline lattices. Inclusion of an organic phase plays a key role in enhancing the mechanical properties of the crystals, which are believed to share structural features with biogenic minerals. Here we report the synthesis and mechanical characterization of composite calcite/SWCNT-COOH single crystals. Once entrapped into the crystals SWCNT-COOH appeared both as aggregates of entangled bundles and nanoropes. Their observation was possible only after crystal etching, fracture or FIB (focused ion beam) cross-sectioning. SWCNT-COOHs occupied a small volume fraction and were randomly distributed into the host crystal. They did not strongly affect the crystal morphology. However, although the Young's modulus of composite calcite/SWCNT-COOH single crystals was similar to that of pure calcite their hardness increased by about 20%. Thus, SWCNT-COOHs provide an obstacle against the dislocation-mediated propagation of plastic deformation in the crystalline slip systems, in analogy with the well-known hardness increase in fiber-reinforced composites.

  14. Marine biogeochemistries of Be and Al: A study based on cosmogenic 10Be, Be and Al in marine calcite, aragonite, and opal

    Indian Academy of Sciences (India)

    Weiquan Dong; Devendra Lal; Barbara Ransom; Wolfgang Berger; Marc W Caffee

    2001-06-01

    The geochemical behaviors of Be and Al in ocean waters have been successfully studied in recent years using natural, cosmogenic, radioactive 10Be and 26Al as tracers. The present day dissolved concentrations and distribution of the stable and radioactive isotopes of Be and Al in ocean waters have revealed their short residence times and appreciable effects of exchange uxes at the coastal and ocean-sediment interfaces. It follows that concentrations of these particle-active elements must have varied in the past with temporal changes in climate, biological productivity and aeolian ux of continental detritus to the oceans. We therefore investigated the feasibility of extending the measurements of Be and Al isotope concentrations in marine systems to the 103-106 BP time scale. We report here the discovery of significant amounts of intrinsic Be and Al in marine foraminiferal calcite and coral aragonite, and of Al in opal (radiolarians) and aragonite (coral), which makes it possible to determine 10Be/Be and 26Al/Al in oceans in the past. We also report measured 10Be/9Be in foraminiferal calcite in Pacific Ocean cores, which reveal that the concentrations and ratios of the stable and cosmogenic isotopes of Be and Al have varied significantly in the past 30 ky. The implications of these results are discussed.

  15. Impact of amorphous precursor phases on magnesium isotope signatures of Mg-calcite

    Science.gov (United States)

    Mavromatis, Vasileios; Purgstaller, Bettina; Dietzel, Martin; Buhl, Dieter; Immenhauser, Adrian; Schott, Jacques

    2017-04-01

    Various marine calcifiers form exoskeletons via an amorphous calcium carbonate (ACC) precursor phase and magnesium plays an important role in the temporary stabilization of this metastable phase. Thus, the use of Mg isotope ratios of marine biogenic carbonates as a proxy to reconstruct past seawater chemistry calls for a detailed understanding of the mechanisms controlling Mg isotope signatures during the formation and transformation of ACC to the final crystalline carbonate mineral. For this purpose we have investigated the Mg isotope fractionation between (Ca,Mg)CO3 solids and aqueous fluids at 25 °C and pH = 8.3 during (i) the direct precipitation of crystalline Mg-calcite and (ii) the formation of Mg-rich ACC (Mg-ACC) and its transformation to Mg-calcite. The outcome documents that the small Mg isotope fractionation between Mg-ACC and reactive fluid (ΔMg26ACC-fluid = - 1.0 ± 0.1 ‰) is not preserved during the transformation of the ACCs into Mg-calcite. Following a pronounced isotopic shift accompanying the transformation of Mg-ACC into Mg-calcite, Δ26Mgcalcite-fluid progressively decreases with reaction progress from ∼ - 3.0 ‰ to - 3.6 ‰, reflecting both the approach of isotopic equilibrium and the increase of calcite Mg content (to near 20 mol % Mg). In contrast the crystalline Mg-calcite precipitated directly from the reacting fluid, i.e. lacking a discernable formation of an amorphous precursor, exhibits only small temporal variations in Δ26Mgcalcite-fluid which overall is affected by the precipitation kinetics. The values found in this study at the onset of Mg-ACC precipitation for Mg isotope fractionation between Mg-ACC and the fluid (ΔMg26ACC-fluid = - 1.0 ‰) and between Mg-ACC and Mg2+(aq) (Δ(aq) 26 Mg ACC-Mg2+ = + 2.0 ‰) are consistent with the formation of a hydrated Ca nanoporous solid accommodating Mg bicarbonate/carbonate species in combination with hydrated magnesium. This material crossed by percolating channels filled with the

  16. Tracing formation and durability of calcite in a Punic-Roman cistern mortar (Pantelleria Island, Italy).

    Science.gov (United States)

    Dietzel, Martin; Schön, Frerich; Heinrichs, Jens; Deditius, Artur P; Leis, Albrecht

    2016-01-01

    Ancient hydraulic lime mortar preserves chemical and isotopic signatures that provide important information about historical processing and its durability. The distribution and isotopic composition of calcite in a mortar of a well-preserved Punic-Roman cistern at Pantelleria Island (Italy) was used to trace the formation conditions, durability, and individual processing periods of the cistern mortar. The analyses of stable carbon and oxygen isotopes of calcite revealed four individual horizons, D, E, B-1 and B-2, of mortar from the top to the bottom of the cistern floor. Volcanic and ceramic aggregates were used for the production of the mortar of horizons E/D and B-1/B-2, respectively. All horizons comprise hydraulic lime mortar characterized by a mean cementation index of 1.5 ± 1, and a constant binder to aggregate ratio of 0.31 ± 0.01. This suggests standardized and highly effective processing of the cistern. The high durability of calcite formed during carbonation of slaked lime within the matrix of the ancient mortar, and thus the excellent resistance of the hydraulic lime mortar against water, was documented by (i) a distinct positive correlation of δ(18)Ocalcite and δ(13)Ccalcite; typical for carbonation through a mortar horizon, (ii) a characteristic evolution of δ(18)Ocalcite and δ(13)Ccalcite through each of the four mortar horizons; lighter follow heavier isotopic values from upper to lower part of the cistern floor, and (iii) δ(18)Ocalcite varying from -10 to -5 ‰ Vienna Pee Dee belemnite (VPDB). The range of δ(18)Ocalcite values rule out recrystallization and/or neoformation of calcite through chemical attack of water stored in cistern. The combined studies of the chemical composition of the binder and the isotopic composition of the calcite in an ancient mortar provide powerful tools for elucidating the ancient techniques and processing periods. This approach helps to evaluate the durability of primary calcite and demonstrates the

  17. The Early Morphological Development of the Near Surface Region of Pickled Grade 91 Tubing Exposed to Steam and Its Long Term Implications

    Directory of Open Access Journals (Sweden)

    David M. Gorman

    2016-03-01

    Full Text Available To improve intra-laboratory consistency and experimental repeatability during high temperature oxidation testing, metallic coupons undergo a standardised surface preparation. It is stipulated in international testing standards that grinding of a coupons surface acceptably replicates surface conditions encountered in industrial settings whilst ensuring that each coupons surface is chemically and topographically homogenised [1,2]. Grade 91 steel tubing exposed in the laboratory to flowing steam at 650 °C and 1 bar for up to 3000 h has been compared with Grade 91 tubing exposed in a commercially operated boiler system at elevated pressures at temperatures in the range of 500 to 650 °C for 91 kh. It has been found that a pre-existing surface structure dissimilar from that of the bulk alloy and that of a ground surface, is present on the inside surface of the tubing. The presence of pre-existing surface features in commercially exposed material has implications on the long term morphological development of the oxidation region and may account for some of the discrepancies between observations made in laboratory and service exposures.

  18. Diagenetic Mg-calcite overgrowths on foraminiferal tests in the vicinity of methane seeps

    Science.gov (United States)

    Panieri, Giuliana; Lepland, Aivo; Whitehouse, Martin J.; Wirth, Richard; Raanes, Morten P.; James, Rachael H.; Graves, Carolyn A.; Crémière, Antoine; Schneider, Andrea

    2017-01-01

    Methane is a potent greenhouse gas and some episodes of past global warming appear to coincide with its massive release from seafloor sediments as suggested by carbon isotope records of foraminifera. Here, we present structural, geochemical, and stable carbon isotope data from single foraminiferal calcite tests and authigenic Mg-calcite overgrowths in a sediment core recovered from an area of active methane seepage in western Svalbard at ca. 340 m water depth. The foraminifera are from intervals in the core where conventional bulk foraminiferal δ13 C values are as low as -11.3 ‰. Mg/Ca analyses of the foraminiferal tests reveal that even tests for which there is no morphological evidence for secondary authigenic carbonate can contain Mg-rich interlayers with Mg/Ca up to 220 mmol/mol. Transmission electron microscopy (TEM) of the contact point between the biogenic calcite and authigenic Mg-calcite layers shows that the two phases are structurally indistinguishable and they have the same crystallographic orientation. Secondary ion mass spectrometry (SIMS) analyses reveal that the Mg-rich layers are strongly depleted in 13C (δ13 C as low as -34.1 ‰). These very low δ13 C values indicate that the authigenic Mg-calcite precipitated from pore waters containing methane-derived dissolved inorganic carbon at the depth of the sulfate-methane transition zone (SMTZ). As the depth of the SMTZ can be located several meters below the sediment-seawater interface, interpretation of low foraminiferal δ13 C values in ancient sediments in terms of the history of methane seepage at the seafloor must be undertaken with care.

  19. Model uncertainties affecting satellite-based inverse modeling of nitrogen oxides emissions and implications for surface ozone simulation

    Directory of Open Access Journals (Sweden)

    J.-T. Lin

    2012-06-01

    for emission inversion without corrections. The modifications however cannot account for the large model underestimates in cities and other extremely polluted areas (particularly in the north as compared to satellite retrievals, likely pointing to underestimates of the a priori emission inventory in these places with important implications for understanding of atmospheric chemistry and air quality. Post-model modifications also have large impacts on surface ozone concentrations with the peak values in July over North China decreasing by about 15 ppb. Individually, modification for the uptake of the hydroperoxyl radical on aerosols has the largest impact for both NO2 and ozone, followed by various other parameters important for some species in some seasons. Note that these modifications are simplified and should be used with caution for error apportionment.

  20. Spatial distribution of calcite and amorphous calcium carbonate in the cuticle of the terrestrial crustaceans Porcellio scaber and Armadillidium vulgare.

    Science.gov (United States)

    Hild, Sabine; Marti, Othmar; Ziegler, Andreas

    2008-07-01

    The crustacean cuticle is an interesting model to study the properties of mineralized bio-composites. The cuticle consists of an organic matrix composed of chitin-protein fibres associated with various amounts of crystalline and amorphous calcium carbonate. It is thought that in isopods the relative amounts of these mineral polymorphs depend on its function and the habitat of the animal. In addition to the composition, the distribution of the various components should affect the properties of the cuticle. However, the spatial distribution of calcium carbonate polymorphs within the crustacean cuticle is unknown. Therefore, we analyzed the mineralized cuticles of the terrestrial isopods Armadillidium vulgare and Porcellio scaber using scanning electron-microscopy, electron probe microanalysis and confocal mu-Raman spectroscopic imaging. We show for the first time that the mineral phases are arranged in distinct layers. Calcite is restricted to the outer layer of the cuticle that corresponds to the exocuticle. Amorphous calcium carbonate is located within the endocuticle that lies below the exocuticle. Within both layers mineral is arranged in rows of granules with diameters of about 20 nm. The results suggest functional implications of mineral distribution that accord to the moulting and escape behaviour of the animals.

  1. Atomic Processes on Mineral Surfaces

    Science.gov (United States)

    Hillner, Paul Everett

    This thesis describes research using atomic force microscopy (AFM) to observe the growth and dissolution mechanisms of crystals. Chapter 1 starts with an overview of crystal growth theory and then outlines the impact of AFM on the field. Chapter 2 introduces the techniques of real-time AFM imaging of crystal growth and shows the strong preferential dissolution of material at defects. Chapter 3 expands the importance of crystal defects, showing the importance of spiral defects to the aqueous growth of calcite. Chapter 4 presents a rigorous analysis of step kinetics on calcite and shows that surface diffusion is not the controlling factor of growth rate. Chapter 5 examines the effect of solvent modifications on the growth morphology of spiral hillocks on calcite and also determines the mechanisms by which manmade and natural poisons stop crystal growth. Chapter 6 presents quantitative calcite spiral rotation rates and step velocities vs. supersaturation as well as contrasting the layer-spiral growth mechanism of calcite with the poly -nucleation growth mechanism of fluorite.

  2. 磷酸盐改性方解石去除水中磷酸盐研究%Removal of phosphate from aqueous solution by phosphate-modified calcite

    Institute of Scientific and Technical Information of China (English)

    林建伟; 李佳; 詹艳慧

    2013-01-01

    Previous literatures have shown that calcite can be used to effectively remove phosphate from aqueous solution. In this study, the calcite-phosphate reaction product, i.e., phosphate-modified calcite was reused to remove phosphate from aqueous solution. The phosphate removal kinetics of natural calcite and phosphate-modified calcite were compared. The effect of various experimental conditions such as solution pH, initial phosphate concentration, temperature, Ca2+ and HCO3- on phosphate removal by phosphate-modified calcite was investigated. The phosphate removal efficiency of phosphate-modified calcite was much higher than that of natural calcite. When the reaction time was 2 h, the phosphate removal efficiency of phosphate-modified calcite was 72%under the experimental conditions, which was much higher than that of natural calcite (35%). The phosphate removal efficiency of phosphate-modified calcite was relatively high at pH 5-7, slightly decreased with increasing pH from 7 to 10, and significantly decreased with increasing pH from 10 to 12. The amount of phosphate removed by phosphate-modified calcite increased with increasing initial phosphate concentration. The phosphate removal efficiency of phosphate-modified calcite decreased with increasing initial phosphate concentration at a relatively high initial phosphate-phosphorus concentration (60-160 mg·L-1). The phosphate removal efficiency of phosphate-modified calcite increased with increasing temperature. The phosphate removal kinetics of phosphate-modified calcite followed a pseudo-second-order kinetic model. The removal of phosphate by phosphate-modified calcite occurred predominantly via the precipitation of calcium phosphate according to two consecutive phases:first, the dissolution of calcite produced an increase in the Ca2+concentration;then the Ca2+ions reacted with the phosphate ions to form the precipitate of calcium phosphate. The precipitation of calcium phosphate took place at the surface of

  3. Temporal Variation in the Stable Isotopic Composition of Water and Sediment in Seneca Lake, NY (USA): Implications for Paleoclimate Reconstructions

    Science.gov (United States)

    Curtin, T.; Finkelstein, D. B.; Gunn, P.

    2014-12-01

    Paleoclimatic studies often use stratigraphic changes in the oxygen isotope composition (δ18O) of lacustrine carbonate to infer changes in water temperature and/or the δ18O of lake water. To better understand the environmental factors that influence the isotopic composition of lacustrine carbonates and the assumptions that need to be made to infer past changes in climate, we undertook a four-year study of the water chemistry and sediment trap material in Seneca Lake (NY, USA), a large, monomictic, glacial, hardwater lake. Sediment trap material collected weekly between May 2009 and 2013 together with isotopic monitoring of surface and bottom water allow for analysis of the controls on calcite precipitation in the lake. We show that calcite mainly accumulates in traps July through September when the lake water column is stratified and epilimnetic water temperature exceeds 20°C. Up to ~70% of the sediment is comprised of calcite during summer and only ~10% of the sediment is calcite during autumn, winter, and spring. The δ18O of Seneca Lake epilimnetic water varies by only ~0.6 ‰ throughout the year whereas the δ18O of bulk carbonate varies by as much as 2.4‰. As calcite precipitates in the eplimnion, the δ18O declines. Likely due to the large volume and residence time of water, the δ18O of Seneca Lake water appears to track changes in temperature. Our temperature reconstruction using the δ18O of calcite and epilimnetic lake water reveals that calcite was a reasonable proxy for lake surface temperature from July through September. During the remainder of the year, reconstructed temperatures exceed actual temperatures by as much as 18°C. Sediment resuspension (including calcite) during isothermal conditions may explain why calcite is a poor predictor of lake surface temperature in late autumn though spring. The δ18O of calcite in this lake records summer temperatures rather than year-round conditions.

  4. Commentary on the state of knowledge of the origins of the Yucca Mountain calcite veins. Special report number 17, Contract number 94/96.0003

    Energy Technology Data Exchange (ETDEWEB)

    Archambeau, C.

    1994-08-01

    This report is a compilation of papers and a letter providing technical information on the origin and geochemistry of calcite veins and calcretes in the vicinity of the Yucca Mountain repository. The information is presented to demonstrate that these deposits may be ``thermogenic`` in origin with some alteration by pedogenic processes. The papers present isotope ratios of uranium, strontium, and carbon to support the claims for a hydrothermal source. The letter provides a critical review of a previous paper presented at the 64th Advisory Committee on Nuclear Waste. The report makes an attempt to emphasize the need to review this possible origin because it has dramatic implications on the geologic history, paleo-ground water levels, and integrity of the repository.

  5. Chiral morphology of calcite through selective binding of amino acids

    Science.gov (United States)

    Orme, Christine

    2002-03-01

    Many living organisms contain biominerals and composites with finely tuned properties, reflecting a remarkable level of control over the nucleation, growth and shape of the constituent crystals. Peptides and proteins play an important role in achieving this control. Using in situ AFM we find that site-specific binding of amino acid residues to surface steps changes the step-edge free energies, giving rise to direction-specific binding energies unique to individual amino acid enantiomers and leading to chiral modifications that propagate from atomic length scales to macroscopic length scales. Molecular modeling studies support an energetic basis for the differences in binding. Our results emphasize that the mechanism under-lying crystal modification through organic molecules is best understood by considering both stereochemical recognition as well as the effects of binding on the interfacial energies of the growing crystal.

  6. A preliminary study of the calcite beef found in the Cretaceous Jinju Formation, Gyeongsang Basin, South Korea

    Science.gov (United States)

    Ha, S.; Chae, Y. U.; Son, M.; Jeong, G. Y.; Paik, I. S.; Lim, H. S.

    2015-12-01

    The term "beef" refers to fibrous minerals in bedding-parallel veins, where the fibers are approximately perpendicular to the vein margins (Cobbold et al., 2013). It mostly appears within organic-rich black shale layers in sedimentary basin. Although the veins can consist of white gangue minerals, such as calcite, gypsum, or quartz, the commonest mineral in the fibers is calcite. According to the worldwide localities of calcite beef compiled by Cobbold et al (2012), they concentrated in some areas, especially around the Atlantic Ocean. However, they have been rarely reported in the western Pacific margin, except Australia and New Zealand. Recently, calcite beefs have been found in the Cretaceous Jinju Formation, Gyeongsang Basin, Korea. As far as we know, this is the first report of calcite beef in Korea. The lacustrine Jinju Formation is about 1,200 m thick, and made up mainly of lacustrine dark grey to black mudstones. In the study area, calcite beefs were commonly found in the organic-rich black shale layers. The vein thickness is anywhere between a few millimeters to maximum 3 centimeters, and their length ranges from a few centimeters to several tens of meters. The interval between successive veins is from a few centimeters to about 1 meter. Most of them occur parallel to the bedding planes, although some of them are developed along fault planes or within deformed layers. In case of relatively thick beefs, the center of veins often shows a dark grey to black central median line, defined by fine-grained calcite grains, fluid inclusion lines, or wall rock particles. Based on the orientation of fibrous calcite, they can be divided into two types: straight and sigmoidal types. The fibrous calcites are thought to have been symmetrically grown from the median lines to top and bottom of wall rock. The formation mechanism of horizontal fractures, and the formation temperature of beefs in the study area remain as a matter to be studied further.

  7. U-Th dating of calcite corals from the Gulf of Aqaba

    Science.gov (United States)

    Yehudai, Maayan; Lazar, Boaz; Bar, Neta; Kiro, Yael; Agnon, Amotz; Shaked, Yonathan; Stein, Mordechai

    2017-02-01

    Most of the fossil corals in the elevated reef terraces along the Gulf of Aqaba (GOA) were extensively altered to calcite. This observation indicates extensive interaction with freshwater, possibly when the terraces passed through a coastal aquifer that existed along the shores of the GOA, implying a wetter climate during the time of recrystallization from aragonite to calcite. Thus, dating of the recrystallization events should yield the timing of past wetter conditions in the current hyper-arid area of the GOA. In the present study, 18 aragonite and calcite corals were collected from several elevated coral reef terraces off the coast, south of the city of Aqaba. While aragonite corals were dated with the conventional closed system age equation (assuming zero initial Th), the dating of the calcite corals required the development of adequate equations to allow the calculation of both the initial formation age of the aragonite corals and the time of recrystallization to calcite. The two age calculations were based on the assumptions that each reef terrace went through a single and rapid recrystallization event and that the pristine aragonite corals were characterized by a rather uniform initial U concentration, typical for pristine modern corals. Two recrystallization events were identified at 104 ± 6 ka and 124 ± 8 ka. The ages coincide with the timing of sapropel events S4 and S5, respectively, when the African monsoon induced enhanced wetness in the desert area. Considering the age uncertainties, the times of formation of the two major reef terraces are estimated to be ∼124 ka (reef terrace R2) and ∼130 ka (reef terrace R3), matching the peaks in the global sea level during the last interglacial MIS 5e stage. Apparently, sea level of the GOA did not fluctuate a lot during the period between ∼130 ka and ∼104 ka and remained close to the Marine Isotopic stage (MIS) 5e highstand. The availability of freshwater (during the sapropel periods) and limited sea

  8. 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

  9. Evaporative Control on Soil Water Isotope Ratios: Implications for Atmosphere-Land Surface Water Fluxes and Interpretation of Terrestrial Proxy Records

    Science.gov (United States)

    Kaushik, A.; Noone, D. C.; Berkelhammer, M. B.; O'Neill, M.

    2014-12-01

    model at the land surface to weight the contributions of rainfall, surface water vapor exchange and sub-surface vapor diffusion to soil water isotope values. This has implications both for modeling short-term gas exchange at the land surface as well as for estimating past evaporative conditions from proxies like cave deposits and tree cellulose.

  10. 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.

  11. 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

  12. Experimental fractionation of stable carbon isotopes during degassing of carbon dioxide and precipitation of calcite from aqueous solutions

    Science.gov (United States)

    Müller, K.; Winde, V.; Escher, P.; von Geldern, R.; Böttcher, M. E.

    2012-04-01

    Processes in the carbonate system of surface waters are in particular sensitive to variations of boundary conditions as, for instance, the partial pressure of carbon dioxide in the atmosphere and the aqueous solution. Examples range from streams, rivers, to coastal marine waters. The flux of carbon dioxide from continental flowing waters was recently included into calculations of the global carbon budget (Butman & Raymond, 2011, Nature Geo.). These solutions, are often supersaturated in carbon dioxide with respect to the atmosphere. The degassing of carbon dioxide is associated with a kinetically controlled fractionation of the stable carbon isotopes, which has to be considered in balancing water-air carbon dioxide fluxes. The degassing process additionally leads to the super-saturation of the aqueous solution with respect to calcium carbonate. Stable isotope fractionation is of particular value to identify and quantify processes at the water-gas phase interface and link these non-equilibrium processes to the formation mechanisms of calcite and the hydrodynamics of surface waters. Experiments were carried out with or without inert N2 gas flow to degas carbon dioxide from initially supersaturated solutions. Natural solutions used are from different stations of the Elbe estuary, the Jade Bay, the backbarrier tidal area of Spiekeroog Island, carbonate springs of Rügen Island, and the Baltic Sea coastline. Results are compared experiments using bottled mineral waters. By following the (physico) chemical changes in the solutions (pH, TA, Ca PHREEQC modeling) it was found, that two evolutionary stages can be differentiated. Reaction progress led to the preferential liberation of carbon dioxide containing the light carbon isotope, following a Rayleigh-type process. After an induction period, where only degassing of carbon dioxide took place, a second stage was observed where calcite began to form from the highly supersaturated solutions. In this stage the carbonate

  13. Ocean acidification: Towards a better understanding of calcite dissolution

    Science.gov (United States)

    Wilhelmus, Monica M.; Adkins, Jess; Menemenlis, Dimitris

    2016-11-01

    The drastic increase of anthropogenic CO2 emissions over the past two centuries has altered the chemical structure of the ocean, acidifying upper ocean waters. The net impact of this pH decrease on marine ecosystems is still unclear, given the unprecedented rate at which CO2 is being released into the atmosphere. As part of the carbon cycle, calcium carbonate dissolution in sediments neutralizes CO2: phytoplankton at the surface produce carbonate minerals, which sink and reach the seafloor after the organisms die. On time scales of thousands of years, the calcium carbonate in these shells ultimately reacts with CO2 in seawater. Research in this field has been extensive; nevertheless, the dissolution rate law, the impact of boundary layer transport, and the feedback with the global ocean carbon cycle remain controversial. Here, we (i) develop a comprehensive numerical framework via 1D modeling of carbonate dissolution in sediments, (ii) approximate its impact on water column properties by implementing a polynomial approximation to the system's response into a global ocean biogeochemistry general circulation model (OBGCM), and (iii) examine the OBGCM sensitivity response to different formulations of sediment boundary layer properties. We find that, even though the burial equilibration time scales of calcium carbonate are in the order of thousands of years, the formulation of a bottom sediment model along with an improved description of the dissolution rate law can have consequences on multi-year to decadal time scales.

  14. Geochemistry of speleothems affected by aragonite to calcite recrystallization - Potential inheritance from the precursor mineral

    Science.gov (United States)

    Domínguez-Villar, David; Krklec, Kristina; Pelicon, Primož; Fairchild, Ian J.; Cheng, Hai; Edwards, Lawrence R.

    2017-03-01

    Formerly aragonite speleothems recrystallized to calcite result from solutions subsaturated in aragonite and supersaturated in calcite that infiltrate into the speleothem through the interconnected porosity. In most cases, the crystal replacement takes place through a thin solution film. This diagenetic process can occur under open or semi-closed geochemical conditions. Thus, secondary calcite crystals record the composition of the fluid at the time of diagenesis affected by calcite partition coefficients and fractionation factors (open system) or partly inherit the composition of the primary aragonite (semi-closed system). So, whether or not recrystallized aragonite speleothems can record reliable geochemical signals from the time of speleothem primary deposition still is an open debate. We studied a stalagmite from Eagle Cave (Spain) predominantly composed of secondary calcite that replaced aragonite, although a core of primary aragonite extending 45 mm along the growth direction was preserved at the base of the sample. We obtained Mg and Sr compositional maps, paired U-Th dating and δ18O and δ13C profiles across the diagenetic front. Additionally, two parallel isotope records were obtained along the speleothem growth direction in the aragonite and calcite sectors. Our results support that recrystallization of this speleothem took place in open system conditions for δ18O, δ13C, Mg and Sr, but in semi-closed system conditions for U and Th. The recrystallization of this sample took place during one or several events, likely after the Younger Dryas as a result of climate change influencing drip water composition. Based on compositional zoned patterns, we suggest that the advance of diagenetic fronts in this speleothem had an average rate of 50 ± 45 μm/yr. Such recrystallization rate can transform any aragonite speleothem into calcite within a few centuries. We suggest that the volume of water interacting with the speleothem at the time of recrystallization is

  15. 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

  16. 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.

  17. Deformation twinning and the role of amino acids and magnesium in calcite hardness from molecular simulation.

    Science.gov (United States)

    Côté, A S; Darkins, R; Duffy, D M

    2015-08-21

    We employ classical molecular dynamics to calculate elastic properties and to model the nucleation and propagation of deformation twins in calcite, both as a pure crystal and with magnesium and aspartate inclusions. The twinning is induced by applying uniaxial strain to the crystal and relaxing all stress components except the uniaxial component. A detailed analysis of the atomistic processes reveal that the twinning mechanism involves small displacements of the Ca ions and cooperative rotations of the CO3 ions. The volume of the twinned region expands under increased uniaxial strain via the propagation of steps along the twin boundaries. The energy cost of the twin boundaries is compensated by the reduced hydrostatic stress and strain energy. The presence of biogenic impurities is shown to decrease the strain required to induce twin formation in calcite and, thus, the yield stress. This increased propensity for twinning provides a possible explanation for the increased hardness and penetration resistance observed experimentally in biominerals.

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

    Science.gov (United States)

    Marsili, Enrico; Beyenal, Haluk; Di Palma, Luca; Merli, Carlo; Dohnalkova, Alice; Amonette, James E; Lewandowski, Zbigniew

    2007-12-15

    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.

  19. Functionalizing single crystals: incorporation of nanoparticles inside gel-grown calcite crystals.

    Science.gov (United States)

    Liu, Yujing; Yuan, Wentao; Shi, Ye; Chen, Xiaoqiang; Wang, Yong; Chen, Hongzheng; Li, Hanying

    2014-04-14

    Synthetic single crystals are usually homogeneous solids. Biogenic single crystals, however, can incorporate biomacromolecules and become inhomogeneous solids so that their properties are also extrinsically regulated by the incorporated materials. The discrepancy between the properties of synthetic and biogenic single crystals leads to the idea to modify the internal structure of synthetic crystals to achieve nonintrinsic properties by incorporation of foreign material. Intrinsically colorless and diamagnetic calcite single crystals are turned into colored and paramagnetic solids, through incorporation of Au and Fe3O4 nanoparticles without significantly disrupting the crystalline lattice of calcite. The crystals incorporate the nanoparticles and gel fibers when grown in agarose gel media containing the nanoparticles, whereas the solution-grown crystals do not. As such, our work extends the long-history gel method for crystallization into a platform to functionalize single-crystalline materials.

  20. Capillarity creates single-crystal calcite nanowires from amorphous calcium carbonate.

    Science.gov (United States)

    Kim, Yi-Yeoun; Hetherington, Nicola B J; Noel, Elizabeth H; Kröger, Roland; Charnock, John M; Christenson, Hugo K; Meldrum, Fiona C

    2011-12-23

    Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product.

  1. Microcracking in calcite and dolomite marble: microstructural influences and effects on properties

    OpenAIRE

    Shushakova, Victoria; Fuller, Edwin; Siegesmund, Siegfried

    2012-01-01

    Microstructure‐based finite-element analysis with a microcracking algorithm was used to simulate an actual degradation phenomenon of marble structures, i.e., microcracking. Both microcrack initiation and crack propagation were characterized, as were their dependence on lattice preferred orientation (LPO), grain shape preferred orientation (SPO), grain size, marble composition (calcite and dolomite) and grain‐boundary fracture toughness. Two LPOs were analyzed: a random orientation distributio...

  2. Identification of spectrally similar materials using the USGS Tetracorder algorithm: The calcite-epidote-chlorite problem

    Science.gov (United States)

    Dalton, J.B.; Bove, D.J.; Mladinich, C.S.; Rockwell, B.W.

    2004-01-01

    A scheme to discriminate and identify materials having overlapping spectral absorption features has been developed and tested based on the U.S. Geological Survey (USGS) Tetracorder system. The scheme has been applied to remotely sensed imaging spectroscopy data acquired by the Airborne Visible and Infrared Imaging Spectrometer (AVIRIS) instrument. This approach was used to identify the minerals calcite, epidote, and chlorite in the upper Animas River watershed, Colorado. The study was motivated by the need to characterize the distribution of calcite in the watershed and assess its acid-neutralizing potential with regard to acidic mine drainage. Identification of these three minerals is difficult because their diagnostic spectral features are all centered at 2.3 ??m, and have similar shapes and widths. Previous studies overestimated calcite abundance as a result of these spectral overlaps. The use of a reference library containing synthetic mixtures of the three minerals in varying proportions was found to simplify the task of identifying these minerals when used in conjunction with a rule-based expert system. Some inaccuracies in the mineral distribution maps remain, however, due to the influence of a fourth spectral component, sericite, which exhibits spectral absorption features at 2.2 and 2.4 ??m that overlap the 2.3-??m absorption features of the other three minerals. Whereas the endmember minerals calcite, epidote, chlorite, and sericite can be identified by the method presented here, discrepancies occur in areas where all four occur together as intimate mixtures. It is expected that future work will be able to reduce these discrepancies by including reference mixtures containing sericite. ?? 2004 Elsevier Inc. All rights reserved.

  3. Higher Order Elastic Constants, Gruneisen Parameters and Lattice Thermal Expansion of Trigonal Calcite

    OpenAIRE

    Thresiamma Phlip; Menon, C S; Indulekha, K.

    2005-01-01

    The second- and third-order elastic constants of trigonal calcite have been obtained using the deformation theory. The strain energy density derived using the deformation theory is compared with the strain dependent lattice energy obtained from the elastic continuum model approximation to get the expressions for the second- and third-order elastic constants. Higher order elastic constants are a measure of the anharmonicity of a crystal lattice. The seven second-order elastic constants and the...

  4. 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.

  5. 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.

  6. Shock Waves Trigger Fault Weakening in Calcite-bearing Rocks During Earthquakes

    Science.gov (United States)

    Spagnuolo, E.; Plumper, O.; Violay, M.; Cavallo, A.; Di Toro, G.

    2014-12-01

    The weakening mechanism of calcite-bearing rocks is still poorly understood though many major earthquakes stroke within carbonate sequences. Insights derive from the laboratory: in experiments performed on calcite-bearing gouges, up to 90% drop in friction is associated to grain size reduction to the nanoscale and the formation of crystal-plastic microstructures suggesting the activation of debated weakening mechanisms (e.g., grain boundary sliding and diffusion creep; nanopowder lubrication). Whatever the case, it is unclear how nanoparticles form and what their role is at the initiation of sliding. To investigate initial fault instability we sheared with a rotary shear apparatus SHIVA pre-cut ring-shaped solid cylinders (50/30 mm ext/int diameter) of Carrara marble (99.9% CaCO3). Rock cylinders were slid for few millimetres(0, 1.5 mm and 5mm) at accelerations (6.5 ms-2) and normal stresses (10 MPa) approaching seismic deformation conditions. Initial slip (nano-fracturing have occurred preserving the grain shape (pulverization) and (3) reaction products attributable to high pressure and high temperature conditions (i.e. calcite decomposition into amorphous carbon rimming the nanograins). All the above features are typical of shock-induced changes in minerals. We interpret the above observations as follows: pre-existing grain boundaries or newly formed defects are the nuclei for the generation of dislocations and for their pile-up; the fast release of those piles-up in avalanches under rapid stress loading (fast moving dislocations) may explain the origin of such a shock-like behaviour responsible for large initial frictional weakening. The passage of the shock wave induces pervasive nanofracturing with grain size reduction to the nano-scale and an abrupt temperature rise responsible for calcite decarbonation and formation of carbon amorphous material.

  7. Biomineralization processes of calcite induced by bacteria isolated from marine sediments.

    Science.gov (United States)

    Wei, Shiping; Cui, Hongpeng; Jiang, Zhenglong; Liu, Hao; He, Hao; Fang, Nianqiao

    2015-06-01

    Biomineralization is a known natural phenomenon associated with a wide range of bacterial species. Bacterial-induced calcium carbonate precipitation by marine isolates was investigated in this study. Three genera of ureolytic bacteria, Sporosarcina sp., Bacillus sp. and Brevundimonas sp. were observed to precipitate calcium carbonate minerals. Of these species, Sporosarcina sp. dominated the cultured isolates. B. lentus CP28 generated higher urease activity and facilitated more efficient precipitation of calcium carbonate at 3.24 ± 0.25 × 10(-4) mg/cell. X-ray diffraction indicated that the dominant calcium carbonate phase was calcite. Scanning electron microscopy showed that morphologies of the minerals were dominated by cubic, rhombic and polygonal plate-like crystals. The dynamic process of microbial calcium carbonate precipitation revealed that B. lentus CP28 precipitated calcite crystals through the enzymatic hydrolysis of urea, and that when ammonium ion concentrations reached 746 mM and the pH reached 9.6, that favored calcite precipitation at a higher level of 96 mg/L. The results of this research provide evidence that a variety of marine bacteria can induce calcium carbonate precipitation, and may influence the marine carbonate cycle in natural environments.

  8. Effects of limestone petrography and calcite microstructure on OPC clinker raw meals burnability

    Science.gov (United States)

    Galimberti, Matteo; Marinoni, Nicoletta; Della Porta, Giovanna; Marchi, Maurizio; Dapiaggi, Monica

    2016-12-01

    Limestone represents the main raw material for ordinary Portland cement clinker production. In this study eight natural limestones from different geological environments were chosen to prepare raw meals for clinker manufacturing, aiming to define a parameter controlling the burnability. First, limestones were characterized by X-Ray Fluorescence, X-Ray Powder Diffraction and Optical Microscopy to assess their suitability for clinker production and their petrographic features. The average domains size and the microstrain of calcite were also determined by X-Ray Powder Diffraction line profile analysis. Then, each limestone was admixed with clay minerals to achieve the adequate chemical composition for clinker production. Raw meals were thermally threated at seven different temperatures, from 1000 to 1450 °C, to evaluate their behaviour on heating by ex situ X-Ray Powder Diffraction and to observe the final clinker morphology by Scanning Electron Microscopy. Results indicate the calcite microstrain is a reliable parameter to predict the burnability of the raw meals, in terms of calcium silicates growth and lime consumption. In particular, mixtures prepared starting from high-strained calcite exhibit a better burnability. Later, when the melt appears this correlation vanishes; however differences in the early burnability still reflect on the final clinker composition and texture.

  9. Biomineralization processes of calcite induced by bacteria isolated from marine sediments

    Directory of Open Access Journals (Sweden)

    Shiping Wei

    2015-06-01

    Full Text Available Biomineralization is a known natural phenomenon associated with a wide range of bacterial species. Bacterial-induced calcium carbonate precipitation by marine isolates was investigated in this study. Three genera of ureolytic bacteria, Sporosarcina sp., Bacillus sp. and Brevundimonas sp. were observed to precipitate calcium carbonate minerals. Of these species, Sporosarcina sp. dominated the cultured isolates. B. lentus CP28 generated higher urease activity and facilitated more efficient precipitation of calcium carbonate at 3.24 ± 0.25 × 10−4 mg/cell. X-ray diffraction indicated that the dominant calcium carbonate phase was calcite. Scanning electron microscopy showed that morphologies of the minerals were dominated by cubic, rhombic and polygonal plate-like crystals. The dynamic process of microbial calcium carbonate precipitation revealed that B. lentus CP28 precipitated calcite crystals through the enzymatic hydrolysis of urea, and that when ammonium ion concentrations reached 746 mM and the pH reached 9.6, that favored calcite precipitation at a higher level of 96 mg/L. The results of this research provide evidence that a variety of marine bacteria can induce calcium carbonate precipitation, and may influence the marine carbonate cycle in natural environments.

  10. Effect of Solute Impurity of Mg on the Microstructure of Calcite

    Science.gov (United States)

    Xu, L.; Evans, B. J.; Renner, J.

    2006-12-01

    We produced synthetic marbles by hot isostatic pressing (HIPing) mixtures of calcite and dolomite powders for different intervals (2 to 30 hrs) at 850°C and 300 MPa confining pressure. The HIP treatment resulted in macroscopically homogeneous calcite aggregates with Mg content ranging from 0.5 to 17 mol%. We performed creep tests on samples after HIP at differential stresses from ~ 20 to 170 MPa using constant strain rate and stress-stepping method. Microstructure of both HIPed and deformed samples were studied using both scanning electron microscope (SEM) and transmitted electron microscope (TEM). Both back- scattered electron images and chemical analysis using ion probe suggested that the dolomite phase is completely dissolved, and that the Mg distribution is homogeneous throughout the samples at a scale of a few microns. Grain sizes increase with HIP time and decrease with increasing Mg content (> 3.0 mol%). The growth exponent varies from 2.7 to 3.5 for samples containing 0.3 to 17.0 mol% Mg. Some HIPed samples have intragranular spherical pores, but the shape of the grain boundaries indicates pore drag. At stresses above 80 MPa, the stress sensitivity of strain, n, is greater than 3, indicating an increasing contribution of dislocation creep. The strength of calcite increases with the Mg content in the dislocation creep regime, but not when the rocks deform by diffusion creep. In some deformed samples (ɛ ~ 0.25), a bimodal distribution of large protoblasts and small recrystallized neoblasts coexisted..

  11. Numerical Simulations of Urea Hydrolysis and Calcite Precipitation in Porous Media Using STOMP

    Energy Technology Data Exchange (ETDEWEB)

    Luanjing Guo; Hai Huang; Bill X. Hu

    2010-11-01

    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 in situ immobilization approach of these contaminants is engineered mineral (co)precipitation of calcite driven by urea hydrolysis that is catalyzed by enzyme urease. The tight nonlinear coupling among flow, transport, reaction and reaction-induced property changes of media of this approach was studied by reactive transport simulations with systematically increasing level of complexities of reaction network and physical/chemical heterogeneities using a numerical simulator named STOMP. Sensitivity studies on the reaction rates of both urea hydrolysis and calcite precipitation are performed via controlling urease enzyme concentration and precipitation rate constant according to the rate models employed. We have found that the rate of ureolysis is a dominating factor in the amount of precipitated mineral; however, the spatial distribution of the precipitates depends on both rates of ureolysis and calcite precipitation. A maximum 5% reduction in the porosity was observed within the simulation time period of 6 pore volumes in our 1-dimensional (1D) column simulations. When a low permeability inclusion is considered in the 2D simulations, the altered flow fields redistribute mineral forming constituents, leading to a distorted precipitation reaction front. The simulations also indicate that mineral precipitation occurs along the boundary of the low permeability zone, which implies that contaminants in the low permeability zone could be encapsulated and isolated from the flow paths.

  12. Morphogenetic control of calcite crystal growth in sulfonic acid based hydrogels.

    Science.gov (United States)

    Grassmann, Olaf; Löbmann, Peer

    2003-03-17

    In this paper the mineralization of CaCO(3) in various hydrogel matrices is presented. Sulfonic acid based hydrogels were prepared by introduction of sulfonate-containing monomers into a polyacrylamide network. The sulfonate content of polyacrylamide-co-vinylsulfonate and polyacrylamide-co-allylsulfonate decreases during elution of the copolymers in demineralized water, indicating insufficient linking of the sulfonate-bearing monomers within the hydrogel. In contrast to this, acrylamidomethylpropanesulfonate (AMPS) effectively copolymerizes with acrylamide (AAm) monomers. To study the influence of spatial arrangement of ionic functional groups within hydrogel networks on the mineralization of CaCO(3), AMPS copolymers with different degrees of AMPS cross-linking were synthesized. For the mineralization experiments the copolymers were placed into a double-diffusion arrangement. Calcite as the thermodynamically stable modification of CaCO(3) was obtained with a particular morphology. The pseudocubic habitus resembles aggregates obtained by mineralization in pure polyacrylamide. However, closer examination of the aggregates by scanning electron microscopy (SEM) shows that the crystal growth in the AMPS copolymers is different from that observed in polyacrylamide. Whereas the morphology of the calcite aggregates could be fine-tuned by using copolymers with different sulfonate content, the spatial distribution of the ionic functional groups alters the course of crystallization. Calcium ions are locally accumulated due to the heterogeneous distribution of functional sulfonate groups within the copolymer network. Thereby the nucleation of calcite is triggered, resulting in enhanced mineralization.

  13. Intermediate-scale tests of sodium interactions with calcite and dolomite aggregate concretes. [LMFBR

    Energy Technology Data Exchange (ETDEWEB)

    Randich, E.; Acton, R.U.

    1983-09-01

    Two intermediate-scale tests were performed to compare the behavior of calcite and dolomite aggregate concretes when attacked by molten sodium. The tests were performed as part of an interlaboratory comparison between Sandia National Laboratories and Hanford Engineering Development Laboratories. Results of the tests at Sandia National Laboratories are reported here. The results show that both concretes exhibit similar exothermic reactions with molten sodium. The large difference in reaction vigor suggested by thermodynamic considerations of CO/sub 2/ release from calcite and dolomite was not realized. Penetration rates of 1.4 to 1.7 mm/min were observed for short periods of time with reaction zone temperatures in excess of 800/sup 0/C during the energetic attack. The penetration was not uniform over the entire sodium-concrete contact area. Rapid attack may be localized due to inhomogeneities in the concrete. The chemical reaction zone is less then one cm thick for the calcite concrete but is about seven cm thick for the dolomite concrete.

  14. Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades

    Science.gov (United States)

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

    2000-01-01

    The crystallization of calcium carbonate minerals plays an integral role in the water chemistry of terrestrial ecosystems. Humic substances, which are ubiquitous in natural waters, have been shown to reduce or inhibit calcite crystal growth in experiments. The purpose of this study is to quantify and understand the kinetic effects of hydrophobic organic acids isolated from the Florida Everglades and a fulvic acid from Lake Fryxell, Antarctica, on the crystal growth of calcite (CaCO3). Highly reproducible calcite growth experiments were performed in a sealed reactor at constant pH, temperature, supersaturation (?? = 4.5), P(CO2) (10-3.5atm), and ionic strength (0.1 M) with various concentrations of organic acids. Higher plant-derived aquatic hydrophobic acids from the Everglades were more effective growth inhibitors than microbially derived fulvic acid from Lake Fryxell. Organic acid aromaticity correlated strongly with growth inhibition. Molecular weight and heteroatom content correlated well with growth inhibition, whereas carboxyl content and aliphatic nature did not. Copyright (C) 1999 Elsevier Science Ltd.

  15. The effect of amorphous silicon surface hydrogenation on morphology, wettability and its implication on the adsorption of proteins

    Energy Technology Data Exchange (ETDEWEB)

    Filali, Larbi, E-mail: larbifilali5@gmail.com [Laboratoire de Physique des Couches Minces et Matériaux pour l' Electronique, Université d' Oran 1, Ahmed Ben Bella, BP 1524, El M' naouar 31100 Oran (Algeria); Brahmi, Yamina; Sib, Jamal Dine [Laboratoire de Physique des Couches Minces et Matériaux pour l' Electronique, Université d' Oran 1, Ahmed Ben Bella, BP 1524, El M' naouar 31100 Oran (Algeria); Bouhekka, Ahmed [Laboratoire de Physique des Couches Minces et Matériaux pour l' Electronique, Université d' Oran 1, Ahmed Ben Bella, BP 1524, El M' naouar 31100 Oran (Algeria); Département de Physique, Université Hassiba Ben Bouali, 02000 Chlef (Algeria); Benlakehal, Djamel; Bouizem, Yahya; Kebab, Aissa; Chahed, Larbi [Laboratoire de Physique des Couches Minces et Matériaux pour l' Electronique, Université d' Oran 1, Ahmed Ben Bella, BP 1524, El M' naouar 31100 Oran (Algeria)

    2016-10-30

    Highlights: • Hydrogenation of the surfaces had the effect of reducing the roughness by way of shadow etching. • Roughness was the driving factor affecting the wettability of the hydrogenated surfaces. • Bovine Serum Albumin proteins favored the surfaces with highest hydrogen content. • Surface modification induced secondary structure change of adsorbed proteins. - Abstract: We study the effect of amorphous silicon (a-Si) surface hydrogenation on Bovine Serum Albumin (BSA) adsorption. A set of (a-Si) films was prepared by radio frequency magnetron sputtering (RFMS) and after deposition; they were treated in molecular hydrogen ambient at different pressures (1–3 Pa). Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy and spectroscopic ellipsometry (SE) were used to study the hydrogenation effect and BSA adsorption. Atomic force microscopy (AFM) was used to evaluate morphological changes caused by hydrogenation. The wettability of the films was measured using contact angle measurement, and in the case of the hydrogenated surfaces, it was found to be driven by surface roughness. FTIR-ATR spectroscopy and SE measurements show that proteins had the strongest affinity toward the surfaces with the highest hydrogen content and their secondary structure was affected by a significant decrease of the α-helix component (-27%) compared with the proteins adsorbed on the un-treated surface, which had a predominantly α-helix (45%) structure. The adsorbed protein layer was found to be densely packed with a large thickness (30.9 nm) on the hydrogen-rich surfaces. The most important result is that the surface hydrogen content was the dominant factor, compared to wettability and morphology, for protein adsorption.

  16. Implications of transient changes of optical and surface properties of solids during femtosecond laser pulse irradiation to the formation of laser-induced periodic surface structures

    Energy Technology Data Exchange (ETDEWEB)

    Bonse, J., E-mail: joern.bonse@bam.de [BAM Bundesanstalt fuer Materialforschung und -pruefung, Unter den Eichen 87, D-12205 Berlin (Germany); Rosenfeld, A. [Max-Born-Institut, Max-Born-Strasse 2a, D-12489 Berlin (Germany); Krueger, J. [BAM Bundesanstalt fuer Materialforschung und -pruefung, Unter den Eichen 87, D-12205 Berlin (Germany)

    2011-04-01

    The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of silicon wafer surfaces by linearly polarized Ti:sapphire femtosecond laser pulses (pulse duration 130 fs, central wavelength 800 nm) is studied experimentally and theoretically. In the experiments, so-called low-spatial frequency LIPSS (LSFL) were found with periods smaller than the laser wavelength and an orientation perpendicular to the polarization. The experimental results are analyzed by means of a new theoretical approach, which combines the widely accepted LIPSS theory of Sipe et al. with a Drude model, in order to account for transient (intra-pulse) changes of the optical properties of the irradiated materials. It is found that the LSFL formation is caused by the excitation of surface plasmon polaritons, SPPs, once the initially semiconducting material turns to a metallic state upon formation of a dense free-electron-plasma in the material and the subsequent interference between its electrical field with that of the incident laser beam resulting in a spatially modulated energy deposition at the surface. Moreover, the influence of the laser-excited carrier density and the role of the feedback upon the multi-pulse irradiation and its relation to the excitation of SPP in a grating-like surface structure is discussed.

  17. Surface heterogeneity, measurement uncertainty, and the implications for using in-situ observations for model validation studies

    Science.gov (United States)

    In-situ observations are critical for developing, calibrating, and validating the remote sensing-based models used to estimate and predict evapotranspiration (ET) along with the other components of the surface energy budget. Field measurements of the surface energy fluxes are collected using a varie...

  18. Clumped isotope thermometry of calcite and dolomite in a contact metamorphic environment

    Science.gov (United States)

    Lloyd, Max K.; Eiler, John M.; Nabelek, Peter I.

    2017-01-01

    Clumped isotope compositions of slowly-cooled calcite and dolomite marbles record apparent equilibrium temperatures of roughly 150-200 °C and 300-350 °C, respectively. Because clumped isotope compositions are sensitive to the details of T-t path within these intervals, measurements of the Δ47 values of coexisting calcite and dolomite can place new constraints on thermal history of low-grade metamorphic rocks over a large portion of the upper crust (from ∼5 to ∼15 km depth). We studied the clumped isotope geochemistry of coexisting calcite and dolomite in marbles from the Notch Peak contact metamorphic aureole, Utah. Here, flat-lying limestones were intruded by a pluton, producing a regular, zoned metamorphic aureole. Calcite Δ47 temperatures are uniform, 156 ± 12 °C (2σ s.e.), across rocks varying from high-grade marbles that exceeded 500 °C to nominally unmetamorphosed limestones >5 km from the intrusion. This result appears to require that the temperature far from the pluton was close to this value; an ambient temperature just 20 °C lower would not have permitted substantial re-equilibration, and should have preserved depositional or early diagenetic Δ47 values several km from the pluton. Combining this result with depth constraints from overlying strata suggests the country rock here had an average regional geotherm of 22.3-27.4 °C/km from the late Jurassic Period until at least the middle Paleogene Period. Dolomite Δ47 in all samples above the talc + tremolite-in isograd record apparent equilibrium temperatures of 328-12+13 °C (1σ s.e.), consistent with the apparent equilibrium blocking temperature we expect for cooling from peak metamorphic conditions. At greater distances, dolomite Δ47 records temperatures of peak (anchi)metamorphism or pre-metamorphic diagenetic conditions. The interface between these domains is the location of the 330 °C isotherm associated with intrusion. Multiple-phase clumped isotope measurements are complemented by

  19. Calcite precipitation on glass substrates and active stalagmites in Katerloch Cave (Austria): Constraints from environmental monitoring

    Science.gov (United States)

    Sakoparnig, Marlene; Boch, Ronny; Wang, Xianfeng; Lin, Ke; Spötl, Christoph; Leis, Albrecht; Gollowitsch, Anna; Dietzel, Martin

    2016-04-01

    Located near Graz at the SE-rim of the Alps Katerloch is well-known for its impressive dripstone decoration, e.g. several metres tall and relatively fast growing (0.2-0.7 mm/yr on average) candle-stick-type stalagmites. In the course of an ongoing multi-annual and partially high-resolution cave monitoring program we study modern (active) sites of carbonate deposition focusing on the site-specific growth dynamics and connection of modern regional and cave environmental conditions with petrographic, chemical and stable isotopic information captured in the speleothems. Fresh calcite precipitates on artificial (glass) substrates underneath active drip sites were collected continuously from 2006 to 2014 (eight years!). The samples (up to 7 mm thick) represent cave sections of different temperature and drip sites of partially different characteristics (e.g. drip rate). We also recovered short drill cores (up to 3 cm length, 1 cm diameter) from the top of active stalagmites probably representing the last decades to centuries of calcite crystallization. Moreover, an actively growing stalagmite (K10) comprising both modern and past calcite deposition was collected. 238U-234U-230Th dating using MC-ICP-MS of K10 (71 cm long) revealed several distinct growth intervals (separated by growth interruptions) starting at 129.1 ±1.2 kyr BP (Last Interglacial) up to now, mostly reflecting warm and humid climate intervals. High-resolution (100 μm) isotope profiles micromilled from the multi-annual modern calcite precipitates on artificial substrates revealed low δ13C values of -12.8 to -8.3 ‰ (VPDB) and relatively high δ18O of -6.9 to -4.9 ‰Ṫhe δ18O curves from all collection sites (different growth rate) record a pronounced decrease during their most recent growth period most likely corresponding to a significant decrease towards lower oxygen isotope values observed in drip waters collected in the year 2014 compared with samples from 2005 to 2007. Drip water δ2H /δ18O

  20. BET surface area distributions in polar stream sediments: Implications for silicate weathering in a cold-arid environment

    Science.gov (United States)

    Marra, Kristen R.; Elwood Madden, Megan E; Soreghan, Gerilyn S.; Hall, Brenda L

    2014-01-01

    BET surface area values are critical for quantifying the amount of potentially reactive sediments available for chemical weathering and ultimately, prediction of silicate weathering fluxes. BET surface area values of fine-grained (glacier surfaces, where dust is trapped and subsequently liberated during summer melting. Additionally, variations in stream discharge rate, which mobilizes sediment in pulses and influences water:rock ratios, the origin and nature of the underlying drift material, and the contribution of organic acids may play significant roles in the production and mobilization of high-surface area sediment. This study highlights the presence of sediments with high surface area in cold-based glacier systems, which influences models of chemical denudation rates and the impact of glacial systems on the global carbon cycle.

  1. Fabrication of calcite blocks from gypsum blocks by compositional transformation based on dissolution-precipitation reactions in sodium carbonate solution.

    Science.gov (United States)

    Ishikawa, Kunio; Kawachi, Giichiro; Tsuru, Kanji; Yoshimoto, Ayami

    2017-03-01

    Calcium carbonate (CaCO3) has been used as a bone substitute, and is a precursor for carbonate apatite, which is also a promising bone substitute. However, limited studies have been reported on the fabrication of artificial calcite blocks. In the present study, cylindrical calcite blocks (ϕ6×3mm) were fabricated by compositional transformation based on dissolution-precipitation reactions using different calcium sulfate blocks as a precursor. In the dissolution-precipitation reactions, both CaSO4·2H2O and CaSO4 transformed into calcite, a polymorph of CaCO3, while maintaining their macroscopic structure when immersed in 1mol/L Na2CO3 solution at 80°C for 1week. The diametral tensile strengths of the calcite blocks formed using CaSO4·2H2O and CaSO4 were 1.0±0.3 and 2.3±0.7MPa, respectively. The fabrication of calcite blocks using CaSO4·2H2O and CaSO4 proposed in this investigation may be a useful method to produce calcite blocks because of the self-setting ability and high temperature stability of gypsum precursors.

  2. Calcite as a bone substitute. Comparison with hydroxyapatite and tricalcium phosphate with regard to the osteoblastic activity

    Energy Technology Data Exchange (ETDEWEB)

    Monchau, F., E-mail: Francine.monchau@univ-artois.fr [Laboratoire Genie Civil et geo-Environnement (EA 4515, Universite Lille Nord de France), Equipe Biomateriaux Artois (Universite d' Artois), IUT/GMP, 1230, rue de l' Universite, BP 819, 62408 Bethune cedex (France); Hivart, Ph.; Genestie, B. [Laboratoire Genie Civil et geo-Environnement (EA 4515, Universite Lille Nord de France), Equipe Biomateriaux Artois (Universite d' Artois), IUT/GMP, 1230, rue de l' Universite, BP 819, 62408 Bethune cedex (France); Chai, F. [Laboratoire Medicaments et Biomateriaux a Liberation Controlee (INSERM U 1008, Universite Lille Nord de France), Groupe de Recherche sur les Biomateriaux (Universite Lille-2), Faculte de Medecine, 1, place de Verdun, 59045 Lille cedex (France); and others

    2013-01-01

    Close to the bone mineral phase, the calcic bioceramics, such as hydroxyapatite (HA) and {beta}-tricalcium phosphate ({beta}-TCP), are commonly used as substitutes or filling materials in bone surgery. Besides, calcium carbonate (CaCO{sub 3}) is also used for their excellent biocompatibility and bioactivity. However, the problem with the animal-origin aragonite demands the new technique to synthesize pure calcite capable of forming 3D bone implant. This study aims to manufacture and evaluate a highly-pure synthetic crystalline calcite with good cytocompatibility regarding to the osteoblasts, comparing to that of HA and {beta}-TCP. After the manufacture of macroporous bioceramic scaffolds with the identical internal architecture, their cytocompatibility is studied through MC3T3-E1 osteoblasts with the tests of cell viability, proliferation, vitality, etc. The results confirmed that the studied process is able to form a macroporous material with a controlled internal architecture, and this synthesized calcite is non-cytotoxic and facilitate the cell proliferation. Indeed requiring further improvement, the studied calcite is definitely an interesting alternative not only to coralline aragonite but also to calcium phosphate ceramics, particularly in bone sites with the large bone remodelling. Highlights: Black-Right-Pointing-Pointer Macroporous calcite manufacturing with controlled architecture as bone substitute Black-Right-Pointing-Pointer Cytotoxicity: adaptation of the colony-forming method with the target cells: MC3T3-E1 osteoblasts Black-Right-Pointing-Pointer Study of osteoblast proliferation and activity on calcite, HA and TCP.

  3. An integrated geophysical survey of Kilbourne Hole, southern New Mexico: Implications for near surface exploration of Mars and the Moon

    Science.gov (United States)

    Maksim, Nisa

    Features such as the Home Plate plateau on Mars, a suspected remnant of an ancient phreatomagmatic eruption, can reveal important information about paleohydrologic conditions. The eruption intensity of a phreatomagmatic volcano is controlled mainly by the quantity of water and magma, the internal geometry of the volcano, and the depth of the interaction zone between magma and water. In order to understand the paleohydrologic conditions at the time of eruption, we must understand all the factors that influenced the phreatomagmatic event. I conducted an integrated geophysical survey, which are magnetic and gravity surveys, and a ground-penetrating radar (GPR) surveys at Kilbourne Hole, a phreatomagmatic crater in southern New Mexico. These investigations serve an analog paleo-hydrogeological study that could be conducted on Mars and the Moon with an implication for planetary exploration. These geophysical surveys are designed to delineate the internal structure of a phreatomagmatic volcano and to define the volumes and masses of volcanic dikes and excavation unit, the depth of feeder dikes, and impacted velocity of the volcanic blocks. For the gravity and magnetic surveys at Kilbourne Hole, I collected data at a total of 171 gravity survey stations and 166 magnetics survey stations. A 2D gravity and magnetic inverse model was developed jointly to map the body of the magma intrusions and the internal structure of Kilbourne Hole. A total of 6 GPR surveys lines were also completed at Kilbourne Hole to image and to define locations of pyroclastic deposits, volcanic sags and blocks, the sizes distribution of volcanic blocks, and the impact velocity of the volcanic blocks. Using the size distribution and impact velocity of volcanic blocks from our GPR data, I derived the initial gas expansion velocity and the time duration of the gas expansion phase of the Kilbourne Hole eruption. These obtained parameters (volumes, masses, and depths of the feeder dikes and the excavation

  4. The effect of amorphous silicon surface hydrogenation on morphology, wettability and its implication on the adsorption of proteins

    Science.gov (United States)

    Filali, Larbi; Brahmi, Yamina; Sib, Jamal Dine; Bouhekka, Ahmed; Benlakehal, Djamel; Bouizem, Yahya; Kebab, Aissa; Chahed, Larbi

    2016-10-01

    We study the effect of amorphous silicon (a-Si) surface hydrogenation on Bovine Serum Albumin (BSA) adsorption. A set of (a-Si) films was prepared by radio frequency magnetron sputtering (RFMS) and after deposition; they were treated in molecular hydrogen ambient at different pressures (1-3 Pa). Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy and spectroscopic ellipsometry (SE) were used to study the hydrogenation effect and BSA adsorption. Atomic force microscopy (AFM) was used to evaluate morphological changes caused by hydrogenation. The wettability of the films was measured using contact angle measurement, and in the case of the hydrogenated surfaces, it was found to be driven by surface roughness. FTIR-ATR spectroscopy and SE measurements show that proteins had the strongest affinity toward the surfaces with the highest hydrogen content and their secondary structure was affected by a significant decrease of the α-helix component (-27%) compared with the proteins adsorbed on the un-treated surface, which had a predominantly α-helix (45%) structure. The adsorbed protein layer was found to be densely packed with a large thickness (30.9 nm) on the hydrogen-rich surfaces. The most important result is that the surface hydrogen content was the dominant factor, compared to wettability and morphology, for protein adsorption.

  5. Effect of Metal Ions on Calcite and Magnesite Flotation Behavior%几种金属阳离子对方解石与菱镁矿浮选的影响

    Institute of Scientific and Technical Information of China (English)

    宋振国

    2014-01-01

    Metal ions have significant effect on the flotation of salt minerals .In this study , the effect of five different metal ions on flotation behavior of two kinds of carbonate minerals , viz, calcite and magnesite was investigated by batch flotation tests and zeta potential measurement .Zeta potential re-sults showed the adsorption of all five metal ions on the surface of calcite and magnesite whereby the potential was observed to increase .But the results obtained by flotation tests showed that , the five metal ions had different effect on the flotation behavior of calcite and magnesite .Fe2+and Fe3+de-pressed calcite and magnesite flotation obviously .Recovery of magnesite was higher in the presence of Cu2+,Ca2+and Mg2+.Mg2+depressed calcite but Cu 2+,Ca2+had little influence on calcite flo-tation.%金属阳离子对盐类矿物浮选具有重要影响。通过浮选试验和动电位测试,研究了油酸钠浮选体系中五种金属阳离子( Fe2+、Fe3+、Cu2+、Ca2+和Mg2+)对常见碳酸盐矿物方解石和菱镁矿浮选行为的影响。动电位测试结果表明,五种金属离子都在方解石和菱镁矿表面发生了吸附,但其对方解石和菱镁矿浮选行为的影响不同:Fe2+、Fe3+对方解石和菱镁矿具有明显抑制作用,Cu2+、Ca2+和Mg2+对菱镁矿有一定活化作用, Mg2+抑制了方解石浮选,而Cu2+和Ca2+对方解石浮选影响较小。

  6. Climate change in the sea: the implications of increasing the carbon dioxide inputs to the surface ocean

    Energy Technology Data Exchange (ETDEWEB)

    Pfister, Cathy [University of Chicago

    2012-12-23

    The oceans are estimated to be absorbing one-third of the fossil fuel carbon released into the atmosphere, a process that is expected to change ocean carbon chemistry. I will present data from the Washington coast showing ocean pH declines and changes to the shell chemistry of bivalves. I will discuss implications of carbon cycle changes for marine species, including insights from a coastal area where I have worked for more than 24 years. I will summarize what we know to date about this process of “ocean acidification”.

  7. Low surface gravitational acceleration of Mars results in a thick and weak lithosphere: Implications for topography, volcanism, and hydrology

    Science.gov (United States)

    Heap, Michael J.; Byrne, Paul K.; Mikhail, Sami

    2017-01-01

    Surface gravitational acceleration (surface gravity) on Mars, the second-smallest planet in the Solar System, is much lower than that on Earth. A direct consequence of this low surface gravity is that lithostatic pressure is lower on Mars than on Earth at any given depth. Collated published data from deformation experiments on basalts suggest that, throughout its geological history (and thus thermal evolution), the Martian brittle lithosphere was much thicker but weaker than that of present-day Earth as a function solely of surface gravity. We also demonstrate, again as a consequence of its lower surface gravity, that the Martian lithosphere is more porous, that fractures on Mars remain open to greater depths and are wider at a given depth, and that the maximum penetration depth for opening-mode fractures (i.e., joints) is much deeper on Mars than on Earth. The result of a weak Martian lithosphere is that dykes-the primary mechanism for magma transport on both planets-can propagate more easily and can be much wider on Mars than on Earth. We suggest that this increased the efficiency of magma delivery to and towards the Martian surface during its volcanically active past, and therefore assisted the exogeneous and endogenous growth of the planet's enormous volcanoes (the heights of which are supported by the thick Martian lithosphere) as well as extensive flood-mode volcanism. The porous and pervasively fractured (and permeable) nature of the Martian lithosphere will have also greatly assisted the subsurface storage of and transport of fluids through the lithosphere throughout its geologically history. And so it is that surface gravity, influenced by the mass of a planetary body, can greatly modify the mechanical and hydraulic behaviour of its lithosphere with manifest differences in surface topography and geomorphology, volcanic character, and hydrology.

  8. Survivability of bare, individual Bacillus subtilis spores to high-velocity surface impact: Implications for microbial transfer through space

    Science.gov (United States)

    Barney, Brandon L.; Pratt, Sara N.; Austin, Daniel E.

    2016-06-01

    Laboratory experiments show that endospores of Bacillus subtilis survive impact against a solid surface at velocities as high as 299 ±28 m/s. During impact, spores experience and survive accelerations of at least 1010 m/s2. The spores were introduced into a vacuum chamber using an electrospray source and accelerated to a narrow velocity distribution by entrainment in a differentially pumped gas flow. Different velocity ranges were studied by modifying the gas flow parameters. The spores were electrically charged, allowing direct measurement of the velocity of each spore as it passed through an image charge detector prior to surface impact. Spores impacted a glass surface and were collected for subsequent analysis by culturing. Most spores survived impact at all measured velocities. These experiments differ fundamentally from other studies that show either shock or impact survivability of bacteria embedded within or on the surface of a projectile. Bacteria in the present experiments undergo a single interaction with a solid surface at the full impact velocity, in the absence of any other effects such as cushioning due to microbe agglomerations, deceleration due to air or vapor, or transfer of impact shock through solid or liquid media. During these full-velocity impact events, the spores experience extremely high decelerations. This study is the first reported instance of accelerations of this magnitude experienced during a bacteria impact event. These results are discussed in the context of potential transfer of viable microbes in space and other scenarios involving surface impacts at high velocities.

  9. Noncontact methods for measuring water-surface elevations and velocities in rivers: Implications for depth and discharge extraction

    Science.gov (United States)

    Nelson, Jonathan M.; Kinzel, Paul J.; McDonald, Richard R.; Schmeeckle, Mark

    2016-01-01

    Recently developed optical and videographic methods for measuring water-surface properties in a noninvasive manner hold great promise for extracting river hydraulic and bathymetric information. This paper describes such a technique, concentrating on the method of infrared videog- raphy for measuring surface velocities and both acoustic (laboratory-based) and laser-scanning (field-based) techniques for measuring water-surface elevations. In ideal laboratory situations with simple flows, appropriate spatial and temporal averaging results in accurate water-surface elevations and water-surface velocities. In test cases, this accuracy is sufficient to allow direct inversion of the governing equations of motion to produce estimates of depth and discharge. Unlike other optical techniques for determining local depth that rely on transmissivity of the water column (bathymetric lidar, multi/hyperspectral correlation), this method uses only water-surface information, so even deep and/or turbid flows can be investigated. However, significant errors arise in areas of nonhydrostatic spatial accelerations, such as those associated with flow over bedforms or other relatively steep obstacles. Using laboratory measurements for test cases, the cause of these errors is examined and both a simple semi-empirical method and computational results are presented that can potentially reduce bathymetric inversion errors.

  10. Understanding changes in the Arctic basin sea ice mass budget as simulated by CCSM4: Implications from melt season characteristics and the surface albedo feedback

    Science.gov (United States)

    Pollak, D. A.; Holland, M. M.; Bailey, D. A.

    2010-12-01

    Observations reveal alarming drops in Arctic sea ice extent, and climate models project that further changes will occur that could have global repercussions. An important aspect of this change is the surface albedo feedback, driven by the contrast between the albedos of snow/ice and the open ocean. In response to warming, this feedback enhances ice melt and amplifies surface warming in the Arctic. The newly released, fully coupled Community Climate System Model Version 4 (CCSM4) is used to assess long-term changes in the Arctic sea ice mass budget. Analysis of monthly-averaged mass budget time series from the 20th and 21st centuries revealed drastic changes from 1980-2050, the focus years of this study. While numerous factors determine the Arctic sea ice mass budget, we focus on the surface melt terms as they are most closely related to the surface albedo feedback. During the study period, annually averaged difference plots of sea ice thickness and area both revealed substantial decreases across the entire Arctic domain. Helping to clarify these long-term changes, new daily output data from this model allowed for the examination of melt season characteristics such as melt onset and cessation dates as well as season duration. One of the most interesting aspects was the shift to earlier melt onset dates throughout the Arctic Basin. This shift, coupled with the seasonal solar cycle has substantial implications. Earlier onset dates imply an earlier decrease of albedo that overlaps with the seasonal maximum of downward shortwave radiation. This leads to increases in shortwave absorption and results in amplified ice melt that directly impacts the strength of the surface albedo feedback. The strong relationship between earlier melt onset dates and increased absorbed radiation therefore is a key factor influencing Arctic amplification. This figure is created from daily model output and displays changes in melt season duration, end date, and onset date from the first and

  11. Chemistry of Cu(acac){sub 2} on Ni(110) and Cu(110) surfaces: Implications for atomic layer deposition processes

    Energy Technology Data Exchange (ETDEWEB)

    Ma Qiang; Zaera, Francisco [Department of Chemistry, University of California, Riverside, California 92521 (United States)

    2013-01-15

    The thermal chemistry of copper(II)acetylacetonate, Cu(acac){sub 2}, on Ni(110) and Cu(110) single-crystal surfaces was probed under vacuum by using x-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). Some data for acetylacetone (Hacac, CH{sub 3}COCH{sub 2}COCH{sub 3}) adsorbed on Ni(110) are also reported as reference. Chemical transformations were identified in several steps covering a temperature range from 150 K to at least 630 K. The desorption of Hacac and a 3-oxobutanal (CH{sub 3}COCH{sub 2}CHO) byproduct was observed first at 150 and 180 K on Ni(110) and at 160 and 185 K on Cu(110), respectively. Partial loss of the acetylacetonate (acac) ligands and a likely change in adsorption geometry are seen next, with the possible production of HCu(acac), which desorbs at 200 and 235 K from the nickel and copper surfaces, respectively. Molecular Cu(acac){sub 2} desorption is observed on both surfaces at approximately 300 K, probably from recombination of Cu(acac) and acac surface species. The remaining copper atoms on the surface lose their remaining acac ligands to the substrate and become reduced directly to metallic copper. At the same time, the organic ligands follow a series of subsequent surface reactions, probably involving several C-C bond-scissions, to produce other fragments, additional Hacac and HCu(acac) in the gas phase in the case of the copper surface, and acetone on nickel. A significant amount of acac must nevertheless survive on the surface to high temperatures, because Hacac peaks are seen in the TPD at about 515 and 590 K and the C 1s XPS split associated with acac is seen up to close to 500 K. In terms of atomic layer deposition processes, this suggests that cycles could be design to run at such temperatures as long as an effective hydrogenation agent is used as the second reactant to remove the surface acac as Hacac. Only a small fraction of carbon is left behind on Ni after heating to 800 K, whereas more carbon

  12. Surface water hydrology and geomorphic characterization of a playa lake system: Implications for monitoring the effects of climate change

    Science.gov (United States)

    Adams, Kenneth D.; Sada, Donald W.

    2014-03-01

    Playa lakes are sensitive recorders of subtle climatic perturbations because these ephemeral water bodies respond to the flux of diffuse and channelized flow from their watersheds as well as from direct precipitation. The Black Rock Playa in northwestern Nevada is one of the largest playas in North America and is noted for its extreme flatness, varying less than one meter across a surface area of 310 km2. Geo-referenced Landsat imagery was used to map surface-area fluctuations of ephemeral lakes on the playa from 1972 to 2013 to provide baseline data on surface water hydrology of this system to compare to future hydrologic conditions caused by climate change. The area measurements were transformed into depth and volumetric estimates using results of detailed topographic global positioning system (GPS) surveys and correlated with available surface hydrological and meteorological monitoring data. Playa lakes reach their maximum size (<350 km2) in spring, fed by melting snows from high mountains on the periphery of the drainage basin, and usually desiccate by early- to mid-summer. The combination of a shallow groundwater table, sediment deposition, and hydro-aeolian planation probably are largely responsible for the flatness of the playa. When lakes do not form for a period of several years, the clay- and silt-rich playa surface transforms from one that is hard and durable into one that is soft and puffy, probably from upward capillary movement of water and resultant evaporation. Subsequent flooding restores the hard and durable surface. The near-global availability of Landsat imagery for the last 41 years should allow the documentation of baseline surface hydrologic characteristics for a large number of widely-distributed playa lake systems that can be used to assess the hydrologic effects of future climate changes.

  13. Estimation of transient deformation on cGPS measurements at Taiwan region: Implications for tectonic and surface processes

    Science.gov (United States)

    Chen, K. H.; Chan, Y. C.

    2015-12-01

    Transient deformation on geodetic time series is usually caused by the tectonic or surface processes. Surface processes include multiple durations that could be trapped or ignored using general time series analysis. We first recognize overall transient signals in Taiwan region recorded by continuous GPS (cGPS) networks. Sparse estimation techniques and Bi-splines function are used to detect the signals on cGPS time series then estimate the parameters. Our study analyzes the transient deformation by using a multi-dataset of the cGPS, seismogram, digital terrain model (DTM), and rainfall gauges. We establish a systematic classification by weighting both the empirical trigger factors and regional criterion to classify the signals into seven types. Spatial and temporal characteristics of transient deformation show three major contributions in Taiwan region including the seismic-related, landslides-related, and slow-slip transients. The cGPS networks in Taiwan region show long-term transient deformation at rates 2-68 mm/yr, ~14%-75% of their tectonic interseismic velocities. Tectonic and surface processes involve ~38%-85% and ~15%-62%, respectively, in the transient deformation under different geological units of Taiwan region. The lack of consideration for the transient deformation in surface processes would underestimate their biases on tectonic interseismic velocity. Statistical linking between cGPS transient deformation, tectonic and surface processes of Taiwan indicate that earthquake, typhoon, and topography play important roles in the occurrence of transient deformation.

  14. Surface-water interface induces conformational changes critical for protein adsorption: Implications for monolayer formation of EAS hydrophobin

    Directory of Open Access Journals (Sweden)

    Kamron eLey

    2015-11-01

    Full Text Available The class I hydrophobin EAS is part of a family of small, amphiphilic fungal proteins best known for their ability to self-assemble into stable monolayers that modify the hydrophobicity of a surface to facilitate further microbial growth. These proteins have attracted increasing attention for industrial and biomedical applications, with the aim of designing surfaces that have the potential to maintain their clean state by resisting non-specific protein binding. To gain a better understanding of this process, we have employed all-atom molecular dynamics to study initial stages of the spontaneous adsorption of monomeric EAS hydrophobin on fully hydroxylated silica, a commonly used industrial and biomedical substrate. Particular interest has been paid to the Cys3-Cys4 loop, which has been shown to exhibit disruptive behavior in solution, and the Cys7-Cys8 loop, which is believed to be involved in the aggregation of EAS hydrophobin at interfaces. Specific and water mediated interactions with the surface were also analyzed. We have identified two possible binding motifs, one which allows unfolding of the Cys7-Cys8 loop due to the surfactant-like behavior of the Cys3-Cys4 loop, and another which has limited unfolding due to the Cys3-Cys4 loop remaining disordered in solution. We have also identified intermittent interactions with water which mediate the protein adsorption to the surface, as well as longer lasting interactions which control the diffusion of water around the adsorption site. These results have shown that EAS behaves in a similar way at the air-water and surface-water interfaces, and have also highlighted the need for hydrophilic ligand functionalization of the silica surface in order to prevent the adsorption of EAS hydrophobin.

  15. Quantifying the time lag between organic matter production and export in the surface ocean: Implications for estimates of export efficiency

    Science.gov (United States)

    Stange, P.; Bach, L. T.; Le Moigne, F. A. C.; Taucher, J.; Boxhammer, T.; Riebesell, U.

    2017-01-01

    The ocean's potential to export carbon to depth partly depends on the fraction of primary production (PP) sinking out of the euphotic zone (i.e., the e-ratio). Measurements of PP and export flux are often performed simultaneously in the field, although there is a temporal delay between those parameters. Thus, resulting e-ratio estimates often incorrectly assume an instantaneous downward export of PP to export flux. Evaluating results from four mesocosm studies, we find that peaks in organic matter sedimentation lag chlorophyll a peaks by 2 to 15 days. We discuss the implications of these time lags (TLs) for current e-ratio estimates and evaluate potential controls of TL. Our analysis reveals a strong correlation between TL and the duration of chlorophyll a buildup, indicating a dependency of TL on plankton food web dynamics. This study is one step further toward time-corrected e-ratio estimates.

  16. Texture evolution in calcite gouge formed at sub-seismic slip

    Science.gov (United States)

    Delle Piane, Claudio; Luzin, Vladimir; Timms, Nick E.; Ben Clennell, M.; Giwelli, Ausama

    2016-04-01

    Carbonate rocks are abundant in the upper crust and are notoriously seismogenic with Mw>6 earthquakes nucleating in fault zones in carbonate dominated units around the world. Field observations describe fault zones as characterised by a narrow principal slip zone at their core, containing fine, granular wear material referred to as fault gouge, produced during cumulative slip. The current literature on the link between texture and frictional properties of calcite gouges is very limited and somewhat contradictory: based on the study of a natural calcite gouge a link has been proposed between the presence of a crystallographic preferred orientation (CPO) and past seismic activity on the gouge hosting fault zone. However, similar features in terms of CPO were also identified on gouges experimentally generated at slip velocities well below the seismic ones, therefore questioning their interpretation as diagnostic of past seismic events. We studied the evolution of friction coefficient and texture on calcite gouges experimentally produced by means of high pressure direct shear experiments on large, water saturated, intact blocks of travertine (calcite 99 % wt.). Several blocks were deformed at room temperature up to different amounts of maximum displacements (20 mm, 70 mm and 120 mm) under an imposed sub-seismic slip rate of approximately 0.1 microns/s. Microstructural characterization of the deformed blocks was subsequently carried out on samples representing the highest strained portion s of each blocks (i.e. gouge zones). Local and bulk texture of the original and deformed materials was studied by means of electron backscattered diffraction (EBSD) and neutron diffraction, respectively. Direct shear experiments consistently indicate an evolution of the friction coefficient stabilizing at around values of 0.6 after 15 mm of slip. Macroscopic observations on the deformed blocks indicate that deformation is localised in a narrow band of extreme grain size reduction

  17. Graphitic carbon formation through calcite reduction in blueschist metasediments from Alpine Corsica (France)

    Science.gov (United States)

    Galvez, M.; Beyssac, O.; Martinez, I.; Benzerara, K.; Malvoisin, B.

    2012-04-01

    The geochemistry of reduced carbon in subduction zones is strongly affected by mineral equilibria. We study here the geochemistry of carbon in siliceous-marbles at the direct contact with serpentinites in the Alpine eclogitic meta-ophiolithic units of northern Corsica (France). We have combined petrology, Raman spectroscopy and carbon isotopy to provide a description of both the organic and carbonate components of the rocks across a reaction front where the reaction CaCO3+SiO2+2H2=CaSiO3+C+2H2O is evidenced. The continuous reaction zone is composed by a centimeter thick pale nephrite layer at the contact with the serpentinites, followed by a thin wollastonite layer and a 5 to 20 cm thick dark zone composed of wollastonite, carbonaceous material (CM), quartz but no carbonates. There is a sharp transition to the overlying original metasediment composed of calcite+quartz which is significantly less rich in CM. Raman spectroscopy shows that CM is much more graphitic in the reaction zone than in the original sediment. Significant isotopic differences are observed apart the reaction front with δ13C (CM) and δ13C (calcite) around -15‰ and 1.3‰ respectively in the original rock far from the reaction zone, whereas δ13C (CM) is around -1‰ in the reaction zone. We interpret the graphitic CM in the reaction zone as formed from the destabilization and reduction of calcite due to the diffusion of reducing fluids from the underlying serpentinite unit. Mass balance calculations support this hypothesis and show that a complete reduction of carbonates might have occurred. The timing of this abiotic macromolecular and graphitic C formation is discussed. We show that the combined study of isotopic geochemistry and structure of inorganic and organic carbon in metamorphic rocks might be suited to reveal with great fidelity redox gradients in subduction zones.

  18. Influence of temperature and CO2 on the strontium and magnesium composition of coccolithophore calcite

    Directory of Open Access Journals (Sweden)

    M. N. Müller

    2013-10-01

    Full Text Available Marine calcareous sediments provide a fundamental basis for paleoceanographic studies aiming to reconstruct past oceanic conditions and understand key biogeochemical element cycles. Calcifying unicellular phytoplankton (coccolithophores are a major contributor to both carbon and calcium cycling by photosynthesis and the production of calcite (coccoliths in the euphotic zone and the subsequent long-term deposition and burial into marine sediments. Here we present data from controlled laboratory experiments on four coccolithophore species and elucidate the relation between the divalent cation (Sr, Mg and Ca partitioning in coccoliths and cellular physiology (growth, calcification and photosynthesis. Coccolithophores were cultured under different seawater temperature and carbonate chemistry conditions. The partition coefficient of strontium (DSr was positively correlated with both carbon dioxide (pCO2 and temperature but displayed no coherent relation to particulate organic and inorganic carbon production rates. Furthermore, DSr correlated positively with cellular growth rates when driven by temperature but no correlation was present when changes in growth rates were pCO2-induced. The results demonstrate the complex interaction between environmental forcing and physiological control on the strontium partitioning in coccolithophore calcite. The partition coefficient of magnesium (DMg displayed species-specific differences and elevated values under nutrient limitation. No conclusive correlation between coccolith DMg and temperature was observed but pCO2 induced a rising trend in coccolith DMg. Interestingly, the best correlation was found between coccolith DMg and chlorophyll a production suggesting that chlorophyll a and calcite associated Mg originate from the same intracellular pool. These results give an extended insight into the driving factors that lead to variations in the coccolith Mg / Ca ratio and can be used for Sr / Ca and Mg / Ca

  19. Measuring the specific surface area of snow with X-ray tomography and gas adsorption: comparison and implications for surface smoothness

    Directory of Open Access Journals (Sweden)

    M. Kerbrat

    2008-03-01

    Full Text Available Chemical and physical processes, such as heterogeneous chemical reactions, light scattering, and metamorphism occur in the natural snowpack. To model these processes in the snowpack, the specific surface area (SSA is a key parameter. In this study, two methods, computed tomography and methane adsorption, which have intrinsically different effective resolutions – molecular and 30 μm, respectively – were used to determine the SSA of similar natural snow samples. Except for very fresh snow, the two methods give identical results, with an uncertainty of 3%. This implies that the surface of aged natural snow is smooth up to a scale of about 30 μm and that if smaller structures are present they do not contribute significantly to the overall SSA. It furthermore implies that for optical methods a voxel size of 10 μm is sufficient to capture all structural features of this type of snow; however, fresh precipitation appears to contain small features that cause an under-estimation of SSA with tomography at this resolution. The methane adsorption method is therefore superior to computed tomography for very fresh snow having high SSA. Nonetheless, in addition to SSA determination, tomography provides full geometric information about the ice matrix. It can also be advantageously used to investigate layered snow packs, as it allows measuring SSA in layers of less than 1 mm.

  20. Reconstructing sea surface temperature, sea surface salinity and partial pressure of carbon dioxide in atmos- phere in the Okinawa Trough during the Holocene and their paleoclimatic implications

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The sediment core DGKS9603 collected from the Okinawa Trough was used as research target. By use of unsaturated index of long-chain alkenone, δ13C of POC and of planktonic foraminifera (G. Sacculifer), the evolutions of sea surface temperature and partial pressure of carbon dioxide in the atmosphere during the Holocene were reconstructed in the Okinawa Trough. And in combination of δ18O of planktonic foraminifera, the relative difference of sea surface salinity during the Holocene was also reconstructed. Consequently, three cooling events (E1-E3) were identified, each of which occurred at 1.7-1.6, 5.1-4.8 and 8.1-7.4 kaBP (cal), respectively. Of the three events, E2 and E3 are globally comparable, their occurrence mechanism would be that the main stream of the Kuroshio Current shifted eastward due to the enhanced circulation of the northeastern Pacific Ocean, which was driven in turn by amplified intensity of sunshine and subsequent enhancement of subtropical high pressure; E1 corresponds to the Small Ice-Age Event occurring between 1550 and 1850AD in China. In the Okinawa Trough, E1 might be also related to the eastward shift of main stream of the Kuroshio current driven by powerful Asia winter monsoon.

  1. Scale-dependency of the global mean surface temperature trend and its implication for the recent hiatus of global warming.

    Science.gov (United States)

    Lin, Yong; Franzke, Christian L E

    2015-08-11

    Studies of the global mean surface temperature trend are typically conducted at a single (usually annual or decadal) time scale. The used scale does not necessarily correspond to the intrinsic scales of the natural temperature variability. This scale mismatch complicates the separation of externally forced temperature trends from natural temperature fluctuations. The hiatus of global warming since 1999 has been claimed to show that human activities play only a minor role in global warming. Most likely this claim is wrong due to the inadequate consideration of the scale-dependency in the global surface temperature (GST) evolution. Here we show that the variability and trend of the global mean surface temperature anomalies (GSTA) from January 1850 to December 2013, which incorporate both land and sea surface data, is scale-dependent and that the recent hiatus of global warming is mainly related to natural long-term oscillations. These results provide a possible explanation of the recent hiatus of global warming and suggest that the hiatus is only temporary.

  2. IMPLICATION OF LAKE WATER RESIDENCE TIME ON THE CLASSIFICATION OF NORWEGIAN SURFACE WATER SITES INTO PROGRESSIVE STAGES OF NITROGEN SATURATION

    Science.gov (United States)

    Seasonal behaviour of NO3- in surface water is often used as an indicator on a catchment's ability to retain N from atmospheric deposition. In this paper, we classify 12 pristine sites (five streams and seven lakes) in southernmost Norway according to the N saturation stage conce...

  3. Size and Fraction of Active Surface Area of Some Jupiter Family Comets: Implications with Respect to their Physical Evolution

    Directory of Open Access Journals (Sweden)

    Julio A. Fernández

    2001-01-01

    Full Text Available We analyze the sample of measured nuclear magnitudes of the observed Jupiter Family comets (taken as those with orbital periods P 2 to derive sizes of comet nuclei, fraction of active surface areas, as well as to try to gain insight about their physical lifetimes and end states.

  4. Sm-Nd isotope dating of hydrothermal calcites from the Xikuangshan antimony deposit, Central Hunan

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The research on Samarium-Neodymium isotope systematics of hydrothermal calcites from the Xikuangshan antimony deposit, Central Hunan, places precise timing constraints on the Sb mineralization in this area. It is revealed that the Xikuangshan deposit formed during the late Jurassic-early Cretaceous Period, the early- and late- stage mineralization took place at (155.5 ± 1.1) Ma and (124.1 ± 3.7) Ma, respectively. The accurate age determination of mineralization is very crucial for revealing the super-enrichment mechanism of the element Sb at the Xikuangshan mine, and lays some foundations for the further understandings of its ore genesis and mineralization mechanism.

  5. 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

  6. Surface multiheme c-type cytochromes from Thermincola potens: Implications for dissimilatory metal reduction by Gram-positive bacteria

    Science.gov (United States)

    Carlson, H. K.; Iavarone, A. T.; Gorur, A.; Yeo, B. S.; Tran, R.; Melnyk, R. A.; Mathies, R. A.; Auer, M.; Coates, J. D.

    2011-12-01

    Almost nothing is known about the mechanisms of dissimilatory metal reduction by Gram-positive bacteria, although they have been shown to be the dominant species in some environments. Thermincola potens strain JR was isolated from the anode of a microbial fuel cell inoculated with anaerobic digester sludge and operated at 55 °C. Preliminary characterization revealed that T. potens coupled acetate oxidation to the reduction of hydrous ferric oxides (HFO) or the humic substances analog, anthraquinone-2,6-disulfonate (AQDS). The genome of T. potens was recently sequenced, and the abundance of multiheme c-type cytochromes (MHCs) is unusual for a Gram-positive bacterium. We present evidence from trypsin shaving LC-MS/MS experiments and surface-enhanced Raman spectroscopy (SERS) that indicates the expression of a number of MHCs during T. potens growth on either HFO or AQDS and that several MHCs are localized to the cell wall or cell surface of T. potens. Furthermore, one of the MHCs can be extracted from cells with low pH or denaturants suggesting a loose association with the cell wall or cell surface. Electron microscopy does not reveal an S-layer, and the precipitation of silver metal on the cell surface is inhibited by cyanide, supporting the involvement of surface-localized redox-active heme proteins in dissimilatory metal reduction. These results are the first direct evidence for cell-wall associated cytochromes and MHC involvement in conducting electrons across the cell envelope of a Gram-positive bacterium.

  7. Halogen and Cl isotopic systematics in Martian phosphates: Implications for the Cl cycle and surface halogen reservoirs on Mars

    Science.gov (United States)

    Bellucci, J. J.; Whitehouse, M. J.; John, T.; Nemchin, A. A.; Snape, J. F.; Bland, P. A.; Benedix, G. K.

    2017-01-01

    The Cl isotopic compositions and halogen (Cl, F, Br, and I) abundances in phosphates from eight Martian meteorites, spanning most rock types and ages currently available, have been measured in situ by Secondary Ion Mass Spectrometry (SIMS). Likewise, the distribution of halogens has been documented by x-ray mapping. Halogen concentrations range over several orders of magnitude up to some of the largest concentrations yet measured in Martian samples or on the Martian surface, and the inter-element ratios are highly variable. Similarly, Cl isotope compositions exhibit a larger range than all pristine terrestrial igneous rocks. Phosphates in ancient (>4 Ga) meteorites (orthopyroxenite ALH 84001 and breccia NWA 7533) have positive δ37Cl anomalies (+1.1 to + 2.5 ‰). These samples also exhibit explicit whole rock and grain scale evidence for hydrothermal or aqueous activity. In contrast, the phosphates in the younger basaltic Shergottite meteorites (<600 Ma) have negative δ37Cl anomalies (-0.2 to - 5.6 ‰). Phosphates with the largest negative δ37Cl anomalies display zonation in which the rims of the grains are enriched in all halogens and have significantly more negative δ37Cl anomalies suggestive of interaction with the surface of Mars during the latest stages of basalt crystallization. The phosphates with no textural, major element, or halogen enrichment evidence for mixing with this surface reservoir have an average δ37Cl of - 0.6 ‰, supporting a similar initial Cl isotope composition for Mars, the Earth, and the Moon. Oxidation and reduction of chlorine are the only processes known to strongly fractionate Cl isotopes, both positively and negatively, and perchlorate has been detected in weight percent concentrations on the Martian surface. The age range and obvious mixing history of the phosphates studied here suggest perchlorate formation and halogen cycling via brines, which have been documented on the Martian surface, has been active throughout Martian

  8. Surface multiheme c-type cytochromes from Thermincola potens and implications for respiratory metal reduction by Gram-positive bacteria.

    Science.gov (United States)

    Carlson, Hans K; Iavarone, Anthony T; Gorur, Amita; Yeo, Boon Siang; Tran, Rosalie; Melnyk, Ryan A; Mathies, Richard A; Auer, Manfred; Coates, John D

    2012-01-31

    Almost nothing is known about the mechanisms of dissimilatory metal reduction by Gram-positive bacteria, although they may be the dominant species in some environments. Thermincola potens strain JR was isolated from the anode of a microbial fuel cell inoculated with anaerobic digester sludge and operated at 55 °C. Preliminary characterization revealed that T. potens coupled acetate oxidation to the reduction of hydrous ferric oxides (HFO) or anthraquinone-2,6-disulfonate (AQDS), an analog of the redox active components of humic substances. The genome of T. potens was recently sequenced, and the abundance of multiheme c-type cytochromes (MHCs) is unusual for a Gram-positive bacterium. We present evidence from trypsin-shaving LC-MS/MS experiments and surface-enhanced Raman spectroscopy (SERS) that indicates the expression of a number of MHCs during T. potens growth on either HFO or AQDS, and that several MHCs are localized to the cell wall or cell surface. Furthermore, one of the MHCs can be extracted from cells with low pH or denaturants, suggesting a loose association with the cell wall or cell surface. Electron microscopy does not reveal an S-layer, and the precipitation of silver metal on the cell surface is inhibited by cyanide, supporting the involvement of surface-localized redox-active heme proteins in dissimilatory metal reduction. These results provide unique direct evidence for cell wall-associated cytochromes and support MHC involvement in conducting electrons across the cell envelope of a Gram-positive bacterium.

  9. Nyctemeral variations of magnesium intake in the calcitic layer of a Chilean mollusk shell ( Concholepas concholepas, Gastropoda)

    Science.gov (United States)

    Lazareth, Claire E.; Guzman, Nury; Poitrasson, Franck; Candaudap, Frederic; Ortlieb, Luc

    2007-11-01

    Mollusk shells are increasingly used as records of past environmental conditions, particularly for sea-surface temperature (SST) reconstructions. Many recent studies tackled SST (and/or sea-surface salinity) tracers through variations in the elementary (Mg and Sr) or stable isotope (δ 18O) composition within mollusk shells. But such attempts, which sometimes include calibration studies on modern specimens, are not always conclusive. We present here a series of Mg and Sr analyses in the calcitic layer of Concholepas concholepas (Muricidae, Gastropoda) with a very high time-resolution on a time window covering about 1 and a half month of shell formation, performed by Laser Ablation Inductively-Coupled Plasma Mass Spectrometry (LA-ICP-MS) and electron probe micro-analysis (EPMA). The selected specimen of this common Chilean gastropod was grown under controlled environmental conditions and precise weekly time-marks were imprinted in the shell with calcein staining. Strontium variations in the shell are too limited to be interpreted in terms of environmental parameter changes. In contrast, Mg incorporation into the shell and growth rate appear to change systematically between night and day. During the day, Mg is incorporated at a higher rate than at night and this intake seems positively correlated with water temperature. The nightly reduced Mg incorporation is seemingly related to metabolically controlled processes, formation of organic-rich shell increments and nocturnal feeding activity of the animals. The nyctemeral Mg changes in the C. concholepas shell revealed in this study might explain at least part of the discrepancies observed in previous studies on the use of Mg as a SST proxy in mollusk shells. In the case of C. concholepas, Mg cannot be used straightforwardly as a SST proxy.

  10. Changes in Surface Wind Speed over North America from CMIP5 Model Projections and Implications for Wind Energy

    Directory of Open Access Journals (Sweden)

    Sujay Kulkarni

    2014-01-01

    Full Text Available The centennial trends in the surface wind speed over North America are deduced from global climate model simulations in the Climate Model Intercomparison Project—Phase 5 (CMIP5 archive. Using the 21st century simulations under the RCP 8.5 scenario of greenhouse gas emissions, 5–10 percent increases per century in the 10 m wind speed are found over Central and East-Central United States, the Californian Coast, and the South and East Coasts of the USA in winter. In summer, climate models projected decreases in the wind speed ranging from 5 to 10 percent per century over the same coastal regions. These projected changes in the surface wind speed are moderate and imply that the current estimate of wind power potential for North America based on present-day climatology will not be significantly changed by the greenhouse gas forcing in the coming decades.

  11. Carbonization in Titan Tholins: implication for low albedo on surfaces of Centaurs and trans-Neptunian objects

    Science.gov (United States)

    Giri, Chaitanya; McKay, Christopher P.; Goesmann, Fred; Schäfer, Nadine; Li, Xiang; Steininger, Harald; Brinckerhoff, William B.; Gautier, Thomas; Reitner, Joachim; Meierhenrich, Uwe J.

    2016-07-01

    Astronomical observations of Centaurs and trans-Neptunian objects (TNOs) yield two characteristic features - near-infrared (NIR) reflectance and low geometric albedo. The first feature apparently originates due to complex organic material on their surfaces, but the origin of the material contributing to low albedo is not well understood. Titan tholins synthesized to simulate aerosols in the atmosphere of Saturn's moon Titan have also been used for simulating the NIR reflectances of several Centaurs and TNOs. Here, we report novel detections of large polycyclic aromatic hydrocarbons, nanoscopic soot aggregates and cauliflower-like graphite within Titan tholins. We put forth a proof of concept stating the surfaces of Centaurs and TNOs may perhaps comprise of highly `carbonized' complex organic material, analogous to the tholins we investigated. Such material would apparently be capable of contributing to the NIR reflectances and to the low geometric albedos simultaneously.

  12. Relationship between heavy metal contents and clay mineral properties in surface sediments: Implications for metal pollution assessment

    Science.gov (United States)

    Chen, Yueh-Min; Gao, Jin-bo; Yuan, Yong-Qiang; Ma, Jun; Yu, Shen

    2016-08-01

    Clay minerals in surface sediments can affect the adsorption of heavy metals. However, few historical studies have focused on the influence of fine clay mineral characteristics on metal sorption. Since the reactions between heavy metals and fine clay minerals in sediments remain obscure, this study investigates the influence of fine clay mineral characteristics on metal sorption in a typical urbanizing small watershed. Clay minerals, including nanoparticles with various size fractions ranging from 1000 to 2000 (clay), 450-1000 (fine clay), and 220-450 (very fine clay) nm were used to demonstrate their transformation from well crystalline to poorly crystalline. The nanoparticles were collected and evaluated by determination of their surface area, X-ray diffraction, scanning electron microscopy (SEM) and chemical analyses. The relationship between metal content and properties of the surface sediments was also revealed by canonical correlation analysis. With smaller particle sizes, nanoparticles (very fine clay) were observed to be poorly crystalline, possibly indicating few repetitions of unit cells as a result of preferential structural disruption of other crystal planes caused by pressure-induced phase transition in the fine-size fractions. The first canonical matrix (M) variables of metal contents can be predicted by both surface area and pore volume, followed by kaolinite and illite contents. On the other hand, the category of metal, i.e., Cu, Cr, Zn, or Pb, was significantly correlated with the first 'M' canonical variables. The data obtained in the present study are of fundamental significance in advancing our understanding of the reactions between heavy metals and fine clay minerals in the terrestrial ecosystem.

  13. Dissected Mantle Terrain on Mars: Formation Mechanisms and the Implications for Mid- latitude Near-surface Ground Ice

    Science.gov (United States)

    Searls, M. L.; Mellon, M. T.

    2008-12-01

    Determining the present and past distribution of surface and subsurface ice on Mars is critical for understanding the volatile inventory and climatic history of the planet. An analysis of a latitude-dependent layer of surface material known as the dissected mantle terrain can provide valuable insight into the distribution of ice in the recent past. The dissected mantle terrain is a surface unit that occurs globally in the mid-latitude of Mars. This unit is characterized by a smooth mantle of uniform thickness and albedo that is draped over the existing topography. This smooth mantle is disaggregated and dissected in places resulting in a hummocky pitted appearance. We propose that the mid-latitude dissected terrain results from collapse of a dusty mantle into the void left from desiccation of an underlying ice-rich (pure or dirty ice) layer. During period(s) of high obliquity, it is possible for ice to become stable at lower latitudes. Due to lack of direct solar insolation, surface ice deposits will preferentially accumulate on pole-ward facing slopes first. A mantle of dust and dirt is then deposited on top of these ice-rich deposits. As the climate changes, desiccation of the now buried ice leads to collapse of the overlying dusty layer resulting in a hummocky pitted appearance. This theory is supported by the pole-ward preference for the dissection pits as well an increase in dissection with increasing latitude. A study of the global distribution of the mid-latitude dissected terrain can provide invaluable clues towards unlocking the distribution of ice in the recent past. An analysis of HiRISE images and MOLA data indicate that the distribution of dissection pits varies from one region to the next. Knowing the distribution of ice in conjunction with ice stability modeling can provide a global view of the climate and orbital history of Mars at the time these features formed.

  14. Analytical model of surface uplift above axisymmetric flat-lying magma intrusions: Implications for sill emplacement and geodesy

    OpenAIRE

    Galland, Olivier; Scheibert, Julien

    2013-01-01

    58 pages, 17 figures, 2 tables. Accepted in Journal of Volcanology and Geothermal Research; International audience; In this paper, we develop a new axisymmetric analytic model of surface uplift upon sills and laccoliths, based on the formulation of a thin bending plate lying on an elastic foundation. In contrast to most former models also based on thin bending plate formulation, our model accounts for (i) axi-symmetrical uplift, (ii) both upon and outside the intrusion. The model accounts for...

  15. Stellar and Gas Phase Metallicity of Low Surface Brighness Galaxies: Implication on Star Formation Process within Young Disk Galaxies

    Science.gov (United States)

    Kim, Ji Hoon

    2015-08-01

    Low surface brightness (LSB) galaxies, whose central surface brightness, μB, is fainter than 23 mag/arcsec2 in the B-band, have been one of the most intriguing galaxy populations. Their unique characteristics, such as blue colors in optical and near-infrared light, low metallicity, low stellar and gas surface densities, low dust content, and high gas mass fraction (up to 90%), resemble physical conditions of young galaxies of the early Universe whose interstellar medium (ISM) has not been enriched before major star formation activities initiated and should provide a testbed for star formation process at the exremly low surface density regime. Given that their star formation histories are still poorly constrained, LSB galaxies are known to have large specific star formation rates (sSFRs) with large gas fractions. There is also a correlation between their sSFRs and gas fractions. One of plausible scenarios is that the star formation efficiency may be an increasing funtion of time, perhaps due in part to the slow build up of metals and dust. Moreover, it is suspected that, being located in low number density area in terms of galaxy environment, LSB galaxies may receive additional gas to fuel their star formation activity via sporadic cold gas accretion, especially toward their outskirt regions analogous to extended ultraviolet disks. Due to their relatively isolated nature without having endured much interactions, LSB galaxies can mimic star formation processes of disk galaxies of the early Universe within their interstellar media (ISM). We present preliminary results based on stellar and gas phase metallicity of LSB galaxies along with their environment parameters to show how star-forming ISM of young disk galaxies before metal enrichment.

  16. Flow and coral morphology control coral surface pH: Implications for the effects of ocean acidification

    Directory of Open Access Journals (Sweden)

    Neil C. S. Chan

    2016-02-01

    Full Text Available The future impact of ocean acidification (OA on corals is disputed in part because mathematical models used to predict these impacts do not seem to capture, or offer a framework to adequately explain, the substantial variability in acidification effects observed in empirical studies. The build-up of a diffusive boundary layer (DBL, wherein solute transport is controlled by diffusion, can lead to pronounced differences between the bulk seawater pH, and the actual pH experienced by the organism, a factor rarely considered in mathematical modelling of ocean acidification effects on corals. In the present study, we developed a simple diffusion-reaction-uptake model that was experimentally parameterized based on direct microsensor measurements of coral tissue pH and O2 within the DBL of a branching and a massive coral. The model accurately predicts tissue surface pH for different coral morphologies and under different flow velocities as a function of ambient pH. We show that, for all cases, tissue surface pH is elevated at lower flows, and thus thicker DBLs. The relative effects of OA on coral surface pH was controlled by flow and we show that under low flow velocities tissue surface pH under OA conditions (pHSWS = 7.8 can be equal to the pH under normal conditions (pHSWS = 8.2. We conclude that OA effects on corals in nature will be complex as the degree to which they are controlled by flow appears to be species specific.

  17. Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

    Science.gov (United States)

    Podder, J.; Lin, J.; Sun, W.; Botis, S. M.; Tse, J.; Chen, N.; Hu, Y.; Li, D.; Seaman, J.; Pan, Y.

    2017-02-01

    Calcium carbonates such as calcite are the dominant hosts of inorganic iodine in nature and are potentially important for the retention and removal of radioactive iodine isotopes (129I and 131I) in contaminated water. However, little is known about the structural environment of iodine in carbonates. In this study, iodate (IO3-) doped calcite and vaterite have been synthesized using the gel-diffusion method at three NaIO3 concentrations (0.002; 0.004; 0.008 M) and a pH value of 9.0, under ambient temperature and pressure. Inductively coupled plasma mass spectrometry (ICP-MS) analyses show that iodine is preferentially incorporated into calcite over vaterite. Synchrotron iodine K-edge X-ray absorption near-edge structure (XANES) spectra confirm that IO3- is the dominant iodine species in synthetic calcite and vaterite. Analyses of iodine K-edge extended X-ray absorption fine structure (EXAFS) data, complemented by periodic first-principles calculations at the density functional theory (DFT) levels, demonstrate that the I5+ ion of the IO3- group in calcite and vaterite is bonded by three and two additional O atoms (i.e., coordination numbers = 6 and 5), respectively, and is incorporated via the charged coupled substitution I5+ + Na+ ↔ C4+ + Ca2+, with the Na+ cation at a nearest Ca2+ site being the most energetically favorable configuration.

  18. Calcite Supersaturation and Precipitation Kinetics in the Lower Colorado River, Ail-American Canal and East Highline Canal

    Science.gov (United States)

    Suarez, D. L.

    1983-06-01

    In situ pH determinations and analysis of major ions in solution indicated that the lower Colorado River is supersaturated with respect to calcite throughout the entire daily cycle, in both winter and summer. Although the ion activity product was 4 to 6 times greater than the calcite solubility product, there was no detectable precipitation. Chemical analyses of water samples taken along 350 km of the river and canals from Parker Dam to the Salton Sea also revealed no evidence of calcium carbonate precipitation despite the inflow of saline and highly supersaturated irrigation return flows. Laboratory kinetic studies indicated that calcite crystal growth rates with Colorado River water are about 30% of the rate for pure Ca-HCO3 waters and about 70% of that for synthetic Colorado River water. Calcite precipitation by crystal growth in the river is limited by the combination of short residence times and unavailability of reactive calcite. Critical supersaturation levels necessary for heterogeneous nucleation do not occur; a high suspended load limits algal photosynthesis and thus prevents large decreases in daytime H2CO3 levels.

  19. Depressant behavior and mechanism of guar and xanthan gums on calcite flotation%瓜尔胶和黄原胶对方解石浮选的抑制行为差异及机理

    Institute of Scientific and Technical Information of China (English)

    高志勇; 宋韶博; 孙伟; 胡岳华; 钟宏

    2016-01-01

    The depressant behavior and mechanism of guar and xanthan gums on calcite flotation were investigated through flotation experiment, adsorption study,zetapotential measurement and infrared spectroscopy measurement. The results show thatwhenpHis8.8 and oleate concentrationis 0.3 mmol/L, xanthan gum with a dosage of 50mg/L can markedly reduce the adsorption capacity of sodium oleate on calcite surfaces, and hence decrease the calcite recovery, while a higher dosage of 100mg/L for guar gum should be added in order to achieve the similar depressant effect.The guar gumisadsorbedon calcite surface through hydrogen bonding, while xanthan interacts with calcite through chemisorption and hydrogen bonding.%采用浮选试验、吸附量测试、zeta电位测试、红外光谱测试等方法研究瓜尔胶(非离子型)和黄原胶(阴离子型)2种天然胶对方解石的浮选抑制行为及机理。研究结果表明:当pH为8.8,油酸钠浓度为0.3 mmol/L时,用量为50 mg/L的黄原胶,可显著降低捕收剂油酸钠在方解石表面的吸附量,降低方解石的浮选回收率,而瓜尔胶要达到相同的抑制效果,用量需超过100 mg/L。上述抑制行为差异主要是由于2种天然胶在方解石表面的吸附方式和强度不同造成的。瓜尔胶通过氢键作用在方解石表面吸附,而黄原胶的主要作用方式为化学键合和氢键作用。

  20. Legacy seismic investigations of karst surfaces: Implications for heavy oil extraction from the Devonian Grosmont Formation, northeastern Alberta, Canada

    Science.gov (United States)

    Bown, Todd Dylan

    The Devonian Grosmont Formation in northeastern Alberta, Canada is the world's largest accumulation of heavy oil in carbonate rock with estimated bitumen in place of 64.5×109 m 3. At the studies location the eroded and buried surface of the Grosmont, referred here as the SubMannville uncoformity (SMU), was analyzed and interpret for a karsted surface. Results from legacy seismic data and available well log information were able to define the SMU as a mature karst surface within observable features such as dolines, karst valleys, karst plain and poljie and a ridge. The large scale topography of the ridge and poljie were geologically controlled by the underlying the Paleozoic rocks. Furthermore, the poljie was observed to contain the majority of the dolines in the area, noted to occur elsewhere. That said, dolines and karst valleys and other such dissolution features have the potential to erode the bitumen reservoir of the upper Grosmont members C and D. It is important for future oil prospectors to map and avoid areas such as the poljie, dolines and karst valley to increase certainty of reservoir presence. A preliminary rock-physics model was developed for the Grosmont reservoir of a bitumen-saturated dolomite. Results suggest that elastic properties of the Grosmont reservoir are temperature-frequency dispersive. This implies that there is a potential to use time-lapse seismic to map and monitor heating of the reservoir.

  1. Aberrant bile ducts, 'remnant surface bile ducts,' and peribiliary glands: descriptive anatomy, historical nomenclature, and surgical implications.

    Science.gov (United States)

    El Gharbawy, Ramadan M; Skandalakis, Lee J; Heffron, Thomas G; Skandalakis, John E

    2011-05-01

    The term "aberrant bile ducts" has been used to designate three heterogeneous groups of biliary structures: (1) bile ducts degenerating or disappearing (unknown etiology, diverse locations); (2) curious biliary structures in the transverse fissure; and (3) aberrant right bile ducts draining directly into the common hepatic duct. We report our observations on these three groups. Twenty-nine fresh human livers of stillborns and adults were injected differentially with colored latex and dissected. Adult livers showed portal venous and hepatic arterial branches, and bile ducts not associated with parenchyma, subjacent to and firmly adherent with the liver capsule: elements of ramifications of normal sheaths were present on the liver's surface. These ramifications, having lost parenchyma associated with them, then sequentially lost their portal branches, bile ducts and arterial branches. This process affected the ramifications of the sheaths in the left triangular ligament, adjacent to the inferior vena cava, in the gallbladder bed and anywhere else on the liver's surface and resulted in the presence of bile ducts accompanied by portal venous and/or hepatic arterial branches and not associated with parenchyma for a period of time. This first group represented normal bile ducts that do not meet the criteria of aberration and could be appropriately designated "remnant surface bile ducts." Such changes were not found in the transverse fissures and review of the literature revealed that the curious biliary structures are the microscopic peribiliary glands. The third group met the criteria of aberration and the anatomy of a representative duct is described.

  2. Surface slip and off-fault deformation patterns in the 2013 MW 7.7 Balochistan, Pakistan earthquake: Implications for controls on the distribution of near-surface coseismic slip

    Science.gov (United States)

    Zinke, Robert; Hollingsworth, James; Dolan, James F.

    2014-12-01

    of 398 fault offsets measured by visual analysis of WorldView high-resolution satellite imagery with deformation maps produced by COSI-Corr subpixel image correlation of Landsat-8 and SPOT5 imagery reveals significant complexity and distributed deformation along the 2013 Mw 7.7 Balochistan, Pakistan earthquake. Average slip along the main trace of the fault was 4.2 m, with local maximum offsets up to 11.4 m. Comparison of slip measured from offset geomorphic features, which record localized slip along the main strand of the fault, to the total displacement across the entire width of the surface deformation zone from COSI-Corr reveals ˜45% off-fault deformation. While previous studies have shown that the structural maturity of the fault exerts a primary control on the total percentage of off-fault surface deformation, large along-strike variations in the percentage of strain localization observed in the 2013 rupture imply the influence of important secondary controls. One such possible secondary control is the type of near-surface material through which the rupture propagated. We therefore compared the percentage off-fault deformation to the type of material (bedrock, old alluvium, and young alluvium) at the surface and the distance of the fault to the nearest bedrock outcrop (a proxy for sediment thickness along this hybrid strike slip/reverse slip fault). We find significantly more off-fault deformation in younger and/or thicker sediments. Accounting for and predicting such off-fault deformation patterns has important implications for the interpretation of geologic slip rates, especially for their use in probabilistic seismic hazard assessments, the behavior of near-surface materials during coseismic deformation, and the future development of microzonation protocols for the built environment.

  3. Calcite Dissolution in Deionized Water from 50℃ to 250℃ at I0 MPa:Rate Equation and Reaction Order

    Institute of Scientific and Technical Information of China (English)

    GONG Qingjie; DENG Jun; WANG Qingfei; YANG Liqiang; SHE Min

    2008-01-01

    Carbonate minerals and water (or geofiuids) reactions are important for modeling of geochemical processes and have received considerable attention over the past decades. The calcite dissolution rates from 50℃ to 250℃ at 10 Mpa in deionized water with a flow rate varying from 0.2 to 5 mL/min were experimentally measured in a continuous flow column pressure vessel reactor. The dissolution began near the equilibrium with clceq > 0.3 and finally reached the equilibrium at 100℃-250℃, so the corresponding solubility was also determined as 1.87, 2.02, 2.02 and 1.88×10-4"mol/L at 100℃, 150℃, 200~C and 2500C respectively, which was first increasing and then switching to decreasing with temperature and the maximum value might occur between 150℃ and 200℃. The experimental dissolution rate not only increased with temperature, but also had a rapid increase between 150℃ and 200℃ at a constant flow rate of 4 mL/min. The measured dissolution rates can be described using rate equations of R = k(1-c/c) or R = kc. In these equations the reaction order n changed with temperature, which indicates that n was a variable rather than a constant, and the activation energy was 13.4 kJ/mol calculated with R = k(1-c/c) or 18.0 kJ/mol with R = kc, which is a little lower than the surface controlled values. The varied reaction order and lower activation energy indicates that calcite dissolution in this study is a complex interplay of diffusion controlled and surface controlled processes.

  4. Tearing the terroir: Details and implications of surface rupture and deformation from the 24 August 2014 M6.0 South Napa earthquake, California

    Science.gov (United States)

    DeLong, Stephen B.; Donnellan, Andrea; Ponti, Daniel J.; Rubin, Ron S.; Lienkaemper, James J.; Prentice, Carol S.; Dawson, Timothy E.; Seitz, Gordon G.; Schwartz, David P.; Hudnut, Kenneth W.; Rosa, Carla M.; Pickering, Alexandra J; Parker, Jay W.

    2016-01-01

    The Mw 6.0 South Napa earthquake of 24 August 2014 caused slip on several active fault strands within the West Napa Fault Zone (WNFZ). Field mapping identified 12.5 km of surface rupture. These field observations, near-field geodesy and space geodesy, together provide evidence for more than ~30 km of surface deformation with a relatively complex distribution across a number of subparallel lineaments. Along a ~7 km section north of the epicenter, the surface rupture is confined to a single trace that cuts alluvial deposits, reoccupying a low-slope scarp. The rupture continued northward onto at least four other traces through subparallel ridges and valleys. Postseismic slip exceeded coseismic slip along much of the southern part of the main rupture trace with total slip 1 year postevent approaching 0.5 m at locations where only a few centimeters were measured the day of the earthquake. Analysis of airborne interferometric synthetic aperture radar data provides slip distributions along fault traces, indicates connectivity and extent of secondary traces, and confirms that postseismic slip only occurred on the main trace of the fault, perhaps indicating secondary structures ruptured as coseismic triggered slip. Previous mapping identified the WNFZ as a zone of distributed faulting, and this was generally borne out by the complex 2014 rupture pattern. Implications for hazard analysis in similar settings include the need to consider the possibility of complex surface rupture in areas of complex topography, especially where multiple potentially Quaternary-active fault strands can be mapped.

  5. Jet-Suspended, Calcite-Ballasted Cyanobacterial Waterwarts in a Desert Spring

    Science.gov (United States)

    Pichel-Garcia, Ferran; Wade, Bman D.; Farmer, Jack D.

    2002-01-01

    We describe a population of colonial cyanobacteria (waterwarts) that develops as the dominant primary producer in a bottom-fed, warm spring in the Cuatro Cienegas karstic region of the Mexican Chihuahuan Desert. The centimeter-sized waterwarts were suspended within a central, conically shaped, 6-m deep well by upwelling waters. Waterwarts were built by an unicellular cyanobacterium and supported a community of epiphytic filamentous cyanobacteria and diatoms but were free of heterotrophic bacteria inside. Sequence analysis of genes revealed that this cyanobacterium is only distantly related to several strains of other unicellular teria Cyanothece, Waterwarts contained orderly arrangements of mineral made up of microcrystalline low-magnesium calcite with high levels of strontium and sulfur. Waterwarts were 95.9% (v/v) glycan, 2.8% cells, and 1.3% mineral grains and had a buoyant density of 1.034 kg/L. An analysis of the hydrological properties of the spring well and the waterwarts demonstrated that both large colony size and the presence of controlled amounts of mineral ballast are required to prevent the population from being washed out of the well. The unique hydrological characteristics of the spring have likely selected for both traits. The mechanisms by which controlled nucleation of extracellular calcite is achieved remain to be explored.

  6. Characterization of Shock Effects in Calcite by Raman Spectroscopy: Results of Experiments

    Science.gov (United States)

    Bell, M. S.

    2016-01-01

    Carbonates comprise approx. 20% by volume of present day Earth's sedimentary rocks and store most of the terrestrial CO2 inventory. Some of the oldest meta-sedimentary rocks found on Earth contain abundant carbonate from which impact-induced release of CO2 could have played a role in the formation and evolution of the atmosphere. Carbonates are also present in the target materials for approx. 30% of all terrestrial impact structures including large impacts such as Chicxulub which happened to occur at a location with extraordinarily thick platform carbonate 3-6 km deep. The impact release of CO2 from carbonates can cause global warming as a result of the well-known greenhouse effect and have subsequent effects on climate and biota. Therefore, the shock behavior of calcite is important in understanding the Cretaceous-Paleogene event and other impacts with carbonate-bearing sediments in their target(s) such as Mars and some asteroids. A comprehensive survey utilizing a variety of techniques to characterize the effects manifest in Calcite (Iceland Spar) experimentally shocked to 60.8 GPa has been completed. Results of analysis by Raman Spectroscopy are reported here.

  7. Impacts of pH and [CO32-] on the incorporation of Zn in foraminiferal calcite

    Science.gov (United States)

    van Dijk, Inge; de Nooijer, Lennart Jan; Wolthers, Mariëtte; Reichart, Gert-Jan

    2017-01-01

    The trace elemental composition of foraminiferal shell calcite is known to reflect the environment in which the shell was precipitated. Whereas conservative elements incorporated in foraminiferal shell carbonate reflect factors such as temperature (Mg), carbonate chemistry (B) and salinity (Na), the nutrient type elements (Ba, Cd, and possibly Zn) are useful tools to reconstruct biogeochemical cycling and past ocean circulation. Still also nutrient-type elements will be most likely influenced by factors other than their relative concentrations. Culturing benthic foraminifera under controlled carbonate chemistry conditions allows for disentanglement of impacts of different parameters of the carbon system on the elemental composition of foraminiferal calcite. Here we show that zinc incorporation in cultured specimens of the benthic foraminifer Ammonia tepida is correlated to changes in carbonate ion concentration ([CO32-]). By modeling activities of different chemical species of Zn in seawater over a range of [CO32-], we suggest that Zn2+ , rather than other relatively abundant Zn-species (e.g. ZnCO30 and ZnHCO3+) is taken up during biomineralization. Our results suggest that foraminiferal Zn/Ca might be especially useful when combined with other [CO32-] proxies, enabling reconstruction of past seawater element concentrations. Conversely, when the nutrient-type element concentrations are known, incorporation of Zn in foraminiferal shells can be used to reconstruct past sea water carbon speciation.

  8. Calcite-graphite thermometry of the Franklin Marble, New Jersey Highlands

    Science.gov (United States)

    Peck, W.H.; Volkert, R.A.; Meredith, M.T.; Rader, E.L.

    2006-01-01

    We present new stable-isotope data for the Mesoproterozoic Franklin Marble from outcrops along an 80-km traverse parallel to and across strike of the structural grain of the western New Jersey Highlands. Calcite and dolomite from marble have an average ??13C of 0.35??? ?? 0.73??? PDB (n = 46) and a more limited range than other Mesoproterozoic marbles from the Adirondacks and the Canadian Grenville Province. The small range of ??13C values from the New Jersey samples is consistent with the preservation of a primary marine isotopic signature and limited postdepositional isotopic modification, except proximal to Zn or Fe ore deposits and fault zones. Fractionations between calcite and well-formed graphite (??13C[Cal-Gr]) for analyzed Franklin Marble samples average 3.31???. ?? 0.25??? (n = 34), and dolomite-graphite fractionations average 3.07??? ?? 0.30??? (n = 6). Taken together, these indicate an average temperature of 769?? ?? 43??C during metamorphism associated with the Ottawan Orogeny in the New Jersey Highlands. Thus, carbon isotope fractionations demonstrate that the Franklin Marble was metamorphosed at granulite facies conditions. Metamorphic temperatures are relatively constant for the area sampled and overprint the metamorphosed carbonatehosted Zn-Fe-Mn ore deposits. The results of this study support recent work proposing that pressure and temperature conditions during Ottawan orogenesis did not vary greatly across faults that partition the Highlands into structural blocks. ?? 2006 by The University of Chicago. All rights reserved.

  9. Continuous 500,000-year climate record from vein calcite in Devils Hole, Nevada

    Science.gov (United States)

    Winograd, I.J.; Coplen, T.B.; Landwehr, J.M.; Riggs, A.C.; Ludwig, K. R.; Szabo, B. J.; Kolesar, Peter T.; Revesz, K.M.

    1992-01-01

    Oxygen-18 (??18O) variations in a 36-centimeter-long core (DH-11) of vein calcite from Devils Hole, Nevada, yield an uninterrupted 500,000-year paleotemperature record that closely mimics all major features in the Vostok (Antarctica) paleotemperature and marine ??18O ice-volume records. The chronology for this continental record is based on 21 replicated mass-spectrometric uranium-series dates. Between the middle and latest Pleistocene, the duration of the last four glacial cycles recorded in the calcite increased from 80,000 to 130,000 years; this variation suggests that major climate changes were aperiodic. The timing of specific climatic events indicates that orbitally controlled variations in solar insolation were not a major factor in triggering deglaciations. Interglacial climates lasted about 20,000 years. Collectively, these observations are inconsistent with the Milankovitch hypothesis for the origin of the Pleistocene glacial cycles but they are consistent with the thesis that these cycles originated from internal nonlinear feedbacks within the atmosphere-ice sheet-ocean system.

  10. The structural, compositional and mechanical features of the calcite shell of the barnacle Tetraclita rufotincta.

    Science.gov (United States)

    Astachov, Liliana; Nevo, Zvi; Brosh, Tamar; Vago, Razi

    2011-09-01

    The microstructure and chemical composition of the calcite shell of the sea barnacle Tetraclita rufotincta (Pilsbry, 1916) were investigated using microscopic and analytical methods. The barnacle shell was separated mechanically into its three substructural units: outer, interior, and inner layers. The organic matrices of these structural parts were further separated into soluble and insoluble constituents and their characteristic functional groups were studied by FTIR. Investigation of the mechanical properties of the interior mass of the shell reveals remarkable viscoelastic behavior. In general, the mechanical behavior of the shell is a function of its geometry as well as of the material, of which it is constructed. In the case of T. rufotincta, as calcite is a brittle material, the elastic behavior of the shell is apparently related to its micro- and macroarchitecture. The latter enables the shell to fulfill its primary function which is to protect the organism from a hostile environment and enables its survival. Our detailed identification of the similarities and differences between the various structural components of the shell in regard to the composition and properties of the organic component will hopefully throw light on the role of organic matrices in biomineralization processes.

  11. Continuous 500,000-year climate record from vein calcite in devils hole, nevada.

    Science.gov (United States)

    Winograd, I J; Coplen, T B; Landwehr, J M; Riggs, A C; Ludwig, K R; Szabo, B J; Kolesar, P T; Revesz, K M

    1992-10-09

    Oxygen-18 (delta(18)O) variations in a 36-centimeter-long core (DH-11) of vein calcite from Devils Hole, Nevada, yield an uninterrupted 500,000-year paleotemperature record that closely mimics all major features in the Vostok (Antarctica) paleotemperature and marine delta(18)O ice-volume records. The chronology for this continental record is based on 21 replicated mass-spectrometric uranium-series dates. Between the middle and latest Pleistocene, the duration of the last four glacial cycles recorded in the calcite increased from 80,000 to 130,000 years; this variation suggests that major climate changes were aperiodic. The timing of specific climatic events indicates that orbitally controlled variations in solar insolation were not a major factor in triggering deglaciations. Interglacial climates lasted about 20,000 years. Collectively, these observations are inconsistent with the Milankovitch hypothesis for the origin of the Pleistocene glacial cycles but they are consistent with the thesis that these cycles originated from internal nonlinear feedbacks within the atmosphere-ice sheet-ocean system.

  12. Characterization of urease and carbonic anhydrase producing bacteria and their role in calcite precipitation.

    Science.gov (United States)

    Achal, Varenyam; Pan, Xiangliang

    2011-03-01

    Urease and carbonic anhydrase (CA) are key enzymes in the chemical reaction of living organisms and have been found to be associated with calcification in a number of microorganisms and invertebrates. Three bacterial strains designated as AP4, AP6, and AP9 were isolated from highly alkaline soil samples using the enrichment culture technique. On the basis of various physiological tests and 16S rRNA sequence analysis, these three bacteria were identified as Bacillus sp., B. megaterium, and B. simplex. Further, these Bacillus species have been characterized for the production of urease and CA in the process of biocalcification. One of the isolates, AP6 produced 553 U/ml of urease and 5.61 EU/ml CA. All the strains were able to produce significant amount of exopolymeric substances and biofilm. Further, efficacy of these strains was tested for calcite production ability and results were correlated with urease and CA. Isolate AP6 precipitated 2.26 mg calcite/cell dry mass (mg). Our observations strongly suggest that it is not only urease but CA also plays an important role in microbially induced calcium carbonate precipitation process. The current work demonstrates that urease and CA producing microbes can be utilized in biocalcification as a sealing agent for filling the gaps or cracks and fissures in constructed facilities and natural formations alike.

  13. Carbon export and transfer to depth across the Southern Ocean Great Calcite Belt

    Directory of Open Access Journals (Sweden)

    S. Z. Rosengard

    2015-02-01

    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-dominated communities produce large and labile POC aggregates, which 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.

  14. Assessing the potential for using biogenic calcites as dosemeters for luminescence dating

    Energy Technology Data Exchange (ETDEWEB)

    Duller, G.A.T. [Institute of Geography and Earth Sciences, Aberystwyth University, Ceredigion, SY23 3DB (United Kingdom)], E-mail: ggd@aber.ac.uk; Penkman, K.E.H. [BioArCh, Department of Chemistry, University of York, YO10 5DD (United Kingdom); Wintle, A.G. [Institute of Geography and Earth Sciences, Aberystwyth University, Ceredigion, SY23 3DB (United Kingdom)

    2009-05-15

    Calcium carbonate emits an intense thermoluminescence (TL) signal and previous work has explored the potential of using this signal to date both inorganic carbonates such as limestones and stalagmites and biogenic calcite produced by marine organisms. Luminescence analysis of biogenic calcites directly dates the secretion of the mineral by the organism and is therefore not reliant upon exposure of the sample to daylight. A method is outlined for using the TL signals from slug plates, from the Limacidae family, and opercula from the snail Bithynia tentaculata to construct a single-aliquot regenerative-dose growth curve. Analysis of slug plates from a number of Quaternary sites show that the equivalent dose (D{sub e}) of a late Holocene sample is close to zero and that the D{sub e} increases with age over the last 500 ka. The TL signal from snail opercula is shown to increase up to doses over 4000 Gy. Replicate measurements from 16 opercula from a site {approx}220 ka show a broad distribution. Potential causes of this scatter are discussed along with recommendations about how it could be reduced. The major challenge which remains to be solved before slug plates or snail opercula could be used to calculate ages is to develop methods for calculating the dose rate received during burial.

  15. Importance of initial buoyancy field on evolution of mantle thermal structure:Implications of surface boundary conditions

    Institute of Scientific and Technical Information of China (English)

    Petar Glisovic; Alessandro M. Forte

    2015-01-01

    Although there has been significant progress in the seismic imaging of mantle heterogeneity, the outstanding issue that remains to be resolved is the unknown distribution of mantle temperature anomalies in the distant geological past that give rise to the present-day anomalies inferred by global tomography models. To address this question, we present 3-D convection models in compressible and self-gravitating mantle initialised by different hypothetical temperature patterns. A notable feature of our forward convection modelling is the use of self-consistent coupling of the motion of surface tectonic plates to the underlying mantle flow, without imposing prescribed surface velocities (i.e., plate-like boundary condition). As an approximation for the surface mechanical conditions before plate tectonics began to operate we employ the no-slip (rigid) boundary condition. A rigid boundary condition dem-onstrates that the initial thermally-dominated structure is preserved, and its geographical location is fixed during the evolution of mantle flow. Considering the impact of different assumed surface boundary conditions (rigid and plate-like) on the evolution of thermal heterogeneity in the mantle we suggest that the intrinsic buoyancy of seven superplumes is most-likely resolved in the tomographic images of present-day mantle thermal structure. Our convection simulations with a plate-like boundary condition reveal that the evolution of an initial cold anomaly beneath the Java-Indonesian trench system yields a long-term, stable pattern of thermal heterogeneity in the lowermost mantle that resembles the present-day Large Low Shear Velocity Provinces (LLSVPs), especially below the Pacific. The evolution of sub-duction zones may be, however, influenced by the mantle-wide flow driven by deeply-rooted and long-lived superplumes since Archean times. These convection models also detect the intrinsic buoyancy of the Perm Anomaly that has been identified as a unique slow feature

  16. Changes in Surface Wind Speed over North America from CMIP5 Model Projections and Implications for Wind Energy

    OpenAIRE

    Sujay Kulkarni; Huei-Ping Huang

    2014-01-01

    The centennial trends in the surface wind speed over North America are deduced from global climate model simulations in the Climate Model Intercomparison Project—Phase 5 (CMIP5) archive. Using the 21st century simulations under the RCP 8.5 scenario of greenhouse gas emissions, 5–10 percent increases per century in the 10 m wind speed are found over Central and East-Central United States, the Californian Coast, and the South and East Coasts of the USA in winter. In summer, climate models proje...

  17. 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

  18. Permafrost thaw and fire history: implications of boreal tree cover changes on land surface properties and turbulent energy fluxes in the Taiga Plains, Canada

    Science.gov (United States)

    Sonnentag, Oliver; Helbig, Manuel; Payette, Fanny; Wischnewski, Karoline; Kljun, Natascha; Chasmer, Laura; Pappas, Christoforos; Detto, Matteo; Baltzer, Jennifer; Quinton, William; Marsh, Philip

    2016-04-01

    Given their large areal coverage, high carbon densities, and unique land surface properties and disturbance regimes (e.g., wildfires), the world's boreal forests are integral components of the global and regional climate systems. A large portion of boreal forests contain permafrost, i.e., perennially cryotic ground. In the Taiga Plains ecozone in northwestern Canada, the northernmost boreal forests grow on cold (100 m) continuous permafrost (>90 % in areal extent). More southerly boreal forests occur in areas with discontinuous (>50 - 90 % in areal extent), sporadic (>10 - 50 % in areal extent) and isolated permafrost (fire history, and permafrost and drainage characteristics, we show that in low-lying, poorly-drained areas along the southern fringe of permafrost, thawing induces widespread decreases in PTC and dominates over PTC increases due to post-fire regrowth. In contrast, PTC appears to be slightly increasing in the central and northern Taiga Plains with more stable discontinuous and continuous permafrost, respectively. While these increases are partly explained by post-fire regrowth, more favourable growing conditions may also contribute to increasing PTC. To better understand the implications of permafrost thaw on land surface properties (e.g., aerodynamic conductance for heat [ga] and surface conductance for water vapour [gs]), and the turbulent fluxes of latent (LE) and sensible heat (H) along the southern fringe of permafrost, we examined nested eddy covariance flux measurements made at two nearby locations at Scotty Creek (61°18' N; 121°18' W) starting May 2013. The low-lying, poorly-drained southern portion of this 152 km2-watershed contains rapidly thawing sporadic permafrost resulting in a highly dynamic mosaic dominated by decreasing forested permafrost peat plateaus, and increasing permafrost-free wetlands. The spatial heterogeneities within the eddy covariance flux footprints (forest/wetland vs. wetland) were resolved with a two

  19. Observed and modeled surface Lagrangian transport between coastal regions in the Adriatic Sea with implications for marine protected areas

    Science.gov (United States)

    Carlson, Daniel F.; Griffa, Annalisa; Zambianchi, Enrico; Suaria, Giuseppe; Corgnati, Lorenzo; Magaldi, Marcello G.; Poulain, Pierre-Marie; Russo, Aniello; Bellomo, Lucio; Mantovani, Carlo; Celentano, Paolo; Molcard, Anne; Borghini, Mireno

    2016-04-01

    Surface drifters and virtual particles are used to investigate transport between seven coastal regions in the central and southern Adriatic Sea to estimate the degree to which these regions function as a network. Alongshore coastal currents and cyclonic gyres are the primary circulation features that connected regions in the Adriatic Sea. The historical drifter observations span 25 years and, thus, provide estimates of transport between regions realized by the mean surface circulation. The virtual particle trajectories and a dedicated drifter experiment show that southeasterly Sirocco winds can drive eastward cross-Adriatic transport from the Italian coast near the Gargano Promontory to the Dalmatian Islands in Croatia. Southeasterly winds disrupt alongshore transport on the west coast. Northwesterly Mistral winds enhanced east-to-west transport and resulted in stronger southeastward coastal currents in the western Adriatic current (WAC) and export to the northern Ionian Sea. The central Italian regions showed strong connections from north to south, likely realized by alongshore transport in the WAC. Alongshore, downstream transport was weaker on the east coast, likely due to the more complex topography introduced by the Dalmatian Islands of Croatia. Cross-Adriatic connection percentages were higher for east-to-west transport. Cross-Adriatic transport, in general, occurred via the cyclonic sub-gyres, with westward (eastward) transport observed in the northern (southern) arms of the central and southern gyres.

  20. Mixing heights and surface fluxes over Galveston Bay and the Gulf of Mexico: Implications for modeling of pollution episodes

    Science.gov (United States)

    Angevine, W. M.; Tucker, S. C.; Fairall, C.; Bariteau, L.; Wolfe, D.; Zagar, M.; Brewer, A.

    2007-12-01

    During the 2006 Texas Air Quality Study, boundary layer measurements were made by in-situ instruments, lidars, and rawinsondes on the NOAA RV Ronald H. Brown as well as by radar wind profilers on land. Brown also carried instruments to measure surface heat and momentum fluxes. This presentation will emphasize measurements made in Galveston Bay and in the Gulf of Mexico near the Houston area. Details of boundary layer depth and turbulence intensity over these waters have not been well known previously, but are quite important to the understanding of high ozone episodes in Houston. One somewhat surprising result is that the boundary layer over water was almost always slightly unstable, with positive surface heat flux. Mixing depths were moderate, although mixing was generally weak compared to that over land. Boundary layer heights over the water were substantially shallower than daytime heights over land. Experiments in modeling ozone episodes with WRF at 1.5-km grid spacing will be shown and compared with the measurements.

  1. Dynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cells

    KAUST Repository

    Brennan, Thomas P.

    2013-11-12

    A dual experimental-computational approach utilizing near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory-molecular dynamics (DFT-MD) is presented for determining the orientation of a large adsorbate on an oxide substrate. A system of interest in the field of dye-sensitized solar cells is studied: an organic cyanoacrylic acid-based donor-π-acceptor dye (WN1) bound to anatase TiO2. Assessment of nitrogen K-edge NEXAFS spectra is supported by calculations of the electronic structure that indicate energetically discrete transitions associated with the two π systems of the C-N triple bond in the cyanoacrylic acid portion of the dye. Angle-resolved NEXAFS spectra are fitted to determine the orientation of these two orbital systems, and the results indicate an upright orientation of the adsorbed dye, 63 from the TiO2 surface plane. These experimental results are then compared to computational studies of the WN1 dye on an anatase (101) TiO2 slab. The ground state structure obtained from standard DFT optimization is less upright (45 from the surface) than the NEXAFS results. However, DFT-MD simulations, which provide a more realistic depiction of the dye at room temperature, exhibit excellent agreement - within 2 on average - with the angles determined via NEXAFS, demonstrating the importance of accounting for the dynamic nature of adsorbate-substrate interactions and DFT-MD\\'s powerful predictive abilities. © 2013 American Chemical Society.

  2. Detection of snow surface thawing and refreezing in the Eurasian Arctic with QuikSCAT: implications for reindeer herding.

    Science.gov (United States)

    Bartsch, Annett; Kumpula, Timo; Forbes, Bruce C; Stammler, Florian

    2010-12-01

    Snow conditions play an important role for reindeer herding. In particular, the formation of ice crusts after rain-on-snow (ROS) events or general surface thawing with subsequent refreezing impedes foraging. Such events can be monitored using satellite data. A monitoring scheme has been developed for observation at the circumpolar scale based on data from the active microwave sensor SeaWinds on QuikSCAT (Ku-band), which is sensitive to changes on the snow surface. Ground observations on Yamal Peninsula were used for algorithm development. Snow refreezing patterns are presented for northern Eurasia above 60 degrees N from autumn 2001 to spring 2008. Western Siberia is more affected than Central and Eastern Siberia in accordance with climate data, and most events occur in November and April. Ice layers in late winter have an especially negative effect on reindeer as they are already weakened. Yamal Peninsula is located within a transition zone between high and low frequency of events. Refreezing was observed more than once a winter across the entire peninsula during recent years. The southern part experienced refreezing events on average four times each winter. Currently, herders can migrate laterally or north-south, depending on where and when a given event occurs. However, formation of ice crusts in the northern part of the peninsula may become as common as they are now in the southern part. Such a development would further constrain the possibility to migrate on the peninsula.

  3. Geochemical assessment of light gaseous hydrocarbons in near-surface soils of Kutch–Saurashtra: Implication for hydrocarbon prospects

    Indian Academy of Sciences (India)

    P Lakshmi Srinivasa Rao; T Madhavi; D Srinu; M S Kalpana; D J Patil; A M Dayal

    2013-02-01

    Light hydrocarbons in soil have been used as direct indicators in geochemical hydrocarbon exploration, which remains an unconventional path in the petroleum industry. The occurrence of adsorbed soil gases, methane and heavier homologues were recorded in the near-surface soil samples collected from Kutch–Saurashtra, India. Soil gas alkanes were interpreted to be derived from deep-seated hydrocarbon sources and have migrated to the surface through structural discontinuities. The source of hydrocarbons is assessed to be thermogenic and could have been primarily derived from humic organic matter with partial contribution from sapropelic matter. Gas chromatographic analyses of hydrocarbons desorbed from soil samples through acid extraction technique showed the presence of methane through -butane and the observed concentrations (in ppb) vary from: methane (C1) from 4–291, ethane (C2) from 0–84, propane (C3) from 0–37, i-butane (iC4) from 0–5 and -butane (nC4) from 0–4. Carbon isotopes measured for methane and ethane by GC-C-IRMS, range between −42.9‰ to −13.3‰ (Pee Dee Belemnite – PDB) and −21.2‰ to −12.4‰ (PDB), respectively. The increased occurrence of hydrocarbons in the areas near Anjar of Kutch and the area south to Rajkot of Saurashtra signifies the area potential for oil and gas.

  4. Effects of spatial pattern of green space on land surface temperature: implications for sustainable urban planning and climate change adaptation

    Science.gov (United States)

    Maimaitiyiming, M.; Ghulam, A.

    2013-12-01

    The urban heat island (UHI) refers to the phenomenon of higher atmospheric and surface temperatures occurring in urban areas than in the surrounding rural areas. Numerous studies have shown that increased percent cover of green space (PLAND) can significantly decrease land surface temperatures (LST). Fewer studies, however, have investigated the effects of configuration of green space on LST. This paper aims at to fill this gap using oasis city Aksu in northwestern China as a case study. PLAND along with two configuration metrics are used to measure the composition and configuration of green space. The metrics are calculated by moving window method based on a green space map derived from Landsat Thematic Mapper (TM) imagery, and LST data are retrieved from Landsat TM thermal band. Normalized mutual information measure is employed to investigate the relationship between LST and the spatial pattern of green space. The results show that while the PLAND is the most important variable that elicits LST dynamics, spatial configuration of green space also has significant effect on LST. In addition, the variance of LST is largely explained by both composition and configuration of green space. Results from this study can expand our understanding of the relationship between LST and vegetation, and provide insights for sustainable urban planning and management under changing climate.