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Sample records for calcite seed crystals

  1. Crystal lattice tilting in prismatic calcite.

    PubMed

    Olson, Ian C; Metzler, Rebecca A; Tamura, Nobumichi; Kunz, Martin; Killian, Christopher E; Gilbert, Pupa U P A

    2013-08-01

    We analyzed the calcitic prismatic layers in Atrina rigida (Ar), Haliotis iris (Hi), Haliotis laevigata (HL), Haliotis rufescens (Hrf), Mytilus californianus (Mc), Pinctada fucata (Pf), Pinctada margaritifera (Pm) shells, and the aragonitic prismatic layer in the Nautilus pompilius (Np) shell. Dramatic structural differences were observed across species, with 100-?m wide single-crystalline prisms in Hi, HL and Hrf, 1-?m wide needle-shaped calcite prisms in Mc, 1-?m wide spherulitic aragonite prisms in Np, 20-?m wide single-crystalline calcite prisms in Ar, and 20-?m wide polycrystalline calcite prisms in Pf and Pm. The calcite prisms in Pf and Pm are subdivided into sub-prismatic domains of orientations, and within each of these domains the calcite crystal lattice tilts gradually over long distances, on the order of 100 ?m, with an angle spread of crystal orientation of 10-20. Furthermore, prisms in Pf and Pm are harder than in any other calcite prisms analyzed, their nanoparticles are smaller, and the angle spread is strongly correlated with hardness in all shells that form calcitic prismatic layers. One can hypothesize a causal relationship of these correlated parameters: greater angle spread may confer greater hardness and resistance to wear, thus providing Pf and Pm with a structural advantage in their environment. This is the first structure-property relationship thus far hypothesized in mollusk shell prisms. PMID:23806677

  2. Pressure effect on magnesian calcite coating calcite and synthetic magnesian calcite seeds added to seawater in a closed system

    NASA Astrophysics Data System (ADS)

    Koch, B.; Disteche, A.

    1984-03-01

    When pure crystalline calcite seeds are added to supersaturated seawater, precipitation results in a coating which with time equilibrates at atmospheric pressure with seawater and corresponds to a calcite containing probably only 2 or 3% of MgCO 3 (mole fraction). If synthetic crystalline magnesian calcite is added, the surface layer equilibrates not only with respect to seawater but also in relation with the crystalline sites initiating precipitation. Adding Mg 0.03Ca 0.97CO 3 results in a coating with a solubility close to that of calcite. This confirms that the surface coating on pure calcite seeds contains about 2 or 3% MgCO 3 ( K' sp = 10-6.30). The surface layer precipitated on a synthetic Mg 0.08Ca 0.92CO 3 equilibrates finally with a carbonate more soluble than calcite ( K' sp = 10-5.94) corresponding to the seeds composition. Experiments at 1000 kg cm t-2 imply that when magnesian calcites are precipitated at the surface of calcite or magnesian calcite seeds, the precipitate must be hydrated, otherwise pressure accelerated recrystallization or rearrangement with loss of Mg would thermodynamically be impossible. By changing the pressure of a seawater sample originally saturated with a solid carbonate phase, changes in pH result from the effect of pressure on the dissociation constants of carbonic acid and boric acid causing either undersaturation or supersaturation with respect to the solid. By changing pressure we can show whether precipitation, dissolution and recrystallization are reversible processes if pH is taken as criteria of reversibility.

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

    USGS Publications Warehouse

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

    1981-01-01

    A highly reproducible seeded growth technique was used to study calcite crystallization from calcium bicarbonate solutions at 25°C and fixed carbon dioxide partial pressures between 0.03 and 0.3 atm. The results are not consistent with empirical crystallization models that have successfully described calcite growth at low PCO2 (< 10−3 atm). Good agreement was found between observed crystallization rates and those calculated from the calcite dissolution rate law and mechanism proposed by Plummer et al. (1978).

  4. Controlled calcite nucleation on polarized calcite single crystal substrates in the presence of polyacrylic acid

    NASA Astrophysics Data System (ADS)

    Wada, Norio; Horiuchi, Naohiro; Nakamura, Miho; Nozaki, Kosuke; Hiyama, Tetsuo; Nagai, Akiko; Yamashita, Kimihiro

    2015-04-01

    We studied theoretically and experimentally the effects of the surface electric field generated by polarization and polyacrylic acid (PAA) additives on the heterogeneous nucleation of calcite on the calcite single crystal substrates with (10.4), (10.0) and (00.1) orientations. A set of "in-situ" experiments with optical microscopy was performed to determine the waiting time of CaCO3 nucleation, defined as the time interval between the onset of the diffusion of CO2 and the appearance of the first visible precipitation. Calcite was nucleated on the oriented calcite substrates through diffusion of NH3 and CO2 gas from a solid ammonium carbonate into calcium chloride solutions. A theoretical analysis showed that the surface electric field of the polarized calcite substrate decrease the activation energy for nucleation and consequently promotes nucleation. Experimentally, the surface electric field and PAA addition were found to decrease both contact angles and waiting times, and as a result, promote the heterogeneous nucleation. Combined effect of PAA and surface electric field further reduced contact angles and waiting times regardless of orientation differences of the calcite substrates. The cooperation acts remarkably on N-surface of the respective calcite substrates. The results were explained by the Cassie's equation, a classical heterogeneous nucleation theory under a surface electric field, and matching of the charged sites on the PAA chain with the ion arrangement on the calcite substrate.

  5. Calcite crystal growth rate inhibition by polycarboxylic acids

    USGS Publications Warehouse

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

    2001-01-01

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

  6. Cross-section of Calcite Crystal Covering in Jewel Cave

    USGS Multimedia Gallery

    Jewel Cave is currently the 3rd most extensive cave network in the world. It is believed to have formed completely underwater, thus leading to the extensive coating of calcite crystals. A cross-sectional view of the crystal coating can be seen in the center of the image, with the surface of the cal...

  7. Inhibition by glycosaminoglycans of CaCO3 (calcite) crystallization.

    PubMed Central

    Grant, D; Long, W F; Williamson, F B

    1989-01-01

    Of a range of glycosaminoglycans, heparin and heparan sulphate were the most effective inhibitors in vitro of CaCO3 (calcite) crystallization as assayed by conductimetric measurements. The possible role of such glycosaminoglycans in modulating calcium-salt crystallizations in vivo is discussed. PMID:2719649

  8. The effect of sulfated polysaccharides on the crystallization of calcite superstructures

    NASA Astrophysics Data System (ADS)

    Fried, Ruth; Mastai, Yitzhak

    2012-01-01

    Calcite with unique morphology and uniform size has been successfully synthesized in the presence of classes of polysaccharides based on carrageenans. In the crystallization of calcite, the choice of different carrageenans, (iota, lambda and kappa), as additives concedes systematic study of the influence of different chemical structures and particularly molecular charge on the formation of CaCO 3 crystals. The uniform calcite superstructures are formed by assemblies and aggregation of calcite crystals. The mechanism for the formation of calcite superstructures was studied by a variety of techniques, SEM, TEM, XRD, time-resolved conductivity and light scattering measurements, focusing on the early stages of crystals' nucleation and aggregation.

  9. Crystallographic orientation inhomogeneity and crystal splitting in biogenic calcite

    PubMed Central

    Checa, Antonio G.; Bonarski, Jan T.; Willinger, Marc G.; Faryna, Marek; Berent, Katarzyna; Kania, Bogusz; González-Segura, Alicia; Pina, Carlos M.; Pospiech, Jan; Morawiec, Adam

    2013-01-01

    The calcitic prismatic units forming the outer shell of the bivalve Pinctada margaritifera have been analysed using scanning electron microscopy–electron back-scatter diffraction, transmission electron microscopy and atomic force microscopy. In the initial stages of growth, the individual prismatic units are single crystals. Their crystalline orientation is not consistent but rather changes gradually during growth. The gradients in crystallographic orientation occur mainly in a direction parallel to the long axis of the prism, i.e. perpendicular to the shell surface and do not show preferential tilting along any of the calcite lattice axes. At a certain growth stage, gradients begin to spread and diverge, implying that the prismatic units split into several crystalline domains. In this way, a branched crystal, in which the ends of the branches are independent crystalline domains, is formed. At the nanometre scale, the material is composed of slightly misoriented domains, which are separated by planes approximately perpendicular to the c-axis. Orientational gradients and splitting processes are described in biocrystals for the first time and are undoubtedly related to the high content of intracrystalline organic molecules, although the way in which these act to induce the observed crystalline patterns is a matter of future research. PMID:23804442

  10. Seeding approach to crystal nucleation

    NASA Astrophysics Data System (ADS)

    Espinosa, Jorge R.; Vega, Carlos; Valeriani, Chantal; Sanz, Eduardo

    2016-01-01

    We present a study of homogeneous crystal nucleation from metastable fluids via the seeding technique for four different systems: mW water, Tosi-Fumi NaCl, Lennard-Jones, and Hard Spheres. Combining simulations of spherical crystal seeds embedded in the metastable fluid with classical nucleation theory, we are able to successfully describe the nucleation rate for all systems in a wide range of metastability. The crystal-fluid interfacial free energy extrapolated to coexistence conditions is also in good agreement with direct calculations of such parameter. Our results show that seeding is a powerful technique to investigate crystal nucleation.

  11. Seeding approach to crystal nucleation.

    PubMed

    Espinosa, Jorge R; Vega, Carlos; Valeriani, Chantal; Sanz, Eduardo

    2016-01-21

    We present a study of homogeneous crystal nucleation from metastable fluids via the seeding technique for four different systems: mW water, Tosi-Fumi NaCl, Lennard-Jones, and Hard Spheres. Combining simulations of spherical crystal seeds embedded in the metastable fluid with classical nucleation theory, we are able to successfully describe the nucleation rate for all systems in a wide range of metastability. The crystal-fluid interfacial free energy extrapolated to coexistence conditions is also in good agreement with direct calculations of such parameter. Our results show that seeding is a powerful technique to investigate crystal nucleation. PMID:26801035

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

    USGS Publications Warehouse

    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 ? = 20, where ? = 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 ? = 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 (? >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 was established and maintained during the constant-composition experiments. CSDs having shapes intermediate between lognormal and Ostwald also were generated by varying the initial levels of supersaturation (initial ? = 28.2 to 69.2) in rapidly mixed solutions. Lognormal CSDs were observed for natural calcite crystals that are found in septarian concretions occurring in southeastern Colorado. Based on the model described above, these CSDs indicate initial growth by surface control, followed by supply-controlled growth. Thus, CSDs may be used to deduce crystal growth mechanisms from which geologic conditions early in the growth history of a mineral can be inferred. Conversely, CSD shape can be predicted during industrial crystallization by applying the appropriate conditions for a particular growth mechanism.

  13. Geobacillus thermoglucosidasius Endospores Function as Nuclei for the Formation of Single Calcite Crystals

    PubMed Central

    Murai, Rie

    2013-01-01

    Geobacillus thermoglucosidasius colonies were placed on an agar hydrogel containing acetate, calcium ions, and magnesium ions, resulting in the formation of single calcite crystals (calcites) within and peripheral to the plating area or parent colony. Microscopic observation of purified calcites placed on the surface of soybean casein digest (SCD) nutrient medium revealed interior crevices from which bacterial colonies originated. Calcites formed on the gel contained [1-13C]- and [2-13C]acetate, demonstrating that G. thermoglucosidasius utilizes carbon derived from acetate for calcite formation. During calcite formation, vegetative cells swam away from the parent colony in the hydrogel. Hard-agar hydrogel inhibited the formation of calcites peripheral to the parent colony. The calcite dissolved completely in 1 M HCl, with production of bubbles, and the remaining endospore-like particles were easily stained with Brilliant green dye. The presence of DNA and protein in calcites was demonstrated by electrophoresis. We propose that endospores initiate the nucleation of calcites. Endospores of G. thermoglucosidasius remain alive and encapsulated in calcites. PMID:23455343

  14. Effects of Chitosan on the Morphology and Alignment of Calcite Crystals Nucleating Under Langmuir Monolayers

    SciTech Connect

    Kim, K.; Uysal, A; Kewalramani, S; Stripe, B; Dutta, P

    2009-01-01

    The growth of calcium carbonate crystals under Langmuir monolayers was investigated in the presence of chitosan, a soluble derivative of chitin added to the subphase to better simulate the polyelectrolyte-containing in vivo environment. Chitosan causes distinct concentration-dependent changes in the orientation, shape and morphology of the calcite crystals nucleating under acid and sulfate monolayers. Our results suggest that polyelectrolytes may play essential roles in controlling the growth of biogenic calcite crystals.

  15. Effects of chitosan on the alignment, morphology and shape of calcite crystals nucleating under Langmuir monolayers

    SciTech Connect

    Kim, Kyungil; Uysal, Ahmet; Kewalramani, Sumit; Stripe, Benjamin; Dutta, Pulak

    2009-04-22

    The growth of calcium carbonate crystals under Langmuir monolayers was investigated in the presence of chitosan, a soluble derivative of chitin added to the subphase to better simulate the polyelectrolyte-containing in vivo environment. Chitosan causes distinct concentration-dependent changes in the orientation, shape and morphology of the calcite crystals nucleating under acid and sulfate monolayers. Our results suggest that polyelectrolytes may play essential roles in controlling the growth of biogenic calcite crystals.

  16. Origin of platy calcite crystals in hot-spring deposits in the Kenya Rift Valley

    SciTech Connect

    Jones, B.; Renault, R.W.

    1998-09-01

    Platy calcite crystals, which have their c axis parallel to their shortest length axis, are common components of travertine deposits found around some hot springs in the Kenya Rift Valley. They are composite crystals formed of numerous paper-thin subcrystals. Individual plates allowed to grow without obstruction develop a hexagonal motif. The Kenyan crystals typically form in hot (>75 C) waters that have a low Ca content (<10 mg/l), a high CO{sub 2} content, and a high rate of CO{sub 2} degassing. At Chemurkeu, aggregates of numerous small platy crystals collectively form lattice crystals that superficially resemble ray crystals. The walls of the lattice crystals are formed of large platy crystals that have their long and intermediate length axes aligned parallel to the plane of the long axis of the lattice crystal. Internally, the lattice crystals are formed of small platy calcite crystals arranged in a boxlike pattern that creates the appearance of a lattice when viewed in thin section. Lattice crystals are highly porous, with each pore being enclosed by platy crystals. At Lorusio, travertines are mainly formed of pseudodentrites that are constructed by numerous small platy crystals attached to a main stem which is a large platy crystal that commonly curves along its long axis. The pseudodentrites are the main construction blocks in ledges and lilypads that form in the vent pool and spring outflow channels, where the water is too hot for microbes other than hyperthermophiles. The platy calcite crystals in the Kenyan travertines are morphologically similar to platy calcite crystals that form as scale in pipes in the geothermal fields of New Zealand and hydrothermal angel wing calcite from the La Fe mine in Mexico. Comparison of the Kenyan and New Zealand crystals indicates that platy calcite crystals form from waters with a low Ca{sup 2+} content and a high CO{sub 3}/Ca ratio due to rapid rates of CO{sub 2} degassing.

  17. Heterogeneous distribution of dye-labelled biomineralizaiton proteins in calcite crystals

    NASA Astrophysics Data System (ADS)

    Liu, Chuang; Xie, Liping; Zhang, Rongqing

    2015-12-01

    Biominerals are highly ordered crystals mediated by organic matters especially proteins in organisms. However, how specific proteins are distributed inside biominerals are not well understood. In the present study, we use fluorescein isothiocyanate (FITC) to label extracted proteins from the shells of bivalve Pinctada fucata. By confocal laser scanning microscopy (CLSM), we observe a heterogeneous distribution of dye-labelled proteins inside synthetic calcite at the microscale. Proteins from the prismatic calcite layers accumulate at the edge of crystals while proteins from the nacreous aragonite layers accumulate at the center of crystals. Raman and X-ray powder diffraction show that both the proteins cannot alter the crystal phase. Scanning electron microscope demonstrates both proteins are able to affect the crystal morphology. This study may provide a direct approach for the visualization of protein distributions in crystals by small-molecule dye-labelled proteins as the additives in the crystallization process and improve our understanding of intracrystalline proteins distribution in biogenic calcites.

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

    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.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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr01568h

  19. Measuring Carbon and Oxygen Isotope Uptake into Inorganic Calcite using Crystal Growth Experiments

    NASA Astrophysics Data System (ADS)

    Baker, E. B.; Watkins, J. M.

    2014-12-01

    Carbon and oxygen isotopes measured on natural calcite crystals provide a record of paleo-environment conditions. Despite the importance of measuring stable isotopes in calcite for paleo-environment reconstructions, there is neither a general theory nor an experimental data set that fully separates the effects of pH, temperature, and precipitation rate on isotope discrimination during calcite growth. Many stable isotope studies of calcite have focused on either carbon or oxygen isotope compositions individually, but few have measured both carbon and oxygen isotope uptake in the same set of crystals. We are precipitating inorganic calcite across a range in temperature, pH, and precipitation rate to guide the development of a general theory for combined carbon and oxygen isotope uptake into calcite crystals grown on laboratory timescales. In our experiments, dissolved inorganic carbon (DIC) is added to an aqueous solution (15 mM CaCl2 + 5 mM NH4Cl) by CO2 bubbling. Once a critical supersaturation is reached, calcite crystals nucleate spontaneously and grow on the beaker walls. A key aspect of this experimental approach is that the ?13C of DIC is relatively constant throughout the crystal growth period, because there is a continuous supply of DIC from the CO2-bearing bubbles. Carbonic anhydrase, an enzyme promoting rapid equilibration of isotopes between DIC and water, was added to ensure that the solution remained isotopically equilibrated during calcite growth. We have conducted experiments at T = 25C and pH = 8.3 - 9.0. We observe that the fractionation of oxygen isotopes between calcite and water decreases with increasing pH, consistent with available data from experiments in which the enzyme carbonic anhydrase was used. Our results for carbon isotopes extend the available data set, which previously ranged from pH 6.62 to 7.75, to higher pH. At pH 8.3, we observe that calcite is isotopically heavier than DIC with respect to carbon isotopes by about 0.25. At pH 9.0, calcite is isotopically indistinguishable from, or perhaps slightly lighter than, DIC. We will present data from additional high-pH experiments and discuss the results in the context of recently developed ion-by-ion growth models for calcite.

  20. Skeletal crystals of calcite and trona from hot-spring deposits in Kenya and New Zealand

    SciTech Connect

    Jones, B.; Renaut, R.W.

    1996-01-01

    Skeletal crystals are hollow crystals that develop because their outer walls grow before their cores. The presence of skeletal crystals of calcite (three types--trigonal prisms, hexagonal prisms, and plates) and trona in hot (> 90 C) spring deposits in New Zealand (Waikite Springs and Ohaaki Pool) and Kenya (Lorusio hot springs) shows that they can form in natural sedimentary regimes. Analysis of samples from these deposits shows that this crystal morphology develops under disequilibrium conditions that are unrelated to a specific environmental or diagenetic setting. Skeletal crystals transform into solid crystals when subsequent precipitation fills their hollow cores. In some cases, this may involve precipitation of crystalline material that has a sieve-like texture. In other examples, the skeletal crystal provides a framework upon which other materials can be precipitated. Walls in the skeletal trigonal calcite prisms from Waikite Springs are formed of subcrystals that mimic the shape of the parent crystal. Similarly, plate-like skeletal crystals from Lorusio are formed of densely packed subcrystals that are < 0.5 {micro}m long. Conversely, the walls of the skeletal hexagonal calcite crystals from Ohaaki Pool and the skeletal trona crystals from Lorusio are not formed of subcrystals. Recognition of skeletal crystals is important because they represent growth that follows the reverse pattern of normal growth. Failure to recognize that crystal growth followed the skeletal motif may lead to false interpretations concerning the growth of a crystal.

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

    PubMed

    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. PMID:23787771

  2. Control of macromolecule distribution within synthetic and biogenic single calcite crystals

    SciTech Connect

    Aizenberg, J.; Weiner, S.; Addadi, L.; Hanson, J.; Koetzle, T.F.

    1997-02-05

    The ability of organisms to exercise control over crystal growth is wonderfully exemplified by skeleton formation in echinoderms. A sea urchin spine is a unique composite of a single crystal of calcite and glycoproteins intercalated inside the crystal during its growth. Here we performed a detailed morphological and high-resolution synchrotron X-ray diffraction study of the textures of synthetic and biogenic calcite crystals. We show that the intracrystalline macromolecules from sea urchin spines, when allowed to interact with growing calcite crystals in vitro, selectively reduce the coherence lengths and degrees of alignment of the perfect domains in specific crystallographic directions. These directions also correspond to the newly-developed stable faces. In contrast, the defect distribution of young sea urchin spines composed entirely of spongy stereomic structure is much more isotropic. In mature spines containing secondarily filled-in wedges of calcite, the degree of anisotropy is intermediate between that of the synthetic crystals and the young spines. The macromolecules extracted from young and mature spines are, however, very similar. These observations demonstrate the inherent capability of occluded matrix macromolecules to finely differentiate between crystal planes by stereochemical recognition processes. 20 refs., 5 figs., 2 tabs.

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    Fluoride is naturally abundant, encountered in rocks, soil and fresh and ocean water. Calcite crystals, during crystal growth may incorporate fluoride ions into their lattice (Okumura et al., 1983). In situ atomic force microscopy (AFM) has been used to study the growth and dissolution of calcite {104} surfaces in aqueous solutions in the presence of fluoride, using a fluid cell in which the supersaturated and the understaturated solutions respectively, flow over a freshly cleaved calcite crystal. For growth experiments, supersaturation index (S.I.) with respect to calcite was equal to 0.89 and the initial solution pH 10.2. The crystal growth rates were measured from the closure of the rhombohedral etch pits along the [010] direction induced by an initial dissolution step using pure water. The spreading rate of 2-dimensional nuclei was also measured along the same direction. In the presence of low fluoride concentrations (?0.33 mM), the crystal growth rate of calcite was unaffected. At higher concentrations (up to 5 mM) growth rate decreased substantially to 50% of the rate in the absence of fluoride. Potential fluoride sorption over the calcite surface may ascribe the decrease of growth rates. Dissolution experiments were conducted at pH= 7.2 and dissolution rates of calcite were measured from the spreading of rhombohedral etch pits along both [010] and [42] directions. The presence of low concentrations of fluoride (?1.1 mM) in the undersaturated solutions enhanced the dissolution rate along the [42] direction by 50% in comparison with pure water. The morphology of rhombohedral etch pits changed to hexagonal in the presence of fluoride in the undersaturated solutions. The AFM dissolution experiments suggested that the fluoride ions adsorbed onto the calcite surface. Further increase of fluoride concentrations (up to 1.6 mM) resulted in the decrease of the calcite dissolution rate by 60% in both [010] and [42] directions. Reference: Okumura, M, Kitano, Y., Idogaki, M., 1983. Inorporation of fluoride ions into calcite - Effect of organic materials and magnesium ions in a parent solution. Geochemical Journal 17, 257-263.

  4. Elemental relationships in synthetic calcite at variable fluid chemistry and crystallization rate.

    NASA Astrophysics Data System (ADS)

    Gabitov, R. I.; Weremeichik, J. M.; Sadekov, A.

    2014-12-01

    Minor and trace elemental relationships in natural calcium carbonate minerals are generally explained by changes in temperature and/or composition of the growth media. However, partitioning of elements between mineral and fluid often occurs at conditions far from equilibrium. Incorporation of minor and trace elements into calcite has been explored over the last several decades, however kinetic and thermodynamic effects were not fully resolved. Here, we present ion microprobe data on Mg, Sr, Ba, and U distribution within individual calcite crystals grown from fluids with continuous increases of element to calcium ratios and decreases of crystal growth rates. Analyses were performed using CAMECA ims-1270 (UCLA). The depletion of fluid in Ca and the above mentioned elements caused a continuous increase in element to calcium ratios during each experiment. However, we were not able to fully resolve the influence of fluid depletion on apparent partition coefficients during disequilibrium crystallization. Our results suggest that growth rate strongly affects incorporation of Mg, Sr, Ba, and U into the calcite lattice. Growth Entrapment Model (GEM) explains observed relationships between growth rate and partition coefficients. However, elemental profiles across individual crystals suggest that the factors controlling incorporation process may not be ubiquitous for each element. Calcite growth velocities obtained from our work overlap with the growth rate range reported for speleothems and marine biogenic carbonates. We anticipate comparing elemental relationships in synthetic calcite with those obtained in natural samples which were reported in previous literature.

  5. Calcite Single Crystals as Hosts for Atomic-Scale Entrapment and Slow Release of Drugs.

    PubMed

    Magnabosco, Giulia; Di Giosia, Matteo; Polishchuk, Iryna; Weber, Eva; Fermani, Simona; Bottoni, Andrea; Zerbetto, Francesco; Pelicci, Pier Giuseppe; Pokroy, Boaz; Rapino, Stefania; Falini, Giuseppe; Calvaresi, Matteo

    2015-07-15

    Doxorubicin (DOX)/CaCO3 single crystals act as pH responsive drug carrier. A biomimetic approach demonstrates that calcite single crystals are able, during their growth in the presence of doxorubicin, to entrap drug molecules inside their lattice along specific crystallographic directions. Alterations in lattice dimensions and microstructural parameters are determined by means of high-resolution synchrotron powder diffraction measurements. Confocal microscopy confirms that doxorubicin is uniformly embedded in the crystal and is not simply adsorbed on the crystal surface. A slow release of DOX was obtained preferentially in the proximity of the crystals, targeting cancer cells. PMID:26033854

  6. Crystallization seeds favour crystallization only during initial growth

    PubMed Central

    Allahyarov, E.; Sandomirski, K.; Egelhaaf, S.U.; Löwen, H.

    2015-01-01

    Crystallization represents the prime example of a disorder–order transition. In realistic situations, however, container walls and impurities are frequently present and hence crystallization is heterogeneously seeded. Rarely the seeds are perfectly compatible with the thermodynamically favoured crystal structure and thus induce elastic distortions, which impede further crystal growth. Here we use a colloidal model system, which not only allows us to quantitatively control the induced distortions but also to visualize and follow heterogeneous crystallization with single-particle resolution. We determine the sequence of intermediate structures by confocal microscopy and computer simulations, and develop a theoretical model that describes our findings. The crystallite first grows on the seed but then, on reaching a critical size, detaches from the seed. The detached and relaxed crystallite continues to grow, except close to the seed, which now prevents crystallization. Hence, crystallization seeds facilitate crystallization only during initial growth and then act as impurities. PMID:25975451

  7. Crystallization of ikaite and its pseudomorphic transformation into calcite: Raman spectroscopy evidence

    NASA Astrophysics Data System (ADS)

    Sánchez-Pastor, N.; Oehlerich, Markus; Astilleros, José Manuel; Kaliwoda, Melanie; Mayr, Christoph C.; Fernández-Díaz, Lurdes; Schmahl, Wolfgang W.

    2016-02-01

    Ikaite (CaCO3·6H2O) is a metastable phase that crystallizes in nature from alkaline waters with high phosphate concentrations at temperatures close to 0 °C. This mineral transforms into anhydrous calcium carbonate polymorphs when temperatures rise or when exposed to atmospheric conditions. During the transformation in some cases the shape of the original ikaite crystal is preserved as a pseudomorph. Pseudomorphs after ikaite are considered as a valuable paleoclimatic indicator. In this work we conducted ikaite crystal growth experiments at near-freezing temperatures using the single diffusion silica gel technique, prepared with a natural aqueous solution from the polymictic lake Laguna Potrok Aike (51°57‧S, 70°23‧W) in Patagonia, Argentina. The ikaite crystals were recovered from the gels and the transformation reactions were monitored by in situ Raman spectroscopy at two different temperatures. The first spectra collected showed the characteristic features of ikaite. In successive spectra new bands at 1072, 1081 and 1086 cm-1 and changes in the intensity of bands corresponding to the OH modes were observed. These changes in the Raman spectra were interpreted as corresponding to intermediate stages of the transformation of ikaite into calcite and/or vaterite. After a few hours, the characteristics of the Raman spectrum were consistent with those of calcite. While ikaite directly transforms into calcite at 10 °C in contact with air, at 20 °C this transformation involves the formation of intermediate, metastable vaterite. During the whole process the external shape of ikaite crystals was preserved. Therefore, this transformation showed the typical characteristics of a pseudomorphic mineral replacement, involving the generation of a large amount of porosity to account for the large difference in molar volumes between ikaite and calcite. A mechanism involving the coupled dissolution of ikaite and crystallization of calcite/vaterite is proposed for this replacement.

  8. Heterogeneous distribution of dye-labelled biomineralizaiton proteins in calcite crystals

    PubMed Central

    Liu, Chuang; Xie, Liping; Zhang, Rongqing

    2015-01-01

    Biominerals are highly ordered crystals mediated by organic matters especially proteins in organisms. However, how specific proteins are distributed inside biominerals are not well understood. In the present study, we use fluorescein isothiocyanate (FITC) to label extracted proteins from the shells of bivalve Pinctada fucata. By confocal laser scanning microscopy (CLSM), we observe a heterogeneous distribution of dye-labelled proteins inside synthetic calcite at the microscale. Proteins from the prismatic calcite layers accumulate at the edge of crystals while proteins from the nacreous aragonite layers accumulate at the center of crystals. Raman and X-ray powder diffraction show that both the proteins cannot alter the crystal phase. Scanning electron microscope demonstrates both proteins are able to affect the crystal morphology. This study may provide a direct approach for the visualization of protein distributions in crystals by small-molecule dye-labelled proteins as the additives in the crystallization process and improve our understanding of intracrystalline proteins distribution in biogenic calcites. PMID:26675363

  9. Heterogeneous distribution of dye-labelled biomineralizaiton proteins in calcite crystals.

    PubMed

    Liu, Chuang; Xie, Liping; Zhang, Rongqing

    2015-01-01

    Biominerals are highly ordered crystals mediated by organic matters especially proteins in organisms. However, how specific proteins are distributed inside biominerals are not well understood. In the present study, we use fluorescein isothiocyanate (FITC) to label extracted proteins from the shells of bivalve Pinctada fucata. By confocal laser scanning microscopy (CLSM), we observe a heterogeneous distribution of dye-labelled proteins inside synthetic calcite at the microscale. Proteins from the prismatic calcite layers accumulate at the edge of crystals while proteins from the nacreous aragonite layers accumulate at the center of crystals. Raman and X-ray powder diffraction show that both the proteins cannot alter the crystal phase. Scanning electron microscope demonstrates both proteins are able to affect the crystal morphology. This study may provide a direct approach for the visualization of protein distributions in crystals by small-molecule dye-labelled proteins as the additives in the crystallization process and improve our understanding of intracrystalline proteins distribution in biogenic calcites. PMID:26675363

  10. Observation of an Organic-Inorganic Lattice Match during Biomimetic Growth of (001)-Oriented Calcite Crystals under Floating Sulfate Monolayers

    SciTech Connect

    Kewalramani, S.; Kim, K; Stripe, B; Evmenenko, G; Dommett, G; Dutta, P

    2008-01-01

    Macromolecular layers rich in amino acids and with some sulfated polysaccharides appear to control oriented calcite growth in living organisms. Calcite crystals nucleating under floating acid monolayers have been found to be unoriented on average. We have now observed directly, using in situ grazing incidence X-ray diffraction, that there is a 1:1 match between the monolayer unit cell and the unit cell of the (001) plane of calcite. Thus, sulfate head groups appear to act as templates for the growth of (001)-oriented calcite crystals, which is the orientation commonly found in biominerals.

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

    PubMed

    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. PMID:26117783

  12. Trigonal dendritic calcite crystals forming from hot spring waters at Waikite, North Island, New Zealand

    SciTech Connect

    Jones, B.; Renault, R.W.; Rosen, M.R.

    2000-05-01

    Amorphous silica and calcite form the deposits in the vent and on the discharge apron of Waikite Spring 100 (WS-100), which is located in the Waikite Geothermal area on North Island, New Zealand. These precipitates formed from spring water that has a temperature of >90 C and a pH of 8.1--8.8. The opaline silica is restricted to areas around the vent where cooling and evaporation of the spring water triggered precipitation. The calcite deposits in the spring vent and on the discharge apron are formed of large (up to 15 cm long) asymmetrical dendrite crystals that are characterized by multiple levels of branching. Branches grew preferentially from the downflow side of their parent branch. All branches have a trigonal transverse cross section except in areas where competition for growth space induced merger of neighboring crystals. The primary branches of the dendrite crystals are (sub)perpendicular to the substrate even in areas where the discharge apron slopes at a high angle (up to 80{degree}). On the steeper parts of the discharge apron, the plate-like primary branches form the floors of the small terrace pools whereas their distal edges form the rims of the pools. Growth of these dendrite crystals is attributed to abiotic processes. High levels of saturation with respect to calcite were caused by rapid CO{sub 2} degassing of the sheets of spring water that flowed down the steep discharge apron. Calcite crystals with different crystal morphologies characterize other springs near this spring. The variation in crystal morphologies from spring to spring is attributed to different levels of saturation that are related to the initial PCO{sub 2} of the spring water upon discharge and the rate of CO{sub 2} degassing at each spring.

  13. Swift heavy ion irradiation induced phase transformation in calcite single crystals

    NASA Astrophysics Data System (ADS)

    Nagabhushana, H.; Nagabhushana, B. M.; Lakshminarasappa, B. N.; Singh, Fouran; Chakradhar, R. P. S.

    2009-11-01

    Ion irradiation induced phase transformation in calcite single crystals have been studied by means of Raman and infrared spectroscopy using 120 MeV Au 9+ ions. The observed bands have been assigned according to group theory analysis. For higher fluence of 510 12 ion/cm 2, an extra peak on either side of the 713 cm -1 peak and an increase in the intensity of 1085 cm -1 peak were observed in Raman studies. FTIR spectra exhibit extra absorption bands at 674, 1589 cm -1 and enhancement in bands at 2340 and 2374 cm -1 was observed. This might be due to the phase transformation from calcite to vaterite. The damage cross section ( ?) for all the Raman and FTIR active modes was determined. The increase of FWHM, shift in peak positions and appearance of new peaks indicated that calcite phase is converted into vaterite.

  14. In situ study of boron partitioning between calcite and fluid at different crystal growth rates

    NASA Astrophysics Data System (ADS)

    Gabitov, Rinat I.; Rollion-Bard, Claire; Tripati, Aradhna; Sadekov, Aleksey

    2014-07-01

    The boron isotopic and chemical content of carbonates (expressed as ?11B and B/Ca ratios) have been proposed as proxies for seawater carbonate system parameters. Thermodynamic and kinetic effects on ?11B and B partitioning are not yet fully constrained, underscoring the importance of exploring possible effects of growth rate on boron incorporation in synthetic calcium carbonate minerals, which is the focus of this study. Secondary Ion Mass Spectrometry (SIMS) measurements of B/Ca and ?11B were performed on single crystal of calcite synthesized by diffusion of CO2 under controlled conditions from a solution of NH4Cl-CaCl2 doped with boron. Growth rates of calcite (V, nm/s) within crystals grown isothermally at 24.6 C were monitored by sequentially spiking calcite-precipitating fluids with rare earth element (REE) dopants. The REE were analyzed with SIMS at spots that match those locations where B/Ca and ?11B ratios were measured. Values for the boron Nernst partition coefficient, defined as DB = B(calcite)/B(fluid), increase from 0.5 (pHNBS = 8.15) to 0.9 (pH = 8.00) with values of V increasing from 0.04 to 0.13 nm/s. For ?11B behavior, it was not possible to draw conclusive results due to the analytical error (2.2; 2?). pH effects on DB during calcite precipitation, associated with an increase in pH from 8.00 to 8.15, appear to be masked by the competing effects of changing V. We conclude that over the range of growth rates and other conditions investigated in this study, growth rate effects on B partitioning need to be accounted for when using B/Ca ratios in biogenic calcite as a proxy for seawater carbonate system parameters.

  15. Effects of chitosan on the alignment, morphology and shape of calcite crystals nucleating under Langmuir monolayers

    NASA Astrophysics Data System (ADS)

    Kim, Kyungil

    The mechanisms governing selective CaCO3 crystal nucleation in living organisms remain unclear. For example, nacreous layers from the inner surfaces of shells are built as brick-and-mortar complexes of plate-like aragonite single crystals and organic layers. Unstable [001] surfaces of calcite columns in prismatic layers are also stabilized by organic molecules. Biogenic calcite crystals show different morphologies compared to geological calcite minerals. Langmuir monolayers are used as structured templates in simulated biomineralization from CaCO3 supersaturated subphases. But pure or mixed Langmuir monolayers do not mimic the nucleation sites of aspartic-rich proteins found within real biominerals. It has previously been shown that there is organic-inorganic lattice relaxation in the cases of BaF2 and hydrocerussite (2PbCO3Pb(OH) 2) nucleation under fatty (carboxylate) acid with preferred orientation of crystals, but no lattice match is observed during CaCO3 crystallization under fatty acid Langmuir monolayers. Overall, geometric influences such as structural match between the interfacial lattices and the interactions between monolayer headgroups and aqueous ions do not guarantee any well-defined orientation of CaCO3 crystallization. CaCO3 mineralization on self-assembled monolayers on metal and alloy substrates have achieved higher degrees of orientations, even though molecules in Langmuir monolayers are better ordered than in self-assembled monolayers. Until now, Langmuir monolayer experiments have emphasized only the function of the acidic proteins. To better mimic the real organic template, it is important to include the hydrophobic and polyelectrolyte characteristics of real organic templates in shells. The organic matrix in actual shells contains hydrophobic silk fibroin (which is hydrophobic) and polyelectrolytes. Some acidic proteins reside on the surface of silk fibroins. There is also semi-crystalline beta-chitin structure whose function has not been fully understood. To better simulate the biological system, chitosan was added to the aqueous subphase. The crystallization processes were monitored using in-situ Grazing incidence X-ray diffraction (GID). Scanning electron microscopy (SEM) was used to perform morphological studies on grown crystals. Dissolved chitosan causes distinct concentration-dependent changes in orientation, shape and morphology of the calcite crystals nucleating under acid and sulfate monolayers. Our results suggest that polyelectrolytes may play essential roles in controlling the growth of biogenic calcite crystals.

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

    PubMed Central

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

    2003-01-01

    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. PMID:12792020

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

    NASA Astrophysics Data System (ADS)

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

    2003-06-01

    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.

  18. Morphology of calcite crystals in clast coatings from four soils in the Mojave desert region

    NASA Technical Reports Server (NTRS)

    Chadwick, Oliver A.; Sowers, Janet M.; Amundson, Ronald G.

    1989-01-01

    Pedogenic calcite-crystal coatings on clasts were examined in four soils along an altitudinal gradient on Kyle Canyon alluvium in southern Nevada. Clast coatings were studied rather than matrix carbonate to avoid the effects of soil matrix on crystallization. Six crystal sizes and shapes were recognized and distinguished. Equant micrite was the dominant crystal form with similar abundance at all elevations. The distributions of five categories of spar and microspar appear to be influenced by altitudinally induced changes in effective moisture. In the drier, lower elevation soils, crystals were equant or parallel prismatic with irregular, interlocking boundaries while in the more moist, higher elevation soils they were randomly oriented, euhedral, prismatic, and fibrous. There was little support for the supposition that Mg(+2) substitution or increased (Mg + Ca)/HCO3 ratios in the precipitating solution produced crystal elongation.

  19. Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades

    NASA Astrophysics Data System (ADS)

    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 (CaCO 3). 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.

  20. Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades

    USGS Publications Warehouse

    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.

  1. Morphological tranformation of calcite crystal growth by prismatic "acidic" polypeptide sequences.

    SciTech Connect

    Kim, I; Giocondi, J L; Orme, C A; Collino, J; Evans, J S

    2007-02-13

    Many of the interesting mechanical and materials properties of the mollusk shell are thought to stem from the prismatic calcite crystal assemblies within this composite structure. It is now evident that proteins play a major role in the formation of these assemblies. Recently, a superfamily of 7 conserved prismatic layer-specific mollusk shell proteins, Asprich, were sequenced, and the 42 AA C-terminal sequence region of this protein superfamily was found to introduce surface voids or porosities on calcite crystals in vitro. Using AFM imaging techniques, we further investigate the effect that this 42 AA domain (Fragment-2) and its constituent subdomains, DEAD-17 and Acidic-2, have on the morphology and growth kinetics of calcite dislocation hillocks. We find that Fragment-2 adsorbs on terrace surfaces and pins acute steps, accelerates then decelerates the growth of obtuse steps, forms clusters and voids on terrace surfaces, and transforms calcite hillock morphology from a rhombohedral form to a rounded one. These results mirror yet are distinct from some of the earlier findings obtained for nacreous polypeptides. The subdomains Acidic-2 and DEAD-17 were found to accelerate then decelerate obtuse steps and induce oval rather than rounded hillock morphologies. Unlike DEAD-17, Acidic-2 does form clusters on terrace surfaces and exhibits stronger obtuse velocity inhibition effects than either DEAD-17 or Fragment-2. Interestingly, a 1:1 mixture of both subdomains induces an irregular polygonal morphology to hillocks, and exhibits the highest degree of acute step pinning and obtuse step velocity inhibition. This suggests that there is some interplay between subdomains within an intra (Fragment-2) or intermolecular (1:1 mixture) context, and sequence interplay phenomena may be employed by biomineralization proteins to exert net effects on crystal growth and morphology.

  2. Development of artificial seed crystal for crystallization of calcium phosphate.

    PubMed

    Moriyama, K; Kojima, T; Minawa, Y; Matsumoto, S; Nakamachi, K

    2001-11-01

    An artifical seed crystal material consisting of calcium silicate hydrate (5CaO x 6SiO2 x 5H2O : tobermorite crystals) applicable for phosphorus removal by crystallization was developed. Card-house shaped tobermorite crystals were developed on the seed material where orthophosphate crystallized as a calcium phosphate. The seed material can be manufactured by mixing siliceous and calcareous raw materials, pelletizing and subsequent autoclaving. Laboratory experiments were conducted to apply the new developed seed crystal material in the phosphorus recovery from sludge sidestreams of a wastewater treatment plant. In this crystallization process, the performance the carbon dioxide degassingprocess usually carried out when applying crystallization was not necessary, the hydroxyapatite was able to crystallize at a pH of 8.0 to 8.5 without precipitation of calcium carbonates. In the treatment of a sidestream with orthophosphate concentrations of 50 mgl(-1) and COD concentrations between 200 to 400 mgl(-1), phosphorus removal efficiencies ranging from 75 to 85% were observed. The seed crystal material was collected after the laboratory experiments and the chemical estimation and the germination test for agricultural reuse were performed. As a result, it was shown that the hydroxyapatite precipitated on the seed material had a 100% fusibility to soil and had characteristics to be a good nutrient source as a fertilizer for plants. PMID:11804345

  3. In vitro calcite crystal morphology is modulated by otoconial proteins otolin-1 and otoconin-90.

    PubMed

    Moreland, K Trent; Hong, Mina; Lu, Wenfu; Rowley, Christopher W; Ornitz, David M; De Yoreo, James J; Thalmann, Ruediger

    2014-01-01

    Otoconia are formed embryonically and are instrumental in detecting linear acceleration and gravity. Degeneration and fragmentation of otoconia in elderly patients leads to imbalance resulting in higher frequency of falls that are positively correlated with the incidence of bone fractures and death. In this work we investigate the roles otoconial proteins Otolin-1 and Otoconin 90 (OC90) perform in the formation of otoconia. We demonstrate by rotary shadowing and atomic force microscopy (AFM) experiments that Otolin-1 forms homomeric protein complexes and self-assembled networks supporting the hypothesis that Otolin-1 serves as a scaffold protein of otoconia. Our calcium carbonate crystal growth data demonstrate that Otolin-1 and OC90 modulate in vitro calcite crystal morphology but neither protein is sufficient to produce the shape of otoconia. Coadministration of these proteins produces synergistic effects on crystal morphology that contribute to morphology resembling otoconia. PMID:24748133

  4. In Vitro Calcite Crystal Morphology Is Modulated by Otoconial Proteins Otolin-1 and Otoconin-90

    PubMed Central

    Moreland, K. Trent; Hong, Mina; Lu, Wenfu; Rowley, Christopher W.; Ornitz, David M.; De Yoreo, James J.; Thalmann, Ruediger

    2014-01-01

    Otoconia are formed embryonically and are instrumental in detecting linear acceleration and gravity. Degeneration and fragmentation of otoconia in elderly patients leads to imbalance resulting in higher frequency of falls that are positively correlated with the incidence of bone fractures and death. In this work we investigate the roles otoconial proteins Otolin-1 and Otoconin 90 (OC90) perform in the formation of otoconia. We demonstrate by rotary shadowing and atomic force microscopy (AFM) experiments that Otolin-1 forms homomeric protein complexes and self-assembled networks supporting the hypothesis that Otolin-1 serves as a scaffold protein of otoconia. Our calcium carbonate crystal growth data demonstrate that Otolin-1 and OC90 modulate in vitro calcite crystal morphology but neither protein is sufficient to produce the shape of otoconia. Coadministration of these proteins produces synergistic effects on crystal morphology that contribute to morphology resembling otoconia. PMID:24748133

  5. In vitro effects of recombinant Otoconin 90 upon calcite crystal growth. Significance of tertiary structure

    PubMed Central

    Lu, Wenfu; Zhou, Dan; Freeman, John J.; Thalmann, Isolde; Ornitz, David M.; Thalmann, Ruediger

    2010-01-01

    Otoconia are biomineral particles of microscopic size essential for perception of gravity and maintenance of balance. Millions of older Americans are affected in their mobility, quality of life and in their health by progressive demineralization of otoconia. Currently, no effective means to prevent or counteract this process are available. Because of prohibitive anatomical and biological constraints, otoconial research is lagging far behind other systems such as bone and teeth. We have overcome these obstacles by generating otoconial matrix proteins by recombinant techniques. In the present study, we evaluated the effects of recombinant Otoconin 90 (OC90), the principal soluble matrix protein upon calcite crystal growth patterns in vitro. Our findings highlight multiple effects, including facilitation of nucleation, and inhibition of crystal growth in a concentration-dependent manner. Moreover, OC90 induces morphologic changes characteristic of native otoconia. OC90 is considerably less acidic than the prototypical invertebrate CaCO3 –associated protein, but is nevertheless an effective modulator of calcite crystal growth. Based on homology modeling of the sPLA2-like domains of OC90, we propose that the lower density of acidic residues of the primary sequence is compensated by formation of major anionic surface clusters upon folding into tertiary conformation. PMID:20595020

  6. Cyclic development of large, complex, calcite dendrite crystals in the Clinton travertine, Interior British Columbia, Canada

    NASA Astrophysics Data System (ADS)

    Jones, Brian; Renaut, Robin W.

    2008-01-01

    Bands of large (up to 4 cm long) three-dimensional crystallographic dendrites form the terrace fronts in an old travertine mound exposed near Clinton, British Columbia. The dendrites, with their long axes perpendicular to the terrace front, are characterized by numerous levels of branching. Each branch is formed of multitudes of skeletal rhombs, four- and six(?)-sided bipyramidal crystals, or prismatic hexagonal crystals that are precisely aligned along crystallographic precepts. Although individual branches are formed of one type of subcrystal, neighbouring branches may be formed of different subcrystal types. Highly supersaturated waters that were generated by rapid CO 2 degassing of the spring water during its turbulent flow over the steep terrace fronts probably drove dendrite precipitation. The presence of growth lines indicates that growth was episodic. Type I growth lines probably formed annually in response to seasonal climate changes whereas Type II growth lines, which formed less frequently, may reflect changes in the flow velocity and/or flow patterns of the spring waters. Early diagenetic modification of the dendrites involved crystal face enlargement, cements formed of trigonal prisms or needle-fiber crystals, microbial infestation that mediated substrate dissolution, and/or deposition of detrital calcite crystals that formed in the water column. Much of the diagenetic modification may have taken place during the periods when the dendrites had temporarily stopped growing. The dendrites in the Clinton travertine are an excellent example of complex, episodic calcite crystal growth that was extensively modified by early diagenetic processes in a surface environment. The same spring waters from which the dendrites were precipitated mediated much of the early diagenesis.

  7. Influence of etidronic acid and tartaric acid on the growth of different calcite morphologies

    NASA Astrophysics Data System (ADS)

    Ukrainczyk, Marko; Stelling, Jan; Vu?ak, Marijan; Neumann, Thomas

    2013-04-01

    The influence of organic additives on the crystal growth of different calcite morphologies in two crystallization processes operating under steady state and batch mode is described. The crystal growth kinetics and overgrown morphological observations of rhombohedral, scalenohedral and prismatic calcite seed crystals in the systems containing etidronic acid (HEDP) and tartaric acid (TA) were investigated. The crystallization systems were of low supersaturations (SI<1.1) and of moderate pH (8.0). Kinetic parameters of the crystal growth in the presence of selected additives, such as reduction of the growth rates, rate constant and reduced critical supersaturation were calculated and correlated with additive concentration and different calcite seeds. The results indicate strong interactions of HEDP molecules and weak but specific interactions of TA for calcite surfaces. Interactions occur at the step edges which finally results in the expression of near-{hk0} faces and highly polar faces, consisting of solely Ca layer on the surface, stabilised by TA and HEDP molecules, respectively. The affinity of both additives is significantly higher for scalenohedral and prismatic calcite in contrast to rhombohedral calcite seeds. The effect of calcite seed morphology was attributed to different surface energetics of the predominant crystal faces of the studied calcite seeds.

  8. Formation of star-shaped calcite crystals with Mg{sup 2+} inorganic mineralizer without organic template

    SciTech Connect

    Zhu Liying; Zhao Qingrui; Zheng Xiuwen; Xie Yi . E-mail: yxielab@ustc.edu.cn

    2006-04-15

    Star-shaped calcite crystals with 3-bar m symmetry were obtained in the mixed solvent of ethanol and H{sub 2}O (4:1vol%) using Mg{sup 2+} as grow mineralizer without any organic template under the solvothermal condition. The crystals branched to the six directions perpendicular to the c-axis. In the process, Mg{sup 2+} takes an important influence on such novel morphology via entering the crystal lattice of calcite to absorb the special plane and change the general growth habit. The aqueous solvent is favorable to form aragonite, while the presence of alcohol promotes the formation of calcite, the thermodynamically stable phase. The products were characterized by the techniques of XRD, SEM, SAED, IR and ICP. The formation process was also primarily studied.

  9. Atomic layer wear of single-crystal calcite in aqueous solution using scanning force microscopy

    NASA Astrophysics Data System (ADS)

    Park, Nam-Seok; Kim, Myoung-Won; Langford, S. C.; Dickinson, J. T.

    1996-09-01

    Scanning force microscopy (SFM) is employed to study nm-scale wear of single-crystal calcite in an aqueous solution. When the SFM tip is drawn back and forth in a linear fashion across the edge of a preexisting single atomic layer etch pit, dissolution is strongly enhanced at the point where the tip crosses the step. The wear rate as a function of contact force is consistent with a thermally activated wear process, where the activation energy is locally reduced in the strain field of the SFM tip. The activation volume for the strain dependence is on the order of the average volume per ion in the CaCO3 lattice. This study provides further support for strain enhanced nucleation of double kinks along preexisting steps.

  10. Corrosion of calcite crystals by metal-rich mud in caves: Study case in Crovassa Ricchi in Argento Cave (SW Sardinia, Italy)

    NASA Astrophysics Data System (ADS)

    Gázquez, Fernando; Calaforra, José-María; Forti, Paolo; De Waele, Jo; Sanna, Laura; Rull, Fernando; Sanz, Aurelio

    2013-09-01

    Unusual orange ochre crusts were recently discovered in Crovassa Ricchi in Argento Cave (San Giovanni Mine, SW Sardinia). These speleothems appear covering the cave walls on hydrothermal calcite spars as well as filling widened spaces between calcite crystals. Planar crusts display geometrical forms following the boundaries between the calcite spars. EDX-SEM microanalyses reveal that these deposits comprise substances of Fe, Mn, Pb, Zn and O that occur as solid inclusions in pits on the surface of altered calcite microcrystals. Micro-Raman spectroscopy analyses suggest the presence of calcite and ferromanganese oxides with a low degree of crystallinity. The genetic mechanism proposed for these speleothems describes an initial stage of precipitation of euhedral calcite crystals from warm water under subaqueous conditions. The crystal surfaces were eroded and corroded by colder aggressive water that smoothed the surfaces of the crystals and slightly widened the spaces between calcite spars. Metal-rich mud coming from alteration of bedrock and ore bodies filled the cave, also penetrating along the spaces between the calcite spars. When the water table fell below the cave level, part of the sediments was eroded but the cave walls remained covered with metal-rich clayey sediments. Under aerobic conditions, metals - which were reduced in previous stages - oxidized to oxides, lowering the pH and thus the crystal surface and the calcite planes between the spars were corroded. Subsequently, the polymetallic crusts became harder through evaporation within the cave, "fossilizing" the products of this process within the planes between spars. Finally, the exposed calcite surfaces continued to be altered due to CO2 diffusion into condensation water, while the boundaries between crystals were preserved against corrosion thanks to the crust coating. As a result, the external crystal edges protrude by several centimeters from the current cave wall, while the crystal surfaces are depressed, giving rise to calcite "ghosts".

  11. Device for isolation of seed crystals during processing of solution

    DOEpatents

    Montgomery, K.E.; Zaitseva, N.P.; Deyoreo, J.J.; Vital, R.L.

    1999-05-18

    A device is described for isolation of seed crystals during processing of solutions. The device enables a seed crystal to be introduced into the solution without exposing the solution to contaminants or to sources of drying and cooling. The device constitutes a seed protector which allows the seed to be present in the growth solution during filtration and overheating operations while at the same time preventing the seed from being dissolved by the under saturated solution. When the solution processing has been completed and the solution cooled to near the saturation point, the seed protector is opened, exposing the seed to the solution and allowing growth to begin. 3 figs.

  12. Applications of the streak seeding technique in protein crystallization

    NASA Astrophysics Data System (ADS)

    Stura, Enrico A.; Wilson, Ian A.

    1991-03-01

    The seeding of protein solutions is a powerful method for growing crystals. Microseeding and macroseeding both require conditions under which spontaneous nucleation is totally absent or extremely rare. A technique where seeds from a crystal are streaked into a protein-precipitant drop along a straight line using a rabbit whisker has been developed to determine suitable conditions for either micro- or macro-seeding. This seeding technique has also been successful in obtaining crystals using crystalline precipitate as the source of seeds, in cross-seeding from Fabpeptide complex crystals to obtain complexes with peptides of longer length, and similarly in cross-seeding from crystals of one monoclonal Fabpeptide complex to obtain crystals of a different monoclonal Fab complexed to the same peptide. This relatively simple technique should be of general applicability in macromolecular crystallizations and offers the potential to test whether new complex crystals mey be obtained by seeding with the native or other complexes, to determine whether cross-seeding may be used with seeds from a related protein or to analyze the crystallization potential of different protein preparations.

  13. Temperature-Controlled Support for a Seed Crystal

    NASA Technical Reports Server (NTRS)

    Reeve, J. L.

    1982-01-01

    A rodlike structure called a sting has been proposed for supporting a seed crystal at center of a body of saturated fluid and for controlling temperature/time profile of seed for experiments on crystal growth. Seed crystal is cooled or heated by thermoelectric modules while surrounding sheath remains at solution temperature. Heat is withdrawn to cooling fins by heat pipe, which replaces solid copper rod in a previous design.

  14. Device for isolation of seed crystals during processing of solution

    DOEpatents

    Montgomery, Kenneth E. (Tracy, CA); Zaitseva, Natalia P. (Livermore, CA); Deyoreo, James J. (Livermore, CA); Vital, Russell L. (Tracy, CA)

    1999-01-01

    A device for isolation of see crystals during processing of solutions. The device enables a seed crystal to be introduced into the solution without exposing the solution to contaminants or to sources of drying and cooling. The device constitutes a seed protector which allows the seed to be present in the growth solution during filtration and overheating operations while at the same time preventing the seed from being dissolved by the under saturated solution. When the solution processing has been completed and the solution cooled to near the saturation point, the seed protector is opened, exposing the seed to the solution and allowing growth to begin.

  15. Ab initio study of single-crystalline and polycrystalline elastic properties of Mg-substituted calcite crystals.

    PubMed

    Zhu, L-F; Frik, M; Lymperakis, L; Titrian, H; Aydin, U; Janus, A M; Fabritius, H-O; Ziegler, A; Nikolov, S; Hemzalov, P; Raabe, D; Neugebauer, J

    2013-04-01

    We employ ab initio calculations and investigate the single-crystalline elastic properties of (Ca,Mg)CO3 crystals covering the whole range of concentrations from pure calcite CaCO3 to pure magnesite MgCO3. Studying different distributions of Ca and Mg atoms within 30-atom supercells, our theoretical results show that the energetically most favorable configurations are characterized by elastic constants that nearly monotonously increase with the Mg content. Based on the first principles-derived single-crystalline elastic anisotropy, the integral elastic response of (Ca,Mg)CO3 polycrystals is determined employing a mean-field self-consistent homogenization method. As in case of single-crystalline elastic properties, the computed polycrystalline elastic parameters sensitively depend on the chemical composition and show a significant stiffening impact of Mg atoms on calcite crystals in agreement with the experimental findings. Our analysis also shows that it is not advantageous to use a higher-scale two-phase mix of stoichiometric calcite and magnesite instead of substituting Ca atoms by Mg ones on the atomic scale. Such two-phase composites are not significantly thermodynamically favorable and do not provide any strong additional stiffening effect. PMID:23507262

  16. A novel acidic matrix protein, PfN44, stabilizes magnesium calcite to inhibit the crystallization of aragonite.

    PubMed

    Pan, Cong; Fang, Dong; Xu, Guangrui; Liang, Jian; Zhang, Guiyou; Wang, Hongzhong; Xie, Liping; Zhang, Rongqing

    2014-01-31

    Magnesium is widely used to control calcium carbonate deposition in the shell of pearl oysters. Matrix proteins in the shell are responsible for nucleation and growth of calcium carbonate crystals. However, there is no direct evidence supporting a connection between matrix proteins and magnesium. Here, we identified a novel acidic matrix protein named PfN44 that affected aragonite formation in the shell of the pearl oyster Pinctada fucata. Using immunogold labeling assays, we found PfN44 in both the nacreous and prismatic layers. In shell repair, PfN44 was repressed, whereas other matrix proteins were up-regulated. Disturbing the function of PfN44 by RNAi led to the deposition of porous nacreous tablets with overgrowth of crystals in the nacreous layer. By in vitro circular dichroism spectra and fluorescence quenching, we found that PfN44 bound to both calcium and magnesium with a stronger affinity for magnesium. During in vitro calcium carbonate crystallization and calcification of amorphous calcium carbonate, PfN44 regulated the magnesium content of crystalline carbonate polymorphs and stabilized magnesium calcite to inhibit aragonite deposition. Taken together, our results suggested that by stabilizing magnesium calcite to inhibit aragonite deposition, PfN44 participated in P. fucata shell formation. These observations extend our understanding of the connections between matrix proteins and magnesium. PMID:24302723

  17. Realisation of four-wave mixing phase matching for frequency components at intracavity stimulated Raman scattering in a calcite crystal

    SciTech Connect

    Smetanin, Sergei N; Fedin, Aleksandr V; Shurygin, Anton S

    2013-06-30

    The possibilities of implementing four-wave mixing (FWM) phase matching at stimulated Raman scattering (SRS) in a birefringent SRS-active crystal placed in a cavity with highly reflecting mirrors have been theoretically and experimentally investigated. Phase-matching angles providing conditions for five types of phase matching are determined for a calcite crystal. These types are characterised by different combinations of polarisation directions for the interacting waves and ensure FWM generation of either an anti-Stokes wave or the second Stokes SRS component. In agreement with the calculation results, low-threshold generation of the second Stokes SRS component with a wavelength 0.602 {mu}m was observed at angles of incidence on a calcite crystal of 4.8 Degree-Sign and 18.2 Degree-Sign , under SRS pumping at a wavelength of 0.532 {mu}m. This generation is due to the FWM coupling of the first and second Stokes SRS components with the SRS-pump wave. (nonlinear optical phenomena)

  18. A Novel Acidic Matrix Protein, PfN44, Stabilizes Magnesium Calcite to Inhibit the Crystallization of Aragonite*

    PubMed Central

    Pan, Cong; Fang, Dong; Xu, Guangrui; Liang, Jian; Zhang, Guiyou; Wang, Hongzhong; Xie, Liping; Zhang, Rongqing

    2014-01-01

    Magnesium is widely used to control calcium carbonate deposition in the shell of pearl oysters. Matrix proteins in the shell are responsible for nucleation and growth of calcium carbonate crystals. However, there is no direct evidence supporting a connection between matrix proteins and magnesium. Here, we identified a novel acidic matrix protein named PfN44 that affected aragonite formation in the shell of the pearl oyster Pinctada fucata. Using immunogold labeling assays, we found PfN44 in both the nacreous and prismatic layers. In shell repair, PfN44 was repressed, whereas other matrix proteins were up-regulated. Disturbing the function of PfN44 by RNAi led to the deposition of porous nacreous tablets with overgrowth of crystals in the nacreous layer. By in vitro circular dichroism spectra and fluorescence quenching, we found that PfN44 bound to both calcium and magnesium with a stronger affinity for magnesium. During in vitro calcium carbonate crystallization and calcification of amorphous calcium carbonate, PfN44 regulated the magnesium content of crystalline carbonate polymorphs and stabilized magnesium calcite to inhibit aragonite deposition. Taken together, our results suggested that by stabilizing magnesium calcite to inhibit aragonite deposition, PfN44 participated in P. fucata shell formation. These observations extend our understanding of the connections between matrix proteins and magnesium. PMID:24302723

  19. Homoepitaxial meso- and microscale crystal co-orientation and organic matrix network structure in Mytilus edulis nacre and calcite.

    PubMed

    Griesshaber, Erika; Schmahl, Wolfgang W; Ubhi, Harbinder Singh; Huber, Julia; Nindiyasari, Fitriana; Maier, Bernd; Ziegler, Andreas

    2013-12-01

    New developments in high-resolution, low accelaration voltage electron backscatter diffraction (EBSD) enable us to resolve and quantify the co-orientation of nanocrystals constituting biological carbonate crystals with a scan step resolution of 125 nm. This allows the investigation of internal structures in carbonate tablets and tower biocrystals in the nacre of mollusc shells, and it provides details on the calcite-aragonite polymorph interface in bivalves. Within the aragonite tablets of Mytilus edulis nacre we find a mesoscale crystallographic mosaic structure with a misorientation distribution of 2 full width at half maximum. Selective etching techniques with critical point drying reveal an organic matrix network inside the nacre tablets. The size scales of the visible aragonite tablet subunits and nanoparticles correspond to those of the open pore system in the organic matrix network. We further observe by EBSD that crystal co-orientation spans over tablet boundaries and forms composite crystal units of up to 20 stacked co-oriented tablets (tower crystals). Statistical evaluation of the misorientation data gives a probability distribution of grain boundary misorientations with two maxima: a dominant peak for very-small-angle grain boundaries and a small maximum near 64, the latter corresponding to {110} twinning orientations. However, the related twin boundaries are typically the membrane-lined {001} flat faces of the tablets and not {110} twin walls within tablets. We attribute this specific pattern of misorientation distribution to growth by particle accretion and subsequent semicoherent homoepitaxial crystallization. The semicoherent crystallization percolates between the tablets through mineral bridges and across matrix membranes surrounding the tablets. In the "prismatic" calcite layer crystallographic co-orientation of the prisms reaches over more than 50 micrometers. PMID:23896564

  20. Composite Magnetite and Protein Containing CaCO3 Crystals. External Manipulation and Vaterite ? Calcite Recrystallization-Mediated Release Performance.

    PubMed

    Sergeeva, Alena; Sergeev, Roman; Lengert, Ekaterina; Zakharevich, Andrey; Parakhonskiy, Bogdan; Gorin, Dmitry; Sergeev, Sergey; Volodkin, Dmitry

    2015-09-30

    Biocompatibility and high loading capacity of mesoporous CaCO3 vaterite crystals give an option to utilize the polycrystals for a wide range of (bio)applications. Formation and transformations of calcium carbonate polymorphs have been studied for decades, aimed at both basic and applied research interests. Here, composite multilayer-coated calcium carbonate polycrystals containing Fe3O4 magnetite nanoparticles and model protein lysozyme are fabricated. The structure of the composite polycrystals and vaterite ? calcite recrystallization kinetics are studied. The recrystallization results in release of both loaded protein and Fe3O4 nanoparticles (magnetic manipulation is thus lost). Fe3O4 nanoparticles enhance the recrystallization that can be induced by reduction of the local pH with citric acid and reduction of the polycrystal crystallinity. Oppositely, the layer-by-layer assembled poly(allylamine hydrochloride)/poly(sodium styrenesulfonate) polyelectrolyte coating significantly inhibits the vaterite ? calcite recrystallization (from hours to days) most likely due to suppression of the ion exchange giving an option to easily tune the release kinetics for a wide time scale, for example, for prolonged release. Moreover, the recrystallization of the coated crystals results in formulation of multilayer capsules keeping the feature of external manipulation. This study can help to design multifunctional microstructures with tailor-made characteristics for loading and controlled release as well as for external manipulation. PMID:26348458

  1. High surface area calcite

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

  2. Adjustment errors of sunstones in the first step of sky-polarimetric Viking navigation: studies with dichroic cordierite/ tourmaline and birefringent calcite crystals

    PubMed Central

    Száz, Dénes; Farkas, Alexandra; Blahó, Miklós; Barta, András; Egri, Ádám; Kretzer, Balázs; Hegedüs, Tibor; Jäger, Zoltán; Horváth, Gábor

    2016-01-01

    According to an old but still unproven theory, Viking navigators analysed the skylight polarization with dichroic cordierite or tourmaline, or birefringent calcite sunstones in cloudy/foggy weather. Combining these sunstones with their sun-dial, they could determine the position of the occluded sun, from which the geographical northern direction could be guessed. In psychophysical laboratory experiments, we studied the accuracy of the first step of this sky-polarimetric Viking navigation. We measured the adjustment error e of rotatable cordierite, tourmaline and calcite crystals when the task was to determine the direction of polarization of white light as a function of the degree of linear polarization p. From the obtained error functions e(p), the thresholds p* above which the first step can still function (i.e. when the intensity change seen through the rotating analyser can be sensed) were derived. Cordierite is about twice as reliable as tourmaline. Calcite sunstones have smaller adjustment errors if the navigator looks for that orientation of the crystal where the intensity difference between the two spots seen in the crystal is maximal, rather than minimal. For higher p (greater than pcrit) of incident light, the adjustment errors of calcite are larger than those of the dichroic cordierite (pcrit=20%) and tourmaline (pcrit=45%), while for lower p (less than pcrit) calcite usually has lower adjustment errors than dichroic sunstones. We showed that real calcite crystals are not as ideal sunstones as it was believed earlier, because they usually contain scratches, impurities and crystal defects which increase considerably their adjustment errors. Thus, cordierite and tourmaline can also be at least as good sunstones as calcite. Using the psychophysical e(p) functions and the patterns of the degree of skylight polarization measured by full-sky imaging polarimetry, we computed how accurately the northern direction can be determined with the use of the Viking sun-dial under 10 different sky conditions at 61° latitude, which was one of the main Viking sailing routes. According to our expermiments, under clear skies, using calcite or cordierite or tourmaline sunstones, Viking sailors could navigate with net orientation errors |Σmax|≤3∘. Under overcast conditions, their net navigation error depends on the sunstone type: |Σmax(calcite)|≤6∘, |Σmax(cordierite)|≤10∘ and |Σmax(tourmaline)|≤17∘. PMID:26909167

  3. Hydration of Cuphea seeds containing crystallized triacylglycerols

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Seeds that exhibit intermediate storage behavior do not appear to survive under conventional -18C storage conditions. Cuphea wrightii, C. laminuligera, C. carthagenensis, and C. aequipetala are considered sensitive to low temperature storage. The seeds of these species have triacylglycerols (TAG) ...

  4. Adjustment errors of sunstones in the first step of sky-polarimetric Viking navigation: studies with dichroic cordierite/ tourmaline and birefringent calcite crystals.

    PubMed

    Száz, Dénes; Farkas, Alexandra; Blahó, Miklós; Barta, András; Egri, Ádám; Kretzer, Balázs; Hegedüs, Tibor; Jäger, Zoltán; Horváth, Gábor

    2016-01-01

    According to an old but still unproven theory, Viking navigators analysed the skylight polarization with dichroic cordierite or tourmaline, or birefringent calcite sunstones in cloudy/foggy weather. Combining these sunstones with their sun-dial, they could determine the position of the occluded sun, from which the geographical northern direction could be guessed. In psychophysical laboratory experiments, we studied the accuracy of the first step of this sky-polarimetric Viking navigation. We measured the adjustment error e of rotatable cordierite, tourmaline and calcite crystals when the task was to determine the direction of polarization of white light as a function of the degree of linear polarization p. From the obtained error functions e(p), the thresholds p* above which the first step can still function (i.e. when the intensity change seen through the rotating analyser can be sensed) were derived. Cordierite is about twice as reliable as tourmaline. Calcite sunstones have smaller adjustment errors if the navigator looks for that orientation of the crystal where the intensity difference between the two spots seen in the crystal is maximal, rather than minimal. For higher p (greater than p crit) of incident light, the adjustment errors of calcite are larger than those of the dichroic cordierite (p crit=20%) and tourmaline (p crit=45%), while for lower p (less than p crit) calcite usually has lower adjustment errors than dichroic sunstones. We showed that real calcite crystals are not as ideal sunstones as it was believed earlier, because they usually contain scratches, impurities and crystal defects which increase considerably their adjustment errors. Thus, cordierite and tourmaline can also be at least as good sunstones as calcite. Using the psychophysical e(p) functions and the patterns of the degree of skylight polarization measured by full-sky imaging polarimetry, we computed how accurately the northern direction can be determined with the use of the Viking sun-dial under 10 different sky conditions at 61° latitude, which was one of the main Viking sailing routes. According to our expermiments, under clear skies, using calcite or cordierite or tourmaline sunstones, Viking sailors could navigate with net orientation errors [Formula: see text]. Under overcast conditions, their net navigation error depends on the sunstone type: [Formula: see text], [Formula: see text] and [Formula: see text]. PMID:26909167

  5. Uranyl incorporation in natural calcite.

    SciTech Connect

    Kelly, S. D.; Newville, M. G.; Cheng, L.; Kemner, K. M.; Sutton, S. R.; Fenter, P.; Sturchio, N. C.; Spotl, C.; Environmental Research; Univ. of Chicago; Univ. of Illiois at Chicago; Univ. of Innsbruck

    2003-01-01

    The occurrence of trace amounts of uranyl in natural calcite has posed a long-standing problem in crystal chemistry because of speculation that the size and shape of the uranyl ion may preclude its incorporation in a stable lattice position in calcite. This also defines an important environmental problem because of its bearing on the transport and sequestration of uranyl released from nuclear facilities and uranium mining operations. Calcite is a nearly ubiquitous mineral in soils and groundwater aquifers. X-ray absorption spectroscopy and X-ray fluorescence microprobe studies of uranium in relatively U-rich {approx}13700-year-old calcite from a speleothem in northernmost Italy indicate substitution of uranyl for a calcium and two adjacent carbonate ions in calcite. These new data imply that uranyl has a stable lattice position in natural calcite, indicating that it may be reliably sequestered in calcite over long time scales.

  6. Laser ablation for protein crystal nucleation and seeding.

    PubMed

    Yoshikawa, Hiroshi Y; Murai, Ryota; Adachi, Hiroaki; Sugiyama, Shigeru; Maruyama, Mihoko; Takahashi, Yoshinori; Takano, Kazufumi; Matsumura, Hiroyoshi; Inoue, Tsuyoshi; Murakami, Satoshi; Masuhara, Hiroshi; Mori, Yusuke

    2014-04-01

    With the recent development in pulsed lasers with ultrashort pulse widths or wavelengths, spatially precise, low-damage processing by femtosecond or deep-UV laser ablation has shown promise for the production of protein single crystals suitable for X-ray crystallography. Femtosecond laser processing of supersaturated solutions can shorten the protein nucleation period or can induce nucleation at low supersaturation, which improves the crystal quality of various proteins including membrane proteins and supra-complexes. In addition to nucleation, processing of protein crystals by femtosecond or deep-UV laser ablation can produce single crystalline micro- or macro-seeds without deterioration of crystal quality. This tutorial review gives an overview of the successful application of laser ablation techniques to nucleation and seeding for the production of protein single crystals, and also describes the advantages from a physico-chemical perspective. PMID:24252936

  7. Seeded Growth of AlN Crystals on Non-Polar Seeds Via Physical Vapor Transport

    SciTech Connect

    Zhuang,D.; Herro, Z.; Schlesser, R.; Ragothamachar, B.; Dudley, M.; Sitar, Z.

    2006-01-01

    Seeded growth of AlN single crystals was demonstrated in an induction-heated, high-temperature reactor via a physical vapor transport (PVT) process. AlN seeds were prepared from a self-seeded boule containing large single-crystalline grains. Seeded growth was interrupted several times in order to refill the AlN powder source, and a dedicated process scheme was used to ensure epitaxial growth on the seed surface, after prior exposure to air. The growth temperatures were in the range of 2200-2300 C, and the reactor pressure was in the range of 500-900 torr of UHP-grade nitrogen during each growth run. Under these growth conditions, a seed (10 mm diameter) expanded at an angle of 45{sup o}, and a larger single crystal up to 18 mm in diameter was obtained. The as-grown surface had three facets, of which facet (1120) was smooth and featureless while the other two, (4150) and (2570), showed serrated morphologies. The double-crystal x-ray rocking curve and glow discharge mass spectroscopy analysis confirmed that the grown crystal was of high crystalline quality with low impurity incorporation.

  8. Crystal chemistry, and thermodynamic and kinetic properties of calcite, dolomite, apatite, and biogenic silica: applications to petrologic problems

    NASA Astrophysics Data System (ADS)

    Tribble, Jane S.; Arvidson, Rolf S.; Lane, Michael; Mackenzie, Fred T.

    1995-02-01

    Sedimentary minerals are generally metastable phases that, given time and changing environmental conditions, recrystallize to more stable phases. The actual pathway of stabilization is governed by a host of kinetic factors. Unfortunately, much of the theoretical and experimental work on thermodynamic and kinetic behavior of sedimentary minerals either has not reached field practitioners in sedimentary petrology, or has been conducted under conditions that are difficult to extrapolate to natural sedimentary environments. In this paper we review and present new data on the basic crystal chemistry, thermodynamic and kinetic properties of calcite, dolomite, apatite, and biogenic silica, and discuss the relevance of these data to the solution of geological and geochemical problems. The crystal chemistry and structure of a given magnesian calcite exert a fundamental control on its solubility and solid solution behavior, and this control can be seen most clearly through comparison of synthetic and biogenic phases. Thus, variations in crystal chemistry and structure, through solubility control during diagenesis, yield a range of possible stabilization pathways, whose documentation is the domain of much field-based study. Experimental work involving dolomite has focused on delineation of phase relations in dry and aqueous systems at moderate to high temperatures, determination of reaction pathways followed during dolomitization of calcium carbonate, and measurement of reaction rate. Uncertainties reside in the relevance of these data to the classic problem of low-temperature dolomite formation. We suggest that the effort must now focus on designing experimental systems that effectively mimic natural environments, and yield reaction rate data as a function of temperature and solution composition. Such an example is presented. A primary goal in experimental work involving carbonate fluorapatite has been an understanding of the mechanism of formation of this mineral. We review the state of this knowledge, and also present the results of ongoing dissolution rate experiments. The importance of this work is that it bears directly on the understanding of the role carbonate fluorapatite plays in the biogeochemical cycle of P in the oceans. Many factors influence the solubilities of opaline silica and the silica polymorphs, and solubility plays an important role in controlling silica diagenesis. A model is presented that relates changes in sediment properties including density and acoustic velocity to the stages of silica diagenesis. The model is applied to sediments of Deep Sea Drilling Project Leg 63. The discussions of the sedimentary phases calcite, dolomite, apatite, and biogenic silica in this paper point to several directions for future experimental research on sedimentary mineral-solution reactions. These include emphasis on: (1) experimental studies of synthetic sedimentary mineral-solution reactions to form a foundation for an understanding of natural mineral-solution reactions; (2) experimental investigations of mineral reactions in aqueous solutions under conditions of composition, temperature, and pressure similar to the natural conditions of mineral formation; and (3) studies of the surface (as opposed to bulk) properties of sedimentary minerals in aqueous solutions and their role in reactions governing precipitation and dissolution of sedimentary phases.

  9. Puzzling calcite-III dimorphism: crystallography, high-pressure behavior, and pathway of single-crystal transitions

    NASA Astrophysics Data System (ADS)

    Pippinger, T.; Miletich, R.; Merlini, M.; Lotti, P.; Schouwink, P.; Yagi, T.; Crichton, W. A.; Hanfland, M.

    2015-01-01

    High-pressure phase transformations between the polymorphic forms I, II, III, and IIIb of CaCO3 were investigated by analytical in situ high-pressure high-temperature experiments on oriented single-crystal samples. All experiments at non-ambient conditions were carried out by means of Raman scattering, X-ray, and synchrotron diffraction techniques using diamond-anvil cells in the pressure range up to 6.5 GPa. The composite-gasket resistive heating technique was applied for all high-pressure investigations at temperatures up to 550 K. High-pressure Raman spectra reveal distinguishable characteristic spectral differences located in the wave number range of external modes with the occurrence of band splitting and shoulders due to subtle symmetry changes. Constraints from in situ observations suggest a stability field of CaCO3-IIIb at relatively low temperatures adjacent to the calcite-II field. Isothermal compression of calcite provides the sequence from I to II, IIIb, and finally, III, with all transformations showing volume discontinuities. Re-transformation at decreasing pressure from III oversteps the stability field of IIIb and demonstrates the pathway of pressure changes to determine the transition sequence. Clausius-Clapeyron slopes of the phase boundary lines were determined as: Δ P/Δ T = -2.79 ± 0.28 × 10-3 GPa K-1 (I-II); +1.87 ± 0.31 × 10-3 GPa K-1 (II/III); +4.01 ± 0.5 × 10-3 GPa K-1 (II/IIIb); -33.9 ± 0.4 × 10-3 GPa K-1 (IIIb/III). The triple point between phases II, IIIb, and III was determined by intersection and is located at 2.01(7) GPa/338(5) K. The pathway of transition from I over II to IIIb can be interpreted by displacement with small shear involved (by 2.9° on I/II and by 8.2° on II/IIIb). The former triad of calcite-I corresponds to the [20-1] direction in the P21/ c unit cell of phase II and to [101] in the pseudomonoclinic C setting of phase IIIb. Crystal structure investigations of triclinic CaCO3-III at non-ambient pressure-temperature conditions confirm the reported structure, and the small changes associated with the variation in P and T explain the broad stability of this structure with respect to variations in P and T. PVT equation of state parameters was determined from experimental data points in the range of 2.20-6.50 GPa at 298-405 K providing = 87.5(5.1) GPa, ( δK T/ δT) P = -0.21(0.23) GPa K-1, α 0 = 0.8(21.4) × 10-5 K-1, and α 1 = 1.0(3.7) × 10-7 K-1 using a second-order Birch-Murnaghan equation of state formalism.

  10. Kinetic and thermodynamic factors controlling the distribution of SO32- and Na+ in calcites and selected aragonites

    USGS Publications Warehouse

    Busenberg, E.; Niel, Plummer L.

    1985-01-01

    Significant amounts of SO42-, Na+, and OH- are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO42-. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na+, but very low concentrations of SO42-. The SO42- content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na+ and SO42- increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO42- beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO42- is the same as that of aragonite. Na+ appears to have very little effect on the solubility product of calcites. The amounts of Na+ and SO42- incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient (D) of SO42- in calcite at 25.0??C and 0.50 molal NaCl is described by the equation D = k0 + k1R where k0 and k1 are constants equal to 6.16 ?? 10-6 and 3.941 ?? 10-6, respectively, and R is the rate of crystal growth of calcite in mg??min-1??g-1 of seed. The data on Na+ are consistent with the hypothesis that a significant amount of Na+ occupies interstitial positions in the calcite structure. The distribution of Na+ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na+ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na+ contents of calcites are not very accurate indicators of environmental salinities. ?? 1985.

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

    USGS Publications Warehouse

    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. Variations in the Sr/Ca, ?44Ca and ?18O composition of calcite as a function of solution chemistry and crystal growth rate

    NASA Astrophysics Data System (ADS)

    Watkins, J. M.; DePaolo, D. J.; Ryerson, F. J.

    2012-12-01

    The trace element and isotopic composition of calcite can be used to probe the temperatures and rates of mineral formation as well as the degree of post-mineralization alteration. The accuracy with which these effects can be interpreted is limited by our ability to distinguish signatures arising from equilibrium partitioning versus kinetic or mass transport effects. Our focus in this work is on mass transport effects in aqueous environments, and specifically, the growth rate-dependence of trace element and isotopic incorporation into calcite. This requires experiments in which the degree of supersaturation, or the solution chemistry, is held constant and the rate of crystal growth can be determined. In our experiments, N2+CO2 gas mixture is bubbled through a beaker containing 1300 mL of solution (30 mM CaCl2 + 5 mM NH4Cl + 0.1 mM SrCl2). The degree of supersaturation with respect to calcite is controlled by the pCO2 of the gas mixture, which is constantly replenished from a gas source. As CO2 from the gas dissolves into solution, calcite crystals grow on the beaker walls and the pH of the solution is maintained by use of an autotitrator with NaOH as the titrant. During an experiment we control the temperature, pH, the pCO2 of the gas inflow, and the gas inflow rate. At the same time we monitor the total alkalinity, the pCO2 of the gas outflow, the gas outflow rate, and the amount of NaOH added. The rate of calcite precipitation can be determined in three ways: (1) the change in total alkalinity due to Ca2+ removal, mass balance of C in the system, and (3) post-run measurement of [Ca2+] in aliquots of solution taken during an experiment. We present results from experiments where growth rates are estimated to range from 0.5 to 16 mmol/m2/hr. Our experiments thus far have yielded calcite crystals that are out of calcium and oxygen isotopic equilibrium with the parent solution. Crystals are enriched in the light isotope of Ca by 0.4 to 1.8. The light isotope enrichment increases with growth rate and is correlated with Sr/Ca in calcite. These results are in excellent agreement with the results of Tang et al. (2008) for crystals grown at 25C and suggest that mass discrimination is controlled by mass transport kinetics at the mineral-solution interface. Oxygen isotopes are more complicated because of the addition of CO2 to the bulk solution. For crystals grown from our stock solution, the O composition is highly variable and not correlated with growth rate. We attribute this to relatively slow kinetics of O isotope exchange between gaseous or dissolved CO2 and water. For crystals grown in the presence of 0.01 grams of bovine carbonic anhydrase (CA), an enzyme which catalyzes the interconversion of CO2 and H2O to bicarbonate and protons, the O isotope composition of calcite appears to be independent of growth rate. Hence addition of CA to solution might offer a means of determining the equilibrium fractionation factor for oxygen isotopes in carbonate minerals. We will present results from additional experiments that test how CA and other organic molecules in solution affect the growth rate and mass discrimination during mineral precipitation.

  13. Growth of silicon carbide crystals on a seed while pulling silicon crystals from a melt

    NASA Technical Reports Server (NTRS)

    Ciszek, T. F.; Schwuttke, G. H. (Inventor)

    1979-01-01

    A saturated solution of silicon and an element such as carbon having a segregation coefficient less than unity is formed by placing a solid piece of carbon in a body of molten silicon having a temperature differential decreasing toward the surface. A silicon carbide seed crystal is disposed on a holder beneath the surface of the molten silicon. As a rod or ribbon of silicon is slowly pulled from the melt, a supersaturated solution of carbon in silicon is formed in the vicinity of the seed crystal. Excess carbon is emitted from the solution in the form of silicon carbide which crystallizes on the seed crystal held in the cool region of the melt.

  14. Crystallization of pumpkin seed globulin: growth and dissolution kinetics

    NASA Astrophysics Data System (ADS)

    Malkin, Alexander J.; McPherson, Alexander

    1993-10-01

    Quasi-elastic light scattering was used to investigate the nucleation and crystallization of pumpkin ( Cucurbita) seed globulin. The diameter of the pumpkin globulin monomer was measured to be ? 5-6 nm. The supersaturation dependence of critical nucleus size was obtained, and this allowed an estimate of the interfacial free energy to be ? ? 6.1 x 10 -2 erg/cm 2. The crystallization and dissolution kinetics were investigated for 4.9-16 mg/ml protein solutions containing 1-7% NaCl. The solubility data as a function of precipitant concentration and temperature were obtained and these will be utilized for optimization of the crystallization conditions for the pumpkin globulin.

  15. Isothermal Crystallization Kinetics of Mango (Mangifera indica) Almond Seed Fat

    NASA Astrophysics Data System (ADS)

    Solis-Fuentes, J. A.; Hernandez-Medel, M. R.; Duran-de-Bazua, M. C.

    In this study, the kinetics of isothermal crystallization of mango (Mangifera indica) almond seed fat var. Manila (MAF) was analyzed, within the theoretical context of the Sestak-Berggren model, the Avrami Equation and its modification by Khanna and Taylor. The results showed that the induction times for the formation of crystalline nuclei increased with the crystallization temperature (3.3 min at 8°C and 10.9 min at 12°C). The supercooling level notably influenced the MAF crystallization rate, since the global constant of crystallization rate, Z, grew 3.3 times from 12 to 8°C (for fractions of fat solids between 0.25 and 0.75, Z was 0.2904, 0.1584 and 0.0879 min-1 at 8, 10 and 12°C, respectively) and the Avrami parameter r was higher than 4; this demonstrates the effect of fat system complexity due to its multi-component nature and the heterogeneous character of this crystallization process, which includes additional participation of nucleation sites. The modified model by Khanna and Taylor provided better parametral values than the other two studied for explaining MAF crystallization kinetic.

  16. Elastic constants of calcite

    USGS Publications Warehouse

    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.

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

    PubMed Central

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

    2009-01-01

    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. PMID:19332795

  18. Large single domain 123 material produced by seeding with single crystal rare earth barium copper oxide single crystals

    DOEpatents

    Todt, Volker; Miller, Dean J.; Shi, Donglu; Sengupta, Suvankar

    1998-01-01

    A method of fabricating bulk YBa.sub.2 Cu.sub.3 O.sub.x where compressed powder oxides and/or carbonates of Y and Ba and Cu present in mole ratios to form YBa.sub.2 Cu.sub.3 O.sub.x are heated in the presence of a Nd.sub.1+x Ba.sub.2-x Cu.sub.3 O.sub.y seed crystal to a temperature sufficient to form a liquid phase in the YBa.sub.2 Cu.sub.3 O.sub.x while maintaining the seed crystal solid. The materials are slowly cooled to provide a YBa.sub.2 Cu.sub.3 O.sub.x material having a predetermined number of domains between 1 and 5. Crack-free single domain materials can be formed using either plate shaped seed crystals or cube shaped seed crystals with a pedestal of preferential orientation material.

  19. Growth of Cadmium-Zinc Telluride Crystals by Controlled Seeding Contactless Physical Vapor Transport

    NASA Technical Reports Server (NTRS)

    Palosz, W.; Grasza, K.; Gillies, D.; Jerman, G.

    1996-01-01

    Bulk crystals of cadmium-zinc telluride, 23 mm in diameter and up to 45 grams in weight were grown. Controlled seed formation procedure was used to limit the number of grains in the crystal. Most uniform distribution of ZnTe in the crystals was obtained using excess (Cd + Zn) pressure in the ampoule.

  20. The role of silicate surfaces on calcite precipitation kinetics

    NASA Astrophysics Data System (ADS)

    Stockmann, Gabrielle J.; Wolff-Boenisch, Domenik; Bovet, Nicolas; Gislason, Sigurdur R.; Oelkers, Eric H.

    2014-06-01

    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 0.5-2 g of mineral, rock, or glass seeds. This led to an inlet fluid calcite saturation index of 0.6 and a pH 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 grains. Calcite precipitated relatively rapidly on labradorite, olivine, enstatite, and peridotite (mainly composed of Mg-olivine) surfaces, but more slowly on augite and basaltic glass. Calcite precipitation rates, however, became independent of substrate identity and mass over time, and all rates approach 10-9.68 0.08 mol/s for ?10 day long experiments and 10-9.21 0.2 mol/s for ?70 day long experiments. Scanning Electron Microscope images showed olivine, enstatite and peridotite surfaces to be covered extensively with calcite coatings at the end of the experiments. Less calcite was found on labradorite and augite, and the least on basaltic glass. In all cases, calcite precipitation occurs on the mineral, rock or glass surfaces. Calcite precipitation on these surfaces, however, negligibly affects the dissolution rates of the silicate grains. These results support ultramafic and basalt carbonation as a long-term carbon storage strategy, as calcite readily precipitates on the surfaces of minerals contained in these rocks without inhibiting their dissolution.

  1. Segregation during directional melting and its implications on seeded crystal growth: A theoretical analysis

    NASA Technical Reports Server (NTRS)

    Bourret, E. D.; Favier, J. J.; Witt, A. F.

    1982-01-01

    Directional melting of binary systems, as encountered during seeding in melt growth, is analyzed for concurrent compositional changes at the crystal-melt interface. It is shown that steady state conditions cannot normally be reached during seeding and that the growth interface temperature at the initial stages of seeded growth is a function of backmelt conditions. The theoretical treatment is numerically applied to Hg1-xCdXTe and Ga-doped Ge.

  2. Fracture-aperture alteration induced by calcite precipitation

    NASA Astrophysics Data System (ADS)

    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 within variable-aperture fields will investigate the dependency of growth patterns on heterogeneous aperture distributions. (a) Aperture strain (Δb/bi) after 14 days. Precipitation is concentrated near the inlet and decreases in the flow direction. (b) Width-averaged profiles of the initial and final aperture field show changes in aperture and smoothing that results from calcite precipitation between the initial discrete crystals.

  3. Zinc isotope fractionation during adsorption on calcite

    NASA Astrophysics Data System (ADS)

    Dong, S.; Wasylenki, L. E.

    2013-12-01

    Zinc is an important element as a nutrient in the marine biosphere. However, our understanding of its biogeochemical cycling in the oceans is relatively limited. The Zn stable isotope system holds the promise of providing novel insights, since published Zn isotopic values for various natural samples reveal significant fractionations in the marine environment. Surface seawater, basalts, shales, deep-sea clay sediments, sediment trap material, bulk plankton and zooplankton samples, and eolian dust fall within a tight range (?66/64Zn from -0.1 to 0.5), but modern ferromanganese crusts (?66/64Zn from 0.5 to 1.2), as well as carbonates (?66/64Zn from 0.3 to 1.4), are notably enriched in heavy Zn isotopes [1-4]. In this study we seek to constrain the mechanism by which carbonates are enriched in heavier isotopes. In particular, we have conducted experiments to quantify isotope fractionation during adsorption of Zn onto the surfaces of calcite crystals that are in equilibrium with solution. The adsorption experiments were carried out in a series of small-volume batch reactions in a clean laboratory environment, using high-purity reagents and calcite seed crystals. The calcite was equilibrated with the solution prior to addition of Zn at atmospheric CO2 pressure (i.e., in air) for 5 days until a stable pH of 8.3 was reached. Later, a small aliquot of dissolved ZnCl2 was added such that the solution remained undersaturated with respect to hydrozincite. Experimental duration varied among the replicates from 6 to 144 hours, and then all solids and solutions were separated by filtration, purified by ion exchange chromatography, and analyzed by MC-ICP-MS. Zn adsorbed on calcite is isotopically heavier than in the co-existing solutions, with ?68/66Zncalcite-solution of approximately 0.3. The variation of ?68/66Zncalcite-solution beyond 24 hours is insignificant, so we infer that isotopic equilibrium is reached by this time. Previous work strongly suggests that a difference in coordination number between dissolved Zn and adsorbed Zn is drives the observed fractionation. Elzinga and Reeder[5] determined using EXAFS (Extended X-ray Absorption Fine Structure) that Zn adsorbed to calcite surfaces is tetrahedrally coordinated, sharing three oxygens with the calcite surface. Meanwhile density functional theory calculations[6] predicted that tetrahedral Zn-O species should be heavier than octahedral Zn-O species. Thus we infer that equilibrium between octahedrally coordinated, dissolved Zn and tetrahedrally coordinated, adsorbed Zn is the mechanism of fractionation in our experiments. Our further studies will determine whether the isotopically heavy pool of adsorbed Zn becomes the Zn incorporated within carbonates; if so, then we are closer to understanding the mechanism by which carbonate rocks in nature are enriched in heavier isotopes of zinc. [1] Bermin et al., 2006, Chem. Geol. 226, 280. [2] Marchal et al., 2000, Geochem. Geophys. Geosyst. 1, 1999GC-000029. [3] Dong et al., 2013, Talanta 114, 103-109. [4] Pichat et al., 2003, Earth Planet. Sci. Lett. 210, 167-178. [5] Elzinga and Reeder, 2002, Geochim. Cosmochim. Acta 66, 3943-3954. [6] Schauble, 2003, EOS, Trans. AGU, Fall Meet. Suppl. 84(46), B12B-0781.

  4. The Influence of Kinetic Growth Factors on the Clumped Isotope Composition of Calcite

    NASA Astrophysics Data System (ADS)

    Hunt, J. D.; Watkins, J. M.; Tripati, A.; Ryerson, F. J.; DePaolo, D. J.

    2014-12-01

    Clumped isotope paleothermometry is based on the association of 13C and 18O within carbonate minerals. Although the influence of temperature on equilibrium 13C-18O bond ordering has been studied, recent oxygen isotope studies of inorganic calcite demonstrate that calcite grown in laboratory experiments and in many natural settings does not form in equilibrium with water. It is therefore likely that the carbon and clumped isotope composition of these calcite crystals are not representative of true thermodynamic equilibrium. To isolate kinetic clumped isotope effects that arise at the mineral-solution interface, clumped isotopic equilibrium of DIC species must be maintained. This can be accomplished by dissolving the enzyme carbonic anhydrase (CA) into the solution, thereby reducing the time required for isotopic equilibration of DIC species by approximately two orders of magnitude between pH 7.7 and 9.3. We conduct calcite growth experiments aimed specifically at measuring the pH-dependence of kinetic clumped isotope effects during non-equilibrium precipitation of calcite. We precipitated calcite from aqueous solution at a constant pH and controlled supersaturation over the pH range 7.7-9.3 in the presence of CA. For each experiment, a gas mixture of N2 and CO2 is bubbled through a beaker of solution without seed crystals. As CO2 from the gas dissolves into solution, calcite crystals grow on the beaker walls. The pH of the solution is maintained by use of an autotitrator with NaOH as the titrant. We control the temperature, pH, the pCO2 of the gas inflow, and the gas inflow rate, and monitor the total alkalinity, the pCO2 of the gas outflow, and the amount of NaOH added. A constant crystal growth rate of ~1.6 mmol/m2/hr is maintained over all experiments. Results from these experiments are compared to predictions from a recently-developed isotopic ion-by-ion growth model of calcite. The model describes the rate, temperature and pH dependence of oxygen isotope uptake into calcite under non-equilibrium conditions. Adaptation of the model for clumped isotope uptake under non-equilibrium conditions requires knowledge of the clumped isotopic compositions of DIC species and any mass-dependent kinetic fractionation that arises during ion transport to or from the mineral surface.

  5. Influence of calcium oxalate crystal accumulation on the calcium content of seeds from Medicago truncatula

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Crystals of calcium oxalate often form in cells adjacent to the vascular bundles in the tissues along the xylem stream. This spatial crystal pattern suggests a role for calcium oxalate formation in regulating calcium transport and partitioning to edible organs such as seeds. To investigate this pote...

  6. A finite element analysis of the seeding process for crystal growth by the Horizontal Bridgeman method. [SOLID6

    SciTech Connect

    Smidebush, M.

    1985-09-01

    A Front Tracking finite element code was used to study movements of the solid-liquid interface which occur during the seeding process of semiconductor crystal growth. The analysis focused on improving control of the interface through use of seed crystal ''blankets.'' Thermal properties of the blanket materials ranged from isotropic to strongly anisotropic. Results showed that a seed blanket can be effective in control of both the interface position and shape during the seeding process.

  7. Characterization of Semi-Insulating CdTe Crystals Grown by Horizontal Seeded Physical Vapor Transport

    NASA Technical Reports Server (NTRS)

    Chattopadhyay, K.; Feth, S.; Chen, H.; Burger, A.; Su, Ching-Hua

    1998-01-01

    CdTe crystals were grown by horizontal seeded physical vapor transport technique in uncoated and boron nitride coated fused silica ampoules with the source materials near the congruent sublimation condition. The grown crystals were characterized by current-voltage measurements, low temperature photoluminescence spectroscopy, near IR transmission optical microscopy, spark source mass spectroscopy and chemical etching. The measured resistivities of the crystals were in the high-10(exp 8) ohm-cm range. Although the crystal grown in the boron nitride coating was contaminated with boron from the photoluminescence measurements, the coating yielded a single crystal with no inclusions or precipitates.

  8. Large single domain 123 material produced by seeding with single crystal rare earth barium copper oxide single crystals

    DOEpatents

    Todt, V.; Miller, D.J.; Shi, D.; Sengupta, S.

    1998-07-07

    A method of fabricating bulk YBa{sub 2}Cu{sub 3}O{sub x} where compressed powder oxides and/or carbonates of Y and Ba and Cu present in mole ratios to form YBa{sub 2}Cu{sub 3}O{sub x} are heated in the presence of a Nd{sub 1+x}Ba{sub 2{minus}x}Cu{sub 3}O{sub y} seed crystal to a temperature sufficient to form a liquid phase in the YBa{sub 2}Cu{sub 3}O{sub x} while maintaining the seed crystal solid. The materials are slowly cooled to provide a YBa{sub 2}Cu{sub 3}O{sub x} material having a predetermined number of domains between 1 and 5. Crack-free single domain materials can be formed using either plate shaped seed crystals or cube shaped seed crystals with a pedestal of preferential orientation material. 7 figs.

  9. Seeding for sirtuins: microseed matrix seeding to obtain crystals of human Sirt3 and Sirt2 suitable for soaking.

    PubMed

    Rumpf, Tobias; Gerhardt, Stefan; Einsle, Oliver; Jung, Manfred

    2015-12-01

    Sirtuins constitute a family of NAD(+)-dependent enzymes that catalyse the cleavage of various acyl groups from the ?-amino group of lysines. They regulate a series of cellular processes and their misregulation has been implicated in various diseases, making sirtuins attractive drug targets. To date, only a few sirtuin modulators have been reported that are suitable for cellular research and their development has been hampered by a lack of structural information. In this work, microseed matrix seeding (MMS) was used to obtain crystals of human Sirt3 in its apo form and of human Sirt2 in complex with ADP ribose (ADPR). Crystal formation using MMS was predictable, less error-prone and yielded a higher number of crystals per drop than using conventional crystallization screening methods. The crystals were used to solve the crystal structures of apo Sirt3 and of Sirt2 in complex with ADPR at an improved resolution, as well as the crystal structures of Sirt2 in complex with ADPR and the indoles EX527 and CHIC35. These Sirt2-ADPR-indole complexes unexpectedly contain two indole molecules and provide novel insights into selective Sirt2 inhibition. The MMS approach for Sirt2 and Sirt3 may be used as the basis for structure-based optimization of Sirt2/3 inhibitors in the future. PMID:26625292

  10. Seeding for sirtuins: microseed matrix seeding to obtain crystals of human Sirt3 and Sirt2 suitable for soaking

    PubMed Central

    Rumpf, Tobias; Gerhardt, Stefan; Einsle, Oliver; Jung, Manfred

    2015-01-01

    Sirtuins constitute a family of NAD+-dependent enzymes that catalyse the cleavage of various acyl groups from the ∊-amino group of lysines. They regulate a series of cellular processes and their misregulation has been implicated in various diseases, making sirtuins attractive drug targets. To date, only a few sirtuin modulators have been reported that are suitable for cellular research and their development has been hampered by a lack of structural information. In this work, microseed matrix seeding (MMS) was used to obtain crystals of human Sirt3 in its apo form and of human Sirt2 in complex with ADP ribose (ADPR). Crystal formation using MMS was predictable, less error-prone and yielded a higher number of crystals per drop than using conventional crystallization screening methods. The crystals were used to solve the crystal structures of apo Sirt3 and of Sirt2 in complex with ADPR at an improved resolution, as well as the crystal structures of Sirt2 in complex with ADPR and the indoles EX527 and CHIC35. These Sirt2–ADPR–indole complexes unexpectedly contain two indole molecules and provide novel insights into selective Sirt2 inhibition. The MMS approach for Sirt2 and Sirt3 may be used as the basis for structure-based optimization of Sirt2/3 inhibitors in the future. PMID:26625292

  11. Purification, crystallization and initial crystallographic characterization of the Ginkgo biloba 11S seed globulin ginnacin

    SciTech Connect

    Jin, Tengchuan; Chen, Yu-Wei; Howard, Andrew; Zhang, Yu-Zhu

    2008-07-01

    The crystallization of ginnacin, the 11S seed storage protein from G. biloba, is reported. Ginkgo biloba, a well known living fossil native to China, is grown worldwide as an ornamental shade plant. Medicinal and nutritional uses of G. biloba in Asia have a long history. However, ginkgo seed proteins have not been well studied at the biochemical and molecular level. In this study, the G. biloba 11S seed storage protein ginnacin was purified by sequential anion-exchange and gel-filtration chromatography. A crystallization screen was performed and well diffracting single crystals were obtained by the vapor-diffusion method. A molecular-replacement structural solution has been obtained. There are six protomers in an asymmetric unit. Structure refinement is currently in progress.

  12. Why calcite can be stronger than quartz

    NASA Astrophysics Data System (ADS)

    Mancktelow, N. S.; Pennacchioni, G.

    2009-04-01

    Calcite and quartz are two of the most common minerals in the continental crust and it is therefore not surprising that these minerals have been extensively studied since the very beginning of laboratory rock mechanics experiments. Extending such laboratory data to geological deformation rates around 10-14 s-1 requires an extrapolation of more than 7 orders of magnitude, with correspondingly large uncertainties. Extrapolation is based on the assumption that flow parameters are constant with changing conditions and that parameters not included in the flow law have a negligible influence on the creep properties. The validity of this extrapolation can only be tested, at least semi-quantitatively, by comparison with naturally deformed rocks. Observations generally indicate that quartz is significantly stronger than calcite in natural rocks, with quartz forming porphyroclasts in calcite marble mylonites, or with quartzite layers being folded or boudinaged within a weaker calcite marble matrix. However, in the Neves area (Tauern Window, Eastern Alps), shearing of Alpine coarse grained quartz-calcite veins under hydrous amphibolite facies conditions (ca. 550? C) produced quartz mylonites containing asymmetric cm-scale single crystal calcite porphyroclasts. Under these conditions, coarse calcite is clearly stronger than the surrounding polycrystalline, dynamically recrystallized, quartz matrix. The important parameter controlling this difference in observed natural behaviour is the grain size of the calcite. Although there is considerable variation, uncertainty and even contradiction in the published experimental results, we show that extrapolation of laboratory creep data on calcite single crystals and coarse marbles, together with the corresponding data for wet quartzites, is indeed consistent with these natural observations. Extrapolation indicates an inversion in the relative strength of coarse calcite and quartz at a strain rate around 10-11 s-1, corresponding to a differential flow stress of ca. 50 MPa. At lower strain rates and stresses, wet quartz should be weaker than coarse calcite crystals. Field evidence (flow of quartz-rich layers even for orientations with very low resolved shear stress) and the preserved microstructure (lack of recrystallized or bulged twins in the calcite porphyroclasts) in the Neves area are also consistent with flow stresses of less than ca. 50 MPa. These low values during deformation under water-rich amphibolite facies conditions are in marked contrast to the much higher differential stresses reported for the flow (and fracture) of quartz-rich rocks under dry conditions in the middle to lower crust.

  13. 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

    USGS Publications Warehouse

    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.

  14. Crystal structure control in Au-free self-seeded InSb wire growth.

    PubMed

    Mandl, Bernhard; Dick, Kimberly A; Kriegner, Dominik; Keplinger, Mario; Bauer, Gnther; Stangl, Julian; Deppert, Knut

    2011-04-01

    In this work we demonstrate experimentally the dependence of InSb crystal structure on the ratio of Sb to In atoms at the growth front. Epitaxial InSb wires are grown by a self-seeded particle assisted growth technique on several different III-V substrates. Detailed investigations of growth parameters and post-growth energy dispersive x-ray spectroscopy indicate that the seed particles initially consist of In and incorporate up to 20at.% Sb during growth. By applying this technique we demonstrate the formation of zinc-blende, 4H and wurtzite structure in the InSb wires (identified by transmission electron microscopy and synchrotron x-ray diffraction), and correlate this sequential change in crystal structure to the increasing Sb/In ratio at the particle-wire interface. The low ionicity of InSb and the large diameter of the wire structures studied in this work are entirely outside the parameters for which polytype formation is predicted by current models of particle seeded wire growth, suggesting that the V/III ratio at the interface determines crystal structure in a manner well beyond current understanding. These results therefore provide important insight into the relationship between the particle composition and the crystal structure, and demonstrate the potential to selectively tune the crystal structure in other III-V compound materials as well. PMID:21346304

  15. Growth of GaN:Mg crystals by high nitrogen pressure solution method in multi-feed-seed configuration

    NASA Astrophysics Data System (ADS)

    Grzegory, I.; Boćkowski, M.; łucznik, B.; Weyher, J.; Litwin-Staszewska, E.; Konczewicz, L.; Sadovyi, B.; Nowakowski, P.; Porowski, S.

    2012-07-01

    Crystallization of GaN by High Nitrogen Pressure Solution method in multi-feed-seed (MFS) configuration without intentional doping [1] results in: (1) Growth of strongly n-type crystals with free electron concentration increasing with growth temperature in ranges of 2-6×1019 cm-3 and 1350-1430 °C, (2) stable growth on Ga-polar surface and unstable growth on N-polar surface, crystals slightly brown, (3) improvement of (0001) crystallographic planes curvature (flattening) with respect to bowing of these planes in the seed crystals. The addition of magnesium into the growth solution causes strong compensation of free electrons in the crystals. Therefore, highly resistive GaN crystals can be grown. In this work, the crystallization of Mg doped GaN on flat ∼1 in. seeds (substrates) grown by HVPE in MFS configuration has been studied. It is shown that: (1) Highly resistive GaN:Mg crystals with resistivity higher than 107 Ω cm were grown, (2) the growth is stable on N-polar surfaces of the seeds whereas it is unstable on the Ga-polar surfaces, which is opposite to the HNPS growth of the n-type crystals. The GaN:Mg crystals are fully transparent with no visible color, (3) shape of (0001) crystallographic planes improves (flattens) with respect to bowing of these planes in the seed crystals (HVPE substrates).

  16. In-situ Ar-Ar white mica ages reveal differences in mica crystallization behaviour in quartz-rich and calcite-rich rocks of the same shear zone

    NASA Astrophysics Data System (ADS)

    Cossette, lise; Schneider, David; Warren, Clare; Grasemann, Bernhard

    2013-04-01

    Conventional Ar-Ar dating of tectonites can result in equivocal ages due to mixed mineral populations, excess 40Ar (decoupled from its parent 40K), or partial resetting of the K-Ar systematics. In-situ Ar-Ar dating was performed on white micas from footwall marbles and schists of the Western Cycladic Detachment System (WCDS) of the Aegean. These rocks are part of the Cycladic Blueschist Unit, which experienced HP conditions during the Eocene and strong extension during the Miocene. The rocks contain undeformed, kinked, and neocrystallized micas with the mica phases recording higher strain (elongated grains and mica-fish structures) in quartz-dominated rocks compared to the calcite-dominated assemblages. In both quartzitic and calcitic rocks, deformed white micas are chemically zoned. Two chemical populations were identified: (1) a high component of Al-celadonite in undeformed portions of grains that likely crystallized during high pressure metamorphism; (2) enrichment in muscovite in deformed portions of grains as a result of Tschermak substitution that took place during deformation-induced neocrystallization under shallow crustal conditions. Neocrystallization occurs preferentially in zones of localized deformation and in zones of enhanced fluid availability. The latter is supported by stable isotope (O, C, H) analyses of calcite, dolomite and white micas that suggest a moderate fluid-rock interaction resulting in a coupled depletion of ?18O vs ?13C and ?18O vs ?D. Recrystallized quartz exhibits planar indentation structures, also consistent with fluid-assisted deformation. Completely neocrystallized grains, in quartzitic rocks from Kea Island at the center of the WCDS yield Ar-Ar deformation ages of c. 18-21 Ma, which are interpreted as dating the timing of ductile extension along the detachment system. Undeformed (unkinked, prismatic) portions of white micas in calcitic rocks from Serifos Island at the southern end of the WCDS yield Ar-Ar ages of c. 40-45 Ma, whereas deformed (kinked or strained) portions of the same grains yield younger ages of c. 31-36 Ma. Calcitic rocks are intrinsically less permeable than quartzitic rocks, thus are less affected by fluid-induced recrystallization. Moreover, in calcite-muscovite aggregates, strain is accommodated in calcite (by dislocation creep) whereas in quartz-muscovite aggregates, strain is accommodated in mica (as mica-fish structures). Hence, ductily deformed and completely neocrystallized micas occur more often in quartzitic rocks, whereas calcitic rocks contain micas that are only partially neocrystallized due to a lack of deformation and fluid infiltration. Consequently, consistent with our empirical results, the minimum age of ductile deformation is more likely to be preserved in quartzitic rocks, such as the c. 18-21 Ma obtained on Kea. Similarly, inherited or partially reset ages are likely to be found in calcitic rocks, such as the c. 31-36 Ma from Serifos.

  17. Top-seeded solution growth of CLBO crystals

    NASA Astrophysics Data System (ADS)

    Pylneva, Ninel A.; Kononova, Nadegda G.; Yurkin, Alexander M.; Kokh, Alexandr E.; Bazarova, Gibzema G.; Danilov, Victor I.; Lisova, Irina A.; Tsirkina, Natalia L.

    1999-05-01

    CsLiB6O10 (CLBO) is a highly promising nonlinear optical material. However, its application is limited due to the difficulties in producing optically uniform CLBO crystals. High viscosity of Cs2O-Li2O-B2O3 melt retards both natural and forced convection in the melt. With the goal to improve the heat and mass transfer in the melt, the study of crystallization in the Cs2O-Li2O- B2O3-MoO3 system was carried out. The CLBO crystals 60 X 40 X 20 mm in size grown using LiCsMoO4 as a solvent were found to be free of cracks, bubbles, and inclusions. Nonlinear optical parameters and physical properties of those crystals turned out to be similar to those reported before. Mohs' hardness is 5.5, transparency window ranges from 0.18 to 2.7 micrometers , nonlinear coefficient is 1 pm/V, angular and spectral bandwidth of synchronism are 0.5 mrad-m and 0.1 nm-cm. The walk-off angle is 2 degree(s) at 0.53 micrometers . The nonlinear optical elements for the 4th harmonic of Nd:YAG laser were fabricated and tested.

  18. Diffusion of Ca and Mg in Calcite

    SciTech Connect

    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.

  19. Optical, structural, thermal and dielectric spectroscopy characterizations of seeded melt grown 2-hydroxy biphenyl single crystal.

    PubMed

    Sadhasivam, S; Rajesh, Narayana Perumal

    2014-09-15

    Organic single crystal of 2-hydroxy biphenyl (2-HB) was grown by top seeded melt growth method. Scanning electron microscopy studies has been carried out on the surface of the grown crystals to investigate the nature of growth and defects. The crystalline perfection and lattice parameters of 2-HB has been determined by single crystal XRD analysis and it belongs to orthorhombic crystal system with space group Fdd2. The functional groups and molecular associations were confirmed by FT-IR. The optical characteristics such as cut-off and transmittance were carried out using UV-Vis-NIR spectra. Absence of absorption in the region between 320 and 1100 nm makes the grown crystal desirable to optical applications. Thermal stability of grown crystals was characterized by thermogravimetric (TGA), differential thermal analysis (DTA) and differential scanning calorimetric (DSC) analyses. Broadband dielectric studies reveals that dielectric constant of grown crystal is low. The resistivity of grown crystal was studied by impedance analysis. The second harmonic generation intensity of 3.8 mJ was studied. The grown crystal belongs to soft material studied by hardness test. PMID:24792201

  20. Optical, structural, thermal and dielectric spectroscopy characterizations of seeded melt grown 2-hydroxy biphenyl single crystal

    NASA Astrophysics Data System (ADS)

    Sadhasivam, S.; Rajesh, Narayana Perumal

    2014-09-01

    Organic single crystal of 2-hydroxy biphenyl (2-HB) was grown by top seeded melt growth method. Scanning electron microscopy studies has been carried out on the surface of the grown crystals to investigate the nature of growth and defects. The crystalline perfection and lattice parameters of 2-HB has been determined by single crystal XRD analysis and it belongs to orthorhombic crystal system with space group Fdd2. The functional groups and molecular associations were confirmed by FT-IR. The optical characteristics such as cut-off and transmittance were carried out using UV-Vis-NIR spectra. Absence of absorption in the region between 320 and 1100 nm makes the grown crystal desirable to optical applications. Thermal stability of grown crystals was characterized by thermogravimetric (TGA), differential thermal analysis (DTA) and differential scanning calorimetric (DSC) analyses. Broadband dielectric studies reveals that dielectric constant of grown crystal is low. The resistivity of grown crystal was studied by impedance analysis. The second harmonic generation intensity of 3.8 mJ was studied. The grown crystal belongs to soft material studied by hardness test.

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

    PubMed

    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. PMID:24291472

  2. Seeded Physical Vapor Transport of Cadmium-Zinc Telluride Crystals: Growth and Characterization

    NASA Technical Reports Server (NTRS)

    Palosz, W.; George, M. A.; Collins, E. E.; Chen, K.-T.; Zhang, Y.; Burger, A.

    1997-01-01

    Crystals of Cd(1-x)Zn(x)Te with x = 0.2 and 40 g in weight were grown on monocrystalline cadmium-zinc telluride seeds by closed-ampoule physical vapor transport with or without excess (Cd + Zn) in the vapor phase. Two post-growth cool-down rates were used. The crystals were characterized using low temperature photoluminescence, atomic force microscopy, chemical etching, X-ray diffraction and electrical measurements. No formation of a second, ZnTe-rich phase was observed.

  3. Novel Fabrication Method for Transparent Conducting Oxide Films Utilizing Solid-Phase Crystallized Seed Layers

    NASA Astrophysics Data System (ADS)

    Itagaki, Naho; Kuwahara, Kazunari; Nakahara, Kenta

    2011-12-01

    High quality ZnO:Al (AZO) films have been obtained by our novel fabrication method utilizing solid-phase crystallized (SPC) seed layers. The crystal grain size of AZO films with seed layers is 5 times larger than that of conventional films, which is due to the low nuclei density of seed layers. As a result, the resistivity of AZO films of 18 nm in total film thickness is drastically reduced from 4010-4 ? cm for the conventional films to 510-4 ? cm for our films. No differences in transparency hve been observed between AZO films with and without seed layers and their optical transmittance is higher than 80% in a wide wavelength range of 400-2500 nm. These results reveal that our method is very promising for fabrication of transparent conducting oxide films. Our method opens up a new avenue for oxide fabrications of nm thick films with excellent crystallinity, because it can be easily extended to other oxides whose amorphous phase is difficult to obtain.

  4. Multi feed seed (MFS) high pressure crystallization of 1-2 in GaN

    NASA Astrophysics Data System (ADS)

    Bockowski, M.; Grzegory, I.; Lucznik, B.; Sochacki, T.; Nowak, G.; Sadovyi, B.; Strak, P.; Kamler, G.; Litwin-Staszewska, E.; Porowski, S.

    2012-07-01

    The growth and physical properties of GaN crystallized in a multi feed-seed (MFS) configuration by High Nitrogen Pressure Solution (HNPS) growth method are presented in detail. The conversion of free standing HVPE-GaN crystals to free standing HNPS-GaN is the basis of the MFS configuration. The influence of the experimental conditions (i.e. growth temperature, temperature gradient, etc.), the c-plane bowing of the initial substrate, the electrical properties of HNPS-GaN, and the rate and mode of growth from solution are analyzed. We show that the HNPS-GaN crystals have better structural quality than their HVPE-GaN seeds. The defect density decreases with increasing growth temperature, reaching 5×105 cm-2 for crystals grown at 1420 °C or higher. In contrast, the free carrier concentration in HNPS-GaN increases with increasing growth temperature, reaching 7×1019 cm-3 for samples crystallized at 1440 °C. Thus the possibility to obtain good quality plasmonic GaN substrates for laser diodes can be realized.

  5. Crystallization and initial crystallographic characterization of a vicilin-type seed storage protein from Pinus koraiensis

    SciTech Connect

    Jin, Tengchuan; Fu, Tong-Jen; Kothary, Mahendra H.; Howard, Andrew; Zhang, Yu-Zhu

    2007-12-01

    In this study, the Korean pine (Pinus koraiensis) vicilin-type 7S seed storage protein was isolated from defatted pine-nut extract and purified by sequential gel-filtration and anion-exchange chromatography. Well diffracting single crystals were obtained by the vapour-diffusion method in hanging drops. The cupin superfamily of proteins includes the 7S and 11S seed storage proteins. Many members of this family of proteins are known allergens. In this study, the Korean pine (Pinus koraiensis) vicilin-type 7S seed storage protein was isolated from defatted pine-nut extract and purified by sequential gel-filtration and anion-exchange chromatography. Well diffracting single crystals were obtained by the vapor-diffusion method in hanging drops. The crystals belong to the primitive cubic space group P2{sub 1}3, with unit-cell parameters a = b = c = 148.174 . Two vicilin molecules were present in the asymmetric unit and the Matthews coefficient was determined to be 2.90 {sup 3} Da{sup ?1}, with a corresponding solvent content of ?58%. A molecular-replacement structural solution has been obtained using the program Phaser. Refinement of the structure is currently under way.

  6. Seed crystals with improved properties for melt processing superconductors for practical applications

    DOEpatents

    Veal, B.W.; Paulikas, A.; Balachandran, U.; Zhong, W.

    1997-03-18

    A method of fabricating bulk superconducting material is disclosed including RBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} comprising heating compressed powder oxides and/or carbonates of R and Ba and Cu present in mole ratios to form RBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} in physical contact with an oxide single crystal seed to a temperature sufficient to form a liquid phase in the RBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} while maintaining the single crystal seed solid to grow the superconducting material and thereafter cooling to provide a material including RBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}}. R is a rare earth or Y or La and the single crystal seed has a lattice mismatch with RBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} of less than about 2% at the growth temperature. The starting material may be such that the final product contains a minor amount of R{sub 2}BaCuO{sub 5}.

  7. Seed crystals with improved properties for melt processing superconductors for practical applications

    DOEpatents

    Veal, Boyd W. (Downers Grove, IL); Paulikas, Arvydas (Downers Grove, IL); Balachandran, Uthamalingam (Hinsdale, IL); Zhong, Wei (Chicago, IL)

    1997-01-01

    A method of fabricating bulk superconducting material including RBa.sub.2 Cu.sub.3 O.sub.7-.delta. comprising heating compressed powder oxides and/or carbonates of R and Ba and Cu present in mole ratios to form RBa.sub.2 Cu.sub.3 O.sub.7-.delta. in physical contact with an oxide single crystal seed to a temperature sufficient to form a liquid phase in the RBa.sub.2 Cu.sub.3 O.sub.7-.delta. while maintaining the single crystal seed solid to grow the superconducting material and thereafter cooling to provide a material including RBa.sub.2 Cu.sub.3 O.sub.7-.delta.. R is a rare earth or Y or La and the single crystal seed has a lattice mismatch with RBa.sub.2 Cu.sub.3 O.sub.7-.delta. of less than about 2% at the growth temperature. The starting material may be such that the final product contains a minor amount of R.sub.2 BaCuO.sub.5.

  8. Catalytic biomineralization of fluorescent calcite by the thermophilic bacterium Geobacillus thermoglucosidasius.

    PubMed

    Yoshida, Naoto; Higashimura, Eiji; Saeki, Yuichi

    2010-11-01

    The thermophilic Geobacillus bacterium catalyzed the formation of 100-?m hexagonal crystals at 60C in a hydrogel containing sodium acetate, calcium chloride, and magnesium sulfate. Under fluorescence microscopy, crystals fluoresced upon excitation at 365 5, 480 20, or 545 15 nm. X-ray diffraction indicated that the crystals were magnesium-calcite in calcite-type calcium carbonate. PMID:20851984

  9. Crystallization and preliminary X-ray diffraction analysis of a lectin from Canavalia maritima seeds

    SciTech Connect

    Almeida Gadelha, Carlos Alberto de; Moreno, Frederico Bruno Mendes Batista; Santi-Gadelha, Tatiane; Cajazeiras, Joo Batista; Rocha, Bruno Anderson M. da; Rustiguel, Joane Kathelen Rodrigues; Freitas, Beatriz Tupinamba; Canduri, Fernanda; Delatorre, Plnio; Azevedo, Walter Filgueira Jr de; Cavada, Benildo S.

    2005-01-01

    A lectin from C. maritima was crystallized using the vapour-diffusion method and crystals diffracted to 2.1 resolution. A molecular-replacement search found a solution with a correlation coefficient of 69.2% and an R factor of 42.5%, refinement is in progress. A lectin from Canavalia maritima seeds (ConM) was purified and submitted to crystallization experiments. The best crystals were obtained using the vapour-diffusion method at a constant temperature of 293 K and grew in 7 d. A complete structural data set was collected to 2.1 resolution using a synchrotron-radiation source. The ConM crystal belongs to the orthorhombic space group P2{sub 1}2{sub 1}2, with unit-cell parameters a = 67.15, b = 70.90, c = 97.37 . A molecular-replacement search found a solution with a correlation coefficient of 69.2% and an R factor of 42.5%. Crystallographic refinement is under way.

  10. Repulsive hydration forces between calcite surfaces and their effect on the brittle strength of calcite-bearing rocks

    NASA Astrophysics Data System (ADS)

    Ryne, Anja; Dalby, Kim N.; Hassenkam, Tue

    2015-06-01

    The long-term mechanical strength of calcite-bearing rocks is highly dependent on the presence and nature of pore fluids, and it has been suggested that the observed effects are due to changes in nanometer-scale surface forces near fracture tips and grain contacts. In this letter, we present measurements of forces between two calcite surfaces in air and water-glycol mixtures using the atomic force microscope. We show a time- and load-dependent adhesion at low water concentrations and a strong repulsion in the presence of water, which is most likely due to hydration of the strongly hydrophilic calcite surfaces. We argue that this hydration repulsion can explain the commonly observed water-induced decrease in strength in calcitic rocks and single calcite crystals. Furthermore, this relatively simple experimental setup may serve as a useful tool for analyzing surface forces in other mineral-fluid combinations.

  11. Formation of Hybrid Perovskite Tin Iodide Single Crystals by Top-Seeded Solution Growth.

    PubMed

    Dang, Yangyang; Zhou, Yian; Liu, Xiaolong; Ju, Dianxing; Xia, Shengqing; Xia, Haibing; Tao, Xutang

    2016-03-01

    Hybrid perovskites have generated a great deal of interest because of their potential in photovoltaic applications. However, the toxicity of lead means that there is interest in finding a nontoxic substitute. Bulk single crystals of both cubic CH3 NH3 SnI3 and CH(NH2 )2 SnI3 were obtained by using the top-seeded solution growth method under an ambient atmosphere. Structural refinement, band gap, thermal properties, and XPS measurements of CH3 NH3 SnI3 and CH(NH2 )2 SnI3 single crystals are also reported in detail. These results should pave the way for further applications of CH3 NH3 SnI3 and CH(NH2 )2 SnI3 . PMID:26889919

  12. Seed

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cottonseed is a second product of the cotton plant that accounts for between 15 and 25% of the crop value. The seed is extracted for oil, producing meal, hulls, and linters as co-products, or it is used whole as a protein feed ingredient for ruminant animals. The oil fraction is the most valuable ...

  13. Interaction of alcohols with the calcite surface.

    PubMed

    Bovet, N; Yang, M; Javadi, M S; Stipp, S L S

    2015-02-01

    A clearer understanding of calcite interactions with organic molecules would contribute to a range of fields including harnessing the secrets of biomineralisation where organisms produce hard parts, increasing oil production from spent reservoirs, remediating contaminated soils and drinking water aquifers and improving manufacturing methods for industrial products such as pigments, soft abrasives, building materials and optical devices. Biomineralisation by some species of blue green algae produces beautifully elaborate platelets of calcite where the individual crystals are of nanometer scale. 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 surfaces. X-ray photoelectron spectroscopy (XPS) provided binding energies and revealed the extent of surface coverage. Molecular dynamics (MD) simulations supplemented with information about molecule ordering, orientation and packing density. The results show that all alcohols studied bond 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. PMID:25533590

  14. Improving the diffraction of full-length human selenomethionyl metavinculin crystals by streak-seeding

    SciTech Connect

    Rangarajan, Erumbi S.; Izard, Tina

    2012-06-28

    Metavinculin is an alternatively spliced isoform of vinculin that has a 68-residue insert in its tail domain (1134 total residues) and is exclusively expressed in cardiac and smooth muscle tissue, where it plays important roles in myocyte adhesion complexes. Mutations in the metavinculin-specific insert are associated with dilated cardiomyopathy (DCM) in man. Crystals of a DCM-associated mutant of full-length selenomethionine-labeled metavinculin grown by hanging-drop vapor diffusion diffracted poorly and were highly sensitive to radiation, preventing the collection of a complete X-ray diffraction data set at the highest possible resolution. Streak-seeding markedly improved the stability, crystal-growth rate and diffraction quality of DCM-associated mutant metavinculin crystals, allowing complete data collection to 3.9 {angstrom} resolution. These crystals belonged to space group P4{sub 3}2{sub 1}2, with two molecules in the asymmetric unit and unit-cell parameters a = b = 170, c = 211 {angstrom}, {alpha} = {beta} = {gamma} = 90{sup o}.

  15. Crystallization and preliminary X-ray diffraction analysis of the seed lectin from Parkia platycephala.

    PubMed

    Gallego del Sol, Francisca; Ramn-Maiques, Santiago; Santos, Claudia F; Grangeiro, Thalles B; Nagano, Celso S; Farias, Creuza M S A; Cavada, Benildo S; Calvete, Juan J

    2002-01-01

    The crystallization and preliminary X-ray diffraction analysis of the seed lectin of Parkia platycephala, a Mimosoideae, regarded as the most primitive group of the Leguminosae plants, are reported. Its amino-acid sequence consists of three tandemly arranged jacalin-related beta-prism domains, which is a novel fold for a leguminous lectin. Furthermore, no other lectin structure with this arrangement of domains has been described. P2(1)2(1)2(1) crystals (unit-cell parameters a = 63.6, b = 68.5, c = 208.5 A), which diffract to a maximum resolution of 2.2 A, were obtained in hanging drops at pH 8 and 293 K by the vapor-diffusion method using 10% 2-propanol and 20% polyethylene glycol 4000 as precipitants. The asymmetric unit contains two lectin molecules and has a solvent content of 46%. Only a single beta-prism domain could be located by molecular replacement using the structure of the Helianthus tuberosus lectin (PDB code 1c3k) as the search model. Isomorphous heavy-atom derivatives are currently being produced to solve the complete structure of the P. platycephala seed lectin. PMID:11752802

  16. Growth of nanofibrous barium carbonate on calcium carbonate seeds

    NASA Astrophysics Data System (ADS)

    Homeijer, Sara J.; Olszta, Matthew J.; Barrett, Richard A.; Gower, Laurie B.

    2008-05-01

    Fibrous barium carbonate (BaCO 3/witherite) crystals 50-100 nm in diameter and several microns in length were grown on calcium carbonate (CaCO 3) seeds at temperatures as low as 4 °C. The BaCO 3 fibers were deposited onto calcite rhombs or CaCO 3 films using the polymer-induced liquid-precursor (PILP) process, which was induced with the sodium salt of polyacrylic acid (PAA). The structure and morphology of the resultant fibers were investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), and polarized light microscopy (PLM). Fibers were successfully grown on calcite seeds of various morphologies, with a range of barium concentrations, and PAA molecular weight and concentration. Two categories of fibers were grown: straight and twisted. Both types of fibers displayed single-crystalline SAED diffraction patterns, but after examining high-resolution TEM lattice images, it was revealed that the fibers were in fact made up of nanocrystalline domains. We postulate that these nanocrystalline domains are well aligned due to a singular nucleation event (i.e., each fiber propagates from a single nucleation event on the seed crystal) with the nanocrystalline domains resulting from stresses caused by dehydration during crystallization of the highly hydrated precursor phase. These BaCO 3 fibers grown on calcite substrates further illustrate the robustness and non-specificity of the PILP process.

  17. Magnetization behavior of RE123 bulk magnets bearing twin seed-crystals in pulsed field magnetization processes

    NASA Astrophysics Data System (ADS)

    Oka, T.; Miyazaki, T.; Ogawa, J.; Fukui, S.; Sato, T.; Yokoyama, K.; Langer, M.

    2016-02-01

    Melt-textured Y-Ba-Cu-O high temperature superconducting bulk magnets were fabricated by the cold seeding method with using single or twin-seed crystals composed of Nd-Ba-Cu-O thin films on MgO substrates. The behavior of the magnetic flux penetration into anisotropic-grown bulk magnets thus fabricated was precisely evaluated during and after the pulsed field magnetization operated at 35 K. These seed crystals were put on the top surfaces of the precursors to grow large grains during the melt-processes. Although we know the magnetic flux motion is restricted by the enhanced pinning effect in temperature ranges lower than 77 K, we observed that flux invasion occurred at applied fields of 3.3 T when the twin seeds were used. This is definitely lower than those of 3.7 T when the single-seeds were employed. This means that the magnetic fluxes are capable of invading into twin-seeded bulk magnets more easily than single-seeded ones. The twin seeds form the different grain growth regions, the narrow-GSR (growth sector region) and wide-GSR, according to the different grain growth directions which are parallel and normal to the rows of seed crystals, respectively. The invading flux measurements revealed that the magnetic flux invades the sample from the wide-GSR prior to the narrow-GSR. It suggests that such anisotropic grain growth leads to different distributions of pinning centers, variations of J c values, and the formation of preferential paths for the invading magnetic fluxes. Using lower applied fields definitely contributed to lowering the heat generation during the PFM process, which, in turn, led to enhanced trapped magnetic fluxes.

  18. Combining site-specific mutagenesis and seeding as a strategy to crystallize ‘difficult’ proteins: the case of Staphylococcus aureus thioredoxin

    SciTech Connect

    Roos, Goedele; Brosens, Elke; Wahni, Khadija; Desmyter, Aline; Spinelli, Silvia; Wyns, Lode; Messens, Joris; Loris, Remy

    2006-12-01

    S. aureus thioredoxin was crystallized using a combination of seeding and site-specific mutagenesis. The P31T mutant of Staphylococcus aureus thioredoxin crystallizes spontaneously in space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 41.7, b = 49.5, c = 55.6 Å. The crystals diffract to 2.2 Å resolution. Isomorphous crystals of wild-type thioredoxin as well as of other point mutants only grow when seeded with the P31T mutant. These results suggest seeding as a valuable tool complementing surface engineering for proteins that are hard to crystallize.

  19. Extracellular matrix protein in calcified endoskeleton: a potential additive for crystal growth and design

    NASA Astrophysics Data System (ADS)

    Azizur Rahman, M.; Fujimura, Hiroyuki; Shinjo, Ryuichi; Oomori, Tamotsu

    2011-06-01

    In this study, we demonstrate a key function of extracellular matrix proteins (ECMPs) on seed crystals, which are isolated from calcified endoskeletons of soft coral and contain only CaCO 3 without any living cells. This is the first report that an ECMP protein extracted from a marine organism could potentially influence in modifying the surface of a substrate for designing materials via crystallization. We previously studied with the ECMPs from a different type of soft coral ( Sinularia polydactyla) without introducing any seed crystals in the process , which showed different results. Thus, crystallization on the seed in the presence of ECMPs of present species is an important first step toward linking function to individual proteins from soft coral. For understanding this interesting phenomenon, in vitro crystallization was initiated in a supersaturated solution on seed particles of calcite (1 0 4) with and without ECMPs. No change in the crystal growth shape occurred without ECMPs present during the crystallization process. However, with ECMPs, the morphology and phase of the crystals in the crystallization process changed dramatically. Upon completion of crystallization with ECMPs, an attractive crystal morphology was found. Scanning electron microscopy (SEM) was utilized to observe the crystal morphologies on the seeds surface. The mineral phases of crystals nucleated by ECMPs on the seeds surface were examined by Raman spectroscopy. Although 50 mM Mg 2+ is influential in making aragonite in the crystallization process, the ECMPs significantly made calcite crystals even when 50 mM Mg 2+ was present in the process. Crystallization with the ECMP additive seems to be a technically attractive strategy to generate assembled micro crystals that could be used in crystals growth and design in the Pharmaceutical and biotechnology industries.

  20. Purification, crystallization and preliminary X-ray characterization of a haemagglutinin from the seeds of Jatropha curcas

    PubMed Central

    Nair, Divya N.; Suresh, C. G.; Singh, Desh Deepak

    2011-01-01

    The plant Jatropha curcas (Euphorbiaceae) is an important source of biofuel from the inedible oil present in its toxic seeds. The toxicity arises from the presence of curcin, a ribosome-inactivating protein showing haemagglutination activity. In this communication, the purification, crystallization and preliminary X-ray characterization are reported of a small protein isolated from J. curcas seeds with a molecular mass of ∼10 kDa that agglutinates rabbit erythrocytes. The protein was crystallized using the hanging-drop vapour-diffusion method and also by the microbatch method in 72-well HLA plates, using PEG 8000 as the precipitant in both conditions. X-ray diffraction data collected from the rod-shaped crystals were processed in the orthorhombic space group P212121. The crystals diffracted to 2.8 Å resolution at 103 K. PMID:22139159

  1. Purification, crystallization and preliminary X-ray characterization of a haemagglutinin from the seeds of Jatropha curcas.

    PubMed

    Nair, Divya N; Suresh, C G; Singh, Desh Deepak

    2011-12-01

    The plant Jatropha curcas (Euphorbiaceae) is an important source of biofuel from the inedible oil present in its toxic seeds. The toxicity arises from the presence of curcin, a ribosome-inactivating protein showing haemagglutination activity. In this communication, the purification, crystallization and preliminary X-ray characterization are reported of a small protein isolated from J. curcas seeds with a molecular mass of ~10 kDa that agglutinates rabbit erythrocytes. The protein was crystallized using the hanging-drop vapour-diffusion method and also by the microbatch method in 72-well HLA plates, using PEG 8000 as the precipitant in both conditions. X-ray diffraction data collected from the rod-shaped crystals were processed in the orthorhombic space group P2(1)2(1)2(1). The crystals diffracted to 2.8 Å resolution at 103 K. PMID:22139159

  2. Growth of organic molecular single crystal trans-stilbene by selective self seeding from vertical Bridgman technique

    NASA Astrophysics Data System (ADS)

    Arulchakkaravarthi, A.; Jayavel, P.; Santhanaraghavan, P.; Ramasamy, P.

    2002-01-01

    Single crystal growth of organic molecular materials by melt growth is plagued by serious difficulties owing to poor thermal conductivity, non-availability of good seed etc. Of all the melt growth techniques, Bridgman technique is widely preferred because of the low cost, versatility, easy adaptability, simple instrumentation etc. In the Bridgman technique the control on the formation/birth of the first single nuclei is still an art and in this paper we have proposed a selective self seeding technique for initiating single crystal growth. Trans-stilbene crystals have been grown using vertical Bridgman technique and using a modified ampoule design. Trans-stilbene crystal grown by using conventional method and by the present method were characterized for quality assessment by DCD and time resolution measurements.

  3. Stable (H, O, C) and noble-gas (He and Ar) isotopic compositions from calcite and fluorite in the Speewah Dome, Kimberley Region, Western Australia: implications for the conditions of crystallization and evidence for the influence of crustal-mantle fluid mixing

    NASA Astrophysics Data System (ADS)

    Czuppon, Gy; Ramsay, R. R.; zgenc, I.; Demny, A.; Gwalani, L. G.; Rogers, K.; Eves, A.; Papp, L.; Palcsu, L.; Berkesi, M.; Downes, P. J.

    2014-12-01

    In this study, the C-O-isotopic data from calcite at Yungul and Wilmott (Speewah. Western-Australia) are integrated with microthermometry, H2O-, CO2-content and H-He-Ar-isotopic data from fluid inclusions in genetically related calcite and fluorite to map the origin and crystallization paths of the fluids. In addition to the hydrogen isotopic compositions of fluid inclusions in fluorite, oxygen isotopic compositions were also determined by cavity ring-down spectroscopy. The geochemical data suggest mixing of a CO2-dominated mantle fluid and a H2O-domintated crustal brine. The fluid produced by this mixing is characterized by radiogenic (crustal-like) 3He/4He ratios, crustal-like ?D values, relatively high salinity (19 - 24wt.% NaCl eq.), moderate homogenization temperatures (150 - 450 C) and mantle-like CO2/3He ratios. Moreover, the large isotopic and elemental variations found in calcite indicate that its formation was accompanied by an extensive degassing (open system) leading to a decrease in ?D and an increase in the CO2/3He values relative to the starting fluid composition. This degassing is consistent with the fluidal- and breccia-like texture of calcite observed in the field. In contrast, the fluorite which has coarse-grained banded to vughy textures formed in a passive aqueous system. Apparently the fluid that formed the fluorite has the same origin as the calcite, but the higher water content and the more radiogenic 3He/4He ratios reflect a greater involvement of crustal fluids. The historical description of the calcite-fluorite system in the Speewah area as "carbonatite" is now considered inappropriate because there is no evidence that crystallization is dominated by magmatic processes.

  4. Sulfated Macromolecules as Templates for Calcite Nucleation and Growth

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

    Mineralization of egg and seashells is controlled by an intimate association of inorganic materials with organic macromolecules. Among them, particular polyanionic sulfated macromolecules referred to as proteoglycans have been described to be involved in the calcification of these biominerals. The sulfated moieties of the proteoglycans are part of polymer chains constituted of building-blocks of disaccharide units, referred to as sulfated glycosaminoglycans (GAGs), which are covalently attached to a protein core. By using a sitting drop crystallization assay under controlled conditions of time, pH and reactants concentration, we have tested several sulfated and non-sulfated GAGs (i.e.: dermatan and keratan sulfate, hyaluronic acid and heparin), differing in their sulfonate and carboxylate degree and pattern, in their ability to modify calcium carbonate crystal morphology as observed under scanning electron microscopy. Without the addition of GAGs, regular \\{104\\} rhombohedral calcite crystals were obtained. When hyaluronic acid (HA), a non-sulfated but carboxylated GAG, was added, 20 mm long piles of unmodified calcite crystals were observed. When desulfated dermatan, which is an epimeric form of HA but shorter polymer, having their carboxylate groups in an inverted configuration, was added, isolated rhombohedral \\{104\\} calcite crystals showing rounded corners with planes oriented parallel to the c axis were observed. When dermatan sulfated was added, isolated calcite crystals exhibit a columnar morphology as a \\{hk0\\} cylinder with three \\{104\\} faces forming a cap at both ends. Heparin activity depends on the fraction added. Fast-moving heparin fraction (FM), is an undersulfated, low-molecular-weight heterogeneous polymer, while slow-moving heparin fraction (SM) is an high-molecular-weight homogeneous polymer rich in trisulfated-disaccharide units. When FM was added, isolated calcite crystals displayed rhombohedrical \\{104\\} faces but flat corners of \\{111\\} faces. The addition of the hypersulfated heparin SM induce the formation of large rosette-like aggregated calcite crystals, where the majority of the \\{104\\} faces appeared not to be lost, although aggregation is done by different kind of faces. It is concluded that, the variation of the sulfate and carboxylate content and configuration drastically changed the morphology of the calcite crystals. The production of calcite particles with defined morphologies could be interesting for the design of novel materials with desirable shape- and texture-depending properties. Granted by FONDAP 11980002.

  5. Nucleation and growth kinetics in synthesizing nanometer calcite

    NASA Astrophysics Data System (ADS)

    Lin, Rong-yi; Zhang, Jia-Yun; Zhang, Pei-xin

    2002-11-01

    The size of nanometer particles uniquely depends not only on the nucleus growth rate but also on the nucleation rate. This paper presents the effect of sodium tripolyphosphate on the microimages, synthesis reaction, nucleation and growth during the synthesizing of nanometer calcite using chemical analysis, SEM technique and Rosin-Ramuler probability statistics theory. The result showed that the calcium hydroxide carbonation reaction was inhibited by sodium tripolyphosphate adsorbed on the active growth sites. The SEM images revealed that the synthesizing of nanometer calcite was a multi-stable state process. When [Na 5P 3O 10]=0, 38.04 ?M, the tiny calcite nuclei re-dissolved and the nucleation rate was negative at the final stage. The supersaturation and the nucleation rate increased in proportion to the concentration of sodium tripolyphosphate. The presence of sodium tripolyphosphate accelerated the nucleation of calcite and inhibited the crystal growth. During the crystallization of nanoscale calcite, the fluctuation nucleation, nucleus growth and coarsening growth may take place in series for a fine particle. To a whole carbonation solution, these three steps may occur simultaneously. At the final stage of the nucleation, the calcite crystal growth was controlled by a short-range diffusion and an interface reaction. The Zener-Ham model could not correctly describe the crystal growth. At the coarsening growth stage, the Zener-Ham model could not correctly describe the crystal growth yet. Once the steady nucleus had been shaped in the solution, the crystal growth was determined by a long-range diffusion, and the growth process accorded with Zener-Ham model quite well.

  6. X-Ray Characterization of Structural Defects in Seeded and Self-Seeded ZnSe Crystal Grown by PVT in Horizontal and Vertical Configurations

    NASA Technical Reports Server (NTRS)

    Raghothamachar, B.; Dudley, M.; Su, C.-H.; Volz, H. M.; Matyi, R.; Whitaker, Ann F. (Technical Monitor)

    2001-01-01

    As part of a pre-flight ground based investigation of crystal growth of II-VI compound semiconductors, a number of ZnSe boules have been grown by physical vapor transport (PVT) at Marshall Space Flight Center. Boules were grown in both horizontal and vertical configurations and seeded and self-seeded growth techniques were employed. As-grown and/or cleaved boules were examined by a combination of synchrotron white beam x-ray topography (SWBXT) and high resolution triple axis diffraction (HRTXD) to characterized the structural defects and correlate them with the growth conditions. Horizontal grown boules tend to grow away from the ampoule wall (contactless growth) and generally exhibit large (110) facets parallel to the gravity vector. Vertical grown boules grew to the full diameter of the ampoule and exhibited no faceting. X-ray topography combined with back reflection x-ray diffraction revealed the presence of lamellar twins (180 deg type about the [111] axis) in horizontal grown boules while vertically grown boules contain a few large grains, some of which are twinned. X-ray topographs and reciprocal space maps recorded from the boules show the better crystal quality of horizontal grown boules. The relationship between crystal quality and gravity vector is investigated. Further, an attempt is made to extend the Hurle theory of twin nucleation in Czochralski grown crystals to explain the twinning mechanisms in horizontal grown boules.

  7. Crystallization and preliminary X-ray diffraction analysis of a new chitin-binding protein from Parkia platycephala seeds

    PubMed Central

    Cavada, Benildo S.; Castelln, Rolando E. R.; Vasconcelos, Georg G.; Rocha, Bruno A. M.; Bezerra, Gustavo A.; Debray, Henri; Delatorre, Plnio; Nagano, Celso S.; Toyama, Marcos; Pinto, Vicente P. T.; Moreno, Frederico B. M. B.; Canduri, Fernanda; de Azevedo, Walter F.

    2005-01-01

    A chitin-binding protein named PPL-2 was purified from Parkia platycephala seeds and crystallized. Crystals belong to the orthorhombic space group P212121, with unit-cell parameters a = 55.19, b = 59.95, c = 76.60?, and grew over several days at 293?K using the hanging-drop method. Using synchrotron radiation, a complete structural data set was collected to 1.73? resolution. The preliminary crystal structure of PPL-2, determined by molecular replacement, presents a correlation coefficient of 0.558 and an R factor of 0.439. Crystallographic refinement is in progress. PMID:16511174

  8. Crystal structure of mature 2S albumin from Moringa oleifera seeds.

    PubMed

    Ullah, Anwar; Mariutti, Ricardo Barros; Masood, Rehana; Caruso, Icaro Putinhon; Costa, Gustavo Henrique Gravatim; Millena de Freita, Cristhyane; Santos, Camila Ramos; Zanphorlin, Leticia Maria; Rossini Mutton, Márcia Justino; Murakami, Mario Tyago; Arni, Raghuvir Krishnaswamy

    2S albumins, the seed storage proteins, are the primary sources of carbon and nitrogen and are involved in plant defense. The mature form of Moringa oleifera (M. oleifera), a chitin binding protein isoform 3-1 (mMo-CBP3-1) a thermostable antifungal, antibacterial, flocculating 2S albumin is widely used for the treatment of water and is potentially interesting for the development of both antifungal drugs and transgenic crops. The crystal structure of mMo-CBP3-1 determined at 1.7 Å resolution demonstrated that it is comprised of two proteolytically processed α-helical chains, stabilized by four disulfide bridges that is stable, resistant to pH changes and has a melting temperature (TM) of approximately 98 °C. The surface arginines and the polyglutamine motif are the key structural factors for the observed flocculating, antibacterial and antifungal activities. This represents the first crystal structure of a 2S albumin and the model of the pro-protein indicates the structural changes that occur upon formation of mMo-CBP3-1 and determines the structural motif and charge distribution patterns for the diverse observed activities. PMID:26505799

  9. Physicochemical characteristics of drip waters: Influence on mineralogy and crystal morphology of recent cave carbonate precipitates

    NASA Astrophysics Data System (ADS)

    Riechelmann, Sylvia; Schröder-Ritzrau, Andrea; Wassenburg, Jasper A.; Schreuer, Jürgen; Richter, Detlev K.; Riechelmann, Dana F. C.; Terente, Mihai; Constantin, Silviu; Mangini, Augusto; Immenhauser, Adrian

    2014-11-01

    Speleothems are one of the most intensively explored continental archives for palaeoclimate variability. The parameters, however, that control speleothem petrography and its changes with time and space, specifically calcite crystal morphology and carbonate mineralogy, are still poorly understood. In order to shed light on processes and their products, precipitation experiments of recent carbonate crystals on watch glasses and glass plates were performed in seven selected caves. Drip water sites were analysed for their fluid Mg/Ca molar ratio, pH, degree of saturation for calcite and aragonite and drip rates. Corresponding precipitates were analysed with respect to their mineralogy, calcite crystal morphology and Mg/Ca molar ratio of calcite. The following results are found: High fluid Mg/Ca ratios are found only for caves situated in dolostone, thus the hostrock lithology indirectly controls the carbonate mineralogy and calcite crystal morphology of speleothems. The precipitation of aragonite in place of calcite occurred only in dolostone caves and is bound to very specific conditions. These are: high fluid Mg/Ca ratios (⩾0.5), high fluid pH (>8.2) and low fluid saturation indices for calcite (<0.8). These specific conditions are induced by slow drip rates of <0.2 ml/min as often under more arid conditions, causing the precipitation of calcite/aragonite prior to reaching the stalagmite top. Due to this, fluid chemistry is altered, which in turn leads to changes in carbonate mineralogy and geochemistry on the stalagmite top. Calcite growth is inhibited at high fluid Mg/Ca ratios and hence, aragonite precipitation is kinetically stabilised. An increase of the drip water Mg/Ca ratio leads to an increased incorporation of Mg2+ into the calcite crystal lattice and thus, to a change in calcite crystal morphology. Four distinctive changes occur with increasing Mg2+ incorporation: (i) development of new forms (steeper rhombohedra and base pinacoid) at the edges and corners of the crystal seed, (ii) crystal habit tend to elongate along [0 0 1] due to slower growth of faces with high Mg2+ densities, (iii) reconstitution of crystal faces with low Mg2+ densities, and (iv) occurrence of calcite crystals with bended faces and edges due to very high Mg2+ (Mg/Ca ratios of 0.009-0.051) incorporation. Growth rates and possibly also organic compounds, however, may also affect the morphology of calcite crystals. Based on the data shown here, the relation of Mg2+ incorporation and the resulting changes in calcite crystal morphologies as well as the conditions of aragonite precipitation are now clearly better understood. Further work should aim at linking the calcite crystal morphology of watch glass precipitates with calcite crystal fabrics in speleothems in order to exploit the petrographic archive of speleothem deposits.

  10. The application of time-dependent ice crystal trajectory and growth model for the evaluation of cloud seeding experiment using liquid carbon dioxide

    NASA Astrophysics Data System (ADS)

    Nishiyama, K.; Wakimizu, K.; Maki, T.; Suzuki, Y.; Morita, O.; Tomine, K.

    2012-12-01

    This study evaluated the results of cloud seeding experiment conducted on 17th January, 2008, in western Kyushu, Japan, using simplified time-dependent ice crystal growth and trajectory cloud model, which is characterized by 1) depositional diffusion growth process only of an ice crystal, and 2) the pursuit of the growing ice crystal based on wind field and ice crystal terminal velocity. For the estimation of the ice crystal growth and trajectory, the model specifies ice supersaturation ratio that expresses the degree of competition growth among ice crystals formed by LC seeding for existing water vapor, assuming no effect of natural ice crystals. The model is based on ice crystal growth along a- and c-axes depending on air temperature and ice supersatuation, according to Chen and Lamb (1994). The cloud seeding experiment was conducted by applying homogeneous nucleation (rapid cooling of air mass and subsequent formation of many ice crystals~1013/g LC) of Liquid Carbon (LC) dioxide seeding under typical winter-type snowfall-inducing weather situation characterized by the outbreak of cold air masses from the Siberia. The result of aircraft horizontally-penetrating seeding of LC into lower layer (-2 degree C) of supercooled convective cloud with 1km thickness above the freezing level led to the formation of an artificially-induced 'isolated' radar echo (the left figures of Fig. 1) in dominant 'no-natural radar echo region'. In other words, natural biases were eliminated by the formation of the isolated radar echo. This fact provides the shortcut for evaluating the result of cloud seeding experiment. In the next, the observed cloud seeding results were evaluated by estimating the trajectory of artificially-induced growing ice crystal. The results show that the trajectory of artificial ice crystals depends on the degree of completion growth mode. Free growth brings rapid growth of an ice crystal and, therefore, the ice crystal falls into lower layers for a short time. On the other hand, as the degree of competition is higher, ice crystal growth and falling are slower. The result (the right figure of Fig. 1) showed that the movement of observed isolated radar echo formed after LC cloud seeding is closely related to the trajectories of artificially-induced ice crystals depending on the specification of ice supersaturation. Therefore, it was found that time-dependent ice crystal growth and trajectory model is a useful tool for the evaluation of cloud seeding results regardless of its simplification and many uncertain factors. Fig.1 The left figure shows the movement of isolated radar echo formed by LC seeding. The right figure shows the comparison between observed radar echo location and estimated ice crystal location.

  11. Chemistry and petrography of calcite in the KTB pilot borehole, Bavarian Oberpfalz, Germany

    USGS Publications Warehouse

    Komor, S.C.

    1995-01-01

    The KTB pilot borehole in northeast Bavaria, Germany, penetrates 4000 m of gneiss, amphibolite, and subordinate calc-silicate, lamprophyre and metagabbro. There are three types of calcite in the drilled section: 1) metamorphic calcite in calc-silicate and marble; 2) crack-filling calcite in all lithologies; and 3) replacement calcite in altered minerals. Crack-filling and replacement calcite postdate metamorphic calcite. Multiple calcite generations in individual cracks suggest that different generations of water repeatedly flowed through the same cracks. Crack-filling mineral assemblages that include calcite originally formed at temperatures of 150-350??C. Presently, crack-filling calcite is in chemical and isotopic equilibrium with saline to brackish water in the borehole at temperatures of ???120??C. The saline to brackish water contains a significant proportion of meteoric water. Re-equilibration of crack-filling calcite to lower temperatures means that calcite chemistry tells us little about water-rock interactions in the crystal section of temperatures higher than ~120??C. -from Author

  12. Low-temperature (180 C) position-controlled lateral solid-phase crystallization of GeSn with laser-anneal seeding

    NASA Astrophysics Data System (ADS)

    Matsumura, Ryo; Chikita, Hironori; Kai, Yuki; Sadoh, Taizoh; Ikenoue, Hiroshi; Miyao, Masanobu

    2015-12-01

    To realize next-generation flexible thin-film devices, solid-phase crystallization (SPC) of amorphous germanium tin (GeSn) films on insulating substrates combined with seeds formed by laser annealing (LA) has been investigated. This technique enables the crystallization of GeSn at controlled positions at low temperature (180 C) due to the determination of the starting points of crystallization by LA seeding and Sn-induced SPC enhancement. The GeSn crystals grown by SPC from LA seeds showed abnormal lateral profiles of substitutional Sn concentration. These lateral profiles are caused by the annealing time after crystallization being a function of distance from the LA seeds. This observation of a post-annealing effect also indicates that GeSn with a substitutional Sn concentration of up to 10% possesses high thermal stability. These results will facilitate the fabrication of next-generation thin-film devices on flexible plastic substrates with low softening temperatures (250 C).

  13. Micro-mechanical model of calcium oxalate monohydrate aggregation in supersaturated solutions: Effect of crystal form and seed concentration

    NASA Astrophysics Data System (ADS)

    Pitt, K.; Mitchell, G. P.; Ray, A.; Heywood, B. R.; Hounslow, M. J.

    2012-12-01

    In this paper we report crystal growth and aggregation behaviour for calcium oxalate monohydrate (COM) in a stirred tank for two differing seed types - rounded and well defined - at various seed loadings. Initially we used our previously developed model [1] to study the growth and aggregation. In this model a dimensionless strength, termed the Mumtaz number, has been formulated, which accounts for the effects of stirring, supersaturation and particle size on the aggregation rate of COM. Subtle differences in growth and aggregation rates were observed between the two populations of crystals; the model was unable to describe this behaviour. These differences were attributed to their different surface characteristics. Growth and aggregation kinetic parameters were also seen to be highly dependent on seed loading. This is attributed to poisoning by an unknown trace impurity, the effect of which is dependent on seed loading. This has led to the development of a new model to account for both surface characteristics and the presence of a trace impurity that adsorbs onto the surface of crystals pinning growth steps. At low seeds loadings, surface coverage by the impurity is higher and so growth rates are reduced. These results are very well described by an extension of the approach of Weaver et al. [2]. We use Liew et al.'s [1] model to represent aggregation by a collision efficiency that depends on a modified Mumtaz number. This model requires the determination of a simple group of parameters that we term the 'aggregation tendency'. The relationship between aggregation tendency and growth rate constant suggests that aggregation is in fact controlled by the growth rate of some high-energy facets not expressed macroscopically. The fact that aggregation tendency increases with surface coverage of impurity further suggests that the presence of impurity gives rise to longer or more numerous linear features along which initial contact between crystals takes place. The combined growth and aggregation models are capable of describing all the experiments reported here for both seed types and over a range of seed loadings.

  14. Effects of self-seeding and crystal post-selection on the quality of Monte Carlo-integrated SFX data.

    PubMed

    Barends, Thomas; White, Thomas A; Barty, Anton; Foucar, Lutz; Messerschmidt, Marc; Alonso-Mori, Roberto; Botha, Sabine; Chapman, Henry; Doak, R Bruce; Galli, Lorenzo; Gati, Cornelius; Gutmann, Matthias; Koglin, Jason; Markvardsen, Anders; Nass, Karol; Oberthur, Dominik; Shoeman, Robert L; Schlichting, Ilme; Boutet, Sbastien

    2015-05-01

    Serial femtosecond crystallography (SFX) is an emerging method for data collection at free-electron lasers (FELs) in which single diffraction snapshots are taken from a large number of crystals. The partial intensities collected in this way are then combined in a scheme called Monte Carlo integration, which provides the full diffraction intensities. However, apart from having to perform this merging, the Monte Carlo integration must also average out all variations in crystal quality, crystal size, X-ray beam properties and other factors, necessitating data collection from thousands of crystals. Because the pulses provided by FELs running in the typical self-amplified spontaneous emission (SASE) mode of operation have very irregular, spiky spectra that vary strongly from pulse to pulse, it has been suggested that this is an important source of variation contributing to inaccuracies in the intensities, and that, by using monochromatic pulses produced through a process called self-seeding, fewer images might be needed for Monte Carlo integration to converge, resulting in more accurate data. This paper reports the results of two experiments performed at the Linac Coherent Light Source in which data collected in both SASE and self-seeded mode were compared. Importantly, no improvement attributable to the use of self-seeding was detected. In addition, other possible sources of variation that affect SFX data quality were investigated, such as crystal-to-crystal variations reflected in the unit-cell parameters; however, these factors were found to have no influence on data quality either. Possibly, there is another source of variation as yet undetected that affects SFX data quality much more than any of the factors investigated here. PMID:25931080

  15. On the complex conductivity signatures of calcite precipitation

    SciTech Connect

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

    2009-11-01

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

  16. Crystallization and preliminary X-ray studies of psophocarpin B1, a chymotrypsin inhibitor from winged bean seeds.

    PubMed

    Dattagupta, J K; Chakrabarti, C; Podder, A; Dutta, S K; Singh, M

    1990-11-20

    Psophocarpin B1 is a 20,000 Mr protein of winged bean (Psophocarpus tetragonolobus) seeds having chymotrypsin inhibitory activity. Single crystals of this protein suitable for X-ray crystallographic studies have been obtained by the vapour diffusion method using ammonium sulphate. The crystals are hexagonal, space group P6(4)22 or P6(2)22, cell dimensions a = b = 61 A, c = 210 A. They are stable to irradiation with X-rays and diffract to at least 2.6 A resolution. PMID:2254924

  17. An approach for phosphate removal with quartz sand, ceramsite, blast furnace slag and steel slag as seed crystal.

    PubMed

    Qiu, Liping; Wang, Guangwei; Zhang, Shoubin; Yang, Zhongxi; Li, Yanbo

    2012-01-01

    The phosphate removal abilities and crystallization performance of quartz sand, ceramsite, blast furnace slag and steel slag were investigated. The residual phosphate concentrations in the reaction solutions were not changed by addition of the ceramsite, quartz sand and blast furnace slag. The steel slag could provide alkalinity and Ca(2+) to the reaction solution due to its hydration activity, and performed a better phosphate removal performance than the other three. Under the conditions of Ca/P 2.0, pH 8.5 and 10 mg P/L, the phosphate crystallization occurred during 12 h. The quartz sand and ceramsite did not improve the phosphate crystallization, but steel slag was an effective seed crystal. The phosphate concentration decreased drastically after 12 h after addition of steel slag, and near complete removal was achieved after 48 h. The XRD analysis showed that the main crystallization products were hydroxyapatite (HAP) and the crystallinity increased with the reaction time. Phosphate was successfully recovered from low phosphate concentration wastewater using steel slag as seed material. PMID:22378001

  18. Cyanobacterial Calcite Precipitation - Laboratory Study on Different Spatial Scales

    NASA Astrophysics Data System (ADS)

    Obst, M.; Mavrocordatos, D.; Gasser, P.; Dittrich, M.

    2003-12-01

    Lacustrine calcite precipitation with sedimentation rates up to 1 mm per year can result in large carbonate deposits. Varved lake sediments high in calcite content are now intensively studied as high-resolution continental archives for environmental change. Especially in oligotrophic hardwater lakes, eukaryotic and prokaryotic picoplankton was found to be important in the overall process of calcite precipitation. Rates and mechanisms of bacteria-surface mediated precipitation reactions, however, remain poorly understood. For interpreting geochemical and isotopic information stored in sediments, it is essential to know the carbonate precipitation mechanisms and the governing environmental factors. Thus, laboratory experiments with picoplankton under controlled conditions were combined with electron and atomic force microscopy in order to obtain insights into the details of the calcite precipitation mechanisms of cyanobacteria. This study aimed at evaluating the potential of such laboratory studies and investigating the influence of environmental parameters as a first step. Under carefully controlled chemical and physical conditions, precipitation of calcite was induced by adding cultures of picocyanobacteria to supersaturated solutions of CaCO3 at different CaCl2/NaHCO3 ratios. The cell suspensions were purged with an artificial atmosphere at constant CO2 concentration. Abiotic solutions were used as reference systems. Chemical conditions such as pH, calcium and carbonate concentrations were continuously monitored by ion selective electrodes. The influence of supersaturation in the range of ? = 2 - 20 on biogenic precipitation was quantified at different ratios of calcium (0.7 - 48 mM) /carbonate (6 ? M - 35 ? M). In a series of bulk experiments it was possible to detect critical values of supersaturation for the onset of precipitation both with and without cells, both in the range of ? = 5 - 10. The morphology of the precipitates was analyzed by scanning electron microscopy. Both, initial crystals (<500 nm) and larger grown crystals (>10 ? m) showed rhombohedral and hexagonal-prism shapes characteristic for calcite. Ultrathin-sections ( 100nm) of the cyanobacteria cells and the attached calcite crystals were prepared by Focused Ion Beam. This technique allowed us to preserve the cell wall - crystal interface as intact as possible in order to perform Transmission Electron Microscopy (TEM) analysis of the sections. Using TEM-Electron Energy Loss Spectroscopy, carbon bonds in both calcite crystals and cyanobacteria cells were detected and identified. The carbon absorption spectra are significantly different to discriminate the organic and inorganic carbon. Thus, the absorption peaks are the fingerprints of the analyzed material and can be used to analyze the transition zone between the cell and the particle.

  19. Controlling the morphology, composition and crystal structure in gold-seeded GaAs(1-x)Sb(x) nanowires.

    PubMed

    Yuan, Xiaoming; Caroff, Philippe; Wong-Leung, Jennifer; Tan, Hark Hoe; Jagadish, Chennupati

    2015-03-21

    While III-V binary nanowires are now well controlled and their growth mechanisms reasonably well understood, growing ternary nanowires, including controlling their morphology, composition and crystal structure remains a challenge. However, understanding and control of ternary alloys is of fundamental interest and critical to enable a new class of nanowire devices. Here, we report on the progress in understanding the complex growth behaviour of gold-seeded GaAs1-xSbx nanowires grown by metalorganic vapour phase epitaxy. The competition between As and Sb atoms for incorporation into the growing crystal leads to a tunability of the Sb content over a broad range (x varies from 0.09 to 0.6), solely by changing the AsH3 flow. In contrast, changing TMSb flow is more effective in affecting the morphology and crystal structure of the nanowires. Inclined faults are found in some of these nanowires and directly related to the kinking of the nanowires and controlled by TMSb flow. Combined with the observed sharp increase of wetting angle between the Au seed and nanowire, the formation of inclined faults are attributed to the Au seed being dislodged from the growth front to wet the sidewalls of the nanowires, and are related to the surfactant role of Sb. The insights provided by this study should benefit future device applications relying on taper- and twin-free ternary antimonide III-V nanowire alloys and their heterostructures. PMID:25692266

  20. Characterization of Al2O3 coatings oxidized from Al with different proportion of seed crystals at a lower temperature

    NASA Astrophysics Data System (ADS)

    Wang, Chen; Lin, Yuebin; He, Fei; Luo, Xinyi; Tao, Jie

    2013-10-01

    Al layer with ?-Al2O3 seed crystals was prepared on the surface of 316L stainless steel (SS) by a double cathodes discharge technique, in which the mixed targets of pure Al doped with different proportions of ?-Al2O3 were used. Then, Al2O3 coatings were obtained after plasma oxidization at 580 C. The phase composition, microstructure and morphology of the coatings were studied respectively by means of glancing-angle (1) X-ray diffractometry (GAXRD) and scanning electron microscopy (SEM). Furthermore, the bonding force and corrosion resistance of the coatings were measured. The results indicated that ?-Al2O3 nucleated and grew surrounding the seed crystals as the Volmer-Weber Mode. The Al2O3 coating was compact, performing a good corrosion resistance and metallurgical bonding. The inducing effects of ?-Al2O3 with different fractions were discussed. ?-Al2O3 (5.5 wt.%) was distributed in the Al layer when the target possessing 10% ?-Al2O3 was used. After plasma oxidation, 65.54 wt.% ?-Al2O3 was obtained which was 10.34% more than that obtained by the oxidation of pure Al at the same condition. However, the inducing effects became weak with the further increment of content of ?-Al2O3 seed crystals.

  1. Human 17β-hydroxysteroid dehydrogenase-ligand complexes: crystals of different space groups with various cations and combined seeding and co-crystallization

    NASA Astrophysics Data System (ADS)

    Zhu, D.-W.; Han, Q.; Qiu, W.; Campbell, R. L.; Xie, B.-X.; Azzi, A.; Lin, S.-X.

    1999-01-01

    Human estrogenic 17β-hydroxysteroid dehydrogenase (17β-HSD1) is responsible for the synthesis of active estrogens that stimulate the proliferation of breast cancer cells. The enzyme has been crystallized using a Mg 2+/PEG (3500)/β-octyl glucoside system [Zhu et al., J. Mol. Biol. 234 (1993) 242]. The space group of these crystals is C2. Here we report that cations can affect 17β-HSD1 crystallization significantly. In the presence of Mn 2+ instead of Mg 2+, crystals have been obtained in the same space group with similar unit cell dimensions. In the presence of Li + and Na + instead of Mg 2+, the space group has been changed to P2 12 12 1. A whole data set for a crystal of 17ß-HSD1 complex with progesterone grown in the presence of Li + has been collected to 1.95 Å resolution with a synchrotron source. The cell dimensions are a=41.91 Å, b=108.21 Å, c=117.00 Å. The structure has been preliminarily determined by molecular replacement, yielding important information on crystal packing in the presence of different cations. In order to further understand the structure-function relationship of 17β-HSD1, enzyme complexes with several ligands have been crystallized. As the steroids have very low aqueous solubility, we used a combined method of seeding and co-crystallization to obtain crystals of 17β-HSD1 complexed with various ligands. This method provides ideal conditions for growing complex crystals, with ligands such as 20α-hydroxysteroid progesterone, testosterone and 17β-methyl-estradiol-NADP +. Several complex structures have been determined with reliable electronic density of the bound ligands.

  2. Biotic Control of Skeletal Growth by Scleractinian Corals in AragoniteCalcite Seas

    PubMed Central

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

    2014-01-01

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

  3. Capillary-Seeding Crystallization and Preliminary Crystallographic Analysis of a Solvent-Tolerant Elastase from Pseudomonas aeruginosa Strain K

    PubMed Central

    Ali, Mohd Shukuri Mohamad; Said, Zatty Syamimi @ Adura Mat; Raja Abd Rahman, Raja Noor Zaliha; Thean Chor, Adam Leow; Basri, Mahiran; Salleh, Abu Bakar

    2013-01-01

    Seeding is a versatile method for optimizing crystal growth. Coupling this technique with capillary counter diffusion crystallization enhances the size and diffraction quality of the crystals. In this article, crystals for organic solvent-tolerant recombinant elastase strain K were successfully produced through microseeding with capillary counter-diffusion crystallization. This technique improved the nucleation success rate with a low protein concentration (3.00 mg/mL). The crystal was grown in 1 M ammonium phosphate monobasic and 0.1 M sodium citrate tribasic dihydrate pH 5.6. The optimized crystal size was 1 0.1 0.05 mm3. Elastase strain K successfully diffracted up to 1.39 at SPring-8, Japan, using synchrotron radiation for preliminary data diffraction analysis. The space group was determined to be monoclinic space group P1211 with unit cell parameters of a = 38.99 ?, b = 90.173 and c = 40.60 . PMID:23989606

  4. Characterization of boron incorporation and speciation in calcite and aragonite from co-precipitation experiments under controlled pH, temperature and precipitation rate

    NASA Astrophysics Data System (ADS)

    Mavromatis, Vasileios; Montouillout, Valérie; Noireaux, Johanna; Gaillardet, Jérôme; Schott, Jacques

    2015-02-01

    About 20 years ago, the boron isotopic composition of marine carbonates was proposed as a proxy of ancient seawater pH. Since that time, a large body of studies has used boron isotopes in carbonates to reconstruct seawater paleo-pH and atmospheric paleo-CO2 concentration. To date, however, no systematic investigation of the physicochemical parameters that control boron incorporation in calcite and aragonite (pH, temperature, precipitation rate, etc.) has been performed. To fill this gap, we have experimentally investigated the inorganic co-precipitation of boron with calcite and aragonite at 5 and 25 °C in the presence and absence of seed crystals and over the pHNBS range 7.4 < pH < 9.5 in 0.1 or 0.2 M NaCl solutions. The boron partition coefficient, DB, between CaCO3 and the fluid is defined as: DB = {(XB/XCO3)CaCO3}/([B]/[CO32-])fluid} with Xi and [i] standing for the mole fraction and molality of the ith species in the solid and fluid, respectively. DB measured in this study are very small (DB ≤ 10-3 and ≤ 10-4 for aragonite and calcite, respectively) and exhibit a strong dependence on the solution pH and the calcium carbonate precipitation rate. High field 11B MAS NMR analyses of the precipitated carbonates show that boron in aragonite is mostly in the form of tetragonal B (≥ 85%[IV]B) but that both trigonal and tetragonal B are present in calcite. A significant amount of tetragonal boron in calcite may be in non-lattice (defect) sites, in addition to the structural site. The relative abundance of [III]B and [IV]B in calcite is independent of the parent solution pH but appears to decrease with increasing precipitation rate. The change in boron coordination during its incorporation in calcite and its distribution in, at least, two different sites strongly suggest that the mechanisms controlling B incorporation in this mineral are more complex than for aragonite. It follows that calcite-based calibrations may be less reliable than aragonite calibrations for ocean paleo-pH reconstructions.

  5. A novel role for calcite in calcium homeostasis.

    PubMed

    Anderson, S; Appanna, V D; Huang, J; Viswanatha, T

    1992-08-10

    Calcium carbonate (CaCO3) minerals are known to be deposited in a wide array of different organisms, ranging from microbes to vertebrates [(1989) On Biomineralization, Oxford University Press, New York]. Calcite, aragonite and vaterite are the major crystalline structural polymorphs of CaCO3 associated with living systems, and participate in a variety of biological functions [(1989) Biomineralization: Chemical and Biochemical Perspectives, VCH Publishers, Weinham, Germany; (1991) Advances in Inorganic Chemistry 36, 137-200]. Here we report on the ability of a soil bacterium to synthesize calcite in a calcium-stressed environment. The elaboration of this exocellular crystalline residue enables the organism to regulate its calcium content. The attainment of calcium homeostasis via the exocellular deposition of bacterial calcite with unique crystal habits is a novel biological phenomenon. PMID:1644205

  6. Time and metamorphic petrology: Calcite to aragonite experiments

    USGS Publications Warehouse

    Hacker, B.R.; Kirby, S.H.; Bohlen, S.R.

    1992-01-01

    Although the equilibrium phase relations of many mineral systems are generally well established, the rates of transformations, particularly in polycrystalline rocks, are not. The results of experiments on the calcite to aragonite transformation in polycrystalline marble are different from those for earlier experiments on powdered and single-crystal calcite. The transformation in the polycrystalline samples occurs by different mechanisms, with a different temperature dependence, and at a markedly slower rate. This work demonstrates the importance of kinetic studies on fully dense polycrystalline aggregates for understanding mineralogic phase changes in nature. Extrapolation of these results to geological time scales suggests that transformation of calcite to aragonite does not occur in the absence of volatiles at temperatures below 200??C. Kinetic hindrance is likely to extend to higher temperatures in more complex transformations.

  7. Use of seeds to control precipitation of calcium carbonate and determination of seed nature.

    PubMed

    Donnet, Marcel; Bowen, Paul; Jongen, Nathalie; Lematre, Jacques; Hofmann, Heinrich

    2005-01-01

    Understanding and controlling precipitation reactions is a major challenge for industrial crystallization. Calcium carbonate is a widely studied system: more than 3000 papers have been devoted to the subject over the past 10 years. The first step of the precipitation of calcium carbonate, from relatively concentrated solutions (0.01 mol/L), involves the formation of an initial gel phase which later transforms into calcite, vaterite, or a mixture of both phases. Our work aimed at controlling this first step. Nanosized seeds (8 nm), formed in situ, were used in order to control the often chaotic nucleation step which normally leads to poor phase selection and broad particle size distributions. Seeding has often been used to avoid spontaneous nucleation in metastable solutions for growth mechanism investigations of single-crystal calcium carbonate. Here the ability of a seeding method to control the precipitation reaction evolution even in the case of high supersaturation is demonstrated. The seeds and the presence of a polymeric additive (poly(acrylic acid)) allow the control of the precipitated polymorph and the specific surface area, while maintaining a narrow particle size distribution in the submicron range. Direct characterization methods did not succeed in identifying these nanoseeds; indirect methods using solubility calculations are used to demonstrate their existence and quantify size and number density of the nanosized seeds. PMID:15620290

  8. Fullerenol entrapment in calcite microspheres.

    PubMed

    Calvaresi, Matteo; Falini, Giuseppe; Bonacchi, Sara; Genovese, Damiano; Fermani, Simona; Montalti, Marco; Prodi, Luca; Zerbetto, Francesco

    2011-10-14

    Hybrid microspheres of calcium carbonate/fullerenol were synthesized and characterized. Their morphology depends on the concentration of the fullerenol solutions. XRD and FT-IR measurements proved that the mineral phase is consistently calcite, while fluorescence confocal microscopy indicated that fullerenol is homogenously included in the crystalline matrix. PMID:21881667

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Unusual calcite cementing of quartz grains on Chandeleur Island Beach, offshore Louisiana

    SciTech Connect

    Mitchell-Tapping, H.J.

    1983-09-01

    A very unusual calcite cement was found in some beachchips from an unconsolidated beach surface of Chandeleur Island offshore approximately 35 nmi (65 km) south of Mississippi in the Gulf of Mexico. The beachchips are irregularly shaped and are well cemented by this unusual calcite. This calcite crystal structure has not been reported previously as existing in a marine environment. A similar cement has been found in freshwater lake beachrock and in some travertine samples. The calcite crystals are elongate parallel to the c-optic axis, and are composed of bunches of crystallite blades. The crystallite blades of each crystal bunch are pointed and are more bladed than freshwater cement crystals. The intercrystallite pore space contains no fine calcite silt as was observed in the lake samples. Fresh water provided by rainfall may be held in the pore spaces and bounded to the quartz-grain surfaces by ionic attraction. Marine spray above and saline water concentrated underneath from a sandwich effect at the micropore level, allowing rapid growth and precipitation of these very unusual calcite crystals in a single-phase low-salinity fluid.

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

    PubMed

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

    2011-09-01

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called "calcite and aragonite seas." Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that -OH, secondary structures (e.g. ?-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

  12. Noncrystallographic calcite dendrites from hot-spring deposits at Lake Bogoria, Kenya

    SciTech Connect

    Jones, B.; Renaut, R.W.

    1995-01-02

    Complex calcite crystals are an integral component of precipitates that form around the orifices of the Loburu and Mawe Moto hot springs on the shores of Lake bogoria, Kenya. Two types of large (up to 4 cm long) noncrystallographic dendrites are important components of these deposits. Feather dendrites are characterized by multiple levels of branching with individual branches developed through crystal splitting and spherulitic growth. Scandulitic (from Latin meaning shingle) dendrites are formed of stacked calcite crystals and are generally more compact than feather dendrites. These developed through the incremental stacking of rectangular-shaped calcite crystals that initially grew as skeletal crystals. Feather and scandulitic dendrites precipitated from the same waters in the same springs. The difference in morphology is therefore related to microenvironments in which they grew. Feather dendrites grew in any direction in pools of free-standing water provided that they were in constant contact with the solute. Conversely, scandulitic dendrites grew on rims of dams where water flowed over the surface in concert with the pulses of spring water. Thus, each calcite crystal in these dendrites represents one episode of crystal growth. The orientation of the component crystals in scandulitic dendrites is controlled by the topography of the dam or surface, not crystallographic criteria. The noncrystallographic dendrites formed from spring waters with initial temperatures of 90--99 C. Surficial water cooling, loss of CO{sub 2}, and presence of other elements that can interfere with crystal growth contributed to the formation of these unusual crystals.

  13. Crystallization and preliminary X-ray diffraction analysis of a new chitin-binding protein from Parkia platycephala seeds

    SciTech Connect

    Cavada, Benildo S. Castelln, Rolando E. R.; Vasconcelos, Georg G.; Rocha, Bruno A. M.; Bezerra, Gustavo A.; Debray, Henri; Delatorre, Plnio; Nagano, Celso S.; Toyama, Marcos; Pinto, Vicente P. T.; Moreno, Frederico B. M. B.; Canduri, Fernanda; Azevedo, Walter F. Jr de

    2005-09-01

    Crystals of P. platycephala chintinase/lectin (PPL-2) belong to the orthorhombic space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 55.19, b = 59.95, c = 76.60 . The preliminary cystal structure of PPL-2 was solved at a resolution of 1.73 by molecular replacement, presenting a correlation coefficient of 0.558 and an R factor of 0.439. A chitin-binding protein named PPL-2 was purified from Parkia platycephala seeds and crystallized. Crystals belong to the orthorhombic space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 55.19, b = 59.95, c = 76.60 , and grew over several days at 293 K using the hanging-drop method. Using synchrotron radiation, a complete structural data set was collected to 1.73 resolution. The preliminary crystal structure of PPL-2, determined by molecular replacement, presents a correlation coefficient of 0.558 and an R factor of 0.439. Crystallographic refinement is in progress.

  14. Design of a diamond-crystal monochromator for the LCLS hard x-ray self-seeding project

    NASA Astrophysics Data System (ADS)

    Shu, D.; Shvyd'ko, Y.; Amann, J.; Emma, P.; Stoupin, S.; Quintana, J.

    2013-03-01

    As the result of collaborations between the Advanced Photon Source (APS), Argonne National Laboratory, and the Linac Coherent Light Source (LCLS) at SLAC National Accelerator Laboratory, we have designed and constructed a diamond crystal monochromator for the LCLS hard x-ray self-seeding project. The novel monochromator is ultrahigh-vacuum compatible to meet the LCLS linear accelerator vacuum environmental requirement. A special graphite holder was designed for strain-free mount of the 110-?m thin synthetic diamond crystal plate provided by Technological Institute for Super-hard and Novel Carbon Materials of Russia (TISNCM). An in-vacuum multi-axis precision positioning mechanism is designed to manipulate the thin-film diamond holder with resolutions and stabilities required by the hard x-ray self-seeding physics. Optical encoders, limit switches, and hardware stops are established in the mechanism to ensure system reliability and to meet the accelerator personal and equipment safety interlock requirements. Molybdenum shields are installed in the monochromator to protect the encoders and associated electronics from radiation damage. Mechanical specifications, designs, and preliminary test results of the diamond monochromator are presented in this paper.

  15. Nickel and manganese interaction with calcite

    SciTech Connect

    Doner, H; Zavarin, M

    1999-08-09

    Many divalent metal cations sorb to calcite surfaces and incorporate into calcite to varying degrees. Since calcite may sorb trace elements in the environment, the factors controlling metal-calcite interactions are critical to understanding element cycling. The interaction of divalent metal cations with calcite can be critical to toxic metal immobilization, nutrient cycling, interpretation of past redox conditions, tracing fluid flow, for example. Sorption of Ni and Mn on calcite surfaces was studied by Zachara et al.. At any particular pH, the sorption of Mn on calcite was greater than Ni. This was attributed in part to the similarity of divalent Mn and Ca with respect to ion size. Although direct spectroscopic evidence was not available, sorption/desorption results suggested that Mn quickly forms a surface precipitate or solid solution while Ni forms a hydrated surface complex that may incorporate into calcite much more slowly via recrystallization. Because Mn(II) ionic radius is similar to that of Ca(II) (0.80 versus 1.0{angstrom}), and because MnCO{sub 3} has a structure similar to calcite, it is likely that Mn can substitute directly for Ca in the calcite structure. The ionic radius of Ni(II) is significantly smaller (0.69{angstrom}) and Ni(OH){sub 2} precipitation is likely to be favored in most systems. For Ni, direct substitution for Ca is less likely or may require more significant calcite lattice deformation.

  16. Fabrication of a good-quality single grain YBCO sample through the control of seed crystals

    SciTech Connect

    Kim, C.J.; Hong, G.W.; Jee, Y.A.; Han, Y.H.; Han, S.C.; Sung, T.H.

    1999-09-01

    The authors investigated the growth mode of YBa{sub 2}Cu{sub 3}O{sub 7{minus}y} (Y123) grains and its effect on the levitation forces and trapped magnetic field of top-seeded melt processed YBCO samples. When a slab-like Sm-seed was used, undesirable subsidiary Y123 grains were formed, while the formation of the subsidiary Y123 grains was suppressed and a nearly single Y123 grain grew when a thick and wide seed was used. The formation of the subsidiary Y123 grains decreased the levitation forces and trapped magnetic field, due to the presence of grain boundaries with weak link characteristics.

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

    NASA Astrophysics Data System (ADS)

    Wombacher, F.; Eisenhauer, A.; Bhm, F.; Gussone, N.; Regenberg, M.; Dullo, W.-Chr.; Rggeberg, A.

    2011-10-01

    This survey of magnesium stable isotope compositions in marine biogenic aragonite and calcite includes samples from corals, sclerosponges, benthic porcelaneous and planktonic perforate foraminifera, coccolith oozes, red algae, and an echinoid and brachiopod test. The analyses were carried out using MC-ICP-MS with an external repeatability of 0.22 (2SD for ? 26Mg; n = 37), obtained from a coral reference sample (JCp-1). Magnesium isotope fractionation in calcitic corals and sclerosponges agrees with published data for calcitic speleothems with an average ? 26Mg calcite-seawater = -2.6 0.3 that appears to be weakly related to temperature. With one exception ( Vaceletia spp.), aragonitic corals and sclerosponges also display uniform Mg isotope fractionations relative to seawater with ? 26Mg biogenic aragonite-seawater = -0.9 0.2. Magnesium isotopes in high-Mg calcites from red algae, echinoids and perhaps some porcelaneous foraminifera as well as in all low-Mg calcites (perforate foraminifera, coccoliths and brachiopods) display significant biological influences. For planktonic foraminifera, the Mg isotope data is consistent with the fixation of Mg by organic material under equilibrium conditions, but appears to be inconsistent with Mg removal from vacuoles. Our preferred model, however, suggests that planktonic foraminifera synthesize biomolecules that increase the energetic barrier for Mg incorporation. In this model, the need to remove large quantities of Mg from vacuole solutions is avoided. For the high-Mg calcites from echinoids, the precipitation of amorphous calcium carbonate may be responsible for their weaker Mg isotope fractionation. Disregarding superimposed biological effects, it appears that cation light isotope enrichments in CaCO 3 principally result from a chemical kinetic isotope effect, related to the incorporation of cations at kink sites. In this model, the systematics of cation isotope fractionations in CaCO 3 relate to the activation energy required for cation incorporation, which probably reflects the dehydration of the cation and the crystal surface and bond formation at the incorporation site. This kinetic incorporation model predicts (i) no intrinsic dependence on growth rate, unless significant back reaction upon slow growth reduces the isotope fractionation towards that characteristic for equilibrium isotope partitioning (this may be observed for Ca isotopes in calcites), (ii) a small decrease of isotope fractionation with increasing temperature that may be amplified if higher temperatures promote back reaction and (iii) a sensitivity to changes in the activation barrier caused by additives such as anions or biomolecules or by the initial formation of amorphous CaCO 3.

  18. Bioremediation of Cd by microbially induced calcite precipitation.

    PubMed

    Kang, Chang-Ho; Han, Sang-Hyun; Shin, Yujin; Oh, Soo Ji; So, Jae-Seong

    2014-03-01

    Contamination by Cd is a significant environmental problem. Therefore, we examined Cd removal from an environmental perspective. Ureolysis-driven calcium carbonate precipitation has been proposed for use in geotechnical engineering for soil remediation applications. In this study, 55 calcite-forming bacterial strains were newly isolated from various environments. Biomineralization of Cd by calcite-forming bacteria was investigated in laboratory-scale experiments. A simple method was developed to determine the effectiveness of microbially induced calcite precipitation (MICP). Using this method, we determined the effectiveness of biomineralization for retarding the flow of crystal violet through a 25-mL column. When the selected bacteria were analyzed using an inductively coupled plasma optical emission spectrometer, high removal rates (99.95%) of Cd were observed following incubation for 48 h. Samples of solids that formed in the reaction vessels were examined using a scanning electron microscope. The CdCO3 compounds primarily showed a spherical shape. The results of this study demonstrate that MICP-based sequestration of soluble heavy metals via coprecipitation with calcite may be useful for toxic heavy metal bioremediation. PMID:24458656

  19. Bioremediation of Cd by microbially induced calcite precipitation.

    PubMed

    Kang, Chang-Ho; Han, Sang-Hyun; Shin, Yujin; Oh, Soo Ji; So, Jae-Seong

    2014-02-01

    Contamination by Cd is a significant environmental problem. Therefore, we examined Cd removal from an environmental perspective. Ureolysis-driven calcium carbonate precipitation has been proposed for use in geotechnical engineering for soil remediation applications. In this study, 55 calcite-forming bacterial strains were newly isolated from various environments. Biomineralization of Cd by calcite-forming bacteria was investigated in laboratory-scale experiments. A simple method was developed to determine the effectiveness of microbially induced calcite precipitation (MICP). Using this method, we determined the effectiveness of biomineralization for retarding the flow of crystal violet through a 25-mL column. When the selected bacteria were analyzed using an inductively coupled plasma optical emission spectrometer, high removal rates (99.95 %) of Cd were observed following incubation for 48 h. Samples of solids that formed in the reaction vessels were examined using a scanning electron microscope. The CdCO3 compounds primarily showed a spherical shape. The results of this study demonstrate that MICP-based sequestration of soluble heavy metals via coprecipitation with calcite may be useful for toxic heavy metal bioremediation. PMID:24293312

  20. Microstructural control of calcite via incorporation of intracrystalline organic molecules in shells

    NASA Astrophysics Data System (ADS)

    Okumura, Taiga; Suzuki, Michio; Nagasawa, Hiromichi; Kogure, Toshihiro

    2013-10-01

    It is widely accepted that organic substances regulate or influence the structure of biominerals, but its direct evidences are not plenty. Here we show that the crystallographic microstructures in biotic calcites arise from incorporated intracrystalline organic molecules (IOMs), through a comparison between biotic calcites in shells and synthetic ones with the IOMs extracted from the shells. Although the prismatic layers of a pearl oyster (Pinctada fucata) and a pen shell (Atrina pectinata) morphologically resemble each other, the crystallographic features of constituent calcites are considerably different; in Pinctada, the IOMs are distributed inhomogeneously to form small-angle grain boundaries and associated crystal defects, whereas in Atrina, the IOMs are distributed almost homogeneously and defects are rare in the calcite crystals. We conducted in vitro calcite syntheses in the presence of the IOMs in EDTA-soluble extracts from the prisms. The IOMs in the extracts from Pinctada and Atrina were incorporated into synthetic calcites in a different manner, exhibiting defect-rich/free features as observed in the natural shells. With regard to amino acid compositions of the IOMs, the extract from Atrina has a higher proportion of acidic amino acids than that from Pinctada, implying that acidic proteins do not correlate directly to their affinity for calcium carbonate crystals.

  1. Crystallization and preliminary X-ray diffraction analysis of the lectin from Dioclea rostrata Benth seeds

    SciTech Connect

    Delatorre, Plnio; Nascimento, Kyria Santiago; Melo, Luciana Magalhes; Souza, Emmanuel Prata de; Rocha, Bruno Anderson Matias da; Benevides, Raquel G.; Oliveira, Taiana Maia de; Bezerra, Gustavo Arruda; Bezerra, Maria Jlia Barbosa; Cunha, Rodrigo Maranguape Silva da; Cunha, Francisco Assis Bezerra da; Freire, Valder Nogueira; Cavada, Benildo Sousa

    2006-02-01

    D. rostrata lectin was crystallized by hanging-drop vapor diffusion. The crystal belongs to the orthorhombic space group I222 and diffracted to 1.87 resolution. Lectins from the Diocleinae subtribe (Leguminosae) are highly similar proteins that promote various biological activities with distinctly differing potencies. The structural basis for this experimental data is not yet fully understood. Dioclea rostrata lectin was purified and crystallized by hanging-drop vapour diffusion at 293 K. The crystal belongs to the orthorhombic space group I222, with unit-cell parameters a = 61.51, b = 88.22, c = 87.76 . Assuming the presence of one monomer per asymmetric unit, the solvent content was estimated to be about 47.9%. A complete data set was collected at 1.87 resolution.

  2. Shock-induced devolatilization of calcite

    NASA Technical Reports Server (NTRS)

    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.

  3. Growth of SiC single crystals on patterned seeds by a sublimation method

    NASA Astrophysics Data System (ADS)

    Yang, Xianglong; Chen, Xiufang; Peng, Yan; Xu, Xiangang; Hu, Xiaobo

    2016-04-01

    Growth of 6H-SiC on patterned seeds with the vertical sidewalls composed of {11-20} and {1-100} faces by a sublimation method at 1700-2000 °C was studied. Anisotropy in lateral growth rates was observed, i.e the growth rate towards <11-20> was faster than that along <1-100>. It was found that free lateral growth on mesas was accompanied by a sharp decrease in the density of threading dislocation. The dependence of lateral growth rate on growth conditions such as reactor pressure and growth temperature was investigated. The factors governing the process of lateral growth of 6H-SiC on patterned seeds were discussed.

  4. Biaxially-Textured Photovoltaic Film Crystal Silicon on Ion Beam Assisted Deposition CaF2 Seed Layers on Glass

    SciTech Connect

    Groves, J. R.; Li, J. B.; Clemens, B. M.; LaSalvia, V.; Hasoon, F.; Branz, H. M.; Teplin, C. W.

    2012-05-01

    We grow biaxially textured heteroepitaxial crystal silicon (c-Si) films on display glass as a low-cost photovoltaic material. We first fabricate textured CaF{sub 2} seed layers using ion-beam assisted deposition, then coat the CaF{sub 2} with a thin, evaporated epitaxial Ge buffer and finally deposit heteroepitaxial silicon on the Ge. The silicon is grown by hot-wire chemical vapor deposition, a high-rate, scalable epitaxy technology. Electron and X-ray diffraction confirm the biaxial texture of the CaF{sub 2} and epitaxial growth of the subsequent layers. Transmission electron microscopy reveals columnar silicon grains about 500 nm across. We fabricate a proof-of-concept epitaxial film c-Si solar cell with an open circuit voltage of 375 mV that is limited by minority carrier lifetime.

  5. Top-Seeded Solution Growth of Pb[(Zn1/3Nb2/3)0.93Ti0.07]O3 Single Crystals

    NASA Astrophysics Data System (ADS)

    Karaki, Tomoaki; Nakamoto, Maki; Adachi, Masatoshi

    2002-11-01

    Top-seeded solution growth (TSSG) of relaxor-based ferroelectric single crystal Pb[(Zn1/3Nb2/3)0.93Ti0.07]O3 (PZNT93/7) was investigated. PbO and PbO+B2O3 were used as fluxes. The solution compositions were (PZNT93/7)/PbO]=70/30 wt% and (PZNT93/7)/PbO/B2O3=70/29/1 wt%. A platinum stick, PZNT93/7 single crystal and Pb[(Mg1/3Nb2/3)0.65Ti0.35]O3 (PMNT65/35) single crystal were used as seeds. The addition of B2O3 was used to lower the growth temperature and reduce the rate of PbO evaporation. Crystals grown inside the melting solution had a pure perovskite structure and their Curie temperature was 168C, corresponding to PZNT93/7 composition. However, it was found that the perovskite crystals decomposed little by little from the crystal surface to undesirable pyrochlore after being pulled out of the melt and exposed to air during the growth. Crystals grown at the melt surface were originally of pyrochlore structure. The investigated results revealed the possibility of growing these single crystals by a continually charged TSSG technique.

  6. Seed Crystal Homogeneity Controls Lateral and Vertical Heteroepitaxy of Monolayer MoS2 and WS2.

    PubMed

    Yoo, Youngdong; Degregorio, Zachary P; Johns, James E

    2015-11-18

    Heteroepitaxy between transition-metal dichalcogenide (TMDC) monolayers can fabricate atomically thin semiconductor heterojunctions without interfacial contamination, which are essential for next-generation electronics and optoelectronics. Here we report a controllable two-step chemical vapor deposition (CVD) process for lateral and vertical heteroepitaxy between monolayer WS2 and MoS2 on a c-cut sapphire substrate. Lateral and vertical heteroepitaxy can be selectively achieved by carefully controlling the growth of MoS2 monolayers that are used as two-dimensional (2D) seed crystals. Using hydrogen as a carrier gas, we synthesize ultraclean MoS2 monolayers, which enable lateral heteroepitaxial growth of monolayer WS2 from the MoS2 edges to create atomically coherent and sharp in-plane WS2/MoS2 heterojunctions. When no hydrogen is used, we obtain MoS2 monolayers decorated with small particles along the edges, inducing vertical heteroepitaxial growth of monolayer WS2 on top of the MoS2 to form vertical WS2/MoS2 heterojunctions. Our lateral and vertical atomic layer heteroepitaxy steered by seed defect engineering opens up a new route toward atomically controlled fabrication of 2D heterojunction architectures. PMID:26488069

  7. Stabilities of calcite and aragonite

    USGS Publications Warehouse

    Christ, C.L.; Hostetler, P.B.; Siebert, R.M.

    1974-01-01

    A revaluation of the 25° C activity-product constants of calcite (KC) and aragonite (KA) was made on the basis of the known solubilities of these phases for which the activity of total dissolved calcium was corrected for the presence of the ion pair CaHCO3+ in the aqueous phase. The value of the dissociation constant of CaHCO3+ was taken to be 10-1.225±0.02. This value, combined with values of the analytical concentrations in solutions with partial pressure PCO2 =0.97 atmosphere, leads to KC=l0-8.52±0.04 and KA= 10-8.36±0.04. Based on these K values, standard free energies of formation of calcite and aragonite were calculated to be -270,144±375 and -269,926±375 calories mole-1, (-1,130,282±1,569 and -1,129,370±1,569 joules mole-1), respectively. From the 25°C K values, using appropriate entropy and heat capacity data, values of KC and KA were calculated over the temperature range 0° to 200°C. Possible errors in interpretation of measured pH values and inferred PCO2values and the bearing of these errors on calculations of K values are discussed.

  8. In-Situ Partial Pressure Measurements and Visual Observation during Crystal Growth of ZnSe by Seeded Physical Vapor Transport

    NASA Technical Reports Server (NTRS)

    Su, Ching-Hua; Feth, Shari; Lehoczky, Sandor L.

    1999-01-01

    An in-situ monitoring furnace was constructed with side windows to perform partial pressure measurements by optical absorption and visual observation of the growing crystal. A fused silica -rowth ampoule with a 4.5 cm long square tube between the source and the seed was prepared for the optical absorption measurements. A ZnSe crystal was grown by the seeded physical vapor transport (PVT) technique in the horizontal configuration. The growth temperature was 1120 C and the furnace translation rate was 3nmVday. Partial pressures of Se2, P(sub Se2), at three locations along the length of the growth ampoule were measured at 90 min intervals during the growth process. The measured P (sub Se2) were in the range of 2.0 to 6.5 x 10(exp -3) atm. The P(sub Se2) results indicated that the partial pressure profile was inconsistent with the results of the one-dimensional diffusion mass transport model and that the source composition shifted toward Se-rich during the run, i.e. the grown crystal was more Zn-rich than the source. The visual observation showed that the seed crystal first etched back, with greater thermal etching occurring along the edges of the seed crystal. Once the growth started, the crystal crew in a predominately contactless mode and facets were evident during growth. The crystal did not grow symmetrically which is believed to be due to the unintentional asymmetry of the radial thermal profile in the furnace.

  9. Experimental study of the aragonite to calcite transition in aqueous solution

    NASA Astrophysics Data System (ADS)

    Perdikouri, Christina; Kasioptas, Argyrios; Geisler, Thorsten; Schmidt, Burkhard C.; Putnis, Andrew

    2011-10-01

    The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200 C using single inorganic aragonite crystals as a starting material. The initial saturation state and the total [Ca 2+]:[CO 32-] ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy. Experiments using carbonate solutions prepared with water enriched in 18O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of 18O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the 18O distribution in the calcite replacement. An activation energy of 109 kJ/mol was calculated for the exchange of oxygen isotopes between [C 16O 32-] aq and [H 218O] and the time for oxygen isotope exchange in the fluid at 200 C was estimated at 0.9 s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution-reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.

  10. Uranium Isotope Fractionation During Coprecipitation with Aragonite and Calcite

    NASA Astrophysics Data System (ADS)

    Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Wasylenki, L. E.; Anbar, A. D.

    2014-12-01

    Natural variations in the 238U/235U ratio of marine carbonates may provide a useful way of constraining past variations in ocean redox conditions. However, before applying this novel redox proxy, it is essential to explore possible isotopic fractionation during U coprecipitation with aragonite and calcite. We investigated these effects in laboratory experiments. Aragonite and calcite coprecipitation experiments were conducted at pH 8.5±0.1 using a constant addition method [1]. More than 90% of the U was incorporated into the solid phase at the end of each experiment. Samples were purified using UTEVA chemistry and δ238/235U was measured using 233U-236U double-spike MC-ICP-MS with a precision of ±0.10‰ [2]. The aragonite experiment demonstrated a 238U/235U Rayleigh fractionation factor of α=1.00008±0.00002 with the 238U preferentially incorporated. In contrast, the calcite experiment demonstrated no resolvable U isotope fractionation (α=1.00001±0.00003). To determine if U isotopes are affected during the early diagenetic conversion of aragonite to calcite, natural carbonate samples were collected along an aragonite-calcite transition across a single coral head in the Key Largo limestone, and characterized for U concentration and δ238/235U [3]. We found that the mean δ238/235U in aragonite (-0.33±0.07‰ 2se) was slightly heavier than that in calcite (-0.37±0.02‰ 2se). Further work is needed to address the mechanisms leading to differential isotopic fractionation of U(VI) during incorporation into aragonite and calcite. Possible drivers include differences in coordination in the crystal structure or equilibrium isotopic fractionation between various aqueous U(VI) species prior to incorporation. [1] Reeder et al. (2001) GCA 65, 3491-3503. [2] Weyer et al., (2008) GCA 72, 345-359. [3] Gill et al., (2008) GCA 72, 4699-4722.

  11. Crystallization and preliminary X-ray studies of a galactose-specific lectin from the seeds of bitter gourd (Momordica charantia).

    PubMed

    Chandran, Thyageshwar; Sharma, Alok; Vijayan, M

    2010-09-01

    A galactose-specific lectin from the seeds of bitter gourd (Momordica charantia) is a four-chain type II ribosome-inactivating protein (RIP) resulting from covalent association through a disulfide bridge between two identical copies of a two-chain unit. The available structural information on such four-chain RIPs is meagre. The bitter gourd lectin was therefore crystallized for structural investigation and the crystals have been characterized. It is anticipated that the structure of the orthorhombic crystals will be analysed using molecular replacement by taking advantage of its sequence, and presumably structural, homology to normal two-chain type II RIPs. PMID:20823520

  12. Seed crystals and catalyzed epitaxy of single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Wang, Yuhuang

    This thesis demonstrates the continued growth of single-walled carbon nanotubes (SWNTs) from seeded SWNTs in a way analogous to epitaxy or cloning; that is, the SWNTs grow as a seamless extension to the existing seeded SWNTs and have the same diameter and chirality as those of the SWNT seeds. The experiments were carried out in three key steps, including: (1) preparing a macroscopic array of open-ended SWNTs; (2) reductively docking transition metals as a catalyst to the nanometer-sized open ends; and then (3) heating the whole up to 700--850°C in the presence of a carbon feedstock such as ethanol or ethylene. The resulting SWNT ropes inherit the diameters and chirality from the seeded SWNTs, as indicated by the closely matched frequencies of Raman radial breathing modes before and after the growth. As a control, only sparse nanotubes grew from closed-ended SWNTs, ruling out spontaneous nucleation as a dominating mechanism in our experiments. This experiment proved for the first time the growth of SWNTs can be separated from the nucleation step. The ability to separate the typically inefficient nucleation step from the growth of SWNTs and to restart the growth opens the possibility of amplifying SWNTs with only the desired (n, m). The success in the continued growth was enabled with the creation of macroscopic arrays of open-ended SWNTs from a neat SWNT fiber. A variety of techniques including cryo-microtoming and surface etching chemistry have been developed to produce a macroscopic (˜1200mum2), aligned, and clean---largely free of amorphous carbon, oxides, and metal residuals---SWNT substrate with open-ended SWNTs aligned along the fiber axis. Alternatively, the fiber was milled perpendicular to the fiber axis with a gallium focused ion beam to produce a planar, free-standing, ultra-thin, "bed-of-nails" SWNT membrane---a single layer of parallel SWNTs densely packed and aligned along the normal of the membrane.

  13. Controls of carbonate mineralogy and solid-solution of Mg in calcite: evidence from spelean systems

    SciTech Connect

    Gonzalez, L.A.; Lohmann, K.C.

    1985-01-01

    Precipitation of carbonate minerals in spelean systems occurs under a wide range of fluid chemistry, Mg-Ca ratios, alkalinities, pH and temperatures; thus, spelean systems provide ideal settings to determine factors controlling the mineralogy of precipitated carbonates and solid-solution of Mg in calcite. Cave waters and actively-precipitating carbonate speleothems were collected from Carlsbad Caverns National Park, New Mexico and the Mammoth-Flint Cave System, Kentucky. Carbonate mineralogy of precipitated phases was determined by x-ray diffraction, and major and minor element composition of waters and accompanying minerals were determined by Atomic Absorption Spectrophotometry. Results demonstrate that at a constant CO3 concentration the precipitation threshold for calcite to aragonite is controlled dominantly by the Mg/Ca ratio of the ambient fluid. Aragonite precipitation is favored by high Mg/Ca ratios. Conversely, with increasing CO3 concentration at constant fluid Mg/Ca ratios, calcite is preferentially precipitated. Solid-solution of Mg in calcite is positively correlated with both increased Mg/Ca ratios and CO3 concentrations. These data suggest that Mg contents of calcite can not be defined solely in terms of a homogeneous distribution coefficient. Rather, Mg concentrations can be also be affected by the CO3 concentration and degree of calcite saturation, suggesting that the rate of crystal growth also plays and important role in Mg solid-solution in calcites.

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

    PubMed

    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⩽0.01M) 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. PMID:26852350

  15. Experimental investigation of surface energy and subcritical crack growth in calcite

    NASA Astrophysics Data System (ADS)

    RYne, Anja; Bisschop, Jan; Dysthe, Dag Kristian

    2011-04-01

    Subcritical cracking behavior and surface energies are important factors in geological processes, as they control time-dependent brittle processes and the long-term stability of rocks. In this paper, we present experimental data on subcritical cracking in single calcite crystals exposed to glycol-water mixtures with varying water content. We find upper bounds for the surface energy of calcite that decrease with increasing water concentration and that are systematically lower than values obtained from molecular dynamics simulations. The relation of surface energy to water concentration can explain water weakening in chalks. The rate of subcritical crack growth in calcite is well described by a reaction rate model. The effect of increasing water on crack velocity is to lower the threshold energy release rate required for crack propagation. The slope of the crack velocity curve remains unaffected, something which strongly suggests that the mechanism for subcritical cracking in calcite does not depend on the water concentration.

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

    USGS Publications Warehouse

    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 <0.1 wt %). The excess Mg was taken up by the calcite grains in between, stabilizing them and causing a few volume percent rodlike relicts of Mg-enriched calcite (up to 10 wt % MgO) to be left behind by the advancing reaction front. The aragonite 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.

  17. Mechanism of Calcite Co-Orientation in the Sea Urchin Tooth

    SciTech Connect

    Killian, Christopher; Metzler, Rebecca; Gong, Y. U. T.; Olson, Ian; Aizenberg, Joanna; Politi, Yael; Wilt, Fred; Scholl, Andreas; Young, Anthony; Doran, Andrew; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan; Gilbert, P. U. P. A.

    2009-12-01

    Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO{sub 3}) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin (Strongylocentrotus purpuratus), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction ({mu}XRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO{sub 3} is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.

  18. Nucleation, growth and evolution of calcium phosphate films on calcite.

    PubMed

    Naidu, Sonia; Scherer, George W

    2014-12-01

    Marble, a stone composed of the mineral calcite, is subject to chemically induced weathering in nature due to its relatively high dissolution rate in acid rain. To protect monuments and sculpture from corrosion, we are investigating the application of thin layers of hydroxyapatite (HAP) onto marble. The motivation for using HAP is its low dissolution rate and crystal and lattice compatibility with calcite. A mild, wet chemical synthesis route, in which diammonium hydrogen phosphate salt was reacted with marble, alone and with cationic and anionic precursors under different reaction conditions, was used to produce inorganic HAP layers on marble. Nucleation and growth on the calcite substrate was studied, as well as metastable phase evolution, using scanning electron microscopy, grazing incidence X-ray diffraction, and atomic force microscopy. Film nucleation was enhanced by surface roughness. The rate of nucleation and the growth rate of the film increased with cationic (calcium) and anionic (carbonate) precursor additions. Calcium additions also influenced phase formation, introducing a metastable phase (octacalcium phosphate) and a different phase evolution sequence. PMID:25233226

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

    SciTech Connect

    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.

  20. Ab initio study of thermodynamic, structural, and elastic properties of Mg-substituted crystalline calcite.

    PubMed

    Elstnerov, Pavlna; Frik, Martin; Fabritius, Helge Otto; Lymperakis, Liverios; Hickel, Tilmann; Petrov, Michal; Nikolov, Svetoslav; Raabe, Dierk; Ziegler, Andreas; Hild, Sabine; Neugebauer, Jrg

    2010-12-01

    Arthropoda, which represent nearly 80% of all known animal species, are protected by an exoskeleton formed by their cuticle. The cuticle represents a hierarchically structured multifunctional biocomposite based on chitin and proteins. Some groups, such as 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 (Becker et al., Dalton Trans. (2005) 1814). Motivated by these facts, we present a theoretical parameter-free quantum-mechanical study of the phase stability and structural and elastic properties of Mg-substituted calcite crystals. The Mg-substitutions were chosen as examples of states that occur in complex chemical environments typical for biological systems in which calcite crystals contain impurities, the role of which is still the topic of debate. Density functional theory calculations of bulk (Ca,Mg)CO? were performed employing 30-atom supercells within the generalized gradient approximation as implemented in the Vienna Ab-initio Simulation Package. Based on the calculated thermodynamic results, low concentrations of Mg atoms are predicted to be stable in calcite crystals in agreement with experimental findings. Examining the structural characteristics, Mg additions nearly linearly reduce the volume of substituted crystals. The predicted elastic bulk modulus results reveal that the Mg substitution nearly linearly stiffens the calcite crystals. Due to the quite large size-mismatch of Mg and Ca atoms, Mg substitution results in local distortions such as off-planar tilting of the CO?? group. PMID:20650336

  1. Structural Characterization of Lateral-grown 6H-SiC am-plane Seed Crystals by Hot Wall CVD Epitaxy

    NASA Technical Reports Server (NTRS)

    Goue, Ouloide Yannick; Raghothamachar, Balaji; Dudley, Michael; Trunek, Andrew J.; Neudeck, Philip G.; Woodworth, Andrew A.; Spry, David J.

    2014-01-01

    The performance of commercially available silicon carbide (SiC) power devices is limited due to inherently high density of screw dislocations (SD), which are necessary for maintaining polytype during boule growth and commercially viable growth rates. The NASA Glenn Research Center (GRC) has recently proposed a new bulk growth process based on axial fiber growth (parallel to the c-axis) followed by lateral expansion (perpendicular to the c-axis) for producing multi-faceted m-plane SiC boules that can potentially produce wafers with as few as one SD per wafer. In order to implement this novel growth technique, the lateral homoepitaxial growth expansion of a SiC fiber without introducing a significant number of additional defects is critical. Lateral expansion is being investigated by hot wall chemical vapor deposition (HWCVD) growth of 6H-SiC am-plane seed crystals (0.8mm x 0.5mm x 15mm) designed to replicate axially grown SiC single crystal fibers. The post-growth crystals exhibit hexagonal morphology with approximately 1500 m (1.5 mm) of total lateral expansion. Preliminary analysis by synchrotron white beam x-ray topography (SWBXT) confirms that the growth was homoepitaxial, matching the polytype of the respective underlying region of the seed crystal. Axial and transverse sections from the as grown crystal samples were characterized in detail by a combination of SWBXT, transmission electron microscopy (TEM) and Raman spectroscopy to map defect types and distribution. X-ray diffraction analysis indicates the seed crystal contained stacking disorders and this appears to have been reproduced in the lateral growth sections. Analysis of the relative intensity for folded transverse acoustic (FTA) and optical (FTO) modes on the Raman spectra indicate the existence of stacking faults. Further, the density of stacking faults is higher in the seed than in the grown crystal. Bundles of dislocations are observed propagating from the seed in m-axis lateral directions. Contrast extinction analysis of these dislocation lines reveals they are edge type basal plane dislocations that track the growth direction. Polytype phase transition and stacking faults were observed by high-resolution TEM (HRTEM), in agreement with SWBXT and Raman scattering.

  2. Calcite (1 0 1 4) surface in humid environments

    NASA Astrophysics Data System (ADS)

    Baltrusaitis, Jonas; Grassian, Vicki H.

    2009-09-01

    In this study, alternating current (AC) mode Atomic Force Microscopy (AFM) height images combined with force measurements and phase imaging were used to investigate the surface reconstruction and chemistry of the lowest energy surface, (1 0 1 4) plane, of calcite, a stable form of calcium carbonate (CaCO 3), in the presence of relative humidity at different temperatures. At 296 K and 70% RH, calcite (1 0 1 4) undergoes rapid restructuring during hydration forming regions on the surface that are most likely characterized as an amorphous hydrate layer similar to what forms in solution under high [Ca 2+] supersaturation conditions. This hydrate layer in turn serves as a substrate for the crystallization of another layer that possesses structural properties which differ from hydrate layer. Phase imaging reveals that these different layer structures formed in the process of water adsorption and surface reconstruction have very different energy dissipation modes. The origin of the different dissipation modes are likely due to differences in water content and hydrophobicity of these regions. The newly formed layer on top of the hydration layer is proposed to be vaterite, another polymorph of calcium carbonate. At 278 K the formation mechanism of the vaterite layer changes due to nucleation of a more crystalline hydrate layer, similar to calcium carbonate hexahydrate, instead of the amorphous hydrate layer that forms at 296 K. Force measurements corroborate the assignment of the speciation of different regions on the surface. Importantly, the AFM data show that the surface of calcite is highly inhomogeneous with regions that vary in water content. This suggests that the reactivity of calcite in humid environments will be highly spatially dependent.

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

    NASA Astrophysics Data System (ADS)

    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 [42-1] and [010] directions in the presence of succinate as observed by Atomic Force Microscopy [Teng et al., 2006]. Finally, the calculated succinate adsorption energies at hydrated steps decreases in the sequence [-441] > [42-1] > [010], which also corresponds to the sequence of steps opening at dissolution etch-pits in the presence of succinate [Teng et al., 2006]. Our study provides a strong example of the utility of MD simulations in exploring organic-mediated mineral crystal dissolution (and growth) mechanisms, resulting in unusual morphologies, that may serve as biosignatures on Earth, and potentially on Mars and other worlds.

  4. Intercalation of sea urchin proteins in calcite: Study of a crystalline composite material

    SciTech Connect

    Berman, A.; Addadi, L.; Leiserowitz, L.; Weiner, S. ); Kvick, A.; Nelson, M. )

    1990-11-02

    Sea urchin skeletal elements are composed of single crystals of calcite. Unlike their synthetic counterparts, these crystals do not have well-developed cleavage and are consequently much more resistant to fracture. This phenomenon is due in part to the presence of acidic glycoproteins occluded within the crystals. By means of x-ray diffraction with synchrotron radiation, it is shown that the presence of the protein in synthetic calcite only slightly decreases the coherence length but significantly increases the angular spread of perfect domains of the crystals. In biogenic calcite, the coherence length is 1/3 to 1/4 as much as that in synthetic calcite and the angular spread is 20 to 50 times as wide. It is proposed that the presence of macromolecules concentrated at mosaic boundaries that are oblique to cleavage planes is responsible for the change in fracture properties. These results may be important in the material sciences, because of the unusual nature of this material, namely, a composite based on the controlled intercalation of macromolecules inside single-crystal lattices. 20 refs., 3 figs.

  5. Alginic Acid Accelerates Calcite Dissolution

    NASA Astrophysics Data System (ADS)

    Perry, T. D.; Duckworth, O. W.; McNamara, C. J.; Martin, S. T.; Mitchell, R.

    2003-12-01

    Accelerated carbonate weathering through biological activity affects both geochemical cycling and the local pH and alkalinity of terrestrial and marine waters. Microbes affect carbonate dissolution through metabolic activity, production of acidic or chelating exudates, and cation binding by cell walls. Dissolution occurs within microbial biofilms - communities of microorganisms attached to stone in an exopolymer matrix. We investigated the effect of alginic acid, a common biological polymer produced by bacteria and algae, on calcite dissolution using a paired atomic force microscopy/flow-through reactor apparatus. The alginic acid caused up to an order of magnitude increase in dissolution rate at 3 < pH < 12. Additionally, the polymer preferentially binds to the obtuse pit steps and increases step velocity. We propose that the polymer is actively chelating surficial cations reducing the activation energy and increasing dissolution rate. The role of biologically produced polymers in mineral weathering is important in the protection of cultural heritage materials and understanding of marine and terrestrial systems.

  6. Project Explorer: Get Away Special #007. [alloy solidification, seed germination, crystal growth, and radio transmission of payload data

    NASA Technical Reports Server (NTRS)

    Henderson, A. J., Jr.

    1984-01-01

    Tentatively scheduled to fly on STS-17 (41G), this get away special aims to demonstrate amateur radio transmissions to global ground stations in the English language. Experiments No. 1, 2, and 3 use the micro-gravity of space flight to study the solidification of lead-antimony and aluminum-copper alloys, the germination of radish seeds, and the growth of potassium-tetracyanoplatinate hydrate crystals in an aqueous solution. Flight results are to be compared with Earth-based data. Experiment No. 4 (the Marshall Amateur Radio Club Experiment - MARCE) features radio transmissions and also provides timing for the start of all other experiments. A microprocessor obtains real-time data from all experiments as well as temperature and pressure measurements within the GAS canister. These data are to be transmitted on previously announced amateur radio frequencies after they are converted into the English language by a digitalker for general reception. The support structure for the G #007 experiments consists of two primary plates and four bumper assemblies.

  7. Do organic ligands affect calcite dissolution rates?

    NASA Astrophysics Data System (ADS)

    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 <0.05 mol/kg of these organic anions changes calcite dissolution rates by less than a factor of 2.5 with the exception of citrate and EDTA 4-. The presence of 0.05 mol/kg citrate and EDTA 4- increases calcite dissolution rates by as much as a factor of 35 and 500, respectively, compared to rates in organic anion-free solutions. Further calcite dissolution experiments were performed in the presence of organic polymers similar to bacterial exudates, cell exopolysaccharides, and analogs of microbial cell envelopes: alginate, lichen 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.

  8. Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes?

    NASA Astrophysics Data System (ADS)

    Bindschedler, S.; Cailleau, G.; Braissant, O.; Millire, L.; Job, D.; Verrecchia, E. P.

    2014-01-01

    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 present-day. Moreover, on a global scale, the organomineralization of organic nanofibres into calcitic nanofibres might have a great, however overlooked, impact on the biogeochemical cycles of both Ca and C.

  9. Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes?

    NASA Astrophysics Data System (ADS)

    Bindschedler, S.; Cailleau, G.; Braissant, O.; Millire, L.; Job, D.; Verrecchia, E. P.

    2014-05-01

    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 paper 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. Moreover, on a global scale, the organomineralization of organic nanofibres into calcitic nanofibres might be an overlooked process deserving more attention to specify its impact on the biogeochemical cycles of both Ca and C.

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

    NASA Astrophysics Data System (ADS)

    Neal, Colin

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

  11. Nickel adsorption on chalk and calcite

    NASA Astrophysics Data System (ADS)

    Belova, D. A.; Lakshtanov, L. Z.; Carneiro, J. F.; Stipp, S. L. S.

    2014-12-01

    Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite 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 = - 1.12 on calcite and log KNi = - 0.43 and - 0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts of polysaccharides and clay nanoparticles on the chalk surface.

  12. Precipitation of calcite induced by Synechocystis sp. PCC6803.

    PubMed

    Han, Zuozhen; Yan, Huaxiao; Zhou, Shixue; Zhao, Hui; Zhang, Yan; Zhang, Ningning; Yao, Chuankai; Zhao, Lin; Han, Chunyan

    2013-10-01

    Calcite with laminate structure was successfully prepared by culturing Synechocystis sp. PCC6803 with different concentrations of calcium chloride (CaCl₂) in BG11 media. S. PCC6803 was examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), laser confocal scanning microscope (LCSM) and energy dispersive spectroscopy (EDS). The effects of Ca²⁺ concentrations and pH values on calcification were investigated and the micro morphs of the CaCO₃ crystals were observed by means of SEM. These results showed that CaCO₃ crystals could be more easily formed with increasing the concentration of CaCl₂ in S. PCC6803 culture solution. S. PCC6803 could largely bind calcium ions, most of which were present in extracellular polymeric substances and on the cell wall. Inside the cells there were a lot of circular areas rich in calcium ions without the crystallization of calcium. Some cells produced a thicker gelatinous sheath outside of the translucent organic thin layer. And the cells inside also produced major changes that the original chloroplasts were almost transformed into starch grains whose sizes were from 0.5 to 1 μm with relatively uniform in sizes. At the same time the cell sizes significantly reduced to only about 8-9 μm almost changing to half of its original diameters. The calcite crystals with a highly preferred orientation induced by S. PCC6803 were observed with X-ray diffraction (XRD). A critical implication was that S. PCC6803 could induce bio-calcification and then mediate the further growth of CaCO₃ crystals in the biological system. PMID:23543209

  13. Coprecipitation of Chromate with Calcite: Batch Experiments and X-ray Absorption Spectroscopy

    SciTech Connect

    Tang,Y.; Elzinga, E.; Lee, Y.; Reeder, R.

    2007-01-01

    Batch experiments, combined with in situ spectroscopic methods, are used to examine the coprecipitation of Cr(VI) with calcite, including partitioning behavior, site-specific distribution of Cr on the surface of calcite single crystals, and local coordination of Cr(VI) in the calcite structure. It is found that the concentration of Cr incorporated in calcite increases with increasing Cr concentration in solution. The calculated apparent partition coefficient, K{sub d}*, is highest at low Cr solution concentration, and decreases to a constant value with increasing Cr solution concentration. DIC images of the (1 0 {bar 1} 4) surface of calcite single crystals grown in the presence of CrO{sub 4}{sup 2-}exhibit well-defined growth hillocks composed of two pairs of symmetrically nonequivalent vicinal faces, denoted as + and -, which reflect the orientation of structurally nonequivalent growth steps. Micro-XRF mapping of the Cr distribution over a growth hillock shows preferential incorporation of Cr into the -- steps, which is considered to result from differences in surface structure geometry. XANES spectra confirm that incorporated Cr is hexavalent, and no reduction of Cr(VI) in the X-ray beam was observed up to 2 days at room temperature. EXAFS fit results show the incorporated Cr(VI) has the expected first shell of 4 O at {approx}1.64 {+-} 0.01 {angstrom}, consistent with CrO{sub 4}{sup 2-}. Best fit results show that the second shell is split with {approx}2.5 Ca at {approx}3.33 {+-} 0.05 and {approx}2.2 Ca at 3.55 {+-} 0.05 {angstrom}, which confirms the incorporation of chromate into calcite. Consideration of possible local coordination indicates that significant distortion or disruption is required to accommodate CrO{sub 4}{sup 2-}in the calcite structure.

  14. Freshwater-phreatic calcite cementation, Schooner Cays, Bahamas

    SciTech Connect

    Budd, D.A.

    1985-02-01

    Freshwater-phreatic calcite cementation is an active process on 700 and 2700 yr-old ooid-sand islands in the Schooner Cays, Bahamas. Cement fabrics and textures indicate a general, four-stage model of pore infilling. (1) The precipitation of isolated, decimicron-sized, rhombohedrons of calcite on grain surfaces forms an incipient circumgranular cement. (2) Continued precipitation enlarges crystal sizes and forms new rhombohedral crystals, resulting in a continuous circumgranular rim of cement. (3) Additional cementation quickly masks the circumgranular fabric, producing a partial pore-filling mosaic. (4) The remaining pore space is occluded with a mosaic of calcite cement. Petrographic evidence for the earlier circumgranular rim of cement is not necessarily apparent after the last stage of cementation. Empty pores and all four stages of phreatic-zone cementation were observed in the diagenetically immature 700 yr-old rocks, but only stages 2 through 4 were observed in the diagenetically more mature 2700 yr-old phreatic zone samples. Cements are distributed homogeneously within each pore at every stage, yet because each pore may proceed through the four stages at different rates, each pore can be at a different stage of infilling. This results in an inhomogeneous distribution of cement between pores during the initial stages of cementation. Recognition of a cement stratigraphy similar to that described here should aid in the identification of freshwater-phreatic diagenesis in ancient carbonate rock sequences. Variability in the amount of freshwater-phreatic cement between pores should be expected and not interpreted as the product of different paragenetic sequences.

  15. Hydrothermal replacement of calcite by Mg-carbonates

    NASA Astrophysics Data System (ADS)

    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 phases increases with increasing distance from the unreacted calcite core, countered by a decrease of Ca incorporated. Both the coexistence of two different product phases and the distinct compositional gradient within the forming reaction rim are unequivocal signs of a chemical zonation of Ca and Mg in the fluid phase which mediates the element exchange between the reaction interface and the bulk solution. Atomic adsorption spectroscopy revealed that the Ca/Mg ratio in the reacted fluid increases as a function of time, reflecting the progressive exchange of Mg and Ca between the fluid and the solid phase. The time-dependence of the evolving Ca/Mg ratio can be fitted with a square root of time relation that indicates a transport controlled reaction. We interpret the hydrothermal replacement of calcite to operate via a dissolution/re-precipitation mechanism, whereas the reaction progress is controlled by the transport of the structure forming elements through the developing reaction rim.

  16. Preliminary Results of Bacteria Distribution in Chinese Loess and Their Control on the Calcite Formation

    NASA Astrophysics Data System (ADS)

    Chen, Y.; Lian, B.; Hu, Q.; Teng, H. H.; Wu, T.; Ji, J.; Chen, J.

    2005-12-01

    Continuous loess-paleosol sequences on the Chinese Loess Plateau are viewed as one of best continental archives of paleoclimatic and paleoenvironmental changes of the Late Cenozoic era. Carbonate, mainly calcite, commonly occurs throughout the entire sequence; though some are detrital, most are in-situ pedogenic. TEM studies have shown various morphologies of calcites in Chinese loess, especially nano-rod calcite widely occurring in loess and paleosols which are biogenic. In this study, we collected fresh and undisturbed loess and paleosol samples and successfully separated dominant microbial communities. These microbes are mainly bacteria, especially Bacillus anthracis, and a few fungi. The amount of bacteria decreases sharply with the depth. Then we added the bacteria into the near saturated solution of CaCl2 and Na2CO3. It is interesting that the original calcite crystals formed under abiotic conditions changed from quadrilateral face to pentagonal or hexagonal and the crystal size enlarged almost twice. SEM and AFM observations display bacteria control on the growth of calcite, which cause the lighter carbon isotopic ratios.

  17. Comparison of dissolution and surface reactions between calcite and aragonite in L-glutamic and L-aspartic acid solutions.

    PubMed

    Ryu, Miyoung; Kim, Hwan; Lim, Mihee; You, Kwangsuk; Ahn, Jiwhan

    2010-01-01

    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. PMID:20110889

  18. Acceleration of calcite kinetics by abalone nacre proteins

    SciTech Connect

    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.

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

    SciTech Connect

    Bracco, Jacquelyn N; Stack, Andrew G; Steefel, Carl I

    2013-01-01

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

  20. Channel Flow Cell Studies of the Inhibiting Action of Gypsum on the Dissolution Kinetics of Calcite: A Laboratory Approach with Implications for Field Monitoring.

    PubMed

    Wilkins, Shelley J.; Compton, Richard G.; Taylor, Mark A.; Viles, Heather A.

    2001-04-15

    The rate of dissolution of surface-treated calcite crystals in aqueous acidic solution has been studied using an adaptation of the channel flow cell method with microdisc electrode detection. Surface treatments of calcite with sulfuric acid lead to the nucleation of gypsum overgrowths, which reduce the rate of dissolution of calcite. Rate constants for untreated calcite and calcite pretreated with sulfuric acid conditions of 0.01 M for 1 h, 0.05 M for 5 h, and 0.1 M for 21 h are found to be 0.035, 0.018, 0.006, and 0.004 cm s(-1), respectively. Deterioration of calcite materials caused by acid deposition was investigated by field exposure of untreated and sulfate pretreated calcite rocks under urban conditions for 12 months. The rate constant for both pretreated and untreated calcite exposed to weathering is 0.003 cm s(-1). This suggests that calcite self-passivates the surface from further reaction when exposed to acid deposition. However, surface studies indicate that the surface undergoes erosion and dissolution before passivation. Pretreatment of the surface with sulfate protects the surface from acid deposition so it remains less reactive toward acid compared with untreated calcite. Copyright 2001 Academic Press. PMID:11401383

  1. 4He behavior in calcite filling viewed by (U-Th)/He dating, 4He diffusion and crystallographic studies

    NASA Astrophysics Data System (ADS)

    Cros, Alexandre; Gautheron, Ccile; Pagel, Maurice; Berthet, Patrick; Tassan-Got, Laurent; Douville, Eric; Pinna-Jamme, Rosella; Sarda, Philippe

    2014-01-01

    Fault-filling calcite crystals sampled from the Eocene/Oligocene Gondrecourt graben, Paris Basin, Eastern France, have been studied in order to test the potentiality of calcite (U-Th)/He dating, based on recognized He retention behavior in crystal lattice at surface temperature (Copeland et al., 2007). The samples have been selected because of their relatively old Eocene to Oligocene precipitation age and cold thermal history (<40 C since precipitation). They were sorted into three main tectonic and morphological groups in order of precipitation, including (1) micro-fracture calcites, (2) breccia and associated geodic calcites, and (3) vein and associated geodic calcites. (U-Th)/He dating of 63 calcite fragments yields ages dispersed from 0.2 0.02 to 35.8 2.7 Ma, as well as two older dates of 117 10 and 205 28 Ma (1?). These He ages correlate with grain chemistry, such as Sr, ?REE concentrations or (La/Yb)N ratios, likely reflecting parent fluid evolution. Only the oldest He ages, which correspond to the most recently precipitated crystals, have preserved the total 4He budget since precipitation. To better understand both the age dispersion and why calcites precipitated earlier show younger ages, 4He diffusion experiments have been conducted on 10 Gondrecourt calcite fragments from 3 samples with He ages of ?0.2-6 Ma. Additionally, a crystallographic investigation by X-ray diffraction (XRD) performed on similar samples reveals that crystal structure evolves with increasing temperature, beginning with micro-cracks and cleavage opening. These XRD results shed light on the (U-Th)/He data, indicating that, in fault-filling calcite, He retention is controlled by multiple diffusion domains (MDD) with various sizes, and therefore, evolves through time with strong consequences on (U-Th)/He age. We thus interpret the Gondrecourt calcite (U-Th)/He age scatter as a consequence of the production of defects due to successive calcite crystallization phases associated with the deformation history.

  2. Calcite dissolution in two deep eutrophic lakes

    SciTech Connect

    Ramisch, F.; Dittrich, M.; Mattenberger, C.; Wehrli, B.; Wueest, A.

    1999-10-01

    The calcium cycle, in particular carbonate dissolution, was analyzed in two deep eutrophic lakes, Lago di Lugano (288 m maximum depth) and Sempachersee (87 m) located in Switzerland. A box model approach was used to calculate calcite dissolution in the water column and at the sediment-water interface based on various lake monitoring data such as sediment traps, sediment cores, water and pore-water interface based on various lake monitoring data such as sediment traps, sediment cores, water and pore-water analysis. A model for stationary conditions allowing the calculation of calcite dissolution in the water column for a given particle size distribution was developed. The relative values of the simulated flux were consistent with sediment trap observations. The best fit of the dissolution rate constant of sinking calcite in Lago di Lugano was on the same order of magnitude (3 {center{underscore}dot} 10{sup {minus}10} kg{sup 1/3} s{sup {minus}1}) as published laboratory values for this surface controlled process. Both lakes show a similar specific calcite precipitation rate of 170 g Ca m{sup {minus}2} a{sup {minus}1}. The diffusive flux across the sediment-water interface amounts to about 15 and 10% of total calcite precipitation in Sempachersee and Lago di Lugano, respectively. However, 61% of the precipitated calcite is dissolved in the water column of Lago di Lugano compared to only 13% in Sempachersee. These results point towards the importance of grain size distributions and settling times in stratified deep waters as the two most important factors determining calcite retention in sediments of hard water lakes.

  3. Origin of cone-in-cone calcite veins during calcitization of dolomites and their subsequent diagenesis: A case study from the Gogolin Formation (Middle Triassic), SW Poland

    NASA Astrophysics Data System (ADS)

    Kowal-Linka, Monika

    2010-03-01

    Although bedding-parallel cone-in-cone structure calcite veins are present in the Middle Triassic Gogolin Formation in Opole Silesia, their occurrence is limited to the Emilwka Cellular Limestone Member. Marly limestones (dedolomites) consisting of calcite pseudospar are the host rocks. The veins, which are up to 3 mm high and 30 cm long, are built of densely packed cone columns, with individual cones up to 0.7 mm high and 0.6 mm wide at their bases, and with vertex angle values ranging from 30 to 50. The cones are microfractured, and the adjacent cones are vertically shifted in oblique planes. The exceptionally small veins consist of calcite fibres up to 0.15 mm high. The veins are built of low-magnesium and non-ferroan calcite, characterized by low ? 18O values ranging from - 6.8 to - 7.4, and low ? 13C values ranging from - 2.9 to - 4.5 vs. PDB. These isotopic values are similar to those obtained from the host rocks (? 18O from - 6.8 to - 7.4, and ? 13C from - 3.2 to - 3.6 vs. PDB) and they are strongly depleted in comparison with the isotopic values of other carbonate particles from the Gogolin Formation. The veins only formed in one lithostratigraphic member, suggesting that their origin is related to processes which acted only locally. There are two unique processes that the Emilwka Cellular Limestone Member alone in the Gogolin Formation underwent: early diagenetic evaporitic dolomitization of lime mud in the sabkha environment, and subsequent calcitization of dolomite. Dolomitization led to sediment cohesion loss, porosity increase and initial horizontal laminae separation as a result of the transformation of calcium carbonate to dolomite within anisotropic deposits. Similar values of geochemical parameters obtained from the vein calcite and the host rock calcite are evidence that vein-filling precipitation was contemporary with dedolomitization. Geochemical data combined with sedimentological research and burial history show meteoric-derived waters saturated with respect to calcite as a source of the vein calcite. Dedolomitization and vein precipitation may have taken place from the Norian/Early Jurassic to the Late Jurassic when the study area became eroded land, and the Emilwka Cellular Limestone Member may have acted as a local paleoaquifer conducting the meteoric-derived waters. Solid inclusions in the veins, detached from the host rock and the calcitized nodules, show that the force of calcite crystallization was the main factor responsible for vein widening. Vertical shifts of adjacent cones, remnants of primary fibrous calcite crystals, as well as the burial history justify the application of Tarr's theory in interpreting the origin of the secondary cone-in-cone structure within the fibrous structure veins. The timing and the particular conditions required for the cones to develop are uncertain.

  4. Ages and Origins of Calcite and Opal in the Exploratory Studies Facility Tunnel, Yucca Mountain, Nevada

    USGS Publications Warehouse

    Paces, James B.; Neymark, Leonid A.; Marshall, Brian D.; Whelan, Joseph F.; Peterman, Zell E.

    2001-01-01

    Deposits of calcite and opal are present as coatings on open fractures and lithophysal cavities in unsaturated-zone tuffs at Yucca Mountain, Nevada, site of a potential high-level radioactive waste repository. Outermost layers of calcite and opal have radiocarbon ages of 16,000 to 44,000 years before present and thorium-230/uranium ages of 28,000 to more than 500,000 years before present. These ages are young relative to the 13-million-year age of the host rocks. Multiple subsamples from the same outer layer typically show a range of ages with youngest ages from the thinnest subsamples. Initial uranium-234/uranium-238 activity ratios between 1 and 9.5 show a distinct negative correlation with thorium-230/uranium age and are greater than 4 for all but one sample younger than 100,000 years before present. These data, along with micrometer-scale layering and distinctive crystal morphologies, are interpreted to indicate that deposits formed very slowly from water films migrating through open cavities. Exchanges of carbon dioxide and water vapor probably took place between downward-migrating liquids and upward-migrating gases at low rates, resulting in oversaturation of mineral constituents at crystal extremities and more or less continuous deposition of very thin layers. Therefore, subsamples represent mixtures of older and younger layers on a scale finer than sampling techniques can resolve. Slow, long-term rates of deposition (less than about 5 millimeters of mineral per million years) are inferred from subsamples of outermost calcite and opal. These growth rates are similar to those calculated assuming that total coating thicknesses of 10 to 40 millimeters accumulated over 12 million years. Calcite has a wide range of delta carbon-13 values from about -8.2 to 8.5 per mil and delta oxygen-18 values from about 10 to 21 per mil. Systematic microsampling across individual mineral coatings indicates basal (older) calcite tends to have the largest delta carbon-13 values and smallest delta oxygen-18 values compared to calcite from intermediate and outer positions. Basal calcite has relatively small strontium-87/strontium-86 ratios, between 0.7105 and 0.7120, that are similar to the initial isotopic compositions of the strontium-rich tuff units, whereas outer calcite has more radiogenic strontium-87/strontium-86 ratios between 0.7115 and 0.7127. Isotopic compositions of strontium, oxygen, and carbon in the outer (youngest) unsaturated-zone calcite are coincident with those measured in Yucca Mountain calcrete, which formed by pedogenic processes. The physical and isotopic data from calcite and opal indicate that they formed from solutions of meteoric origin percolating through a limited network of connected fracture pathways in the unsaturated zone rather than by inundation from ascending ground water originating in the saturated zone. Mineral assemblages, textures, and distributions within the unsaturated zone are distinctly different from those deposited below the water table at Yucca Mountain. The calcite and opal typically are present only on footwall surfaces of a small fraction of fractures and only on floors of a small fraction of lithophysal cavities. The similarities in the carbon, oxygen, and strontium isotopic compositions between fracture calcite and soil-zone calcite, as well as the gradation of textures from detritus-rich micrite in the soil to detritus-free spar 10 to 30 meters below the surface, also support a genetic link between the two depositional environments. Older deposits contain oxygen isotope compositions that indicate elevated temperatures of mineral formation during the early stages of deposition; however, in the youngest deposits these values are consistent with deposition under geothermal gradients similar to modern conditions. Correlations between mineral ages and varying Pleistocene climate conditions are not apparent from the current data. Cumulative evidence from calcite and opal deposits indicate

  5. The role of citrate and phthalate during Co(II) coprecipitation with calcite

    NASA Astrophysics Data System (ADS)

    Lee, Young J.; Reeder, Richard J.

    2006-05-01

    The influence of citrate and phthalate on Co coprecipitation with calcite was investigated using a combination of batch experiments, Fourier-transform infra-red (FT-IR) spectroscopy, and thermogravimetric analysis (TGA) over a wide range of precipitation rates. Steady-state growth conditions (at constant [Ca], [Co], DIC, and pH) were generally achieved within 3-5 h, after which Co(II) partitioning into calcite was evaluated. Only minor differences are observed in the partition coefficient ( Kd) trends with and without citrate and phthalate as a function of calcite precipitation rate except at very low rates. Slight inhibition of calcite growth is observed in the presence of citrate or phthalate, which can be attributed to adsorption at surface sites. TGA curves for samples coprecipitated with citrate show a significant mass loss between 375 and 550 C, whereas the weight-loss curves for the Co-phthalate coprecipitates are indistinguishable from those of the organic-free Co coprecipitates. This indicates that citrate is incorporated into calcite during calcite crystallization, whereas phthalate is excluded. FT-IR spectra for the sample with citrate show a broad absorption in the range 3700-3100 cm -1, which is attributable to water molecules coordinated to citrate coprecipitated with calcite. The preferential incorporation of citrate over phthalate likely reflects differences in both aqueous speciation and conformation of the carboxylate groups. This new finding may provide new insight to the factors that control the behavior of macromolecules and their incorporation into the structure of calcium carbonate during biomineralization.

  6. Experimental and theoretical study of red-shifted solitonic resonant radiation in photonic crystal fibers and generation of radiation seeded Raman soliton

    NASA Astrophysics Data System (ADS)

    Bose, S.; Roy, S.; Chattopadhyay, R.; Pal, M.; Bhadra, S. K.

    2015-10-01

    Redshifted solitonic resonant radiation (RR) is a fascinating phase-matching phenomenon that occurs when an optical pulse, launched in the normal dispersion regime of photonic crystal fiber, radiates across the zero-dispersion point. The formation of such phase-matched radiation is independent of the generation of any optical soliton and mainly governed by the leading edge of an input pump which forms a shock front. The radiation is generated at the anomalous dispersion regime and found to be confined both in the time and frequency domain. We experimentally investigate the formation of such radiation in fabricated photonic crystal fiber for two different pulse width regimes (femtosecond and picosecond) with detailed theoretical analyses. Theoretically predicted results corroborate well with experimental results and confirm the existence of such unique radiation which is robust in nature. Further, we extend the study to long-length fiber and investigate the interplay between redshifted solitonic RR and intrapulse Raman scattering (IPRS). The consequence of the formation of such solitonic RR in an anomalous dispersion domain is found to be very interesting where it seeds a series of Raman solitons and behaves like a secondary source. These Raman solitons are now continuously redshifted and open up the possibility of wideband supercontinuum generation even in normal dispersion pumping. We fabricate a suitable photonic crystal fiber and experimentally demonstrate the RR-seeded IPRS process.

  7. Radiaxial-fibrous calcites: A new look at an old problem

    NASA Astrophysics Data System (ADS)

    Richter, D. K.; Neuser, R. D.; Schreuer, J.; Gies, H.; Immenhauser, A.

    2011-07-01

    Marine radiaxial-fibrous and fascicular-optic calcites are very common but poorly understood pore-filling cements in Paleozoic and Mesozoic marine neritic and upper bathyal limestones. The main diagnostic feature of these cements is their converging or diverging crystal c-axis, respectively. The reasons for this anomalous texture are at present unknown. Another controversy is due to the relative lack of occurrences in Cenozoic strata and their apparent absence in Quaternary marine limestones. Despite these uncertainties, marine fibrous cements are thought by some to be amongst the best proxies for the geochemistry of ancient oceans because of the absence of metabolic effects during their precipitation. Applying electron backscatter diffraction analysis, we here for the first time document radiaxial-fibrous and subordinate fascicular-optic fibrous biominerals from well-preserved Jurassic and Cretaceous low-Mg calcite belemnite rostra. The finding of fibrous biogenic calcites in combination with the recent description of Holocene and modern fibrous calcites in stalagmites representsin the view of the authorsa significant advance in carbonate research. Here, these findings are placed in their wider, processes-oriented context and the significance of biogenic and speloan fibrous calcite for their marine counterparts is assessed. Comparing the physico-chemical and organomineralic properties of different precipitation sites indicates that the diagnostic variations in the crystal c-axis orientation are not related to a specific nucleation environment or substratum. In contrast, preliminary crystallographic analyses suggest that kinetic factors during nucleation or subtle gradients in the statistical replacements of Ca 2+ by Mg 2+ in the crystal structure may lead to local strain resulting in converging or diverging crystal c-axes.

  8. Two-phase flow and calcite deposition

    SciTech Connect

    Gudmudsson, J.S.; Granadso-G, E.; Ortiz-R, J.

    1984-04-01

    The literature on two-phase flow in geothermal wells shows that the Orkiszewski method has found wide application in state-of-the-art wellbore simulators. Such a simulator was developed and then used for the problem of wellbore deposition of calcite in the Miravalles geothermal field in Costa Rica. The output of wells suffering calcite deposition decreases slowly at early time but rapidly at late time. The simulator was also used to estimate the deliverability curve for a large diameter well in the Svartsengi geothemal field in Iceland. The view is presented that more accurate wellbore simulators will make new reservoir engineering studies possible in geothermal fields.

  9. Low-magnesium calcite produced by coralline algae in seawater of Late Cretaceous composition

    PubMed Central

    Stanley, Steven M.; Ries, Justin B.; Hardie, Lawrence A.

    2002-01-01

    Shifts in the Mg/Ca ratio of seawater driven by changes in midocean ridge spreading rates have produced oscillations in the mineralogy of nonskeletal carbonate precipitates from seawater on time scales of 108 years. Since Cambrian time, skeletal mineralogies of anatomically simple organisms functioning as major reef builders or producers of shallow marine limestones have generally corresponded in mineral composition to nonskeletal precipitates. Here we report on experiments showing that the ambient Mg/Ca ratio actually governs the skeletal mineralogy of some simple organisms. In modern seas, coralline algae produce skeletons of high-Mg calcite (>4 mol % MgCO3). We grew three species of these algae in artificial seawaters having three different Mg/Ca ratios. All of the species incorporated amounts of Mg into their skeletons in proportion to the ambient Mg/Ca ratio, mimicking the pattern for nonskeletal precipitation. Thus, the algae calcified as if they were simply inducing precipitation from seawater through their consumption of CO2 for photosynthesis; presumably organic templates specify the calcite crystal structure of their skeletons. In artificial seawater with the low Mg/Ca ratio of Late Cretaceous seas, the algae in our experiments produced low-Mg calcite (<4 mol % MgCO3), the carbonate mineral formed by nonskeletal precipitation in those ancient seas. Our results suggest that many taxa that produce high-Mg calcite today produced low-Mg calcite in Late Cretaceous seas. PMID:12399549

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

    NASA Technical Reports Server (NTRS)

    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.

  11. Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule

    PubMed Central

    Politi, Yael; Metzler, Rebecca A.; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H.; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P. U. P. A.

    2008-01-01

    Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40–200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism. PMID:18987314

  12. The Crystal Hotel: A Microfluidic Approach to Biomimetic Crystallization.

    PubMed

    Gong, Xiuqing; Wang, Yun-Wei; Ihli, Johannes; Kim, Yi-Yeoun; Li, Shunbo; Walshaw, Richard; Chen, Li; Meldrum, Fiona C

    2015-12-01

    A "crystal hotel" microfluidic device that allows crystal growth in confined volumes to be studied in situ is used to produce large calcite single crystals with predefined crystallographic orientation, microstructure, and shape by control of the detailed physical environment, flow, and surface chemistry. This general approach can be extended to form technologically important, nanopatterned single crystals. PMID:26479157

  13. Calcitic microlenses as part of the photoreceptor system in brittlestars

    NASA Astrophysics Data System (ADS)

    Aizenberg, Joanna; Tkachenko, Alexei; Weiner, Steve; Addadi, Lia; Hendler, Gordon

    2001-08-01

    Photosensitivity in most echinoderms has been attributed to `diffuse' dermal receptors. Here we report that certain single calcite crystals used by brittlestars for skeletal construction are also a component of specialized photosensory organs, conceivably with the function of a compound eye. The analysis of arm ossicles in Ophiocoma showed that in light-sensitive species, the periphery of the labyrinthic calcitic skeleton extends into a regular array of spherical microstructures that have a characteristic double-lens design. These structures are absent in light-indifferent species. Photolithographic experiments in which a photoresist film was illuminated through the lens array showed selective exposure of the photoresist under the lens centres. These results provide experimental evidence that the microlenses are optical elements that guide and focus the light inside the tissue. The estimated focal distance (4-7m below the lenses) coincides with the location of nerve bundles-the presumed primary photoreceptors. The lens array is designed to minimize spherical aberration and birefringence and to detect light from a particular direction. The optical performance is further optimized by phototropic chromatophores that regulate the dose of illumination reaching the receptors. These structures represent an example of a multifunctional biomaterial that fulfills both mechanical and optical functions.

  14. The coordination and distribution of B in foraminiferal calcite

    NASA Astrophysics Data System (ADS)

    Branson, Oscar; Kaczmarek, Karina; Redfern, Simon A. T.; Misra, Sambuddha; Langer, Gerald; Tyliszczak, Tolek; Bijma, Jelle; Elderfield, Henry

    2015-04-01

    The isotopic ratio and concentration of B in foraminiferal calcite appear to reflect the pH and bicarbonate concentration of seawater. The use of B as a chemical proxy tracer has the potential to transform our understanding of the global carbon cycle, and ocean acidification processes. However, discrepancies between the theory underpinning the B proxies, and mineralogical observations of B coordination in biomineral carbonates call the basis of these proxies into question. Here, we use synchrotron X-ray spectromicroscopy to show that B is hosted solely as trigonal BO3 in the calcite test of Amphistegina lessonii, and that B concentration exhibits banding at the micron length scale. In contrast to previous results, our observation of trigonal B agrees with the predictions of the theoretical mechanism behind B palaeoproxies. These data strengthen the use of B for producing palaeo-pH records. The observation of systematic B heterogeneity, however, highlights the complexity of foraminiferal biomineralisation, implying that B incorporation is modulated by biological or crystal growth processes.

  15. Anisotropic Transverse Stress in Calcite and Sapphire Measured Using Birefringence

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    Many significant geological minerals have anisotropic crystal structures leading to material properties that are anisotropic, including compressive elastic behaviour. A non-invasive approach to investigate the directional dependence of transverse stress in these materials during shock compression would supplement current understanding. As many geological minerals are transparent and hence optically anisotropic, measuring the change in birefringence induced by transverse stress in the material offers the possibility of a fast, non-invasive approach to probe transverse behaviour. Shock compression experiments have been performed on a-cut calcite and a-cut sapphire for strain rates of order 105 s-1 and up to longitudinal stresses of 2 GPa for calcite and 12 GPa for sapphire. We present measured changes in birefringence for these materials under shock compression, comparing with current and past literature as well as an in house optical model. The authors would like to thank Mr Steve Johnson and Mr David Pittman for technical support. The Institute of Shock Physics acknowledges the continued support of AWE and Imperial College London.

  16. Functionalization of biomineral reinforcement in crustacean cuticle: Calcite orientation in the partes incisivae of the mandibles of Porcellio scaber and the supralittoral species Tylos europaeus (Oniscidea, Isopoda).

    PubMed

    Huber, Julia; Griesshaber, Erika; Nindiyasari, Fitriana; Schmahl, Wolfgang W; Ziegler, Andreas

    2015-05-01

    In arthropods the cuticle forms an exoskeleton with its physical and chemical properties adapted to functions of distinct skeletal elements. The cuticle of the partes incisivae (PI) in mandibles of terrestrial isopods is a composite of chitin-protein fibrils/fibres and minerals. It consists of an unmineralized tip, a middle region with organic fibrils reinforced mainly with amorphous calcium phosphate and a base region mineralized with amorphous calcium carbonate and calcite. In this study we extend our work on the structure and material properties of the incisive cuticle employing electron backscatter diffraction (EBSD), and investigate calcite orientation patterns in the PI of two terrestrial isopod species from different habitats. We trace small-scale differences in texture sharpness and calcite microstructure, and compare calcite organization and orientation patterns in the PI with those in the tergites of the same isopod species. We observe that in the PI calcite orientation, the degree of crystal alignment, and mode of crystalline domain assemblage is highly varied within short length scales. This contrasts to calcite organization in the tergite cuticle, where calcite has only one specific texture pattern. Such a large range in the variation of calcite organization has not been observed in other carbonate biological hard tissues, such as shells and teeth, where one specific texture and microstructure prevails. Thus, the investigated isopod species are able to control crystallization of the amorphous carbonate precursor in a differential way, most probably related to the function of the individual skeletal element and the animals' behavior. PMID:25818510

  17. Strain rate dependent calcite microfabric evolution at natural conditions

    NASA Astrophysics Data System (ADS)

    Rogowitz, Anna; Grasemann, Bernhard; Huet, Benjamin; Habler, Gerlinde

    2014-05-01

    Crystal plastic deformational behaviour of calcite has been the focus of many experimental studies. Different strain rates, pressure and temperature conditions have been addressed to investigate a wide range of deformation regimes. However, a direct comparison with natural fault rocks remains difficult because of extreme differences between experimental and natural strain rates. A flanking structure developed in almost pure calcite marble on Syros (Cyclades, Greece). Due to rotation of a planar feature (crack) a heterogeneous strain field in the surrounding area occurred resulting in different strain domains and the formation of the flanking structure. Assuming that deformation was active continuously during the development of the flanking structure, the different strain domains correspond to different strain-rate domains. The outcrop thus represents the final state of a natural experiment and gives us a great opportunity to get natural constraints on strain rate dependent deformation behaviour of calcite. Comparing the microfabrics in the 1 to 2.5 cm thick shear zone and the surrounding host rocks, which formed under the same metamorphic conditions but with different strain rates, is the central focus of this study. Due to the extreme variation in strain and strain rate, different microstructures and textures can be observed corresponding to different deformation mechanisms. With increasing strain rate we observe a change in dominant deformation mechanism from dislocation glide to dislocation creep and finally diffusion creep. Additionally, a change from subgrain rotation to bulging recrystallization can be observed in the dislocation creep regime. Crystallographic preferred orientations (CPO) and the grade of intracrystalline deformation were measured on a FEI Quanta 3D FEG instrument equipped with an EDAX Digiview IV EBSD camera. At all strain rates clear CPOs developed leading to the assumption that calcite preferentially deforms within the dislocation creep field. However, we can also find clear evidence for grain size sensitive deformation mechanisms at smaller grain sizes (3.6 ?m) consistent with experimental observations and determined flaw laws. The results of this study are compared with experimental data, closing the gap between experimental and natural geological strain rates.

  18. Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

    ERIC Educational Resources Information Center

    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…

  19. Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

    ERIC Educational Resources Information Center

    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

  20. Solar bleaching of thermoluminescence of calcites

    NASA Astrophysics Data System (ADS)

    Liritzis, I.; Guibert, P.; Foti, F.; Schvoerer, M.

    1996-09-01

    Original results of solar bleaching of thermoluminescence (TL) of twelve Greek calcitic (limestone, marble) stone profiles have been obtained. The residual TL signal due to sunlight exposures (zero to 130 h) differs in samples, but in general follows an exponential decay form consisting of one or two components. The first component bleaches fast within the first 30-70 h and the second component bleaches slowly; the latter, occasionally, formed a residual plateau. The first exponential term decays with different rates ranging between 1 - 6 (%/h) for the 280C TL peak and slower, 0.1-0.3 (%/h) for the 350C TL peak. Phototransferred TL (PTTL) of the 280 and 350C TL peaks giving rise to a PTTL peak at around 180C, was observed. The residual TL glow curve shape variation as a function of daylight exposure time is provisionally used to further develop the method of dating carved megalithic masonry [1]. The solar bleached TL signal of calcites provides bleached TL curves characterestics which inhere useful information regarding dating of calcitic stones derived from archaeological sites, and contribute to the complex luminescence phenomenon in calcites.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    The origin of spherical-radial calcite bodies - spherulites - in sublacustrine, hyperalkaline and saline systems is unclear, and therefore their palaeoenvironmental significance as allochems is disputed. Here, we experimentally investigate two hypotheses concerning the origin of spherulites. The first is that spherulites precipitate from solutions super-saturated with respect to magnesium-silicate clays, such as stevensite. The second is that spherulite precipitation happens in the presence of dissolved, organic acid molecules. In both cases, experiments were performed under sterile conditions using large batches of a synthetic and cell-free solution replicating waters found in hyperalkaline, saline lakes (such as Mono Lake, California). Our experimental results show that a highly alkaline and highly saline solution supersaturated with respect to calcite (control solution) will precipitate euhedral to subhedral rhombic and trigonal bladed calcite crystals. The same solution supersaturated with respect to stevensite precipitates sheet-like stevensite crystals rather than a gel, and calcite precipitation is reduced by ~ 50% compared to the control solution, producing a mixture of patchy prismatic subhedral to euhedral, and minor needle-like, calcite crystals. Enhanced magnesium concentration in solution is the likely the cause of decreased volumes of calcite precipitation, as this raised equilibrium ion activity ratio in the solution. On the other hand, when alginic acid was present then the result was widespread development of micron-size calcium carbonate spherulite bodies. With further growth time, but falling supersaturation, these spherules fused into botryoidal-topped crusts made of micron-size fibro-radial calcite crystals. We conclude that the simplest tested mechanism to deposit significant spherical-radial calcite bodies is to begin with a strongly supersaturated solution that contains specific but environmentally-common organic acids. Furthermore, we found that this morphology is not a universal consequence of having organic acids dissolved in the solution, but rather spherulite development requires specific binding behaviour. Finally, we found that the location of calcite precipitation was altered from the air:water interface to the surface of the glassware when organic acids were present, implying that attached calcite precipitates reflect precipitation via metal-organic intermediaries, rather than direct forcing via gas exchange.

  2. Planktic Foraminiferal Sedimentation and Calcite Budget

    NASA Astrophysics Data System (ADS)

    Schiebel, R.

    2002-12-01

    Vertical flux and sedimentation rate of planktic foraminiferal tests is quantified on a global scale. The planktic foraminiferal test flux is a consequence of the population dynamics, and the differential settling modes for different species are a precondition for the differences in the regional flux rates. The average planktic foraminiferal calcite flux rate at the 100-m depth-level is estimated at 50% of the global-marine calcite flux and 6% of the total carbon flux. The most significant decrease in the planktic foraminiferal test flux rates between 100-700 m water depth possibly results from increased bacterially-mediated decomposition of cytoplasm and a decreasing pH in microenvironments within foraminiferal tests. Throughout most of the year, on average only 1-3% of the initially exported CaCO3 reaches the deep sea floor. Pulsed flux events, mass dumps of fast settling particles, yield a major contribution of tests to the formation of deep-sea sediments. On a global average, ~25% of the total calcite produced by planktic foraminifers arrives in the deep ocean and at the sediment surface. To complete the open-marine, particulate CaCO3 inventory, the contribution of coccolithophores, pteropods, and calcareous dinophytes is discussed. The global planktic foraminiferal calcite flux rate at 100 m depth amounts to 23-56% of the total open marine CaCO3 flux. The total planktic foraminiferal contribution of CaCO3 to global surface sediments is estimated at 0.36-0.88 Gt per year, ~30-80% of the total deep-marine calcite budget.

  3. Inhibition of calcite precipitation by natural organic material: Kinetics, mechanism, and thermodynamics

    USGS Publications Warehouse

    Lin, Y.-P.; Singer, P.C.; Aiken, G.R.

    2005-01-01

    The inhibition of calcite precipitation by natural organic material (NOM) in solutions seeded with calcite was investigated using a pH-stat system. Experiments were carried out using three NOMs with different physical/chemical properties. For each of the materials, inhibition was found to be more effective at lower carbonate/calcium ratios and lower pH values. The reduction in the precipitation rate could be explained by a Langmuir adsorption model using a conditional equilibrium constant. By identification of the type of site on the NOM molecules that is involved in the adsorption reaction, the "conditional" equilibrium constants obtained at different solution compositions converged to a single "nonconditional" value. The thermodynamic data determined at 25??C and 1 atm suggest that the interaction between NOM molecules and the calcite surface is chemisorptive in nature and that adsorption is an endothermic reaction driven by the entropy change. The greatest degree of inhibition was observed for the NOM with the highest molecular weight and aromatic carbon content. For a given type of NOM, the degree of inhibition of calcite precipitation was dictated by the balance between the enthalpy change and the entropy change of the adsorption reaction. ?? 2005 American Chemical Society.

  4. The puzzling presence of calcite in skeletons of modern solitary corals from the Mediterranean Sea

    NASA Astrophysics Data System (ADS)

    Goffredo, Stefano; Caroselli, Erik; Mezzo, Francesco; Laiolo, Leonardo; Vergni, Patrizia; Pasquini, Luca; Levy, Oren; Zaccanti, Francesco; Tribollet, Aline; Dubinsky, Zvy; Falini, Giuseppe

    2012-05-01

    The skeleton of scleractinian corals is commonly believed to be composed entirely of aragonite due to the current Mg/Ca molar ratio of seawater, which thermodynamically favours the deposition of this polymorph of calcium carbonate (CaCO3). However, some studies have shown that other forms of CaCO3 such as calcite can be present in significant amount (1-20%) inside tropical coral skeletons, significantly impacting paleo-reconstructions of SST or other environmental parameters based on geochemical proxies. This study aims at investigating for the first time, (1) the skeletal composition of two Mediterranean solitary corals, the azooxanthellate Leptopsammia pruvoti and the zooxanthellate Balanophyllia europaea, across their life cycle, (2) the distribution of the different CaCO3 forms inside skeletons, and (3) their implications in paleoclimatology. The origin of the different forms of CaCO3 observed inside studied coral skeletons and their relationships with the species' habitat and ecological strategies are also discussed. CaCO3 composition of L. pruvoti and B. europaea was investigated at six sites located along the Italian coasts. Skeleton composition was studied by means of X-ray powder diffraction and Fourier transform infrared spectroscopy. A significant amount of calcite (1-23%) was found in more than 90% of the studied coral skeletons, in addition to aragonite. This calcite was preferentially located in the basal and intermediate areas than at the oral pole of coral skeletons. Calcite was also mainly located in the epitheca that covered the exposed parts of the coral in its aboral region. Interestingly in B. europaea, the calcite content was negatively correlated with skeleton size (age). The presence of calcite in scleractinian corals may result from different mechanisms: (1) corals may biologically precipitate calcite crystals at their early stages in order to insure their settlement on the substrate of fixation, especially in surgy environments; (2) calcite presence may result from skeletons of other calcifying organisms such as crustose coralline algae; and/or (3) calcite may result from the infilling of galleries of boring microorganisms which are known to colonize coral skeletons. We suggest that more than one of the above mentioned processes are involved.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  6. EXAFS Characterization of Uranyl Interaction at the Calcite-Water Interface

    NASA Astrophysics Data System (ADS)

    Reeder, R. J.; Elzinga, E. J.; Tait, C. D.

    2002-12-01

    Recent studies using X-ray absorption and luminescence spectroscopies have demonstrated uptake and incorporation of uranyl by calcite. X-ray microprobe studies on uranyl-reacted calcite single crystals reveal that uranyl exhibits preferences for specific surface sites. These preferences are likely expressed upon adsorption of uranyl species at the calcite-water interface. We have used X-ray absorption fine structure (EXAFS), combined with luminescence spectroscopy, to characterize the interactions of uranyl carbonate species with the calcite surface in the pH range 7.4-8.3. To minimize the potential for dissolution or precipitation, solutions were pre-equilibrated with reagent calcite powder for 3 weeks, with pH stabilizing at 8.3. For other experiments, the pH was adjusted initially to achieve a final pH of 7.4 after aging for 3 weeks. Uranyl carbonate solution was added to the pre-equilibrated suspensions to achieve initial U(VI) concentrations ranging from 5 uM to 5 mM. Suspensions were filtered to recover the calcite, but were kept moist to retain the sorbed complexes at the calcite-water interface. Multiple EXAFS spectra were collected using a multi-element Ge detector at beamline 12-BM at the APS and analyzed using standard methods. Fourier transforms (FT) of the spectra contain features corresponding to two axial oxygens and a shell of equatorial oxygens, as well as weaker features at higher R. For suspensions having initial U(VI) concentrations from 5-100 uM, a shoulder is observed in the FT on the high-R side of the equatorial oxygen, and fitting suggests minor splitting of this shell. For higher initial U(VI) concentrations, including the highest U(VI) concentration, 5 mM, the splitting becomes more pronounced. Weak features in the FT at higher-R can be fitted with backscattering from carbon, oxygen, and calcium shells, although fits without calcium provide nearly the same agreement. Luminescence spectroscopy reveals the presence of multiple uranyl species sorbed on the calcite from suspensions with 100 uM U(VI) and lower concentrations. The presence of multiple species may account for the splitting of the equatorial coordination indicated by EXAFS. For higher U(VI) concentrations, the luminescence results are consistent with formation of a schoepite-like precipitate. Understanding the complex interactions of uranyl at the calcite-water interface requires complementary data from multiple techniques.

  7. Understanding control of calcitic biomineralization-proteomics to the rescue.

    PubMed

    Hincke, Maxwell T

    2013-12-01

    The avian eggshell is one of the fastest calcifying processes known and represents a unique model for studying biomineralization. Eggshell strength is a crucial economic trait for table egg production, and ensures that a safe egg reaches the consumer kitchen. However, a common toolkit for eggshell mineralization has not yet been defined. In this issue, label-free MS-based protein quantification technology has been used by Sun et al. (Proteomics 2013, 13, 3523-3536) to detect differences in protein abundance between eggshell matrix from strong and weak eggs and between the corresponding uterine fluids bathing strong and weak eggs. Proteins associated with the formation of strong eggshells are identified, which are now candidates for further investigations to define the regulatory relationship between specific eggshell matrix proteins and calcite crystal texture. PMID:24307661

  8. Shock-induced effects in calcite from Cactus Crater

    NASA Technical Reports Server (NTRS)

    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.

  9. Controls on trace-element partitioning in cave-analogue calcite

    NASA Astrophysics Data System (ADS)

    Day, Christopher C.; Henderson, Gideon M.

    2013-11-01

    We report trace-element data from a series of carbonate growth experiments in cave-analogue conditions in the laboratory with the goal of better understanding environmental controls on trace-element incorporation in stalagmites. The experimental setup closely mimics natural processes (e.g. precipitation driven by CO2-degassing, low ionic strength solution, thin solution-film) but with a tight control on growth conditions (temperature, pCO2, drip rate, calcite saturation index and the composition of the initial solution). Calcite is dissolved in deionized water in a 20,000 ppmV pCO2 environment, with trace-elements (Li, Na, Mg, Co, Sr, Cd, Ba, U) at appropriate concentrations to mimic natural cave drip-waters. This solution is dripped onto glass plates (coated with seed-calcite) in a lower pCO2 environment at 7, 15, 25 and 35 C and drip rates of 2, 6 and 10 drips per minute. D(Sr) was shown to be statistically invariant over the full range of temperature and growth rate studied. No relationship between Sr/Ca and growth rate is therefore expected in stalagmite samples over comparable growth rates. D(Mg) has a relationship with temperature defined by D(Mg) = 0.01e0.02[0.006]T, but temperature is not expected to be the dominant control on Mg/Ca in cave calcite due to the larger impact of calcite precipitation on Mg/Ca. Over short timescales, in conditions where temperature is well buffered, the fraction of calcium remaining in solution (f) is likely to be the dominant control on Mg/Ca and other trace-element ratios. But differences in the response of trace-elements to f and T may allow their combined use to assess past cave conditions. High Cd/Castalagmite is particularly indicative of low amounts of prior calcite precipitation and Cd/Ca would be a useful addition to trace-element studies of natural stalagmites. Significant scatter is observed in trace-element ratios during the laboratory experiments, which cannot be explained by simple Rayleigh distillation. This scatter is well explained by solution mixing and by the mixing of calcite with different fractions of calcite growth. Accounting for the effects of mixing on trace-element concentrations or ratios may help to achieve more robust interpretations of stalagmite chemistry as part of a multi-proxy approach to assessment of past environments.

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

    USGS Publications Warehouse

    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 protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.

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

    SciTech Connect

    Roedder, E.; Whelan, J.F.; Vaniman, D.T.

    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.

  12. in situ Calcite Precipitation for Contaminant Immobilization

    SciTech Connect

    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 a well (which can lead to clogging). A final particularly attractive characteristic of this approach is its long-term sustainability; the remediation scheme is geared toward environments that are already saturated with respect to calcite, and in such systems the bulk of any newly precipitated calcite will remain stable once engineered manipulations cease. This means that the co-precipitated contaminants will be effectively sequestered over the long term. We are currently conducting integrated field, laboratory, and computational research to evaluate a) the relationships between urea hydrolysis rate, calcite precipitation rate, and trace metal partitioning under environmentally relevant conditions; and b) the coupling between flow/flux manipulations and calcite precipitate distribution and metal uptake. We are also assessing the application of geophysical and molecular biological tools to monitor the relevant chemical and physical processes. The primary emphasis is on field-scale processes, with the laboratory and modeling activities designed specifically to support the field studies. Field experiments are being conducted in perched water (vadose zone) at the Vadose Zone Research Park (VZRP) at the Idaho National Laboratory; the VZRP provides an uncontaminated setting that is an analog of the 90Sr-contaminated vadose zone at the Idaho Nuclear Technology and Engineering Center. A summary of results to date will be presented.

  13. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    SciTech Connect

    Gorman, Brian P

    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 growth mechanism was confirmed by grazing incidence X-ray diffraction, µ-Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and electron diffraction. Extended time studies out to 45 days confirmed the epitaxial relationship of the overgrowth layer with the substrate. Under NSW conditions, overgrowths were found to have ~0.4 to 0.8 nm / hr growth rates and accommodating 4 at% Mg, resulting in a highly strained overgrowth layer. Following the initial layer by layer growth mechanism, the growth changes to Stranski-Krastanov type after a critical thickness of approximately 100 nm.

  14. Dissolution Kinetics of Biogenic Magnesian Calcites

    NASA Astrophysics Data System (ADS)

    Thompson, R.; Guidry, M.; Mackenzie, F. T.; De Carlo, E. H.

    2014-12-01

    Ocean acidification (OA) is a serious concern for the health of calcifying ecosystems in the near future. During the past century, surface ocean pH has decreased by ~0.1 pH units, and is expected to decrease further by 0.3-0.4 pH units by the end of this century. The process of OA will likely result in both decreased calcification rates and increased rates of carbonate mineral dissolution, particularly involving the magnesian calcite (Mg-calcite) calcifiers found in shallow-water reef and other carbonate environments. Many Mg-calcite compositions are the most soluble of the carbonate phases commonly found in reef environments (often comprising much of the cementation and structure within a reef), and are therefore potentially the most susceptible to dissolution processes associated with OA. However, the dissolution kinetics of these phases is poorly known, limiting our ability to understand their behavior in nature. Laboratory experiments designed to investigate the mechanisms and dissolution rates of biogenic Mg-calcite mineral phases in distilled water and seawater over a range of CO2 and T conditions were conducted employing both batch and fluidized-bed reactor systems and using a variety of cleaned and annealed biogenic Mg-calcite phases. Our initial results have shown that the dissolution rate at 298 K and a pCO2 of ~350 ppm of the crustose coralline alga Amphiroa rigida (~20 mol% MgCO3) in seawater undersaturated with respect to this phase is 3.6 ?mol g-1 hr-1, nearly 50% greater than that under similar conditions for aragonite. This rate and the derived experimental rate law are consistent with the preliminary findings of Walter and Morse (1985). Additional kinetic (and also solubility) data will be presented for the following species: Chiton tuberculatus (~0-4 mol% MgCO3); Echinometra mathei and/or Lytechinus variegatus (~8-12 mol% MgCO3); Homotrema rubrum (12-16 mol% MgCO3); and Lithothamnion sp. (~18-24 mol% MgCO3). Quantification of the rates of dissolution for a broad range of Mg-calcite phases, along with determination of sediment mineralogy, is necessary to allow managers to model and predict quantitatively the impacts of OA on a variety of coral reef and other carbonate-dominated sedimentary environments.

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

    USGS Publications Warehouse

    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.

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

    PubMed

    Ct, 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. PMID:26177610

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

    PubMed

    Du, Yang; Lian, Fei; Zhu, Lingyan

    2011-07-01

    The potential of using mollusk shell powder in aragonite (razor clam shells, RCS) and calcite phase (oyster shells, OS) to remove Pb(2+), Cd(2+) and Zn(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. PMID:21550150

  18. Preparation and formation mechanism of wood-block-like calcite particles

    SciTech Connect

    Guo Hua; Yu Jiaguo . E-mail: jiaguoyu@yahoo.com; Cheng Bei

    2006-08-15

    Pure calcite crystal with different morphologies such as wood-block and spherical aggregates were prepared by a precipitation reaction in the presence of citric acid. The as-prepared products were characterized with scanning electron microscope (SEM) and X-ray diffraction (XRD). The results showed that citric acid obviously influenced the formation of precipitates and the morphology of final products. The formation mechanism of wood-block-like particles was proposed according to theoretical deduction and the proposed growth mode. - Graphical abstract: Pure calcite crystal with different morphologies such as wood-block and spherical aggregates were prepared by a simple precipitation reaction in the presence of citric acid and the formation mechanism was proposed.

  19. Frictional behavior of talc-calcite mixtures

    NASA Astrophysics Data System (ADS)

    Giorgetti, C.; Carpenter, B. M.; Collettini, C.

    2015-09-01

    Faults involving phyllosilicates appear weak when compared to the laboratory-derived strength of most crustal rocks. Among phyllosilicates, talc, with very low friction, is one of the weakest minerals involved in various tectonic settings. As the presence of talc has been recently documented in carbonate faults, we performed laboratory friction experiments to better constrain how various amounts of talc could alter these fault's frictional properties. We used a biaxial apparatus to systematically shear different mixtures of talc and calcite as powdered gouge at room temperature, normal stresses up to 50 MPa and under different pore fluid saturated conditions, i.e., CaCO3-equilibrated water and silicone oil. We performed slide-hold-slide tests, 1-3000 s, to measure the amount of frictional healing and velocity-stepping tests, 0.1-1000 µm/s, to evaluate frictional stability. We then analyzed microstructures developed during our experiments. Our results show that with the addition of 20% talc the calcite gouge undergoes a 70% reduction in steady state frictional strength, a complete reduction of frictional healing and a transition from velocity-weakening to velocity-strengthening behavior. Microstructural analysis shows that with increasing talc content, deformation mechanisms evolve from distributed cataclastic flow of the granular calcite to localized sliding along talc-rich shear planes, resulting in a fully interconnected network of talc lamellae from 20% talc onward. Our observations indicate that in faults where talc and calcite are present, a low concentration of talc is enough to strongly modify the gouge's frictional properties and specifically to weaken the fault, reduce its ability to sustain future stress drops, and stabilize slip.

  20. Calcite Precipitation and Trace Metal Partitioning in Groundwater and the Vadose Zone: Remediation of Strontium-90 and Other Divalent Metals and Radionuclides in Arid Western Environments

    SciTech Connect

    Smith, Robert W.; Colwell, F. ''Rick'' S.; Ingram, Jani C.; Ferris, F. Grant; Reysenbach, Anna-Louise

    2001-08-09

    Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) weapons complex. Demonstrating in situ immobilization of these contaminants in vadose zones or groundwater plumes is a cost-effective remediation strategy. However, the implementation of in situ remediation requires definition of the mechanism that controls sequestration of the contaminants. One such mechanism for metals and radionuclides is co-precipitation of these elements in authigenic calcite and calcite overgrowths. Calcite, a common mineral in many aquifers and vadose zones in the arid western U.S., can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of solid solutions. 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, solid solution properties of the trace metal in calcite, 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 may occur in aquifers and vadose environments is lacking. The focus of the research proposed here is to investigate the facilitated partitioning of metal and radionuclides by their coprecipitation with calcium carbonate. Our specific research objectives include: (1) Elucidating the mechanisms and rates of microbially facilitated calcite precipitation and divalent cation adsorption/co-precipitation occurring in a natural aquifer as a result of the introduction of urea. (2) Assessing the effects of spatial variability in aquifer host rock and the associated hydro/biogeochemical processes on calcite precipitation rates and mineral phases within an aquifer.

  1. Trace elements in calcite from carbonatite of the Bear Lodge deposit, northeast Wyoming: evidence of hydrothermal alteration?

    NASA Astrophysics Data System (ADS)

    Olinger, D.

    2012-12-01

    The Bear Lodge Mountains of northeast Wyoming is the locality of a carbonatite-hosted rare earth element deposit. The carbonatite is emplaced as subvertical, northwest trending dikes primarily situated within three diatreme structures. Carbonatite dikes located outside the northern boundary of the Bull Hill diatremenorthwest Bull Hillare narrower, trend north-south, and have lower ore grades. Characterization of carbonatite dikes from northwest Bull Hill reveals several calcite textures. These textures include: fine-grained, anhedral, inclusion free calcite frequently displaying 120 degree contacts; coarser-grained, consertal to serrated, equant to elongate, inclusion rich calcite; and coarser-grained, euhedral, rhombic calcite. The fine-grained calcite was first theorized to be related to chill margins except it was found to be mottled with coarser-grained calcite throughout the samples and/or proximal to hexagonal pseudomorphs. Rare earth mineralization in the Bear Lodge deposit is primarily secondary rare earth element carbonate mineral aggregates in hexagonal pseudomorphs after a primary rare earth mineral. The differing calcite textures could be a result of hydrothermal alteration and/or fluid driven recrystallization associated with the production of hexagonal pseudomorphs. Calcite from carbonatite samples of varying texture and mineralogy were analyzed using LA-ICPMS. The majority of samples contain calcite with two or more chondrite normalized rare earth element patterns: 1) A majority of coarser-grained calciterhombic and consertalhave log-linear, steep (La/YbCN= 500 to 4000) to moderate (La/YbCN=7 to 37), negative patterns from La (values 1000 to 4000 times chondrites) to Lu (values 2 to 30 times chondrites). 2) Several coarse-grained calcite and finer-grained, consertal calcite in samples containing abundant hexagonal pseudomorphs have relatively flat patterns with slight undulations at the middle rare earth elements. Rare earth element values range from 20 to 300 times chondrites. 3) A majority of fine-grained, anhedral calcite proximal and distal to hexagonal pseudomorphs have convex up, "humped", chondrite normalized rare earth element patterns with a positive slope (La/GdCN= 0.01 to 0.36) from La to Sm or Gd and a steeper negative slope from Sm or Gd to Tm which flattens from Tm to Lu. The slope from the middle rare earth elements to Lu parallels the trends of observed linear patterns. Linear, negative chondrite normalized rare earth element trends have been ascribed to calcite crystallizing as the main phase in a light rare earth element-rich carbonatite. The relatively flat chondrite normalized rare earth element patterns could relate to cumulate processes or late-stage calcite crystallization after a rare earth element enriched phase/phases. Hydrothermal processes or co-crystallization of a light rare earth element bearing phase could explain the "humped" chondrite normalized rare earth element patterns with light rare earth element depletion while a seemingly "magmatic" trend from middle to heavy rare earth elements is maintained.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  3. Orientation and Mg Incorporation of Calcite Grown on Functionalized Self-Assembled Monolayers: A Synchrotron X-ray Study

    SciTech Connect

    Kwak,S.; DiMasi, E.; Han, Y.; Aizenberg, J.; Kuzmenko, I.

    2005-01-01

    Calcite crystals were nucleated from MgCl2/CaCl2 solutions onto functionalized self-assembled monolayers adsorbed onto E-beam evaporated Au films. Synchrotron X-ray scattering studies of the crystals reveal new information about preferred orientation and Mg incorporation. The Au [111] axis is distributed within 2.6 degrees of the film surface normal, but the oriented crystals may be tilted up to 6 degrees away from this axis. For low Mg{sup 2+} content, SO{sub 3}--functionalized films nucleated primarily near the (106) calcite face, odd-chain-length carboxylic acid terminated alkanethiol films nucleated near the (012) face, and even-chain-length carboxylic acid terminated alkanethiol films nucleated near the (113) face. [Mg{sup 2+}]/[Ca{sup 2+}] concentration ratios (n) of 2 and greater defeated this preferred orientation and created a powder texture. Diffraction patterns within the layer plane from the coarse calcite powders indicated a shift to higher 2 accompanied by peak broadening with increasing n. For 0.5 < n < 3.5, a double set of calcite peaks is observed, showing that two distinct Mg calcite phases form: one of comparatively lower Mg content, derived from the templated crystals, and a Mg-rich phase derived from amorphous precursor particles. According to the refinement of lattice parameters, Mg incorporation of up to 18 mol % occurs for n = 4, independent of film functionality. We discuss the differences between the differently functionalized monolayers and also introduce the hypothesis that two separate routes to Mg calcite formation occur in this system.

  4. Crystallization and preliminary X-ray diffraction studies of frutalin, an α-D-galactose-specific lectin from Artocarpus incisa seeds.

    PubMed

    Monteiro-Moreira, Ana Cristina de Oliveira; D'Muniz Pereira, Humberto; Vieira Neto, Antonio Eufrasio; Mendes Batista Moreno, Frederico Bruno; Duarte Pinto Lobo, Marina; de Sousa, Felipe Domingos; Moreira, Renato de Azevedo

    2015-10-01

    Frutalin is an α-D-galactose-specific carbohydrate-binding glycoprotein with antitumour properties and is a powerful tool for tumour biomarker discovery. The crystallization and preliminary X-ray diffraction analysis of this lectin, which was isolated from Artocarpus incisa seeds, are reported here. Frutalin was purified and submitted to mass-spectrometric analysis. Diverse masses at approximately 16 kDa were observed in the deconvoluted spectra, which support the presence of isoforms. The best frutalin crystals were grown within a week in 0.1 M citric acid pH 3.5 which contained 25% PEG 3350 as a precipitant at 293 K, and diffracted to a maximum resolution of 1.81 Å. The monoclinic crystals belonged to space group I2, with unit-cell parameters a = 76.17, b = 74.56, c = 118.98 Å, β = 96.56°. A molecular-replacement solution was obtained which indicated the presence of four monomers per asymmetric unit. Crystallographic refinement of the structure is in progress. PMID:26457519

  5. Arsenate Uptake by Calcite: Macroscopic and Spectroscopic Characterization of Adsorption and Incorporation Mechanisms

    SciTech Connect

    Alexandratos,V.; Elzinga, E.; Reeder, R.

    2007-01-01

    Batch uptake experiments and X-ray element mapping and spectroscopic techniques were used to investigate As(V) (arsenate) uptake mechanisms by calcite, including adsorption and coprecipitation. Batch sorption experiments in calcite-equilibrated suspensions (pH 8.3; PCO{sub 2} = 10{sup -3.5} atm) reveal rapid initial sorption to calcite, with sorption rate gradually decreasing with time as available sorption sites decrease. An As(V)-calcite sorption isotherm determined after 24 h equilibration exhibits Langmuir-like behavior up to As concentrations of 300 {mu}M. Maximum distribution coefficient values (K{sub d}), derived from a best fit to a Langmuir model, are {approx}190 L kg{sup -1}. Calcite single crystals grown in the presence of As(V) show well-developed rhombohedral morphology with characteristic growth hillocks on (10{bar 1}4) surfaces at low As(V) concentrations ({<=}5 {mu}M), but habit modification is evident at As(V) concentrations {>=}30 {mu}M in the form of macrostep development preferentially on the - vicinal surfaces of growth hillocks. Micro-X-ray fluorescence element mapping of (10{bar 1}4) surfaces shows preferential incorporation of As in the - vicinal faces relative to + vicinals. EXAFS fit results for both adsorption and coprecipitation samples confirm that As occurs in the 5+ oxidation state in tetrahedral coordination with oxygen, i.e., as arsenate. For adsorption samples, As(V) forms inner-sphere surface complexes via corner-sharing with Ca octahedra. As(V) coprecipitated with calcite substitutes in carbonate sites but with As off-centered, as indicated by two Ca shells, and with likely disruption of local structure. The results indicate that As(V) interacts strongly with the calcite surface, similar to often-cited analog phosphate, and uptake can occur via both adsorption and coprecipitation reactions. Therefore, calcite may be effective for partial removal of dissolved arsenate from aquatic and soil systems.

  6. The Influence of Temperature, pH, and Growth Rate on the Stable Isotope Composition of Calcite

    NASA Astrophysics Data System (ADS)

    Watkins, J. M.; Hunt, J. D.; Ryerson, F. J.; DePaolo, D. J.

    2014-12-01

    The oxygen isotope composition of carbonate minerals varies with temperature as well as other environmental variables. For carbonates that precipitate slowly, under conditions that approach thermodynamic equilibrium, the temperature-dependence of 18O uptake is the dominant signal and the measured 18O content can be used as a paleotemperature proxy. In the more common case where carbonate minerals grow in a regime where they are not in isotopic equilibrium with their host solution, their stable isotope compositions are a convolution of the effects of multiple environmental variables. We present results from inorganic calcite growth experiments demonstrating the occurrence of non-equilibrium oxygen isotope effects that vary systematically with pH and crystal growth rate. We have developed an isotopic ion-by-ion crystal growth model that quantifies the competing roles of temperature, pH, and growth rate, and provides a general description of calcite-water oxygen isotope fractionation under non-equilibrium conditions. The model predicts that (1) there are both equilibrium and kinetic contributions to calcite oxygen isotopes at biogenic growth rates, (2) calcite does not inherit the stable isotopic composition of dissolved inorganic carbon (DIC), (3) for oxygen isotopes there is a kinetically controlled variation of about 1 per pH unit between pH=7.7 and 9.3 at constant growth rate for inorganic calcite as well as the foraminifera Orbulina universa, and (4) extreme light isotope enrichments in calcite in alkaline environments are likely due to disequilibrium among DIC species in aqueous solution. The experimental and modeling approaches can be extended to carbon isotope as well as clumped isotope uptake into calcite but additional data are needed to constrain the kinetic fractionation factors for carbon isotopes and doubly-substituted isotopologues. The results will be discussed in the context of separating the relative influence of inorganic and biologic processes on isotopic fractionation.

  7. Intrinsic versus extrinsic controls on the development of calcite dendrite bushes, Shuzhishi Spring, Rehai geothermal area, Tengchong, Yunnan Province, China

    NASA Astrophysics Data System (ADS)

    Jones, Brian; Peng, Xiaotong

    2012-04-01

    In the Rehai geothermal area, located near Tengchong, there is an old succession of crystalline calcite that formed from a spring that is no longer active. The thin-bedded succession, exposed on the south bank of Zaotang River, is formed of three-dimensional dendrite bushes that are up to 6 cm high and 3 cm in diameter with multiple levels of branching. Bedding is defined by color, which ranges from white to gray to almost black and locally accentuated by differential weathering that highlights the branching motif of the dendrites. The succession developed through repeated tripartite growth cycles that involved: Phase I that was characterized by rapid vertical growth of the dendrite bushes with ever-increasing branching; Phase II that developed once growth of the dendrites had almost or totally ceased, and involved an initial phase of etching that was followed by the precipitation of various secondary minerals (sheet calcite, trigonal calcite crystals, hexagonal calcite crystals, hexagonal plates formed of Ca and P, Mn precipitates, Si-Mg reticulate coatings, opal-CT lepispheres) on the branches of the calcite dendrites, and Phase III that involved deposition of detrital quartz, feldspar, clay, and calcite on top of the dendrite bushes. The tripartite growth cycle is attributed primarily to aperiodic cycles in the CO2 content of the spring water that was controlled by subsurface igneous activity rather than climatic controls. High CO2 coupled with rapid CO2 degassing triggered growth of the dendrite bushes. As CO2 levels waned, saturation levels in the spring water decreased and calcite dendrite growth ceased and precipitation of the secondary minerals took place, possibly in the microcosms of microbial mats. Deposition of the detrital sediment was probably related to surface runoff that was triggered by periods of high rainfall. Critically, this study shows that intrinsic factors rather than extrinsic factors (e.g., climate) were the prime control on the development of the tripartite growth cycle.

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Visualising the molecular alteration of the calcite (104) - water interface by sodium nitrate.

    PubMed

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

    2016-01-01

    The reactivity of calcite, one of the most abundant minerals in the earth's crust, is determined by the molecular details of its interface with the contacting solution. Recently, it has been found that trace concentrations of NaNO3 severely affect calcite's (104) surface and its reactivity. Here we combine molecular dynamics (MD) simulations, X-ray reflectivity (XR) and in situ atomic force microscopy (AFM) to probe the calcite (104) - water interface in the presence of NaNO3. Simulations reveal density profiles of different ions near calcite's surface, with NO3(-) able to reach closer to the surface than CO3(2-) and in higher concentrations. Reflectivity measurements show a structural destabilisation of the (104) surfaces' topmost atomic layers in NaNO3 bearing solution, with distorted rotation angles of the carbonate groups and substantial displacement of the lattice ions. Nanoscale AFM results confirm the alteration of crystallographic characteristics, and the ability of dissolved NaNO3 to modify the structure of interfacial water was observed by AFM force spectroscopy. Our experiments and simulations consistently evidence a dramatic deterioration of the crystals' surface, with potentially important implications for geological and industrial processes. PMID:26877225

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

    SciTech Connect

    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.

  11. Nanoscale effects of strontium on calcite growth: An in situ AFM study in the absence of vital effects

    NASA Astrophysics Data System (ADS)

    Wasylenki, Laura E.; Dove, Patricia M.; Wilson, Darren S.; De Yoreo, James J.

    2005-06-01

    This experimental study presents in situ measurements of step migration rates for layer growth of calcite at various levels of superaturation and fluid Sr concentrations. Our results show that Sr has complex behavior as an impurity. At low concentrations, Sr promotes faster growth. This effect may be associated with slight shifts in calcite solubility when Sr is incorporated or may be due to as yet uncharacterized kinetic effects. At higher concentrations, Sr stops step advancement by pinning kink-sites or step edges. The threshold concentration of Sr needed to halt growth is positively correlated with supersaturation. Addition of Sr to the calcite growth system leads to significant changes in hillock morphology. Hillocks become elongate perpendicular to the projection of the c-glide plane, in contrast to the changes previously reported for Mg. Step edges also become scalloped, and the boundary between the obtuse-stepped flanks disappears and is replaced by a new step direction with edges parallel to [010]. Incorporation of Sr was measured at two supersaturation levels and identical fluid [Sr]. The results indicate a strong positive correlation between fluid supersaturation and crystal Sr content. Further, Sr is strongly fractionated between obtuse- and acute-stepped flanks by a factor of approximately two. The sensitivity of Sr uptake to supersaturation may explain apparently contradictory results in the literature regarding whether Sr uptake in the calcite produced by one-celled marine organisms is controlled by temperature. In addition, Sr contents of natural calcite samples may be good indicators of the levels of supersaturation at which the crystals grew. Results of this investigation demonstrate the importance of understanding impurity-specific interactions with calcite growth surfaces at the microscopic scale. Despite similar chemical behavior in some systems, Mg and Sr clearly have very different effects on calcite growth. If Sr and other impurities are to be used as robust indicators of growth conditions in natural calcite samples, well grounded understanding of the mechanisms of recording trace element signatures in calcite is an essential step toward correctly deciphering paleoenvironmental signals from fossil calcite compositions.

  12. Crystallization and preliminary X-ray crystallographic analysis of probable amylase/protease inhibitor-B from rice seeds.

    PubMed

    Hwang, K Y; Kim, K K; Min, K; Eom, S H; Yu, Y G; Kim, S; Sweet, R M; Suh, S W

    1993-01-01

    Large crystals of probable amylase/protease inhibitor-B have been grown at room temperature from ammonium sulfate solution. The crystals grow within five days to dimensions of 0.6 mm x 0.6 mm x 0.6 mm. They diffract to at least 1.7 A upon exposure to synchrotron X-rays. The crystals belong to the space group P4(1)2(1)2 (or P4(3)2(1)2) with unit cell dimensions of a = 38.02 A and c = 98.98 A. The presence of one molecule per asymmetric unit gives the unit cell volume per protein mass (Vm) of 1.99 A3/Da and the solvent fraction of 38.2% by volume. X-ray data have been collected to 2.0 A Bragg spacing from native crystals. PMID:8421310

  13. Effect of a High Magnetic Field on Microstructures of Ni-Based Single Crystal Superalloy During Seed Melt-Back

    NASA Astrophysics Data System (ADS)

    Xuan, Weidong; Liu, Huan; Li, Chuanjun; Ren, Zhongming; Zhong, Yunbo; Li, Xi; Cao, Guanghui

    2016-01-01

    The effects of a high magnetic field on microstructures during seed melt-back of superalloy were investigated. Experimental results indicated that the high magnetic field significantly modified the melt-back interface shape and the melt-back zone length. In addition, stray grain on the edge of sample was effectively suppressed in the high magnetic field. Based on experimental results and quantitative analysis, the above results should be attributed to the increasing temperature gradient in a high magnetic field.

  14. Characterization and In-Situ Monitoring of ZnSe Crystal Growth by Seeded PVT for Microgravity Applications

    NASA Technical Reports Server (NTRS)

    Feth, Shari T.

    2001-01-01

    Crystal growth from the vapor phase continues to play a significant role in the production of II-VI semiconductor compounds (ZnO, ZnTe, CdTe, etc.) and SiC. As compared to melt growth methods (where available) the advantages are: (1) lower growth temperature(s); (2) reduction in defect concentration; (3) additional purification; and (4) enhanced crystal perfection. A powerful tool in determining the mechanism of PVT is microgravity. Under normal gravity conditions the transport mechanism is a superposition of diffusive and convective fluxes. Microgravity offers the possibility of studying the transport properties without the influence of convective effects. Research on the crystal growth of ZnSe by PVT (P.I.: Su of NASA/MSFC) will help to clarify the effects of convection on crystal growth. A crystal growth furnace with in-situ and real time optical monitoring capabilities was constructed and used to monitor the vapor composition and growing crystal surface morphology during the PVT growth of ZnSe. Using photoluminescence and SIMS, ex-situ, the incorporation of point defects (Zn vacancy) and impurities was found to be correlated to the gravity vector due to the influence of the convective flow. A summary of the results to date will be presented.

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

    USGS Publications Warehouse

    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 gradual cooling of nearby plutons. The physical restriction of the deposits (and, therefore, fluid flow) to fracture footwalls and cavity floors and the heterogeneous and limited distribution of the deposits provides compelling evidence that they do not reflect flooding of the thick UZ at Yucca Mountain. The textures and isotopic and chemical compositions of these mineral deposits are consistent with deposition in a UZ setting from meteoric waters percolating downward along fracture flow paths.

  16. Removal of organic magnesium in coccolithophore calcite

    NASA Astrophysics Data System (ADS)

    Blanco-Ameijeiras, S.; Lebrato, M.; Stoll, H. M.; Iglesias-Rodriguez, M. D.; Mndez-Vicente, A.; Sett, S.; Mller, 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 (NH2OHHCl + 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 (<10%). The reliable determination of Mg/Ca and Sr/Ca, and the low levels of organic contamination (Fe/Ca and P/Ca) make this protocol applicable to field and laboratory studies of trace elemental composition in coccolithophore calcite.

  17. Occurrence of microdiamond in UHP calcite marble from the Kokchetav Massif

    NASA Astrophysics Data System (ADS)

    Ogasawara, Y.; Adachi, T.; Aoki, K.

    2004-12-01

    Small amount of microdiamond was discovered in UHP calcite marble from Kumdy-kol, the Kokchetav Massif northern Kazakhstan. UHP calcite marble is characterized by 1) pure calcite (after aragonite) is only one carbonate phase, 2) presence of titanite, K-feldspar and diopside with phengite and K-feldspar lamella, 3) coesite exsolution from supersilicic titanite. This marble contains UHP evidence as coesite of exsolution origin in titanite and lamella texture in diopside. Minimum P condition was constrained as 6 GPa by precursor composition of titanite. So far, we have described this calcite marble as diamond-free UHP carbonate rock (Ogasawara et al., 2002); however, our recent observation found microdiamond in some domains (B-type) of this rock. Microdiamond occurs only in diopside and its amount is very low compared with diamond-bearing dolomite marble. We found 61 microdiamond grains in two thin sections (c.f. in dolomite marble, highest concentration domain contains over 4000 grains in one thin section). Microdiamond grains are heterogeneously distributed in some layers. The domain (A-type) containing relatively large amount of titanite does not contain diamond. The microdiamond in calcite marble shows 3 to 20 micrometers in diameter, rounded or cubic form, pale yellowish color and translucent character. Laser Raman spectroscopy indicated that FWHM of a Raman band at about 1332 cm-1 ranges from 2.99 to 3.64 cm-1 (average: 3.28 cm-1) and this average value is the smallest among core of S-type, rim of S-type, R-type and diamond in gneiss. Based on the morphology and other features except for FWHM of Raman band, the microdiamond in calcite marble is similar to R-type in dolomite marble (Ishida et al., 2003). No S-type diamond (_gStar_h-shaped form with core and rim) occurs in this calcite marble, and this indicates that the second stage growth of microdiamond probably from multicomponent aqueous fluid had not occurred in calcite marble. Low amount of microdiamond occurs only in diopside, no diamond occurs in titanite (stable at extremely low-XCO2 conditions), and lack of the second stage growth of microdiamond in calcite marble; all these features may be related with extremely low-XCO2 condition under UHP metamorphism. One of the possible explanations for this diamond occurrence is that microdiamonds in calcite marble are relic crystal formed before the second stage growth (the rim stage of S-type microdiamond in dolomite marble). Therefore, it is very important to confirm whether these microdiamond in B-type calcite marble had been growing or dissolving under such extremely low-XCO2 conditions. References Ishida et al. (2003): Journal of Metamorphic Geology, Vol. 21, p. 515-522. Ogasawara et al. (2000): The Island Arc, Vol. 9, p. 400-416. Ogasawara et al. (2002): American Mineralogist, Vol. 87, p. 454-461.

  18. New Shocked Calcite and Fe Grains from Noerdlingen Ries Impact Crater

    NASA Astrophysics Data System (ADS)

    Miura, Y.

    1995-09-01

    Shocked minerals with simple chemical composition of silica, carbon or iron material reveal high-pressure phase during compression process [1]. As calcite mineral shows high-pressure phase of aragonite it should have the "shocked phase" formed from high-pressure phase mixed with quenched materials of gas-melt reaction [2,3,4]. The main purposes of this paper are (1) to discuss new shocked materials of calcite found in the Noerdlingen Ries impact crater. Germany and artificial impact phases. and (2) to show new findings of fine Fe-grains and anomalous plagioclase in suevite. Single grains of anomalous calcite for X-ray analysis were selected from limestone with wormy or bubble-included texture in Buschelberg Ries impact crater (sample R8) [3 4]. Powdered and single grain samples of anomalous calcites show low X-ray intensity and high Bragg angle shift. compared with standard calcite of Akiyoshi limestone as listed in Table 1 [2.3.4]. The unit-cell dimensions of the single grain measured with the four-axes X-ray diffractometer in Yamaguchi University were determined by the least square calculation from the "highest X-ray intensity peak" of each crystal plane which is the same data of the powdered X-ray diffraction sample as an average structure . Both powdered and single grain data reveal high density of 2.76 g/cm^3 (between aragonite of density: rho=2.8g/cm^3, and normal calcite: rho=2.71g/cm^3) of the calcite cell which is the same characters of shocked phases of quartz or graphite [1,2,3,4] (Table 1). Anomalous calcite contains minor amount of Si Fe Ti, though major cation is Ca of 99.4% in cation content. These foreign elements are mixed with during the formation in vapor plume [5]. Table 1, showing the x-ray density and unit-cell parameters of anomalous shocked calcite with high density from Ries and artificial impact craters, appears here in the hard copy. Two types of shocked calcites are found in artificial impact experiments of railgun of the ISAS. Japan. (a) Shocked calcite formed on oxidation condition (near the rim of vapor plume of impact [7]). (b)Shocked calcite formed on reduction condition (interior of vapor plume of impact [7]). The shocked calcites of the Buschelberg (R8) inside the crater are correspondent to shocked calcite with reduction state. which suggests recrystallization inside the crater. The detailed experiments of the R8 samples are checked on yellow (Fe-rich) colored sample of R8Yl and white colored sample (R8W). From the X-ray diffraction data of Bragg angle shift, the R8W1 is more close to reduction state during impact. The shocked calcites under oxidation state are formed as non-stoichiometric compound (and high density) after gas of C02 formation mainly near rim of vapor plume, which is the same data of artificial impact experiments of oxidation condition (i.e. sample No. LSRGl). The shocked calcite under reduction state are formed relatively as normal calcite (with normal or a little high density) and carbon after formation of gaseous materials of CO, 02 and Ca. Thus cabon source from target rock of limestone [2,3,4] can be explained as reduction formation of impact, as listed in Table 2. Table 2, showing, the formation process of shocked calcite materials by shock impact, appears here in the hard copy. References [1] Miura Y.(l991): Shock Waves, 1, 135-141. ?2] Miura Y. (1994): Proc. ISAS Lunar & Planet. Sci. (ISAS, Japan), 27, 204-207. [3] Miura Y. et al. (1995): Shock Waves, Japan, 613-624. [4] Miura Y. and Okanoto M. (19995): Antarctic Meteorites (NIP?), 20, 169-171. ?1989): Tma;l(-.t. r?r;lt.?rin? ?rhrfnr? llniv?r?i?v Pr? )A? 7?;

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    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.

  1. Impact of trace metals on the water structure at the calcite surface

    NASA Astrophysics Data System (ADS)

    Wolthers, Mariette; Di Tommaso, Devis; De Leeuw, Nora

    2014-05-01

    Carbonate minerals play an important role in regulating the chemistry of aquatic environments, including the oceans, aquifers, hydrothermal systems, soils and sediments. Through mineral surface processes such as dissolution, precipitation and sorption, carbonate minerals affect the biogeochemical cycles of not only the constituent elements of carbonates, such as Ca, Mg, Fe and C, but also H, P and trace elements. Surface charging of the calcite mineral-water interface, and its reactivity towards foreign ions can be quantified using a surface structural model that includes, among others, the water structure at the interface (i.e. hydrogen bridging) [1,2] in accordance with the CD-MUSIC formalism [3]. Here we will show the impact of foreign metals such as Mg and Sr on the water structure around different surface sites present in etch pits and on growth terraces at the calcite (10-14) surface. We have performed Molecular Dynamics simulations of metal-doped calcite surfaces, using different interatomic water potentials. Results show that the local environment around the structurally distinct sites differs depending on metal presence, suggesting that metal substitutions in calcite affect its reactivity. The information obtained in this study will help in improving existing macroscopic surface model for the reactivity of calcite [2] and give more general insight in mineral surface reactivity in relation to crystal composition. [1] Wolthers, Charlet, & Van Cappellen (2008). Am. J. Sci., 308, 905-941. [2] Wolthers, Di Tommaso, Du, & de Leeuw (2012). Phys. Chem. Chem. Phys. 14, 15145-15157. [3] Hiemstra and Van Riemsdijk (1996) J. Colloid Interf. Sci. 179, 488-508.

  2. A biophysical elucidation for less toxicity of Agglutinin than Abrin-a from the Seeds of Abrus Precatorius in consequence of crystal structure

    PubMed Central

    2010-01-01

    X-ray crystal structure determination of agglutinin from abrus precatorius in Taiwan is presented. The crystal structure of agglutinin, a type II ribosome-inactivating protein (RIP) from the seeds of Abrus precatorius in Taiwan, has been determined from a novel crystalline form by the molecular replacement method using the coordinates of abrin-a as the template. The structure has space group P41212 with Z = 8, and been refined at 2.6 Å to R-factor of 20.4%. The root-mean-square deviations of bond lengths and angles from the standard values are 0.009 Å and 1.3°. Primary, secondary, tertiary and quaternary structures of agglutinin have been described and compared with those of abrin-a to a certain extent. In subsequent docking research, we found that Asn200 of abrin-a may form a critical hydrogen bond with G4323 of 28SRNA, while corresponding Pro199 of agglutinin is a kink hydrophobic residue bound with the cleft in a more compact complementary relationship. This may explain the lower toxicity of agglutinin than abrin-a, despite of similarity in secondary structure and the activity cleft of two RIPs. PMID:20433687

  3. Spectroscopic characterization of natural calcite minerals

    NASA Astrophysics Data System (ADS)

    Gunasekaran, S.; Anbalagan, G.

    2007-11-01

    The FT-IR, FT-Raman, NMR spectral data of ten different limestone samples have been compared. FT-IR and FT-Raman spectral data show that calcium carbonate in limestone, principally in the form of calcite, as identified by its main absorption bands at 1426, 1092, 876 and 712 cm -1. The sharp diffractions at the d-spacings, 3.0348, 1.9166 and 1.8796 confirm the presence of calcite structure and the calculated lattice parameters are: a = 4.9781 , c = 17.1188 . The range of 13C chemical shifts for different limestone samples is very small, varying from 198.38 to 198.42 ppm. The observed chemical shifts are consistent with the identical C-O bonding in different limestone samples. 27Al MAS NMR spectra of the samples exhibit a central line at 1 ppm and another line at 60 ppm corresponding to octahedral and tetrahedral Al ions, respectively. The five component resonances were observed in 29Si MAS NMR spectrum of limestone and these resonances were assigned to Si (4 Al), Si (3 Al), Si (2 Al), Si (1 Al) and Si (0 Al) from low field to high field.

  4. Biomineralization processes of calcite induced by bacteria isolated from marine sediments

    PubMed Central

    Wei, Shiping; Cui, Hongpeng; Jiang, Zhenglong; Liu, Hao; He, Hao; Fang, Nianqiao

    2015-01-01

    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. PMID:26273260

  5. Basal slip and texture development in calcite: new results from torsion experiments

    SciTech Connect

    Barber, D. J.; Wenk, H.-R.; Gomez-Barreiro, J.; Rybacki, E.; Dresen, G.

    2008-06-09

    The deformation behavior of calcite has been of longstanding interest. Through experiments on single crystals, deformation mechanisms were established such as mechanical twinning on e = {l_brace}{bar 1}018{r_brace} <40{bar 4}1> in the positive sense and slip on r = {l_brace}10{bar 1}4{r_brace} <20{bar 2}{bar 1}> and f = {l_brace}{bar 1}012{r_brace} <0{bar 2}2{bar 1}> both in the negative sense. More recently it was observed that at higher temperatures f{l_brace}{bar 1}012{r_brace} <10{bar 1}1> slip in both senses becomes active and, based on slip line analysis, it was suggested that e(0001) <11{bar 2}0> slip may occur. So far there had been no direct evidence for basal slip, which is the dominant system in dolomite. With new torsion experiments on calcite single crystals at 900 K and transmission electron microscopy, this study identifies (0001) <11{bar 2}0> slip unambiguously by direct imaging of dislocations and diffraction contrast analysis. Including this slip system in polycrystal plasticity simulations, enigmatic texture patterns observed in compression and torsion of calcite rocks at high temperature can now be explained, resolving a long-standing puzzle.

  6. A Reacidification Model for Acidified Lakes Neutralized With Calcite

    NASA Astrophysics Data System (ADS)

    Sverdrup, Harald; Warfvinge, Per

    1985-09-01

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

  7. The Coordination of Mg in Foraminiferal Calcite

    NASA Astrophysics Data System (ADS)

    Branson, O.; Redfern, S. A.; Tyliszczak, T.; Sadekov, A.; Langer, G.; Elderfield, H.

    2012-12-01

    The Mg/Ca ratio in calcite shells ('tests') of foraminifera is an empirical ocean temperature proxy widely used to interpret palaeoclimates. We explore the distribution and local environment of Mg in foram tests using STXM and NEXAFS spectroscopy to test the fundamental assumptions behind the proxy, and shed light on the mechanisms underpinning this vital oceanographic tool. Throughout the development of the Mg/Ca proxy, it has been assumed that Mg in foraminifera tests substitutes directly into the calcite lattice (1). This assumption is based on XRD analyses of various high-Mg biogenic carbonates, where Mg concentrations are manifest in the shifted position of diffraction peaks (2, 3). The extrapolation of this trend to foraminiferal calcite links the proxy to inorganic precipitation experiments, and provides a theoretical mechanistic framework to understand the link between Mg/Ca and temperature: the substitution of Mg is endothermic, and favoured at higher temperatures. However, the concentration of Mg in most foraminifera (0-10 mmol/mol Mg/Ca) is below the detection limit of XRD methods, and the analogy to inorganic systems has not been explicitly tested. Electron microprobe (4-6), LA-ICP-MS (7) and high-resolution nanoSIMS mapping (Sadekov, unpub.) of foraminifera tests have revealed the presence of high 'trace element' bands running in plane with the test surface, enriched in Mg, Sr, S, organic molecules and other trace elements. This emphasises a key question highlighted by Dodd (1) when the proxy was still in its infancy: how is Mg incorporated into mineral skeletons? By direct substitution into the calcite lattice, interstitially in a separate distinct mineral phase, or associated with organic compounds? We address this fundamental question using scanning transmission X-ray microscopy (STXM) and X-ray absorption spectroscopy at ALS beamline 11.0.2 to examine the distribution and local atomic environment of Mg in two contrasting species of foraminifera. Our data conclusively demonstrate that the Mg in the high- and low-trace element bands in the two different species is incorporated in the same mode. Foraminiferal Mg K-edge spectra are most similar to that of dolomite, where Ca and Mg are interchangeable and both present in octahedral sites. This indicates that Mg directly substitutes for Ca in the calcite test, validating the assumptions underlying the use of the Mg/Ca proxy. The uniformity of Mg environment also sheds light on the drivers of Mg heterogeneity, suggesting that Mg banding is driven by fluctuations in medium chemistry, rather than any change in Mg incorporation mechanism. The ultimate cause of Mg heterogeneity remains an open question, however. 1. J. R. Dodd, J Paleontology, 1313-1329 (1967). 2. K. E. Chave, J Geol 62, 266-283 (1954). 3. J. Titschack, F. Goetz-Neunhoeffer, J. Neubauer, Am Min 96, 1028 (2011). 4. J. Lipps, P. Ribbe, J Paleontology 41, 492-496 (1967). 5. A. Y. Sadekov, S. M. Eggins, P. de Deckker, G3 6, Q12P06 (2005). 6. J. Erez, Rev Min Geochem 54, 115 (2003). 7. A. Y. Sadekov, S. M. Eggins, G. P. Klinkhammer, Y. Rosenthal, Earth Planet Sc Lett 292, 312-324 (2010).

  8. Carbonates in thrust faults: High temperature investigations into deformation processes in calcite-dolomite systems

    NASA Astrophysics Data System (ADS)

    Kushnir, A.; Kennedy, L.; Misra, S.; Benson, P.

    2012-04-01

    The role of dolomite on the strength and evolution of calcite-dolomite fold and thrust belts and nappes (as observed in the Canadian Rockies, the Swiss Alps, the Italian Apennines, and the Naukluft Nappe Complex) is largely unknown. Field investigations indicate that strain in natural systems is localized in calcite, resulting in a ductile response, while dolomite deforms in a dominantly brittle manner. To date, experimental studies on polymineralic carbonate systems are limited to homogeneous, fine-grained, calcite-dolomite composites of relatively low dolomite content. The effect of dolomite on limestone rheology, the onset of crystal-plastic deformation in dolomite in composites, and the potential for strain localization in composites have not yet been fully quantified. Constant displacement rate (3x10-4 s-1and 10-4 s-1), high confining pressure (300 MPa) and high temperature (750 C and 800 C) torsion experiments were conducted to address the role of dolomite on the strength of calcite-dolomite composites. Experiments were performed on samples produced by hot isostatic pressing (HIP) amalgams of a natural, pure dolomite and a reagent, pure calcite. We performed experiments on the following mixtures (given as dolomite%): 25%, 35%, 50%, and 75%. These synthetic HIP products eliminated concerns of mineralogical impurities and textural anomalies due to porosity, structural fabrics (e.g., foliation) and fossil content. The samples were deformed up to a maximum finite shear strain of 5.0 and the experimental set up was unvented to inhibit sample decarbonation. Mechanical data shows a considerable increase in sample yield strength with increasing dolomite content. Experimental products with low starting dolomite content (dol%: 25% and 35%) display macroscopic strain localization along compositionally defined foliation. Experimental products with high dolomite content (dol%: 50% and 75%) demonstrate no macroscopic foliation. Post-deformation microstructure analysis shows that small dolomite grains (~50 ?m) are characterized by well-defined grain boundaries and cleavage controlled fracture. There is evidence of the interruption of foliation development due to the presence of large-grained dolomite. Calcite grains are characterized by triple junction grain boundaries, providing evidence for recrystallization. Ongoing microstructural analyses (including: thin section analysis, EBSD, SEM, and Microprobe analysis) are being conducted to better constrain the deformation mechanisms and the degree of strain localization in these composites. Our experiments provide insights into the processes controlling rheology within bimodal calcite-dolomite systems, which can be used to improve models of the evolution of fold and thrust belt systems.

  9. Dissolution dynamics of the calcite-water interface observed in situ by glancing-incidence X-ray scattering

    SciTech Connect

    Sturchio, N.C.; Chiarello, R.P.

    1995-06-02

    Glancing-incidence X-ray scattering measurements made at the National Synchrotron Light Source were used to investigate dissolution dynamics in situ at the calcite-water interface. The relation between calcite saturation state and roughness of the calcite (1014) cleavage surface as a function of time was examined during pH titrations of an initially calcite-saturated solution. Systematic variations in roughness were observed as a function of saturation state as pH was titrated to values below that of calcite saturation. Different steady-state values of roughness were evident at fixed values of {Delta}G{sub r}, and these were correlated with the extent of undersaturation. A significant increase in roughness begins to occur with increasing undersaturation at a {Delta}G{sub r} value of approximately {minus}2.0 kcal/mol. The dissolution rate corresponding to this increase is about 1.5 x 10{sup 7} mmol/cm {center_dot} sec. This increase in roughness is attributed to a transition in the principal rate-determining dissolution mechanism, and is consistent with both powder-reaction studies of dissolution kinetics and single-crystal dissolution studies by atomic force microscopy. These data indicate some important potential applications of GIXS in the study of mineral-water interface geochemistry.

  10. Emission polarization study on quartz and calcite.

    NASA Technical Reports Server (NTRS)

    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.

  11. Corrosion protection of mild steel by a calcite layer

    SciTech Connect

    Keysar, S.; Hasson, D.; Semiat, R.; Bramson, D.

    1997-08-01

    Artificial calcite lining represents a novel technique for the rehabilitation of water mains. Calcite linings, similar to the commonly used cement-mortar linings, are of porous nature. The corrosion protection mechanisms of calcinite linings were investigated by polarization techniques, complemented by scanning electron microscopy observations and energy dispersive spectrometry analyses. The effect of time on lining durability was examined by exposure of coated mild steel (1020) coupons in a controlled flowing water system. Iron ion distributions in calcite sections, before and after exposure to water flow, indicate that the calcite corrosion protection mechanism is based mainly on accumulation of corrosion products inside the lining. At the calcite-metal interface, a protective film is formed. At the calcite-water interface, the calcite structure, being alkaline with respect to the water, promotes precipitation of the iron ions and blockage of the pores near that interface. The formation of this protective oxide film was evident from the polarization data which showed that both the anodic Tafel constant and the polarization resistance increase with time. This paper also examines the applicability of potentiodynamic and linear polarization techniques for the characterization of the corrosion protection of a porous lining, such as calcite. It is shown that these convenient electrochemical techniques provide reliable and meaningful corrosion protection information.

  12. Dissolution of coccolithophorid calcite by microzooplankton and copepod grazing

    NASA Astrophysics Data System (ADS)

    Antia, A. N.; Suffrian, K.; Holste, L.; Mller, M. N.; Nejstgaard, J. C.; Simonelli, P.; Carotenuto, Y.; Putzeys, S.

    2008-01-01

    Independent of the ongoing acidification of surface seawater, the majority of the calcium carbonate produced in the pelagial is dissolved by natural processes above the lysocline. We investigate to what extent grazing and passage of coccolithophorids through the guts of copepods and the food vacuoles of microzooplankton contribute to calcite dissolution. In laboratory experiments where the coccolithophorid Emiliania huxleyi was fed to the rotifer Brachionus plicatilis, the heterotrophic flagellate Oxyrrhis marina and the copepod Acartia tonsa, calcite dissolution rates of 45-55%, 37-53% and 5-22% of ingested calcite were found. We ascribe higher loss rates in microzooplankton food vacuoles as compared to copepod guts to the strongly acidic digestion and the individual packaging of algal cells. In further experiments, specific rates of calcification and calcite dissolution were also measured in natural populations during the PeECE III mesocosm study under differing ambient pCO2 concentrations. Microzooplankton grazing accounted for between 27 and 70% of the dynamic calcite stock being lost per day, with no measurable effect of CO2 treatment. These measured calcite dissolution rates indicate that dissolution of calcite in the guts of microzooplankton and copepods can account for the calcite losses calculated for the global ocean using budget and model estimates.

  13. pH-dependence of calcite growth kinetics at constant solution calcium to carbonate activity ratio and supersaturation: an in situ Atomic Force Microscopy study

    NASA Astrophysics Data System (ADS)

    Ruiz-Agudo, Encarnacin; Putnis, Christine V.; Rodriguez-Navarro, Carlos Manuel; Putnis, Andrew

    2010-05-01

    Calcite-solution reactions (growth, dissolution and replacement) are critical in a range of both engineering and natural processes. Classical crystal growth theory relates calcite growth rates to the degree of supersaturation. The solution composition may also affect the growth rate of carbonate minerals, via the Ca2+ to CO32- concentration ratio (Nehrke et al., 2007; Perdikouri et al., 2009), ionic strength (Zuddas and Mucci, 1998) or the presence of organic matter (Hoch et al., 2000). Most calcite growth studies so far have been performed at a constant pH of ca. 8 or 10, or changing the pH together with the degree of supersaturation with respect to calcite and/or the aCa2+ to aCO32- ratio in solution, which hinders an evaluation of the pH effect on calcite growth kinetics. In this work, in situ Atomic Force Microscopy (AFM) was employed to study the growth of calcite at a constant supersaturation (? = 6.46) and solution stoichiometry (Ca2+-CO32- = 1) in the pH range 7.5 to 12. How pH may influence calcite growth is relevant to improve our understanding of the effects on carbonate-solution reactions when variations in atmospheric CO2result in changes in the pH of the oceans and surface waters. We observed that the calcite growth rate decreases with increasing pH in the studied range. The results can be successfully explained by the mechanistic model for calcite growth based on surface complexation proposed by Nilsson and Sternbeck (1999) and by solute hydration. At pH below 8.5, growth occurs mainly by CaCO30 incorporation at >CaHCO30 surface sites. CaCO30 should be more easily incorporated than free Ca2+ ions, as water exchange usually is faster if water molecules in the ion hydration shells are substituted for by other ligands, as in CaCO30. However, at pH above 9, Ca2+ incorporation at >CaHCO30 sites also contributes to calcite growth as a result of increased frequency of water exchange in calcium hydration shells due to the presence of strongly hydrated OH-. The decrease in calcite growth rate is a consequence of decreasing surface concentration of growth active sites (i.e. >CaHCO30) with increasing pH in our experimental conditions. Changes in 2D island morphology were observed at high pH (12), possibly due to the stabilization of polar scalenohedral faces by the presence of OH- ions. References Hoch, A.R.; Reddy, M.M.; Aiken, G.R. Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades. Geochim. Cosmochim. Acta 2000, 64, 61-72. Nehrke, G.; Reichart, G. J.; Van Cappellen, P.; Meile, C.; Bijma, J. Dependence of calcite growth rate and Sr partitioning on solution stoichiometry: Non-Kossel crystal growth. Geochim. Cosmochim. Acta 2007, 71, 2240-2249 Nilsson O.; Sternbeck J. A mechanistic model for calcite crystal growth using surface speciation. Geochim. Cosmochim.Acta 1999, 63, 217-225. Perdikouri, C.; Putnis, C.V.; Kasioptas, A.; Putnis, A. An Atomic Force Microscopy Study of the Growth of a Calcite Surface as a Function of Calcium/Total Carbonate Concentration Ratio in Solution at Constant Supersaturation. Cryst. Growth Des. 2009, 9, 4344-4350. Zuddas, P.; Mucci, A. Kinetics of Calcite Precipitation from Seawater: II. The Influence of the Ionic Strength. Geochim. Cosmochim. Acta 1998, 62, 757-766.

  14. Calcite and dolomite in intrusive carbonatites. II. Trace-element variations

    NASA Astrophysics Data System (ADS)

    Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Couëslan, Christopher; Yang, Panseok

    2015-06-01

    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 rocks, calcite invariably has higher REE and LILE levels than dolomite. Hydrothermal reworking of carbonatites does not produce a unique geochemical fingerprint, leading instead to a variety of evolutionary trends that range from light-REE and LILE enrichment (Turiy Mys, Russia) to heavy-REE enrichment and LILE depletion (Bear Lodge, USA). These differences clearly attest to variations in the chemistry of carbonatitic fluids and, consequently, their ability to mobilize specific trace elements from earlier-crystallized minerals. An important telltale indicator of hydrothermal reworking is deviation from the primary, chondrite-like REE ratios (in particular, Y/Ho and Eu/Eu*), accompanied by a variety of other compositional changes depending on the redox state of the fluid (e.g., depletion of carbonates in Mn owing to its oxidation and sequestration by secondary oxides). The effect of supergene processes was studied on a single sample from Bear Lodge, which shows extreme depletion in Mn and Ce (both due to oxidation), coupled with enrichment in Pb and U, possibly reflecting an increased availability of Pb2+ and (UO2)2+ species in the system. On the basis of these findings, several avenues for future research can be outlined: (1) structural mechanisms of REE uptake by carbonates; (2) partitioning of REE and LILE between cogenetic calcite and dolomite; (3) the effects of fluorapatite, phlogopite and pyrochlore fractionation on the LILE budget of magmatic carbonates; (4) the cause(s) of coupled Mn-Ce depletion in some primary calcite; and (5) relations between fluid chemistry and compositional changes in hydrothermal carbonates.

  15. The influence of impurities on the growth rate of calcite

    NASA Astrophysics Data System (ADS)

    Meyer, H. J.

    1984-05-01

    The effects of 34 different additives on the growth rate of calcite were investigated. An initial growth rate of about one crystal monolayer (3 10 -8 cm) per minute was adjusted at a constant supersaturation which was maintained by a control circuit. Then the impurity was added step by step and the reduction of the growth rate was measured. The impurity concentration necessary to reduce the initial growth rate by a certain percentage increased in the order Fe 2+, ATP, P 3O 5-10, P 2O 4-7, (PO 3) 6-6, Zn 2+, ADP, Ce 3+, Pb 2+, carbamyl phosphate, Fe 3+, PO 3-4, Co 2+, Mn 2+, Be 2+, ?-glycerophosphate, Ni 2+, Cd 2+, "Tris", phenylphosphate, chondroitine sulphate, Ba 2+, citrate, AMP, Sr 2+, tricarballylate, taurine, SO 2-4, Mg 2+ by 4 orders of magnitude. The most effective additives halved the initial growth rate in concentrations of 2 10 -8 mol/1. For Fe 2+ the halving concentration was nearly proportional to the initial rate. The mechanism of inhibition by adsorption of the impurities at growth sites (kinks) is discussed.

  16. Effect of fluid salinity on subcritical crack propagation in calcite

    NASA Astrophysics Data System (ADS)

    Rostom, Fatma; Ryne, Anja; Dysthe, Dag Kristian; Renard, Franois

    2013-01-01

    The slow propagation of cracks, also called subcritical crack growth, is a mechanism of fracturing responsible for a ductile deformation of rocks under crustal conditions. In the present study, the double-torsion technique was used to measure the effect of fluid chemistry on the slow propagation of cracks in calcite single crystals at room temperature. Time-lapse images and measurements of force and load-point displacement allowed accurate characterization of crack velocities in a range of 10- 8 to 10- 4 m/s. Velocity curves as a function of energy-release rates were obtained for different fluid compositions, varying NH4Cl and NaCl concentrations. Our results show the presence of a threshold in fluid composition, separating two regimes: weakening conditions where the crack propagation is favored, and strengthening conditions where crack propagation slows down. We suggest that electrostatic surface forces that modify the repulsion forces between the two surfaces of the crack may be responsible for this behavior.

  17. Bent crystal spectrometer for both frequency and wavenumber resolved x-ray scattering at a seeded free-electron laser

    NASA Astrophysics Data System (ADS)

    Zastrau, Ulf; Fletcher, Luke B.; Frster, Eckhart; Galtier, Eric Ch.; Gamboa, Eliseo; Glenzer, Siegfried H.; Heimann, Philipp; Marschner, Heike; Nagler, Bob; Schropp, Andreas; Wehrhan, Ortrud; Lee, Hae Ja

    2014-09-01

    We present a cylindrically curved GaAs x-ray spectrometer with energy resolution ?E/E = 1.1 10-4 and wave-number resolution of ?k/k = 3 10-3, allowing plasmon scattering at the resolution limits of the Linac Coherent Light Source (LCLS) x-ray free-electron laser. It spans scattering wavenumbers of 3.6 to 5.2/ in 100 separate bins, with only 0.34% wavenumber blurring. The dispersion of 0.418 eV/13.5 ?m agrees with predictions within 1.3%. The reflection homogeneity over the entire wavenumber range was measured and used to normalize the amplitude of scattering spectra. The proposed spectrometer is superior to a mosaic highly annealed pyrolytic graphite spectrometer when the energy resolution needs to be comparable to the LCLS seeded bandwidth of 1 eV and a significant range of wavenumbers must be covered in one exposure.

  18. crystal

    NASA Astrophysics Data System (ADS)

    Bai, Fen; Wang, Qingpu; Tao, Xutang; Li, Ping; Zhang, Xingyu; Liu, Zhaojun; Shen, Hongbin; Lan, Weixia; Gao, Liang; Gao, Zeliang; Zhang, Junjie; Fang, Jiaxiong

    2014-08-01

    An eye-safe Raman laser is realized with BaTeMo2O9 (BTM) nonlinear crystal for the first time. By using a diode-end-pumped acousto-optically Q-switched Nd:YVO4 laser as the pumping source, the BTM crystal converts the fundamental laser at 1,342 nm to first-Stokes laser at 1,531 nm successfully. With an incident power of 10.8 W and a pulse repetition rate of 25 kHz, the average output power at 1,531 nm is obtained to be 0.83 W, corresponding to a diode-to-Stokes conversion efficiency of 7.7 %. The pulse width is 11 ns, and the peak power is 3.0 kW.

  19. Nano-structured calcite produced by micro-organisms in ancient and modern loess in Chinese Loess Plateau

    NASA Astrophysics Data System (ADS)

    Xu, H.; Chen, T.; Lu, H.; Wang, X.

    2005-12-01

    The results from transmission electron microscopy (TEM) and field emission gun scanning microscopy (FEG-SEM) investigation show that there are calcite nano-fibers (CNFs) formed during pedogenic process. The CNFs are widely distributed in the loess and red clay samples of Caoxian, Luochuan, Lingtai, Lantian, and Xifeng profiles as well as the samples of modern surface loess soils in Chinese Loess Plateau. Diameters of all the NFCs are about 40 nm, the length of the CNFs ranges from tens nanometer to several micrometers. Elongation direction of NFCs is unusual near parallel (105)* or (115)*. Crystals of NFCs arrange as bird net like and lattice-like frameworks. X-ray EDS spectra show the weak peaks of magnesium, phosphorous, and sulfur. Our investigation indicates that CNFs are in pore space of loess and paleosol and made up most of carbonate except for caliche nodular layers. Concentration of NFCs in the loess layers are significantly higher than those of paleosol layers because of leaching of carbonate in the paleosol forming environment (warn and wet paleoclimate). The "nanobacteria-like CNFs are well crystalline calcite single crystals with smoothes surfaces. The morphologies of CNFs are very unusual and different from the calcite single crystals observed in most geological environments. The CNFs are directly related to microbial activities in both ancient and modern loess. It is proposed that the intervention of organic compounds derived from microbial activities control the formation of the calcite nano-fibers. Both morphology and bulk composition of CNFs indicate that the formation of the CNFs involves bio-organics derived from microorganisms in loess deposit environment. Formation conditions of the calcite nano-fibers may information about paleoclimate, paleo-environment and paleoecology. So, the discovery of CNFs in loess-paloesol sequences can provide a new route for reconstruct paleoclimate by oxygen and carbon isotope from the CNFs.

  20. Enhanced energy resolution ( 22Na, 137Cs and 241Am) and alpha-gamma ( 241Am + 60Co) and neutron-gamma ( 241Am-Be) pulse shape discrimination properties of p-terphenyl crystals prepared by modified selective self-seeded vertical Bridgman technique (SSVBT)

    NASA Astrophysics Data System (ADS)

    Selvakumar, S.; Arulchakkaravarthi, A.; Kumar, Rakesh; Muralithar, S.; Sankar, S.; Sivaji, K.

    2008-03-01

    p-Terphenyl crystals were grown by modified selective self-seeded vertical Bridgman technique (SSVBT). This new technique has been adopted for nucleation and growth of seed crystals and the bulk crystals were grown by selective self-seeding method. The scintillation properties of the grown p-terphenyl crystal by the aforementioned method have been studied for different radioactive isotopes. Its particle-detection ability has been brought out by pulse-shape discrimination studies for alpha-gamma ( Am241+Co60) and neutron-gamma ( 241Am-Be) sources. The results show that there is an enhancement in the scintillation characteristics of the SSVBT p-terphenyl crystals when compared to the commercially available p-terphenyl crystals.

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

    NASA Astrophysics Data System (ADS)

    Yokoyama, Yuka; Tanaka, Kazuya; Takahashi, Yoshio

    2012-08-01

    The sorption and coprecipitation experiments of arsenic (As) with calcite coupled with determinations of the chemical state of As both in the reaction fluid and in calcite were conducted to investigate the influence of the As oxidation state on its immobilization into calcite. The oxidation states of As in calcite and water were determined via As K-edge XANES and HPLC-ICP-MS analysis, respectively. The results of the sorption experiments at pH 8.2 show that only As(V) is distributed to calcite regardless of the As oxidation state in the solution. In coprecipitation experiments, As(V) is preferentially incorporated into calcite over a wide range of pH (7-12). On the other hand, the incorporation of As(III) into calcite is not observed at circumneutral pH. This difference between As(III) and As(V) is attributed to the fact that their dissolved species are neutral vs. negatively charged, respectively, at circumneutral pH (arsenite as H3AsO3; arsenate as H2AsO4- or HAsO42-). As the pH increases (>9), up to 33% of As(III)/Astotal ratio is partitioned into calcite or a precursor of calcite (metastable vaterite formed during the early stage of precipitation). The higher interaction of As with calcite at an alkaline pH compared with circumneutral pH is due to the negative charge of As(III) at alkaline pH. However, the As(III)/Astotal ratio decreases as time progresses and only As(V) can be found finally in calcite. The ratio of distribution coefficients of As(III) and As(V) into calcite (KAs(V)/KAs(III)) at pH 7 is larger than 2.1 103, suggesting that the oxidation state of As is a significant issue in considering the interaction between As and calcite in groundwater. Moreover, low KAs(III) shows that the sequestration of As via coprecipitation with calcite is not an important chemical process under reducing conditions, such as in the groundwaters in Bangladesh and other As-contaminated areas where As(III) is the dominant dissolved species of As. In the system spiked only with As(III), the XANES analysis detected As(V) in calcite, where the partitioning of As into calcite is very limited as stated above. Therefore, HPLC-ICP-MS and cyclic voltammetric measurements were performed to clarify the As(V)-incorporation mechanism in the As(III) system. As a result, the oxidation of As(III) to As(V) and the stabilization of As(V) in a solution in the presence of the Ca2+ ion are observed. These phenomena result from the formation of calcium arsenate complexes in the aqueous phase. This complexation is an important process for the coprecipitation of As with calcite. Hence, As is incorporated into calcite as As(V) even from the As(III) solution at circumneutral pH, wherein As(III) exists as neutral arsenite with little interaction with calcite.

  2. Organic Surfaces Promote Calcite Nucleation Through Biomolecule-Specific Reductions in Interfacial Free Energy

    NASA Astrophysics Data System (ADS)

    Hamm, L. M.; Han, N.; Giuffre, A. J.; De Yoreo, J.; Dove, P. M.

    2012-12-01

    Sites of biogenic calcification are comprised of complex macromolecular assemblages that are implicated in regulating the onset of mineralization. Classical nucleation theory predicts that the organic templates provided by these proteins and polysaccharides significantly affect nucleation rate by modulating interfacial free energy, which determines the thermodynamic barrier to nucleation. Recent evidence suggests that calcium carbonate (CaCO3) formation often involves pre-nucleation clusters and transient precursor phases, which raises the question of how biomolecular controls on crystallization are related to emerging concepts in non-classical mineralization. While previous studies qualitatively demonstrate that the chemical functionalities of biomolecules influence the nucleating mineral phase and morphology, a mechanistic understanding of their control over nucleation kinetics and thermodynamics is not well established. Here we test the hypothesis that specific chemical functional groups regulate the kinetics and thermodynamics of CaCO3 formation by using self-assembled monolayers (SAMs) as substrates for calcite nucleation. We measured nucleation rates on substrates with different termini (-COOH, -PO4, and -SH) and alkanethiol chain lengths (16-C and 11-C) at a variety of chemical driving forces, both above and below the reported solubility of amorphous calcium carbonate (ACC). Using classical nucleation theory to interpret the kinetic data, we calculated calcite-substrate interfacial energies and estimated substrate-specific effects on the thermodynamic barrier to nucleation. Calcite - substrate interaction forces were quantified with independent dynamic force spectroscopy (DFS) measurements. The nucleation rate measurements show that organic templates reduce the thermodynamic barrier to calcite nucleation compared to homogeneous nucleation through reductions in interfacial free energy. These free energies are correlated with independent DFS measurements of calcite-substrate interaction force by a systematic relationship that is general to chemistry and chain length. Calcite nucleation in these systems is accurately described with classical models of nucleation. The findings demonstrate a physical basis for how organic surfaces reduce the thermodynamic barrier to nucleation and show that precursor phases and pre-nucleation clusters are not required for template-directed mineralization.

  3. Epitaxial high saturation magnetization FeN thin films on Fe(001) seeded GaAs(001) single crystal wafer using facing target sputterings

    SciTech Connect

    Ji Nian; Wu Yiming; Wang Jianping

    2011-04-01

    It was demonstrated that Fe-N martensite ({alpha}') films were grown epitaxially on Fe(001) seeded GaAs(001) single crystal wafer by using a facing target sputtering method. X-ray diffraction pattern implies an increasing c lattice constant as the N concentration increases in the films. Partially ordered Fe{sub 16}N{sub 2} films were synthesized after in situ post-annealing the as-sputtered samples with pure Fe{sub 8}N phase. Multiple characterization techniques including XRD, XRR, TEM, and AES were used to determine the sample structure. The saturation magnetization of films with pure Fe{sub 8}N phase measured by VSM was evaluated in the range of 2.0-2.2 T. The post annealed films show systematic and dramatic increase on the saturation magnetization, which possess an average value of 2.6 T. These observations support the existence of giant saturation magnetization in {alpha}''-Fe{sub 16}N{sub 2} phase that is consistent with a recent proposed cluster-atom model and the first principles calculation [N. Ji, X. Q. Liu, and J. P. Wang, New J. Phys. 12 063032 (2010)].

  4. Strain rate dependent calcite microfabric evolution - An experiment carried out by nature

    NASA Astrophysics Data System (ADS)

    Rogowitz, Anna; Grasemann, Bernhard; Huet, Benjamin; Habler, Gerlinde

    2014-12-01

    A flanking structure developed along a secondary shear zone in calcite marbles, on Syros (Cyclades, Greece), provides a natural laboratory for directly studying the effects of strain rate variations on calcite deformation at identical pressure and temperature conditions. The presence and rotation of a fracture during progressive deformation caused extreme variations in finite strain and strain rate, forming a localized ductile shear zone that shows different microstructures and textures. Textures and the degree of intracrystalline deformation were measured by electron backscattered diffraction. Marbles from the host rocks and the shear zone, which deformed at various strain rates, display crystal-preferred orientation, suggesting that the calcite preferentially deformed by intracrystalline-plastic deformation. Increasing strain rate results in a switch from subgrain rotation to bulging recrystallization in the dislocation-creep regime. With increasing strain rate, we observe in fine-grained (3 ?m) ultramylonitic zones a change in deformation regime from grain-size insensitive to grain-size sensitive. Paleowattmeter and the paleopiezometer suggest strain rates for the localized shear zone around 10-10 s-1 and for the marble host rock around 10-12 s-1. We conclude that varying natural strain rates can have a first-order effect on the microstructures and textures that developed under the same metamorphic conditions.

  5. Effect of calcite on lead-rich cementitious solid waste forms

    SciTech Connect

    Lee, Dongjin; Swarbrick, Gareth; Waite, T. David . E-mail: D.waite@unsw.edu.au

    2005-06-01

    The effect of calcite on lead-rich solidified waste forms generated using Portland cement has been investigated. Samples of cementitious wastes in the absence and presence of Pb and in the absence and presence of calcite were examined separately at 2, 7, 14 and 28 days of hydration by X-ray diffraction and SEM/EDS and for compressive strength. The presence of lead was observed to produce lead carbonate sulfate hydroxide (Pb{sub 4}SO{sub 4}(CO{sub 3}){sub 2}(OH){sub 2}), lead carbonate hydroxide hydrate (3PbCO{sub 3}.2Pb(OH){sub 2}.H{sub 2}O) and two other unidentified lead salts in cavity areas, and was observed to significantly retard the hydration of cement. Calcite addition to the Pb wastes was found to induce the rapid crystallization of calcium hydroxide coincident with the onset of C-S-H gel germination. The rapid dissolution of lead precipitates was observed with the subsequent development of very insoluble gel products of the form C-Pb-S-H. These products are formed by chemical incorporation of re-dissolved Pb species into silicate structures.

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

    PubMed

    Andersson, M P; Sakuma, H; Stipp, S L S

    2014-06-01

    We have used density functional theory to predict the ion exchange energies for divalent cations Ni(2+), Sr(2+), Cd(2+), and Pb(2+) into a calcite {10.4} surface in equilibrium with water. Exchange energies were calculated for substitution into the topmost surface layer, at the mineral-fluid interface, and into the second layer of the solid. This information can be used as an indicator for cation substitution in the bulk phase, such as for the uptake of toxic metals from the environment and the growth of secondary phases. In both the surface and in the second layer, Ni(2+), Cd(2+), and Pb(2+) substitute exothermically and Sr(2+) substitutes endothermically. Our results agree with published experimental data that demonstrate trace metal coprecipitation with calcite as a sink for Ni(2+), Cd(2+), and Pb(2+), whereas Sr(2+) has a distribution constant significantly smaller than 1. Ni(2+) substitution is favored at the mineral-fluid interface compared with bulk substitution, which also agrees with experimental data. Our results predict that Ni(2+), Cd(2+), and Pb(2+) form a stable solid solution with calcite. Successful prediction of the experimental results gives us confidence in our ability to predict the divalent cation preference for surfaces rather than for sites within the bulk crystal structure, which cannot be directly derived from experiment. PMID:24823264

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

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

  8. The dissolution of calcite in aqueous acid: The influence of humic species

    SciTech Connect

    Compton, R.G.; Sanders, G.H.W. )

    1993-07-01

    The kinetics of proton-induced calcite dissolution in aqueous solution in the presence of humic acids and their sodium salts are reported. In equilibrated acid solutions (pH <4) there is no inhibition by humic material and dissolution proceeds at a rate simply determined by the solution pH. Contrastingly the sodium salts of humic acids were found to have a significant inhibitory effect on the acid catalyzed dissolution. This was quantified using a novel channel flow cell experiment which employed two electrodes, the upstream of which was used to inject protons into a neutral solution, which also contained sodium salts of humic acid, via electrolytic oxidation of dissolved hydroquinone. The two electrodes were located immediately upstream and downstream of a calcite crystal so that the proton injection served to dissolve the calcite in the (inhibiting) presence of humic salts unequilibrated with the solution pH. The amount of H[sup +] which survived passage to the downstream detector'' electrode was used to quantify the rate of dissolution and hence the inhibitory effects of the humic acid. The latter were found to operate in a manner not inconsistent with Langmuirian adsorption.

  9. Strontium Incorporation into Calcite Generated by Bacterial Ureolysis

    SciTech Connect

    Yoshiko Fujita; George D. Redden; Jani C. Ingram; Marnie M. Cortez; Robert W. Smith

    2004-08-01

    Strontium incorporation into calcite generated by bacterial ureolysis was investigated as part of an assessment of a proposed remediation approach for 90Sr contamination in groundwater. Urea hydrolysis produces ammonium and carbonate and elevates pH, resulting in the promotion of calcium carbonate precipitation. Urea hydrolysis by the bacterium Bacillus pasteurii in a medium designed to mimic the chemistry of the Snake River Plain Aquifer in Idaho resulted in a pH rise from 7.5 to 9.1. Measured average distribution coefficients (DEX) for Sr in the calcite produced by ureolysis (0.5) were up to an order of magnitude higher than values reported in the literature for natural and synthetic calcites (0.02–0.4). They were also higher than values for calcite produced abiotically by ammonium carbonate addition (0.3). The precipitation of calcite in these experiments was verified by X-ray diffraction. Time-of-flight secondary ion mass spectrometry (ToF SIMS) depth profiling (up to 350 nm) suggested that the Sr was not merely sorbed on the surface, but was present at depth within the particles. X-ray absorption near edge spectra showed that Sr was present in the calcite samples as a solid solution. The extent of Sr incorporation appeared to be driven primarily by the overall rate of calcite precipitation, where faster precipitation was associated with greater Sr uptake into the solid. The presence of bacterial surfaces as potential nucleation sites in the ammonium carbonate precipitation treatment did not enhance overall precipitation or the Sr distribution coefficient. Because bacterial ureolysis can generate high rates of calcite precipitation, the application of this approach is promising for remediation of 90Sr contamination in environments where calcite is stable over the long term.

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

    PubMed

    Rusznyk, Anna; Akob, Denise M; Nietzsche, Sndor; Eusterhues, Karin; Totsche, Kai Uwe; Neu, Thomas R; Frosch, Torsten; Popp, Jrgen; Keiner, Robert; Geletneky, Jrn; Katzschmann, Lutz; Schulze, Ernst-Detlef; Ksel, 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. PMID:22179248

  11. Calcite Biomineralization by Bacterial Isolates from the Recently Discovered Pristine Karstic Herrenberg Cave

    PubMed Central

    Rusznyk, Anna; Akob, Denise M.; Nietzsche, Sndor; Eusterhues, Karin; Totsche, Kai Uwe; Neu, Thomas R.; Frosch, Torsten; Popp, Jrgen; Keiner, Robert; Geletneky, Jrn; Katzschmann, Lutz; Schulze, Ernst-Detlef

    2012-01-01

    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. PMID:22179248

  12. Tectonic Evolution of Chingshui Geothermal Field Inferred from Evidence of Quartz and Calcite Veins

    NASA Astrophysics Data System (ADS)

    Lu, Y. C.; Song, S. R.; Wang, P. L.; Liu, C. M.; Yeh, E. C.

    2014-12-01

    The Chingshui geothermal field is located in the valley of Chingshui stream, where is about 27 km SW of Ilan, northeastern Taiwan. It is a tectonically complex area occurred by the Philippine Plate subducting beneath the Eurasian plate in the south with Okinawa Trough opening in the Ilan Plain. Owing to complicated geological structure, the heat source of Chingshui geothermal field is still controversial. For understanding hot fluid sources and tectonic evolution, this study focuses on field survey of veins and scaling in the Chingshui geothermal field, and the results inferred from the data of SEM, XRD, carbon and oxygen isotope, and Uranium-thorium dating. The Chingshui hot fluid contains both high concentrations of SiO2 and HCO3-, therefore, temperature and pressure both drop when the hot fluids inject into shallower fractures, and calcite and quartz both could be precipitated with competition or simultaneously. In Chilukeng River, many euhedral quartz crystals occurred in large damage zone of Xioananao fault that indicated the temperature drop played the dominated role when the hot fluids injected into the shallow. It inferred that the quartz crystal precipitated under compression stress, evidenced by the Xioananao thrust fault with no surface rupture. Whiles, there are gouges in normal fault with abundant calcite or calcite with quartz veins cropped out in the confluence of Chingshui River and Chilukeng River. The results indicate that those veins occurred in more recent period by U-Th dating data, because of degassing CO2 occurred in open fractures by normal faulting or the stress changing from compression to extension. The standard oxygen isotopes range from 1.29 to 20.73 permil of SMOW and the clumped isotope of ?47 outcrop is 0.385 in calcite veins, suggest that the highest temperature of thermal fulids with calcite precipitations is 222?9? by calibrated equation of Passey and Henkes 2012. Meanwhile, it also indicates that the oxygen isotope of initial water is 6.31 permil of SMOW which is totally different from the values of -5.36 and -6.5~-7.1 in the meteoric water of Chingshui area and the scaling of Well IC-13, respectively. This result infers that the compositions of hot fluids may be changed with different source in the Chingshui geothermal field.

  13. A pore scale description of calcium isotope exchange and equilibration with calcite

    NASA Astrophysics Data System (ADS)

    Druhan, J. L.; Huber, C.; Parmigiani, A.

    2014-12-01

    The distribution of stable isotope ratios between dissolved and solid phases are commonly used to assess processes of mineral formation, alteration and dissolution in a variety of low temperature systems. In order to model this partitioning, a description of isotopic exchange occurring at the fluid-solid surface is required. The use of continuum scale reactive transport models to describe heterogeneous isotopic fractionation is thus hindered by the ability to discretize isotopic gradients within a solid phase. Here we present a multi-component pore scale model for the partitioning of calcium isotopes between dissolved Ca2+ and calcite using a lattice Boltzmann method capable of describing the isotopic composition of an evolving mineral surface distinct from the bulk calcite composition. A key feature of our model is the ability to simultaneously track isotopic exchange at the fluid-solid surface as well as the isotopic composition of both bulk fluid and bulk calcite. This is significant in that the surface exchange dictates the evolution of isotopic compositions through time, while the bulk isotope ratios represent the actual measured values of samples collected in the field. Using this approach, we reexamine the distribution of calcium isotope ratios in pore fluids and carbonates reported for deep-sea core profiles with particular emphasis on interpretation of the equilibrium fractionation factor. Based on simulations of an initially supersaturated fluid surrounding a calcite crystal at a range of porosities, we show that the fluid can achieve both chemical and isotopic equilibrium with the solid surface while maintaining the appearance of disequilibrium with the bulk solid. The extent to which the final equilibrated calcium isotope ratio of the bulk fluid and bulk solid agree is therefore a function of the depth into the mineral surface that is exchangeable with the fluid.

  14. Calcitization and silicification of evaporites in Guadalupian back-reef carbonates of the Delaware basin, west Texas and New Mexico

    SciTech Connect

    Ulmer, D.S.; Scholle, P.A. )

    1991-03-01

    Outcrop of the Seven Rivers, Yates, and Tansill formations contain numerous examples of evaporites that have been replaced by both quartz and calcite. The original evaporites consisted of discrete horizons, scattered nodules, enterolithic layers, and individual crystal laths of gypsum and/or anhydrite within a predominantly dolomitic matrix. Based on field and petrographic observations, evaporite replacement proceeded from the exterior to the interior of the nodules. The earliest replacement was by euhedral, black megaquartz containing abundant hydrocarbon inclusions. Calcite replacement followed silicification and consists of coarse, equant, blocky spar. Isotopic analyses of these calcites form two distinct groups: the first group ranges from -10.9 to -20.1{per thousand} (average -16.4{per thousand}) {delta}{sup 13}C and -6.4 to -13.8{per thousand} (average -10.9{per thousand}) {delta}{sup 18}O; the second group ranges from +1.4 to 5.8{per thousand} (average -2.4{per thousand}) {delta}{sup 13}C and -6.2 to 14.1{per thousand} (average -9.2{per thousand}) {delta}{sup 18}O. Evaporite silicification was coeval with hydrocarbon migration as indicated by the inclusion data. Calcitization, however, was associated with mid-Tertiary block faulting that uplifted the area causing deep groundwater circulation. The isotopically very light calcites resulted from the mixing of meteoric fluids and hydrocarbon-rich pore fluids, probably during early uplift while these strata were still at significant depth. The calcites with heavier isotopic values were produced somewhat later by meteoric fluids that had little or no contact with hydrocarbons. Evaporite diagenesis in the Delaware basin is an ongoing process that started during hydrocarbon migration, continued over millions of years, and has the potential to significantly change the porosity of these units.

  15. Magnesium inhibition of calcite dissolution kinetics

    SciTech Connect

    Arvidson, Rolf S.; Collier, Martin; Davis, Kevin J.; Vinson, Michael D.; Amonette, James E.; Luttge, Andreas

    2006-02-01

    We present evidence of inhibition of calcite dissolution by dissolved magnesium through direct observations of the (104) surface using atomic force microscopy (AFM) and vertical scanning interferometry (VSI). Far from equilibrium, the pattern of magnesium inhibition is dependent on solution composition and specific to surface step geometry. In CO2-free solutions (pH 8.8), dissolved magnesium brings about little inhibition even at concentrations of 0.8 x 10-3 molal. At the same pH, magnesium concentrations of less than 0.05 x 10-3 molal in carbonate-buffered solutions generate significant inhibition, although no changes in surface and etch pit morphology are observed. As concentrations exceed magnesite saturation, the dissolution rate shows little additional decrease; however, selective pinning of step edges results in unique etch-pit profiles, seen in both AFM and VSI datasets. Despite the decreases in step velocity, magnesium addition in carbonated solutions also appears to activate the surface by increasing the nucleation rate of new defects. These relationships suggest that the modest depression of the bulk rate measured by VSI reflects a balance between competing reaction mechanisms that simultaneously depress the rate through selective inhibition of step movement, but also enhance reactivity on terraces by lowering the energy barrier to new etch-pit formation.

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

    PubMed

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

    2012-11-21

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

  17. Seed Germination

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Initiation of seed germination is a critical decision for plants. It is important for seed populations under natural conditions to spread the timing of germination of individual seeds to maximize the probability of species survival. Therefore, seeds have evolved the multiple layers of mechanisms tha...

  18. Sr 2+/Ca 2+ and 44Ca/ 40Ca fractionation during inorganic calcite formation: III. Impact of salinity/ionic strength

    NASA Astrophysics Data System (ADS)

    Tang, Jianwu; Niedermayr, Andrea; Khler, Stephan J.; Bhm, Florian; K?sakrek, Basak; Eisenhauer, Anton; Dietzel, Martin

    2012-01-01

    In order to apply Sr/Ca and 44Ca/40Ca fractionation during calcium carbonate (CaCO3) formation as a proxy to reconstruct paleo-environments, it is essential to evaluate the impact of various environmental factors. In this study, a CO2 diffusion technique was used to crystallize inorganic calcite from aqueous solutions at different ionic strength/salinity by the addition of NaCl at 25 C. Results show that the discrimination of Sr2+ versus Ca2+ during calcite formation is mainly controlled by precipitation rate (R in ?mol/m2/h) and is weakly influenced by ionic strength/salinity. In analogy to Sr incorporation, 44Ca/40Ca fractionation during precipitation of calcite is weakly influenced by ionic strength/salinity too. At 25 C the calcium isotope fractionation between calcite and aqueous calcium ions (?44/40Cacalcite-aq = ?44/40Cacalcite - ?44/40Caaq) correlates inversely to log R values for all experiments. In addition, an inverse relationship between ?44/40Cacalcite-aq and log DSr, which is independent of temperature, precipitation rate, and aqueous (Sr/Ca)aq ratio, is not affected by ionic strength/salinity either. Considering the log DSr and ?44/40Cacalcite-aq relationship, Sr/Ca and ?44/40Cacalcite values of precipitated calcite can be used as an excellent multi-proxy approach to reconstruct environmental conditions (e.g., temperature, precipitation rate) of calcite growth and diagenetic alteration.

  19. Frictional Properties and Microstructure of Calcite-Rich Fault Gouges Sheared at Sub-Seismic Sliding Velocities

    NASA Astrophysics Data System (ADS)

    Verberne, B. A.; Spiers, C. J.; Niemeijer, A. R.; De Bresser, J. H. P.; De Winter, D. A. M.; Plmper, O.

    2014-10-01

    We report an experimental and microstructural study of the frictional properties of simulated fault gouges prepared from natural limestone (96 % CaCO3) and pure calcite. Our experiments consisted of direct shear tests performed, under dry and wet conditions, at an effective normal stress of 50 MPa, at 18-150 C and sliding velocities of 0.1-10 ?m/s. Wet experiments used a pore water pressure of 10 MPa. Wet gouges typically showed a lower steady-state frictional strength ( ? = 0.6) than dry gouges ( ? = 0.7-0.8), particularly in the case of the pure calcite samples. All runs showed a transition from stable velocity strengthening to (potentially) unstable velocity weakening slip above 80-100 C. All recovered samples showed patchy, mirror-like surfaces marking boundary shear planes. Optical study of sections cut normal to the shear plane and parallel to the shear direction showed both boundary and inclined shear bands, characterized by extreme grain comminution and a crystallographic preferred orientation. Cross-sections of boundary shears, cut normal to the shear direction using focused ion beamSEM, from pure calcite gouges sheared at 18 and 150 C, revealed dense arrays of rounded, ~0.3 ?m-sized particles in the shear band core. Transmission electron microscopy showed that these particles consist of 5-20 nm sized calcite nanocrystals. All samples showed evidence for cataclasis and crystal plasticity. Comparing our results with previous models for gouge friction, we suggest that frictional behaviour was controlled by competition between crystal plastic and granular flow processes active in the shear bands, with water facilitating pressure solution, subcritical cracking and intergranular lubrication. Our data have important implications for the depth of the seismogenic zone in tectonically active limestone terrains. Contrary to recent claims, our data also demonstrate that nanocrystalline mirror-like slip surfaces in calcite(-rich) faults are not necessarily indicative of seismic slip rates.

  20. High-pressure deformation of calcite marble and its transformation to aragonite under non-hydrostatic conditions

    USGS Publications Warehouse

    Hacker, B.R.; Kirby, S.H.

    1993-01-01

    We conducted deformation experiments on Carrara marble in the aragonite and calcite stability fields to observe the synkinematic transformation of calcite to aragonite, and to identify any relationships between transformation and deformation or sample strength. Deformation-induced microstructures in calcite crystals varied most significantly with temperature, ranging from limited slip and twinning at 400??C, limited recrystallization at 500??C, widespread recrystallization at 600 and 700??C, to grain growth at 800-900??C. Variations in confining pressure from 0.3 to 2.0 GPa have no apparent effect on calcite deformation microstructures. Aragonite grew in 10-6-10-7 s-1strain rate tests conducted for 18-524 h at confining pressures of 1.7-2.0 GPa and temperatures of 500-600??C. As in our previously reported hydrostatic experiments on this same transformation, the aragonite nucleated on calcite grain boundaries. The extent of transformation varied from a few percent conversion near pistons at 400??C, 2.0 GPa and 10-4 s-1 strain rate in a 0.8 h long experiment, to 98% transformation in a 21-day test at a strain rate of 10-7 s-7, a temperature of 600??C and a pressure of 2.0 GPa. At 500??C, porphyroblastic 100-200 ??m aragonite crystals grew at a rate faster than 8 ?? 10-1m s-1. At 600??C, the growth of aragonite neoblasts was slower, ???6 ?? 10-1 m s -1, and formed 'glove-and-finger' cellularprecipitation-like textures identical to those observed in hydrostatic experiments. The transformation to aragonite is not accompanied by a shear instability or anisotropic aragonite growth, consistent with its relatively small volume change and latent heat in comparison with compounds that do display those features. ?? 1993.

  1. TRIACYLGLYCEROL PHASE AND SEED STORAGE BEHAVIOR

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Anecdotal stories have long suggested that oil-rich seeds store poorly; however, laboratory studies show that lipid content does not correlate with seed quality. Recently, we found that the tendency of triacylglycerols (TAG) to crystallize during storage of Cuphea seeds has a profound effect on see...

  2. Experimental Study of Sr, Mg, and Ba Partitioning Into Calcite at Various Linear Growth Rates Using Elemental and Isotopic Spikes: Preliminary Results.

    NASA Astrophysics Data System (ADS)

    Gabitov, R. I.; Adkins, J. F.; Eiler, J. M.

    2007-12-01

    The ratios of Mg/Ca and Sr/Ca in calcium carbonates are widely used as paleothermometers. However, inconsistencies in the relationship between temperature and composition amongst inorganic and biogenic calcites suggest the influence of factors other than temperature, including precipitation rate. We examine the influence of growth rate on Mg, Sr, and Ba partition coefficients between calcite and aqueous fluid (Kdi= XiCalcite*XCaFluid/XCaCalcite*XiFluid, where i is the cation of interest and X is the mole fraction). Previous experimental studies of growth-rate-dependent partitioning were based on bulk analysis of carbonate precipitates; here we develop an alternative approach based on in situ measurements of single crystals having known linear growth rates. Experiments were performed by continuously adding two titrates (Na2CO3 and CaCl2) into growth solution of NaCl doped with trace elements. Linear growth rates of calcite crystals are determined by adding of elemental and isotopic spikes into the growth medium (episodically for elemental spikes; continuously for isotopic spikes). Harvested crystals were randomly mounted into high vacuum epoxy and examined with NanoSIMS and SEM techniques. Our NanoSIMS measurements of product calcite crystals document approximately concentric growth, the rate of which is marked by the sequential appearance of the various elemental and isotopic spikes we added to the parental fluid during growth. For example, ratios of 55Mn/42Ca in carbonate are 1e-5 in crystal cores and sharply increase up to 1.6e-3 in crystal rims, in response to our addition of Mn to the parental liquid at a known time. Similarly, the 26Mg/24Mg ratio is close to natural abundances in crystal cores and monotonically increases toward the crystal edges, reflecting monotonic addition of 26Mg spike throughout the experiment. Such data, combined with known timing of elemental spike additions and rates of increase of the 26Mg/24Mg ratio of the solution, permitted us to quantitatively reconstruct the growth histories of individual calcite crystals. Calcite growth rates were calculated as the ratio of the distance between two adjacent analytical spots and the corresponding time interval required to explain their difference in composition. This is straightforward for the portions of the experiments when 26Mg/24Mg changed monotonically at a known rate, but generally provides only limits to the growth rate during the period when elemental spikes were added episodically. The linear growth rates estimated in this way varied from 0.6 to 6 microns per hour, with uncertainties as good as 6 percents, relative. The lower edge of our growth rate interval is similar to those of benthonic foraminifera, suggesting that partitioning data based on our experiments will constrain growth-rate effects relevant to common paleothermometry applications. Note that the growth rates we derive could be under- estimates because analyzed sections of the crystals do no necessarily expose the center of calcite crystallization. We anticipate determining Sr/Ca, Mg/Ca, and Ba/Ca ratios in the fluid, after which we shall report the partition coefficients for Sr, Mg, and Ba as function of growth rate of the calcite crystals.

  3. Paleoclimatic and paleohydrologic records from secondary calcite: Yucca Mountain, Nevada

    SciTech Connect

    Whelan, J.F.; Stuckless, J.S.; Moscati, R.J.; Vaniman, D.T.

    1994-12-31

    Stable isotope analyses of calcite and opal, fluid inclusion formation conditions and gas compositions, Sr isotope ratios, and REE compositions all support formation of secondary calcite in the unsaturated zone of Yucca Mountain from infiltration of surface-derived (and soil zone buffered) waters of meteoric origin. Detailed sampling of growth-banding preserved by the secondary calcite should provide a record of past variations in the stable isotope chemistry of these infiltrating waters, and, hence, of precipitation at Yucca Mountain, i.e., a proxy of past climate at Yucca Mountain. The precision of this record depends on how well it can be dated. The distribution and texture of secondary calcite occurrences, if mapped in careful detail from existing bore hole samples and underground workings (as exposures become accessible), could provide a time/space map of fracture and fault unsaturated-zone ground water flow-paths during past wetter climates which might prevail in the future with change in climate.

  4. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    SciTech Connect

    Chapman, Piers; *Morse, John W.

    2010-11-15

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

  5. Climate and cave control on Pleistocene/Holocene calcite-to-aragonite transitions in speleothems from Morocco: Elemental and isotopic evidence

    NASA Astrophysics Data System (ADS)

    Wassenburg, Jasper A.; Immenhauser, Adrian; Richter, Detlev K.; Jochum, Klaus Peter; Fietzke, Jan; Deininger, Michael; Goos, Manuela; Scholz, Denis; Sabaoui, Abdellah

    2012-09-01

    The occurrence of aragonite in speleothems has commonly been related to high dripwater Mg/Ca ratios, because Mg is known to be a growth inhibitor for calcite. Laboratory aragonite precipitation experiments, however, suggested a more complex array of controlling factors. Here, we present data from Pleistocene to Holocene speleothems collected from both a dolostone and a limestone cave in northern Morocco. These stalagmites exhibit both lateral and stratigraphic calcite-to-aragonite transitions. Aragonite fabrics are well-preserved and represent primary features. In order to shed light on the factors that control alternating calcite and aragonite precipitation, elemental (Mg, Sr, Ba, U, P, Y, Pb, Al, Ti and Th) abundances were measured using LA-ICP-MS, and analysed with Principal Component Analysis. Samples were analyzed at 100-200 ?m resolution across stratigraphic and lateral transitions. Carbon and oxygen isotope ratios were analysed at 100 ?m resolution covering stratigraphic calcite-to-aragonite transitions. Results show that the precipitation of aragonite was driven by a decrease in effective rainfall, which enhanced prior calcite precipitation. Different geochemical patterns are observed between calcite and aragonite when comparing data from the Grotte de Piste and Grotte Prison de Chien. This may be explained by the increased dripwater Mg/Ca ratio and enhanced prior aragonite precipitation in the dolostone cave versus lower dripwater Mg/Ca ratio and prior calcite precipitation in the limestone cave. A full understanding for the presence of lateral calcite-to-aragonite transitions is not reached. Trace elemental analysis, however, does suggest that different crystallographic parameters (ionic radius, amount of crystal defect sites, adsorption potential) may have a direct effect on the incorporation of Sr, Mg, Ba, Al, Ti, Th and possibly Y and P.

  6. Relative Shock Effects in Mixed Powders of Calcite, Gypsum, and Quartz: A Calibration Scheme from Shock Experiments

    NASA Technical Reports Server (NTRS)

    Bell, Mary S.

    2009-01-01

    The shock behavior of calcite and gypsum is important in understanding the Cretaceous/Tertiary event and other terrestrial impacts that contain evaporite sediments in their targets. Most interest focuses on issues of devolatilization to quantify the production of CO2 or SO2 to better understand their role in generating a temporary atmosphere and its effects on climate and biota [e.g., papers in 1,2,3,4]. Devolatilization of carbonate is also important because the dispersion and fragmentation of ejecta is strongly controlled by the expansion of large volumes of gas during the impact process as well [5,6]. Shock recovery experiments for calcite yield seemingly conflicting results: early experimental devolatilization studies [7,8,9] suggested that calcite was substantially outgassed at 30 GPa (> 50%). However, the recent petrographic work of [10,11,12] presented evidence that essentially intact calcite is recovered from 60 GPa experiments. [13] reported results of shock experiments on anhydrite, gypsum, and mixtures of those phases with silica. Their observations indicate little or no devolatilization of anhydrite shocked to 42 GPa and that the fraction of sulfur, by mass, that degassed is approx.10(exp -2) of theoretical prediction. In another (preliminary) report of shock experiments on calcite, anhydrite, and gypsum, [14] observe calcite recrystallization when shock loaded at 61 GPa, only intensive plastic deformation in anhydrite shock loaded at 63 GPa, and gypsum converted to anhydrite when shock loaded at 56 GPa. [15] shock loaded anhydrite and quartz to a peak pressure of 60 GPa. All of the quartz grains were trans-formed to glass and the platy anhydrite grains were completely pseudomorphed by small crystallized anhydrite grains. However, no evidence of interaction between the two phases could be observed and they suggest that recrystallization of anhydrite grains is the result of a solid state transformation. [16] reanalyzed the calcite and anhydrite shock wave experiments of [17] using improved equations of state of porous materials and vaporized products. They determined the pressures for incipient and complete vaporization to be 32.5 and 122 GPa for anhydrite and 17.8 and 54.1 GPa for calcite, respectively, a factor of 2 to 3 lower than reported earlier by [17].

  7. Vertical Distribution of Calcite at Yucca Mountain, Nevada, as an Indicator of Flow Through a Thick Unsaturated Zone

    SciTech Connect

    J.B. Paces; Z.E. Peterman

    2001-07-20

    Meteoric water percolating through 500 to 700 m of hydrologically unsaturated felsic tuffs provides a mechanism for release and transport of radionuclides from a potential high-level radioactive waste repository at Yucca Mountain, Nevada. Modern flow through the unsaturated zone (UZ) is low (probably <20 mm/year) and has not been observed directly. However, calcite formed from water percolating through fracture and lithophysal cavities over the last 12.8 million years provides, in part, a time-integrated record of UZ flow. Calcite concentration profiles were determined in dry-drilled boreholes USW WT-24 and USW SD-6 by acidifying samples of powdered rock cuttings collected over 5-foot intervals and measuring the evolved CO{sub 2} using gas chromatography. Resulting CO{sub 2}-derived calcite concentrations ranged from 30,800 to less than 20 ppm. Aliquots of the same powders also were analyzed for Ca, Ti, and Zr by energy-dispersive X-ray fluorescence. Concentrations of Ti and Zr in the crystal-poor, high-silica rhyolite parts of the Topopah Spring Tuff are uniform (standard deviations of 3 to 4%); however, Ca scatters widely (standard deviations of 21 and 32%). Concentrations of Ca are positively correlated to CO{sub 2}-derived calcite concentrations and regressions for samples of the two major rhyolitic tuffs yielded r{sup 2} values >0.9, CO{sub 2}-intercept Ca concentrations in the range of values determined on fresh rock samples, and slopes equivalent to addition of stoichiometric calcite. Therefore, combined CO{sub 2} and Ca data provide a means of determining the amount of secondary calcite added to the rock mass from percolating water. The vertical distribution of calcite is related to lithostratigraphy with the largest concentrations in the welded hydrogeologic unit of the Tiva Canyon Tuff near the land surface and progressively smaller values with depth into the underlying nonwelded units. Large values also may be present in the upper parts of the underlying welded hydrogeologic unit of the Topopah Spring Tuff, but generally decrease in the deeper parts of the unit. The spatial distribution of calcite is complex and likely is related, in part, to spatial variations in the amount of water and vapor transported through the thick UZ.

  8. A novel determination of calcite dissolution kinetics in seawater

    NASA Astrophysics Data System (ADS)

    Subhas, Adam V.; Rollins, Nick E.; Berelson, William M.; Dong, Sijia; Erez, Jonathan; Adkins, Jess F.

    2015-12-01

    We present a novel determination of the dissolution kinetics of inorganic calcite in seawater. We dissolved 13 C -labeled calcite in unlabeled seawater, and traced the evolving δ13 C composition of the fluid over time to establish dissolution rates. This method provides sensitive determinations of dissolution rate, which we couple with tight constraints on both seawater saturation state and surface area of the dissolving minerals. We have determined dissolution rates for two different abiotic calcite materials and three different grain sizes. Near-equilibrium dissolution rates are highly nonlinear, and are well normalized by geometric surface area, giving an empirical dissolution rate dependence on saturation state (Ω) of: This result substantiates the non-linear response of calcite dissolution to undersaturation. The bulk dissolution rate constant calculated here is in excellent agreement with those determined in far from equilibrium and dilute solution experiments. Plots of dissolution versus undersaturation indicates the presence of at least two dissolution mechanisms, implying a criticality in the calcite-seawater system. Finally, our new rate determination has implications for modeling of pelagic and seafloor dissolution. Nonlinear dissolution kinetics in a simple 1-D lysocline model indicate a possible transition from kinetic to diffusive control with increasing water depth, and also confirm the importance of respiration-driven dissolution in setting the shape of the calcite lysocline.

  9. The differnces between bond lengths in biogenic and geologocal calcite.

    SciTech Connect

    Zlotoyabko, E.; Caspi, E. N.; Fieramosca, J. S.; Von Dreele, R. B.; Marin, F.; Mor, G.; Politi, Y.; Addadi, L.; Weiner, S.

    2010-01-01

    We used high-resolution neutron powder diffraction to accurately measure the atomic positions and bond lengths in biogenic and geological calcite. A special procedure for data analysis was developed in order to take into account the considerable amounts of magnesium present in all the investigated samples. As a result, in biogenic calcite we found some atomic bonds to have significantly different lengths as compared to those in geological calcite, after the contribution of magnesium is accounted for. The maximum effect (elongation up to 0.7%) was found for the C-O bonds. We also analyzed changes in frequencies and spectral widths of normal vibrations of carbonate groups in biogenic calcite (as compared to geological calcite) measured by Raman and Fourier transform IR techniques. Surprisingly, the frequency shifts after subtracting the magnesium contribution are close to zero. At the same time, substantial spectral broadening (up to 1.2%) in biogenic calcite as compared to geological samples was detected. Possible explanations for the experimental findings are discussed.

  10. The kinetics of the ordering of 13C-18O bonds in calcite and apatite

    NASA Astrophysics Data System (ADS)

    Stolper, D. A.; Halevy, I.; Eiler, J. M.

    2011-12-01

    Eiler and Schauble (2004) showed that the isotopes of C and O are not randomly distributed within single phases such as CO2 gas and carbonates, and in particular, that heavy isotopes of C and O tend to bond preferentially (clump) at lower temperatures. Consequently, the measurement of the deviation from a random distribution of C and O isotope distributions in a single phase can be used as a thermometer. As with other geothermometers based on homogeneous or heterogeneous equilibria, the clumped-isotope thermometer is susceptible to resetting (e.g., if the phase is reheated or experiences slow cooling). Thus, clumped-isotope "temperatures" of phases that have experienced complex thermal histories may, in fact, be closure temperatures, the interpretation of which requires quantification of the kinetics of redistribution of C and O isotopes as a function of temperature. These kinetics have received increasing attention (Dennis and Schrag, 2010; Passey 2010), and are likely to be critical for understanding clumped-isotope temperatures of samples that have been buried for long periods of time. To better constrain these kinetics we performed experiments on natural optical calcite from Mexico and carbonate-bearing apatite from the Siilinjarvi carbonatite (Finland). For each experiment, multiple single crystal grains (~2 mm in diameter) of calcite or apatite were loaded in open Pt capsules, pressurized with Ar gas, and held at 400-700 C, 550 bars using a rapid quench TZM apparatus for 5 min to 520 hrs. After quenching, 13C-18O clumping was measured in the samples; the change from the initial ?47 with time for each phase at each temperature was fit to simple mechanistic models of isotope exchange between sites in these phases. One conclusion of the experimental study is that resetting the internal ordering of carbonate groups proceeds more rapidly in calcites than in apatites. For example, heating apatite at 400 C results in no change in clumping over a 24 hr period, while the ?47 of calcite changes by ~0.13% for the same conditions. We also measured clumping in cogenetic apatite and calcite from three carbonatites; these intrusive rocks cooled slowly from igneous temperatures and thus comparison of the apatite and calcite closure temperatures provides constraints on the differences in kinetics of resetting of clumping in these two phases. Apparent temperatures for apatites are 90-140 C and are cooler than cogenetic calcites in all cases with differences of 30-60 C. This contrasts with the expectation from the laboratory experiments we have done. Possible explanations of this include a change in the mechanism of the kinetics of reordering in calcite and apatite at temperatures lower than 300-400 C or resetting of ?47 due to recrystalization or diagenesis for natural samples. Using the results of our models and measurements we are able to calculate activation energies and estimate expected changes in apparent temperatures of samples for geologically plausible scenarios. As such, this study has relevance for our interpretation of ancient samples that have thermal histories involving any significant heating. Additionally, it provides the groundwork for using apatites and carbonates together in paleotemperature studies to determine if thermal overprinting could be present.

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

    Stable isotope (?18O and ?13C) 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 ?D and ?18O, dripwater Ca2+, pH, ?13C and TCO2, cave air pCO2 and ?13C, and farmed calcite ?18O and ?13C 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 ?13C 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 ??13C = -7 . A whole-cave "Hendy test" at distributed contemporaneous farming sites reveals that ventilation induces a +1.9 0.96 ?13C offset between calcite precipitated in a ventilation flow path and out of flow paths. Farmed calcite ?18O exhibits a +0.82 0.24 offset from values predicted by both theoretical calcite-water calculations and by laboratory-grown calcite [2]. Unlike calcite ?13C, 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 ? = 16.1(1000/T) - 24.6 We analyzed anions, cations, and trace elements in dripwater, bedrock, and farmed calcite to examine the relationships between net rainfall, drip rates, drip water chemistry, and calcite chemistry. Dripwater Mg/Ca and Sr/Ca ratios fall on coherent mixing lines between three geochemical endmembers: rainwater, dissolved dolomite, and dissolved limestone. Dripwater Sr/Ca vs. Mg/Ca ratios are also influenced by evaporative enrichment within the epikarst as a function of net rainfall amount [3]. Farmed calcite trace Cation/Ca ratios faithfully track short-term seasonal variations in dripwater chemistry for Na, Mg, Sr, Ba and U. However, speleothem calibrations are unique to each drip site regardless of proximity to one another, suggesting that individual speleothems are unlikely to be useful as a whole-cave hydrologic proxy. [1] Kowalczk, A. J., Froelich, P. N., 2010. Cave air ventilation and CO2 outgassing by radon-222 modeling: How fast do caves breathe? Earth & Planet. Sci. Lett. 289, 209-219. [2] Tremaine, D. M., Froelich, P. N., Wang, Y., 2011. Speleothem calcite farmed in situ: Modern calibration of ?18O and ?13C paleoclimate proxies in a continuously-monitored natural cave system. Geochim. Cosmochim. Acta 75, 4929-4950. [3] Tremaine, D. M., Froelich, P. N., 2012. Speleothem trace element signatures: A modern hydrologic geochemical study of cave drip waters and farmed calcite. Geochim. Cosmochim. Acta (submitted)

  12. Crystallization Pathways in Biomineralization

    NASA Astrophysics Data System (ADS)

    Weiner, Steve; Addadi, Lia

    2011-08-01

    A crystallization pathway describes the movement of ions from their source to the final product. Cells are intimately involved in biological crystallization pathways. In many pathways the cells utilize a unique strategy: They temporarily concentrate ions in intracellular membrane-bound vesicles in the form of a highly disordered solid phase. This phase is then transported to the final mineralization site, where it is destabilized and crystallizes. We present four case studies, each of which demonstrates specific aspects of biological crystallization pathways: seawater uptake by foraminifera, calcite spicule formation by sea urchin larvae, goethite formation in the teeth of limpets, and guanine crystal formation in fish skin and spider cuticles. Three representative crystallization pathways are described, and aspects of the different stages of crystallization are discussed. An in-depth understanding of these complex processes can lead to new ideas for synthetic crystallization processes of interest to materials science.

  13. Role of Temperature and Saturation State in Determining Growth Rate and Sr-content in Calcite

    NASA Astrophysics Data System (ADS)

    Stephenson, Allison; Oelkers, Eric

    2010-05-01

    Impurity contents in biogenic and inorganically precipitated carbonates are widely used as proxies for a variety of environmental conditions such as temperature and ocean chemistry. However, the dominant factors controlling element-uptake and their interplay, both at the environmental and organism scale, must be sorted out before proposed proxies can be robustly used to interpret environmental conditions. Recent studies have demonstrated the importance of cation:anion ratio in determining mineral growth rates (Chernov, 2006; Perdikouri, 2009) and their subsequent impact on impurity contents, specifically Sr in calcite (Nehrke, 2007). We further investigated the relationships between Sr-content in calcite and growth rate, by changing precipitation rates though variations in saturation index, temperature, addition of other growth modifiers like [Mg++], and the [Ca++]:[CO3=] ratio. Experiments were conducted in seeded flow-through reactors with controlled pH, solution chemistry (modeled in Phreeq), alkalinity, and temperature. Reaction solutions were analyzed throughout the duration of the experiment using atomic adsorption spectrometry. Mineral contents were analyzed using XRD, and surfaces were analyzed using SEM. Results allow us to weigh the importance of different solution parameters, and thus global environmental conditions and biomineralization processes, in determining impurity contents in carbonate minerals.

  14. Effect of Free Energy and Dislocation Density on Calcite Dissolution Kinetics

    NASA Astrophysics Data System (ADS)

    Fan, C.; Teng, H.

    2007-12-01

    Mineral dissolution plays a central role in regulating various geochemical processes at both global and local scales and consequently has been a vital research subject in geosciences. To date, the accelerated buildup of atmospheric CO2 is spurring a growing interest in understanding carbonate dissolution. Significant progress has been made on this topic through intensive studies in the past decades. Yet, the dissolution behavior of carbonate minerals remains controversial when it comes to the relationship between kinetics and free energy as well as the significance of dislocation density in the overall dissolution processes. Here, we investigate the dissolution of calcite at near and far from equilibrium conditions to examine the controlling factors for the reaction kinetics. Mixed-flow experiments were conducted at various saturation states under room temperature. Fragmental and powdered calcite samples with different defect densities were used to explore the effect of dislocation density on dissolution kinetics, and geometric surface area of the mineral grains was used to normalize the dissolution rate. The experiments were conducted in both closed and open (to air) settings. Experimental observations show a highly nonlinear dependence of dissolution rate on the Gibbs free energy. Furthermore, dissolution rates do not seem to be affected by dislocation density near and far from equilibrium. Finally, dissolution rates measured at same saturation conditions are similar regardless the experimental settings, closed or open. These results suggest that: (i) The classic TST model may not be sufficient to depict the relation between dissolution rate and Gibbs free energy for calcite in all saturation conditions. The sigmoidal trend in the R- ΔG relationship indicates that, though the TST rate equation yields a fairly precise description of calcite dissolution kinetics when ΔG < -12 KJ/mol, it clearly overestimates the dissolution rate when the system approaches far-from equilibrium. (ii) The effect of high-energy surface sites associated with crystal imperfections may be overwhelmed by that of the growing steps generated by dissolution. (iii) The partial pressure of CO2 in ambient environment bears little importance to calcite dissolution once the saturation conditions of the solutions are fixed.

  15. Seed proteomics

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Seeds comprise a protective covering, a small embryonic plant, and a nutrient-storage organ. Seeds are protein-rich, and have been the subject of many mass spectrometry-based analyses. Seed storage proteins (SSP), which are transient depots for reduced nitrogen, have been studied for decades by cel...

  16. Grain size dependency in clumped isotope ratios in high temperature calcites

    NASA Astrophysics Data System (ADS)

    Banerjee, Y.; Ghosh, P.; Misra, S.

    2013-12-01

    Here we have extended the application of clumped isotope thermometry for understanding the geospeedometers using calcite produced at high temperature and pressure. Static recrystallization experiments were conducted on cylindrical discs of AR grade carbonate with three different grain sizes (40?m, 200?m and 400?m) at constant pressure (1705 MPa) and two different temperatures (600010C and 800010C) for 24 hours. The rate of temperature ramps for heating and cooling were set at 20C/min and 60C/min, respectively, mimicking a laboratory scale metamorphic condition of sudden burial and exhumation. The carbonate rocks, with prominent calcite mineral composition were prepared in a cylindrical capsule and were investigated for grain size distribution using Mastersizer, a laser technology to measure grain size. We identified three categories of crystals with grain size varying between 40?m, 200?m and 400?m. 15mg carbonate powder drilled from the periphery of the cylindrical discs were analysed for Clumped isotope ratio (Ghosh et al., 2006). Calcite formation experiment allowed re-crystallization of original powder produced at ambient temperature by subjecting the experimental setup to the temperatures of 800 and 600C (Pressure was maintained constant at 1705 MPa). We found broadly three different grain size fractions measured using in-situ laser probe. The present experiments were performed in dry environment unlike the wet high pressure experiment presented in the Passey and Henkes (2012). The present experimental value for ? 47 was translated into absolute temperature using thermometry equation proposed by Ghosh et al., (2006). We observed a strong relationship of clumped isotopic composition with grain sizes of carbonates, which was rather inconsistent with the earlier presumption (Passey and Henkes 2012). The clumped temperature value was found matching with the true temperature in cases where grain size attained 400 micron, while finer fraction registered values of lower temperature. We also observed a lower limit of 150100 C as clumped temperature for all the Calcite analysed irrespective of final temperature. We attribute this as closure temperature or apparent equilibrium temperature in our experiment. The results of this study have important implication in the application of clumped isotope technique in high temperature carbonates. References: Ghosh et al., 2006, GCA (70) , 1439-1456; Passey and Henkes, 2012, EPSL (351-352) , 223-236 Figure 1: Relationship between clumped isotope based temperature (in degree celsius),calculated using Ghosh et al., 2006 equation and grain size (in micron) of the carbonates of present study.

  17. Calcite and Picocyanobacteria in Lakes: Factors Affecting Their Interaction

    NASA Astrophysics Data System (ADS)

    Dittrich, M.; Obst, M.; Mavrocordatos, D.

    2003-12-01

    Calcites build large deposits which have been observed in the rock record throughout geological time at various localities around the globe. Carbonate deposits have affected atmospheric carbon dioxide concentration. As it has been generally accepted, inorganic precipitation represents a source of carbon dioxide on short geological time scales and a sink of inorganic carbon at long time scales from millions to thousands of millions years. However, recent research indicates that calcite deposits may result from microbial calcification instead of inorganic precipitation. In this case the process may reduce atmospheric carbon dioxide on geologically short time scales. Thus the effect of carbonate sediment deposition on global carbon cycling depends on the origin of carbonate. Thus it is essential to understand the cause and the key parameters affecting calcite precipitation. The role of algae and bacteria in calcite formation in lakes has not been evaluated in detail. Some evidence, however, exists supporting precipitation of calcium carbonate by microbes as the origin of whiting. Several field studies on lakes have also produced puzzling results: The peaks of algal blooms were often not found at the same time as precipitation events of calcite. We suspect that parts of the discrepancies in the interpretation of field observations are due to the activity of autotrophic picoplankton. The unicellular autotrophic picoplankton (APP) is a ubiquitous component of pelagic ecosystems. But it has often been overlooked due to its small cell size of 0.2 - 2 ? m in diameter. Coccoid picocyanobacteria of the Synechococcus-type dominate the picoplankton community in most oligotrophic systems. Recently, laboratory experiments and field observations suggested that APP may play an important role in calcite precipitation. The aim of this study was to examine the influence of environmental factors such as saturation state, concentration of different dissolved ions and characteristics of the surface of cells on interaction between calcite and picocyanobacteria under both laboratory and field conditions. Laboratory experiments were performed with a picocyanobacteria strain Synechococcus-type. Using ion selective electrodes we monitored calcite precipitation induced by bacteria in the solutions of a different composition (calcium 0.7 - 48 mM, inorganic carbonate 6 - 35 ? M). Electron and atomic force microscopy measurements provided insight into the cell-mineral interface. Furthermore, quantitative investigations of the types and densities of proton binding sites on a bacterial surface will be reported from the acid-base titrations on bacteria. Results of these initial experiments are encouraging and demonstrate by direct measurements the potential of picocyanobacteria to precipitate calcite. The amount of the precipitated calcite varied in experiments with a different ratio of dissolved inorganic carbon and calcium. The microscopic observations provide some evidence that the cell walls of cyanobacteria act as a substrate of nucleation of calcite. Temporal and spatial correlations of cyanobacteria and calcite, as well as images of bacterial shape particles indicated that picoplankton plays an important role in calcite precipitation in Lake Lucerne. This class of phytoplankton has to be considered in studying the biogeochemical cycling of oligotrophic hardwater lakes.

  18. Sequestration of selenium on calcite surfaces revealed by nanoscale imaging

    NASA Astrophysics Data System (ADS)

    Putnis, Christine V.; Renard, Franois; King, Helen E.; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion

    2014-05-01

    Selenium is an important element because of its high toxicity in natural systems. In-situ atomic force microscopy observations of calcite surfaces during contact with selenium-bearing solutions demonstrate that selenium trapping can occur under conditions in which calcite both dissolves and precipitates. The contact of solutions containing selenium in two states of oxidation (either Se(IV ) or Se(V I)) onto a growing or dissolving calcite surface either changes the growth pattern or results in precipitates formed during dissolution. In the form of selenite (Se(IV )), but not as selenate (Se(IV )), selenium can be incorporated into calcite during growth. During dissolution, in the presence of selenate (Se(V I)), the precipitates formed remained small during the observation period. When injecting selenite (Se(IV )), the precipitates grew significantly, and were identified as CaSeO3H2O, based on SEM observations, Raman spectroscopy and thermodynamic calculations. An interpretation is proposed where dissolution of calcite increases the calcium concentration in a thin boundary layer in contact with the surface, allowing the precipitation of a selenium phase. This process of dissolution-precipitation provides a new mechanism for selenium sequestration and extends the range of thermodynamic conditions under which such a process is efficient.

  19. A Raman spectroscopic comparison of calcite and dolomite

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  20. A Raman spectroscopic comparison of calcite and dolomite.

    PubMed

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

    2014-01-01

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

  1. Effect of Otoconial Proteins Fetuin A, Osteopontin, and Otoconin 90 on the Nucleation and Growth of Calcite

    PubMed Central

    2015-01-01

    We investigated the roles of three proteins associated with the formation of otoconia including fetuin A, osteopontin (OPN), and otoconin 90 (OC90). In situ atomic force microscopy (AFM) studies of the effects of these proteins on the growth of atomic steps on calcite surfaces were performed to obtain insight into their effects on the growth kinetics. We also used scanning electron microscopy to examine the effects of these proteins on crystal morphology. All three proteins were found to be potent inhibitors of calcite growth, although fetuin A promoted growth at concentrations below about 40 nM and only became an inhibitor at higher concentrations. We then used in situ optical microscopy to observe calcite nucleation on films of these proteins adsorbed onto mica surfaces. By measuring the calcite nucleation rate as a function of supersaturation, the value of the interfacial energy that controls the free energy barrier to heterogeneous nucleation was determined for each protein. OPN and OC90 films led to significantly reduced interfacial energies as compared to the value for homogeneous calcite nucleation in bulk solution. The value for fetuin A was equal to that for bulk solution within experimental error. Zeta potential measurements showed all of the proteins possessed negative surface charge and varied in magnitude according to sequence fetuin A > OC90 > OPN. In addition, the interfacial energies exhibited an inverse scaling with the zeta potential. In analogy to previous measurements on polysaccharide films, this scaling indicates the differences between the proteins arise from the effect of protein surface charge on the solution–substrate interfacial energy. PMID:25709560

  2. Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solution

    SciTech Connect

    DePaolo, D.

    2010-10-15

    A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R{sub p}) to the gross forward precipitation rate (R{sub f}), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R{sub p} has been experimentally measured under varying conditions, but the magnitude of R{sub f} is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R{sub f} can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R{sub b} or k{sub b}), since at equilibrium R{sub f} = R{sub b}, and R{sub p} = 0. Hence it can be inferred that R{sub f} {approx} R{sub p} + R{sub b}. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R{sub p} (= R{sub f} - R{sub b}) << R{sub b}. For precipitation rates high enough that R{sub p} >> R{sub b}, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R{sub p} {approx} R{sub b} for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R{sub f} for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R{sub p}. Allowing R{sub b} to vary as R{sub p}{sup 1/2}, consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where R{sub b} is constant. This model can account for most of the experimental data in the literature on the dependence of {sup 44}Ca/{sup 40}Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for {sup 18}O/{sup 16}O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of R{sub b} on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that equire hyper-fast diffusivity in near-surface layers of the solid.

  3. Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solution

    SciTech Connect

    DePaolo, Donald J.

    2011-01-01

    A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (Rp) to the gross forward precipitation rate (Rf), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of Rp has been experimentally measured under varying conditions, but the magnitude of Rf is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, Rf can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (Rb or kb), since at equilibrium Rf = Rb, and Rp = 0. Hence it can be inferred that Rf ? Rp + Rb. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when Rp (=Rf - Rb) Rb. For precipitation rates high enough that Rp Rb, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near Rp ? Rb for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate Rf for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence Rp. Allowing Rb to vary as Rp1/2, consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where Rb is constant. This model can account for most of the experimental data in the literature on the dependence of 44Ca/40Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for 18O/16O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of Rb on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that require hyper-fast diffusivity in near-surface layers of the solid.

  4. The Raman spectrum of CaCO{sub 3} polymorphs calcite and aragonite: A combined experimental and computational study

    SciTech Connect

    De La Pierre, Marco E-mail: marco.delapierre@unito.it; Maschio, Lorenzo; Orlando, Roberto; Dovesi, Roberto; Carteret, Cédric E-mail: marco.delapierre@unito.it; André, Erwan

    2014-04-28

    Powder and single crystal Raman spectra of the two most common phases of calcium carbonate are calculated with ab initio techniques (using a “hybrid” functional and a Gaussian-type basis set) and measured both at 80 K and room temperature. Frequencies of the Raman modes are in very good agreement between calculations and experiments: the mean absolute deviation at 80 K is 4 and 8 cm{sup −1} for calcite and aragonite, respectively. As regards intensities, the agreement is in general good, although the computed values overestimate the measured ones in many cases. The combined analysis permits to identify almost all the fundamental experimental Raman peaks of the two compounds, with the exception of either modes with zero computed intensity or modes overlapping with more intense peaks. Additional peaks have been identified in both calcite and aragonite, which have been assigned to {sup 18}O satellite modes or overtones. The agreement between the computed and measured spectra is quite satisfactory; in particular, simulation permits to clearly distinguish between calcite and aragonite in the case of powder spectra, and among different polarization directions of each compound in the case of single crystal spectra.

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

    NASA Astrophysics Data System (ADS)

    Nishio, Takashi; Naka, Kensuke

    2015-06-01

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

  6. Narrow-bandwidth, mid-infrared, seeded optical parametric generation in 90 phase-matched CdSiP2 crystal pumped by diffraction limited 500 ps pulses at 1064 nm.

    PubMed

    Marchev, Georgi; Pirzio, Federico; Piccoli, Riccardo; Agnesi, Antonio; Reali, Giancarlo; Schunemann, Peter G; Zawilski, Kevin T; Tyazhev, Aleksey; Petrov, Valentin

    2012-08-01

    Low-threshold, efficient optical parametric generation at ~6100 nm is demonstrated using CdSiP2 nonlinear crystal at 1 to 10 kHz repetition rates with relatively long 500 ps pump pulses at 1064 nm. Maximum single pulse energy of 8.7 ?J and average power of 79 mW are achieved for the idler. Seeding at the signal wavelength is employed using a distributed feedback laser diode, which enables approximately tenfold narrowing of the idler bandwidth down to less than 1 nm. PMID:22859138

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

    NASA Astrophysics Data System (ADS)

    Andersson, M. P.; Rodriguez-Blanco, J. D.; Stipp, S. L. S.

    2016-03-01

    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 < pH < 6.35, where H2CO30 is the dominant dissolved species. When bicarbonate is adsorbed on calcite, the predicted pKa for deprotonation is 7.5, which is ∼3 pH units lower than in aqueous solution, 10.35. This means that adsorbed carbonate is stable even when the concentration of dissolved CO32- is several orders of magnitude lower. This has a significant effect on surface charge and thus the behaviour of the calcite surface. Our results help explain the potential determining behaviour of the carbonate species in calcite-water systems, particularly in the pH range where the bicarbonate species dominates in water and where the carbonate species dominates at the surface, i.e. when 7.5 < pH < 10.35. Our atomic scale data for the various calcite surface sites provide the needed input to improve and constrain surface complexation modelling and are especially useful for predicting behaviour in systems where experiments are difficult or impossible, such as at high temperature and pressure.

  8. Microbially Induced Calcite Precipitation for Subsurface Immobilization of Contaminants

    NASA Astrophysics Data System (ADS)

    Smith, R. W.; Fujita, Y.; Ginn, T. R.; Hubbard, S. S.; Dafflon, B.; Delwiche, M.; Gebrehiwet, T.; Henriksen, J. R.; Peterson, J.; Taylor, J. L.

    2011-12-01

    Subsurface radionuclide and metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of the greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent trace ions, such as the short-lived radionuclide 90Sr, is co-precipitation in calcite. We have found that calcite precipitation and co-precipitation of Sr can be accelerated by the activity of urea hydrolyzing microorganisms, that higher calcite precipitation rates can result in increased Sr partitioning, and that nutrient additions can stimulate ureolytic activity. To extend our understanding of microbially induced calcite precipitation (MICP) in an aquifer setting a continuous recirculation field experiment evaluating MICP was conducted at the Integrated Field Research Challenge (IFRC) site located at Rifle, CO. In this experiment, groundwater extracted from an onsite well was amended with urea (total mass of 42.5 kg) and molasses (a carbon and electron donor) and re-injected into a well approximately 4 meters up-gradient for a period of 12 days followed by 10 months of groundwater sampling and monitoring. Crosshole radar and electrical tomographic data were collected prior, during, and after the MICP treatment. The urea and molasses treatment resulted in an enhanced population of sediment associated urea hydrolyzing organisms as evidenced by increases in the number of ureC gene copies, increases in 14C urea hydrolysis rates, and long-term observations of ammonium (a urea hydrolysis product) in the injection, extraction and down gradient monitoring wells. Permeability changes and increases in the calcite saturation indexes in the well field suggest that mineral precipitation has occurred; ongoing analysis of field samples seeks to confirm this. Changes in dielectric constant and electrical conductivity were used to interpret the spatiotemporal distribution of the injectate and subsequent calcite precipitation. Modeling activities are underway to define field-scale urea hydrolysis rates.

  9. Geochemical Proxy Distribution at the Atomic-Scale: Atom Probe Tomography of Foraminiferal Calcite

    NASA Astrophysics Data System (ADS)

    Branson, O.; Perea, D. E.; Winters, M. A.; Fehrenbacher, J. S.; Russell, A. D.; Spero, H. J.; Gagnon, A. C.

    2014-12-01

    Biomineral composition reflects a complex interplay between minute-scale biological control, mineral growth processes, and the influence of environmental conditions. For this reason, the mechanisms responsible for the formation of these minerals, as well as the incorporation of trace elements during biomineral growth, are poorly understood. Potential mechanisms governing the production and composition of biominerals can be organized into two distinct groups: a) biological mechanisms controlling the calcifying environment and b) mineral growth processes from this controlled environment. Despite significant advances in both these areas, critical gaps remain in our understanding of biomineral production and geochemical tracer incorporation. We are adapting Atom Probe Tomography (APT), a technique that maps the arrangement and identity of individual atoms within a bulk material, to analyze foraminiferal calcite for the first time. These data-rich atom-scale chemical maps provide a unique opportunity to deconvolve the effects of biological and crystal growth processes in the incorporation of geochemical tracers. Our first experiments have examined the influence of the biological-mineral interface on geochemical proxy element incorporation. Preliminary measurements show that (1) we can successfully map impurities in calcite biominerals, while also distinguishing between mineral and organic zones, overcoming a major technical hurdle; and (2) that elements like sodium appear to be recruited to the organic-mineral interface. The high-resolution chemical data from the APT will further allow us to investigate the fundamental basis for geochemical proxy behavior. For example, we can determine for a certain set of conditions whether the substitution of trace elements into the calcite follows ideal solid-solution behavior, as tacitly assumed in many geochemical proxy systems, or is modulated by intra-shell organics, or coupled-substitution interactions. Collectively, the application of APT to biominerals will lead to a mechanistic understanding of the processes controlling proxy behavior, with applications in climate science, geochemistry, and the design of complex biomimetic materials.

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

    NASA Astrophysics Data System (ADS)

    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 18C, 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 26C, Sr/Ca ratios increased by more than 25% (i.e., 1%/1C), 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 (? p) on CO 2(aq) at a range of growth rates and temperatures. Consequently, using coccolith Sr/Ca in combination with alkenone ? p may improve paleo-CO 2 determinations.

  11. On the Formation and Functions of High and Very High Magnesium Calcites in the Continuously Growing Teeth of the Echinoderm Lytechinus variegatus: Development of Crystallinity and Protein Involvement

    PubMed Central

    Veis, Arthur; Stock, Stuart R.; Alvares, Keith; Lux, Elizabeth

    2011-01-01

    Sea urchin teeth grow continuously and develop a complex mineralized structure consisting of spatially separate but crystallographically aligned first stage calcitic elements of high Mg content (515 mol% mineral). These become cemented together by epitaxially oriented second stage very high Mg calcite (3040 mol% mineral). In the tooth plumula, ingressing preodontoblasts create layered cellular syncytia. Mineral deposits develop within membrane-bound compartments between cellular syncytial layers. We seek to understand how this complex tooth architecture is developed, how individual crystalline calcitic elements become crystallographically aligned, and how their Mg composition is regulated. Synchrotron microbeam X-ray scattering was performed on live, freshly dissected teeth. We observed that the initial diffracting crystals lie within independent syncytial spaces in the plumula. These diffraction patterns match those of mature tooth calcite. Thus, the spatially separate crystallites grow with the same crystallographic orientation seen in the mature tooth. Mineral-related proteins from regions with differing Mg contents were isolated, sequenced, and characterized. A tooth cDNA library was constructed, and selected matrix-related proteins were cloned. Antibodies were prepared and used for immunolocaliztion. Matrix-related proteins are acidic, phosphorylated, and associated with the syncytial membranes. Time-of-flight secondary ion mass spectroscopy of various crystal elements shows unique amino acid, Mg, and Ca ion distributions. High and very high Mg calcites differ in Asp content. Matrix-related proteins are phosphorylated. Very high Mg calcite is associated with Asp-rich protein, and it is restricted to the second stage mineral. Thus, the composition at each part of the tooth is related to architecture and function. PMID:21555859

  12. Petrology of UHP calcite marble from the Kokchetav Massif

    NASA Astrophysics Data System (ADS)

    Aoki, K.; Adachi, T.; Kikuchi, M.; Ogasawara, Y.

    2004-12-01

    In the Kumdy-kol area, Kokchetav Massif, northern Kazakhstan, three types of UHP marbles have been described: diamond-bearing dolomite marble, Ti-clinohumite-bearing dolomitic marble (Ogasawara et al., 2000) and titanite-bearing calcite marble (Ogasawara et al., 2002). UHP calcite marble is distinguished from other types of UHP marbles by pure calcite (after aragonite) as a dominant carbonate phase. This calcite marble has unique evidence of UHP metamorphism; titanite with coesite exsolution and its precursor compositions indicated that the peak P-T conditions was > 6 GPa and 980-1250 C (Ogasawara et al., 2000; 2002). This rock shows typical granoblastic texture consisting of calcite, diopside, K-feldspar, titanite and symplectite (diopside + zoisite) after garnet. The peak assemblage was aragonite + diopside + K-feldspar + garnet + titanite. Based on the phase relations in the system CaO-MgO-TiO2-SiO2-CO2-H2O, aragonite + diopside + rutile tie-triangle is stable under UHP conditions and divides the compositional space into dolomite-bearing or dolomite-free tetrahedrons (Kikuchi et al., 2003). The presence of titanite in calcite marble means that P-T condition was located at the right-hand side of the reaction rutile + aragonite + coesite = titanite + CO2. Previously described titanite-bearing calcite marble is diamond-free (A-type) and is characterized by titanite with coesite exsolution (Ogasawara et al., 2002). Recently, we found a small amount of diamond in calcite marble (B-type) that is characterized by microdiamond in diopside, and by the lack of K-feldspar and low amount of titanite. No diamond occurs in titanite. Rutile, aragonite and calcite inclusions in titanite were found in titanite of B-type calcite marble. These three inclusion phases in titanite that were confirmed by laser Raman spectroscopy are the evidence for titanite formation reaction described above. This titanite forming reaction occurs at extremely low XCO2 conditions as 0.02. In B-type calcite marble, microdiamond occurs locally and its amount is low; only 61 grains were found in two thin sections. Distributions of titanite, K-feldspar and diamond are heterogeneous and seem to form layers. Diamond occurs in the domain where amounts of titanite and K-feldspar are relatively low. Low amount of microdiamond may be related with extremely low-XCO2 condition under UHP metamorphism. References Ishida et al. (2003: Journal of Metamorphic Geology, Vol. 21, p. 515-522. Kikuchi et al. (2003): EOS Transactions AGU, Vol. 84, F1532. Ogasawara et al. (2000): The Island Arc, Vol. 9, p 400-416. Ogasawara et al. (2002): American Mineralogist, Vol. 87, p. 454-461.

  13. Field test of a calcite dissolution rate law: Fort's Funnel Cave, Mammoth Cave National Park

    SciTech Connect

    Slunder, J.S. ); Groves, C.G. . Center for Cave and Karst Studies)

    1994-03-01

    The laboratory-derived calcite dissolution rate law of Plummer et al. (1978) is the most widely used and mechanistically detailed expression currently available for predicting dissolution rates as a function of water chemistry. Such rate expressions are of great use in understanding timescales associated with limestone karst development. Little work has gone into the field testing of the rate law under natural conditions. This work measured dissolution rates by a crystal weight loss experiment in Buffalo Creek within Fort's funnel Cave, which lies within a pristine, forested catchment of Mammoth Cave National Park. Continuous water chemistry sampling over the same period allowed a time-integrated prediction of the dissolution based on the Plummer et al. (1978) expression. Results indicate that the rate law overpredicted dissolution by a factor of about ten. This concurs with earlier laboratory work suggesting that the law tends to overpredict rates in solutions close to equilibrium with respect to calcite, as were the waters within this part of the groundwater flow system.

  14. Chalk-calcite-microfluidic experiments: construction and flooding of microsystems with reactive fluids

    NASA Astrophysics Data System (ADS)

    Neuville, Amélie; Thuy Luu, Thi; Dysthe, Dag Kristian; Vinningland, Jan Ludvig; Hiorth, Aksel

    2015-04-01

    Direct in situ observation of the pore structure changes that occur when chalk is flooded with brines could resolve many of the open questions that remain about the interactions between mineralogical alterations and oil-liberating mechanisms. Experiments on core scale and field tests that have been carried out the last decade have clearly shown that water chemistry affects the final oil recovery. However, there is generally no consensus in the scientific community of why additional oil is released. In this work, our aim is to focus on in-situ observations of single phase flow and interactions at the pore scale. To do so, we create several types of custom-made microsystems with chalk and calcite crystals. We then do experiments with reacting fluids in these microsystems. During these experiments, we realize in-situ observations (geometrical characteristics, reaction rate) using microsopy techniques (white light vertical/phase shift interferometric microscopy, and classical microscopy), and show how they vary as function as the water chemistry. In simple systems made of calcite, we obtain reactive rates that are coherent with the litterature and with numerical simulations based on Lattice-Boltzmann methods.

  15. Structure and properties of Bi(Zn0.5Ti0.5)O3- Pb(Zr(1-x)Ti(x))O3 ferroelectric single crystals grown by a top-seeded solution growth technique.

    PubMed

    Wang, Bixia; Wu, Xiaoqing; Ren, Wei; Ye, Zuo-Guang

    2015-06-01

    Bi(Zn0.5Ti0.5)O3 (BZT)-modified Pb(Zr(1-x)Ti(x))O3 (PZT) single crystals have been grown using a top-seeded solution growth technique and characterized by various methods. The crystal structure is found to be rhombohedral by means of X-ray powder diffraction. The composition and homogeneity of the as-grown single crystals are studied by laser ablation inductively coupled plasma mass spectrometry and X-ray photoelectron spectroscopy. The domain structure of a (001)(cub) platelet is investigated by polarized light microscopy (PLM), which confirms the rhombohedral symmetry. The paraelectric-to-ferroelectric phase transition temperature T(C) is found to be 313°C with the absence of rhombohedral-tetragonal phase transition. The ferroelectric properties of the ternary crystals are enhanced by the BZT substitution with a remanent polarization of 28 μC/cm(2) and a coercive field E(C) of 22.1 kV/cm. PMID:26067036

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

    NASA Astrophysics Data System (ADS)

    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 and its coordinates entered in a file later used to pilot automatically the EBSD spot. This new procedure is applied on sections from natural samples; the EBSD data are converted and restored into the geographical framework and analyzed using the improved Etchecopar stress inversion technique. The results are compared to the results obtained from classical, optically-based measurements of the same sections using the Universal-stage. The advantages and limitations of this approach are discussed.

  17. Shock Waves Trigger Fault Weakening in Calcite-bearing Rocks During Earthquakes

    NASA Astrophysics Data System (ADS)

    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 (<2 mm) was concomitant with large frictional weakening (up to 30% of static friction) and CO2emission. Microanalytical observations (FE-SEM, FIB-SEM and TEM) showed that the experimental slipping zones consisted of (1) defects structures, including dislocations, cleavage surfaces and deformation features such as mechanical twins, partially burden beneath (2) a 2-10 micrometer thick layer of nanograins where pervasive 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.

  18. Top-Seeded Solution Growth of Pb[(In1/2Nb1/2),(Mg1/3Nb2/3),Ti]O3 Single Crystals

    NASA Astrophysics Data System (ADS)

    Karaki, Tomoaki; Nakamoto, Maki; Sumiyoshi, Yoichi; Adachi, Masatoshi; Hosono, Yasuharu; Yamashita, Yohachi

    2003-09-01

    The crystal growth of relaxor-based ferroelectric single crystals Pb[(In1/2Nb1/2),(Mg1/3Nb2/3),Ti]O3 (PIMNT) was investigated using the top-seeded solution growth (TSSG) method. The concentration of Pb(In1/2Nb1/2)O3 in a melt was chosen to be 0.24 mole, and that of Pb(Mg1/3Nb2/3)O3 was changed from 0.36 to 0.42 mole. A mixture of PbO+B2O3 was used as a flax and the melt composition was PIMNT/PbO/B2O3=70/29/1 wt%. The obtained crystals showed that the concentration of Pb(In1/2Nb1/2)O3 slightly changed but that of Pb(Mg1/3Nb2/3)O3 increased by about 12%, 0.05 mole, compared to those of the melt. All crystals had a complete perovskite structure. A crystal with a composition of Pb[(In1/2Nb1/2)0.24(Mg1/3Nb2/3)0.43Ti0.33]O3 was obtained, and its Curie temperature was Tc = 208°C and rhombohedral-to-tetragonal phase transition temperature was Trt = 120°C. A phase diagram for crystal growth near the morphotropic phase boundary mentioned above was obtained.

  19. Utricular otoconia of some amphibians have calcitic morphology

    NASA Technical Reports Server (NTRS)

    Pote, K. G.; Ross, M. D.

    1993-01-01

    This report concerns the morphological features of otoconia removed from the inner ear of four amphibian species. Results from scanning electron microscopic examination are compared based on the site of origin. These results show that utricular otoconia have a mineral structure that mimics calcite, rather than the widely accepted idea that they are mineralized by calcium carbonate of the aragonite polymorph.

  20. Aragonite / Calcite seas and the evolution of biomineralization

    NASA Astrophysics Data System (ADS)

    Balthasar, Uwe

    2015-04-01

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

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

    PubMed

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

    2015-12-01

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

  2. Effect of Calcite Surfaces on Chiral Separtion of Amino Acids

    NASA Astrophysics Data System (ADS)

    Kwon, K.; Kubicki, J. D.

    2003-12-01

    Studies have suggested that mineral surfaces break chirality of biomolecules by selective adsorption of amino acids to mineral surfaces and mineral surfaces catalyze amino acid polymerization. Recently, a plausible chiral-separation of amino acids was proposed by showing aspartic acids adsorb selectively on chiral calcite surfaces (Hazen et al., 2001, P NATL ACAD SCI USA). However, the selective adsorption is still phenomenal observation without a theoretical model. We have applied molecular modeling tools to explain the selective adsorption in terms of structures and energetics of interactions between aspartic acids and calcite surfaces. Molecular dynamics (MD) simulations were used to obtain structures of L- and D-aspartic acids and calcite surfaces. The Universal Force Field with Ewald sum and canonical ensemble at 300K were used. Simulations were run with a time step of 1 fs for 100,000 steps. The charges of each atom were calculated every 300 steps using the charge equilibration method (QEq). The interactions between one type of aspartic acid (D or L) and a calcite surface ((21\\~{3}1) or (3\\~{1}\\~{2}1)) were simulated in a 3-D periodic box model. Gas-phase MD simulations predicted that D-aspartic acid has stronger binding energy (averaged internal energy of a system) than L-aspartic acid to calcite (21\\~{3}1) surface, while L-aspartic acid has stronger binding energy than D-aspartic acid to calcite (3\\~{1}\\~{2}1) surface. The gas-phase simulations are in a good agreement with the experimental observation of aspartic acids preferential adsorption in that lager binding energy corresponds to more adsorption. Because the adsorption occurs in solution, we simulated the interactions in solution by adding 451 water molecules in the lowest-energy configurations obtained from gas phase simulations. The solution simulations predicted a similar trend to the gas phase simulations, but the averaged binding-energy differences between D/L amino acids with calcite surfaces were within the range of energy deviation of each simulation. Therefore, molecular orbital calculations were carried out using the program GAMESS to calculate more accurate interaction-energies from minimum-energy configurations of solution-phase MD simulations. Molecular orbital calculations combined with MD simulations are expected to give a theoretical basis to understand the selective adsorption.

  3. Dissolution enthalpies of synthetic magnesian calcites: Comparison with biogenic phases

    SciTech Connect

    Bischoff, W.D. . Geology Dept.); Wollast, R. )

    1992-01-01

    A series of synthetic magnesian calcites (0--15 mol% MgCO[sub 3]) were dissolved in weak acetic acid solutions to measure enthalpies of the reaction at 25 C. Heat released was 33.5 KJ/mol for calcite, decreasing to 33 KJ/mol for a Mg-Calcite of 2 mol% MgCO[sub 3], and increasing to 35 KJ/mol for a phase of 15 mol%. Excess enthalpies of formation Hf for these phases were calculated using calcite and magnesite as end-members. Values of Hf average about [minus]1 KJ/mol for the synthetic phases with a trend of increasingly negative values of Hf with Mg content. Excess entropies of formation Sf, corrected for excess entropies associated with ideal solid solutions, were calculated form available data on Gibbs free energies of formation and the values of Hf from this study. These values of Sf range from about [minus]2 J/mol-K for the phase with 2 mol% MgCO[sub 3] to [minus]5 J/mol-K at 15 mol%. The values of Sf suggest that some form of ordering (probably cation ordering) is obtained from these phases. In contrast, biogenic phases have positive values of Hf, increasing from about 1 KJ/mol for phases containing 5 mol% MgCO[sub 3] to 3 KJ/mol for those with 20 mol%. Values of Sf for the biogenic phases are positive, approximately 5 J/mol-K for a phase containing 15 mol% MgCO[sub 3]. For the biogenic phases, some form of disordering is suggested from the entropy calculations and may be the result of positional disordering is suggested from the entropy calculations and may be the result of positional disordering of the carbonate ion. The disorder in biogenic phases compared to the ordering in synthetic phases indicates significant structural differences that account for the higher solubilities of biogenic Mg-Calcites.

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  5. Origin of authigenic calcite and aragonite in pelagic sediments of the Mendeleev Ridge (Arctic Ocean) and their paleoceanographicimplications

    NASA Astrophysics Data System (ADS)

    Woo, K. S.; Ji, H. S.; Nam, S.; Stein, R. H.; Mackensen, A.; Matthiessen, J. J.

    2013-12-01

    Carbonate minerals were discovered from the giant box core (PS72/410-1) of the pelagic sediments recovered from the Canadian Arctic across the central Mendeleev Ridge (Station location= Lat. 8030.37"N, Long. 17544.38"W) during the Arctic cruise by Polarstern in 2008. The core was 39 cm long and was collected from the water depth of 1802 meters. The sediments show various colours from grey to brown as previously reported in other Arctic pelagic sediments. The sediments include planktonic foraminifers together with carbonate minerals. The contents of planktonic foraminifers and carbonate minerals vary with core depth, however these carbonate minerals are present through the whole sequence except for a few centimetres. After wet sieving, coarse fractions were texturally examined with binocular microscope and SEM, and stable isotope and trace element contents were obtained. Mineralogy of carbonate minerals were determined using crystal shapes and qualitative Sr contents by EDAX together with trace element analysis. The carbonates are composed of high Mg-calcite, low Mg-calcite and aragonite. Aragonite crystals show (1) radiating fibrous texture, (2) randomly oriented fibrous texture, (3) spherulitic fibrous texture, and (4) bladed texture, and calcite crystals show (1) foliated texture, (2) randomly bladed texture, (3) spherulitic fibrous texture, and (4) equant texture. Various crystal shapes of aragonite and calcite together with clear growth shapes of the crystals suggest that they are inorganic in origin. Highly enriched carbon isotope compositions (?13C = 0 ~ +5 vs. PDB) strongly indicate that they formed in methanogenic zone below sediment/water interface by the reaction between anoxic pore fluids and host sediments induced by methanogenic bacteria. However, a wide range of oxygen isotope values (?18O = -5 ~ +5 vs. PDB) may indicate that porewater has been changed due to reaction between residual seawater and volcanic sediments. Four types of stable isotope compositions are recognized and they imply complicated evolution of early diagenetic pore waters. Because the core sediments are not organic-rich, the presence of the authigenic carbonates may be related to paleoceanograhic conditions of the Arctic Ocean which resulted in anoxic pore water conditions just a few centimetres below the sediment/water interface. Trace elemental compositions show clear divisions at the boundary of ca. 10 cm in core depth. Carbonates found shallower than this depth show higher Mg, Mn, Fe and Sr compositions which may imply paleoenvironmental changes with time.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  7. Aragonite, breunnerite, calcite and dolomite in the CM carbonaceous chondrites: High fidelity recorders of progressive parent body aqueous alteration

    NASA Astrophysics Data System (ADS)

    Lee, Martin R.; Lindgren, Paula; Sofe, Mahmood R.

    2014-11-01

    Carbonate minerals in CM carbonaceous chondrite meteorites, along with the silicates and sulphides with which they are intergrown, provide a detailed record of the nature and evolution of parent body porosity and permeability, and the chemical composition, temperature and longevity of aqueous solutions. Fourteen meteorites were studied that range in petrologic subtype from mildly aqueously altered CM2.5 to completely hydrated CM2.0. All of them contain calcite, whereas aragonite occurs only in the CM2.5-CM2.2 meteorites and dolomite in the CM2.2-CM2.0. All of the aragonite crystals, and most of the calcite and dolomite grains, formed during early stages of parent body aqueous alteration by cementation of pores produced by the melting of tens of micrometre size particles of H2O-rich ice. Aragonite was the first carbonate to precipitate in the CM2.5 to CM2.2 meteorites, and grew from magnesium-rich solutions. In the least altered of these meteorites the aragonite crystals formed in clusters owing to physical restriction of aqueous fluids within the low permeability matrix. The strong correlation between the petrologic subtype of a meteorite, the abundance of its aragonite crystals and the proportion of them that have preserved crystal faces, is because aragonite was dissolved in the more altered meteorites on account of their higher permeability, and/or greater longevity of the aqueous solutions. Dolomite and breunnerite formed instead of aragonite in some of the CM2.1 and CM2.2 meteorites owing to higher parent body temperatures. The pore spaces that remained after precipitation of aragonite, dolomite and breunnerite cements were occluded by calcite. Following completion of cementation, the carbonates were partially replaced by phyllosilicates and sulphides. Calcite in the CM2.5-CM2.2 meteorites was replaced by Fe-rich serpentine and tochilinite, followed by Mg-rich serpentine. In the CM2.1 and CM2.0 meteorites dolomite, breunnerite and calcite were replaced by Fe-rich serpentine and Fe-Ni sulphide, again followed by Mg-rich serpentine. The difference between meteorites in the mineralogy of their replacive sulphides may again reflect greater temperatures in the parent body regions from where the more highly altered CMs were derived. This transition from Fe-rich to Mg-rich carbonate replacement products mirrors the chemical evolution of parent body solutions in response to consumption of Fe-rich primary minerals followed by the more resistant Mg-rich anhydrous silicates. Almost all of the CMs examined contain a second generation of calcite that formed after the sulphides and phyllosilicates and by replacement of remaining anhydrous silicates and dolomite (dedolomitization). The Ca and CO2 required for this replacive calcite is likely to have been sourced by dissolution of earlier formed carbonates, and ions may have been transported over metre-plus distances through high permeability conduits that were created by impact fracturing.

  8. Modelling of the thermal dependence of structural and elastic properties of calcite, CaCO3

    NASA Astrophysics Data System (ADS)

    Pavese, A.; Catti, M.; Parker, S. C.; Wall, A.

    1996-03-01

    A computational method, based on the quasiharmonic approximation, has been computer-coded to calculate the temperature dependence of elastic constants and structural features of crystals. The model is applied to calcite, CaCO3; an interatomic potential based on a C-O Morse function and Ca-O and O-O Borntype interactions, including a shell model for O, has been used. Equilibrations in the range 300 800 K reproduce the experimental unit-cell edges and bond lengths within 1%. The simulated thermal expansion coefficients are 22.3 (//c) and 2.6 (? c), against 25.5 and-3.710-6K-1 experimental values, respectively. The thermal coefficients of elastic constants tend to be underestimated; for the bulk modulus, -2.3 against-3.710-4K-1 is obtained.

  9. SEED PRODUCTION

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This book chapter provides information at the upper division undergraduate and graduate student levels that describe the environmental factors and production practices that affect the capacity of forage crops to produce seeds. Consumers require dependable quantities of high quality seeds. Special ru...

  10. Formation of a ternary neptunyl(V) biscarbonato inner-sphere sorption complex inhibits calcite growth rate.

    PubMed

    Heberling, Frank; Scheinost, Andreas C; Bosbach, Dirk

    2011-06-01

    Neptunyl, Np(V)O(2)(+), along with the other actinyl ions U(VI)O(2)(2+) and Pu(V,VI)O(2)((+,2+)), is considered to be highly mobile in the geosphere, while interaction with mineral surfaces (inner- or outer-sphere adsorption, ion-exchange, and coprecipitation/structural incorporation) may retard its migration. Detailed information about the exact interaction mechanisms including the structure and stoichiometry of the adsorption complexes is crucial to predict the retention behavior in diverse geochemical environments. Here, we investigated the structure of the neptunyl adsorption complex at the calcite-water interface at pH 8.3 in equilibrium with air by means of low-temperature (15K) EXAFS spectroscopy at the Np-L(III) edge. The coordination environment of neptunyl consists of two axial oxygen atoms at 1.87(±0.01)Å, and an equatorial oxygen shell of six atoms at 2.51(±0.01)Å. Two oxygen backscatterers at 3.50(±0.04)Å along with calcium backscatterers at 3.95(±0.03)Å suggest that neptunyl is linked to the calcite surface through two monodentate bonds towards carbonate groups of the calcite surface. Two additional carbon backscatterers at 2.94(±0.02)Å are attributed to two carbonate ions in bidentate coordination. This structural environment is conclusively interpreted as a ternary surface complex, where a neptunyl biscarbonato complex sorbs through two monodentate carbonate bonds to steps at the calcite (104) face, while the two bidentately coordinated carbonate groups point away from the surface. This structural information is further supported by Mixed Flow Reactor (MFR) experiments. They show a significant decrease of the calcite growth rate in the presence of neptunyl(V), in line with blockage of the most active crystal growth sites, step and kink sites, by adsorption of neptunyl. Formation of this sorption complex constitutes an important retention mechanism for neptunyl in calcite-rich environments. PMID:21429616

  11. Fluid mediated transformation of aragonitic cuttlebone to calcite

    NASA Astrophysics Data System (ADS)

    Perdikouri, C.; Kasioptas, A.; Putnis, A.

    2009-04-01

    The aragonite to calcite transition has been studied extensively over the years because of its wide spectra of applications and of its significant geochemical interest. While studies of kinetics (e.g. Topor et al., 1981), thermodynamics (e.g. Wolf et al., 1996) and behavior of ions such as Sr and Mg (e.g. Yoshioka et al., 1986) have been made there are still unanswered questions regarding this reaction especially in the cases where the effects of fluid composition are considered. It is well known that when heated in air, aragonite transforms by a solid state reaction to calcite. The aragonite cuttlebone of the sepia officinalis that was used for our experiments undergoes a phase transition at ~370-390˚ C, measured by in situ heating experiments in a Philips X'pert X-ray powder diffractometer equipped with a HTK 1200 High temperature oven. Successive X-ray scans were taken at isothermal temperatures at 200C intervals. A similar temperature range was found by Vongsavat et al. 2006, who studied this transition in Acropora corals. It is possible however to promote this transition at considerably lower temperatures by means of a fluid mediated reaction where the replacement takes place by a dissolution-precipitation mechanism (Putnis & Putnis, 2007). We have successfully carried out hydrothermal experiments where cuttlebone has been converted to calcite at 200˚ C. Using the PhreeqC program we calculated the required composition of a solution that would be undersaturated with respect to aragonite and saturated with respect to calcite leading to dissolution of the aragonite and to a consequent precipitation of the new calcite phase, similar to the experiments described in an earlier study (Perdikouri et al, 2008). This reaction is not pseudomorphic and results in the destruction of the morphology, presumably due to the molar volume increase. A total transformation of the cuttlebone produced a fine calcite powder. The cuttlebone exhibits a unique microstructure, made up of interconnected chambers. The aragonite grown during biomineralization of the cuttlebone is interlaced with a β-chitin organic phase that provides the framework for the morphology that is observed. Experiments carried out with the same constant conditions but for different periods of time have revealed the evolution of the transformation to calcite. At shorter reaction times the product was made up of calcite powder and of well preserved aragonite septa, as was confirmed by powder X-ray diffraction. In other words, the vertical pillars appear to react at faster rates than the horizontal septa. It has been reported by Florek et al. 2008 that the septa contain higher quantities of β-chitin. The aim of this study is the investigation of these observations and the determination of the effect of the organic component on the kinetics of the aragonite to calcite transformation. Florek M., Fornal E., Gómez-Romero P., Zieba E., Paszkowicz W., Lekki J.,Nowak J., Kuczumow A. Materials Science and Engineering C, In Press (2008) Perdikouri C., Kasioptas A., Putnis C.V., Putnis A. Mineralogical Magazine 72, 111-114 (2008) Putnis A., Putnis C.V. Solid State Chemistry 180, 1783-1786 (2007) Topor N. D., Tolokonnikova L. I., Kadenatsi B. M. Journal of Thermal Analysis 20, 169-174 (1981) Vongsavat V., Winotai P., Meejoo S. Nuclear Instruments and Methods in Physics Research B 243, 167-173 (2006) Wolf G., Lerchner J., Schmidt H., Gamsjäger H., Königsberger E., Schmidt P. Journal of Thermal Analysis 46, 353-359 (1996) Yoshioka S., Ohde S., Kitano Y., Kanamori N. Marine Chemistry 18, 35-48 (1986)

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

    NASA Technical Reports Server (NTRS)

    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-cylinder experiments at 1 GPa between 950 and 1700 C using a mixture of 70wt% tholeiitic basalt + 15wt% anhydrite + 15wt% calcite. Up to 1440 C, an ultracalcic (CaO>13.5 wt%; CaO/Al2O3>1 wt%) picrobasaltic (SiO240-45 wt%; Na2O+K2O<2 wt%) melt containing up to 5 wt% SO3 and up to 5.3 wt% CO2+H2O (calculated by difference) is present in equilibrium with clinopyroxene, anhydrite, spinel-chromite, a CAS-phase and a gas composed mainly of CO and an aliphatic thiol (CH2)4SH. Hydrogen was incorporated either by contact between the starting material and air or by diffusion through the capsule during the experiments. The S content in the gas increases with temperature and run duration, implying that gases with various C/S ratios might be released during an impact or at subduction zones, depending on the P-T-t path and on the H content. Above approx.1440 C, a Ca-rich carbonate-sulfate melt forms (in equilibrium with the picrobasaltic melt) which contains a few percents of Na and K. Such melt is not expected to form at Earth s subduction temperatures. If it forms by meteorite impact, it might crystallize too fast to explain long flows like Venus canali. A different basalt/anhydrite/calcite ratio might, however, decrease its formation temperature.

  13. Stability of basalt+anhydrite+calcite at HP-HT: implications for Venus, the Earth and Mars

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

    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 Venus surface temperature. 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 may 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 Earths 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 the 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-cylinder experiments at 1 GPa between 950 and 1700C using a mixture of 70wt% tholeiitic basalt + 15wt% anhydrite + 15wt% calcite. Up to ~1440C, an ultracalcic (CaO>13.5 wt%; CaO/Al2O3>1 wt%) picrobasaltic (SiO2~40-45 wt%; Na2O+K2O<2 wt%) melt containing up to 5 wt% SO3 and up to 5.3 wt% CO2+H2O (calculated by difference) is present in equilibrium with clinopyroxene, anhydrite, spinel-chromite, a CAS-phase and a gas composed mainly of CO and an aliphatic thiol (CH2)4SH. Hydrogen was incorporated either by contact between the starting material and air or by diffusion through the capsule during the experiments. The S content in the gas increases with temperature and run duration, implying that gases with various C/S ratios might be released during an impact or at subduction zones, depending on the P-T-t path and on the H content. Above ~1440C, a Ca-rich carbonate-sulfate melt forms (in equilibrium with the picrobasaltic melt) which contains a few percents of Na and K. Such melt is not expected to form at Earths subduction temperatures. If it forms by meteorite impact, it might crystallize too fast to explain long flows like Venus canali. A different basalt/anhydrite/calcite ratio might, however, decrease its formation temperature.

  14. Determination of seeded supersolubility of lithium carbonate using FBRM

    NASA Astrophysics Data System (ADS)

    Sun, Yuzhu; Song, Xingfu; Wang, Jin; Luo, Yan; Yu, Jianguo

    2010-01-01

    The supersolubility data of Li 2CO 3 in the seeded aqueous solution were measured by focused beam reflectance measurement (FBRM). The effect of seed crystals on the supersolubility was investigated, where two kinds of seed crystals were considered, namely 2# seed with 318 ?m volume mean crystal size and 5# seed with 21 ?m volume mean crystal size, respectively. It was found that the supersolubility level of Li 2CO 3 in the presence of 2# seed is lower than that with 5# seed when using the same amount of seed; and with the increase of the seed loading, the supersolubility with 2# seed decreases slightly, whereas that with 5# seed becomes greater. The seeded supersolubility decreases when increasing both temperature and the stirring speed, and goes up with the increase of the feeding rate of Na 2CO 3. Moreover, by comparing the laser method with FBRM technology, FBRM is confirmed to be a better apparatus to detect the nucleation phenomena in the presence of seed.

  15. Microbes Caught in the Act: Disentangling the Role of Biofilms in the Formation of Low Mg Calcite Ooids in a Freshwater Lake

    NASA Astrophysics Data System (ADS)

    Plee, K.; Ariztegui, D.; Sahan, E.; Martini, R.; Davaud, E.

    2006-12-01

    Biofilms and molds of cyanobacteria infilling depressions within the outermost cortex of ooids have been previously described in recent ooidal sands of Lake Geneva (Switzerland). Detailed sedimentological and mineralogical analyses of these ooids further indicated a low-Mg calcite composition of their cortex. Observed ooidal morphological features called for a fundamental role of biofilms triggering carbonate precipitation. A detailed microbiological study was much needed, however, in order to decipher the relative role of organic versus purely physicochemical processes during ooid formation. An experimental device consisting of frosted microscope slides was set at 2.50 m water depth in western Lake Geneva. These slides provide an attractive substrate for the microorganisms involved in low-Mg calcite precipitation allowing the in-situ harvesting of biofilms on a regular basis during more than three years. The inspection of the frosted slides showed the development of biofilms on their surface containing coccoid and filamentous cyanobacteria, heterotrophic bacteria and diatom frustules. Microscopical observations under natural light and autoflorescence show a close association between freshly low Mg-calcite precipitates and biofilms containing at least five species of filamentous and coccoid cyanobacteria. Carbonate precipitation peaks at early spring and late summer, and low Mg calcite crystals are always in close association with mostly cyanobacteria filaments (e.g., Tolipothrix, Oscillatoria). Ultra high-resolution elemental analyses performed immediately after recovering the samples confirmed the microscopical observations. Further SEM inspection of the samples revealed a clear seasonal pattern of carbonate precipitation identifying low Mg- calcite with crystal shapes varying from poorly to not crystallized compact aggregates; subautomorph to automorph rhomboedric crystals; and snowy cluster in which particles are very little or not crystallized. Liquid and solid cultures were further developed in the laboratory from the harvested biofilms allowing the determination of the microbial community using a PCR-DGGE approach. Two different primers were used to target all bacteria, and cyanobacteria and diatoms (341F-GC/907RM and 359F-GC/781 (a+b), respectively). Initial results indicate a similar microbial diversity between the sampled natural biofilms and those from BG11 enriched cultures. These data will allow us to design further laboratory experiments on low-Mg calcite precipitation including changes in pH, temperature and light intensity that mimic the natural biological and physicochemical cycle of the modern lake water throughout the year. Hence, this first dataset illustrates the significance of the in situ experiment to validate previous observations. Combined with the ongoing microbial cultures under laboratory-controlled conditions the outcome of our investigations will bring new light behind the role of biofilms in freshwater ooids formation.

  16. Low-threshold collinear parametric Raman comb generation in calcite under 532 and 1064?nm picosecond laser pumping

    NASA Astrophysics Data System (ADS)

    Smetanin, S. N.; Jelnek, M., Jr.; Kube?ek, V.; Jelnkov, H.

    2015-09-01

    Optimal conditions of low-threshold collinear parametric Raman comb generation in calcite (CaCO3) are experimentally investigated under 20 ps laser pulse excitation, in agreement with the theoretical study. The collinear parametric Raman generation of the highest number of Raman components in the short calcite crystals corresponding to the optimal condition of Stokes-anti-Stokes coupling was achieved. At the excitation wavelength of 1064?nm, using the optimum-length crystal resulted in the effective multi-octave frequency Raman comb generation containing up to five anti-Stokes and more than four Stokes components (from 674?nm to 1978?nm). The 532?nm pumping resulted in the frequency Raman comb generation from the 477?nm 2nd anti-Stokes up to the 692?nm 4th Stokes component. Using the crystal with a non-optimal length leads to the Stokes components generation only with higher thresholds because of the cascade-like stimulated Raman scattering with suppressed parametric coupling.

  17. Sr2+/Ca2+ and 44Ca/40Ca fractionation during inorganic calcite formation: III. Impact of salinity/ionic strength

    PubMed Central

    Tang, Jianwu; Niedermayr, Andrea; Khler, Stephan J.; Bhm, Florian; K?sakrek, Basak; Eisenhauer, Anton; Dietzel, Martin

    2012-01-01

    In order to apply Sr/Ca and 44Ca/40Ca fractionation during calcium carbonate (CaCO3) formation as a proxy to reconstruct paleo-environments, it is essential to evaluate the impact of various environmental factors. In this study, a CO2 diffusion technique was used to crystallize inorganic calcite from aqueous solutions at different ionic strength/salinity by the addition of NaCl at 25C. Results show that the discrimination of Sr2+ versus Ca2+ during calcite formation is mainly controlled by precipitation rate (R in ?mol/m2/h) and is weakly influenced by ionic strength/salinity. In analogy to Sr incorporation, 44Ca/40Ca fractionation during precipitation of calcite is weakly influenced by ionic strength/salinity too. At 25C the calcium isotope fractionation between calcite and aqueous calcium ions (?44/40Cacalcite-aq=?44/40Cacalcite??44/40Caaq) correlates inversely to logR values for all experiments. In addition, an inverse relationship between ?44/40Cacalcite-aq and logDSr, which is independent of temperature, precipitation rate, and aqueous (Sr/Ca)aq ratio, is not affected by ionic strength/salinity either. Considering the logDSr and ?44/40Cacalcite-aq relationship, Sr/Ca and ?44/40Cacalcite values of precipitated calcite can be used as an excellent multi-proxy approach to reconstruct environmental conditions (e.g., temperature, precipitation rate) of calcite growth and diagenetic alteration. PMID:22347722

  18. The inhibition of calcium carbonate crystal growth by the cysteine-rich Mdm2 peptide.

    PubMed

    Dalas, E; Chalias, A; Gatos, D; Barlos, K

    2006-08-15

    The crystal growth of calcite, the most stable calcium carbonate polymorph, in the presence of the cysteine-rich Mdm2 peptide (containing 48 amino acids in the ring finger configuration), has been investigated by the constant composition technique. Crystallization took place exclusively on well-characterized calcite crystals in solutions supersaturated only with respect to this calcium carbonate salt. The kinetic results indicated a surface diffusion spiral growth mechanism. The presence of the Mdm2 peptide inhibited the crystal growth of calcite by 22-58% in the concentration range tested, through adsorption onto the active growth sites of the calcite crystal surface. The kinetic results favored a Langmuir-type adsorption model, and the value of the calculated affinity constant was k(aff)=147x10(4) dm(3)mol(-1), a(ads)=0.29. PMID:16678843

  19. The solubility of Fish Produced High Magnesium Calcite in Seawater

    NASA Astrophysics Data System (ADS)

    Woosley, R. J.; Millero, F. J.; Grosell, M.

    2011-12-01

    Fish have been shown to produce high 10 to 30% magnesium calcite as part of the physiological mechanisms responsible for maintaining salt and water balance. The importance of this source to the marine carbon cycle is only now being considered. In this paper we report the first measurements of the solubility of this CaCO3 in seawater. The resulting solubility (pKsp = 5.85 0.07) is more than two times higher than aragonite and similar to the high magnesium calcite generated on the Bahamas Banks (pKsp = 5.90). This high solubility of fish produced CaCO3 renders it soluble in near surface (<2000 m) waters contributing to the input of carbonate to surface ocean waters, and at least partially explaining the increase in total alkalinity above the aragonite saturation horizon.

  20. U(VI) behaviour in hyperalkaline calcite systems

    NASA Astrophysics Data System (ADS)

    Smith, Kurt F.; Bryan, Nicholas D.; Swinburne, Adam N.; Bots, Pieter; Shaw, Samuel; Natrajan, Louise S.; Mosselmans, J. Frederick W.; Livens, Francis R.; Morris, Katherine

    2015-01-01

    The behaviour of U(VI) in hyperalkaline fluid/calcite systems was studied over a range of U(VI) concentrations (5.27 × 10-5 μM to 42.0 μM) and in two high pH systems, young and old synthetic cement leachate in batch sorption experiments. These systems were selected to be representative of young- (pH 13.3) and old-stage (pH 10.5) leachate evolution within a cementitious geological disposal facility. Batch sorption experiments, modelling, extended X-ray absorption fine structure spectroscopy, electron microscopy, small angle X-ray scattering and luminescence spectroscopy were used to define the speciation of U(VI) across the systems of study. At the lowest concentrations (5.27 × 10-5 μM 232U(VI)) significant U removal was observed for both old and young cement leachates, and this was successfully modelled using a first order kinetic adsorption modelling approach. At higher concentrations (>4.20 μM) in the young cement leachate, U(VI) showed no interaction with the calcite surface over an 18 month period. Small angle X-ray scattering techniques indicated that at high U concentrations (42.0 μM) and after 18 months, the U(VI) was present in a colloidal form which had little interaction with the calcite surface and consisted of both primary and aggregated particles with a radius of 7.6 ± 1.1 and 217 ± 24 Å, respectively. In the old cement leachate, luminescence spectroscopy identified two surface binding sites for U(VI) on calcite: in the system with 0.21 μM U(VI), a liebigite-like Ca2UO2(CO3)3 surface complex was identified; at higher U(VI) concentrations (0.42 μM), a second binding site of undetermined coordination was identified. At elevated U(VI) concentrations (>2.10 μM) in old cement leachate, both geochemical data and luminescence spectroscopy suggested that surface mediated precipitation was controlling U(VI) behaviour. A focused ion beam mill was used to create a section across the U(VI) precipitate-calcite interface. Transmission electron microscope images of the section revealed that the calcite surface was coated with a nano crystalline, U containing phase. Selected area electron diffraction images of the U precipitate which was formed at a U(VI) concentration of 4.20 μM were consistent with the formation of calcium uranate. XAS spectroscopy at higher concentrations (⩾21.0 μM) suggested the formation of a second U(VI) phase, possibly a uranyl oxyhydroxide phase. These results indicated that in the young cement leachate, U(VI) did not react with the calcite surface unless U(VI) concentrations were very low (5.27 × 10-5 μM). At higher concentrations, speciation calculations suggested that U(VI) was significantly oversaturated and experimental observations confirmed it existed in a colloidal form that interacted with the mineral surface only weakly. In the old cement leachate systems at low concentrations batch sorption and luminescence data suggested that U(VI) removal was being driven by a surface complexation mechanism. However, at higher concentrations, spectroscopic methods suggest a combination of both surface complexation and surface mediated precipitation was responsible for the observed removal. Overall, U(VI) behaviour in hyperalkaline calcite systems is distinct from that at circumneutral pH conditions: at high pH and anything but low U(VI) concentrations, a surface mediated precipitation mechanism occurs; this is in contrast to circumneutral pH conditions where U(VI) surface complexation reactions tend to dominate.

  1. Incorporation of Mg and Sr in calcite of cultured benthic foraminifera: impact of calcium concentration and associated calcite saturation state

    NASA Astrophysics Data System (ADS)

    Raitzsch, M.; Dueas-Bohrquez, A.; Reichart, G.-J.; de Nooijer, L. J.; Bickert, T.

    2010-03-01

    We investigated the effect of the calcium concentration in seawater and thereby the calcite saturation state (?) on the magnesium and strontium incorporation into benthic foraminiferal calcite under laboratory conditions. For this purpose individuals of the shallow-water species Heterostegina depressa (precipitating high-Mg calcite, symbiont-bearing) and Ammonia tepida (low-Mg calcite, symbiont-barren) were cultured in media under a range of [Ca2+], but similar Mg/Ca ratios. Trace element/Ca ratios of newly formed calcite were analysed with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and normalized to the seawater elemental composition using the equation DTE=(TE/Cacalcite)/(TE/Caseawater). The culturing study shows that DMg of A. tepida significantly decreases with increasing ? at a gradient of -4.310-5 per ? unit. The DSr value of A. tepida does not change with ?, suggesting that fossil Sr/Ca in this species may be a potential tool to reconstruct past variations in seawater Sr/Ca. Conversely, DMg of H. depressa shows only a minor decrease with increasing ?, while DSr increases considerably with ? at a gradient of 0.009 per ? unit. The different responses to seawater chemistry of the two species may be explained by a difference in the calcification pathway that is, at the same time, responsible for the variation in the total Mg incorporation between the two species. Since the Mg/Ca ratio in H. depressa is 50-100 times higher than that of A. tepida, it is suggested that the latter exhibits a mechanism that decreases the Mg/Ca ratio of the calcification fluid, while the high-Mg calcite forming species may not have this physiological tool. If the dependency of Mg incorporation on seawater [Ca2+] is also valid for deep-sea benthic foraminifera typically used for paleostudies, the higher Ca concentrations in the past may potentially bias temperature reconstructions to a considerable degree. For instance, 25 Myr ago Mg/Ca ratios in A. tepida would have been 0.2 mmol/mol lower than today, due to the 1.5 times higher [Ca2+] of seawater, which in turn would lead to a temperature underestimation of more than 2 C.

  2. Interaction of copper with the surface of calcite

    SciTech Connect

    Franklin, M.L.; Morse, J.W.

    1981-05-01

    The interaction of Cu ions in solution with the surface of calcite has been studied in a range of solutions from pure water to seawater. Observations of the uptake of Cu from solution onto calcite indicates that the process is rapid and strong in both distilled water and seawater. In distilled water, Cu uptake is directly proportional to the concentration of Cu in solution; Cu/sub s/ = K/sub s/Cu/sub 1/. This Cu/sub s/ dependence on Cu/sub 1/ is linear over the entire Cu concentration range studied (0.1 to 200 ..mu..M). Results do not indicate the formation of a precipitate of either malachite or copper carbonate. In seawater, the uptake of Cu is also directly proportional to the concentration of Cu/sub 1/ up to a limiting value of approximately 13 ..mu..M. The average value for K/sub s/ in seawater, 0.24 +- 0.06 (Cu/sub 1/ less than or equal to 13 ..mu..M), is approximately an order of magnitude less than in distilled water. This is probably the result of smaller Cu/sub 1/ activity coefficients and increased site competition by other ions in seawater. Attempts to increase the Cu/sub 1/ concentration above 13 ..mu..M resulted in the additional Cu being deposited on the surface of the calcite. A possible explanation for this behavior is the formation of a precipitate of malachite on the calcite surface. The value of K/sub s/ decreased slightly with increasing solid to solution ratios in seawater.

  3. Use of coupled passivants and consolidants on calcite mineral surfaces

    SciTech Connect

    Nagy, K.L.; Cygan, R.T.; Brinker, C.J.; Ashley, C.S.; Scotto, C.S.

    1997-02-01

    Deterioration of monuments, buildings, and works of art constructed of carbonate-based stone potentially can be arrested by applying a combination of chemical passivants and consolidants that prevent hydrolytic attack and mechanical weakening. The authors used molecular modeling and laboratory synthesis to develop an improved passivating agent for the calcite mineral surface based on binding strength and molecular packing density. The effectiveness of the passivating agent with and without a linked outer layer of consolidant against chemical weathering was determined through leaching tests conducted with a pH-stat apparatus at pH 5 and 25 C. For the range of molecules considered, modeling results indicate that the strongest-binding passivant is the trimethoxy dianionic form of silylalkylaminocarboxylate (SAAC). The same form of silylalkylphosphonate (SAP) is the second strongest binder and the trisilanol neutral form of aminoethylaminopropylsilane (AEAPS) is ranked third. Short-term leaching tests on calcite powders coated with the trisilanol derivative of SAAC, the triethoxy neutral form of SAP, and the trimethoxy neutral form of AEAPS show that the passivant alone does not significantly slow the dissolution rate. However, all passivants when linked to the sol consolidant result in decreased rates. Combined AEAPS plus consolidant results in a coating that performs better than the commercial product Conservare{reg_sign} OH and at least as well as Conservare{reg_sign} H. The modeling results indicate that there may be a threshold binding energy for the passivant above which the dissolution rate of calcite is actually enhanced. More strongly-binding passivants may aid in the dissolution mechanism or dissociate in aqueous solution exposing the calcite surface to water.

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

    NASA Astrophysics Data System (ADS)

    Wada, Hideki; Suzuki, Kazuhiro

    1983-04-01

    The temperature dependence of carbon isotopic fractionations between calcite and graphite, and between dolomite and graphite are calibrated by the calcite-dolomite solvus geothermometry using marbles collected from the contact metamorphic aureole in the Kasuga area, central Japan. The carbon isotopic fractionations ( ?13CCc- Gr and ?13CDo? Gr) systematically decrease with increasing metamorphic temperature. The concordant relationships between the fractionations and solvus temperatures are approximately linear with T-2 over the temperature range. 400 to 680C: ?13CCc? Gr (%.) = 5.6 10 6 T-2 (K) - 2.4 ?13CDo? Gr (%.) = 5.9 10 6 T-2 ( K) - 1.9 These systematic relationships between fractionation and temperature suggest that carbon isotopic equilibria between carbonates and graphite were attained in many cases. The equation for the calcite-graphite system has a slope steeper than BOTTINGA'S (1969) results. It is, however, in good agreement with that of VALLEY and O'NEIL (1981) in the temperature range from 600 to 800C. Because of the relatively high sensitivity to temperature, these isotopic geothermometers are useful for determining the temperatures in moderate- to high-grade metamorphosed carbonate rocks.

  5. Earthworm-produced calcite granules: A new terrestrial palaeothermometer?

    NASA Astrophysics Data System (ADS)

    Versteegh, Emma A. A.; Black, Stuart; Canti, Matthew G.; Hodson, Mark E.

    2013-12-01

    In this paper we show for the first time that calcite granules, produced by the earthworm Lumbricus terrestris, and commonly recorded at sites of archaeological interest, accurately reflect temperature and soil water ?18O values. Earthworms were cultivated in an orthogonal combination of two different (granule-free) soils moistened by three types of mineral water and kept at three temperatures (10, 16 and 20 C) for an acclimatisation period of three weeks followed by transfer to identical treatments and cultivation for a further four weeks. Earthworm-secreted calcite granules were collected from the second set of soils. ?18O values were determined on individual calcite granules (?18Oc) and the soil solution (?18Ow). The ?18Oc values reflect soil solution ?18Ow values and temperature, but are consistently enriched by 1.51 ( 0.12) in comparison to equilibrium in synthetic carbonates. The data fit the equation 1000 ln ? = [20.21 0.92] (103 T-1) - [38.58 3.18] (R2 = 0.95; n = 96; p < 0.0005). As the granules are abundant in modern soils, buried soils and archaeological contexts, and can be dated using U-Th disequilibria, the developed palaeotemperature relationship has enormous potential for application to Holocene and Pleistocene time intervals.

  6. Microbially-Mediated Subsurface Calcite Precipitation for Removal of Hazardous Divalent Cations

    SciTech Connect

    Colwell, Frederick S.; Smith, R.W.; Ferris, F. Gratn; Ingram, Jani C.; Reysenbach, A.-L.; Fujita, Yoshiko; Tyler, T.L.; Taylor, J.L.; Banta, A.; Delwiche, M.E.; McLing, T.; Cortez, Marnie, M.; Watwood, M.E.

    2003-03-27

    We are investigating microbially-mediated acceleration of calcite precipitation and co-precipitation of hazardous divalent cations (e.g., 90Sr) in calcite saturated subsurface systems. In theory, the addition of urea to an aquifer or vadose zone and its subsequent hydrolysis by indigenous microbes will cause an increase in alkalinity, pH and calcite precipitation. Lab studies indicated the ability of various bacteria to precipitate calcite through urea hydrolysis and that incorporation of strontium in biogenically-formed calcite is greater than in abiotically formed calcite. Results from a field experiment in a pristine location in the Snake River Plain aquifer involving the phased addition of molasses and then urea showed increases in total cell numbers, rate of urea hydrolysis and calcite formation during the study. The combined diagnostic approaches of microbiology, molecular ecology and analytical chemistry demonstrate the feasibility of this biogeochemical manipulation for subsurface remediation at arid Western DOE sites such as Hanford and INEEL.

  7. Interaction of copper with the surface of calcite

    SciTech Connect

    Franklin, M.L.; Morse, J.W.

    1981-12-01

    The interaction of Cu ions in solution with the surface of calcite has been studied in a range of solutions from pure water to seawater. Observations of the uptake of Cu from solution onto calcite indicates that the process is rapid and strong in both distilled water and seawater. In distilled water, Cu uptake is directly proportional to the concentration of Cu in solution; Cu/sub s/ = K/sub s/Cu/sub 1/. The average value for K/sub s/ is 3.5 +- 1.7. The Cu/sub s/ dependence on Cu/sub 1/ is linear over the entire Cu concentration range studied (0.1 to 200 ..mu..M). Results do not indicate the formation of a precipitate of either malachite or copper carbonate. A precipitate of the form Cu/sub x/Ca/sub 1-x/CO/sub 3/ may be deposited onto the calcite surface in distilled water. The value of K/sub s/ in distilled water decreased sharply over the solid to solution ratio range of 0.1 to 2 g CaCO/sub 3/ 1/sup -1/. This was followed by a small change in K/sub s/ for solid to solution ratios in the range of 2 to 10 g CaCO/sub 3/ 1/sup -1/. In seawater, the uptake of Cu is also directly proportional to the concentration of Cu/sub 1/ up to a limiting value of approximately 13 ..mu..M. The average value for K/sub s/ in seawater, 0.24 +- 0.06 (Cu/sub 1/ less than or equal to 13 ..mu..M), is approximately an order of magnitude less than in distilled water. This is probably the result of smaller Cu/sub 1/ activity coefficients and increased site competition by other ions in seawater. Attempts to increase the Cu/sub 1/ concentration above 13 ..mu..M resulted in the additional Cu being deposited on the surface of the calcite. A possible explanation for this behavior is the formation of a precipitate of malachite on the calcite surface. The value of K/sub s/ decreased slightly with increasing solid to solution ratios in seawater.

  8. Strontium isotope fractionation of planktic foraminifera and inorganic calcite

    NASA Astrophysics Data System (ADS)

    Bhm, Florian; Eisenhauer, Anton; Tang, Jianwu; Dietzel, Martin; Krabbenhft, Andre; Kisakrek, Basak; Horn, Christian

    2012-09-01

    We have investigated the strontium isotope fractionation (?88/86Srcarb-aq) between inorganic calcite and aqueous Sr2+ ions by precipitation experiments at a constant temperature of 25 C and precipitation rates (R) ranging from 102.3 to 104.2 ?mol/m2/h. Strontium isotope ratios were measured using the 87Sr-84Sr double spike technique. It was found that strontium isotope fractionation in these calcites is strongly dependent on the precipitation rate: ?Sr carb-aq =-0.08?log(R[?mol/m/h])+0.08 The measured ?88/86Sr values are significantly correlated with previously measured ?44/40Ca and Sr/Ca values of the same calcite samples: ?Sr=+0.18??Ca-0.01 ?Sr=-1.5?KdSr-0.03 The slope of 88Sr/86Sr versus 44Ca/40Ca fractionation is 0.18 0.04 and compatible with a kinetic fractionation during dehydration of the strontium and calcium ions, but not with isotope fractionation in a diffusive boundary layer. Using published equilibrium ?44/40Cacarb-aq and KdSr values we estimate the equilibrium isotope fractionation of strontium to be very close to zero (?88/86Sreq(carb-aq) = -0.01 0.06). This estimate is confirmed by strontium isotope values of natural inorganic calcites that precipitated very slowly in basalts of the ocean crust. The results from the inorganic calcites are used to explain strontium isotope fractionation of planktic foraminifera. Specimens of two warm water species (Globigerinoides ruber and Globigerinoides sacculifer) were picked from the Holocene section of a Caribbean sediment core. We found no significant difference in ?88/86Sr between the two species. In addition, G. ruber specimens from Marine Isotope Stage 2 in the same core show ?88/86Sr values identical to the Holocene specimens. The strontium isotopes of both foraminifera species are strongly fractionated (?88/86Srcarb-aq = -0.248 0.005) when compared to published data of other major marine calcifiers. Applying the results from the inorganic precipitation experiments we find that the strong foraminiferal strontium isotope fractionation can be explained by calcification in a largely open system at high precipitation rates, comparable in magnitude to rates known from scleractinian reef corals. This interpretation is in good agreement with the kinetic calcification model for planktic foraminifera by Kisakrek et al. (2011), which was based on calcium isotopes and elemental Sr/Ca ratios.

  9. Reactive uptake of acetic acid on calcite and nitric acid reacted calcite aerosol in an environmental reaction chamber.

    PubMed

    Prince, Amy Preszler; Kleiber, Paul D; Grassian, Vicki H; Young, Mark A

    2008-01-01

    The heterogeneous chemistry of gas-phase acetic acid with CaCO(3)(calcite) aerosol was studied under varying conditions of relative humidity (RH) in an environmental reaction chamber. Infrared spectroscopy showed the loss of gas-phase reactant and the appearance of a gaseous product species, CO(2). The acetic acid is observed to adsorb onto the calcite aerosol through both a fast and a slow uptake channel. While the fast channel is relatively independent of RH, the slow channel exhibits enhanced uptake and reaction as the RH is increased. In additional experiments, the calcite aerosol was exposed to both nitric and acetic acids in the presence of water vapor. The rapid conversion of the particulate carbonate to nitrate and subsequent deliquescence significantly enhances the uptake and reaction of acetic acid. These results suggest a possible mechanism for observed correlations between particulate nitrate and organic acids in the atmosphere. Calcium rich mineral dust may be an important sink for simple organic acids. PMID:18075693

  10. Origin of gem corundum in calcite marble: The Revelstoke occurrence in the Canadian Cordillera of British Columbia

    NASA Astrophysics Data System (ADS)

    Dzikowski, Tashia J.; Cemprek, Jan; Groat, Lee A.; Dipple, Gregory M.; Giuliani, Gaston

    2014-06-01

    The calcite marble-hosted gem corundum (ruby, sapphire) occurrence near Revelstoke, British Columbia, Canada, occurs in the Monashee Complex of the Omineca Belt of the Canadian Cordillera. Corundum occurs in thin, folded and stretched layers with green muscovite + Ba-bearing K-feldspar + anorthite (An0.85-1) phlogopite Na-poor scapolite. Other silicate layers within the marble are composed of: (1) diopside + tremolite quartz and (2) garnet (Alm0.7-0.5Grs0.2-0.4) + Na-rich scapolite + diopside + tremolite + Na,K-amphiboles. Non-silicate layers in the marble are either magnetite- or graphite-bearing. Predominantly pink (locally red or purple) opaque to transparent corundum crystals have elevated Cr2O3 (? 0.21 wt.%) and variable amounts of TiO2; rare blue rims on the corundum crystals contain higher amounts of TiO2 (? 0.53 wt.%) and Fe2O3 (? 0.07 wt.%). The associated micas have elevated Cr, V, Ti, and Ba contents. Petrography of the silicate layers show that corundum formed from muscovite at the peak of metamorphism (~ 650-700 C at 8.5-9 kbar). Because the marble is almost pure calcite (dolomite is very rare), the corundum was preserved because it did not react with dolomite to spinel + calcite during decompression. The scapolite-bearing assemblages formed during or after decompression of the rock at ~ 650 C and 4-6 kbar. Gem-quality corundum crystals formed especially on borders of the mica-feldspar layers in an assemblage with calcite. Whole rock geochemistry data show that the corundum-bearing silicate (mica-feldspar) layers formed by mechanical mixing of carbonate with the host gneiss protolith; the bulk composition of the silicate layers was modified by Si and Fe depletion during prograde metamorphism. High element mobility is supported by the homogenization of ?18O and ?13C values in carbonates and silicates for the marble and silicate layers. The silicate layers and the gneiss contain elevated contents of Cr and V due to the volcanoclastic component of their protolith.

  11. Temperature Dependence of the Structural Parameters in the Transformation of Aragonite to Calcite, as Determined from In Situ Synchrotron Powder X-ray-Diffratction Data

    SciTech Connect

    Antao, Sytle M.; Hassan, Ishmael

    2011-09-06

    The temperature dependency of the crystal structure and the polymorphic transition of CaCO{sub 3} from aragonite to calcite were studied using Rietveld structure refinement and high-temperature in situ synchrotron powder X-ray-diffraction data at ambient pressure, P. The orthorhombic metastable aragonite at room P, space group Pmcn, transforms to trigonal calcite, space group R{bar 3}c, at about T{sub c} = 468 C. This transformation occurs rapidly; it starts at about 420 C and is completed by 500 C, an 80 C interval that took about 10 minutes using a heating rate of 8 C/min. Structurally, from aragonite to calcite, the distribution of the Ca atom changes from approximately hexagonal to cubic close-packing. A 5.76% discontinuous increase in volume accompanies the reconstructive first-order transition. Besides the change in coordination of the Ca atom from nine to six from aragonite to calcite, the CO{sub 3} groups change by a 30{sup o} rotation across the transition.

  12. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

    NASA Astrophysics Data System (ADS)

    Kimball, J.; Tripati, R. E.; Dunbar, R.

    2015-12-01

    Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near constant temperature, salinity and pH, and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop "clumped" isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly-substituted isotopologue 13C18O16O2 in carbonate minerals, analyzed in CO2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ47 values. We analyzed Δ47 in live-collected aragonitic scleractinian (Enallopsammia sp.) and calcitic gorgonian (Isididae and Coralliidae) deep-sea corals, and compared results to published data for other aragonitic scleractinian taxa. Measured Δ47 values were compared to in situ temperatures and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than calcitic gorgonian corals and the two groups of coral produce statistically different relationship between Δ47-temperature calibrations. These data are significant in the interpretation of all carbonate "clumped" isotope calibration data as they show that distinct Δ47-temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite, although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect that crystals may attain nominal mineral equilibrium clumped isotope signatures only under conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological "vital-effect" influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological "vital" effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ47 is a subject that warrants further investigation.

  13. Interrogating coccolith calcite: paleoceanographic proxy data from nannofractions, foraminifera and single coccolith specimens

    NASA Astrophysics Data System (ADS)

    Bown, P. R.; Lees, J. A.; Young, J.; Robinson, S. A.; MacLeod, K. G.; Grocke, D. R.; Schmidt, D. N.; Hinton, R.

    2009-12-01

    Nannofossils are the calcareous cell-wall coverings of oceanic phytoplankton and the most abundant but smallest routinely studied fossil group. Small size (typically <8 microns and <400 pg of calcite per lith) has limited their use as geochemical proxies because it is difficult to separate them by mechanical picking or using centrifuge or filtration techniques. However, the <63m fraction of marine sediments is often implied to represent the bulk nannofossil signal in geochemical studies, but actually represents a spectrum of oceanic carbonate, from parts of larger organisms (potentially benthic, nektonic and planktonic) to micarb (of unknown, possibly non-biological, origin), consequently obfuscating the true nannofossil signal. Additionally, it is known that certain nannofossil taxa are more responsive to paleoenvironmental change than others, and so a bulk nannofossil signal is potentially misleading. Consequently, there has been a strong incentive to develop techniques that overcome these difficulties, as coccoliths represent a potentially invaluable and inexhaustible geochemical archive of paleoenvironmental information. Most importantly, coccoliths are hugely abundant in marine sediments deposited above the calcite compensation depth (billions of specimens per gram) and their chemical composition is resistant to the modifying effects of diagenesis since they are relatively non-porous structures formed from a small number of solid calcite crystals. Here we compare a range of paleoceanographic geochemical proxies (element ratios, stable isotopes) measured from (a) bulk sediment, single foraminifers and sieved near-monotaxic nannofossil fractions using wet chemistry and (b) single coccolith specimens using an ion microprobe SIMS. The data come from the PETM interval of ODP Leg 207 Site 1259 (Demerara Rise, western equatorial Atlantic) and enable comparisons between paleontological, assemblage-based productivity proxies and geochemical proxies based on nannofraction samples and single-species/single-nannofossil specimens. The latter technique is particularly informative, with low Mg and very low B values demonstrating that coccolithophores exert a far greater selectivity on incorporation of trace elements during calcification compared with, for example, foraminifera. Sr values, however, reveal clear and distinct taxon-specific ranges that are consistent with paleoecological interpretations inferred by other means (e.g. regarding eutrophs vs. oligotrophs). The lack of significant change in the Sr values into and through the PETM, despite major nannofossil assemblage shifts and inferred paleoenvironmental change, suggests that production of nannoplankton was not greatly affected at this site. However, Sr measured in nannofraction samples and bulk showed distinctly different trends that require explanation.

  14. String stabilized ribbon growth a method for seeding same

    DOEpatents

    Sachs, Emanuel M. (39 Harding Ave., Belmont, MA 02178)

    1987-08-25

    This invention is a method of initiating or seeding the growth of a crystalline or polycrystalline ribbon by the String Stabilized Ribbon Growth Method. The method for seeding the crystal growth comprises contacting a melt surface with a seed and two strings used in edge stabilization. The wetted strings attach to the wetted seed as a result of the freezing of the liquid melt. Upon drawing the seed, which is attached to the strings, away from the melt surface a melt liquid meniscus, a seed junction, and a growth interface forms. Further pulling of the attached seed causes a crystal ribbon to grow at the growth interface. The boundaries of the growing ribbon are: at the top the seed junction, at the bottom the freezing boundary of the melt liquid meniscus, and at the edges frozen-in strings.

  15. Calcite strains, kinematic indicators, and magnetic flow fabric of a Proterozoic pseudotachylyte swarm, Minnesota River valley, USA

    NASA Astrophysics Data System (ADS)

    Craddock, John P.; Magloughlin, Jerry F.

    2005-06-01

    Near Granite Falls, Minnesota sub-parallel pseudotachylyte, mafic dikes, and calcite veins crosscut Archean granulite facies rocks in the Minnesota River valley adjacent to the north-dipping Yellow Medicine Shear Zone (YMSZ; N80E) that separates the Montevideo and Morton tectonic terranes. The docking of these two Archean terranes occurred prior to intrusion of the 2.067 Ga Kenora-Kabetogama dike swarm as demonstrated by aeromagnetic anomalies (correlated with field exposures) that cross the YMSZ without offset. Tectonic adjustments along the YMSZ associated with the Penokean Orogeny ( 1.8 Ga) are likely responsible for pseudotachylyte formation. Pseudotachylyte is exposed in 22 sub-parallel veins ( N80E, 90) each less than 2 cm wide across an outcrop width of 45 m. The pseudotachylyte matrix is commonly banded, and contains crystal fragments (quartz, plagioclase, amphibole, rutile, apatite, ilmenite, ulvspinel), magnetite microlites, flow banding swirls, amygdules (filled with calcite, ankerite and siderite), collapsed vesicles, and abundant lithic clasts. Pseudotachylyte formed in a number of phases. Kinematic reconstruction is complex, utilizing winged porphyroclasts, S-C structures in the country rock, and fault drag indicators along the pseudotachylyte zones. Dextral motion along the YMSZ is the most common observation. Mechanically twinned calcite within amygdules in the pseudotachylyte preserves horizontal shortening normal to the pseudotachylyte strike. Calcite veins are apparently contemporaneous with the pseudotachylyte; one set preserves twinning strains identical to the calcite amygdule strains, and the second set contains a horizontal, vein-parallel (N70E) shortening strain. The pseudotachylyte contains a flow fabric, as determined by AMS techniques, that is a proxy for vertical flow ( Kmax is vertical). The Kenora-Kabetogama dikes, identified geochemically, are locally parallel to the pseudotachylyte and the adjacent YMSZ tectonic suture and preserve a vertical-to-horizontal, dike-parallel AMS fabric from east (Franklin) to west (Granite Falls). Hornblende andesite dikes (055, 1.8 Ga) are not found south of the suture, are not associated with pseudotachylyte and have a different paleopole and AMS fabric.

  16. Patterns of biomediated CaCO3 crystal bushes in hot spring deposits

    NASA Astrophysics Data System (ADS)

    Peng, Xiaotong; Jones, Brian

    2013-08-01

    In the Eryuan hot spring, located in south China, the vent pool is covered with crystal bushes, up to 2 cm high, 1 cm in diameter, that grew in the biofilms that thrive in the spring waters that have a pH of 7.5 and a temperature of 88 C. The biofilms are formed largely of phototrophic purple bacteria and green bacteria. Growth of the crystal bushes, which are formed of aragonite crystals (wheat-sheaves, radiating clusters), rhombohedral and dodecahedral calcite crystals, amorphous CaCO3 (ACC), and opal-A, is attributed to precipitation in the micro-domains of the biofilms where physiochemical conditions can vary on the sub-micron scale. There is no evidence that the calcite was formed through recrystallization of the metastable aragonite and most of the calcite crystals developed as mesocrystals that are characterized by incomplete growth and porous crystal faces. With the onset of diagenesis, there is a high probability that the crystal bushes will lose much of their identity as the (1) biofilm is lost through decay, (2) ACC and aragonite change to calcite, (3) identities of the mesocrystals and incompletely formed crystals are lost through continued precipitation and/or recrystallization, and (4) porous crystal faces are converted to solid crystal faces. This means that most of the features considered indicative of biomediated calcite precipitation have a low preservation potential and that the recognition of biomediated precipitates in old spring deposits may remain problematical.

  17. Pyrite-pyrrhotite intergrowths in calcite marble from Bistriški Vintgar, Slovenia

    NASA Astrophysics Data System (ADS)

    Zavašnik, J.

    2016-02-01

    Roman marble quarry in Bistrica gorge in southern Pohorje Mt. (north-eastern Slovenia) is situated in a 20 m thick lens of layered marble, at the contact zone between granodiorite and metamorphites. Grey and yellowish non-homogenous calcite marble is heavily included by mica, quartz, feldspars, zoisite, pyrite and amphiboles. In the present research, we have studied numerous pyrite (FeS2) crystals associated with yellowish-bronze non-stoichiometric pyrrhotite (Fe1‑xS), not previously reported from this locality. SEM investigation revealed unusual sequence of crystallisation: primary skeletal pyrrhotite matrix is sparsely overgrown by well-crystalline pyrite, both being overgrown by smaller, well-developed hexagonal pyrrhotite crystals of the second generation. With TEM we identify the pyrrhotite as 5T-Fe1-xS phase, where x is about 0.1 and is equivalent to Fe9S10. The pyrite-pyrrhotite coexistence allows us a construction of fO2-pH diagram of stability fields, which reflects geochemical conditions at the time of marble re-crystallisation.

  18. The sensitized luminescence of manganese-activated calcite

    USGS Publications Warehouse

    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.".

  19. Dynamic recrystallization processes of calcitic fossils in deformed marble

    NASA Astrophysics Data System (ADS)

    Lee, S.; Ree, J. H.; Jung, H.

    2014-12-01

    Here we report dynamic recrystallization processes of calcitic fossils in weakly to fully recrystallized marbles to discuss the survivability of fossils and possible recognition of former fossils in fully recrystallized marbles. The marble is from the early Paleozoic sequence in the Jeongseon area of South Korea. Each crinoid stem in a weakly or non-recrystallized marble cut perpendicular to its length appears as a donut shape and consists of five calcite grains (300-500m in size) with the same c-axis but different a-axis orientations. The misorientation angle between adjacent grains in a crinoid stem is 40-50. The outer and inner diameters of the donut-shaped crinoid stems are about 900 and 500 m, respectively. The recrystallization processes initiate on grain boundaries as bulging recrystallization while transgranular subgrain walls form within lattice-distorted grains. New grains also nucleate on twin boundaries and subgrain boundaries. Some subgrain walls become grain boundaries as they collect more dislocations with subgrain boundary migration. The newly recrystallized grains grow to reach a steady-state grain size of 20-50m. In fully recrystallized and deformed marbles, the crinoid stems occur as elongated donut-shaped calcite aggregates. The crinoid stems can be recognized by their size larger than that of recrystallized matrix grains (5-20m), With a higher degree of dynamic recrystallization, the randomness of the misorientation angle distribution of the recrystallized grains within a crinoid stem increases, indicating weaker lattice preferred orientation. We are trying to test whether lattice orientation maps (or AVA diagrams) can be used to recognize former fossil traces in fully recrystallized marbles.

  20. Calcite saturation in the River Dee, NE Scotland.

    PubMed

    Wade, A J; Neal, C; Smart, R P; Edwards, A C

    2002-01-23

    The spatial and temporal variations in calcite (calcium carbonate) solubility within the Dee basin of NE Scotland were assessed using water chemistry data gathered from a network of 59 sites monitored for water quality from June 1996 to May 1997. Calcite solubility, expressed in terms of a saturation index (SIcalcite), was determined from measured streamwater pH, Gran alkalinity and calcium concentrations and water temperature. In general, the waters of the Dee system are undersaturated with respect to calcite, though the saturation index is higher during the summer months indicating a dependency on flow conditions and biological activity. Under low-flow conditions, the streamwaters are dominated by water derived from the lower soil horizons and deeper groundwater stores and therefore, ions such as Gran alkalinity and calcium are at their highest concentrations as they are derived mainly from bedrock weathering. The influence of biological activity on the carbonate system is also evident as the observed pH and estimated EpCO2 values indicate strong seasonal patterns, with the highest pH and lowest EpCO2 values occurring during the summer low-flow periods. Only at three sites in the lowland region of the catchment, during the summer low-flow period, are the waters oversaturated. As such, the Dee system represents an extreme 'end-member' case when compared to many UK rivers that span both under- and oversaturated conditions during the year. Regression analysis highlights a systematic change in the SIcalcite-pH relationship in a broad east-west direction across the Dee system. At sites draining the relatively impermeable upland areas, the regression of SIcalcite against pH gives a straight line with a gradient in the range 1.6-2.4. Correspondingly, under the most extreme alkaline conditions found at sites draining lowland agricultural areas, a straight-line relationship exists but with a gradient of unity. It is concluded that these changes in the SIcalcite-pH relationship are due to variations in the bicarbonate system induced by the flow conditions and biological activity. Given the waters are undersaturated, then calcite precipitation and hence phosphorus co-precipitation cannot occur within the water column. PMID:11846077

  1. Top-seed solution growth and characterization of AlSb single crystals for gamma-ray detectors. Final report, 1 October 1994--30 September 1995

    SciTech Connect

    Witt, A.F.; Becla, P.; Counterman, C.; DiFrancesco, J.; Landahl, G.; Morse, K.; Sanchez, J.

    1996-01-26

    The ultimate objective of the conducted research is to ascertain the potential of AlSb (in single crystal form) for application as {gamma}-detector material operating at room temperature. To this end approaches to crystal growth were to be developed which permit control of growth parameters affecting critical application specific properties of AlSb. The research was focused on exploration of the effectiveness of the Czochralski method and on the development of methods and procedures leading to AlSb crystals with low free carrier concentration and a high mobility-lifetime product. Conventional melt growth of AlSb by the Czochralski technique (from stoichiometric charges) generally yielded material with high net carrier concentrations and low mobility-lifetime products. Significant improvement in crystal properties was achieved, when operating with non-stoichiometric melts, containing Sb in excess at levels of 3 to 10 mol%, further improvements were obtained when changing ambient argon pressure from atmospheric to 300 psi, and using high purity alumina crucibles which were inductively heated with a graphite susceptor CVD coated with silicon-carbide. Initial efforts to reduce evaporative loss of Sb through application of the LEC technique (liquid encapsulated Czochralski) with conventional encapsulants (B{sub 2}O{sub 3}, LiF, CaF{sub 2}) failed because of their interaction with the crucible and the AlSb melt. Compensation techniques (based on extrinsic doping) were found to lead to the desired reduction of free carriers in AlSb. Such material, however, exhibits a significant decrease of charge carrier mobility and lifetime. Early termination of this research program prevented optimization of critical materials properties in AlSb and precluded at this time a realistic assessment of the potential of this material for solid state detector applications.

  2. Synthesis of KCa2Nb3O10 Crystals with Varying Grain Sizes and Their Nanosheet Monolayer Films As Seed Layers for PiezoMEMS Applications.

    PubMed

    Yuan, Huiyu; Nguyen, Minh; Hammer, Tom; Koster, Gertjan; Rijnders, Guus; Ten Elshof, Johan E

    2015-12-16

    The layered perovskite-type niobate KCa2Nb3O10 and its derivatives show advantages in several fields, such as templated film growth and (photo)catalysis. Conventional synthesis routes generally yield crystal size smaller than 2 μm. We report a flux synthesis method to obtain KCa2Nb3O10 crystals with significantly larger sizes. By using different flux materials (K2SO4 and K2MoO4), crystals with average sizes of 8 and 20 μm, respectively, were obtained. The KCa2Nb3O10 crystals from K2SO4 and K2MoO4 assisted synthesis were protonated and exfoliated into monolayer nanosheets, and the optimal exfoliation conditions were determined. Using pulsed laser deposition, highly (001)-oriented piezoelectric stacks (SrRuO3/PbZr0.52Ti0.48O3/SrRuO3, SRO/PZT/SRO) were deposited onto Langmuir-Blodgett films of Ca2Nb3O10(-) (CNO) nanosheets with varying lateral nanosheet sizes on Si substrates. The resulting PZT thin films showed high crystallinity irrespective of nanosheet size. The small sized nanosheets yielded a high longitudinal piezoelectric coefficient d33 of 100 pm/V, while the larger sized sheets had a d33 of 72 pm/V. An enhanced transverse piezoelectric coefficient d31 of -107 pm/V, an important input parameter for the actuation of active structures in microelectromechanical systems (MEMS) devices, was obtained for PZT films grown on CNO nanosheets with large lateral size, while the corresponding value on small sized sheets was -96 pm/V. PMID:26583282

  3. Project SEED.

    ERIC Educational Resources Information Center

    Chemical and Engineering News, 1986

    1986-01-01

    Reports on Project SEED (Summer Educational Experience for the Disadvantaged) a project in which high school students from low-income families work in summer jobs in a variety of academic, industrial, and government research labs. The program introduces the students to career possibilities in chemistry and to the advantages of higher education.

  4. Hydrodynamic control of inorganic calcite precipitation in Huanglong Ravine, China: Field measurements and theoretical prediction of deposition rates

    NASA Astrophysics Data System (ADS)

    Zaihua, Liu; Svensson, U.; Dreybrodt, W.; Daoxian, Yuan; Buhmann, D.

    1995-08-01

    Hydrochemical and hydrodynamical investigations are presented to explain tufa deposition rates along the flow path of the Huanglong Ravine, located in northwestern Sichuan province, China, on an altitude of about 3400 m asl. Due to outgassing of CO 2 the mainly spring-fed stream exhibits, along a valley of 3.5 km, calcite precipitation rates up to a few mm/year. We have carried out in situ experiments to measure calcite deposition rates at rimstone dams, inside of pools and in the stream-bed. Simultaneously, the downstream evolution of water chemistry was investigated at nine locations with respect to Ca 2+, Mg 2+, Na +, Cl -, SO 42-, and alkalinity. Temperature, pH, and conductivity were measured in situ, while total hardness, Ca T, and alkalinity have been determined immediately after sampling, performing standard titration methods. The water turned out to be of an almost pure Ca?Mg?HCO 3 type. The degassing of CO 2 causes high supersaturation with respect to calcite and due to calcite precipitation the Ca 2+ concentration decreases from 610 -3 mole/1 upstream down to 2.510 -3 mole/1 at the lower course. Small rectangular shaped tablets of pure marble were mounted under different flow regimes, i.e., at the dam sites with fast water flow as well as inside pools with still water. After the substrate samples had stayed in the water for a period of a few days, the deposition rates were measured by weight increase, up to several tens of milligrams. Although there were no differences in hydrochemistry, deposition rates in fast flowing water were higher by as much as a factor of four compared to still water, indicating a strong influence of hydrodynamics. While upstream rates amounted up to 5 mm/year, lower rates of about 1 mm/year were observed downstream. Inspection of the marble substrate surfaces by EDAX and SEM (scanning electron microscope) revealed authigeneously grown calcite crystals of about 10 ?m. Their shape and habit are indicative of a chemically controlled inorganic origin. By applying a mass transfer model for calcite precipitation taking into account the reaction rates at the surface given by Plummer et al. (1978), slow conversion of CO 2 into H + and HCO 3- , and diffusional mass transport across a diffusion boundary layer, we have calculated the deposition rates from the hydrochemistry of the corresponding locations. The calculated rates agree within a factor of two with the experimental results. Our findings confirm former conclusions with respect to fast flow conditions: reasonable rates of calcite precipitation can be estimated in reducing the PWP-rate calculated from the chemical composition of the water by a factor of about ten, thus correcting for the influence of the diffusion boundary layer.

  5. Environmental controls on the Emiliania huxleyi calcite mass

    NASA Astrophysics Data System (ADS)

    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.

  6. Environmental controls on the Emiliania huxleyi calcite mass

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    Although ocean acidification is expected to impact (bio) calcification by decreasing the seawater carbonate ion concentration, [CO32-], there is evidence of nonuniform response of marine calcifying plankton to low seawater [CO32-]. This raises questions about the role of environmental factors other than acidification and about the complex physiological responses behind calcification. Here we investigate the synergistic effect of multiple environmental parameters, including seawater temperature, nutrient (nitrate and phosphate) availability, and 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 above the modern lysocline (with the exception of eight samples that are located at or below the 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 seawater nutrient availability (phosphate and nitrate) and carbonate chemistry (pH and pCO2) in determining coccolith mass by affecting primary calcification and/or the geographic distribution of E. huxleyi morphotypes. 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.

  7. Utilization of calcite and waste glass for preparing construction materials with a low environmental load.

    PubMed

    Maeda, Hirotaka; Imaizumi, Haruki; Ishida, Emile Hideki

    2011-11-01

    In this study, porous calcite materials are hydrothermally treated at 200 °C using powder compacts consisting of calcite and glasses composed of silica-rich soda-lime. After treatment, the glasses are converted into calcium aluminosilicate hydrates, such as zeolite phases, which increase their strength. The porosity and morphology of new deposits of hydrothermally solidified materials depend up on the chemical composition of glass. The use of calcite and glass in the hydrothermal treatment plays an important role in the solidification of calcite without thermal decomposition. PMID:21794973

  8. Microstructural and compositional study of a bulk Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}-PbTiO{sub 3} single crystal grown from a BaTiO{sub 3} seed

    SciTech Connect

    Samardzija, Zoran . E-mail: zoran.samardzija@ijs.si; Jeon, Jae-Ho; Ceh, Miran

    2007-06-15

    The microstructure, composition and homogeneity of a Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}-PbTiO{sub 3} (PMNT) single crystal were studied using a combination of electron-microprobe techniques: scanning electron microscopy, orientation analysis and quantitative X-ray microanalysis. A PMNT single crystal was grown from a polycrystalline PMNT matrix using a BaTiO{sub 3} single crystal as a seed. The PMNT crystal retained the same crystallographic orientation as the seed with no interdiffusion at the interface. The average chemical composition, determined with optimized quantitative wavelength-dispersive X-ray microanalysis, was Pb(Mg{sub 1/3}Nb{sub 2/3}){sub 1-X}Ti {sub X}O{sub 3} where x = 0.33. A statistical evaluation of the data using the analysis of variance showed that the achieved experimental uncertainty was below {+-} 1% relative. The compositional homogeneity of the crystal was verified on the micrometer-scale; however on the macro-scale slight fluctuations of the Mg, Nb and Ti concentrations were observed across the crystal. The measured variations from the average composition were {+-} 2.3% relative for Ti, {+-} 1.3% for Nb and {+-} 1.4% for Mg. In contrast, the Pb concentration was found to be uniform on both the micro- and macro-scale, showing a variation below {+-} 0.5% relative.

  9. Brine induced low-Magnesium calcite formation at cold seeps

    NASA Astrophysics Data System (ADS)

    Feng, Dong; Roberts, Harry; Joye, Samantha; Heydari, Ezat

    2013-04-01

    Low-Mg calcite (LMC; < 5 mol% Mg), commonly observed during time intervals of "calcite seas," since the beginning of the Paleozoic Era, is a good indicator of low Mg/Ca ratio (< 2) in seawater. Calcite seas were coincident with times of active seawater-basalt interactions along mid-ocean ridges at high temperatures, which extract Mg from seawater and release Ca to it. In the modern aragonite sea, most carbonate minerals precipitate at the seafloor, including deposits from cold seep environments are primarily either aragonite or high-Mg calcite (HMC). Here, we report the finding of non-skeletal LMC from cold seeps in Alaminos Canyon block 601 (AC 601), 2200 m below the sea surface on northern Gulf of Mexico (GOM) continental slope. Low-Mg calcite usually represents the only carbonate mineral in the studied samples. Dominant allochems in these seep carbonates are peloids, grain aggregates, pelagic forams, and fragments of mollusks and echinoids. The limestone is heavily cemented. The observed cements include micrite, microspar, mosaic, bladed, fan, and needle cements. The dissolution of grains and cements was observed. Not only originally aragonitic mollusks shells, but also carbonate cement have been dissolved. The aerobic oxidation of reduced chemical species such as methane and H2S is responsible for an increase in pCO2 and a decrease of pH, leading to local carbonate dissolution. The occurrence of oxic conditions is confirmed by the presence of negative Ce anomalies of the carbonates. Further, we report on analyses showing that the ambient porewater Mg/Ca ratio actually governs the carbonate mineralogy. The occurrence of LMC may be attributed to the brine fluids, which is relatively Mg-depleted (Mg/Ca mole ratio is below 0.7) compared to pore fluid of the subsurface sediments from the reference site (Mg/Ca mole ratio is above 4.1) that usually produce HMC. The 87Sr/86Sr values of LMC (mean = 0.708001, sd = 0.000034, n=2) are significantly lower than that of the seawater (0.709175). Strong deviation of the Sr isotope ratios of LMC from seawater is interpreted as the modification of the strontium from less radiogenic sources like older marine sediments and/or the locally abundant Jurassic salt. Therefore, we speculate that the seep fluids at the studied site most likely have a deep origin and may also have been influenced by dissolved halite during their ascent through conduits along the margins of salt bodies. The understanding of the processes that control the LMC precipitation in the GOM will also contribute to an improved understanding of the presence or absence of LMC in other oceans margin settings today, and in geological deposits as well.

  10. Partitioning of Sr 2+ and Mg 2+ into calcite under karst-analogue experimental conditions

    NASA Astrophysics Data System (ADS)

    Huang, Yiming; Fairchild, Ian J.

    2001-01-01

    There is a paucity of experimental data on calcite precipitation from waters at low ionic strength and low ratios of Mg/Ca and Sr/Ca, using controlled and constant precipitation rates. Such data are particularly needed for studies of speleothem geochemistry in relation to palaeoclimates. We carried out a series of experiments using a karst-analogue set-up in a chamber of constant temperature and 100% humidity. A steady flow of NaHCO 3 and CaCl 2 solutions at PCO 2 around 10 -3.2 were mixed just before passage through a tube (analogous to a soda-straw stalactite) and allowed to drip onto a surface, analogous to a stalagmite. Growth rates were comparable with linear extension rates of natural speleothems. Analytical spots gave reproducible analyses in later analytical cycles after ablation of surface calcite with Na and Mg contamination. Different crystals from the same experiment tended to show positive covariation of Na and Mg with negative covariation with Sr. This may be due to the presence of growth hillocks with vicinal faces with differential partitioning behaviour. The result for the partition coefficient for Mg (D Mg) at 25C is 0.031 0.004, which is quantitatively in good agreement with the trends of previous workers. At 15C, the result is 0.019 0.003. The temperature dependency is higher than experimental data on seawater-analogue solutions, but lower than a previous estimate based on a comparison of speleothem chemistry with single water analyses. Data for D Sr are mainly in the range of 0.057 to 0.078, with a possible weak dependency on growth rate, consistent with previous experimental work. Absolute values are higher than studies in Mg-free saline solutions, which is attributed mainly to salinity effects. Values of D Sr are nevertheless somewhat lower than in natural caves, which may relate to crystal growth factors. Mg partition coefficient values should allow robust determination of solution Mg/Ca compositions in enclosed caves, which are at constant temperature on the decadal timescale. The inferred sensitivity of D Sr to growth rate factors implies that Sr values should be interpreted more cautiously. Muted changes could relate entirely to growth rate variations, whereas changes of large magnitude imply a control by solution composition. The absence of local (tens of micron scale) antipathetic variations in Sr and Mg in studied natural speleothems, implies that intracrystalline zoning phenomena, if present, are on a finer scale in those natural materials compared with experimental products.

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

    PubMed

    Mbamba, Christian Kazadi; Batstone, Damien J; Flores-Alsina, Xavier; Tait, Stephan

    2015-01-01

    Process simulation models used across the wastewater industry have inherent limitations due to over-simplistic descriptions of important physico–chemical reactions, especially for mineral solids precipitation. As part of the efforts towards a larger Generalized Physicochemical Modelling Framework, the present study aims to identify a broadly applicable precipitation modelling approach. The study uses two experimental platforms applied to calcite precipitating from synthetic aqueous solutions to identify and validate the model approach. Firstly, dynamic pH titration tests are performed to define the baseline model approach. Constant Composition Method (CCM) experiments are then used to examine influence of environmental factors on the baseline approach. Results show that the baseline model should include precipitation kinetics (not be quasi-equilibrium), should include a 1st order effect of the mineral particulate state (Xcryst) and, for calcite, have a 2nd order dependency (exponent n = 2.05 ± 0.29) on thermodynamic supersaturation (σ). Parameter analysis indicated that the model was more tolerant to a fast kinetic coefficient (kcryst) and so, in general, it is recommended that a large kcryst value be nominally selected where insufficient process data is available. Zero seed (self nucleating) conditions were effectively represented by including arbitrarily small amounts of mineral phase in the initial conditions. Both of these aspects are important for wastewater modelling, where knowledge of kinetic coefficients is usually not available, and it is typically uncertain which precipitates are actually present. The CCM experiments confirmed the baseline model, particularly the dependency on supersaturation. Temperature was also identified as an influential factor that should be corrected for via an Arrhenius-style correction of kcryst. The influence of magnesium (a common and representative added impurity) on kcryst was found to be significant but was considered an optional correction because of a lesser influence as compared to that of temperature. Other variables such as ionic strength and pH were adequately captured by the quasi-equilibrium description of the aqueous-phase and no further kinetic corrections were required. The baseline model is readily expandable to include other precipitation reactions. For simple representations, large values for kcryst with n = 2 (or n = 2 or 3 for other minerals, as appropriate) should be selected without corrections to kcryst. Where accuracy is required (e.g., in mechanistic studies), machine estimation of kcryst should be performed with robust process data and kcryst should at least be corrected for temperature. PMID:25462741

  12. Circular economy in drinking water treatment: reuse of ground pellets as seeding material in the pellet softening process.

    PubMed

    Schetters, M J A; van der Hoek, J P; Kramer, O J I; Kors, L J; Palmen, L J; Hofs, B; Koppers, H

    2015-01-01

    Calcium carbonate pellets are produced as a by-product in the pellet softening process. In the Netherlands, these pellets are applied as a raw material in several industrial and agricultural processes. The sand grain inside the pellet hinders the application in some high-potential market segments such as paper and glass. Substitution of the sand grain with a calcite grain (100% calcium carbonate) is in principle possible, and could significantly improve the pellet quality. In this study, the grinding and sieving of pellets, and the subsequent reuse as seeding material in pellet softening were tested with two pilot reactors in parallel. In one reactor, garnet sand was used as seeding material, in the other ground calcite. Garnet sand and ground calcite performed equally well. An economic comparison and a life-cycle assessment were made as well. The results show that the reuse of ground calcite as seeding material in pellet softening is technologically possible, reduces the operational costs by €38,000 (1%) and reduces the environmental impact by 5%. Therefore, at the drinking water facility, Weesperkarspel of Waternet, the transition from garnet sand to ground calcite will be made at full scale, based on this pilot plant research. PMID:25746637

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

    NASA Astrophysics Data System (ADS)

    Renard, Francois; Putnis, Christine; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hvelmann, Jrn; Sarret, Graldine

    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.

  14. Stable carbon isotopes and lipid biomarkers provide new insight into the formation of calcite and siderite concretions in organic-matter rich deposits

    NASA Astrophysics Data System (ADS)

    Baumann, Lydia; Birgel, Daniel; Wagreich, Michael; Peckmann, Jörn

    2015-04-01

    Carbonate concretions from two distinct settings have been studied for their petrography, stable carbon and oxygen isotopes, and lipid biomarker content. Carbonate concretions are in large part products of microbial degradation of organic matter, as for example by sulfate-reducing bacteria, iron-reducing bacteria, and methanogenic archaea. For these prokaryotes certain lipid biomarkers such as hopanoids, terminally-branched fatty acids (bacteria) and isoprenoids (archaea) are characteristic. Two different types of concretions were studied: a) Upper Miocene septarian calcite concretions of the southern Vienna Basin embedded in brackish sediments represented by partly bituminous calcareous sands, silts and clays; b) Paleocene-Eocene siderite concretions enclosed in marine, sandy to silty turbidites with varying carbonate contents and marl layers from the Upper Gosau Subgroup in northern Styria. Calcite concretions consist of abundant calcite microspar (80-90 vol.%), as well as detrital minerals and iron oxyhydroxides. The septarian cracks show beginning cementation with dog-tooth calcite to varying degrees. Framboidal pyrite occurs in some of the calcite concretions, pointing to bacterial sulfate reduction. Siderite concretions consist of even finer carbonate crystals, mainly siderite (40-70 vol.%) but also abundant ferroan calcite, accompanied by iron oxyhydroxides and detrital minerals. The δ13C values of the calcite concretions (-6.8 to -4.1o ) most likely reflect a combination of bacterial organic matter oxidation and input of marine biodetrital carbonate. The δ18O values range from -8.9 to -7.8o agreeing with a formation within a meteoric environment. The surrounding host sediment shows about 1-2o higher δ13C and δ18O values. The siderite δ13C values (-11.1 to -7.5o ) point to microbial respiration of organic carbon and the δ18O values (-3.5 to +2.2o ) agree with a marine depositional environment. In contrast to the calcite concretions, the stable isotope composition of the host sediment differs significantly from the siderite concretions. The δ13C values of the Gosau host sediment reflect marine conditions, whereas the oxygen isotope values are best explained by meteoric overprint. Lipid biomarkers have been extracted before and after dissolution of the concretions in order to assess their authenticity and to exclude recent surface contamination. In the following, only the biomarkers extracted after dissolution are discussed, since they are thought to be related to concretion formation. The calcite concretions comprise abundant plant wax derived long-chain n-alkanes, reflecting high terrestrial input. Bacterial, terminally-branched fatty acids were found, but in overall low abundance. The siderite concretions did not yield biomarkers due to their high maturity. No archaeal biomarkers were found in any of the concretions. Considering the presence of framboidal pyrite, the moderately low δ13C values, and the biomarker inventory, bacterial sulfate reduction apparently contributed to the formation of the calcite concretions in a brackish environment. In contrast, ongoing sulfate reduction and resultant hydrogen sulfide production inhibit siderite precipitation. Therefore, the low δ13C values of the siderite concretions are best explained by bacterial iron reduction.

  15. Calcite orientations and composition ranges within teeth across Echinoidea

    PubMed Central

    Stock, Stuart R.; Ignatiev, Konstantin; Lee, Peter L.; Almer, Jonathan D.

    2016-01-01

    Sea urchin’s teeth from four families of order Echinoida and from orders Temnopleuroida, Arbacioida and Cidaroida were studied with synchrotron x-ray diffraction. The high and very high Mg calcite phases of the teeth, i.e. the first and second stage mineral constituents, respectively, have the same crystallographic orientations. The co-orientation of first and second stage mineral, which the authors attribute to epitaxy, extends across the phylogenic width of the extant regular sea urchins and demonstrates that this is a primitive character of this group. The range of compositions Δx for the two phases of Ca1−xMgxCO3 is about 0.20 or greater and is consistent with a common biomineralization process. PMID:25158180

  16. Age constraints on fluid inclusions in calcite at Yucca Mountain

    SciTech Connect

    Neymark, Leonid A.; Amelin, Yuri V.; Paces, James B.; Peterman, Zell E.; Whelan, Joseph F.

    2001-04-29

    The {sup 207}Pb/{sup 235}U ages for 14 subsamples of opal or chalcedony layers younger than calcite formed at elevated temperature range between 1.88 {+-} 0.05 and 9.7 {+-} 1.5 Ma with most values older than 6-8 Ma. These data indicate that fluids with elevated temperatures have not been present in the unsaturated zone at Yucca Mountain since about 1.9 Ma and most likely since 6-8 Ma. Discordant U-Pb isotope data for chalcedony subsamples representing the massive silica stage in the formation of the coatings are interpreted using a model of the diffusive loss of U decay products. The model gives an age estimate for the time of chalcedony formation around 10-11 Ma, which overlaps ages of clay minerals formed in tuffs below the water table at Yucca Mountain during the Timber Mountain thermal event.

  17. Isotopic composition of a calcite-cemented layer in the Lower Jurassic Bridport Sands, southern England: Implications for formation of laterally extensive calcite-cemented layers

    SciTech Connect

    Bjoerkum, P.A. ); Walderhaug, O. )

    1993-07-01

    [delta][sup 18]O[sub PDB] and [delta][sup 13]C[sub PDB] values have been measured on 107 calcite cement samples from a laterally extensive (> 3 km) and continuous calcite-cemented layer 0.5 m thick in the coastal exposures of the Lower Jurassic shallow-marine Bridport Sands in Dorset, southern England. The samples were taken from a two-dimensional grid with 10-cm horizontal and vertical spacing between samples and along individual vertical lines across the calcite-cemented layer, [delta][sup 18]O[sub PDB] values vary between [minus]4.8% and [minus]9.2% and decrease radially outwards from points with lateral spacings on the order of 0.5-1 m in the middle of the calcite-cemented layer. The [delta][sup 18]O[sub PDB] values therefore indicate that the calcite-cemented layer was formed by merging of concretions. All [delta][sup 13]C[sub PDB] values measured are in the narrow range [minus]2.2% to [minus]0.5%, which suggests that the dominant source of calcite cement in the layer was biogenic carbonate.

  18. In situ study of the R{bar 3}c-R{bar 3}m orientational disorder in calcite.

    SciTech Connect

    Antao, S. M.; Hassan, I.; Mulder, W. H.; Lee, P. L.; Toby, B. H.; X-Ray Science Division; Univ. of West Indies

    2009-01-01

    The temperature dependences of the crystal structure and intensities of the (113) and (211) reflections in calcite, CaCO{sub 3}, were studied using Rietveld structure refinements based on synchrotron powder X-ray diffraction data. Calcite transforms from R{bar 3}c to R{bar 3}m at about T{sub c} = 1240 K. A CO{sub 3} group occupies, statistically, two positions with equal frequency in the disordered R{bar 3}m phase, but with unequal frequency in the partially ordered R{bar 3}c phase. One position for the CO{sub 3} group is rotated by 180{sup o} with respect to the other. The unequal occupancy of the two orientations in the partially ordered R{bar 3}c phase is obtained directly from the occupancy factor, x, for the O1 site and gives rise to the order parameter, S = 2x - 1. The a cell parameter shows a negative thermal expansion at low T, followed by a plateau region at higher T, then a steeper contraction towards T{sub c}, where the CO{sub 3} groups disorder in a rapid process. Using a modified Bragg-Williams model, fits were obtained for the order parameter S, and for the intensities of the (113) and (211) reflections.

  19. [Research on Raman spectra of calcite phase transition at high pressure].

    PubMed

    Wang, Shi-Xia; Zheng, Hai-Fei

    2011-08-01

    The present research studied the process of phase transition from calcite-I to calcite-III under the condition of high hydrostatic pressure using hydrothermal diamond anvil cell and Raman spectrum technique. The hydrothermal diamond anvil cell is the most useful instrument to observe sample in-situation under high temperature and high pressure. The authors can get effective results from this instrument and pursue further research. The method of Raman spectra is the most useful measure tool and it can detect the material according to the spectrum. The result shows that three characteristic Raman peaks of calcite-I move to high-position with adding pressure. Water media in system becomes frozen at the pressure of 1103 MPa, and there is no change in the structure of calcite-I. The abrupt change of characteristic Raman peaks of calcite-I happens when the system pressure reaches 1752 MPa, and changed characteristic Raman peaks explain that calcite-I changes to calcite-III. There are two types of calcite-III, and type A happens in the system because of the effect of hydrostatic pressure. The characteristic Raman peak in different areas of minerals shows that the degree of phase transition becomes larger from inner part to edge part. The research also shows the advantage of hydrothermal diamond anvil cell and Raman spectrum for qualitative analysis of mineral structure using in-situ technique. PMID:22007398

  20. Carbon and oxygen isotopes in apatite CO/sub 2/ and co-existing calcite

    SciTech Connect

    Kolodny, Y.; Kaplan, I. R.

    1981-04-01

    Carbon and oxygen isotopes were analyzed in carbonate apatite CO/sub 2/ and in co-existing calcite. Both C and O in apatite CO/sub 2/ are enriched in the respective light isotopes relative to calcite. These results confirm the proposition that carbonate is part of the apatite structure.

  1. Molecular tectonics: from crystals to crystals of crystals.

    PubMed

    Marinescu, Gabriela; Ferlay, Sylvie; Kyritsakas, Nathalie; Hosseini, Mir Wais

    2013-12-11

    The in situ combination of M(II) cations (Co, Ni, Cu or Zn) with 2,4,6-pyridinetricarboxylic acid as a ligand, a bisamidinium dication as a H-bond donor tecton and NaOH leads to the formation of anionic metal complexes ML2(2-) and their interconnection into isomorphous 3D H-bonded networks displaying different colours which were used as preformed seed crystals for the formation of crystals of crystals by 3D epitaxial growth. PMID:24154609

  2. Microbially induced calcite precipitation-based sequestration of strontium by Sporosarcina pasteurii WJ-2.

    PubMed

    Kang, Chang-Ho; Choi, Jae-Ho; Noh, JunGu; Kwak, Dae Young; Han, Sang-Hyun; So, Jae-Seong

    2014-12-01

    Contamination by radioactive strontium ((90)Sr) is a significant environmental problem. Ureolytically driven calcium carbonate precipitation has been proposed for use in geotechnical engineering for soil remediation applications. In this study, 68 ureolytic bacterial strains were newly isolated from various environments. Of these, 19 strains were selected based on ureolytic activity shown when cultured on urea agar plates and identified through 16S rRNA gene sequencing. From these selected strains, Sporosarcina pasteurii WJ-2 (WJ-2) was selected for subsequent study. A simple method was developed to determine the effectiveness of microbially induced calcite precipitation (MICP). Unlike any other methods, it does not require advanced skills and sophisticated tools. Using this method, we were able to determine the ability of the bioconsolidated sand to retard the flow of crystal violet through the 25-mL column. Also, MICP by WJ-2 was evaluated for its potential to counteract Sr contamination in column experiments using natural sand. WJ-2-induced precipitation led to successful sequestration of approximately 80 % of the Sr from the soluble fraction of the sand. The utility of MICP in bioremediation was further confirmed through X-ray diffraction, scanning electron microscopy, and inductively coupled plasma mass spectrometry. PMID:25190302

  3. Diagenetic calcite from the Chazyan Group (Vermont): an example of aragonite alteration in a greenhouse ocean

    NASA Astrophysics Data System (ADS)

    Tobin, Kenneth J.; Walker, Kenneth R.

    1998-11-01

    Marine diagenetic calcite with both a calcitic (low-to-intermediate Mg) and aragonitic origin was examined from the middle Ordovician buildups of the Chazyan Group in Vermont. All marine phases have elevated Sr (up to 1800 ppm) compared with that observed from marine precipitates in other middle Ordovician units. Stromatoporoids (labechiids), which were originally aragonitic, have higher Sr values than phases with an original calcite mineralogy (trilobites, marine cement). Additional evidence supporting precursor mineralogy interpretations includes elevated Mg values (up to 3.6 mole% MgCO 3) and the presence of microdolomite in interpreted calcitic phases. Originally aragonitic precipitates have lower Mg values and most significantly lack microdolomite. This study demonstrates the presence of elevated Sr values in marine precipitates that formed during a period when calcite, not aragonite, was the dominant physiochemically precipitated calcium carbonate mineralogy that formed from sea water. Elevated Sr is attributable to at least a partially open system diagenetic stabilization of biogenic aragonite.

  4. Influence of calcite on uranium(VI) reactive transport in the groundwater–river mixing zone

    SciTech Connect

    Ma, Rui; Liu, Chongxuan; Greskowiak, Janek; Prommer, Henning; Zachara, John M.; Zheng, Chunmiao

    2014-01-23

    Calcite is an important mineral that can affect uranyl reactive transport in subsurface sediments. This study investigated the distribution of calcite and its influence on uranyl adsorption and reactive transport in the groundwater-river mixing zone at US Hanford 300A, Washington State. Simulations using a 2D reactive transport model under field-relevant hydrogeochemical conditions revealed a complex distribution of calcite concentration as a result of dynamic groundwater-river interactions. The calcite concentration distribution in turn affected the spatial and temporal changes in aqueous carbonate, calcium, and pH, which subsequently influenced U(VI) mobility and discharge rates into the river. The results implied that calcite distribution and its concentration dynamics is an important consideration for field characterization, monitoring, and reactive transport prediction.

  5. The quantitative determination of calcite associated with the carbonate-bearing apatites

    USGS Publications Warehouse

    Silverman, Sol R.; Fuyat, Ruth K.; Weiser, Jeanne D.

    1951-01-01

    The CO2 combined as calcite in carbonate-bearing apatites as been distinguished from that combined as carbonate-apatite, or present in some form other than calcite, by use of X-ray powder patterns, differential thermal analyses, and differential solubility tests. These methods were applied to several pure apatite minerals, to one fossil bone, and to a group of phosphorites from the Phosphoria formation of Permian age from Trail Canyon and the Conda mine, Idaho, and the Laketown district, Utah. With the exceptions of pure fluorapatite, pure carbonate-flueorapatite, and one phosphorite from Trail Canyon, these substances contain varying amounts of calcite, but in all the samples an appreciable part of the carbonite content is not present as calcite. The results of solubility tests, in which the particle size of sample and the length of solution time were varied, imply that the carbonate content is not due to shielded calcite entrapped along an internal network of surfaces.

  6. Seed Treatment. Manual 92.

    ERIC Educational Resources Information Center

    Missouri Univ., Columbia. Agricultural Experiment Station.

    This training manual provides information needed to meet minimum EPA standards for certification as a commercial applicator of pesticides in the seed treatment category. The text discusses pests commonly associated with seeds; seed treatment pesticides; labels; chemicals and seed treatment equipment; requirements of federal and state seed laws;

  7. Seed Treatment. Bulletin 760.

    ERIC Educational Resources Information Center

    Lowery, Harvey C.

    This manual gives a definition of seed treatment, the types of seeds normally treated, diseases and insects commonly associated with seeds, fungicides and insecticides used, types of equipment used for seed treatment, and information on labeling and coloring of treated seed, pesticide carriers, binders, stickers, and safety precautions. (BB)

  8. Diel cycles in calcite production and dissolution in a eutrophic basin

    SciTech Connect

    Cicerone, D.S.; Stewart, A.J.; Roh, Y.

    1999-10-01

    Calcite production is understood largely as a longer-term phenomenon (e.g., seasonal whitings) that can occur in hardwater lakes, and is significant ecologically because it can slow the rate of eutrophication by reducing, through adsorption, the availability of nutrients to primary producers. In this study the authors show that rapid changes in concentration of dissolved CO{sub 2} by photosynthesis and respiration within a eutrophic basin generated strong day-to-night cycles in calcite production and dissolution. Diel cycles in calcite production and dissolution were large enough that they could drive secondary diel cycles in the availability of metals that strongly sorb to the surfaces of calcite particles. They explored the possibility of the secondary diel cycling of metals by intensive 7-d in situ monitoring of water-quality conditions in a shallow, eutrophic spill-control basin near an industrial facility in eastern Tennessee; inspecting data from a 7-year record of water-quality parameters for this basin; analyzing physicochemical characteristics and mineralogic composition of sediments in the basin; and conducting laboratory experiments to characterize the interaction of calcite with Cd, under solid-liquid nonequilibrium conditions. The authors found that the basin accumulated and stored calcite. In situ monitoring showed that calcite was produced during daylight, and tended to dissolve again at night; the calcite production and dissolution processes seemed to be modulated by dissolved-phase CO{sub 2} dynamics, in concert with large diel fluctuations in pCa, pH, and Po{sub 2}. Laboratory experiments showed a rapid interaction ({lt}6 h) of Cd with calcite, in response to dissolved CO{sub 2} changes. Thus, concentrations of dissolved Cd can vary over daily cycles, mediated by diel changes in calcite production and dissolution. Thermodynamic considerations suggest that other metals, such as Zn, Sr, Ni, and Ba, may demonstrate this behavior as well.

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

    NASA Astrophysics Data System (ADS)

    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 composites, calcite is finer grained than dolomite. The synthesized materials were deformed in torsion at constant strain rate (3נ10-4 and 1נ10-4s-1), high effective pressure (262MPa), and high temperature (750C) to variable finite shear strains. Mechanical data show an increase in yield strength with increasing dolomite content. Composites with <75% dolomite (the remaining being calcite), accommodate significant shear strain at much lower shear stresses than pure dolomite but have significantly higher yield strengths than anticipated for 100% calcite. The microstructure of the fine-grained calcite suggests grain boundary sliding, accommodated by diffusion creep and dislocation glide. At low dolomite concentrations (i.e. 25%), the presence of coarse-grained dolomite in a micritic calcite matrix has a profound effect on the strength of composite materials as dolomite grains inhibit the superplastic flow of calcite aggregates. In high (>50%) dolomite content samples, the addition of 25% fine-grained calcite significantly weakens dolomite, such that strain can be partially localized along narrow ribbons of fine-grained calcite. Deformation of dolomite grains by shear fracture is observed; there is no intracrystalline deformation in dolomite irrespective of its relative abundance and finite shear strain.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

    Renard, Franois; Putnis, Christine V.; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hovelmann, Jrn; Sarret, Graldine

    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.

  12. Genesis of amethyst geodes in basaltic rocks of the Serra Geral Formation (Ametista do Sul, Rio Grande do Sul, Brazil): a fluid inclusion, REE, oxygen, carbon, and Sr isotope study on basalt, quartz, and calcite

    NASA Astrophysics Data System (ADS)

    Gilg, H. Albert; Morteani, Giulio; Kostitsyn, Yuri; Preinfalk, Christine; Gatter, Istvan; Strieder, Adelir J.

    2003-12-01

    In the Ametista do Sul area, Rio Grande do Sul, Brazil, amethyst-bearing geodes are hosted by a ~40- to 50-m-thick subhorizontal high-Ti basaltic lava flow of the Lower Cretaceous Paran Continental Flood Basalt Province. The typically spherical cap-shaped, sometimes vertically elongated geodes display an outer rim of celadonite followed inwards by agate and colorless and finally amethystine quartz. Calcite formed throughout the whole crystallization sequence, but most commonly as very late euhedral crystals, sometimes with gypsum, in the central cavity. Fluid inclusions in colorless quartz and amethyst are predominantly monophase and contain an aqueous liquid. Two-phase liquid-vapor inclusions are rare. Some with a consistent degree of fill homogenize into the liquid between 95 and 98 C. Ice-melting temperatures in the absence of a vapor phase between -4 and +4 C indicate low salinities. Chondrite-normalized REE patterns of calcites are highly variable and show generally no systematic correlation with the paragenetic sequence. The oxygen isotope composition of calcites is very homogeneous (?18OVSMOW=24.91.1, n=34) indicating crystallization temperatures of less than 100 C. Carbon isotope values of calcites show a considerable variation ranging from -18.7 to -2.9 (VPDB). The 87Sr/86Sr ratio of calcites varies between 0.706 and 0.708 and is more radiogenic than that of the host basalt (~0.705). The most likely source of silica, calcium, carbon, and minor elements in the infill of the geodes is the highly reactive interstitial glass of the host basalts leached by gas-poor aqueous solutions of meteoric origin ascending from the locally artesian Botucat aquifer system in the footwall of the volcanic sequence. The genesis of amethyst geodes in basalts at Ametista do Sul, Brazil, is thus considered as a two-stage process with an early magmatic protogeode formation and a late, low temperature infill of the cavity.

  13. Distinguishing Phosphate Structural Defects From Inclusions in Calcite and Aragonite by NMR Spectroscopy (Invited)

    NASA Astrophysics Data System (ADS)

    Phillips, B. L.; Mason, H. E.

    2010-12-01

    Variations in the concentration of minor and trace elements are being studied extensively for potential use as proxies to infer environmental conditions at the time of mineral deposition. Such proxies rely fundamentally on a relationship between the activities in the solution and in the solid that would seem to be simple only in the case that the species substitutes into the mineral structure. Other incorporation mechanisms are possible, including inclusions (both mineral and fluid) and occlusion of surface adsorbate complexes, that might be sensitive to other factors, such as crystallization kinetics, and difficult to distinguish analytically. For example, it is known from mineral adsorption studies that surface precipitates can be nanoscopic, and might not be apparent at resolutions typical of microchemical analysis. Techniques by which a structural relationship between the substituting element and the host mineral structure are needed to provide a sound basis for geochemical proxies. NMR spectroscopy offers methods for probing such spatial relationship. We are using solid-state NMR spectroscopy to investigate phosphate incorporation in calcium carbonate minerals, including calcite speleothems and coral skeletal aragonite, at concentrations of the order 100 ?g P g -1. In 31P NMR spectra of most samples, narrow peaks arising from crystalline inclusions can be resolved, including apatite in coral aragonite and an unidentified phase in calcite. All samples studied yield also a broad 31P signal, centered near chemical shifts of +3 to +4 ppm, that could be assigned to phosphate defects in the host mineral and from which the fraction of P occurring in the carbonate mineral structure can be determined. To test this assignment we applied rotational-echo double-resonance (REDOR) NMR techniques that probe the molecular-scale proximity of carbonate groups to the phosphate responsible for the broad 31P peak. This method measures dipole-dipole coupling between 31P of phosphate and carbonate carbon, which varies with the inverse-cube of the internuclear distance. 31P{13C} REDOR NMR results for synthetic phosphate/(13C)-aragonite coprecipitates show that the broad peak is closely associated with carbonate, exhibiting a 31P-13C dipolar coupling qualitatively consistent with phosphate occupying an anion structural site (i.e., 6 C at 0.32 nm). 31P-detected 1H NMR spectra, which contain signal only from H located near P, show that structural water molecules help accommodate phosphate in the structure. Similar methods can be applied to other elements of potential paleo-proxy interest having NMR-active isotopes, including B, Mg, and Cd.

  14. Stable calcium isotope composition of a pedogenic carbonate in forested ecosystem: the case of the needle fibre calcite (NFC).

    NASA Astrophysics Data System (ADS)

    Milliere, Laure; Verrecchia, Eric; Gussone, Nikolaus

    2014-05-01

    Calcium (Ca), carbon (C) and oxygen (O) are important elements in terrestrial environment, as their biogeochemical cycles are directly related to the storage of atmospheric carbon. Nevertheless, contrarily to C and O, Ca isotope composition has been only poorly studied in the terrestrial carbonates. Needle Fibre Calcite (NFC) is one of the most common pedogenic carbonates, unless its origin is still under debate. Recent studies explain its formation by precipitation inside fungal hyphae. Due to this possible biogenic origin, NFC can be considered as a potential bridge between the biochemistry (precipitation inside organic structure) and geochemistry (pedogenic carbonate related to soil conditions) of the Ca. Thus, the study of the Ca isotope composition of NFC seem to be of first interest in order to shed light on the behaviour of Ca in terrestrial environment, especially when precipitation of secondary carbonates is involved. The sampling site is situated in the Swiss Jura Mountains and has been chosen due to a previous complete study of the C and O isotope composition of NFC in relation to the ecosystem, which represent a good precondition for the understanding of the NFC Ca isotope signatures in this context. In this study, the implication of the fungi in the origin of NFC is investigated, by comparing the Ca isotope composition of NFC and a purely physicochemical calcite cement (LCC), both precipitated in the same environment. The ?44Ca signature of NFC and LCC crystals were used to determine possible differences of the precipitation rate during their formation. NFC and LCC have similar ?18O composition and are supposed to precipitate at the same temperature (Milliere et al., 2011a). Thus the study of Ca isotope composition of NFC seems to demonstrate that the elongated shape of the calcite needle can be explained by different precipitation processes than the rhombohedric calcite crystals precipitated in the same environment; and more precisely, the specific shape of NFC could be ascribed to a growth related to fungal organic molecules or potentially inside fungal hyphae. Three microscopic morphologies of NFC, previously defined (Milliere et al., 2011a), have been also examined in order to trace the evolution of the NFC inside the soil porosity. The Ca isotope composition of the simple needles, which are supposed to be the original form of NFC are the less fractionated compared to the soil solution, whereas the Ca isotope composition of the two other microscopic morphologies, namely the simple needle with nanofibres and the simple needle with overgrowths, are more fractionated, like the LCC, indicating potentially the influence of biogenic processes in the formation of the simple needles. Milliere L, Hasinger O, Bindschedler S, Cailleau G, Spangenberg JE, Verrecchia EP. 2011a. Stable carbon and oxygen isotopic signatures of pedogenic needle fibre calcite. Geoderma 161, 74-87.

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

    SciTech Connect

    B.D. Marshall; K. Futa

    2001-02-07

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

  16. Orientation with a Viking sun-compass, a shadow-stick, and two calcite sunstones under various weather conditions.

    PubMed

    Bernth, Balzs; Blah, Mikls; Egri, Adm; Barta, Andrs; Kriska, Gyrgy; Horvth, Gbor

    2013-09-01

    It is widely accepted that Vikings used sun-compasses to derive true directions from the cast shadow of a gnomon. It has been hypothesized that when a cast shadow was not formed, Viking navigators relied on crude skylight polarimetry with the aid of dichroic or birefringent crystals, called "sunstones." We demonstrate here that a simple tool, that we call "shadow-stick," could have allowed orientation by a sun-compass with satisfying accuracy when shadows were not formed, but the sun position could have reliably been estimated. In field tests, we performed orientation trials with a set composed of a sun-compass, two calcite sunstones, and a shadow-stick. We show here that such a set could have been an effective orientation tool for Vikings only when clear, blue patches of the sky were visible. PMID:24085076

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

    NASA Astrophysics Data System (ADS)

    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 chalk surfaces and partly by adsorbed organic material. GS < GS after extraction < WS < WS after extraction < lborg after extraction ? lborg. The increase of spreading work for WS chalk for ethanol is 21 mN/m and for water is 26 mN/m, a ratio of 21/26 = 0.81. The increase of spreading work for GS chalk for ethanol and water are 36 and 42 mN/m, a ratio of 36/42 = 0.86. The similarity between these ratios leads us to conclude, that the surface that was produced by extraction of the organic material is quite similar for these two samples.The total surface energy increase, after the extraction of organics, for GS and WS was 67 and 49 mJ/m2. Further separation of surface energy into polar and dispersive parts showed that, for both samples, removing organic matter by extraction preferably increases the dispersive component of the surface energy. The contribution from dispersive surface energy to the increase in total surface energy was 87% for GS and 73% for WS chalk. A high relative proportion of dispersive component in the total surface energy is also typical for clay minerals (Chassin et al., 1986; Jouany and Chassin, 1987; Kdr et al., 2006).This demonstrates that the additional adsorption sites that are exposed by the extraction procedure are less polar than the sites originally exposed. Based on these results, we can conclude that chalk particles have surface sites of different polarity and that organic compounds preferentially adsorb at the less polar sites. These additional sites have quite similar surface properties for both North Sea chalk samples with an energy distribution that is similar to clays, that are described in the literature (Chassin et al., 1986; Jouany and Chassin, 1987; Kdr et al., 2006).The lborg chalk initially has minimal adsorbed organic material and the work of wetting changes very little after the treatment for extracting organic material. Considering the lower reproducibility of the results on lborg chalk, the differences in surface energies before and after extraction are considered insignificant and

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

    PubMed Central

    Cama, Jordi; Soler, Josep Maria; Putnis, Christine V

    2014-01-01

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

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

    PubMed

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

    2014-01-01

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

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

    PubMed

    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 ?m 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. PMID:25649514

  1. Bean Seed Imbibition.

    ERIC Educational Resources Information Center

    Hershey, David R.

    1998-01-01

    Enables students to examine the time course for seed imbibition and the pressure generated by imbibing seeds. Provides background information, detailed procedures, and ideas for further investigation. (DDR)

  2. Effect of Second-phase Particles on Static Adjustment of Calcite Grain Boundaries in Carbonate Mylonites

    NASA Astrophysics Data System (ADS)

    Ree, J.; Lee, S.; Jung, H.

    2010-12-01

    Static adjustment of grain boundaries during the waning stage of deformation with sustained heat (e.g. at the end of an orogeny) has not been studied much, although it is important for the interpretation of microstructural status during the main stage of deformation. We report here that static adjustment of calcite grain boundaries is dependent on second-phase particles in carbonate mylonites from the Geounri Shear Zone in the Taebaeksan Basin of South Korea. The carbonate mylonites consist of relic (porphyroclastic) calcites (120-400 ?m) and dynamically recrystallized calcites (30-35 ?m) with second-phase particles (15-20 ?m) of quartz and phyllosilicates. Both calcite grains contain mechanical twins and the twins are wider (10-20 ?m thick) in the relic calcites than in the dynamically recrystallized ones (1-3 ?m thick). In the layers of carbonate mylonite with less than 3% of second phases, grain boundaries of calcites are straight with triple junctions. In contrast, calcite grain boundaries are lobate to wavy in the layers with more than 3% of second phases, suggesting dynamic grain boundary migration. Calcite grains in both layers show a strong lattice preferred orientation indicating dominant slip system of basal with minor one of rhomb . We interpret that the foam texture of calcite in the mylonite layers with less than 3% of second phases was produced during the waning stage of the main deformation with a sustained heat since both syntectonic and posttectonic chloritoid porphyroblasts occur in adjacent phyllonite layers in the shear zone. 3% volume fraction of second-phase particles might be a critical value above which deformation microstructures of the main phase were frozen without static adjustment in our carbonate mylonites.

  3. Low-magnesium uranium-calcite with high degree of crystallinity and gigantic luminescence emission.

    PubMed

    Valle-Fuentes, Francisco-Jose; Garcia-Guinea, Javier; Cremades, Ana; Correcher, Virgilio; Sanchez-Moral, Sergio; Gonzalez-Martin, Rafael; Sanchez-Muoz, Luis; Lopez-Arce, Paula

    2007-01-01

    Cabrera (Madrid) low-Mg calcites exhibit: (i) an unusual twofold elevation in X-ray diffraction pattern intensity; (ii) a 60-fold elevation of luminescence emission, compared to six common natural calcites selected for comparison purposes; (iii) a natural relatively high radiation level of circa 200 nSvh(-1) not detected in 1300 other calcites from the Natural History Museum of Madrid. Calcites were analysed by the X-ray diffraction powder method (XRD), cathodo-luminescence spectroscopy in scanning electron microscopy (CL-SEM), thermoluminescence (TL), differential thermal analysis (DTA), X-ray fluorescence spectrometry (XRF) and particle size distribution (PSD). The Cabrera calcite study shows: (i) helicoidally distributed steps along the (0001) orientation; (ii) protuberance defects onto the (0001) surface, observed by SEM; (iii) XRF chemical contents of 0.03% MgO, 0.013% of Y(2)O(3), and 0.022% of U(3)O(8), with accessory amounts of rare earth elements (REE); (iv) DTA dissociation temperature of 879 degrees C; (v) TL maxima peaks at 233 and 297 degrees C whose areas are 60 times compared to other calcites; (vi) spectra CL-SEM bands at 2.0 and 3.4 eV in the classic structure of Mn(2+) activators; (vii) a twofold XRD pattern explained given that sample is a low-Mg calcite. The huge TL and CL emissions of the Cabrera calcite sample must be linked with the uranyl group presence. This intense XRD pattern in low-Mg calcites could bring into being analytical errors. PMID:17011199

  4. Activators of photoluminescence in calcite: evidence from high-resolution, laser-excited luminescence spectroscopy

    USGS Publications Warehouse

    Pedone, V.A.; Cercone, K.R.; Burruss, R.C.

    1990-01-01

    Laser-excited luminescence spectroscopy of a red-algal, biogenic calcite and a synthetic Mn-calcite can make the distinction between organic and trace-element activators of photoluminescence. Organic-activated photoluminescence in biogenic calcite is characterized by significant peak shifts and increasing intensity with shorter-wavelength excitation and by significant decreases in intensity after heating to ??? 400??C. In contrast, Mn-activated photoluminescence shows no peak shift, greatest intensity under green excitation and limited changes after heating. Examination of samples with a high-sensitivity spectrometer using several wavelengths of exciting light is necessary for identification of photoluminescence activators. ?? 1990.

  5. Calcium isotope ratios in calcitic tests of benthic foraminifers

    NASA Astrophysics Data System (ADS)

    Gussone, Nikolaus; Filipsson, Helena L.

    2010-02-01

    We analysed Ca isotope ratios of the infaunal foraminiferal species Cassidulina laevigata, Elphidium spp., Gyroidinoides spp., and Uvigerina peregrina as well as the epifaunal Cibicidoides wuellerstorfi over a depth-temperature gradient. The calcium isotope ratios of the benthic foraminifers' tests show a distinct anomaly around 4 C. This anomaly is observed in both epi- and infaunal species, but there are also characteristic differences between both. The ?44/40Ca characteristics of benthic foraminifers may be explained by the interference of temperature and carbonate chemistry of the fluid on Ca isotope fractionation. We suggest that Ca isotope composition of benthic foraminifer tests is dominantly controlled by temperature at temperatures higher than 5 C, while in the temperature range below 5 C, calcite saturation ( ?Cc) becomes an increasingly important controlling factor, due to the non linear shape of the ?Cc- ?44/40Ca relation of actively transported calcium. The potential applicability of Ca isotope ratios in benthic foraminifers for reconstruction of either temperatures or ?44/40Ca sw is limited by the complex fractionation pattern below 5 C. However, due to the minor temperature dependence in the temperature range above 5 C, benthic foraminifers might provide a possible alternative archive for ?44Ca sw avoiding some uncertainties associated with planktic records (relocation, habitat/calcification depth, short time climate variability) as long as a defined bottom water temperature above 5 C can be secured.

  6. Alkaline flocculation of Phaeodactylum tricornutum induced by brucite and calcite.

    PubMed

    Vandamme, Dries; Pohl, Philip I; Beuckels, Annelies; Foubert, Imogen; Brady, Patrick V; Hewson, John C; Muylaert, Koenraad

    2015-11-01

    Alkaline flocculation holds great potential as a low-cost harvesting method for marine microalgae biomass production. Alkaline flocculation is induced by an increase in pH and is related to precipitation of calcium and magnesium salts. In this study, we used the diatom Phaeodactylum tricornutum as model organism to study alkaline flocculation of marine microalgae cultured in seawater medium. Flocculation started when pH was increased to 10 and flocculation efficiency reached 90% when pH was 10.5, which was consistent with precipitation modeling for brucite or Mg(OH)2. Compared to freshwater species, more magnesium is needed to achieve flocculation (>7.5mM). Zeta potential measurements suggest that brucite precipitation caused flocculation by charge neutralization. When calcium concentration was 12.5mM, flocculation was also observed at a pH of 10. Zeta potential remained negative up to pH 11.5, suggesting that precipitated calcite caused flocculation by a sweeping coagulation mechanism. PMID:26310384

  7. Ultrasonic Observation of the Calcite-Aragonite Transition

    NASA Technical Reports Server (NTRS)

    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.

  8. Alkaline flocculation of Phaeodactylum tricornutum induced by brucite and calcite

    DOE PAGESBeta

    Vandamme, Dries; Pohl, Philip I.; Beuckels, Annelies; Foubert, Imogen; Brady, Patrick Vane; Muylaert, Koenraad; Hewson, John C.

    2015-08-20

    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 (>7.5 mM). Zeta potential measurementsmore » suggest that brucite precipitation caused flocculation by charge neutralization. When calcium concentration was 12.5 mM, flocculation was also observed at a pH of 10. Furthermore, zeta potential remained negative up to pH 11.5, suggesting that precipitated calcite caused flocculation by a sweeping coagulation mechanism.« less

  9. Control of carbonate alkalinity on Mg incorporation in calcite: Insights on the occurrence of high Mg calcites in diagenetic environments

    NASA Astrophysics Data System (ADS)

    Purgstaller, Bettina; Mavromatis, Vasileios; Dietzel, Martin

    2015-04-01

    High Mg calcites (HMC), with up to 25 mol % of Mg, are common features in early diagenetic environments and are frequently associated with bio-induced anaerobic oxidation of methane (AOM). Such archives hold valuable information about the biogeochemical processes occurring in sedimentary environments in the geological past. Despite the frequency AOM-induced HMC observed in marine diagenetic settings and their potential role in dolomitization, only a minor number of experimental studies has been devoted on deciphering their formation conditions. Thus, in order to improve our understanding on the formation mechanism of HMC induced by elevated carbonate ion concentrations, we precipitated HMC by computer controlled titration of a (Mg,Ca)Cl2 solution at different Mg/Ca ratios into a NaHCO3 solution under precisely defined physicochemical conditions (T = 25.00 0.03C; pH = 8.3 0.1). The formation of carbonates was monitored at a high temporal resolution using in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. We identified two distinct mechanisms of HMC formation. In solutions with molar Mg/Ca ratios ? 1/8 calcium carbonate was precipitated as crystalline phases directly from homogeneous solution. In contrast, higher Mg/Ca ratios induced the formation of Mg-rich ACC (up to 10 mol % of Mg), which was subsequently transformed to HMC with up 20 mol % of Mg. Our experimental results highlight that the finally formed HMC has a higher Mg content than the ACC precursor phase. Considering experimental data for Mg containing ACC transformation to crystalline calcium carbonate from literature, the continuous enrichment of Mg in the precipitate throughout transformation of amorphous to crystalline CaCO3 most likely occurs due to the high carbonate alkalinity (DI