Sample records for calcite

  1. High surface area calcite (United States)

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


    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. Elastic constants of calcite (United States)

    Peselnick, L.; Robie, R.A.


    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.

  3. Arsenic uptake in bacterial calcite (United States)

    Catelani, Tiziano; Perito, Brunella; Bellucci, Francesco; Lee, Sang Soo; Fenter, Paul; Newville, Matthew; Rimondi, Valentina; Pratesi, Giovanni; Costagliola, Pilario


    Bio-mediated processes for arsenic (As) uptake in calcite were investigated by means of X-ray Diffraction (XRD) and X-ray Absorption Spectroscopy (XAS) coupled with X-ray Fluorescence measurements. The environmental bacterial strain Bacillus licheniformis BD5, sampled at the Bullicame Hot Springs (Viterbo, Central Italy), was used to synthesize calcite from As-enriched growth media. Both liquid and solid cultures were applied to simulate planktonic and biofilm community environments, respectively. Bacterial calcite samples cultured in liquid media had an As enrichment factor (Kd) 50 times higher than that from solid media. The XRD analysis revealed an elongation of the crystal lattice along the c axis (by 0.03 Å) for biogenic calcite, which likely resulted from the substitution of larger arsenate for carbonate in the crystal. The XAS data also showed a clear difference in the oxidation state of sorbed As between bacterial and abiotic calcite. Abiotic chemical processes yielded predominantly As(V) uptake whereas bacterial precipitation processes led to the uptake of both As(III) and As(V). The presence of As(III) in bacterial calcite is proposed to result from subsequent reduction of arsenate to arsenite by bacterial activities. To the best of our knowledge, this is the first experimental observation of the incorporation of As(III) in the calcite crystal lattice, revealing a critical role of biochemical processes for the As cycling in nature.

  4. Arsenic uptake in bacterial calcite

    Energy Technology Data Exchange (ETDEWEB)

    Catelani, Tiziano; Perito, Brunella; Bellucci, Francesco; Lee, Sang Soo; Fenter, Paul; Newville, Matthew G.; Rimondi, Valentina; Pratesi, Giovanni; Costagliola, Pilario


    Bio-mediated processes for arsenic (As) uptake in calcite were investigated by means of X-ray Diffraction (XRD) and Xray Absorption Spectroscopy (XAS) coupled with X-ray Fluorescence measurements. The environmental bacterial strain Bacillus licheniformis BD5, sampled at the Bullicame Hot Springs (Viterbo, Central Italy), was used to synthesize calcite from As-enriched growth media. Both liquid and solid cultures were applied to simulate planktonic and biofilm community environments, respectively. Bacterial calcite samples cultured in liquid media had an As enrichment factor (Kd) 50 times higher than that from solid media. The XRD analysis revealed an elongation of the crystal lattice along the c axis (by 0.03Å) for biogenic calcite, which likely resulted from the substitution of larger arsenate for carbonate in the crystal. The XAS data also showed a clear difference in the oxidation state of sorbed As between bacterial and abiotic calcite. Abiotic chemical processes yielded predominantly As(V) uptake whereas bacterial precipitation processes led to the uptake of both As(III) and As(V). The presence of As(III) in bacterial calcite is proposed to result from subsequent reduction of arsenate to arsenite by bacterial activities. To the best of our knowledge, this is the first experimental observation of the incorporation of As(III) in the calcite crystal lattice, revealing a critical role of biochemical processes for the As cycling in nature.

  5. Calcite Dissolution Kinetics (United States)

    Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.


    A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations rate at low degrees of undersaturation by >500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics

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

    DEFF Research Database (Denmark)

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


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

  7. Interaction of alcohols with the calcite surface

    DEFF Research Database (Denmark)

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


    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...

  8. Diffusion of Ca and Mg in Calcite

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  9. Do organic ligands affect calcite dissolution rates? (United States)

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


    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 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.

  10. Calcite Biohybrids as Microenvironment for Stem Cells

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    Razi Vago


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

  11. Two-phase flow and calcite deposition

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


    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.

  12. Acidization of shales with calcite cemented fractures (United States)

    Kwiatkowski, Kamil; Szymczak, Piotr; Jarosiński, Marek


    Investigation of cores drilled from shale formations reveals a relatively large number of calcite-cemented fractures. Usually such fractures are reactivated during fracking and can contribute considerably to the permeability of the resulting fracture network. However, calcite coating on their surfaces effectively excludes them from production. Dissolution of the calcite cement by acidic fluids is investigated numerically with focus on the evolution of fracture morphology. Available surface area, breakthrough time, and reactant penetration length are calculated. Natural fractures in cores from Pomeranian shale formation (northern Poland) were analyzed and classified. Representative fractures are relatively thin (0.1 mm), flat and completely sealed with calcite. Next, the morphology evolution of reactivated natural fractures treated with low-pH fluids has been simulated numerically under various operating conditions. Depth-averaged equations for fracture flow and reactant transport has been solved by finite-difference method coupled with sparse-matrix solver. Transport-limited dissolution has been considered, which corresponds to the treatment with strong acids, such as HCl. Calcite coating in reactivated natural fractures dissolves in a highly non-homogeneous manner - a positive feedback between fluid transport and calcite dissolution leads to the spontaneous formation of wormhole-like patterns, in which most of the flow is focused. The wormholes carry reactive fluids deeper inside the system, which dramatically increases the range of the treatment. Non-uniformity of the dissolution patterns provides a way of retaining the fracture permeability even in the absence of the proppant, since the less dissolved regions will act as supports to keep more dissolved regions open. Evolution of fracture morphology is shown to depend strongly on the thickness of calcite layer - the thicker the coating the more pronounced wormholes are observed. However the interaction between

  13. Calcite dissolution kinetics at the interface between a calcite-rich simulated sediment and natural seawater. (United States)

    Sulpis, O.; Lix, C.; Mucci, A.; Boudreau, B. P.


    Over the past decades, numerous studies of CaCO3 mineral dissolution kinetics have been performed in seawater. Despite this continuous effort, the mechanisms controlling the dissolution are still poorly understood and large discrepancies exist between results of in-situ and laboratory studies, most of which have been carried out under conditions (e.g., mineral suspensions) that are not representative of processes taking place at the seafloor. In this study, we addressed this issue by using a synthetic sediment disk composed of a mixture of calcite and montmorillonite, in a thermostated, stirred-flow reactor over a range of seawater undersaturations in an attempt to simulate conditions encountered at the seafloor. We show that, unlike the higher reaction orders reported in previous studies, the dissolution kinetics of calcite are almost linearly dependent on the seawater undersaturation with respect to calcite when normalized to the exposed surface area of the disks, with a rate constant similar to that derived by Keir (1983) using reagent calcite. Even under quiescent conditions, the calcite dissolution appears to extend well below the sediment-water interface of our synthetic sediment disks. When normalized to the geometric surface area of calcite within the apparent reaction volume, the dissolution kinetics are also nearly linear, with a dissolution rate constant whose value is orders of magnitude lower than previously reported. Keir, R. S. (1983), Variation in the carbonate reactivity of deep-sea sediments: determination from flux experiments, Deep Sea Res., Part A, 30, 279-296.

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

    NARCIS (Netherlands)

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


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

  15. High-Magnesian Calcite Mesocrystals : A Coordination Chemistry Approach

    NARCIS (Netherlands)

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


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

  16. in situ Calcite Precipitation for Contaminant Immobilization

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    Yoshiko Fujita; Robert W. Smith


    in situ Calcite Precipitation for Contaminant Immobilization Yoshiko Fujita ( (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

  17. Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation (United States)

    Reddy, Michael M.


    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.

  18. Neptunium(V) coprecipitation with calcite. (United States)

    Heberling, Frank; Denecke, Melissa A; Bosbach, Dirk


    Coprecipitation experiments of Np(V) and U(VI) with calcite were performed in mixed-flow reactors under steady state conditions at room temperature for up to 400 h at precipitation rates of 1.0 x 10(-8) to 6.8 x 10(-8) mol/(m2 s). The saturation index with respect to calcite varied between 0.04 and 0.95. Initial Np(V) or U(VI) concentrations were 1 micromol/L, 0.01 mol/L NaCl was used as background electrolyte, and pH ranged from 7.8 to 12.8. Partition coefficients for Np(V) were in the range of 0.5-10.3, compared to 0.02 for U(VI). Np L(III) and U L(III) EXAFS were used to characterize the local structural environment of the incorporated actinides. In the case of U(VI), the structural environment is not unambiguously characterized. Our data suggest that Np(V) ions occupy calcium lattice sites. The two axial oxygen atoms of the linear neptunyl moiety substitute two calcite carbonate groups in the first coordination sphere. Thus, four carbonate groups coordinate the neptunyl-ion in a monodentate fashion with four equatorial oxygen atoms (Oeq) at 2.4 A and associated carbon atoms (C) at 3.2 A. The interatomic distances indicate slight structural relaxation of the carbonate groups from their ideal sites. A similar structural model has been reported for U(VI) incorporated into natural calcite.

  19. Relative wettability alteration of calcite surfaces (United States)

    Prabhakar, Sanjay; Liu, Jian; Pantelides, Sokrates

    Enhancement of crude oil recovery from calcite reservoirs remains a major challenge in the oil industry. Crude oil recovery can be enhanced by modifying the relative wettability of calcite reservoirs by injecting sea water. In this work, we consider acetic acid as a model component of crude oil and use the changes of adsorption energies of oil and water molecules induced by additives as a measure of relative wettability alteration of the calcite surface. More specifically, we investigate the influence of Na+, Mg2+, Ca2+, SO42- and Cl- ions on the adsorption energies of water and acetic acid. It is expected that crude oil recovery is enhanced if the modified acetic acid molecule binds weaker than acetic acid. We use density functional theory calculations and show that the presence of Na+ ions reduces oil recovery whereas the presence of Mg and SO4 ions enhance oil recovery. Additionally, we propose a novel possibility of lifting two oil molecules by one Mg2+ ion, which yields enhanced oil recovery, as observed. We also found that Cl merely binds to the surface and has no effect on the adsorption energy of acetic acid, which means that Cl has no effect on oil recovery. This work was supported by a Grant from the Petroleum Institute of Abu Dhabi.

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

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


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

  1. Zinc isotope fractionation during adsorption on calcite (United States)

    Dong, S.; Wasylenki, L. E.


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

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

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


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

  3. The origin of carbon isotope vital effects in coccolith calcite (United States)

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


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

  4. A High-Pressure Phase Transition of Calcite-III (United States)

    Catalli, K. C.; Williams, Q.


    We document the presence of a high-pressure phase transition in metastable calcite-III using infrared spectroscopy. The post-calcite-III transition initiates at a pressure of 15.5 (±2) GPa, and is completed between 25 and 30 GPa. The transition is particularly apparent in the ν4-in-plane bending vibration of the carbonate group, in which two new peaks gradually supplant the doublet associated with calcite-III. Furthermore, both the ν3-asymmetric and ν1-symmetric stretches of the carbonate group in the high-pressure phase appear at considerably lower frequencies than the extrapolated positions of the corresponding calcite-III peaks. The geometry of the carbonate unit within the high-pressure phase is likely closer to trigonal symmetry than in the calcite-III structure, and the C-O bond is probably longer than in the lower pressure calcite-III phase.

  5. Origin of calcite in the glacigenic Virttaankangas complex

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    Nina M. Kortelainen


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

  6. Mechanisms of Subcritical Cracking in Calcite (United States)

    Royne, A.; Dysthe, D. K.; Bisschop, J.


    Brittle materials are characterized by a critical stress intensity factor above which they will fail catastrophically by dynamic cracking. However, it has been observed that materials can also fail at much lower stresses, through slow crack growth, often referred to as subcritical cracking. This phenomenon can take place even in vacuum, but is greatly enhanced by water and other reactive species in the environment. For a given material and environmental condition there is a systematic relationship between the crack tip velocity and the stress intensity factor. The presence of a lower stress limit to subcritical cracking has been predicted from thermodynamics but has not been firmly demonstrated experimentally. This parameter would control the long- term strength of geological materials. Subcritical cracking must necessarily be important in controlling the rock strength in near-surface processes where water and other active species are present and the displacements and stresses are low. Weathering is one example of such a process. Modelling has shown that fracture networks generated by a high degree of subcritical cracking will percolate at much lower fracture densities than purely stochastical fracture networks. This has important implications for how water can move through the crust. Understanding the mechanisms for subcritical crack growth in geological materials is also important in assessing the stability and long term performance of sequestration reservoirs for CO2 or nuclear waste. The mechanism for stress corrosion is well known for glasses and quartz. For carbonate minerals, the mechanism for subcritical crack growth has not been identified, and the only experimental studies on calcitic materials have been on polycrystalline rocks such as marble. Suggested mechanisms include stress corrosion (weakening reactions at the crack tip), preferential dissolution at the crack tip with rapid removal of dissolved species, and environmentally controlled

  7. Neptunium(V) adsorption to calcite. (United States)

    Heberling, Frank; Brendebach, Boris; Bosbach, Dirk


    The migration behavior of the actinyl ions U(VI)O2(2+), Np(V)O2+ and Pu(V,VI)O2(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO2+ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0-9.4) and concentration (0.4 microM-40 microM) conditions. pH is adjusted by variation of CO2 partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85+/-0.01 angstroms for the adsorbed and 1.82+/-0.01 angstroms for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45+/-0.02 angstroms. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46+/-0.01 angstroms. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05+/-0.03 angstroms and 3 to 6 oxygen backscatterers (O-eq2) at 3.31+/-0.02 angstroms. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased KD values after desorption compared to adsorption.

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

    NARCIS (Netherlands)

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


    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.

  9. Molecular ordering of ethanol at the calcite surface

    DEFF Research Database (Denmark)

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


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

  10. Biocementation of Concrete Pavements Using Microbially Induced Calcite Precipitation. (United States)

    Jeong, Jin-Hoon; Jo, Yoon-Soo; Park, Chang-Seon; Kang, Chang-Ho; So, Jae-Seong


    In this study, the feasibility of introducing calcite-forming bacteria into concrete pavements to improve their mechanical performance was investigated. Lysinibacillus sphaericus WJ-8, which was isolated in a previous study and is capable of exhibiting high urease activity and calcite production, was used. When analyzed via scanning electron microscopy (SEM) and X-ray diffraction, WJ-8 showed a significant amount of calcite precipitation. The compressive strength of cement mortar mixed with WJ-8 cells and nutrient medium (urea with calcium lactate) increased by 10% compared with that of the controls. Energy dispersive x-ray spectroscopy analyses confirmed that the increase in strength was due to the calcite formed by the WJ-8 cells.

  11. Immobilization of nanoparticles by occlusion into microbial calcite

    DEFF Research Database (Denmark)

    Skuce, Rebecca L.; Tobler, Dominique Jeanette; MacLaren, Ian


    systems. In this study, the ureolytic bacteria Sporosarcina pasteurii was used to induce calcium carbonate precipitation in the presence of organo-metallic manufactured nanoparticles. As calcite crystals grew the nanoparticles in the solution became trapped inside these crystals. Capture of NPs within...... not influence calcite precipitation at the concentrations used here. Overall, these findings demonstrate that microbially driven mineral precipitation has potential to immobilize nanoparticles in the environment via occlusion....

  12. The role of silicate surfaces on calcite precipitation kinetics

    DEFF Research Database (Denmark)

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


    , labradorite, olivine, basaltic glass and peridotite rock. Calcite saturation was achieved by mixing a CaCl2-rich aqueous solution with a NaHCO3-Na2CO3 aqueous buffer in mixed-flow reactors containing 0.5-2g of mineral, rock, or glass seeds. This led to an inlet fluid calcite saturation index of 0.6 and a p...

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

    Directory of Open Access Journals (Sweden)

    Zhiyong Gao


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

  14. Calcite Farming at Hollow Ridge Cave: Calibrating Net Rainfall and Cave Microclimate to Dripwater and Calcite Chemical Variability (United States)

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


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

  15. On the complex conductivity signatures of calcite precipitation

    Energy Technology Data Exchange (ETDEWEB)

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


    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. Defluoridation of drinking water by boiling with brushite and calcite. (United States)

    Larsen, M J; Pearce, E I F


    Existing methods for defluoridating drinking water involve expensive high technology or are slow, inefficient and/or unhygienic. A new method is now suggested, encompassing brushite and calcite suspension followed by boiling. Our aim was to examine the efficiency of the method and the chemical reactions involved. Brushite, 0.3-0.5 g, and an equal weight of calcite were suspended in 1 litre water containing 5-20 ppm fluoride. The suspensions were boiled in an electric kettle, left to cool and the calcium salts to sediment. Solution ion concentrations were determined and sediments were examined by X-ray diffraction. In distilled water initially containing 5, 10 and 20 ppm fluoride the concentration was reduced to 0.06, 0.4 and 5.9 ppm, respectively. Using Aarhus tap water which contained 2.6 mmol/l calcium the final concentrations were 1.2, 2.5 and 7.7 ppm, respectively, and runs without calcite gave results similar to those with calcite. Without boiling the fluoride concentration remained unaltered, as did the brushite and calcite salts, despite occasional agitation by hand. All solutions were supersaturated with respect to fluorapatite and hydroxyapatite and close to saturation with respect to brushite. Boiling produced well-crystallised apatite and traces of calcite, while boiling of brushite alone left a poorly crystallised apatite. We conclude that boiling a brushite/calcite suspension rapidly converts the two salts to apatite which incorporates fluoride if present in solution, and that this process may be exploited to defluoridate drinking water. Copyright 2002 S. Karger AG, Basel

  17. A Raman spectroscopic comparison of calcite and dolomite. (United States)

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


    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. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Nuclear anomalies in the buccal cells of calcite factory workers. (United States)

    Diler, Songül Budak; Ergene, Serap


    The micronucleus (MN) assay on exfoliated buccal cells is a useful and minimally invasive method for monitoring genetic damage in humans. To determine the genotoxic effects of calcite dust that forms during processing, MN assay was carried out in exfoliated buccal cells of 50 (25 smokers and 25 non-smokers) calcite factory workers and 50 (25 smokers and 25 non-smokers) age- and sex-matched control subjects. Frequencies of nuclear abnormalities (NA) other than micronuclei, such as binucleates, karyorrhexis, karyolysis and 'broken eggs', were also evaluated. Micronuclei and the other aforementioned anomalies were analysed by two way analysis of covariance. The linear correlations between the types of micronucleus and nuclear abnormalities were determined by Spearman's Rho. There was a positive correlation between micronuclei and other types of nuclear abnormalities in accordance with the Spearman's Rho test. Results showed statistically significant difference between calcite fabric workers and control groups. MN and NA frequencies in calcite fabric workers were significantly higher than those in control groups (p < 0.05). The results of this study indicate that calcite fabric workers are under risk of significant cytogenetic damage.

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

    Directory of Open Access Journals (Sweden)

    Songül Budak Diler


    Full Text Available The micronucleus (MN assay on exfoliated buccal cells is a useful and minimally invasive method for monitoring genetic damage in humans. To determine the genotoxic effects of calcite dust that forms during processing, MN assay was carried out in exfoliated buccal cells of 50 (25 smokers and 25 non-smokers calcite factory workers and 50 (25 smokers and 25 non-smokers age- and sex-matched control subjects. Frequencies of nuclear abnormalities (NA other than micronuclei, such as binucleates, karyorrhexis, karyolysis and 'broken eggs', were also evaluated. Micronuclei and the other aforementioned anomalies were analysed by two way analysis of covariance. The linear correlations between the types of micronucleus and nuclear abnormalities were determined by Spearman's Rho. There was a positive correlation between micronuclei and other types of nuclear abnormalities in accordance with the Spearman's Rho test. Results showed statistically significant difference between calcite fabric workers and control groups. MN and NA frequencies in calcite fabric workers were significantly higher than those in control groups (p < 0.05. The results of this study indicate that calcite fabric workers are under risk of significant cytogenetic damage.

  20. Catalysis and chemical mechanisms of calcite dissolution in seawater. (United States)

    Subhas, Adam V; Adkins, Jess F; Rollins, Nick E; Naviaux, John; Erez, Jonathan; Berelson, William M


    Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric [Formula: see text] on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve (13)C-labeled calcites in natural seawater. We show that the time-evolving enrichment of [Formula: see text] in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the (13)C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution-precipitation shifts significantly toward a dissolution-dominated mechanism below about [Formula: see text] Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of [Formula: see text] is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid-solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at [Formula: see text], which we interpret as the onset of homogeneous etch pit nucleation.

  1. Fabrication of Single-Crystalline Calcite Needle-Like Particles Using the Aragonite–Calcite Phase Transition

    Directory of Open Access Journals (Sweden)

    Yuki Kezuka


    Full Text Available Calcium carbonate (CaCO3 occurs in two major polymorphs: rhombohedral calcite and orthorhombic aragonite, the latter is thermodynamically metastable. In this study, we first prepared aragonite needle-like particles by introducing CO2-containing gas into Ca(OH2 aqueous slurry. Then, the resulted aragonite particles were heat treated at 500 °C for 1 h, in order to induce the aragonite–calcite phase transition. Particle structures before and after the heat treatment were characterized mainly by powder X-ray diffractometry (XRD, field emission-scanning electron microscopy (FE-SEM and transmission electron microscopy (TEM. We found that single-crystalline calcite needle-like particles with zigzag surface structures can be fabricated using the phase transition.

  2. Cretaceous joints in southeastern Canada: dating calcite-filled fractures (United States)

    Schneider, David; Spalding, Jennifer; Gautheron, Cécile; Sarda, Philippe; Davis, Donald; Petts, Duane


    To resolve the timing of brittle tectonism is a challenge since the classical chronometers required for analyses are not often in equilibrium with the surrounding material or simply absent. In this study, we propose to couple LA-ICP-MS U-Pb and (U-Th)/He dating with geochemical proxies in vein calcite to tackle this dilemma. We examined intracratonic Middle Ordovician limestone bedrock that overlies Mesoproterozoic crystalline basement, which are cut by NE-trending fault zones that have historic M4-5 earthquakes along their trace. E-W to NE-SW vertical joint sets, the relatively youngest stress recorded in the bedrock, possess 1-7 mm thick calcite veins that seal fractures or coat fracture surfaces. The veins possess intragranular calcite that are lined with fine-grained calcite along the vein margin and can exhibit µm- to mm-scale offset (e.g. displaced fossil fragments in host rock). Calcite d18O and d13C values are analogous to the bulk composition of Middle to Late Ordovician limestones, and suggest vein formation from a source dominated by connate fluids. The calcite contain trails of fluid inclusions commonly along fractures, and 3He/4He analyses indicate a primitive, deep fluid signature (R/Ra: 0.5-2.7). Trace element geochemistry of the calcite is highly variable, generally following the elevated HREE and lower LREE of continental crust trends but individual crystals from a single vein may vary by three orders of magnitude. LA-ICP-MS geochemical traverse across veins show elevated concentrations along (sub)grain boundaries and the vein-host rock contact. Despite abundant helium concentrations, (U-Th)/He dating was unsuccessful yielding highly dispersed dates likely from excess helium derived from the fluid inclusions. However, LA-ICP-MS U-Pb dating on calcite separated from the veins yielded model ages of 110.7 ± 6.8 Ma (MSWD: 0.53; n: 16) to 81.4 ± 8.3 Ma (MSWD: 2.6; n: 17). Since all veins are from the same ENE-trend, we regressed all the calcite dates

  3. Copper incorporation in foraminiferal calcite: results from culturing experiments

    NARCIS (Netherlands)

    Nooijer, L.J. de; Reichart, G.-J.; Dueñas Bohórquez, A.D.B.; Wolthers, M.; Ernst, S.R.; Mason, P.R.D.; Zwaan, G.J. van der


    A partition coefficient for copper (DCu) in foraminiferal calcite has been determined by culturing individuals of two benthic species under controlled laboratory conditions. The partition coefficient of a trace element (TE) is an emperically determined relation between the TE/Ca ratio in seawater

  4. NMR spectroscopic study of organic phosphate esters coprecipitated with calcite (United States)

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


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

  5. Temperature limits for preservation of primary calcite clumped isotope paleotemperatures (United States)

    Henkes, Gregory A.; Passey, Benjamin H.; Grossman, Ethan L.; Shenton, Brock J.; Pérez-Huerta, Alberto; Yancey, Thomas E.


    Solid-state reordering of C-O bonds in the calcite lattice can alter the clumped isotope composition of paleotemperature archives such as fossil brachiopod shells without inducing significant changes in shell microstructure and trace element concentrations, metrics commonly used to gauge preservation quality. To correctly interpret the paleoenvironmental significance of clumped isotope-derived paleotemperatures, it is necessary to understand the temperature-time domain in which solid-state C-O bond reordering is important. We address this question using a combination of laboratory and natural geological experiments on Paleozoic brachiopod shells. The laboratory experiments involve heating fossil brachiopod calcite at different temperatures and times to directly observe rates of 13C-18O bond reordering. The resulting Arrhenius parameters are indistinguishable from values previously determined for an optical calcite with similar trace element compositions. We develop an alternative kinetic model for reordering that accounts for non-first-order reaction progress observed during the initial several hundred minutes of laboratory heating experiments, and show that the simplified first-order approximation model (Passey and Henkes, 2012) predicts reaction progress equally well for temperatures and timescales relevant to sedimentary basins. We evaluate our laboratory-based rate predictions by studying brachiopod calcite from several sedimentary basins with independently constrained burial temperature histories. Specifically, we use the laboratory-derived Arrhenius parameters to predict the evolution of brachiopod calcite clumped isotope compositions during successive one million-year time steps reflecting the burial and exhumation temperature paths of each basin. While this exercise is limited by the relatively large uncertainties in the temperature histories of these basins, we find general correspondence, within error, between predicted and observed clumped isotope values

  6. Uranium Isotope Fractionation During Coprecipitation with Aragonite and Calcite (United States)

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


    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.

  7. Seawater-softening process through formation of calcite ooids

    Directory of Open Access Journals (Sweden)

    A.A. Bakr


    Full Text Available Conventional water-softening processes usually involve the exchange of Na+ ions for Ca2+ and Mg2+ using commercial or synthesized ion exchangers. The differences in chemical compositions of the ooids can be attributed to the formation in different environments. In this paper, ooid grains form inside assembled semi-pilot softening unit through a continuous chemical process involving reaction between bicarbonate ions and added lime using natural seawater. Our sample of Mediterranean seawater has low Mg2+/Ca2+ ratio (1.98% within the range chemically favorable for precipitation of low-Mg calcite ooids. Precipitation of calcite occurs around pure quartz sand grains which act as nucleation points (the bed required for sand vessel is 1.65 l. The shape of the sand grains controls the overall external morphology of the resulting ooids; they vary in size from 0.5 to 3.0 mm and have a high degree of polish due to surface abrasion caused by continuous agitation inside the softening system. Calcite ooid grains (1.53 kg formed within the seawater-softening unit every 18 days have many of the ooid features formed in marine environments. Ooids grow to a significant size, at a rate of about 0.17 mm of one layer thickness per day inside the softening unit. The average weight percent of calcite precipitate is 35.48% after 18 days, at 10 °C, 60 l/min and pH 9.0. The pellets comprise mainly CaCO3 and SiO2 and some metal ions which may substitute for calcium ions in calcite are present only in trace amounts of the total composition.

  8. Molecular ordering of ethanol at the calcite surface. (United States)

    Pasarín, I S; Yang, M; Bovet, N; Glyvradal, M; Nielsen, M M; Bohr, J; Feidenhans'l, R; Stipp, S L S


    To produce biominerals, such as shells, bones, and teeth, living beings create organic compounds that control the growth of the solid phase. Investigating the atomic scale behavior of individual functional groups at the mineral-fluid interface provides fundamental information that is useful for constructing accurate predictive models for natural systems. Previous investigations of the activity of coccolith-associated polysaccharides (CAP) on calcite, using atomic force microscopy (AFM) [Henriksen, K., Young, J. R., Bown, P. R., and Stipp, S. L. S. Palentology 2004, 43 (Part 3), 725-743] and molecular dynamics (MD) modeling [Yang, M., Stipp, S. L. S., and Harding, J. H. Cryst. Growth Des. 2008, 8 (11), 4066-4074], have suggested that OH functional groups control polysaccharide attachment. The purpose of this work was to characterize, using X-ray reflectivity (XR) combined with molecular dynamics (MD) simulations, the structuring on calcite of a layer of the simplest carbon chain molecule that contains an OH group, ethanol (CH(3)-CH(2)-OH). We found evidence that EtOH forms a highly ordered structure at the calcite surface, where the first layer molecules bond with calcite. The ethanol molecules stand up perpendicularly at the interface or nearly so. As a consequence, the fatty, CH(3) ends form a new surface, about 6 Å from the termination of the bulk calcite, and beyond that, there is a thin gap where ethanol density is low. Following is a more disordered layer that is two to three ethanol molecules thick, about 14 Å, where density more resembles that of bulk liquid ethanol. The good agreement between theory and experiment gives confidence that a theoretical approach can offer information about behavior in more complex systems.

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

    DEFF Research Database (Denmark)

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


    The interaction of water and organic molecules with mineral surfaces controls many processes in nature and industry. The thermodynamic property, surface tension, is usually determined from the contact angle between phases, but how does one understand the concept of surface tension at the nanoscale...... in the pore water. Incorporation of MgSO4 into calcite, which is energetically favored, decreases surface tension and releases polar oil compounds......., where particles are smaller than the smallest droplet? We investigated the energy required to exchange Mg2+ and SO4 2- from aqueous solution into calcite {10.4} surfaces using density functional theory. Mg2+ substitution for Ca2+ is favored but only when SO4 2- is also present and MgSO4 incorporates...

  10. Copper incorporation in foraminiferal calcite: results from culturing experiments

    Directory of Open Access Journals (Sweden)

    G. J. van der Zwaan


    Full Text Available A partition coefficient for copper (DCu in foraminiferal calcite has been determined by culturing individuals of two benthic species under controlled laboratory conditions. The partition coefficient of a trace element (TE is an emperically determined relation between the TE/Ca ratio in seawater and the TE/Ca ratio in foraminiferal calcite and has been established for many divalent cations. Despite its potential to act as a tracer of human-induced, heavy metal pollution, data is not yet available for copper. Since partition coefficients are usually a function of multiple factors (seawater temperature, pH, salinity, metabolic activity of the organism, etc., we chose to analyze calcite from specimens cultured under controlled laboratory conditions. They were subjected to different concentrations of Cu2+ (0.1–20 µmol/l and constant temperature (10 and 20°C, seawater salinity and pH. We monitored the growth of new calcite in specimens of the temperate, shallow-water foraminifer Ammonia tepida and in the tropical, symbiont-bearing Heterostegina depressa. Newly formed chambers were analyzed for Cu/Ca ratios by laser ablation-ICP-MS. The estimated partition coefficient (0.1–0.4 was constant to within experimental error over a large range of (Cu/Caseawater ratios and was remarkably similar for both species. Neither did the presence or absence of symbionts affect the DCu, nor did we find a significant effect of temperature or salinity on Cu-uptake.

  11. Effect of Mica and Hematite (001 Surfaces on the Precipitation of Calcite

    Directory of Open Access Journals (Sweden)

    Huifang Xu


    Full Text Available The substrate effect of mica and hematite on the nucleation and crystallization of calcite was investigated using scanning electron microscope (SEM, X-ray diffraction (XRD, and electron backscatter diffraction (EBSD methods. On mica, we found, in the absence of Mg2+, the substrates’ (001 surfaces with hexagonal and pseudo-hexagonal two-dimensional (2-D structure can affect the orientation of calcite nucleation with calcite (001 ~// mica (001 and calcite (010 ~// mica (010 to be the major interfacial relationship. On hematite, we did not observe frequent twinning relationship between adjacent calcite gains, but often saw preferentially nucleation of calcite at surface steps on hematite substrate. We suggest that calcite crystals initially nucleate from the Ca2+ layers adsorbed on the surfaces. The pseudo-hexagonal symmetry on mica (001 surface also leads to the observed calcite (001 twinning. A second and less common orientation between calcite {104} and mica (001 was detected but could be due to local structure damage of the mica surface. Results in the presence of Mg2+ show that the substrate surfaces can weaken Mg toxicity to calcite nucleation and lead to a higher level of Mg incorporation into calcite lattice.

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

    DEFF Research Database (Denmark)

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


    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 bicarbonate is adsorbed on calcite, the predicted pKa for deprotonation is 7.5, which is ∼3 pH units lower than in aqueous solution...

  13. Rheological characterization of the influence of PVOH on calcite suspensions. (United States)

    Eriksson, Rasmus; Kokko, Annaleena; Rosenholm, Jarl B


    Flow properties of the calcite/poly(vinyl alcohol) (PVOH) system were studied and related to the microstructure of the suspension. Adsorption of PVOH on calcite was confirmed, and it results in a shift of the slipping plane out from the surface. The charge density at the surface is assumed to remain unchanged. Since the PVOH used is only partially hydrolyzed, the most likely adsorption conformation consists of residual acetate groups adsorbed to the surface and vinylalcohol groups extending outward from the surface as loops and tails. The microstructure and flow properties of the calcite/PVOH system was found to go through several different stages as a function of PVOH concentration. At low PVOH concentrations a gradual weakening of the initially formed floc network is observed as a function of PVOH concentration. Further addition of PVOH eventually leads to breakdown of the flocs which results in a sterically stabilized suspension with a very low viscosity. This state persists for a narrow concentration range of PVOH, and increasing the PVOH concentration over a certain limit leads to a second gradual increase in viscosity. The system is believed not to undergo reflocculation at high PVOH concentrations as judged from the nonelastic nature of the suspensions. Instead, the polymers form a viscous matrix in the solution while the particles remain well-dispersed. At high enough PVOH concentration, the free volume available for the particles is greatly reduced, and the viscosity increases sharply.

  14. Rate of radiocarbon retention onto calcite by isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Directory of Open Access Journals (Sweden)

    Vučinić Dušica R.


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

  16. Novel Determination of the Orientation of Calcite on Mineral Substrates (United States)

    Zhao, L.; Ji, X.; Teng, H.


    In the threat of global warming, the transformation from CO2 to stable carbonate minerals is significant to geological CO2 sequestration in the long term.Previous efforts have found that when carbonate minerals nucleate on some mineral substrates ,the time of carbon capture can be shorted .Many efforts have been focused on the dynamics when carbonate minerals nucleate on mineral substrates, but few have studied the orientation of carbonate minerals on mineral substrates. In our experiment, we mainly focused on the orientation of calcite on mineral substrates.We mixed NaHCO3 and CaCl2 to nucleate when mineral substrates were added and a multi-parameter analyzer was used to monitor in real time to determine the induction time for nucleation. On the basis of classical nucleation theory, we got a brand new formula to decide the orientation of calcite on mineral substrates. lntind=(2-cosθ+cos3θ)*16πγ3vm2(12*(kBT)3*(lnS)2)+ln(1/N0v)+ ΔEa/(kBT)where θ is the angle between the substrate and the nuclei, tind is the induction time for nucleation, γ is he average surface free energy, N0 is the total number of particles per unit volume of solution, ΔEa is the activation energy for molecular motion across the embryo-matrix interface, S is the supersaturation index ,kB is the Boltzmann constant. Using the new formula above , when biotite was used as substrate mineral ,we found that the angle between the biotite and the nuclei was 119°. Angle measured on SEM images also supported our conclusion above. Combined with SEM and Debye ring analysed by Rigaku 2D data processing software, we only found one point of (006) in Debye ring, unlike (104)(many points in one ring and it meant that the orientation of (104) is random ). That meant (001) of calcite was first formed on biotite (001). In that case we inferred that 119° was formed by (001) of botite and (012) of calcite for the intersection angle of (001) and (012) was 120°. Future research will focus on the orientation of

  17. Incorporation of Mg and Sr in calcite of cultured benthic foraminifera: impact of calcium concentration and associated calcite saturation state

    Directory of Open Access Journals (Sweden)

    M. Raitzsch


    Full Text Available We investigated the effect of the calcium concentration in seawater and thereby the calcite saturation state (Ω 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 Ω at a gradient of −4.3×10−5 per Ω unit. The DSr value of A. tepida does not change with Ω, 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 Ω, while DSr increases considerably with Ω at a gradient of 0.009 per Ω 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

  18. Utilization of calcite produced in Turkey for paper coating

    Directory of Open Access Journals (Sweden)

    Hüdaverdi Eroğlu


    Full Text Available Calcium carbonate is one of the coating pigments widely used in paper industry. Especially, in recent years calcium carbonate filler has gained high importance in alkaline pulping. In Turkey industry actually imports calcium carbonate; whereas, there are rich calcite reservoirs in the country. In this study two different types of domestic ground (GCC calcite samples were used. Physical and chemical properties of calcite samples were tested firstly. CaCO3 percentages of both samples were 97.3 % and 97.6 % (min. 95 % CaCO3. MgCO3 and Fe2O3 percentages were within the desired limits. Brightness values were 95.5 % and 94.5 % and yellowness 1.1 % and 1.5 % elrepho. These values also were within the requested limits. Under 2 microns particle size and over 10 microns particle size fractions were 95 % and 89 % (min. 80 and 1 % and 2 % (max. 2 respectively. Dry matter rates were between 40 %-65 %, for the pilot plant-coating machine. During the preparation of coating color calcium carbonate has been used together with kaolin. The ratios of calcium carbonate to kaolin were 30/70, 40/60, 50/50, 60/40, 70/30, 100/0. In coating color preparation latex was used as a binder because of its wide applications. Latex percentages were 11, 12, and 13 %. Coated papers were glossed and physically tested. As a result, both calcium carbonate samples were found suitable for using in coating color preparation. By the utilization of domestic calcium carbonate in coated paper production, there will be foreign currencies saving.

  19. The sensitized luminescence of manganese-activated calcite (United States)

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


    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.".

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

    Directory of Open Access Journals (Sweden)

    Leif Erik Walther

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

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

    Directory of Open Access Journals (Sweden)

    L. Beaufort


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

  2. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    DEFF Research Database (Denmark)

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


    The wettability of hydrocarbon reservoirs depends on how and to what extent the organic compounds are adsorbed onto the surfaces of calcite, quartz and clay. A model system of synthetic call cite, cyclohexane and the three probe molecules: benzoic acid, benzyl alcohol and benzylamine, have been...... studied by adsorption experiments. The results clearly demonstrate the differences in the adsorption behaviour between probes with different functional groups of varying polarity and acidity. The maximum adsorption decreases in the order: benzoic acid, benzyl alcohol and benzylamine. The order...

  3. Incorporation of Eu(III) into calcite under recrystallization conditions

    Energy Technology Data Exchange (ETDEWEB)

    Hellebrandt, S.E. [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology; Jordan, Norbert [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes; Barkleit, Astrid [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Chemistry of the F-Elements; Schmidt, Moritz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). HGF Young Investigator Group; Hofmann, S.


    The interaction of three calcite powders with Eu(III) under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). Batch contact studies with reaction times from 1 week up to 3 years revealed that the speciation differs from that observed previously in co-precipitation experiments and is dominated by a newly identified species ''γ''. The speed of formation of this species was found to depend greatly on the recrystallization rate of the studied minerals.

  4. Gallium isotope fractionation during Ga adsorption on calcite and goethite (United States)

    Yuan, Wei; Saldi, Giuseppe D.; Chen, JiuBin; Vetuschi Zuccolini, Marino; Birck, Jean-Louis; Liu, Yujie; Schott, Jacques


    Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △71Gasolid-solution up to -1.27‰ and -0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for 'closed system' equilibrium and 'Rayleigh fractionation' models indicates that the experimental data are consistent with a 'closed system' equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga-O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH)4- to 6 and 1.94 Å in the >Ca-O-GaOH(OH2)4+ surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH)20 surface complexes (Ga-O distances of 1.96-1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH)4- is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga-O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its

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

    DEFF Research Database (Denmark)

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


    . Generally the model captures the variation in phosphate adsorption onto calcite as a function of solution composition, though it was necessary to include two types of sorption sites (strong and weak) in the model to reproduce the convex shape of the sorption isotherms.......The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3h) and low concentrations of phosphate (⩽50μM). Sorption of phosphate on calcite...... was studied in 11 different calcite-equilibrated solutions that varied in pH, PCO2, ionic strength and activity of Ca2+, CO32- and HCO3-. Our results show strong sorption of phosphate onto calcite. The kinetics of phosphate sorption onto calcite are fast; adsorption is complete within 2–3h while desorption...

  6. Strong kinetic effects on Sr/Ca ratios in the calcitic bivalve


    Lorrain, Anne; Gillikin, David Paul; Paulet, Yves-Marie; Chauvaud, L.; Le Mercier, Alain; Navez, Jacques; André, Luc


    International audience; Although Sr/Ca ratios in abiogenic calcite are strongly controlled by precipitation rates, such a kinetic effect has never been demonstrated in calcitic bivalve shells. Therefore, we report Sr/Ca ratios together with daily growth rates in the calcitic shells of 4 individuals of the bivalve Pecten maximus (age class I). Ratios of Sr/Ca were found to be variable among individuals that grew at the same location, illustrating that vital effects dominate over environmental ...

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

    Energy Technology Data Exchange (ETDEWEB)

    Bakke, N.E.


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

  8. Isotopic analysis for degradation diagnosis of calcite matrix in mortar. (United States)

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


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

  9. Alternative origins for nannobacteria-like objects in calcite (United States)

    Kirkland, Brenda L.; Lynch, F. Leo; Rahnis, Michael A.; Folk, Robert L.; Molineux, Ian J.; McLean, Robert J. C.


    More than 40 calcite-precipitation experiments were performed under sterile conditions in order to investigate the origins of 25 300 nm spherical-, rod-, and ovoid-shaped objects that have been widely interpreted as evidence of nanometer-scale life (i.e., nannobacteria). Individual experiments included the addition of soluble organic compounds, common species of eubacteria, or phage-induced eubacterial lysates. These experiments indicate that many of the nanometer-scale objects have inorganic or nonnannobacterial origins. In the precipitation experiments, calcite formed euhedral crystals 50 800 nm in diameter and smaller (Bacterial fragments occur as rounded to irregularly shaped particles that included cell-wall fragments, expulsed cytoplasm, and relict capsules that also closely resembled nannobacteria. Acid etching of the large euhedral crystals produced in the precipitation experiments also resulted in the formation of nanometer-scale features that resembled nannobacteria in natural carbonates. The shapes of the etching artifacts vary as a function of the strength of the acid and the duration of etching. Much caution is advisable in interpreting the origin of rounded features <50 nm.

  10. Direct observation of microbial inhibition of calcite dissolution. (United States)

    Lüttge, Andreas; Conrad, Pamela G


    Vertical scanning interferometry (VSI) provides a method for quantification of surface topography at the angstrom to nanometer level. Time-dependent VSI measurements can be used to study the surface-normal retreat across crystal and other solid surfaces during dissolution or corrosion processes. Therefore, VSI can be used to directly and nondestructively measure mineral dissolution rates with high precision. We have used this method to compare the abiotic dissolution behavior of a representative calcite (CaCO(3)) cleavage face with that observed upon addition of an environmental microbe, Shewanella oneidensis MR-1, to the crystal surface. From our direct observations, we have concluded that the presence of the microbes results in a significant inhibition of the rate of calcite dissolution. This inhibition appears to be a 2nd-order effect that is related to the formation of etch pits. The opening of etch pits was greatly inhibited in the presence of added bacteria, suggesting that the bacterial cells exert their effect by inhibiting the formation of etch pits at high-energy sites at the crystal surface caused by lattice defects, e.g., screw or point dislocations. The experimental methodology thus provides a nondestructive, directly quantifiable, and easily visualized view of the interactions of microbes and minerals during weathering (or corrosion) processes or during mineral precipitation.

  11. Angle-dependent rotation of calcite in elliptically polarized light (United States)

    Herne, Catherine M.; Cartwright, Natalie A.; Cattani, Matthew T.; Tracy, Lucas A.


    Calcite crystals trapped in an elliptically polarized laser field exhibit intriguing rotational motion. In this paper, we show measurements of the angle-dependent motion, and discuss how the motion of birefringent calcite can be used to develop a reliable and efficient process for determining the polarization ellipticity and orientation of a laser mode. The crystals experience torque in two ways: from the transfer of spin angular momentum (SAM) from the circular polarization component of the light, and from a torque due to the linear polarization component of the light that acts to align the optic axis of the crystal with the polarization axis of the light. These torques alternatingly compete with and amplify each other, creating an oscillating rotational crystal velocity. We model the behavior as a rigid body in an angle-dependent torque. We experimentally demonstrate the dependence of the rotational velocity on the angular orientation of the crystal by placing the crystals in a sample solution in our trapping region, and observing their behavior under different polarization modes. Measurements are made by acquiring information simultaneously from a quadrant photodiode collecting the driving light after it passes through the sample region, and by imaging the crystal motion onto a camera. We finish by illustrating how to use this model to predict the ellipticity of a laser mode from rotational motion of birefringent crystals.

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

    Directory of Open Access Journals (Sweden)

    Tomihiko Higuchi

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

  13. Ion beam modifications of defect sub-structure of calcite cleavages

    Indian Academy of Sciences (India)


    Planar plastic anisotropy has been studied on irradiated calcite cleavages by measurement of micro- hardness. Keywords. Calcite crystals; ion-bombardment; optical microscopy; ... in the near surface composition (Arnold and Peercy 1980). The ultimate physical properties depend on the inherent defects together with those ...

  14. Removal of Pb(II from aqueous solution by natural and synthetic calcites

    Directory of Open Access Journals (Sweden)

    Ayomadewa Mercy Adesola


    Full Text Available A comparative evaluation of the adsorption capacity and kinetics of Pb(II uptake by both synthetic and natural calcites has been undertaken using batch equilibration technique. The originality of the calcite materials was confirmed by XRD and elemental composition by XRF. The point of zero charge values of 9.57 and 8.20 were obtained by mass titration method for synthetic and natural calcite, respectively. The maximum adsorption capacities of 200 mg/g and 150 mg/g Pb(II of synthetic calcite and natural calcite were obtained at initial lead loading of 1200 mg/L at 25±2 °C, respectively. The study showed a very slight dependence of sorption capacity on the ionic strength and pH, but a strong dependence on the particle size and contact time. The sorption data results fitted better the Langmuir than the Freundlich isotherms. The kinetic data fitted well to pseudo-first order sorption kinetic model with a regression coefficient value of 0.96 and 0.94 for synthetic and natural calcites, respectively. Desorption of Pb(II from calcite surface was achieved with efficiency of 95% using 4 M HNO3. The extent of reversibility of sorption reaction was a function of the equilibrium pH of calcite-Pb(II solution suspension.DOI:

  15. Structure and reactivity of the calcite-water interface. (United States)

    Heberling, Frank; Trainor, Thomas P; Lützenkirchen, Johannes; Eng, Peter; Denecke, Melissa A; Bosbach, Dirk


    The zetapotential of calcite in contact with aqueous solutions of varying composition is determined for pre-equilibrated suspensions by means of electrophoretic measurements and for non-equilibrium solutions by means of streaming potential measurements. Carbonate and calcium are identified as charge determining ions. Studies of the equilibrium solutions show a shift of isoelectric point with changing CO(2) partial pressure. Changes in pH have only a weak effect in non-equilibrium solutions. The surface structure of (104)-faces of single crystal calcite in contact to solutions corresponding to those of the zetapotential investigations is determined from surface diffraction measurements. The results reveal no direct indication of calcium or carbonate inner-sphere surface species. The surface ions are found to relax only slightly from their bulk positions; the most significant relaxation is a ∼4° tilt of the surface carbonate ions towards the surface. Two ordered layers of water molecules are identified, the first at 2.35±0.05Å above surface calcium ions and the second layer at 3.24±0.06Å above the surface associated with surface carbonate ions. A Basic-Stern surface complexation model is developed to model observed zetapotentials, while only considering outer-sphere complexes of ions other than protons and hydroxide. The Basic-Stern SCM successfully reproduces the zetapotential data and gives reasonable values for the inner Helmholtz capacitance, which are in line with the Stern layer thickness estimated from surface diffraction results. Copyright © 2010 Elsevier Inc. All rights reserved.

  16. The quantitative determination of calcite associated with the carbonate-bearing apatites (United States)

    Silverman, Sol R.; Fuyat, Ruth K.; Weiser, Jeanne D.


    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.

  17. Investigating calcite growth rates using a quartz crystal microbalance with dissipation (QCM-D) (United States)

    Cao, Bo; Stack, Andrew G.; Steefel, Carl I.; DePaolo, Donald J.; Lammers, Laura N.; Hu, Yandi


    Calcite precipitation plays a significant role in processes such as geological carbon sequestration and toxic metal sequestration and, yet, the rates and mechanisms of calcite growth under close to equilibrium conditions are far from well understood. In this study, a quartz crystal microbalance with dissipation (QCM-D) was used for the first time to measure macroscopic calcite growth rates. Calcite seed crystals were first nucleated and grown on sensors, then growth rates of calcite seed crystals were measured in real-time under close to equilibrium conditions (saturation index, SI = log ({Ca2+}/{CO32-}/Ksp) = 0.01-0.7, where {i} represent ion activities and Ksp = 10-8.48 is the calcite thermodynamic solubility constant). At the end of the experiments, total masses of calcite crystals on sensors measured by QCM-D and inductively coupled plasma mass spectrometry (ICP-MS) were consistent, validating the QCM-D measurements. Calcite growth rates measured by QCM-D were compared with reported macroscopic growth rates measured with auto-titration, ICP-MS, and microbalance. Calcite growth rates measured by QCM-D were also compared with microscopic growth rates measured by atomic force microscopy (AFM) and with rates predicted by two process-based crystal growth models. The discrepancies in growth rates among AFM measurements and model predictions appear to mainly arise from differences in step densities, and the step velocities were consistent among the AFM measurements as well as with both model predictions. Using the predicted steady-state step velocity and the measured step densities, both models predict well the growth rates measured using QCM-D and AFM. This study provides valuable insights into the effects of reactive site densities on calcite growth rate, which may help design future growth models to predict transient-state step densities.

  18. Infrared spectroscopy and density functional theory investigation of calcite, chalk, and coccoliths-do we observe the mineral surface?

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Hem, Caroline Piper; Schultz, Logan Nicholas


    We have measured infrared spectra from several types of calcite: chalk, freshly cultured coccoliths produced by three species of algae, natural calcite (Iceland Spar), and two types of synthetic calcite. The most intense infrared band, the asymmetric carbonate stretch vibration, is clearly asymme...

  19. Direct nanoscale observations of the coupled dissolution of calcite and dolomite and the precipitation of gypsum. (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    Francesco G. Offeddu


    Full Text Available 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.

  1. Fabrication of porous calcite using chopped nylon fiber and its evaluation using rats. (United States)

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


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

  2. Evaluation of Various Synthesis Methods for Calcite-Precipitated Calcium Carbonate (PCC) Formation

    Energy Technology Data Exchange (ETDEWEB)

    Ramakrishna, Chilakala [Hanil Cement Corporation, Danyang (Korea, Republic of); Thenepalli, Thriveni; Ahn, Ji Whan [Korea Institute of Geoscience and Mineral Resources, Daejeon (Korea, Republic of)


    This review paper evaluates different kinds of synthesis methods for calcite precipitated calcium carbonates by using different materials. The various processing routes of calcite with different compositions are reported and the possible optimum conditions required to synthesize a desired particle sizes of calcite are predicted. This paper mainly focuses on that the calcite morphology and size of the particles by carbonation process using loop reactors. In this regard, we have investigated various parameters such as CO{sub 2} flow rate, Ca (OH){sub 2} concentration, temperature, pH effect, reaction time and loop reactor mechanism with orifice diameter. The research results illustrate the formation of well-defined and pure calcite crystals with controlled crystal growth and particle size, without additives or organic solvents. The crystal growth and particle size can be controlled, and smaller sizes are obtained by decreasing the Ca (OH){sub 2} concentration and increasing the CO{sub 2} flow rate at lower temperatures with suitable pH. The crystal structure of obtained calcite was characterized by using X-ray diffraction method and the morphology by scanning electron microscope (SEM). The result of x-ray diffraction recognized that the calcite phase of calcium carbonate was the dominating crystalline structure.

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

    Directory of Open Access Journals (Sweden)

    C. Neal


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

  4. Measuring Carbon and Oxygen Isotope Uptake into Inorganic Calcite using Crystal Growth Experiments (United States)

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


    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 δ13C 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 = 25°C 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

  5. Monitoring of Calcite Precipitation in Hardwater Lakes with Multi-Spectral Remote Sensing Archives

    Directory of Open Access Journals (Sweden)

    Iris Heine


    Full Text Available Calcite precipitation is a common phenomenon in calcium-rich hardwater lakes during spring and summer, but the number and spatial distribution of lakes with calcite precipitation is unknown. This paper presents a remote sensing based method to observe calcite precipitation over large areas, which are an important prerequisite for a systematic monitoring and evaluation of restoration measurements. We use globally archived satellite remote sensing data for a retrospective systematic assessment of past multi-temporal calcite precipitation events. The database of this study consists of 205 data sets that comprise freely available Landsat and Sentinel 2 data acquired between 1998 and 2015 covering the Northeast German Plain. Calcite precipitation is automatically identified using the green spectra and the metric BGR area, the triangular area between the blue, green and red reflectance value. The validation is based on field measurements of CaCO3 concentrations at three selected lakes, Feldberger Haussee, Breiter Luzin and Schmaler Luzin. The classification accuracy (0.88 is highest for calcite concentrations ≥0.7 mg/L. False negative results are caused by the choice of a conservative classification threshold. False positive results can be explained by already increased calcite concentrations. We successfully transferred the developed method to 21 other hardwater lakes in Northeast Germany. The average duration of lakes with regular calcite precipitation is 37 days. The frequency of calcite precipitation reaches from single time detections up to detections nearly every year. False negative classification results and gaps in Landsat time series reduce the accuracy of frequency and duration monitoring, but in future the image density will increase by acquisitions of Sentinel-2a (and 2b. Our study tested successfully the transfer of the classification approach to Sentinel-2 images. Our study shows that 15 of the 24 lakes have at least one phase of

  6. 88Sr/86Sr fractionation and calcite accumulation rate in the Sea of Galilee (United States)

    Fruchter, N.; Lazar, B.; Nishri, A.; Almogi-Labin, A.; Eisenhauer, A.; Be'eri Shlevin, Y.; Stein, M.


    This study used the Sea of Galilee (Lake Kinneret, northern Israel) as a ;natural laboratory; to investigate the fractionation of the stable Sr isotope ratio (88Sr/86Sr) during precipitation of inorganic (primary) calcite from the lake's water. It was found that the absolute value of the 88Sr/86Sr fractionation factor, Δ88/86Sr, increases as a function of calcite accumulation rate (Δ88/86Sr [‰] = -0.05 to 0.042·log(R) [μmol·m-2·d-1], where R is the accumulation rate). Furthermore, the 87Sr/86Sr and 88Sr/86Sr ratios in the freshwater and brines that enter the lake were used to calculate the contributions of these sources to the lake Sr budget. The 87Sr/86Sr and 88Sr/86Sr ratios were measured in primary calcite, aragonite shells of live Melanopsis, lake water and various water sources to the lake. While the lake's 87Sr/86Sr ratios are determined by the mixture of freshwater of the Jordan River and saline springs, the 88Sr/86Sr ratios of the lake reflect a more complex mass balance that includes the effect of isotopic fractionation associated with the precipitation of primary calcite. Data analysis suggests that long-term accumulation of inorganic calcite depleted in the heavy isotope 88Sr, results in an increase of the δ88/86Sr value of the lake water by 0.05‰. In contrast to the primary inorganic calcite, biogenic aragonite of the Melanopsis shells show a rather constant 88Sr/86Sr water-CaCO3 fractionation of Δ88/86Sr = -0.21‰. Similar Δ88/86Sr values were reported for the precipitation of coralline and inorganic aragonite from seawater and the precipitation of inorganic calcite from various continental waters. The Δ88/86Sr value of inorganic calcite is modulated by the rate of carbonate precipitation, as noted above and shown by precipitation experiments. Massive precipitation of primary calcite with a wide spread of accumulation rates occurs during the spring phytoplankton bloom in Lake Kinneret. The bloom dictates the degree of calcite saturation

  7. Effect of fluid salinity on subcritical crack propagation in calcite (United States)

    Rostom, Fatma; Røyne, Anja; Dysthe, Dag Kristian; Renard, François


    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.

  8. Calcite-forming bacteria for compressive strength improvement in mortar. (United States)

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


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

  9. Biogenic calcite particles from microalgae-Coccoliths as a potential raw material. (United States)

    Jakob, Ioanna; Chairopoulou, Makrina Artemis; Vučak, Marijan; Posten, Clemens; Teipel, Ulrich


    Synthetic calcite (CaCO3) particles are found in a broad range of applications. The geometry of particles produced from limestone or precipitation are versatile but limited to basic shapes. The microalga Emiliania huxleyi produces micro-structured calcite platelets, called coccoliths. This article presents the results of an application-orientated study, which includes characteristic values also used in the calcite industry for particle evaluation. It is demonstrated that coccoliths are significantly different from all industrial particles produced so far. Coccoliths are porous particles, mainly consisted of calcium carbonate, with further elements such as Mg, Si, Sr, and Fe often embedded in their structure. Their structure is extremely sophisticated, while the overall particle morphology and particle size distribution are homogeneous. This study gives a first inside into the potential of these exceptional objects and may set further impulses for their utilization in specific calcite particle applications.

  10. The sixteenth century Alderney crystal: a calcite as an efficient reference optical compass?

    National Research Council Canada - National Science Library

    Albert Le Floch; Guy Ropars; Jacques Lucas; Steve Wright; Trevor Davenport; Michael Corfield; Michael Harrisson


    ... the crystal by inducing roughness of its surface. Although both phenomena have reduced the transparency of the Alderney calcite crystal, we demonstrate that Alderney-like crystals could really have been used as an accurate optical sun compass...

  11. Machine learning approach for predicting the effect of CO2 solubility on dissolution rate of calcite (United States)

    Nomeli, Mohammad


    A machine learning-assisted model is developed to predict the dissolution rate of calcite in saline solutions that are imbibed with dissolved CO2 over a broad range of both subcritical and supercritical conditions. This study focuses on determining the rate of calcite dissolution within a temperature range of 50-100 C and pressures up to 600 bar, relevant for CO2 sequestration in saline aquifers. A general reaction kinetic model is used that is based on the extension of the standard Arrhenius equation with an added, solubility dependent, pH term to account for the saturated concentration of dissolved CO2. The kinetic model helps to obtain a predictive rate equation using machine learning methods to determine the dissolution of calcite as a function of temperature, pressure and salinity. The new rate equation helps us obtain good agreement with experimental data, and it is applied to study the geochemically induced alterations of fracture geometry due to calcite dissolution.

  12. Atomic modifications by synchrotron radiation at the calcite-ethanol interface

    DEFF Research Database (Denmark)

    Pasarín, I. S.; Bovet, Nicolas Emile; Glyvradal, Magni


    -mineral interfaces where the polar OH group, as present in ethanol, plays a key role in their molecular structure and bonding. Also, the chemical evolution observed in the interface provides new insight into the behavior of some complex organic molecules involved in biomineralization processes.......This article reports on studies of the chemical alterations induced by synchrotron radiation at the calcite-ethanol interface, a simple model system for interfaces between minerals and more complex organic molecules containing OH groups. A combination of X-ray reflectivity and X-ray photoelectron...... spectroscopy of natural calcite, cleaved in distilled ethanol to obtain new clean interfaces, indicated that, during a 5 h period, the two top atomic layers of calcite, CaCO3, transform into calcium oxide, CaO, by releasing CO2. Also, the occupation of the first ordered layer of ethanol attached to calcite...

  13. Total alignment of calcite at acidic polydiacetylene films: cooperativity at the organic-inorganic interface. (United States)

    Berman, A; Ahn, D J; Lio, A; Salmeron, M; Reichert, A; Charych, D


    Biological matrices can direct the absolute alignment of inorganic crystals such as calcite. Cooperative effects at an organic-inorganic interface resulted in similar co-alignment of calcite at polymeric Langmuir-Schaefer films of 10,12-pentacosadiynoic acid (p-PDA). The films nucleated calcite at the (012) face, and the crystals were co-aligned with respect to the polymer's conjugated backbone. At the same time, the p-PDA alkyl side chains reorganized to optimize the stereochemical fit to the calcite structure, as visualized by changes in the optical spectrum of the polymer. These results indicate the kinds of interactions that may occur in biological systems where large arrays of crystals are co-aligned.

  14. Kinetic and thermodynamic factors controlling the distribution of SO 32- and Na + in calcites and selected aragonites (United States)

    Busenberg, Eurybiades; Niel Plummer, L.


    Significant amounts of SO 42-, Na +, and OH - are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO 42-. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na +, but very low concentrations of SO 42-. The SO 42- content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na + and SO 42- increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO 42- beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO 42- 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 SO 42- incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient ( D) of SO 42- in calcite at 25.0°C and 0.50 molal NaCl is described by the equation D = k 0 + k 1R where k 0 and k 1 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.

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


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


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

  16. Precipitation of Calcite during the Deposition of Paleogene Sangkarewang Oil Shale, Ombilin Basin, West Sumatra, Indonesia

    Directory of Open Access Journals (Sweden)

    Agus Haris Widayat


    Full Text Available DOI: 10.17014/ijog.2.3.185-197Geochemical and petrographical analyses were carried out to investigate the occurrence of calcite in theformer Ombilin lacustrine lake. The study involves eight samples taken from a 56 m long drill core of Sangkarewangoil shale. Geochemical investigation showed that the samples consist of varied terrigenous input represented by Si, Al, K, and Ti, and autochthonous input represented by S, total organic carbon (TOC, and d13C of bulk organic matter. Along the drill core profile the abundance of autochthonous input decreases upwards, while that of terrigenous input oppositely increases upwards. Petrographical analysis revealed that calcite is a major mineral in the samples. In this study, the abundance of calcite could be represented by the abundance of Ca, as calcite is the only significant Ca containing mineral. Ca is abundant in the samples (8.4% in average and its concentration varies similarly with those of S, TOC, and d13C, suggesting that the element as well as calcite incorporates the autochthonous input. Thevariation of calcite abundance in the drill core profile is considered to be related with primary productivity changes during the development of the former lake. Higher primary productivity represented by more positive of d13C value(-24.8‰ during the deposition of the lower part of the drill core profile promoted the higher amount of deposited organic matter. In such environment, the supersaturation of carbonate ion in lake water was also reached and significant precipitation of authigenic calcite occurred. As the lake developed, the primary productivity decreased as indicated by more negative of d13C value (eventually -26.8‰. This condition led to the decreases of deposited organic matterand calcite in the lake sediments.

  17. Chromium isotopic fractionation in aquatic systems and foraminiferal calcite (United States)

    Wang, X.; Wu, W.; Reinhard, C. T.; Planavsky, N.


    The stable chromium (Cr) isotope system is an emerging proxy for studying the reduction/oxidation (redox) state of the early earth. However, the distribution and isotopic composition of Cr in many modern environments is still poorly known. For this reason, Cr isotope fractionation during biological processes, in rivers, estuaries, seawaters, and modern sediments need to be constrained to calibrate this potentially very useful paleoredox proxy. Here we report concentrations and isotope systematics of dissolved and suspended Cr in the Connecticut River system, and from core-top planktonic foraminiferal calcite from the global ocean. In the Connecticut River system, soil profile samples are unfractionated from bulk silicate Earth (BSE) values. River waters range from -0.2‰ to 0.9‰ (δ53Cr expressed as 53Cr/52Cr relative to NIST SRM 979 standard), with some, but not all tributaries showing seasonal differences. Suspended particulate samples range from -0.1 to 0‰ in autumn and from 0 to 0.1‰ in spring. Modern planktonic foraminifera show a wide range of δ53Cr values, from 0.2‰ to 2.2‰. Such variability seems to be controlled by both seawater heterogeneity and biological fractionation. In summary, weathering environments studied so far suggest wide variability of δ53Cr in rivers and weathered rocks, but with indiscernible correlation with climate types (temperate vs. tropical). In addition, large spatial variability has been detected in the modern seawater and large biological fractionation has been observed during marine biological calcification. These observations provide important guidelines for interpreting the ancient Cr isotope record.

  18. Calcite/aragonite-biocoated artificial coral reefs for marine parks

    Directory of Open Access Journals (Sweden)

    Volodymyr Ivanov


    Full Text Available Natural formation of the coral reefs is complicated by slow biomediated precipitation of calcium carbonate from seawater. Therefore, manufactured artificial coral reefs can be used for the formation of “underwater gardens” in marine parks for the recreational fishing and diving that will protect natural coral reefs from negative anthropogenic effects. Additionally, the coating of the concrete, plastic or wooden surfaces of artificial coral reef with calcium carbonate layer could promote attachment and growth of coral larvae and photosynthetic epibiota on these surfaces. Three methods of biotechnological coating of the artificial coral reefs have been tested: (1 microbially induced calcium carbonate precipitation from concentrated calcium chloride solution using live bacterial culture of Bacillus sp. VS1 or dead but urease-active cells of Yaniella sp. VS8; (2 precipitation from calcium bicarbonate solution; (3 precipitation using aerobic oxidation of calcium acetate by bacteria Bacillus ginsengi strain VSA1. The thickness of biotechnologically produced calcium carbonate coating layer was from 0.3 to 3 mm. Biocoating using calcium salt and urea produced calcite in fresh water and aragonite in seawater. The calcium carbonate-coated surfaces were colonized in aquarium with seawater and hard corals as inoculum or in aquarium with fresh water using cyanobacteria Chlorella sorokiana as inoculum. The biofilm on the light-exposed side of calcium carbonate-coated surfaces was formed after six weeks of incubation and developed up to the average thickness of 250 µm in seawater and about 150 µm in fresh water after six weeks of incubation. The biotechnological manufacturing of calcium carbonate-coated concrete, plastic, or wooden surfaces of the structures imitating natural coral reef is technologically feasible. It could be commercially attractive solution for the introduction of aesthetically pleasant artificial coral reefs in marine parks and

  19. Effect of inorganic anions on the morphology and structure of magnesium calcite. (United States)

    Kralj, Damir; Kontrec, Jasminka; Brecević, Ljerka; Falini, Giuseppe; Nöthig-Laslo, Vesna


    Calcium carbonate was precipitated from calcium hydroxide and carbonic acid solutions at 25 degrees C, with and without addition of different magnesium (MgSO(4), Mg(NO(3))(2) and MgCl(2)) and sodium salts (Na(2)SO(4), NaNO(3) and NaCl) of identical anions, in order to study the mode of incorporation of magnesium and inorganic anions and their effect on the morphology of calcite crystals over a range of initial reactant concentrations and limited c(i)(Mg(2+))/c(i)(Ca(2+)) molar ratios. The morphology, crystal size distribution, composition, structure, and specific surface area of the precipitated crystals, as well as the mode of cation and anion incorporation into the calcite crystal lattice, were studied by a combination of optical and scanning electron microscopy (SEM), electronic counting, a multiple BET method, thermogravimetry, FT-IR spectroscopy, X-ray diffraction (XRD), and electron paramagnetic resonance (EPR) spectroscopy. In the systems of high initial relative supersaturation, precipitation of an amorphous precursor phase preceded the formation of calcite, whereas in those of lower supersaturation calcite was the first and only polymorphic modification of calcium carbonate that appeared in the system. The magnesium content in calcite increased with the magnesium concentration in solution and was correlated with the type of magnesium salt used. Mg incorporation caused the formation of crystals elongated along the calcite c axis and, in some cases, the appearance of new [011] faces. Polycrystalline aggregates were formed when the c(i)(Mg(2+))/c(i)(Ca(2+)) molar ratios in solution were increased. Addition of sulfate ions, alone, caused formation of spherical calcite polycrystalline aggregates.

  20. Microbial dissolution of calcite at T = 28 °C and ambient pCO 2 (United States)

    Jacobson, Andrew D.; Wu, Lingling


    This study used batch reactors to quantify the mechanisms and rates of calcite dissolution in the presence and absence of a single heterotrophic bacterial species ( Burkholderia fungorum). Experiments were conducted at T = 28°C and ambient pCO 2 over time periods spanning either 21 or 35 days. Bacteria were supplied with minimal growth media containing either glucose or lactate as a C source, NH 4+ as an N source, and H 2PO 4- as a P source. Combining stoichiometric equations for microbial growth with an equilibrium mass-balance model of the H 2O-CO 2-CaCO 3 system demonstrates that B. fungorum affected calcite dissolution by modifying pH and alkalinity during utilization of ionic N and C species. Uptake of NH 4+ decreased pH and alkalinity, whereas utilization of lactate, a negatively charged organic anion, increased pH and alkalinity. Calcite in biotic glucose-bearing reactors dissolved by simultaneous reaction with H 2CO 3 generated by dissolution of atmospheric CO 2 (H 2CO 3 + CaCO 3 → Ca 2+ + 2HCO 3-) and H + released during NH 4+ uptake (H + + CaCO 3 → Ca 2+ + HCO 3-). Reaction with H 2CO 3 and H + supplied ˜45% and 55% of the total Ca 2+ and ˜60% and 40% of the total HCO 3-, respectively. The net rate of microbial calcite dissolution in the presence of glucose and NH 4+ was ˜2-fold higher than that observed for abiotic control experiments where calcite dissolved only by reaction with H 2CO 3. In lactate bearing reactors, most H + generated by NH 4+ uptake reacted with HCO 3- produced by lactate oxidation to yield CO 2 and H 2O. Hence, calcite in biotic lactate-bearing reactors dissolved by reaction with H 2CO 3 at a net rate equivalent to that calculated for abiotic control experiments. This study suggests that conventional carbonate equilibria models can satisfactorily predict the bulk fluid chemistry resulting from microbe-calcite interactions, provided that the ionic forms and extent of utilization of N and C sources can be constrained. Because

  1. The Influence of Kinetic Growth Factors on the Clumped Isotope Composition of Calcite (United States)

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


    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

  2. 88Sr/86Sr fractionation and calcite accumulation rate in the Sea of Galilee (United States)

    Fruchter, Noa; Lazar, Boaz; Nishri, Aminadav; Almogi-Labin, Ahuva; Eisenhauer, Anton; Beeri-Shlevin, Yaron; Stein, Mordechai


    This study uses Lake Kinneret (Sea of Galilee, northern Israel) as a natural laboratory to investigate the fractionation of the stable Sr isotope ratio (88Sr/86Sr) during precipitation of authigenic calcite in the water column, and evaluates the dependence of the fractionation 87Sr/86Sr and 88Sr/86Sr ratios in the freshwater and brines that enter the lake are used to calculate the relative contributions of these sources to the Sr budget of the modern lake. The 87Sr/86Sr and 88Sr/86Sr ratios were measured in authigenic calcite, living Melanopsis shells, lake water and various water sources to the lake. While the lake's 87Sr/86Sr ratios are determined by the mixture of freshwater supplied mainly by the Jordan River and saline springs, the 88Sr/86Sr ratios of the lake reflect a more complex mass balance that includes the effect of isotopic fractionation during the precipitation of authigenic calcite. The data show a significant long-term effect of calcite accumulation on the stable Sr isotope ratio of the lake, increasing the 88Sr/86Sr of the water by 0.04 ‰. In contrast to the authigenic calcite, biogenic aragonite shells are shown to have a rather constant 88Sr/86Sr water-CaCO3 fractionation of precipitation of coralline and chemical aragonite from seawater and the precipitation of authigenic calcite from various continental waters. The field data of the present study suggests that the fractionation of 88Sr/86Sr in authigenic calcite represents a kinetic fractionation that varies with precipitation rate, in addition to the constant thermodynamic property. Massive precipitation of authigenic calcite occurs in Lake Kinneret during the spring phytoplankton bloom as the latter increases considerably the degree of calcite saturation. The correlation between accumulation rate can be therefore used as a tool to reconstruct paleo-environmental variations by analyzing the 88Sr/86Sr ratio in authigenic CaCO3 in core sections.

  3. Modeling results of calcium-containing minerals precipitation in the alkaline hydrotherms of Baikal Rift Zone: calcite and dolomite


    Tokarenko, Olga Grigorievna; Zippa, E. V.


    The calculation modeling results of the nitric hydrotherms saturation in Baikal Rift Zone with calcite and dolomite are presented. The calcite and dolomite make the carbonate barrier to thermal waters equilibrium with primary minerals of igneous rocks. In the research territory, there are three main types of geochemical thermal waters which are characterized by the saturation degree with the calcite and dolomite and the proportion of precipitating minerals phases. It has been established that...

  4. Strong kinetic effects on Sr/Ca ratios in the calcitic bivalve Pecten maximus


    A. Lorrain; Gillikin, D. P.; Paulet, Y.-M.; Chauvaud, L.; Le Mercier, A.; Navez, J.; André, L.


    Although Sr/Ca ratios in abiogenic calcite are strongly controlled by precipitation rates, such a kinetic effect has never been demonstrated in calcitic bivalve shells. Therefore, we report Sr/Ca ratios together with daily growth rates in the calcitic shells of four individuals of the bivalve Pecten maximus (age class I). Ratios of Sr/Ca were found to be variable among individuals that grew at the same location, illustrating that vital effects dominate over environmental controls. Although da...

  5. Oxygen isotope fractionation processes in the water-calcite-aragonite system (United States)

    Fohlmeister, Jens; Spötl, Christoph; Plessen, Birgit; Tjallingii, Rik; Schröder-Ritzrau, Andrea; Frank, Norbert; Arps, Jennifer; Leutz, Kathrin; Vollweiler, Nicole; Trüssel, Martin


    The O isotopic composition of speleothems in their pure calcite or pure aragonite polymorphs provides valuable insight into past climate variability. However, robust climatic interpretations become difficult when both polymorphs are present either in different growth layers or as intergrown fabrics. Experimental studies show that the O isotope fractionation between the dissolved carbonate species and CaCO3 is about 0.75‰ (at 10°C) larger for aragonite than for calcite (e.g., Kim et al., 2007, Kim and O'Neil, 1997). The temperature dependence of this offset is negligible for temperature variations typical of most cave systems. However, cave analogue experiments examining this offset are still lacking. Here, we present stable O isotope measurements of a Holocene speleothem from the Swiss Alps, which shows exactly one calcite-aragonite transition along individual growth layers. Oxygen isotope measurements along 'Hendy test'-like traverses across those transitions provide insight into the fractionation behavior of the water-calcite vs. water-aragonite system. We observed a fractionation offset smaller than predicted by laboratory experiments that varies by at least a factor of two. In addition, the observed variations correlate positively with growth rate and negatively with the isotopic composition of the calcite precipitating at the growth axis. The reason for this behavior is still unclear. Trace element analyses across the transitions of growth layers are planned to help understanding this pattern.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  7. Strong kinetic effects on Sr/Ca ratios in the calcitic bivalve Pecten maximus (United States)

    Lorrain, Anne; Gillikin, David P.; Paulet, Yves-Marie; Chauvaud, Laurent; Le Mercier, Alain; Navez, Jacques; André, Luc


    Although Sr/Ca ratios in abiogenic calcite are strongly controlled by precipitation rates, such a kinetic effect has never been demonstrated in calcitic bivalve shells. Therefore, we report Sr/Ca ratios together with daily growth rates in the calcitic shells of four individuals of the bivalve Pecten maximus (age class I). Ratios of Sr/Ca were found to be variable among individuals that grew at the same location, illustrating that vital effects dominate over environmental controls. Although daily growth rate was correlated with shell Sr/Ca ratios, it explained only half of the Sr/Ca variations. However, daily shell surface area increment, an estimation of the total quantity of carbonate precipitated for a given time, explained 74% of the Sr/Ca variability in the shells of P. maximus. This proves, for the first time in a calcitic bivalve, that shell Sr/Ca partitioning is mainly controlled by kinetic effects. The Sr/Ca ratio should therefore be tested as a potential proxy of calcification rate in modern or fossil calcitic biocarbonates.

  8. Influence of calcite on uranium(VI) reactive transport in the groundwater-river mixing zone. (United States)

    Ma, Rui; Liu, Chongxuan; Greskowiak, Janek; Prommer, Henning; Zachara, John; Zheng, Chunmiao


    Calcite is an important, relatively soluble mineral phase that can affect uranium reactive transport in subsurface sediments. This study was conducted to investigate the distribution of calcite and its influence on uranium adsorption and reactive transport in the groundwater-river mixing zone of the Hanford 300A site, Washington State. Simulations using a two-dimensional (2D) reactive transport model under field-relevant hydrological and hydrogeochemical conditions revealed the development of a calcite reaction front through the mixing zone as a result of dynamic groundwater-river interactions. The calcite concentration distribution, in turn, affected the concentrations of aqueous carbonate and calcium, and pH through dissolution, as river waters intruded and receded from the site at different velocities in response to stage changes. The composition variations in groundwater subsequently influenced uranium mobility and discharge rates into the river in a complex fashion. The results implied that calcite distribution and concentration are important variables that need to be quantified for accurate reactive transport predictions of uranium, especially in dynamic groundwater-river mixing zones. © 2013.

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

    Directory of Open Access Journals (Sweden)

    Zijie Ren


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

  10. Modeling results of calcium-containing minerals precipitation in the alkaline hydrotherms of Baikal Rift Zone: calcite and dolomite (United States)

    Tokarenko, O. G.; Zippa, E. V.


    The calculation modeling results of the nitric hydrotherms saturation in Baikal Rift Zone with calcite and dolomite are presented. The calcite and dolomite make the carbonate barrier to thermal waters equilibrium with primary minerals of igneous rocks. In the research territory, there are three main types of geochemical thermal waters which are characterized by the saturation degree with the calcite and dolomite and the proportion of precipitating minerals phases. It has been established that nitric thermal waters-rock system has equilibrium with these minerals, which leads to bonding migrated from the rocks calcium and magnesium by the secondary formed minerals - calcite and dolomite.

  11. Structure of the (1014) Surfaces of Calcite, Dolomite, and Magnesite under Wet and Dry Conditions

    Energy Technology Data Exchange (ETDEWEB)



    Atomistic computer simulation methods have been employed to model the structure of the (10{bar 1}4) surfaces of calcite, dolomite and magnesite. The authors calculations show that under vacuum conditions, calcite undergoes the greatest degree of surface relaxation with rotation and distortion of the carbonate group accompanied by movement of the calcium ion. The magnesite surface is the least distorted of the three carbonates, with dolomite being intermediate to the two end members. When water molecules are placed on the surface to produce complete monolayer coverage, the calcite surface is stabilized and the amount of relaxation is substantially reduced. In contrast, the dolomite and magnesite surfaces are destabilized by hydration as indicated by a significant increase in the surface energies relative to the dry surface.

  12. Experimental and simulated scattering matrices of small calcite particles at 647nm (United States)

    Dabrowska, D. D.; Muñoz, O.; Moreno, F.; Nousiainen, T.; Zubko, E.; Marra, A. C.


    We present measurements of the complete scattering matrix as a function of the scattering angle of a sample of calcite particles. The measurements are performed at 647nm in the scattering angle range from 3° to 177°. To facilitate the use of the experimental data we present a synthetic scattering matrix based on the measurements and defined in the full range from 0° to 180°. The scattering matrix of the calcite sample is modeled using the discrete-dipole approximation. Two sets of shapes, flake-like and rhomboid-like particles giving a total of 15 different targets are considered since both types of shapes have been found in our calcite sample. In our computations we use the measured size distribution of the calcite sample truncated at 1.2μm. We present a theoretical study of the impact of birefringence on the computed scattering matrix elements for both sets of shapes. Four different cases regarding the composition of the calcite particles are considered: two isotropic cases corresponding to the ordinary and extraordinary refractive index of calcite, respectively; one equivalent isotropic case analogous to internal mixing; and birefringence fully accounted for. Numerical simulations are compared with the experimental data. We find that birefringence has little impact on the calculated phase functions but it has a significant effect on the polarization-related elements of the scattering matrix. Moreover, we conclude that the shape of the targets (flakes or irregular rhomboids) has a much stronger effect on the computed scattering matrix elements than birefringence.

  13. Characteristics of a calcite "limestone"-marble from Macedonia, used as flux material

    Directory of Open Access Journals (Sweden)

    Hristova E.


    Full Text Available The phase characteristics of calcite "limestone"-marble from Banjany area village (near Skopje, Macedonia were examined by means of XRD, SEM microscope in polarizing and reflected lights, chemical, DT/TG-analyses. It was concluded as follows: - calcite (CaCO3 is a major mineral component (cca 80-90 % prevailing in the marble over the other minerals - dolomite is generally of minor importance (cca 10-20 % in the rock - quartz, micas graphite, pyrite represent typical accessories. As result of the mentioned phase characteristics, this raw materials was for a long time (more than 30 years used as flux in the iron and steel metallurgy in Macedonia.

  14. Thickness and structure of the water film deposited from vapour on calcite surfaces

    DEFF Research Database (Denmark)

    Bohr, Jakob; Wogelius, Roy A.; Morris, Peter M.


    Synchrotron X-ray reflectivity (SXR) was used to measure the thickness of the water film that adsorbs on a {10¯14} cleavage surface of calcite (CaCO3) in a sample chamber where relative humidity could be controlled within the range from......Synchrotron X-ray reflectivity (SXR) was used to measure the thickness of the water film that adsorbs on a {10¯14} cleavage surface of calcite (CaCO3) in a sample chamber where relative humidity could be controlled within the range from...

  15. Field Experiment to Stimulate Microbial Urease Activity in Groundwater for in situ Calcite Precipitation (United States)

    Fujita, Y.; Taylor, J. L.; Tyler, T. L.; Banta, A. B.; Reysenbach, A. L.; Delwiche, M. E.; McLing, T. L.; Colwell, F. S.; Smith, R. W.


    Groundwater contamination by radionuclides and metals from past weapons processing activities is a significant problem for the United States Department of Energy. Removal of these pollutants from the subsurface can be prohibitively expensive and result in worker exposure, and therefore in situ containment and stabilization is an attractive remediation alternative. One potential approach for the immobilization of certain radionuclides and metals (e.g., 90Sr, 60Co, Pb, Cd) is to induce geochemical conditions that promote co-precipitation in calcite. Many aquifers in the arid western US are calcite-saturated, and calcite precipitated under an engineered remediation scheme in such aquifers should remain stable even after return to ambient conditions. We have proposed that an effective way to promote calcite precipitation is to utilize native microorganisms that hydrolyze urea. Urea hydrolysis results in carbonate and ammonium production, and an increase in pH. The increased carbonate alkalinity favors calcite precipitation, and the ammonium serves the additional role of promoting desorption of sorbed metal ions from the aquifer matrix by ion exchange. The desorbed metals are then accessible to co-precipitation in calcite, which can be a longer-term immobilization mechanism than sorption. The ability to hydrolyze urea is common among environmental microorganisms, and we have shown in the laboratory that microbial urea hydrolysis can be linked to calcite precipitation and co-precipitation of the trace metal strontium. As a next step in the development of our remediation approach, we aimed to demonstrate that we can stimulate the native microbial community to express urease in the field. In 2002 we conducted a preliminary field trial of our approach, using a well in the Eastern Snake River Plain Aquifer in Idaho Falls, Idaho, USA. A dilute molasses solution (0.00075%) was injected to promote overall biological growth, and then urea (50 mM) was added to the aquifer

  16. New Shocked Calcite and Fe Grains from Noerdlingen Ries Impact Crater (United States)

    Miura, Y.


    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

  17. Interactions of the Calcite {10.4} Surface with Organic Compounds: Structure and Behaviour at Mineral – Organic Interfaces

    DEFF Research Database (Denmark)

    Hakim, S. S.; Olsson, M. H. M.; Sørensen, H. O.


    that control crystal growth with organic macromolecules. Carbonate rocks, composed almost exclusively of calcite, host drinking water aquifers and oil reservoirs. In this study, we examined the ordering behaviour of several organic compounds and the thickness of the adsorbed layers formed on calcite {10...

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

    DEFF Research Database (Denmark)

    Sand, K K; Yang, M; Makovicky, E


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

  19. Morphology and formation mechanism in precipitation of calcite induced by Curvibacter lanceolatus strain HJ-1 (United States)

    Zhang, Chonghong; Li, Fuchun; Lv, Jiejie


    Precipitation of calcium carbobate induced by microbial activities is common occurrence in controlled solution, but the formation mechanism and morphology in precipitation of calcite in solution systems is unclear, and the role of microbes is disputed. Here, culture experiment was performed for 50 days using the Curvibacter lanceolatus strain HJ-1 in a M2 culture medium, and the phase composition and morphology of the precipitates were characterized by the X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and scanning electron microscopy (SEM) techniques. We show that the precipitation processes in our experiment lead to unusual morphologies of crystals corresponding to different growth stages, and the morphologies of the precipitated crystal aggregates ranging from the main rod-, cross-, star-, cauliflower-like morphologies to spherulitic structure. The complex and unusual morphologies of the precipitated calcite by strain HJ-1 may provide a reference point for better understanding the biomineralization mechanism of calcite, moreover, morphological transition of minerals revealed that the multi-ply crystals-aggregation mechanism for calcite growth in crystallisation media.

  20. Simple, simultaneous gravimetric determination of calcite and dolomite in calcareous soils (United States)

    Literature pertaining to determination of calcite and dolomite is not modern and describes slow methods that require expensive specialized apparatus. The objective of this paper was to describe a new method that requires no specialized equipment. Linear regressions and correlation coefficients for...

  1. Impacts of pH and [CO32-] on the incorporation of Zn in foraminiferal calcite

    NARCIS (Netherlands)

    van Dijk, Inge; de Nooijer, Lennart J.; Wolthers, Mariëtte; Reichart, Gert-Jan


    The trace elemental composition of foraminiferal shell calcite is known to reflect the environment in which the shell was precipitated. Whereas conservative elements incorporated in foraminiferal shell carbonate reflect factors such as temperature (Mg), carbonate chemistry (B) and salinity (Na), the

  2. Unusual biogenic calcite structures in two shallow lakes, James Ross Island, Antarctica (United States)

    Elster, J.; Nedbalová, L.; Vodrážka, R.; Láska, K.; Haloda, J.; Komárek, J.


    The floors of two shallow endorheic lakes, located on volcanic surfaces on James Ross Island, are covered with calcareous organosedimentary structures. Their biological and chemical composition, lake water characteristics, and seasonal variability of the thermal regime are introduced. The lakes are frozen down to the bottom for 8-9 months a year and their water chemistry is characterised by low conductivity and neutral to slightly alkaline pH. The photosynthetic microbial mat is composed of filamentous cyanobacteria and microalgae that are considered to be Antarctic endemic species. The mucilaginous black biofilm is covered by green spots formed by a green microalga and the macroscopic structures are packed together with fine material. Thin sections consist of rock substrate, soft biofilm, calcite spicules and mineral grains originating from different sources. The morphology of the spicules is typical of calcium carbonate monocrystals having a layered structure and specific surface texture, which reflect growth and degradation processes. The spicules' chemical composition and structure correspond to pure calcite. The lakes' age, altitude, morphometry, geomorphological and hydrological stability, including low sedimentation rates, together with thermal regime predispose the existence of this community. We hypothesise that the precipitation of calcite is connected with the photosynthetic activity of the green microalgae that were not recorded in any other lake in the region. This study has shown that the unique community producing biogenic calcite spicules is quite different to any yet described.

  3. Fulvic acid-like organic compounds control nucleation of marine calcite under suboxic conditions

    NARCIS (Netherlands)

    Neuweiler, F.; D'Orazio, M.; Immenhauser, A.M.; Geipel, G.; Heise, K.H.; Cocozza, C.; Miano, T.M.


    Intracrystalline organic compounds, enclosed within in situprecipitated marine microcrystalline calcite (automicrite), might represent either an inclusion or the catalyst of such precipitation. We use evidence from a Lower Cretaceous deep-water carbonate mound to show (1) the original source, (2)

  4. Binding of ethanol on calcite: the role of the OH bond and its relevance to biomineralization. (United States)

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


    The interaction of OH-containing compounds with calcite, CaCO(3), such as is required for the processes that control biomineralization, has been investigated in a low-water solution. We used ethanol (EtOH) as a simple, model, OH-containing organic compound, and observed the strength of its adsorption on calcite relative to OH from water and the consequences of the differences in interaction on crystal growth and dissolution. A combination of atomic force microscopy (AFM) and molecular dynamics (MD) simulations showed that EtOH attachment on calcite is stronger than HOH binding and that the first adsorbed layer of ethanol is highly ordered. The strong ordering of the ethanol molecules has important implications for mineral growth and dissolution because it produces a hydrophobic layer. Ethanol ordering is disturbed along steps and at defect sites, providing a bridge from the bulk solution to the surface. The strong influence of calcite in structuring ethanol extends further into the liquid than expected from electrical double-layer theory. This suggests that in fluids where water activity is low, such as in biological systems optimized for biomineralization, organic molecules can control ion transport to and from the mineral surface, confining it to specific locations, thus providing the organism with control for biomineral morphology.


    Directory of Open Access Journals (Sweden)

    Jan Ondruska


    Full Text Available The temperature dependences of the electrical DC conductivity of calcite waste, kaolinite and illite based ceramics were measured in the temperature range of 20 - 1050oC. The ceramic mass that was used was a mixture of 60 wt. % kaolinitic-illitic clay, 20 - 40 wt. % of this clay was fired at 1000oC for 90 min and 0, 10 and 20 wt. % of calcite waste. During heating, several processes take place - the release of the physically bound water, the burning of organic impurities, the dehydroxylation of kaolinite and illite, the decomposition of calcite, and the creation of anorthite and mullite. All of these processes were checked by means of differential thermal analysis (DTA, derivative thermogravimetry (DTG and thermodilatometry (TDA. At low temperatures (20 - 200oC, due to the release and decomposition of physically bound water, H+ and OH- are dominant charge carriers. After completion of release of physically bound water, up to the start of dehydroxylation at the temperature of ~ 450oC, the DC conductivity is dominated by a transport of Na+, K+, and Ca2+ ions. During dehydroxylation, H+ and OH- ions, which are released from kaolinite and illite lattices, contribute to the DC conductivity. Decomposition of calcite runs between ~ 700oC and 900oC. The glassy phase has a dominant influence on the DC conductivity in the fired ceramics. Its high conductivity is determined by the high mobility of Na+, K+, and Ca2+ ions.

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

    DEFF Research Database (Denmark)

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


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

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

    DEFF Research Database (Denmark)

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


    , 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...

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

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


    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

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

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


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

  10. The influence of mineralization pathways on the Mg content and fractionation patterns in calcite (United States)

    Dove, P. M.; Wang, D.; DeYoreo, J.


    Chemical proxy models are based upon the long-standing assumption that the uptake of minor and trace elements into a growing mineral reflects equilibrium fractionation processes. This picture is rooted in fundamental assumptions from BCF crystal growth theory- the thermodynamic-based model that was derived for step growth at very near equilibrium conditions. However, the original assumptions of this theory have been lost. Moreover, the applicability of step growth processes to biomineralization is being called into question with the realization that many carbonate biominerals form by non-classical processes. Here, mineralization begins with the accumulation of an amorphous calcium carbonate (ACC) in a localized environment that subsequently transforms to the complex mesocrystal/organic composites we know as skeletal structures. This study investigates the Mg content of calcites that form from ACC over a range of Mg/Ca ratios. At low Mg/Ca levels where Mg content is insufficient to inhibit step growth, the ACC transforms into crystallites of Mg calcites with 0-20 mol % MgCO3. These calcites exhibit the expected linear fractionation with Mg/Ca of the initial solution. In contrast, when initial Mg levels are above the threshold where step growth is prohibited, ACC transforms to nanoparticle aggregates of very high Mg calcite (30-50 mol% MgCO3). The Mg content of calcites formed by this process is approximately independent of solution composition- without evidence of fractionation. Mineralization is biased to this alternative pathway when the Mg content of the local environment is too high for calcite growth and saturation increases rapidly to reach ACC solubility before aragonite precipitation can occur. The pathway is allowed because high levels of supersaturation render thermodynamic barriers to nucleation less significant than kinetic barriers, which are apparently larger for the crystalline phases. Thus, the alternative pathway is a consequence of interplays

  11. Impact of amorphous precursor phases on magnesium isotope signatures of Mg-calcite (United States)

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


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

  12. Controlling the size and morphology of precipitated calcite particles by the selection of solvent composition (United States)

    Konopacka-Łyskawa, Donata; Kościelska, Barbara; Karczewski, Jakub


    Precipitated calcium carbonate is used as an additive in the manufacture of many products. Particles with specific characteristics can be obtained by the selection of precipitation conditions, including temperature and the composition of solvent. In this work, calcium carbonate particles were obtained in the reaction of calcium hydroxide with carbon dioxide at 65 °C. Initial Ca(OH)2 suspensions were prepared in pure water and aqueous solutions of ethylene glycol or glycerol of the concentration range up to 20% (vol.). The course of reaction was monitored by conductivity measurements. Precipitated solids were analyzed by FTIR, XRD, SEM and the particles size distribution was determined by a laser diffraction method. The adsorption of ethylene glycol or glycerol on the surface of scalenohedral and rhombohedral calcite was testes by a normal-phase high-performance liquid chromatography. The addition of organic solvents changed the viscosity of reaction mixtures, the rate of carbon dioxide absorption and the solubility of inorganic components and therefore influence calcium carbonate precipitation conditions. All synthesized calcium carbonate products were in a calcite form. Scalenohedral calcite crystals were produced when water was a liquid phase, whereas addition of organic solvents resulted in the formation of rhombo-scalenohedral particles. The increase in organic compounds concentration resulted in the decrease of mean particles size from 2.4 μm to 1.7 μm in ethylene glycol solutions and to 1.4 μm in glycerol solutions. On the basis of adsorption tests, it was confirm that calcite surface interact stronger with glycerol than ethylene glycol. The interaction between scalenohedral calcite and used organic additives was higher in comparison to the pure rhombohedral form applied as a stationary phase.

  13. Review of aragonite and calcite crystal morphogenesis in thermal spring systems (United States)

    Jones, Brian


    Aragonite and calcite crystals are the fundamental building blocks of calcareous thermal spring deposits. The diverse array of crystal morphologies found in these deposits, which includes monocrystals, mesocrystals, skeletal crystals, dendrites, and spherulites, are commonly precipitated under far-from-equilibrium conditions. Such crystals form through both abiotic and biotic processes. Many crystals develop through non-classical crystal growth models that involve the arrangement of nanocrystals in a precisely controlled crystallographic register. Calcite crystal morphogenesis has commonly been linked to a ;driving force;, which is a conceptual measure of the distance of the growth conditions from equilibrium conditions. Essentially, this scheme indicates that increasing levels of supersaturation and various other parameters that produce a progressive change from monocrystals and mesocrystals to skeletal crystals to crystallographic and non-crystallographic dendrites, to dumbbells, to spherulites. Despite the vast amount of information available from laboratory experiments and natural spring systems, the precise factors that control the driving force are open to debate. The fact that calcite crystal morphogenesis is still poorly understood is largely a reflection of the complexity of the factors that influence aragonite and calcite precipitation. Available information indicates that variations in calcite crystal morphogenesis can be attributed to physical and chemical parameters of the parent water, the presence of impurities, the addition of organic or inorganic additives to the water, the rate of crystal growth, and/or the presence of microbes and their associated biofilms. The problems in trying to relate crystal morphogenesis to specific environmental parameters arise because it is generally impossible to disentangle the controlling factor(s) from the vast array of potential parameters that may act alone or in unison with each other.

  14. Impact of trace metals on the water structure at the calcite surface (United States)

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


    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.

  15. Calcite dissolution by Brevibacterium sp. SOTI06: A futuristic approach for the reclamation of calcareous sodic soils

    Directory of Open Access Journals (Sweden)

    Tamilselvi S.M


    Full Text Available Assessing the ability of soil microorganisms to dissolute poorly soluble native calcite to supply Ca2+ is a new area to be explored in reclaiming sodic soils by supplying adequate Ca2+ and reducing the recurrent sodicity. Hence, the present study aimed to isolate a calcite dissolving bacteria (CDB from calcareous sodic soils and to understand the mechanism of calcite dissolution. Of the thirty three CDB isolates recovered from the calcareous sodic soils of Tamil Nadu (Coimbatore, Ramnad and Trichy, eleven isolates were screened for calcite dissolution based on titratable acidity. 16S rRNA gene sequence analysis of the three best isolates viz., SORI09, SOTI05 and SOTI06 revealed 99 % similarity to Bacillus aryabhattai, 100 % to B. megaterium and 93 % to Brevibacterium sp., respectively. Among them, Brevibacterium sp. SOTI06 released more Ca2+ (3.6 g.l-1 by dissolving 18.6 % of the native calcite. The spectral data of FTIR also showed reduction in the intensity of calcite (55.36 to 41.27 by the isolate at a wave number of 1636 cm-1 which confirmed the dissolution. Besides producing organic acids (gluconic acid and acetic acid, Brevibacterium sp. SOTI06 also produced siderophore (91.6 % and extracellular polysaccharides (EPS, 13.3 µg. ml-1 which might have enhanced the calcite dissolution.

  16. Calcite Dissolution by Brevibacterium sp. SOTI06: A Futuristic Approach for the Reclamation of Calcareous Sodic Soils. (United States)

    Tamilselvi, S M; Thiyagarajan, Chitdeshwari; Uthandi, Sivakumar


    Assessing the ability of soil microorganisms to dissolute poorly soluble native calcite to supply Ca2+ is a new area to be explored in reclaiming sodic soils by supplying adequate Ca2+ and reducing the recurrent sodicity. Hence, the present study aimed to isolate a calcite dissolving bacteria (CDB) from calcareous sodic soils and to understand the mechanism of calcite dissolution. Of the 33 CDB isolates recovered from the calcareous sodic soils of Tamil Nadu (Coimbatore, Ramnad, and Trichy), 11 isolates were screened for calcite dissolution based on titratable acidity. 16S rRNA gene sequence analysis of the three best isolates viz., SORI09, SOTI05, and SOTI06 revealed 99% similarity to Bacillus aryabhattai, 100% to B. megaterium, and 93% to Brevibacterium sp., respectively. Among them, Brevibacterium sp. SOTI06 released more Ca2+ (3.6 g.l-1) by dissolving 18.6% of the native calcite. The spectral data of FTIR also showed reduction in the intensity of calcite (55.36-41.27) by the isolate at a wave number of 1636 cm-1 which confirmed the dissolution. Besides producing organic acids (gluconic acid and acetic acid), Brevibacterium sp. SOTI06 also produced siderophore (91.6%) and extracellular polysaccharides (EPS, 13.3 μg. ml-1) which might have enhanced the calcite dissolution.

  17. Influence of water on clumped-isotope bond reordering kinetics in calcite (United States)

    Brenner, Dana C.; Passey, Benjamin H.; Stolper, Daniel A.


    Oxygen self-diffusion in calcite and many other minerals is considerably faster under wet conditions relative to dry conditions. Here we investigate whether this "water effect" also holds true for solid-state isotope exchange reactions that alter the abundance of carbonate groups with multiple rare isotopes ('clumped' isotope groups) via the process of solid-state bond reordering. We present clumped-isotope reordering rates for optical calcite heated under wet, high-pressure (100 MPa) conditions. We observe only modest increases in reordering rates under such conditions compared with rates for the same material reacted in dry CO2 under low-pressure conditions. Activation energies under wet, high-pressure conditions are indistinguishable from those for dry, low-pressure conditions, while rate constants are resolvably higher (up to ∼3 times) for wet, high-pressure relative to dry, low-pressure conditions in most of our interpretations of experimental results. This contrasts with the water effect for oxygen self-diffusion in calcite, which is associated with lower activation energies, and diffusion coefficients that are ≥103 times higher compared with dry (pure CO2) conditions in the temperature range of this study (385-450 °C). The water effect for clumped-isotopes leads to calculated apparent equilibrium temperatures ("blocking temperatures") for typical geological cooling rates that are only a few degrees higher than those for dry conditions, while O self-diffusion blocking temperatures in calcite grains are ∼150-200 °C lower in wet conditions compared with dry conditions. Since clumped-isotope reordering is a distributed process that occurs throughout the mineral volume, our clumped-isotope results support the suggestion of Labotka et al. (2011) that the water effect in calcite does not involve major changes in bulk (volume) diffusivity, but rather is primarily a surface phenomenon that facilitates oxygen exchange between the calcite surface and external

  18. Microstructure of calcite deformed by high-pressure torsion: An X-ray line profile study (United States)

    Schuster, Roman; Schafler, Erhard; Schell, Norbert; Kunz, Martin; Abart, Rainer


    Calcite aggregates were deformed to high strain using high-pressure torsion and applying confining pressures of 1-6 GPa and temperatures between room temperature and 450 °C. The run products were characterized by X-ray diffraction, and key microstructural parameters were extracted employing X-ray line profile analysis. The dominant slip system was determined as r { 10 1 bar 4 } ⟨ 2 bar 021 ⟩ with edge dislocation character. The resulting dislocation density and the size of the coherently scattering domains (CSD) exhibit a systematic dependence on the P-T conditions of deformation. While high pressure generally impedes recovery through reducing point defect mobility, the picture is complicated by pressure-induced phase transformations in the CaCO3 system. Transition from the calcite stability field to those of the high-pressure polymorphs CaCO3-II, CaCO3-III and CaCO3-IIIb leads to a change of the microstructural evolution with deformation. At 450 °C and pressures within the calcite stability field, dislocation densities and CSD sizes saturate at shear strains exceeding 10 in agreement with earlier studies at lower pressures. In the stability field of CaCO3-II, the dislocation density exhibits a more complex behavior. Furthermore, at a given strain and strain rate, the dislocation density increases and the CSD size decreases with increasing pressure within the stability fields of either calcite or of the high-pressure polymorphs. There is, however, a jump from high dislocation densities and small CSDs in the upper pressure region of the calcite stability field to lower dislocation densities and larger CSDs in the low-pressure region of the CaCO3-II stability field. This jump is more pronounced at higher temperatures and less so at room temperature. The pressure influence on the deformation-induced evolution of dislocation densities implies that pressure variations may change the rheology of carbonate rocks. In particular, a weakening is expected to occur at

  19. 3D Mapping of calcite and a demonstration of its relevance to permeability evolution in reactive fractures (United States)

    Ellis, Brian R.; Peters, Catherine A.


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

  20. Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure (United States)

    Busenberg, Eurybiades; Plummer, L. Niel


    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

  1. Uranium immobilization by sulfate-reducing biofilms grown on hematite, dolomite, and calcite. (United States)

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


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

  2. Geochemistry of speleothems affected by aragonite to calcite recrystallization - Potential inheritance from the precursor mineral (United States)

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


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

  3. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers. (United States)

    Ihli, Johannes; Clark, Jesse N; Côté, Alexander S; Kim, Yi-Yeoun; Schenk, Anna S; Kulak, Alexander N; Comyn, Timothy P; Chammas, Oliver; Harder, Ross J; Duffy, Dorothy M; Robinson, Ian K; Meldrum, Fiona C


    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates.

  4. Calcite and dolomite in intrusive carbonatites. II. Trace-element variations (United States)

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


    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

  5. The kinetics of the ordering of 13C-18O bonds in calcite and apatite (United States)

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


    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 Δ47 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

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

    DEFF Research Database (Denmark)

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


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

  7. The surface interactions of a near-neutral carbon nanoparticle tracer with calcite

    KAUST Repository

    Li, Yan Vivian


    A new class of nearly charge-neutral carbon-cored nanoparticle tracers are remarkably non-interactive with solid surfaces and could provide a valuable baseline for diverse hydrological and environmental studies of subsurface flow and particle transport. We investigate the causes of inertness by studying the interactions with calcite of a nanoparticle of this class synthesized from malic acid and ethanolamine (M-dots) dispersed in brine (NaCl, CaCl2, and MgCl2) solutions. None of the M-dots are retained in calcite sand-packed columns when dispersed in DI water. Dispersed in the NaCl and mixed brine solutions, 5.6 % of and 7.3 % of the M-dots are initially retained, but 65 and 13 % of these retained particles are subsequently released when the column is flushed with DI water. When dispersed in the CaCl2 and MgCl2 solutions, 65 and 54 % of the M-dots are initially retained, and 28 and 26 % subsequently released in the DI water flush. The M-dots have a small negative zeta potential in all solutions, but the calcite zeta potential changes from strongly negative to strongly positive across the solution series, and the particle retention tracks this change. Derjaguin–Landau–Verwey–Overbeek (DLVO) modeling of the force between a calcite probe and an M-dot coated surface shows that hydration forces repel the particles in the DI water, NaCl, and mixed solutions, but not in the CaCl2 and MgCl2 solutions. These results show that near-zero charge and strongly hydrophilic decoration are the causes of the remarkable inertness of carbon-cored nanoparticles, and also suggest that nanoparticles could be useful in solute-surface interaction studies.

  8. Aragonite→calcite transformation studied by EPR of Mn 2+ ions (United States)

    Lech, J.; Śl|zak, A.


    The irreversible transformation aragonite→calcite has been studied both at different fixed heating rates (5, 10, 15 and 20 K/min) and at different fixed temperatures. Apparent progression rates of the transformation were observed above 685 K. At 730 K the transformation became sudden and violent. Time developments of the transformation at fixed temperatures have been discussed in terms of Avrami-Lichti's approach to transitions involving nucleation processes.



    Heriansyah ePutra; Heriansyah ePutra; Hideaki eYasuhara; Naoki eKinoshita; Debendra eNeupane


    The optimization of enzyme-mediated calcite precipitation (EMCP) was evaluated as a soil improvement technique. In our previous works, purified urease was utilized to bio-catalyze the hydrolysis of urea, which causes the supplied Ca2+ to precipitate with CO32- as calcium carbonate. In the present work, magnesium chloride was newly added to the injecting solutions to delay the reaction rate and to enhance the amount of carbonate precipitation. Soil specimens were prepared in PVC cylinders and ...

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


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


    Coccolithophore contributions to the global marine carbon cycle are regulated by the calcite content of their scales (coccoliths) and the relative cellular levels of photosynthesis and calcification rates. All three of these factors vary between coccolithophore species and with response to the growth environment. Here, water samples were collected in the northern basin of the South China Sea (SCS) during summer 2014 in order to examine how environmental variability influence...

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

    DEFF Research Database (Denmark)

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


    We demonstrate that the electron paramagnetic resonance spectrum of Mn2+ impurities in calcite, and therefore also in marble, may be accurately reproduced by a traditional spin Hamiltonian formalism. The success of such a treatment, however, very much depends on the spin Hamiltonian parameters...... having the correct signs as well as magnitudes. We present data that determine the sign of the axial anisotropy parameter and thereby facilitate future quantum mechanical characterizations of marble electron paramagnetic resonance spectra that supplement provenance determination...


    DEFF Research Database (Denmark)

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


    We demonstrate that the electron paramagnetic resonance spectrum of Mn2+ impurities in calcite, and therefore also in marble, may be accurately reproduced by a traditional spin Hamiltonian formalism. The success of such a treatment, however, very much depends on the spin Hamiltonian parameters...... having the correct signs as well as magnitudes. We present data that determine the sign of the axial anisotropy parameter and thereby facilitate future quantum mechanical characterizations of marble electron paramagnetic resonance spectra that supplement provenance determination....

  13. An efficient phosphorus scavenging from aqueous solution using magnesiothermally modified bio-calcite. (United States)

    Ahmad, Munir; Ahmad, Mahtab; Usman, Adel R A; Al-Faraj, Abdullah S; Ok, Yong Sik; Hussain, Qaiser; Abduljabbar, Adel S; Al-Wabel, Mohammad I


    Bio-calcite (BC) derived from waste hen eggshell was subjected to thermal treatments (calcined bio-calcite (CBC)). The BC and CBC were further modified via magnesiothermal treatments to produce modified bio-calcite (MBC) and modified calcined bio-calcite (MCBC), respectively, and evaluated as a novel green sorbent for P removal from aqueous solutions in the batch experiments. Modified BC exhibited improved structural and chemical properties, such as porosity, surface area, thermal stability, mineralogy and functional groups, than pristine material. Langmuir and Freundlich models well described the P sorption onto both thermally and magnesiothermally sorbents, respectively, suggesting mono- and multi-layer sorption. Langmuir predicted highest P sorption capacities were in the order of: MCBC (43.33 mg g -1 ) > MBC (35.63 mg g- 1 ) > CBC (34.38 mg g -1 ) > BC (30.68 mg g -1 ). The MBC and MCBC removed 100% P up to 50 mg P L -1 , which reduced to 35.43 and 39.96%, respectively, when P concentration was increased up to 1000 mg L -1 . Dynamics of P sorption was well explained by the pseudo-second-order rate equation, with the highest sorption rate of 4.32 mg g -1  min -1 for the MCBC. Hydroxylapatite [Ca 10 (PO 4 ) 6 (OH) 2 ] and brushite [CaH(PO 4 )·2H 2 O] were detected after P sorption onto the modified sorbents by X-ray diffraction analysis, suggesting chemisorption as the operating sorption mechanism.

  14. Quantitative laboratory measurements of biogeochemical processes controlling biogenic calcite carbon sequestration.

    Energy Technology Data Exchange (ETDEWEB)

    Zendejas, Frank; Lane, Todd W.; Lane, Pamela D.


    The purpose of this LDRD was to generate data that could be used to populate and thereby reduce the uncertainty in global carbon cycle models. These efforts were focused on developing a system for determining the dissolution rate of biogenic calcite under oceanic pressure and temperature conditions and on carrying out a digital transcriptomic analysis of gene expression in response to changes in pCO2, and the consequent acidification of the growth medium.

  15. The surface interactions of a near-neutral carbon nanoparticle tracer with calcite

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan Vivian, E-mail: [Colorado State University, Department of Design and Merchandising (United States); Cathles, Lawrence M., E-mail: [Cornell University, Earth and Atmospheric Sciences (United States)


    A new class of nearly charge-neutral carbon-cored nanoparticle tracers are remarkably non-interactive with solid surfaces and could provide a valuable baseline for diverse hydrological and environmental studies of subsurface flow and particle transport. We investigate the causes of inertness by studying the interactions with calcite of a nanoparticle of this class synthesized from malic acid and ethanolamine (M-dots) dispersed in brine (NaCl, CaCl{sub 2}, and MgCl{sub 2}) solutions. None of the M-dots are retained in calcite sand-packed columns when dispersed in DI water. Dispersed in the NaCl and mixed brine solutions, 5.6 % of and 7.3 % of the M-dots are initially retained, but 65 and 13 % of these retained particles are subsequently released when the column is flushed with DI water. When dispersed in the CaCl{sub 2} and MgCl{sub 2} solutions, 65 and 54 % of the M-dots are initially retained, and 28 and 26 % subsequently released in the DI water flush. The M-dots have a small negative zeta potential in all solutions, but the calcite zeta potential changes from strongly negative to strongly positive across the solution series, and the particle retention tracks this change. Derjaguin–Landau–Verwey–Overbeek (DLVO) modeling of the force between a calcite probe and an M-dot coated surface shows that hydration forces repel the particles in the DI water, NaCl, and mixed solutions, but not in the CaCl{sub 2} and MgCl{sub 2} solutions. These results show that near-zero charge and strongly hydrophilic decoration are the causes of the remarkable inertness of carbon-cored nanoparticles, and also suggest that nanoparticles could be useful in solute-surface interaction studies.Graphical Abstract.

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

    DEFF Research Database (Denmark)

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


    The growth and nucleation of biominerals are directed and affected by associated biological molecules. In this paper, we investigate the influence of occluded biomolecules on biogenic calcite from the coccolithophorid Pleurochrysis carterae and from chalk, a rock composed predominantly of fossil...... and the coccolithophorids. These differences were reflected in lattice deformation (macrostrain), structure (microstrain), and atomic disorder distributions (δorganic). The influence of the biological macromolecules on the inorganic phase was consistently smaller in the P. carterae compared to P. nobilis...

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  18. Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface (United States)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  20. Intermediate-scale tests of sodium interactions with calcite and dolomite aggregate concretes. [LMFBR

    Energy Technology Data Exchange (ETDEWEB)

    Randich, E.; Acton, R.U.


    Two intermediate-scale tests were performed to compare the behavior of calcite and dolomite aggregate concretes when attacked by molten sodium. The tests were performed as part of an interlaboratory comparison between Sandia National Laboratories and Hanford Engineering Development Laboratories. Results of the tests at Sandia National Laboratories are reported here. The results show that both concretes exhibit similar exothermic reactions with molten sodium. The large difference in reaction vigor suggested by thermodynamic considerations of CO/sub 2/ release from calcite and dolomite was not realized. Penetration rates of 1.4 to 1.7 mm/min were observed for short periods of time with reaction zone temperatures in excess of 800/sup 0/C during the energetic attack. The penetration was not uniform over the entire sodium-concrete contact area. Rapid attack may be localized due to inhomogeneities in the concrete. The chemical reaction zone is less then one cm thick for the calcite concrete but is about seven cm thick for the dolomite concrete.

  1. Sulfur in foraminiferal calcite as a potential proxy for seawater carbonate ion concentration (United States)

    van Dijk, I.; de Nooijer, L. J.; Boer, W.; Reichart, G.-J.


    Sulfur (S) incorporation in foraminiferal shells is hypothesized to change with carbonate ion concentration [CO32-], due to substitution of sulfate for carbonate ions in the calcite crystal lattice. Hence S/Ca values of foraminiferal carbonate shells are expected to reflect sea water carbonate chemistry. To generate a proxy calibration linking the incorporation of S into foraminiferal calcite to carbonate chemistry, we cultured juvenile clones of the larger benthic species Amphistegina gibbosa and Sorites marginalis over a 350-1200 ppm range of pCO2 values, corresponding to a range in [CO32-] of 93 to 211 μmol/kg. We also investigated the potential effect of salinity on S incorporation by culturing juvenile Amphistegina lessonii over a large salinity gradient (25-45). Results show S/CaCALCITE is not impacted by salinity, but increases with increasing pCO2 (and thus decreasing [CO32-] and pH), indicating S incorporation may be used as a proxy for [CO32-]. Higher S incorporation in high-Mg species S. marginalis suggests a superimposed biomineralization effect on the incorporation of S. Microprobe imaging reveals co-occurring banding of Mg and S in Amphistegina lessonii, which is in line with a strong biological control and might explain higher S incorporation in high Mg species. Provided a species-specific calibration is available, foraminiferal S/Ca values might add a valuable new tool for reconstructing past ocean carbonate chemistry.

  2. Adsorption Behavior and Mechanism of SCA-1 on a Calcite Surface: A Molecular Dynamics Study. (United States)

    Xue, Zhengyang; Shen, Qiying; Liang, Lijun; Shen, Jia-Wei; Wang, Qi


    The crystallization mechanism for natural mineral, especially the role of biological molecules in biomineralization, is still under debate. Protein adsorption on material surfaces plays a key role in biomineralization. In this article, molecular dynamics (MD) simulations were performed to systematically investigate the adsorption behavior of struthio camelus eggshell protein struthiocalcin-1 (SCA-1) on the calcite (104) surface with several different starting orientations in an explicit water environment. For each binding configuration, detailed adsorption behaviors and a mechanism were presented with the analysis of interaction energy, binding residues, hydrogen bonding, and structures (such as DSSP, dipole moment, and the electrostatic potential calculation). The results indicate that the positively charged and polar residues are the dominant residues for protein adsorption on the calcite (104) surface, and the strong electrostatic interaction drives the binding of model protein to the surface. The hydrogen bond bridge was found to play an important role in surface interactions as well. These results also demonstrate that SCA-1 is relatively rigid in spite of strong adsorption with few structural changes in α-helix and β-sheet contents. The results of the orientation calculation suggest that the dipole moment of the protein tends to remain parallel to calcite in most stable cases, which was confirmed by electrostatic potential isosurfaces analysis.

  3. Ternary iron, magnesium, calcium carbonates; a thermodynamic model for dolomite as an ordered derivative of calcite-structure solutions

    National Research Council Canada - National Science Library

    Davidson, Paula M


      The simplest solution model that can account for dolomite as an ordered derivative structure of the disordered calcite structure solution, based on a ternary extension of the generalized point approximation given by C...

  4. Differential early diagenetic low-Mg calcite cementation and rhythmic hardground development in Campanian-Maastrichtian chalk

    DEFF Research Database (Denmark)

    Molenaar, Nicolaas; J.J.P., Zijlstra


    calcite cementation is proposed, in which early calcite cementation occurred within the sediment at some distance below the seafloor as a result of organic matter degradation and internal redistribution of bioclastic carbonate. Bacterial organic matter degradation caused dissolution of relatively unstable...... older burrowed sediment with a more advanced stage of organic matter degradation, in particular iron reduction. Cementation also occurred when redox boundaries repeatedly moved through the same layers during periods with low nett sedimentation and increased storm activity and erosion. The differences...... in the degree of early diagenetic calcite cementation were further enhanced during Paleocene karstification and development of secondary porosity by dissolution of remaining unstable carbonate grains and by associated meteoric water calcite cementation....

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

    NARCIS (Netherlands)

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


    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

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

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt

    is complete after 1 and 2-3 hours, respectively). Also desorption is fast and complete for both ions within 0.5 h. The reversibility of the sorption process indicates that neither arsenate nor phosphate is readily incorporated into the calcite crystal lattice under our experimental conditions. The phosphate....... The primary effect of the ionic strength on phosphate sorption onto calcite is its influence on the activity of the different aqueous phosphate species. For the adsorption of arsenate onto calcite, the effect of the ionic strength is more pronounced and cannot fully be accounted for by changes in the aqueous...... and sequential addition (3 hours apart) yields the same reduction in adsorption, underlining the high reversibility of the system. The reduction in adsorption of both arsenate and phosphate is most likely due to competition for the same sorption sites at the calcite surface, considering the similarity...

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

    DEFF Research Database (Denmark)

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


    that adsorption of arsenate onto calcite is of minor importance in most groundwater aquifers, as phosphate is often present at concentration levels sufficient to significantly reduce arsenate adsorption. The CD-MUSIC model for calcite was used successfully to model adsorption of arsenate and phosphate separately....... This study clearly shows the importance of performing competitive adsorption studies for validation of multi-component models and for estimating the mobility of an ion in the environment....

  8. Mn and Zn incorporation into calcite as a function of chloride aqueous concentration (United States)

    Temmam, M.; Paquette, J.; Vali, H.


    During spiral growth of the calcite rhombohedron {10 overline14}, divalent metals substituting for Ca 2+ are differentially incorporated due to steric differences inherent to the asymmetric kink sites exposed at nonequivalent growth steps. Hence, ions "larger" than Ca 2+ (e.g., Sr 2+ and Ba 2+) exhibit an incorporation trend opposite to that of "smaller" ions (e.g., Mn 2+ and Co 2+). However, Zn 2+ exhibits the same incorporation trend as large ions in coprecipitation experiments conducted from strong NH 4Cl electrolytes. In this study we compared the incorporation trends of Zn and Mn from solutions with various chloride content to test the possibility that the adsorption of "large" ZnCl n2-n aqueous complexes influences the site preference of Zn. The incorporation trends of Mn and Zn were opposite at the symmetrically nonequivalent growth steps. From a 0.4 M NH 4Cl solution, where Zn aqueous speciation was thermodynamically dominated by the "free" aquo ion, Zn maintained its site preference for the geometrically less constrained surface sites. Thus, Zn exhibits a particular interaction with surface sites and its incorporation trend is not controlled by the prevalence of ZnCl n2-n complexes. Other factors like the electronic configuration must be considered. The surface microtopography of calcite was found to be sensitive to changes in the aqueous concentrations of NH 4Cl and Zn. Decreases in NH 4Cl concentration resulted in an increase of the density of growth hillocks. The strong adsorbing behaviour of Zn increased the surface roughness, decreased the rate of growth, perturbed the spiral growth mechanism, and triggered the nucleation of discrete surface precipitates (˜0.2 μm) along macrosteps. An increase of Cl incorporation, despite the decrease of its aqueous concentration by dilutions of the parent solution, suggests that surface roughness at the calcite-solution interface is another factor involved in the nonequilibrium process of impurity element

  9. Clumped isotope thermometry of calcite and dolomite in a contact metamorphic environment (United States)

    Lloyd, Max K.; Eiler, John M.; Nabelek, Peter I.


    Clumped isotope compositions of slowly-cooled calcite and dolomite marbles record apparent equilibrium temperatures of roughly 150-200 °C and 300-350 °C, respectively. Because clumped isotope compositions are sensitive to the details of T-t path within these intervals, measurements of the Δ47 values of coexisting calcite and dolomite can place new constraints on thermal history of low-grade metamorphic rocks over a large portion of the upper crust (from ∼5 to ∼15 km depth). We studied the clumped isotope geochemistry of coexisting calcite and dolomite in marbles from the Notch Peak contact metamorphic aureole, Utah. Here, flat-lying limestones were intruded by a pluton, producing a regular, zoned metamorphic aureole. Calcite Δ47 temperatures are uniform, 156 ± 12 °C (2σ s.e.), across rocks varying from high-grade marbles that exceeded 500 °C to nominally unmetamorphosed limestones >5 km from the intrusion. This result appears to require that the temperature far from the pluton was close to this value; an ambient temperature just 20 °C lower would not have permitted substantial re-equilibration, and should have preserved depositional or early diagenetic Δ47 values several km from the pluton. Combining this result with depth constraints from overlying strata suggests the country rock here had an average regional geotherm of 22.3-27.4 °C/km from the late Jurassic Period until at least the middle Paleogene Period. Dolomite Δ47 in all samples above the talc + tremolite-in isograd record apparent equilibrium temperatures of 328-12+13 °C (1σ s.e.), consistent with the apparent equilibrium blocking temperature we expect for cooling from peak metamorphic conditions. At greater distances, dolomite Δ47 records temperatures of peak (anchi)metamorphism or pre-metamorphic diagenetic conditions. The interface between these domains is the location of the 330 °C isotherm associated with intrusion. Multiple-phase clumped isotope measurements are complemented by

  10. Bulk and Surface Aqueous Speciation of Calcite: Implications for Low-Salinity Waterflooding of Carbonate Reservoirs

    KAUST Repository

    Yutkin, Maxim P.


    Low-salinity waterflooding (LSW) is ineffective when reservoir rock is strongly water-wet or when crude oil is not asphaltenic. Success of LSW relies heavily on the ability of injected brine to alter surface chemistry of reservoir crude-oil brine/rock (COBR) interfaces. Implementation of LSW in carbonate reservoirs is especially challenging because of high reservoir-brine salinity and, more importantly, because of high reactivity of the rock minerals. Both features complicate understanding of the COBR surface chemistries pertinent to successful LSW. Here, we tackle the complex physicochemical processes in chemically active carbonates flooded with diluted brine that is saturated with atmospheric carbon dioxide (CO2) and possibly supplemented with additional ionic species, such as sulfates or phosphates. When waterflooding carbonate reservoirs, rock equilibrates with the injected brine over short distances. Injected-brine ion speciation is shifted substantially in the presence of reactive carbonate rock. Our new calculations demonstrate that rock-equilibrated aqueous pH is slightly alkaline quite independent of injected-brine pH. We establish, for the first time, that CO2 content of a carbonate reservoir, originating from CO2-rich crude oil and gas, plays a dominant role in setting aqueous pH and rock-surface speciation. A simple ion-complexing model predicts the calcite-surface charge as a function of composition of reservoir brine. The surface charge of calcite may be positive or negative, depending on speciation of reservoir brine in contact with the calcite. There is no single point of zero charge; all dissolved aqueous species are charge determining. Rock-equilibrated aqueous composition controls the calcite-surface ion-exchange behavior, not the injected-brine composition. At high ionic strength, the electrical double layer collapses and is no longer diffuse. All surface charges are located directly in the inner and outer Helmholtz planes. Our evaluation of

  11. Influence of solution chemistry on the boron content in inorganic calcite grown in artificial seawater (United States)

    Uchikawa, Joji; Harper, Dustin T.; Penman, Donald E.; Zachos, James C.; Zeebe, Richard E.


    The ratio of boron to calcium (B/Ca) in marine biogenic carbonates has been proposed as a proxy for properties of seawater carbonate chemistry. Applying this proxy to planktic foraminifera residing in the surface seawater largely in equilibrium with the atmosphere may provide a valuable handle on past atmospheric CO2 concentrations. However, precise controls on B/Ca in planktic foraminifera remain enigmatic because it has been shown to depend on multiple physicochemical seawater properties. To help establish a firm inorganic basis for interpreting the B/Ca records, we examined the effect of a suite of chemical parameters ([Ca2+], pH, [DIC], salinity and [PO43-]) on B/Ca in inorganic calcite precipitated in artificial seawater. These parameters were primarily varied individually while keeping all others constant, but we also tested the influence of pH and [DIC] at a constant calcite precipitation rate (R) by concurrent [Ca2+] adjustments. In the simple [Ca2+], pH and [DIC] experiments, both R and B/Ca increased with these parameters. In the pH-[Ca2+] and [DIC]-[Ca2+] experiments at constant R, on the other hand, B/Ca was invariant at different pH and decreased with [DIC], respectively. These patterns agree with the behavior of solution [BTotal/DIC] ratio such that, at a fixed [BTotal], it is independent of pH but decreases with [DIC]. Based on these results, R and [BTotal/DIC] ratio appear to be the primary controls on B/Ca in inorganic calcite, suggesting that both B(OH)4- and B(OH)3 are possibly involved in B incorporation. Moreover, B/Ca modestly increased with salinity and [PO43-]. Inorganic calcite precipitated at higher R and in the presence of oxyanions such as SO42- and PO43- in growth solutions often undergoes surface roughening due to formation of crystallographic defects, vacancies and, occasionally, amorphous/hydrous CaCO3. These non-lattice sites may provide additional space for B, particularly B(OH)3. Consequently, besides the macroscopic influence of

  12. Investigating the Physical Basis of Amorphous Precursor Transformation to Calcite Using Patterned Alkanethiol Surfaces (United States)

    Wang, D.; Wallace, A.; Han, T. Y.; Lee, J. R.; Hailey, P. D.; de Yoreo, J. J.; Dove, P. M.


    Increasing evidence from X-ray Absorption Spectroscopy and Environmental Scanning Electron Microscopy (ESEM) studies of biominerals extracted from calcifying organisms show that amorphous calcium carbonate (ACC) plays a key role in the initial formation of carbonate minerals and in shaping them into complex morphologies. Echinoderms and possibly a wide variety of other organisms, use ACC as a precursor phase. The ACC is first formed within spatial and temporally controlled environments such as vesicles, followed by a subsequent onset of mineralization that transforms the precursor into a fully crystalline material. Recent studies on sea urchin embryos have shown that during this transformation, ACC develops short-range order that resembles calcite before fully crystallizing. While this "non-traditional" process is recognized, the mechanisms and factors that govern this transformation remain poorly understood. Of particular interest are the roles of water, and the functional group chemistry of surfaces and macromolecules within mineralization environments. To investigate these questions, we have developed an experimental approach using ESEM that allows us to control impurity concentration, surface functionality and water content through the degree of water condensation. Patterned self-assembled monolayers (SAM) of hydrophilic moieties with domains of approximately 25 microns in diameter are used to form an array of micro-reactors. ACC particles with known composition are then deposited on the patterns. Condensing water in the ESEM initializes the transformation of ACC to calcite. Our results show that in saturated water vapor, ACC swells, but no obvious faceting of the material occurs. It is only in bulk water, via dissolution/crystallization, where the calcite grown on carboxyl-terminated surfaces is found with the often-observed \\{013\\} nucleation face. We use this insight to understand the role of the different chemical moieties on ACC to calcite transformation

  13. Simulated oxygen isotopes in cave drip water and speleothem calcite in European caves

    Directory of Open Access Journals (Sweden)

    A. Wackerbarth


    Full Text Available Interpreting stable oxygen isotope (δ18O records from stalagmites is still one of the complex tasks in speleothem research. Here, we present a novel model-based approach, where we force a model describing the processes and modifications of δ18O from rain water to speleothem calcite (Oxygen isotope Drip water and Stalagmite Model – ODSM with the results of a state-of-the-art atmospheric general circulation model enhanced by explicit isotope diagnostics (ECHAM5-wiso. The approach is neither climate nor cave-specific and allows an integrated assessment of the influence of different varying climate variables, e.g. temperature and precipitation amount, on the isotopic composition of drip water and speleothem calcite.

    First, we apply and evaluate this new approach under present-day climate conditions using observational data from seven caves from different geographical regions in Europe. Each of these caves provides measured δ18O values of drip water and speleothem calcite to which we compare our simulated isotope values. For six of the seven caves modeled δ18O values of drip water and speleothem calcite are in good agreement with observed values. The mismatch of the remaining caves might be caused by the complexity of the cave system, beyond the parameterizations included in our cave model.

    We then examine the response of the cave system to mid-Holocene (6000 yr before present, 6 ka climate conditions by forcing the ODSM with ECHAM5-wiso results from 6 ka simulations. For a set of twelve European caves, we compare the modeled mid-Holocene-to-modern difference in speleothem calcite δ18O to available measurements. We show that the general European changes are simulated well. However, local discrepancies are found, and might be explained either by a too low model resolution, complex local soil-atmosphere interactions affecting evapotranspiration or by cave specific factors

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  15. Calcite as a bone substitute. Comparison with hydroxyapatite and tricalcium phosphate with regard to the osteoblastic activity

    Energy Technology Data Exchange (ETDEWEB)

    Monchau, F., E-mail: [Laboratoire Genie Civil et geo-Environnement (EA 4515, Universite Lille Nord de France), Equipe Biomateriaux Artois (Universite d' Artois), IUT/GMP, 1230, rue de l' Universite, BP 819, 62408 Bethune cedex (France); Hivart, Ph.; Genestie, B. [Laboratoire Genie Civil et geo-Environnement (EA 4515, Universite Lille Nord de France), Equipe Biomateriaux Artois (Universite d' Artois), IUT/GMP, 1230, rue de l' Universite, BP 819, 62408 Bethune cedex (France); Chai, F. [Laboratoire Medicaments et Biomateriaux a Liberation Controlee (INSERM U 1008, Universite Lille Nord de France), Groupe de Recherche sur les Biomateriaux (Universite Lille-2), Faculte de Medecine, 1, place de Verdun, 59045 Lille cedex (France); and others


    Close to the bone mineral phase, the calcic bioceramics, such as hydroxyapatite (HA) and {beta}-tricalcium phosphate ({beta}-TCP), are commonly used as substitutes or filling materials in bone surgery. Besides, calcium carbonate (CaCO{sub 3}) is also used for their excellent biocompatibility and bioactivity. However, the problem with the animal-origin aragonite demands the new technique to synthesize pure calcite capable of forming 3D bone implant. This study aims to manufacture and evaluate a highly-pure synthetic crystalline calcite with good cytocompatibility regarding to the osteoblasts, comparing to that of HA and {beta}-TCP. After the manufacture of macroporous bioceramic scaffolds with the identical internal architecture, their cytocompatibility is studied through MC3T3-E1 osteoblasts with the tests of cell viability, proliferation, vitality, etc. The results confirmed that the studied process is able to form a macroporous material with a controlled internal architecture, and this synthesized calcite is non-cytotoxic and facilitate the cell proliferation. Indeed requiring further improvement, the studied calcite is definitely an interesting alternative not only to coralline aragonite but also to calcium phosphate ceramics, particularly in bone sites with the large bone remodelling. Highlights: Black-Right-Pointing-Pointer Macroporous calcite manufacturing with controlled architecture as bone substitute Black-Right-Pointing-Pointer Cytotoxicity: adaptation of the colony-forming method with the target cells: MC3T3-E1 osteoblasts Black-Right-Pointing-Pointer Study of osteoblast proliferation and activity on calcite, HA and TCP.

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

    Energy Technology Data Exchange (ETDEWEB)

    DePaolo, D.


    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

  17. Resetting of Mg isotopes between calcite and dolomite during burial metamorphism: Outlook of Mg isotopes as geothermometer and seawater proxy (United States)

    Hu, Zhongya; Hu, Wenxuan; Wang, Xiaomin; Lu, Yizhou; Wang, Lichao; Liao, Zhiwei; Li, Weiqiang


    Magnesium isotopes are an emerging tool to study the geological processes recorded in carbonates. Calcite, due to its ubiquitous occurrence and the large Mg isotope fractionation associated with the mineral, has attracted great interests in applications of Mg isotope geochemistry. However, the fidelity of Mg isotopes in geological records of carbonate minerals (e.g., calcite and dolomite) against burial metamorphism remains poorly constrained. Here we report our investigation on the Mg isotope systematics of a dolomitized Middle Triassic Geshan carbonate section in eastern China. Magnesium isotope analysis was complemented by analyses of Sr-C-O isotopic compositions, major and trace element concentrations, and petrographic and mineralogical features. Multiple lines of evidence consistently indicated that post-depositional diagenesis of carbonate minerals occurred to the carbonate rocks. Magnesium isotope compositions of the carbonate rocks closely follow a mixing trend between a high δ26Mg dolomite end member and a low δ26Mg calcite end member, irrespective of sample positions in the section and calcite/dolomite ratio in the samples. By fitting the measured Mg isotope data using a two-end member mixing model, an inter-mineral Δ26Mgdolomite-calcite fractionation of 0.72‰ was obtained. Based on the experimentally derived Mg isotope fractionation factors for dolomite and calcite, a temperature of 150-190 °C was calculated to correspond to the 0.72‰ Δ26Mgdolomite-calcite fractionation. Such temperature range matches with the burial-thermal history of the local strata, making a successful case of Mg isotope geothermometry. Our results indicate that both calcite and dolomite had been re-equilibrated during burial metamorphism, and based on isotope mass balance of Mg, the system was buffered by dolomite in the section. Therefore, burial metamorphism may reset Mg isotope signature of calcite, and Mg isotope compositions in calcite should be dealt with caution in

  18. Growing spherulitic calcite grains in saline, hyperalkaline lakes: experimental evaluation of the effects of Mg-clays and organic acids (United States)

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


    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

  19. Calcite growth-rate inhibition by fulvic acids isolated from Big Soda Lake, Nevada, USA, The Suwannee River, Georgia, USA and by polycarboxylic acids (United States)

    Reddy, Michael M.; Leenheer, Jerry


    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.

  20. A quantitative analysis of microbially-induced calcite precipitation employing artificial and naturally-occurring sediments (United States)

    Lokier, Stephen; Krieg Dosier, Ginger


    Microbially-induced calcite precipitation is a strong candidate for the production of sustainable construction materials. The process employs the microbe Sporosarcina pasteurii as an agent to microbially mediate the precipitation of calcium carbonate to bind unconsolidated sediment. As this process can be achieved under ambient temperature conditions and can utilise a wide variety of easily-available sediments, potentially including waste materials, it is envisioned that this procedure could significantly reduce carbon-dioxide emissions in the construction industry. This study describes and quantifies the precipitation of calcite cement in a range of naturally-occurring sediments compared with a control matrix. The study establishes the optimum treatment time for effective cement precipitation in order to produce a material that meets the standards required for construction whilst keeping economic and environmental outlays at a minimum. The 'control sediment' employed industrial-grade glass beads with a grain size range of 595-1180 microns (16-30 US mesh). Sporosarcina pasteurii were mixed in a solution of urea and calcium chloride and then inoculated into the control sediment. The microbes attach to the surface of the sediment grains and employ urea as a source of energy to produce ammonia and carbon dioxide. By so doing, they increase the pH of the solution allowing calcium carbonate to precipitate at the cell walls to act as nucleation points facilitating the precipitation of cements as a grain-coating and biocementing the unconsolidated sediment. The solution treatment was repeated at eight hour intervals with samples removed for detailed analysis after each every five consecutive treatments (i.e. 40 hours). The process was repeated to produce 20 samples with treatment times between 40 and 800 hours. Cemented samples were impregnated with blue epoxy and examined petrographically to monitor cement development. Modal analysis was undertaken on each cemented

  1. Competitive adsorption of arsenate and phosphate onto calcite; experimental results and modeling with CCM and CD-MUSIC (United States)

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


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

  2. An explanation for the 18O excess in Noelaerhabdaceae coccolith calcite (United States)

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


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

  3. Testing Novel pH Proxies through Inorganic Calcite Precipitations and K/Pg Foraminifera (United States)

    Super, J. R.; Pagani, M.; Wang, Z.


    Ocean pH proxies help constrain the carbon system in the paleocean and can be used to infer atmospheric CO2 when coupled with estimates of total alkalinity, aqueous pCO2 or dissolved inorganic carbon. This project investigates two novel pH proxies (cerium abundance and kinetically-controlled oxygen isotopes) through a series of precipitations of inorganic calcite, as well as the previously established boron isotope pH proxy. Precipitations are performed using varied pH and carbonate saturation states that span the range of typical ocean values as well as a 'free drift' that allows pH and saturation state to vary. The light rare earth element cerium speciates, depending on local oxidation-reduction conditions, between the soluble Ce3+ and highly insoluble Ce4+ ions, causing a relative depletion of cerium in ocean water. This project demonstrates how a suite rare earth elements, including cerium, partitions into inorganic calcite and how partitioning varies with changing pH and carbonate saturation state. Oxygen isotope fractionation is primarily controlled by temperature, but this project examines how pH and carbonate saturation state correlate with oxygen isotope values under kinetic conditions during the initial stage of precipitation. The effect of diagenesis on each proxy is simulated by dissolution of precipitated calcite in a pressure vessel. Results from the precipitations are used to inform a record of well-preserved benthic and planktonic foraminifera from DSDP Site 356 that range in age from the K/Pg boundary to the period when the δ13C gradient between the surface and deep ocean returned to pre-event levels. The pH record is used to infer the magnitude and length of the perturbation to the oceanic carbon system following the extinction event, particularly in terms of export productivity.

  4. Subglacial Calcites from Northern Victoria Land: archive of Antarctic volcanism in the Last Glacial Maximum (United States)

    Frisia, Silvia; Weirich, Laura; Hellstrom, John; Borsato, Andrea; Golledge, Nicholas R.; Anesio, Alexandre M.; Bajo, Petra; Drysdale, Russell N.; Augustinus, Paul C.; Barbante, Carlo; Cooper, Alan


    Subglacial carbonates bear similarities to stalagmites in their fabrics and the potential to obtain precise chronologies using U-series methods. Their chemical properties also reflect those of their parent waters, which, in contrast to stalagmites, are those of subglacial meltwaters. In analogy to speleothems, stable Carbon isotope ratios and trace elements such as Uranium, Iron and Manganese provide the opportunity to investigate ancient extreme environments without the need to drill through thousands of metres of ice. Sedimentological, geochemical and microbial evidence preserved in LGM subglacial calcites from Northern Victoria Land, close to the East Antarctic Ice Sheet margin, allow us to infer that subglacial volcanism was active in the Trans Antarctic Mountain region and induced basal ice melting. We hypothesize that a meltwater reservoir was drained and injected into interconnected basal pore systems where microbial processes enhanced bedrock weathering and, thus, released micronutrients. Volcanic influence is supported by the presence of fluorine (F) and sulphur in sediment-laden calcite layers containing termophilic species. Notably, calcite δ13C points to dissolved inorganic carbon evolved from subglacial metabolic processes. Once transported to the sea, soluble iron likely contributed to fertilizing the Southern Ocean and CO2 drawdown. This is the first well-dated evidence for LGM volcanism in Antarctica, which complements the record of volcanic eruptions retrieved from Talos Dome ice core, and supports the hypothesis of large-scale volcanism as an important driver of climate change. We conclude that subglacial carbonates are equivalent to speleothems in their palaeoclimate potential and may become a most useful source of information of ecosystems and processes at peak glacials in high altitude/high latitude settings.

  5. Timescale for hygroscopic conversion of calcite mineral particles through heterogeneous reaction with nitric acid. (United States)

    Sullivan, Ryan C; Moore, Meagan J K; Petters, Markus D; Kreidenweis, Sonia M; Roberts, Greg C; Prather, Kimberly A


    Atmospheric heterogeneous reactions can potentially change the hygroscopicity of atmospheric aerosols as they undergo chemical aging processes in the atmosphere. A particle's hygroscopicity influences its cloud condensation nuclei (CCN) properties with potential impacts on cloud formation and climate. In this study, size-selected calcite mineral particles were reacted with controlled amounts of nitric acid vapour over a wide range of relative humidities in an aerosol flow tube to study the conversion of insoluble and thus apparently non-hygroscopic calcium carbonate into soluble and hygroscopic calcium nitrate. The rate of hygroscopic change particles undergo during a heterogeneous reaction is derived from experimental measurements for the first time. The chemistry of the reacted particles was determined using an ultrafine aerosol time-of-flight mass spectrometer (UF-ATOFMS) while the particles' hygroscopicity was determined through measuring CCN activation curves fit to a single parameter of hygroscopicity, kappa. The reaction is rapid, corresponding to atmospheric timescales of hours. At low to moderate HNO3 exposures, the increase in the hygroscopicity of the particles is a linear function of the HNO3(g) exposure. The experimentally observed conversion rate was used to constrain a simple but accurate kinetic model. This model predicts that calcite particles will be rapidly converted into hygroscopic particles (kappa>0.1) within 4 h for low HNO3 mixing ratios (10 pptv) and in less than 3 min for 1000 pptv HNO3. This suggests that the hygroscopic conversion of the calcite component of atmospheric mineral dust aerosol will be controlled by the availability of nitric acid and similar reactants, and not by the atmospheric residence time.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  7. The evolution of Carbon isotopes in calcite in the presence of cyanobacteria (United States)

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


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

  8. Interaction of ethanol and water with the {1014} surface of calcite

    DEFF Research Database (Denmark)

    Cooke, David; Gray, R J; Sand, K K


    Molecular dynamics simulations have been used to model the interaction between ethanol, water, and the {1014} surface of calcite. Our results demonstrate that a single ethanol molecule is able to form two interactions with the mineral surface (both Ca-O and O-H), resulting in a highly ordered...... with water and for growth at the {1014} surface to occur. This observation, and its corresponding molecular explanation, may give some insight into the ability to control crystal form using mixtures of different organic solvents....

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

    Energy Technology Data Exchange (ETDEWEB)

    Asperger, R.G.


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  11. Sea Urchin Spine Calcite Forms via a Transient Amorphous Calcium Carbonate Phase (United States)

    Politi, Yael; Arad, Talmon; Klein, Eugenia; Weiner, Steve; Addadi, Lia


    The skeletons of adult echinoderms comprise large single crystals of calcite with smooth convoluted fenestrated morphologies, raising many questions about how they form. By using water etching, infrared spectroscopy, electron diffraction, and environmental scanning electron microscopy, we show that sea urchin spine regeneration proceeds via the initial deposition of amorphous calcium carbonate. Because most echinoderms produce the same type of skeletal material, they probably all use this same mechanism. Deposition of transient amorphous phases as a strategy for producing single crystals with complex morphology may have interesting implications for the development of sophisticated materials.

  12. Scattering matrix measurements and light-scattering calculations of calcite particles

    Directory of Open Access Journals (Sweden)

    D. D. Dabrowska


    Full Text Available We present measurements of the complete scattering matrix as a function of the scattering angle of a sample of calcite particles collected near Lecce, Italy. The measurements are done at a wavelength of 647 nm in the scattering angle range 3°−177°. FESEM and SEM images show that the sample consists largely of flake-like particles. Ten different flake-like geometries are randomly generated and their scattering properties are simulated with DDA for sizes from 0.1 μm to 1 μm. Some preliminary comparisons of the simulations and the measurements are shown.

  13. Pulsed cathodoluminescence of diamond, calcite, spodumene, and fluorite under the action of subnanosecond electron beam (United States)

    Baksht, E. Kh.; Burachenko, A. G.; Tarasenko, V. F.


    Amplitude and temporal characteristics of pulsed cathodoluminescence (PCL) of diamond (natural and synthetic), calcite, spodumene, and fluorite have been studied at a temporal resolution of ˜0.3 ns. The PCL was generated by electron beam pulses with a full width at half maximum (FWHM) of 0.1, 0.25, and 0.65 ns. The PCL spectra have been measured for the emission induced by 0.1- and 0.25-ns pulses at a beam current density of ˜90 A/cm2.

  14. Annual 18O/16O composition of authigenic calcite in varved lake sediments reflects regional air temperature (United States)

    Wirth, Stefanie; Gilli, Adrian


    The oxygen isotopic composition (18O/16O) of authigenic calcite in lake sediments reflects the temperature and the isotopic composition of the lake water from which the calcite is precipitated and thus contains information about the climatic conditions at the time of calcite formation. Varved lake sediments containing laminae of authigenically precipitated calcite provide the possibility to analyze the 18O/16O composition at an annual resolution, thus yielding high-resolution climatic information. Yet, despite this high potential the number of studies having used this approach is relatively low. Reasons for this are probably sampling challenges, the scarceness of suitable varved sediments, missing instrumental records to compare with, as well as uncertainties regarding the factors influencing the calcite isotopic composition (water/air temperature, precipitation, lake-internal factors). Still, annually resolved data of the 18O/16O composition of calcite seems a promising climate proxy and we therefore investigated the 18O/16O pattern of the authigenic calcite in the varved sediments of Lake Zurich. Lake Zurich is a pre-alpine lake with a surface area of 88 km2, a maximal water depth of 137 m and a theoretical water residence time of 1.4 years. Sediments are varved since the late 19th century due to anthropogenic lake eutrophication. For this calibration study, we analyzed the 18O/16O composition of the authigenic calcite for the time period 1960-2010 at annual resolution. The δ18O values range from -10.8 to -13.4 o; and the pattern is dominated by a conspicuous shift to more enriched values between 1985 and 1987. The same shift has been observed for local to large-scale climatic parameters such as lake, river, and groundwater temperatures throughout Switzerland, the mean air temperature for Switzerland, and the NAO index. The consistency of the instrumental temperature data sets with the 18O/16O composition of the authigenic calcite emphasizes the high potential

  15. Unraveling the Formation of Large Amounts of Calcite Scaling in Geothermal Wells in the Bavarian Molasse Basin: A Reactive Transport Modeling Approach


    Wanner, Christoph; Eichinger, Florian; Jahrfeld, Thomas; Diamond, Larryn W.


    Results from reactive transport simulations performed for the geothermal plant in Kirchstockach, located in the Bavarian Molasse Basin in southern Germany, are presented to unravel the formation of calcite scaling. Simulation results successfully predict the calcite scaling profile observed along the production well if supersaturation with respect to calcite is specified for the model water leaving the pump at 800 m depth. This observation is in good agreement with a previous study suggesting...

  16. Three-dimensional hydration layer mapping on the (10.4) surface of calcite using amplitude modulation atomic force microscopy (United States)

    Marutschke, Christoph; Walters, Deron; Cleveland, Jason; Hermes, Ilka; Bechstein, Ralf; Kühnle, Angelika


    Calcite, the most stable modification of calcium carbonate, is a major mineral in nature. It is, therefore, highly relevant in a broad range of fields such as biomineralization, sea water desalination and oil production. Knowledge of the surface structure and reactivity of the most stable cleavage plane, calcite (10.4), is pivotal for understanding the role of calcite in these diverse areas. Given the fact that most biological processes and technical applications take place in an aqueous environment, perhaps the most basic—yet decisive—question addresses the interaction of water molecules with the calcite (10.4) surface. In this work, amplitude modulation atomic force microscopy is used for three-dimensional (3D) mapping of the surface structure and the hydration layers above the surface. An easy-to-use scanning protocol is implemented for collecting reliable 3D data. We carefully discuss a comprehensible criterion for identifying the solid-liquid interface within our data. In our data three hydration layers form a characteristic pattern that is commensurate with the underlying calcite surface.

  17. Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations (United States)

    Podder, J.; Lin, J.; Sun, W.; Botis, S. M.; Tse, J.; Chen, N.; Hu, Y.; Li, D.; Seaman, J.; Pan, Y.


    Calcium carbonates such as calcite are the dominant hosts of inorganic iodine in nature and are potentially important for the retention and removal of radioactive iodine isotopes (129I and 131I) in contaminated water. However, little is known about the structural environment of iodine in carbonates. In this study, iodate (IO3-) doped calcite and vaterite have been synthesized using the gel-diffusion method at three NaIO3 concentrations (0.002; 0.004; 0.008 M) and a pH value of 9.0, under ambient temperature and pressure. Inductively coupled plasma mass spectrometry (ICP-MS) analyses show that iodine is preferentially incorporated into calcite over vaterite. Synchrotron iodine K-edge X-ray absorption near-edge structure (XANES) spectra confirm that IO3- is the dominant iodine species in synthetic calcite and vaterite. Analyses of iodine K-edge extended X-ray absorption fine structure (EXAFS) data, complemented by periodic first-principles calculations at the density functional theory (DFT) levels, demonstrate that the I5+ ion of the IO3- group in calcite and vaterite is bonded by three and two additional O atoms (i.e., coordination numbers = 6 and 5), respectively, and is incorporated via the charged coupled substitution I5+ + Na+ ↔ C4+ + Ca2+, with the Na+ cation at a nearest Ca2+ site being the most energetically favorable configuration.

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

    National Research Council Canada - National Science Library

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


    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...

  19. Calcite Wettability in the Presence of Dissolved Mg2+ and SO42-

    DEFF Research Database (Denmark)

    Generosi, Johanna; Ceccato, Marcel; Andersson, Martin Peter


    with calcite even after rinsing with CaCO3-saturated deionized water, suggesting sorption on or in calcite. When the calcite-saturated solution of MgSO4 was replaced by calcite-saturated NaCl at the same ionic strength, adhesion force increased again, indicating that the effect is reversible and suggesting Mg...... replacement by Ca. Experiments with solutions of Na2SO4 and MgCl2 suggest that Mg2+ uptake is favored when SO42– is also present...

  20. Fluoride removal by calcite: evidence for fluorite precipitation and surface adsorption. (United States)

    Turner, Brett D; Binning, Philip; Stipp, S L S


    Fluoride contamination of groundwater, both anthropogenic and natural, is a major problem worldwide. In this study, fluoride removal by crushed limestone (99% pure calcite) was investigated by batch studies and surface-sensitive techniques from solutions with fluoride concentrations from 150 micromol/L (3 mg/L) to 110 mM (approximately 2100 mg/L). Surface-sensitive techniques, including atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) as well as zeta potential measurements, confirm that, in addition to precipitation reactions, adsorption of fluoride also occurs. Results indicate that fluoride adsorption occurs immediately over the entire calcite surface with fluorite precipitating at step edges and kinks, where dissolved Ca2+ concentration is highest. The PHREEQ geochemical model was applied to the observed data and indicates that existing models, especially at low fluoride concentrations and high pH (>7.5) are not equipped to describe this complex system, largely because the PHREEQ model includes only precipitation reactions, whereas a combination of adsorption and precipitation parameters are required.

  1. Environmentally acceptable effect of hydrogen peroxide on cave "lamp-flora", calcite speleothems and limestones. (United States)

    Faimon, Jirí; Stelcl, Jindrich; Kubesová, Svatava; Zimák, Jirí


    Mosses, algae, and cyanobacteria (lamp-flora) colonize illuminated areas in show caves. This biota is commonly removed by a sodium hypochlorite solution. Because chlorine and other deleterious compounds are released into a cave environment during lamp-flora cleansing, hydrogen peroxide was tested as an alternative agent. In a multidisciplinary study conducted in the Kateinská Cave (Moravian Karst, Czech Republic), 12 algae- and cyanobacteria taxons and 19 moss taxons were detected. The threshold hydrogen peroxide concentration for the destruction of this lamp-flora was found to be 15 vol.%. Based on laboratory experiments in stirred batch reactors, the dissolution rates of limestones and calcite speleothems in water were determined as 3.77 x 10-3 and 1.81 x 10-3 mol m-2 h-1, respectively. In the 15% peroxide solution, the limestone and speleothem dissolution rates were one order of magnitude higher, 2.00 x 10-2 and 2.21 x 10-2 mol m-2 h-1, respectively. So, the peroxide solution was recognised to attack carbonates somewhat more aggressively than karst water. In order to prevent the potential corrosion of limestone and speleothems, the reaching of preliminary peroxide saturation with respect to calcite is recommended, for example, by adding of few limestone fragments into the solution at least 10 h prior to its application.

  2. The effect of water on strain localization in calcite fault gouge sheared at seismic slip rates (United States)

    Rempe, Marieke; Smith, Steven; Mitchell, Thomas; Hirose, Takehiro; Di Toro, Giulio


    Strain localization during coseismic slip in fault gouges is a critical mechanical process that has implications for understanding frictional heating, the earthquake energy budget and the evolution of fault rock microstructure. To assess the nature of strain localization during shearing of calcite fault gouges, high-velocity (vmax = 1m /s) rotary-shear experiments at normal stresses of 3-20 MPa were conducted under room-dry and wet conditions on synthetic calcite gouges containing dolomite gouge strain markers. When sheared at 1 m/s, the room-dry gouges showed a prolonged strengthening phase prior to dynamic weakening, whereas the wet gouges weakened nearly instantaneously. Microstructural analysis revealed that a thin (<600 μm) high-strain layer and through-going principal slip surface (PSS) developed after several centimeters of slip in both dry and wet gouges, and that strain localization at 1 m/s occurred progressively and rapidly. The strain accommodated in the bulk gouge layer did not change significantly with increasing displacement indicating that, once formed, the high-strain layer and PSS accommodated most of the displacement. Thus, a substantial strain gradient is present in the gouge layer. In water-dampened gouges, localization likely occurs during and after dynamic weakening. Our results suggest that natural fault zones in limestone are more prone to rapid dynamic weakening if water is present in the granular slipping zones.

  3. Remineralization of permeate water by calcite bed in the Daoura's plant (south of Morocco) (United States)

    Biyoune, M. G.; Atbir, A.; Bari, H.; Hassnaoui, L.; Mongach, E.; Khadir, A.; Boukbir, L.; Bellajrou, R.; Elhadek, M.


    To face water shortage and to fight drought, the National office of Water and Electricity (ONEE) carried out a program aiming at constructing several desalination stations of seawater in the South of Morocco. However, the final product water after desalination (osmosis water) has turned out to be unbalanced and has an aggressive character. Therefore, a post-treatment of remineralization is necessary to recover the calco-carbonic equilibrium of water and to protect the distribution network from corrosion degradation. Thereby, our work aims to examine the performance of the remineralization used in Daoura plant by the calcite bed in the absence of carbon dioxide CO2 (without acidification), we have followed many parameters indicating the performance of this technique adopted such as pH, TAC (hydroxide, carbonate and bicarbonate content), Ca content, Langelier saturation index (LSI), Larson index (LR). The results obtained show that this technique adopted in Daoura plant brings to water back its entire calco-carbonic balance to measure up to the Moroccan standards of drinking water. Generally, the exploitation of the calcite bed technique for remineralization is simple, easy and it does not require any major efforts or precautions.

  4. Genesis and microstratigraphy of calcite coralloids analysed by high resolution imaging and petrography (United States)

    Vanghi, V.; Frisia, S.; Borsato, A.


    The genesis of calcite coralloid speleothems from Lamalunga cave (Southern Italy) is here investigated from a purely petrographic perspective, which constitutes the basis for any subsequent chemical investigation. Lamalunga cave coralloids formed on bones and debris on the floor of the cave. They consist of elongated columnar crystals whose elongation progressively increases from the flanks to the tips of the coralloid, forming a succession of lens-shaped layers, which may be separated by micrite or impurity-rich layers. Organic molecules are preferentially concentrated toward the centre of convex lenses as highlighted by epifluorescence. Their occurrence on cave floor, lens-shaped morphology and concentration of impurities toward the apex of the convex lenses supports the hypothesis that their water supply was hydroaerosol, generated by the fragmentation of cave drips. Evaporation and degassing preferentially occurred on tips, enhancing the digitated morphology and trapping the organic molecules and impurities, carried by the hydroaerosol, between the growing crystals which became more elongated. Micrite layers, that cap some coralloid lenses, likely identify periods when decreasing in hydroaerosol resulted in stronger evaporation and higher supersaturation with respect to calcite of the parent film of fluid. This interpretation of coralloid formation implies that these speleothems can be used to extract hydroclimate information.

  5. Characterization of urease and carbonic anhydrase producing bacteria and their role in calcite precipitation. (United States)

    Achal, Varenyam; Pan, Xiangliang


    Urease and carbonic anhydrase (CA) are key enzymes in the chemical reaction of living organisms and have been found to be associated with calcification in a number of microorganisms and invertebrates. Three bacterial strains designated as AP4, AP6, and AP9 were isolated from highly alkaline soil samples using the enrichment culture technique. On the basis of various physiological tests and 16S rRNA sequence analysis, these three bacteria were identified as Bacillus sp., B. megaterium, and B. simplex. Further, these Bacillus species have been characterized for the production of urease and CA in the process of biocalcification. One of the isolates, AP6 produced 553 U/ml of urease and 5.61 EU/ml CA. All the strains were able to produce significant amount of exopolymeric substances and biofilm. Further, efficacy of these strains was tested for calcite production ability and results were correlated with urease and CA. Isolate AP6 precipitated 2.26 mg calcite/cell dry mass (mg). Our observations strongly suggest that it is not only urease but CA also plays an important role in microbially induced calcium carbonate precipitation process. The current work demonstrates that urease and CA producing microbes can be utilized in biocalcification as a sealing agent for filling the gaps or cracks and fissures in constructed facilities and natural formations alike.

  6. TEM study of Pt-C replicas of calcite overgrowths precipitated from electrolyte solutions (United States)

    Paquette, Jeanne; Vali, Hojatollah; Mucci, Alfonso


    The surface microtopography of synthetic magnesian calcite overgrowths on calcite powders was imaged on Pt-C replicas by transmission electron microscopy. The overgrowths were precipitated at room temperature under steady-state conditions from seawater-like solutions, in the presence and absence of Mg2+, SO42- and PO43- ions, and over a range of saturation states. Overgrowths produced from the Mg-free electrolyte show smooth coverage of the substrate with a few hillocks suggestive of spiral growth. Electrolytes containing Mg consistently produced patchy overgrowths on the {1014} faces of the seed crystals and differential inhibition of growth at their corners and edges. The patchy over-growths consist of flat-topped islands whose morphology is consistent with two-dimensional surface nucleation rather than spiral growth. The density of islands, their rounding, and their degree of coalescence increased with the saturation state of the precipitating solution. The effect of SO42- on the surface topography was imperceptible. Soluble reactive phosphate (SRP), on the other hand, clearly inhibited growth and dissolution along specific crystallographic directions. The development of irregular surfaces along specific edges and corners of the seed crystals shows that foreign ions promote the development of complex crystal morphology even at high saturation states.

  7. Study on effect of Microbial Induced Calcite Precipitates on strength of fine grained soils

    Directory of Open Access Journals (Sweden)

    Animesh Sharma


    Full Text Available For construction purposes, it is very essential to provide a strong foundation for the structure. If required, the suitability of soil has to be improved; this process of improving properties of soil is called Soil Stabilisation. This study intends to experimentally analyse the effectiveness of use of an unorthodox liquid soil stabiliser, Microbial Induced Calcite Precipitates (MICP for improving the shear strength parameters of two different types of fine grained soils. For this process, a species of Bacillus group, B. pastuerii was used to activate and catalyse the calcite precipitation caused by reaction between urea and calcium chloride. Two types of soils, i.e. intermediate compressible clay and highly compressible clay were used for the study. Parameters included concentration of B. pasteurii, concentration of the cementation reagent and duration of treatment. These parameters were applied on both the soils in a specified range in order to optimise their usage. The results proved that with the use of MICP, there was a noticeable improvement (1.5–2.9 times in the unconfined compressive strength of both type of soils. It was also found that the strength increased with an increase in duration of treatment. Based on this study, optimum quantity and concentration of liquid additive to be added for different soil types for better strength increments were established.

  8. Effects of Citrate and Arginine on Sorption of Nickel to Yazd Sepiolite and Calcite

    Directory of Open Access Journals (Sweden)

    Ahmadreza Sheikhhosseini


    Full Text Available Introduction: Pollution of soil and water environment by release of heavy metals is of great concerns of the last decades. Sorption of heavy metals by low cost materials is considered as an inexpensive and efficient method used for removal of heavy metals from soil-water systems. The presence of different ligands with various complexing abilities can change the sorption properties of heavy metals and their fate in the environment as well. In order to assess the effect of citrate and arginine as natural organic ligands in soil environment, in a batch study we investigated the effects of these ligands on equilibrium sorption of nickel to sepiolite and calcite minerals and also kinetics of Ni sorption by these minerals. Materials and Methods: Minerals used in this study included sepiolite from Yazd (Iran and pure calcite (Analytical grade, Merck, Germany. Sepiolite was purified, saturated with Ca using 0.5 M CaCl2, powdered in a mortar and sieved by non-metal 230 mesh standard wire sieve. For equilibrium sorption study, in a 50-mL polyethylene centrifuge tube,0.3 g sample of each mineral was suspended in 30 mL of a 0.01 M CaCl2 solution containing 0, 5, 10, 20, 40, 60, 80 and 100 mg L-1 Ni (NiCl2 and containing zero (as control or 0.1mmol L-1 citrate or arginine ligands. The applied concentrationsfor each ligand can naturally occur in soils. Preparedtubes were shaken (180±2 rpm, 25±1oC for 24 h using an orbital shaker and centrifuged (4000×g for 10 min and the supernatants were analyzed for Ni concentration using an atomic absorption spectrophotometer (AAnalyst 200 Perkin-Elmer at a wavelength of 232 nm and a detection limit of 0.05 mg L-1. The quantity of Ni retained by each mineral at equilibrium was calculated using equation qe = (Ci - CeV/W where qe was the amount of nickel retained by mineral surface at equilibrium. Ci and Ce were the initial and the equilibrium concentrations (mg L-1 of Ni, respectively, V was the volume (L of the solution

  9. Constraints on the vital effect in coccolithophore and dinoflagellate calcite by oxygen isotopic modification of seawater (United States)

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


    In this study, we show that there are independent controls of 18O/16O and 13C/12C fractionation in coccolithophore and dinoflagellate calcite due to the contrasting kinetics of each isotope system. We demonstrate that the direction and magnitude of the oxygen isotope fractionation with respect to equilibrium is related to the balance between calcification rate and the replenishment of the internal pool of dissolved inorganic carbon (DIC). As such, in fast growing cells, such as those of Emiliania huxleyi and Gephyrocapsa oceanica (forming the so-called ;heavy group;), calcification of the internal carbon pool occurs faster than complete isotopic re-adjustment of the internal DIC pool with H2O molecules. Hence, coccoliths reflect the heavy oxygen isotope signature of the CO2 overprinting the whole DIC pool. Conversely, in large and slow growing cells, such as Coccolithus pelagicus ssp. braarudii, complete re-equilibration is achieved due to limited influx of CO2 leading to coccoliths that are precipitated in conditions close to isotopic equilibrium (;equilibrium group;). Species exhibiting the most negative oxygen isotope composition, such as Calcidiscus leptoporus (;light group;), precipitate coccolith under increased pH in the coccolith vesicle, as previously documented by the ;carbonate ion effect;. We suggest that, for the carbon isotope system, any observed deviation from isotopic equilibrium is only ;apparent;, as the carbon isotopic composition in coccolith calcite is controlled by a Rayleigh fractionation originating from preferential incorporation of 12C into organic matter. Therefore, species with low PIC/POC ratios as E. huxleyi and G. oceanica are shifted towards positive carbon isotope values as a result of predominant carbon fixation into the organic matter. By contrast, cells with higher PIC/POC as C. braarudii and C. leptoporus maintain, to some extent, the original negative isotopic composition of the CO2. The calcareous dinoflagellate

  10. Calcite Precipitation at an Arctic Geothermal Spring Leads to Endolith Colonization and Ecological Succession (United States)

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


    A critical question in microbial ecology concerns how environmental conditions affect community makeup. Troll Springs, a geothermal spring at 79°23'N, 13°26'E on Svalbard in the high Arctic, provides an opportunity to study microbial communities and succession along steep environmental gradients that impose strong selective pressures. At Troll, warm water is released into cold, dry climate conditions. Precipitation of calcite from the spring's waters has built terraces that host a range of microbial communities. Microorganisms exist in warm water as periphyton, in moist granular materials, and in cold, dry rock as endoliths. Troll therefore has two distinct ecosystems, aquatic and terrestrial, in close proximity, with different underlying environmental factors shaping their microbial communities. We use microscopic and phylogeny-based molecular methods to study microbial community makeup at Troll Springs. Periphyton are entrapped by precipitation of calcite, becoming precursors for endolithic communities. Much of the pore space originally occupied by periphyton becomes inhabited either by organisms that were already present in minor quantities in the periphyton, or by new organisms that colonized an environment for which they were well suited. This process differs from most endolith colonization, where rock predates the communities that colonize it. In the aquatic environments, the strongest dependence of community makeup is on pH and temperature, with gradual changes in community makeup along a pH/temperature gradient among the pools. Illumination (as limited by calcite precipitation) and thermal stability also appear to exert influence. In contrast, in the granular and endolithic terrestrial environments, where water is scarce and therefore exerts selective pressure, there is a strong relationship between community makeup and water content. The richness, evenness, and diversity of microbial taxa are all strongly correlated at Troll Springs. These parameters all

  11. Molecular dynamics simulations of the calcite/solution interface as a means to explore surface modifications induced by nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, Sascha; Schmidt, Moritz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Surface Processes; Spijker, P. [Aalto Univ., Helsinki (Finland). Dept. of Applied Physics; Voitchovsky, K. [Durham Univ. (United Kingdom). Physics Dept.


    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 NaNO{sub 3} severely affect calcite's (104) surface and its reactivity. Molecular dynamics (MD) simulations reveal density profiles of different ions near calcite's surface, with NO{sub 3}{sup -} able to reach closer to the surface than CO{sub 3}{sup 2-} and in higher concentrations. Additionally, incorporation of NO{sub 3}{sup -} into the surface significantly disturbs the water structure at the interface.

  12. Common Ion Effects In Zeoponic Substrates: Dissolution And Cation Exchange Variations Due to Additions of Calcite, Dolomite and Wollastonite (United States)

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


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

  13. A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation (United States)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  15. Relative Shock Effects in Mixed Powders of Calcite, Gypsum, and Quartz: A Calibration Scheme from Shock Experiments (United States)

    Bell, Mary S.


    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

  16. Effect of annealing on natural calcitic crystals-A thermostimulated luminescence (TSL) study

    Energy Technology Data Exchange (ETDEWEB)

    Ponnusamy, V., E-mail: [Department of Physics, Division of Applied Sciences and Humanities, M.I.T. Campus, Anna University, Chennai 600044, Tamilnadu (India); Ramasamy, V. [Department of Physics, Annamalai University, Annamalainagar 608002, Tamilnadu (India); Jose, M.T. [Radiological Safety Division, IGCAR, Kalpakkam, Tamilnadu (India); Anandalakshmi, K. [Department of Physics, Annamalai University, Annamalainagar 608002, Tamilnadu (India)


    The quality crystals (Calcitic limestone) were selected using the UV-visible methylene blue adsorption method. The thermostimulated luminescence (TSL) glow curve characteristics of six well crystallized limestone samples were analyzed. The glow curves of unannealed sample show only one peak in the range 320-330 Degree-Sign C. The sample irradiated with a gamma dose of 100 Gy shows two additional peaks in the range of 113-125 Degree-Sign C and 242-260 Degree-Sign C when recorded with linear heating rate of 10 Degree-Sign C/s. The annealed sample also shows the same trend as that of irradiated sample. Annealing treatment above 250 Degree-Sign C increases the sensitivity of all TSL peaks except 320 Degree-Sign C. On the other hand, annealing at 750 Degree-Sign C caused a collapse in the TSL sensitivity. The enhancement in TSL sensitivity was found to depend on the annealing temperature and time. Annealing treatment at 650 Degree-Sign C for 4 h followed by quenching in air is the optimum condition for TSL sensitization. The response to gamma irradiation is linear in the range from 0.5 Gy to 10{sup 4} Gy. The emission spectra of all the samples show an emission at around 610 nm but with different intensities for each TSL peak. With reference to earlier work, it may be assumed that the recombination site always involves Mn{sup 2+} ions. The observation made through infra-red (IR) and X-ray diffraction (XRD) studies with thermal treatment shows the structural changes of calcite from D{sub 3h} to C{sub s} symmetry at 750 Degree-Sign C. The Thermogravimetric-Differential Thermal Analysis (TG-DTA) analysis shows the calcite gets disordered at 760 Degree-Sign C. Hence, the collapse in the TSL sensitivity at 750 Degree-Sign C is due to structural change or structural disorderedness. - Highlights: Black-Right-Pointing-Pointer Normally, the synthetic material was used as radiation dosimeter but the natural material can also be used for the same application. Black

  17. Calcitic sclerites at base of malacostracan pleopods (Crustacea)--part of a coxa. (United States)

    Kutschera, Verena; Maas, Andreas; Mayer, Gerd; Waloszek, Dieter


    Cuticular specialisations such as joints and membranes play an important role in the function of arthropod limbs. This includes sclerotisations and mineral incrustations of cuticular areas to achieve either more rigidity or flexibility. The anterior eight thoracopods of Malacostraca have limb stems comprising a coxa and a basipod, which carries the two rami. Their pleopods, the limbs of the posterior trunk part, have for long been regarded to lack a coxa. Several calcitic sclerites occur in the area between ventral body and limb stem. This raises the questions: do these elements represent specialisations of the membrane due to functional requirements, and do they originate from an originally larger limb portion, i.e., the coxa, or in fact represent it. We investigated 16 species of selected malacostracan taxa from all major in-groups. Calcitic sclerites occur in constant numbers and position within a species (no individual variation, and independent of specific modification such as in genital appendages). These are even constant within a supra-specific taxon, which facilitates comparisons. In general the sclerites connect via two pivot joints to the sternite medially and the tergopleura laterally, and two more to the limb stem. Based on this, we reconstructed putative ground-pattern conditions for the sclerites of the examined taxa of Malacostraca. The pattern of sclerites is characteristic for each monophyletic malacostracan taxon. The highest number of sclerites most likely represents the plesiomorphic state. Reduction of sclerite numbers occurs in Caridoida and its in-groups. Sclerite arrangement in these taxa provides an important character complex for phylogenetic studies. The presence of pivot joints to the body proximally and basipod distally demonstrates the existence of a coxa, which is just slightly less sclerotised, particularly on its posterior side. This can be explained by enhanced flexibility of the pleopods evolved in the course to their major role

  18. Two-dimensional X-ray diffraction as a tool for the rapid, nondestructive detection of low calcite quantities in aragonitic corals (United States)

    Smodej, Jörg; Reuning, Lars; Wollenberg, Uwe; Zinke, Jens; Pfeiffer, Miriam; Kukla, Peter A.


    Paleoclimate reconstructions based on reef corals require precise detection of diagenetic alteration. Secondary calcite can significantly affect paleotemperature reconstructions at very low amounts of ˜1%. X-ray powder diffraction is routinely used to detect diagenetic calcite in aragonitic corals. This procedure has its limitations as single powder samples might not represent the entire coral heterogeneity. A conventional and a 2-D X-ray diffractometer were calibrated with gravimetric powder standards of high and low magnesium calcite (0.3% to 25% calcite). Calcite contents slabs. The calcite detection performance of the 2-D-XRD setup was tested on thin sections from fossil Porites sp. samples that, based on powder XRD measurements, showed analysis showed very similar results. This enables spot measurements with diameters of ˜4 mm, as well as systematic line scans along potential tracks previous to geochemical proxy sampling. In this way, areas affected by diagenetic calcite can be avoided and alternative sampling tracks can be defined. Alternatively, individual sampling positions that show dubious proxy results can later be checked for the presence of calcite. The presented calibration and quantification method can be transferred to any 2-D X-ray diffractometer.

  19. Morphology of calcite crystals in clast coatings from four soils in the Mojave desert region (United States)

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


    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.

  20. Impact of the distribution of calcite concretions on performance of SAGD

    Energy Technology Data Exchange (ETDEWEB)

    Gates, Ian [University of Calgary (Canada)


    In the heavy oil industry, the steam assisted gravity drainage (SAGD) process is often used to enhance oil recovery. In Grand Rapids oil sands reservoirs, carbonate cemented concretions can be found. In terms of SAGD process, these concretions can have an impact on the growth of steam chambers and thus on the method's performance. Calcite concretions are non productive rock but this can also enhance heat transfer through thermal dispersion depending on the length scales of its spatial distribution, sizes and shapes. The aim of this paper is then to study the effects of the concretion's spatial distributions and size on the performance of SAGD. Tests were conducted to assess several parameters of the steam chamber and results showed that steam chamber conformance depends on the heterogeneity of the concretions. This paper highlighted that SAGD performance can be optimized by deciding length scales for placement of well pairs and provided a means to do it.

  1. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals (United States)

    Kimball, Justine; Eagle, Robert; Dunbar, Robert


    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 high-Mg 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 high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships 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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  3. Calcite-impregnated defluidization structures in littoral sands of mono lake, california. (United States)

    Cloud, P; Lajoie, K R


    Associated locally with well-known tufa mounds and towers of Mono Lake, California, are subvertical, concretionary sand structures through which fresh calcium-containing artesian waters moved up to sites of calcium carbonate precipitation beneath and adjacent to the lake. The structures include closely spaced calcite-impregnated columns, tubes, and other configurations with subcylindrical to bizarre cross sections and predominantly vertical orientation in coarse, barely coherent pumice sands along the south shore of the lake. Many structures terminate upward in extensive calcareous layers of caliche and tufa. Locally they enter the bases of tufa mounds and towers. A common form superficially resembles root casts and animal burrows except that branching is mostly up instead of down. Similar defluidization structures in ancient sedimentary rocks have been mistakenly interpreted as fossil burrows.

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

    DEFF Research Database (Denmark)

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


    The fate of pesticides in aquifers is influenced by the small but not insignificant adsorption of pesticides to mineral surfaces. Batch experiments with five pesticides and four minerals were conducted to quantify the contributions to adsorption from different mineral surfaces and compare...... adsorption characteristics of selected pesticides. Investigated mineral phases included quartz, calcite, kaolinite, and alpha -alumina. Selected pesticides comprised atrazine (6-chloro-N-2-ethyl-N-4-isopropyl-1,3,5-triazine-2,4-diamine isoproturon [3-(4-isopropyl-phenyl)-1,1-dimethylurea)], mecoprop [(RS)-2......-(4-chloro-2-methyl phenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2-dioxide]. Specific surface area and mineral surface charge proved to be important for the adsorption of these pesticides. Detectable adsorption...

  5. Seasonal and Interannual Variability of Calcite in the Sub-Polar North Atlantic (United States)

    Signorini, S. R.; McClain, C. R.


    Coccolithophores, among which Emiliania huxleyi (E. huxleyi) is the most abundant and widespread species, are considered to be the most productive calcifying organisms on Earth. They inhabit the surface layer (MLD ~20m) in highly stratified waters where light intensity is high. E. huxleyi often forms massive blooms in temperate and sub-polar oceans. Coupling of the coccolithophore organic carbon and carbonate pumps interact to consume (photosynthesis) and produce (calcification) CO2. The so-called Rain Ratio, defined as the ratio of particulate inorganic carbon (PIC) to particulate organic carbon (POC) in exported biogenic matter, determines the relative strength of the two biological carbon pumps and influences the flux of CO2 across the surface ocean - atmosphere interface. Here we use a combination of satellite ocean color algorithms and numerical model products to describe the seasonal and interannual variability of PIC in the sub-polar North Atlantic. Phytoplankton and calcite production have strong spatial variability. Nutrient supply, biomass and calcite concentrations are modulated by light and MLD seasonal cycle. The size, intensity, and location of coccolithophore blooms vary from year to year, but the peak bloom is always in June in the Central Basin (45°W - 10°W, 50°N - 65°N) and August in the Barents Sea. Calcification rates range from 5% to 27% of net primary production. The Barents Sea PIC production is about twice that of the Central Basin. Predicted freshening and warming of polar seas may increase stratification, thus favoring an increase in coccolithophore bloom development. However, although significant interannual changes were identified, there were no obvious trends in the satellite-derived PIC concentrations over the past 10 years.

  6. First-principles study of boron speciation in calcite and aragonite (United States)

    Balan, Etienne; Pietrucci, Fabio; Gervais, Christel; Blanchard, Marc; Schott, Jacques; Gaillardet, Jérome


    Despite the importance of boron as a proxy of past ocean pH, the crystal-chemical factors controlling its incorporation in the structure of calcium carbonates are still poorly understood. This is partly linked to an imperfect knowledge of the coordination, protonation state and local environment of boron species in these minerals. In the present study, we use first-principles quantum mechanical tools to model selected trigonal and tetragonal boron species in calcite and aragonite. The stable geometry of the models is obtained from standard energy minimization schemes or using a more advanced metadynamics exploration of their configurational space. The computation of 11B NMR chemical shifts and quadrupolar coupling parameters enables a straightforward comparison of the models to existing experimental NMR data. The results show that B in calcium carbonates does occur as structural species substituted for CO32- anions. The B speciation depends on the polymorph considered. In calcite, structural boron is present as partially deprotonated trigonal BO2(OH)2- species coexisting with a fraction of substituted B(OH)4- groups. In aragonite, the B(OH)4- substitution for CO32- anions is dominant. Different species, including entrapped B(OH)3 molecules and substituted BO33- groups also occur in biogenic samples. The diversity of B speciation reflects a diversity of B incorporation mechanisms and sheds light on previous studies confronting B isotopic composition determination with NMR observations. The mechanisms of boron incorporation in calcium carbonates are probably more complex than usually assumed in the literature using boron isotopes as a proxy of paleo-atmospheric CO2 reconstructions. Although not invalidating the empirical paleo-pH proxy, these results call for a better understanding of the fundamental mechanisms of boron incorporation in carbonates.

  7. Altervalent substitution of sodium for calcium in biogenic calcite and aragonite (United States)

    Yoshimura, Toshihiro; Tamenori, Yusuke; Suzuki, Atsushi; Kawahata, Hodaka; Iwasaki, Nozomu; Hasegawa, Hiroshi; Nguyen, Luan T.; Kuroyanagi, Azumi; Yamazaki, Toshitsugu; Kuroda, Junichiro; Ohkouchi, Naohiko


    Sodium concentrations in biogenic CaCO3 are several thousands of parts per million, and, on a molar basis, Na is among the most abundant constituent minor element in these carbonates. Nevertheless, the chemical form of Na in CaCO3 is not well constrained. We used synchrotron X-ray spectroscopy to identify the dominant molecular host sites for Na in biogenic calcite and aragonite precipitated by corals, bivalves, and foraminifera. We also used the K-edge X-ray absorption near-edge structure to investigate the chemical environment of Na in biogenic calcium carbonates and identify the altervalent substitution of Na into Ca sites in the lattice structures of calcite and aragonite. Minor cation and anion concentrations in biogenic CaCO3 suggest that the principal substitution mechanism involves charge compensation through the creation of CO32- vacancies. The mostly homogeneous Na concentrations in the skeletal microstructures of the various biota we examined indicate that environmental and biological controls, such as temperature, skeletal microstructure, and calcification rates, have only minor influences on skeletal Na concentrations. A decrease of Na:Ca ratios with increasing age of foraminiferal shells picked from a Quaternary sediment core, indicates progressive release of Na, which suggests that structurally-substituted Na in biogenic CaCO3 is readily leached during burial diagenesis. Whereas the sediment that undergo diagenesis release some Na back to the water column, sodium co-precipitation in biogenic CaCO3 serves as a potential sink of Na for the ocean.

  8. Anisotropic Growth of Otavite on Calcite: Implications for Heteroepitaxial Growth Mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Riechers, Shawn L. [Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Kerisit, Sebastien N. [Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States


    Elucidating how cation intermixing can affect the mechanisms of heteroepitaxial growth in aqueous media has remained a challenging endeavor. Toward this goal, in situ atomic force microscopy was employed to image the heteroepitaxial growth of otavite (CdCO3) at the (10-14) surface of calcite (CaCO3) single crystals in static aqueous conditions. Heteroepitaxial growth proceeded via spreading of three-dimensional (3D) islands and two-dimensional (2D) atomic layers at low and high initial saturation levels, respectively. Experiments were carried out as a function of applied force and imaging mode thus enabling determination of growth mechanisms unaltered by imaging artifacts. This approach revealed the significant anisotropic nature of heteroepitaxial growth on calcite in both growth modes and its dependence on supersaturation, intermixing, and substrate topography. The 3D islands not only grew preferentially along the [42-1] direction relative to the [010] direction, resulting in rod-like surface precipitates, but also showed clear preference for growth from the island end rich in obtuse/obtuse kink sites. Pinning to step edges was observed to often reverse this tendency. In the 2D growth mode, the relative velocities of acute and obtuse steps were observed to switch between the first and second atomic layers. This phenomenon stemmed from the significant Cd-Ca intermixing in the first layer, despite bulk thermodynamics predicting the formation of almost pure otavite. Composition effects were also responsible for the inability of 3D islands to grow on 2D layers in cases where both modes were observed to occur simultaneously. Overall, the AFM images highlighted the effects of intermixing on heteroepitaxial growth, particularly how it can induce thickness-dependent growth mechanisms at the nanoscale.

  9. An Exercise on Calibration: DRIFTS Study of Binary Mixtures of Calcite and Dolomite with Partially Overlapping Spectral Features (United States)

    De Lorenzi Pezzolo, Alessandra


    Unlike most spectroscopic calibrations that are based on the study of well-separated features ascribable to the different components, this laboratory experience is especially designed to exploit spectral features that are nearly overlapping. The investigated system consists of a binary mixture of two commonly occurring minerals, calcite and…

  10. Calcite growth rates as a function of aqueous calcium-to-carbonate ratio, saturation index and strontium concentration

    Energy Technology Data Exchange (ETDEWEB)

    Bracco, Jacquelyn N [ORNL; Grantham, Ms. Meg [Georgia Institute of Technology; Stack, Andrew G [ORNL


    Using in situ atomic force microscopy, the growth rates of the obtuse and acute step orientations on the calcite surface were measured at two saturation indices as a function of the aqueous calcium-to-carbonate ratio and aqueous strontium concentration. The amount of strontium required to inhibit growth was found to correlate with the aqueous calcium concentration, but did not correlate with carbonate. This suggests that strontium inhibits attachment of calcium ions to the reactive sites on the calcite surface. Strontium/calcium cation exchange selectivity coefficients for those sites, Kex, of 1.09 0.09 and 1.44 0.19 are estimated for the obtuse and acute step orientations, respectively. The implication of this finding is that to avoid poisoning calcite growth, the concentration of calcium should be higher than the quotient of the strontium concentration and Kex, regardless of saturation state. Additionally, analytical models of nucleation and propagation of steps are expanded from previous work to capture growth rates of these steps at multiple saturation indices and the effect of strontium. This work will have broader implications for naturally occurring or engineered calcite growth, such as to sequester subsurface strontium contamination.

  11. Early- to late-Holocene contrast in productivity, OMZ intensity and calcite dissolution in the eastern Arabian Sea

    Digital Repository Service at National Institute of Oceanography (India)

    Naik, S.S.; Godad, S.P.; Naidu, P.D.; Tiwari, M.; Paropkari, A.L.

    , vol.24(6); 2014; 749-755 Early to Late Holocene Contrast in productivity, OMZ Intensity and Calcite Dissolution in the Eastern Arabian Sea Sushant S. Naik*,1, Shital P. Godad2, P. Divakar Naidu3, Manish Tiwari4, A. L. Paropkari5 1,2,3,5 CSIR...

  12. Evaluation of sediment capping with active barrier systems (ABS) using calcite/zeolite mixtures to simultaneously manage phosphorus and ammonium release. (United States)

    Lin, Jianwei; Zhan, Yanhui; Zhu, Zhiliang


    The efficiency and mechanism of sediment capping with an active barrier system (ABS) using calcite/zeolite mixtures to simultaneously prevent phosphorus (P) and ammonium (NH(4)(+)) release from eutrophic lake sediments under anaerobic conditions was investigated through a series of batch and sediment incubation experiments. For this, natural calcite and various zeolites (natural, NaCl-pretreated and CaCl(2)-pretreated zeolites) were applied. Batch tests showed that the calcite was efficient for the removal of phosphate in aqueous solution and the zeolite was an efficient adsorbent for the removal of NH(4)(+) from aqueous solution. Sediment incubation experiments showed that the P and NH(4)(+) fluxes from the anaerobic sediments were significantly reduced by the ABS using the mixture of calcite and natural zeolite. Higher calcite dosage was found to be favorable for the prevention of P release from the sediments using the ABS. For controlling the P release from the sediments, the mixture of calcite and CaCl(2)-pretreated zeolite as a capping material was more efficient than that of calcite and natural zeolite, whereas the mixture of calcite and NaCl-pretreated zeolite was less efficient than that of calcite and natural zeolite. Batch and sediment incubation experiments proved that the zeolite as a component of the ABS using the mixture of calcite and CaCl(2)-pretreated zeolite has a dual function: (i) preventing NH(4)(+) release from the sediments; and (ii) supplying Ca(2+) through a Ca(2+)/NH(4)(+) exchange to improve the ability of the capping material to immobilize P release from the sediments. Copyright © 2010 Elsevier B.V. All rights reserved.

  13. High-pressure deformation of calcite marble and its transformation to aragonite under non-hydrostatic conditions (United States)

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


    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.

  14. Friction characteristics of Cd-rich carbonate films on calcite surfaces: implications for compositional differentiation at the nanometer scale

    Directory of Open Access Journals (Sweden)

    Cubillas Pablo


    Full Text Available Abstract Lateral Force Microscopy (LFM studies were carried out on cleaved calcite sections in contact with solutions supersaturated with respect to otavite (CdCO3 or calcite-otavite solid solutions (SS as a means to examine the potential for future application of LFM as a nanometer-scale mineral surface composition mapping technique. Layer-by-layer growth of surface films took place either by step advancement or by a surface nucleation and step advancement mechanisms. Friction vs. applied load data acquired on the films and the calcite substrate were successfully fitted to the Johnson Kendall Roberts (JKR model for single asperity contacts. Following this model, friction differences between film and substrate at low loads were dictated by differences in adhesion, whereas at higher load they reflect differences in contact shear strength. In most experiments at fixed load, the film showed higher friction than the calcite surface, but the friction-load dependence for the different surfaces revealed that at low loads (0–40 nN, a calcian otavite film has lower friction than calcite; a result that is contrary to earlier LFM reports of the same system. Multilayer films of calcian-otavite displayed increasing friction with film thickness, consistent with the expectation that the film surface composition will become increasingly Cd-rich with increasing thickness. Both load- and thickness-dependence trends support the hypothesis that the contact shear strength correlates with the hydration enthalpy of the surface ions, thereby imparting friction sensitivity in the LFM to mineral-water interface composition.

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

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


    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

  16. Formation of a ternary neptunyl(V) biscarbonato inner-sphere sorption complex inhibits calcite growth rate. (United States)

    Heberling, Frank; Scheinost, Andreas C; Bosbach, Dirk


    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. Copyright © 2011 Elsevier B.V. All rights

  17. Seawater Mg/Ca controls polymorph mineralogy of microbial CaCO3: a potential proxy for calcite-aragonite seas in Precambrian time. (United States)

    Ries, J B; Anderson, M A; Hill, R T


    A previously published hydrothermal brine-river water mixing model driven by ocean crust production suggests that the molar Mg/Ca ratio of seawater (mMg/Ca(sw)) has varied significantly (approximately 1.0-5.2) over Precambrian time, resulting in six intervals of aragonite-favouring seas (mMg/Ca(sw) > 2) and five intervals of calcite-favouring seas (mMg/Ca(sw) mineralogical proxy for Precambrian calcite-aragonite seas, calcifying microbial marine biofilms were cultured in experimental seawaters formulated over the range of Mg/Ca ratios believed to have characterized Precambrian seawater. Biofilms cultured in experimental aragonite seawater (mMg/Ca(sw) = 5.2) precipitated primarily aragonite with lesser amounts of high-Mg calcite (mMg/Ca(calcite) = 0.16), while biofilms cultured in experimental calcite seawater (mMg/Ca(sw) = 1.5) precipitated exclusively lower magnesian calcite (mMg/Ca(calcite) = 0.06). Furthermore, Mg/Ca(calcite )varied proportionally with Mg/Ca(sw). This nearly abiotic mineralogical response of the biofilm CaCO3 to altered Mg/Ca(sw) is consistent with the assertion that biofilm calcification proceeds more through the elevation of , via metabolic removal of CO2 and/or H+, than through the elevation of Ca2+, which would alter the Mg/Ca ratio of the biofilm's calcifying fluid causing its pattern of CaCO3 polymorph precipitation (aragonite vs. calcite; Mg-incorporation in calcite) to deviate from that of abiotic calcification. If previous assertions are correct that the physicochemical properties of Precambrian seawater were such that Mg/Ca(sw) was the primary variable influencing CaCO3 polymorph mineralogy, then the observed response of the biofilms' CaCO3 polymorph mineralogy to variations in Mg/Ca(sw), combined with the ubiquity of such microbial carbonates in Precambrian strata, suggests that the original polymorph mineralogy and Mg/Ca(calcite )of well-preserved microbial carbonates may be an archive of calcite-aragonite seas throughout Precambrian

  18. Calcite scale prediction at the near-well region: A radiotracer approach

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    Bjørnstad T.


    Full Text Available Effective prediction of calcite scaling requires a reliable thermodynamic model for the prediction of the scaling tendency, a kinetic model for the prediction of scaling rate and a transport model to simulate flow in a porous medium. The accurate prediction of the scale deposition can warn the engineers to “treat” the formation around the wellbore in time. In addition, the prediction of the distribution of the scale deposition can direct the engineers to ensure the placement of the inhibitors into the formation zones where the deposition is expected, thus maximizing the probability of successful prevention of formation damage and minimizing at the same time the amount of the required inhibitors. In this contribution, we present a geochemical computational model that combines existing thermodynamic and kinetic models for CaCO3 precipitation, with treatments of flow and diffusion in electrolyte systems, in an one-dimensional porous medium. The geochemical model has the ability to predict the distribution of scale deposition along and around the production wells, as well as the distribution of formation damage (pore blocking, permeability reduction around the wells.

  19. Comparative study of nanoscale surface structures of calcite microcrystals using FE-SEM, AFM, and TEM. (United States)

    Chien, Yung-Ching; Mucci, Alfonso; Paquette, Jeanne; Sears, S Kelly; Vali, Hojatollah


    The bulk morphology and surface features that developed upon precipitation on micrometer-size calcite powders and millimeter-size cleavage fragments were imaged by three different microscopic techniques: field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) of Pt-C replicas, and atomic force microscopy (AFM). Each technique can resolve some nanoscale surface features, but they offer different ranges of magnification and dimensional resolutions. Because sample preparation and imaging is not constrained by crystal orientation, FE-SEM and TEM of Pt-C replicas are best suited to image the overall morphology of microcrystals. However, owing to the decoration effect of Pt-C on the crystal faces, TEM of Pt-C replicas is superior at resolving nanoscale surface structures, including the development of new faces and the different microtopography among nonequivalent faces in microcrystals, which cannot be revealed by FE-SEM. In conjunction with SEM, Pt-C replica provides the evidence that crystals grow in diverse and face-specific modes. The TEM imaging of Pt-C replicas has nanoscale resolution comparable to AFM. AFM yielded quantitative information (e.g., crystallographic orientation and height of steps) of microtopographic features. In contrast to Pt-C replicas and SEM providing three-dimensional images of the crystals, AFM can only image one individual cleavage or flat surface at a time.

  20. Bio-mitigation of CO(2), calcite formation and simultaneous biodiesel precursors production using Chlorella sp. (United States)

    Fulke, Abhay B; Mudliar, S N; Yadav, Raju; Shekh, Ajam; Srinivasan, N; Ramanan, Rishiram; Krishnamurthi, K; Devi, S Saravana; Chakrabarti, T


    In this study, an attempt was made to use micro-algal system for the production of biodiesel precursors and simultaneous CO(2) mitigation. Chlorella sp. was found to have a higher growth rate as compared to the other algal species tested namely Chlamydomonas sp. and Synnecococcus sp. At different CO(2) concentrations (0.03%, 3%, 10% and 15%), the lipid productivity was 23.0, 20.0 and 27.3mg/L/d respectively. Calcite produced was characterized using FT-IR, SEM and XRD. The FAME in crude biofuel was analyzed by GC-FID that found to contain palmitic acid (C16:0), docosapentaenoic acid (C22:5) and docosahexaenoic acid (C22:6). The calorific value of Chlorella sp. was found to be 29kJ/g which is higher than values reported for fresh water microalgae making it a potential candidate to be used as an alternate fuel. Copyright 2010 Elsevier Ltd. All rights reserved.

  1. Calcite dissolution rate spectra measured by in situ digital holographic microscopy. (United States)

    Brand, Alexander S; Feng, Pan; Bullard, Jeffrey W


    Digital holographic microscopy in reflection mode is used to track in situ, real-time nanoscale topography evolution of cleaved (104) calcite surfaces exposed to flowing or static deionized water. The method captures full-field holograms of the surface at frame rates of up to 12.5 s(-1). Numerical reconstruction provides 3D surface topography with vertical resolution of a few nanometers and enables measurement of time-dependent local dissolution fluxes. A statistical distribution, or spectrum, of dissolution rates is generated by sampling multiple area domains on multiple crystals. The data show, as has been demonstrated by Fischer et al. (2012), that dissolution is most fully described by a rate spectrum, although the modal dissolution rate agrees well with published mean dissolution rates (e.g., 0.1 µmol m(-2) s(-1) to 0.3 µmol m(-2) s(-1)). Rhombohedral etch pits and other morphological features resulting from rapid local dissolution appear at different times and are heterogeneously distributed across the surface and through the depth. This makes the distribution in rates measured on a single crystal dependent both on the sample observation field size and on time, even at nominally constant undersaturation. Statistical analysis of the inherent noise in the DHM measurements indicates that the technique is robust and that it likely can be applied to quantify and interpret rate spectra for the dissolution or growth of other minerals.

  2. Verification of the causes of glaciations and sea level changes using the records of calcite speleothems.

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    Shopov Yavor Y.


    Full Text Available The luminescence of calcite speleothems displays an exponential dependence on soil temperature unless there is a dense cover of forest over the cave to dampen it. This relationship is determined primarily by the strength of solar visible and infrared radiation. It is suggested that, as a consequence, the microzonal variations of luminescence often found in speleothems can be used as a proxy index of Solar Insolation. The luminescence solar insolation proxy record of a speleothem from Jewel Cave, South Dakota, USA, was found to display millenial and centennial cycles in the record. It exhibits a rapid increase in solar insolation at 139 ± 5.5 kyrs. This increase precedes that suggested by the Orbital theory by about 10,000 years and is due to superimposition of the most powerful cycle in solar luminosity of 11.5 kyrs, upon the curve of orbital variations. The record from a speleothem in Duhlata Cave, Bulgaria matches that of South Dakota within the limits of dating error, indicating that both of these records (which are 10,000 km apart measure global solar insolation controls rather than local paleotemperature variations.


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    Heriansyah ePutra


    Full Text Available The optimization of enzyme-mediated calcite precipitation (EMCP was evaluated as a soil improvement technique. In our previous works, purified urease was utilized to bio-catalyze the hydrolysis of urea, which causes the supplied Ca2+ to precipitate with CO32- as calcium carbonate. In the present work, magnesium chloride was newly added to the injecting solutions to delay the reaction rate and to enhance the amount of carbonate precipitation. Soil specimens were prepared in PVC cylinders and treated with concentration-controlled solutions composed of urea, urease, calcium, and magnesium chloride. The mechanical properties of the treated soil specimens were examined through unconfined compressive strength (UCS tests. A precipitation ratio of the carbonate up to 90% of the maximum theoretical precipitation was achieved by adding a small amount of magnesium chloride. Adding magnesium chloride as a delaying agent was indeed found to reduce the reaction rate of the precipitation, which may increase the volume of the treated soil if used in real fields because of the slower precipitation rate and the resulting higher injectivity. A mineralogical analysis revealed that magnesium chloride decreases the crystal size of the precipitated materials and that another carbonate of aragonite is newly formed. Mechanical test results indicated that carbonate precipitates within the soils and brings about a significant improvement in strength. A maximum UCS of 0.6 MPa was obtained from the treated samples.

  4. Avian embryonic development does not change the stable isotope composition of the calcite eggshell. (United States)

    Maurer, G; Portugal, S J; Boomer, I; Cassey, P


    The avian embryo resorbs most of the calcium for bone formation from the calcite eggshell but the exact mechanisms of the resorption are unknown. The present study tested whether this process results in variable fractionation of the oxygen and carbon isotopes in shell calcium carbonate, which could provide a detailed insight into the temporal and spatial use of the eggshell by the developing embryo. Despite the uncertainty regarding changes in stable isotope composition of the eggshell across developmental stages or regions of the shell, eggshells are a popular resource for the analysis of historic and extant trophic relationships. To clarify how the stable isotope composition varies with embryonic development, the δ(13)C and δ(18)O content of the carbonate fraction in shells of black-headed gull (Larus ridibundus) eggs were sampled at four different stages of embryonic development and at five eggshell regions. No consistent relationship between the stable isotope composition of the eggshell and embryonic development, shell region or maculation was observed, although shell thickness decreased with development in all shell regions. By contrast, individual eggs differed significantly in isotope composition. These results establish that eggshells can be used to investigate a species' carbon and oxygen sources, regardless of the egg's developmental stage.

  5. Factors regulating the Great Calcite Belt in the Southern Ocean and its biogeochemical significance (United States)

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


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

  6. Utilization of microbial induced calcite precipitation for sand consolidation and mortar crack remediation

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    S.A. Abo-El-Enein


    Full Text Available The microbes can hydrolyze urea by urease enzyme to produce ammonium as well as carbonate ions and in the presence of calcium ions which can precipitate calcium carbonate; this process is called “biocalcification” or microbial induced calcite precipitation (MICP.This technology is environmentally friendly not only because it gives strength to sand body, but also it allows water to penetrate to sand body, which is unlike silicate cement that will destroy the ecosystem of the earth. Calcium carbonate precipitated by bacteria acts as a binding material to sand particles, so incompact sand will be consolidated. Calcium chloride, calcium acetate and calcium nitrate (1 M as calcium sources were tested for their ability to consolidate sand by mixing with urea (1 M and bacteria cells (one optical density, 1 OD. The key point of this study aimed to choose the suitable calcium source which produces higher compressive strength and lower water absorption. The results showed that the degree of crystallinity and amount of precipitated calcium carbonate, as well as the consequent increase in strength of consolidated sand, in case of calcium chloride medium are higher than those precipitated in case of calcium acetate as well as calcium nitrate media. In addition, consolidated sand by calcium chloride was also used for cement mortar crack remediation.

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

    DEFF Research Database (Denmark)

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


    action has been found to be replacement of oil at the solid surface by the enzyme. Other mechanisms (modification of the surface tension or catalytic modification of hydrocarbons resulting in reducing the oil viscosity) have shown to be much less pronounced from the measurements reported here.......Enzymes have recently been considered as possible agents for enhanced oil recovery (EOR) acting at the liquid-solid interface. One way to assess this is via measuring the wettability of calcite surfaces, important for EOR methods in carbonaceous reservoirs. In the present work, we have...... experimentally investigated the effect of enzymes on the wettability of calcite mineral surfaces with oil-brine systems. The action of various enzymes, including esterases/lipases, carbohydrases, proteases and oxidoreductases (along with two commercial mixtures) was studied by contact angle measurements...

  8. MicroRaman, PXRD, EDS and microscopic investigation of magnesium calcite biomineral phases. The case of sea urchin biominerals (United States)

    Borzęcka-Prokop, B.; Wesełucha-Birczyńska, A.; Koszowska, E.


    This study concerns Mg-calcite characterization (and in particular molecular structure and microstructural studies of mineral phases) of a sea urchin mineralised test and spines. Sea urchins are spiny sea animals (kingdom Animalia, phylum Echinodermata, class Echinoidea). Microscopic observations, SEM, EDS, PXRD and spectroscopic microRaman methods have been applied to characterize the biomineral parts of the sea urchin. The latter technique is very useful in research of biological systems and especially suitable for monitoring differences within biomineral phases exhibiting varieties of morphological forms. Crystalline magnesium calcium carbonate, Mg xCa 1- xCO 3 (magnesian calcite; space group R-3 cH; a = 4.9594(8) Å, c = 16.886(6) Å), has been identified as the predominant biomineral component.

  9. Effect of Magnesium as Substitute Material in Enzyme-Mediated Calcite Precipitation for Soil-Improvement Technique


    Putra, Heriansyah; Yasuhara, Hideaki; Kinoshita, Naoki; Neupane, Debendra; Lu, Chih-Wei


    The optimization of enzyme-mediated calcite precipitation was evaluated as a soil-improvement technique. In our previous works, purified urease was utilized to bio-catalyze the hydrolysis of urea, which causes the supplied Ca2+ to precipitate with C O 3 2 ? as calcium carbonate. In the present work, magnesium chloride was newly added to the injecting solutions to delay the reaction rate and to enhance the amount of carbonate precipitation. Soil specimens were prepared in PVC cylinders and tre...

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

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


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

  11. Adsorption studies of COD and Fe2+ from stabilized landfill leachate on activated carbon and calcite containing alginate (United States)

    Isa, Awatif Md; Yusoff, Mohd Suffian; Kamaruddin, Mohamad Anuar; Aziz, Hamidi Abdul


    In this study, composite adsorbent was produced from the combination of activated carbon (AC) and calcite by four (4) different mixing ratios (AC:Calcite) of 9:1, 7:3, 1:1, 3:7, 1:9. The mixture was mixed with alginate as the binder. The composite adsorbent was tested in batch of experimental study to observe the effectiveness of removing COD and Fe2+ from sample of leachate collected from semi-aerobic sanitary landfill at Pulau Burung, Penang, Malaysia. The effect on contact time was conducted to observe its impact on the adsorption of COD and Fe2+. Besides, the adsorption kinetic model was also conducted to study the mechanism of adsorption process by applying pseudo-first order and pseudo-second-order rate equations. Based on experimental results, optimum removal of COD and Fe2+ was obtained at mixing ratio of 7:3 with optimum removal of 54.6% for COD and 68.06% for Fe2+. This result indicates that high amount of AC in mixing ratio of adsorbent contributed to the highest removal of both COD and Fe2+. In addition, the study also proves that a combination of AC and calcite has improved the adsorption efficiency. The results of adsorption kinetic model indicate that both COD and Fe2+ followed the pseudo-second order kinetic model which means that the chemisorptions is the favorable mechanism of adsorption process.

  12. Iron oxide and calcite associated with Leptothrix sp. biofilms within an estavelle in the upper Floridan aquifer

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    Florea Lee J.


    Full Text Available In Thornton’s Cave, an estavelle in west-central Florida, SEM, EDS, and XRD data reveal biofilms that are predominantly comprisedof FeOOH-encrusted hollow sheaths that are overgrown and intercalated with calcite. Fragments of this crystalline biofilm adhereto the walls and ceiling as water levels vary within the cave. Those on the wall have a ‘cornflake’ appearance and those affixed tothe ceiling hang as fibrous membranes. PCR of DNA in the active biofilm, combined with morphologic data from the tubes in SEMmicrographs, point to Leptothrix sp., a common Fe-oxidizing bacteria, as the primary organism in the biofilm. Recent discoveries of‘rusticles’ in other Florida caves suggest that Fe-oxidizing bacteria may reside elsewhere in Florida groundwater and may play a rolein the mobility of trace metals in the Upper Florida aquifer. SEM micrographs from two marble tablets submerged for five months, oneexposed to microbial activity and a second isolated from microbial action, revealed no visible etchings or borings and very limited lossof mass. EDS data from the electron micrographs of the unfiltered tablet document the same FeOOH-encrusted hollow sheaths andsimilar deposits of calcite as seen in the ‘cornflakes’. These results, combined with water chemistry data imply that the biofilm mayfocus or even promote calcite precipitation during low-water level conditions when CO2 degasses from the cave pools.

  13. Caspartin and calprismin, two proteins of the shell calcitic prisms of the Mediterranean fan mussel Pinna nobilis. (United States)

    Marin, Frédéric; Amons, Reinout; Guichard, Nathalie; Stigter, Martin; Hecker, Arnaud; Luquet, Gilles; Layrolle, Pierre; Alcaraz, Gérard; Riondet, Christophe; Westbroek, Peter


    We used the combination of preparative electrophoresis and immunological detection to isolate two new proteins from the shell calcitic prisms of Pinna nobilis, the Mediterranean fan mussel. The amino acid composition of these proteins was determined. Both proteins are soluble, intracrystalline, and acidic. The 38-kDa protein is glycosylated; the 17-kDa one is not. Ala, Asx, Thr, and Pro represent the dominant residues of the 38-kDa protein, named calprismin. An N-terminal sequence was obtained from calprismin. This sequence, which comprises a pattern of 4 cysteine residues, is not related to any known protein. The second protein, named caspartin, exhibits an unusual amino acid composition, since Asx constitutes by far the main amino acid residue. Preliminary sequencing surprisingly suggests that the first 75 N-terminal residues are all Asp. Caspartin self-aggregates spontaneously into multimers. In vitro tests show that it inhibits the precipitation of calcium carbonate. Furthermore, it strongly interferes with the growth of calcite crystals. A polyclonal antiserum raised against caspartin was used to localize this protein in the shell by immunogold. The immunolocalization demonstrates that caspartin is distributed within the prisms and makes a continuous film at the interface between the prisms and the surrounding insoluble sheets. Our finding emphasizes the prominent role of aspartic acid-rich proteins for the building of calcitic prisms among molluscs.

  14. [Study on Mineralogical Characteristics of Quartz and Calcite from Feieling Skarn-Type Pb-Zn Deposit in Southwest Margin of Yunkai Massif]. (United States)

    Zeng, Chang-yu; Zhao, Ming-zhen; Li, Hong-zhong; Niu, Jia; Zhang, Jie-tang; He, Jun-guo; Zhou, Yong-zhang; Yang, Zhi-jun


    The Feieling Pb-Zn deposit of skarn-type is located the in Southwest margin of Yunkai massif, China. This ore deposit can be divided into wall rock near ore, concealed rock mass, endoskarn, exoskarn and orebody. The Raman and FTIR spectrum are conducted to study the mineralogical characteristics of quartz and calcite from five types of rocks from Feieling skarn-type deposit. The analysis shows that the quartz included in the near ore wall rock, endoskarn and exoskarn, comparing with recrystallized quartz of concealed rock mass, has a tend to change into low symmetry quartz in varying degrees. The crystalinity and order degree of quartz from near ore wall rock to concealed rock mass and to endoskarn are becoming higher, but that of quartz from different exoskarn samples display no regular. The origin or the quartz microstructure changes may be related to the multi-stage evolution of skarn mineralization process. The quartz, included in near ore wall rock, endoskarn and exoskarn, become easier to recrystallize and adjust microstructure under the influence of the multi-stage hydrothermal and temperature effect. In anyone sample, the earlier crystalline calcite, showing subhedral-euhedral crystal, display higher crystalinity and order degree. On the contrary, the later crystalline calcite, showing xenomorphic crystal, display lower crystalinity and order degree. Calcite crystal of exoskarn rock contains some silica impurity, while endoskarn and orebody rock is pure. The purity of calcite crystal may relate to Multi-stage evolution of skarn mineralization process. At the early and late skarn stage, active silica-containing fluid is easier to join into calcite, which is under higher temperature environments. On the contrary, at the late quartz-surfide stage, the later crystalized calcite displays higher purity, which is under lower temperature environments. Therefore, spectral characteristics of quartz and calcite reflect multi-stage evolution of skarn mineralization

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

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    John P. Craddock


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

  16. Ice cores and calcite precipitates from alpine ice caves as useful proxies in paleoclimate reconstructions (United States)

    Colucci, Renato R.; Barbante, Carlo; Bertò, Michele; Dreossi, Giuliano; Festi, Daniela; Forte, Emanuele; Gabrieli, Jacopo; Guglielmin, Mauro; Lenaz, Davide; Luetscher, Marc; Maggi, Valter; Princivalle, Francesco; Schwikowski, Margit; Stenni, Barbara; Žebre, Manja


    In the last years a growing set of research campaigns have been undertaken in the European southeastern Alps. The aim of such interest is mainly due to the peculiar climatic conditions of this area, allowing the existence of periglacial and glacial evidence at the lowest altitude in the Alps. The reason for such "anomaly" is likely ascribable to very high mean annual precipitation and local topoclimatic amplifications. In the frame of this research, in the fall 2013 a 7.8 m long ice-core has been extracted from a permanent cave ice deposit located in the area of Mt. Canin (2,587 masl) in the Julian Alps. The ice-core has been cut and analysed in terms of: a) oxygen and hydrogen isotope composition; b); black carbon and dust concentrations; c) water conductivity; d) mineralogical analyses via X-ray powder diffraction. In the fall 2016, in the same area, a set of 1.0 m long horizontal ice cores have been extracted in another ice cave deposit, intercepting a preserved layer of coarse cryogenic cave carbonates (CCCcoarse). Such original finding represents the first alpine evidence of in situ CCCcoarse and the first occurrence from the southern side of the Alps. A unique opportunity to better understand the processes associated with the formation of CCCcoarse and the well-preserved status of samples allow planning, besides U/Th datings, several different analyses which may be associated with the precipitation of CCC. Subglacial calcite crusts, widespread in the area, represents a further proxy able to help understanding the evolution of climate during the holocene in this alpine sector. In the light of accelerated climate change we discuss here the potential of this still untapped and fragile cryospheric archives for paleoclimatic reconstructions in high elevated areas of the Alps.

  17. Evolution of permeability and microstructure of tight carbonates due to numerical simulation of calcite dissolution (United States)

    Miller, Kevin; Vanorio, Tiziana; Keehm, Youngseuk


    The current study concerns fundamental controls on fluid flow in tight carbonate rocks undergoing CO2 injection. Tight carbonates exposed to weak carbonic acid exhibit order of magnitude changes in permeability while maintaining a nearly constant porosity with respect to the porosity of the unreacted sample. This study aims to determine—if not porosity—what are the microstructural changes that control permeability evolution in these rocks? Given the pore-scale nature of chemical reactions, we took a digital rock physics approach. Tight carbonate mudstone was imaged using X-ray microcomputed tomography. We simulated calcite dissolution using a phenomenological numerical model that stands from experimental and microstructural observations under transport-limited reaction conditions. Fluid flow was simulated using the lattice-Boltzmann method, and the pore wall was adaptively eroded at a rate determined by the local surface area and velocity magnitude, which we use in place of solvent flux. We identified preexisting, high-conductivity fluid pathways imprinted in the initial microstructure. Though these pathways comprise a subset of the total connected porosity, they accommodated 80 to 99% of the volumetric flux through the digital sample and localized dissolution. Porosity-permeability evolution exhibited two stages: selective widening of narrow pore throats that comprised preferential pathways and development and widening of channels. We quantitatively monitored attributes of the pore geometry, namely, porosity, specific surface area, tortuosity, and average hydraulic diameter, which we qualitatively linked to permeability. This study gives a pore-scale perspective on the microstructural origins of laboratory permeability-porosity trends of tight carbonates undergoing transport-limited reaction with CO2-rich fluid.

  18. Growth rate effects on Mg/Ca and Sr/Ca ratios constrained by belemnite calcite (United States)

    Vinzenz Ullmann, Clemens


    Multiple temperature proxies from single species are important to achieve robust palaeotemperature estimates. Besides the commonly employed oxygen isotope thermometer, also Mg/Ca and Sr/Ca ratios perform well as proxies for calcification temperature in the shells of some species. While salinity changes affect the ratios of earth alkaline elements much less than the δ18O thermometer, metabolic effects may exert a strong control on the expression of element ratios. Such effects are hard to study because biomineralization experiments have to overcome large intraspecific variability and can hardly ever isolate the controls of a single parameter on shell geochemistry. The unique geometry of the belemnite rostrum constitutes an exception to this rule. Its shape, large size, and the visibility of growth increments as bands enable the analysis of multiple, correlatable, high resolution geochemical profiles in a single fossil. The effects of the growth rate variability amongst these profiles on Mg/Ca and Sr/Ca ratios has been tested here. Within a specimen of Passaloteuthis bisulcata (Early Toarcian, Cleveland Basin, UK), Mg/Ca and Sr/Ca data were obtained from four profiles. With respect to growth rate in the first profile, which was taken as a reference, the relative growth rates in the remaining three profiles varied by a factor of 0.9 to 2.7. Results suggest that relative growth rate is linearly correlated with Mg/Ca and Sr/Ca, with a decrease of Mg/Ca by 8 % and increase of Sr/Ca by 6 % per 100 % increase in relative growth rate. The observed trends are consistent with abiogenic precipitation experiments and suggest that crystal precipitation rate exerts a significant, predictable control on the element distribution in biogenic calcite.

  19. Time-lapse 3D imaging of calcite precipitation in a microporous column (United States)

    Godinho, Jose R. A.; Withers, Philip J.


    Time-lapse X-ray computed tomography is used to image the evolution of calcite precipitation during flow through microporous quartz over the course of 400 h. The growth rate decreases by more than seven times, which is linked to the clogging of flow paths that restricts flow to some regions of the column. Fewer precipitates are observed as a function of column depth, which is found to be related to a differential nucleation density along the sample. A higher nucleation density closer to the inlet implies more crystal volume increase per unit of time without affecting the rate if normalized to the surface area of crystals. Our overall growth rates measured in porous media are orders of magnitude slower than growth rates derived from traditional precipitation experiments on free surfaces. Based on our time-lapse results we hypothesize a scenario where the evolving distribution of precipitates within a pore structure during precipitation progressively modifies the local transport through the pores. Within less permeable regions the saturation index may be lower than along the main flow paths. Therefore, the reactive crystal surfaces within those regions grow at a slower rate than that expected from the bulk fluid composition. Since the amount of reactive surface area within these less permeable regions increases over time, the overall growth rate decreases without a necessary significant change of the bulk fluid composition along more permeable flow paths. In conclusion, the overall growth rates in an evolving porous media expected from bulk fluid compositions alone can be overestimated due to the development of stagnant sub-regions where the reactive surface area is bath by a solution with lower saturation index. In this context we highlight the value of time-lapse 3D studies for understanding the dynamics of mineral precipitation in porous media.

  20. A novel salinity proxy based on Na incorporation into foraminiferal calcite

    Directory of Open Access Journals (Sweden)

    J. C. Wit


    Full Text Available Salinity and temperature determine seawater density, and differences in both thereby control global thermohaline circulation. Whereas numerous proxies have been calibrated and applied to reconstruct temperature, a direct and independent proxy for salinity is still missing. Ideally, a new proxy for salinity should target one of the direct constituents of dissolved salt, such as [Na+] or [Cl−]. This study investigates the impact of salinity on foraminiferal Na/Ca values by laser ablation ICP-MS analyses of specimens of the benthic foraminifer Ammonia tepida cultured at a range of salinities (30.0–38.6. Foraminifera at lower salinities (30.0 and 32.5 added more chambers (10–11 to their test over the course of the culturing experiment than those maintained at higher salinities (36.1, 7–8 chambers, and 38.6, 6–7 chambers, suggesting that growth rates in this species are promoted by lower salinities. The Na/Ca of cultured specimens correlates significantly with seawater salinity (Na/Ca = 0.22S–0.75, R2 = 0.96, p DNa vary between 5.17 and 9.29 mmol mol−1 and 0.12–0.16 × 10−3, which are similar to values from inorganic precipitation experiments. The significant correlation between test size and Na/Ca results from co-variation with salinity. This implies that foraminiferal Na/Ca could serve as a robust and independent proxy for salinity, enabling salinity reconstructions independent of calcitic δ18O.

  1. Evaluation of ground calcite/water heavy media cyclone suspensions for production of residual plastic concentrates. (United States)

    Gent, Malcolm; Sierra, Héctor Muñiz; Menéndez, Mario; de Cos Juez, Francisco Javier


    Viable recycled residual plastic (RP) product(s) must be of sufficient quality to be reusable as a plastic or source of hydrocarbons or fuel. The varied composition and large volumes of such wastes usually requires a low cost, high through-put recycling method(s) to eliminate contaminants. Cyclone separation of plastics by density is proposed as a potential method of achieving separations of specific types of plastics. Three ground calcite separation medias of different grain size distributions were tested in a cylindrical cyclone to evaluate density separations at 1.09, 1.18 and 1.27 g/cm3. The differences in separation recoveries obtained with these medias by density offsets produced due to displacement of separation media solid particles within the cyclone caused by centrifugal settling is evaluated. The separation density at which 50% of the material of that density is recovered was found to increase from 0.010 to 0.026 g/cm3 as the separation media density increased from 1.09 to 1.27 g/cm3. All separation medias were found to have significantly low Ep95values of 0.012-0.033 g/cm3. It is also demonstrated that the presence of an excess content of 75%) resulted in reduced separation efficiencies. It is shown that the optimum separations were achieved when the media density offset was 0.03-0.04 g/cm3. It is shown that effective heavy media cyclone separations of RP denser than 1.0 g/cm3 can produce three sets of mixed plastics containing: PS and ABS/SAN at densities of >1.0-1.09 g/cm3; PC, PMMA at a density of 1.09-1.18 g/cm3; and PVC and PET at a density of >1.27 g/cm3. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Nanoscale observations of the effect of citrate on calcium oxalate precipitation on calcite surfaces. (United States)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  4. Aragonite-calcite precipitation in vertical fractures of the "Erzberg" siderite deposit (Austria): Hydrogeochemical and neotectonic implications (United States)

    Boch, Ronny; Wang, Xianfeng; Kluge, Tobias; Kurz, Walter; Leis, Albrecht; Lin, Ke; Pluch, Hannes; Mittermayr, Florian; Dietzel, Martin


    The ore deposit "Erzberg" represents the worldwide largest FeCO3 occurrence and is amongst Austria's most prominent geological places due to its historic, economic and scientific value. The iron-ore (siderite/ankerite) bearing Devonian carbonates of the open pit mine locally host sequential aragonite-calcite precipitates infilling vertical fractures. These typically laminated carbonates are referred to as erzbergite in mineral collections. To study their formation conditions we recovered samples on-site, i.e. from the rare veins being cm to dm in horizontal and tenths of meters in vertical extension. Additionally, samples from our university collection and private collectors were investigated. Some of the fractures filled with aragonite/calcite further exhibit cataclastic sediments, damage zones and slickenside striations. Modern water samples were collected from fractures currently accessible to conduct hydrochemical analyses and modeling. Selected precipitates were analyzed applying microscopic techniques, XRD, electron microprobe elemental mapping, stable and clumped isotopes, and 238U-234U-230Th radiometric dating. Erzbergite veins show either uni- or bidirectional growth, i.e. on one or both fracture/fault planes toward complete infilling depending on vadose water flow. The laminated precipitates are dominated by aragonite relative to pristine as well as partially diagenetic (Mg)-calcite. Intercalated and recurrent brownish Fe-rich layers consisting of goethite, quartz, muscovite are probably of detrital origin. Stable C and O isotopes of the precipitates reveal pronounced spatiotemporal variations in which low δ18O values (-10.4 to -5.1 ‰ VPDB) reflect a meteoric origin and low temperatures of the erzbergite depositing solutions. Carbonate clumped isotope measurements verify formation temperatures ≤25 °C. High δ13C values (-0.7 to +6.8 ‰ VPDB) of the precipitates indicate an origin from dissolution of local ankerite and limestone, without a

  5. Quantifying the impact of early calcite cementation on the reservoir quality of carbonate rocks: A 3D process-based model (United States)

    Hosa, Aleksandra; Wood, Rachel


    The reservoir properties of carbonate rocks are controlled by both deposition and diagenesis. The latter includes the early precipitation of calcite cements, which can exert a strong control on the evolution of subsequent diagenetic pathways. We quantify the impact of early marine cement growth in grainstones on evolving pore space by examining trends in the relationship between cementation and permeability using a 3D process-based model (Calcite3D). The model assumes varying proportions of polycrystalline and monocrystalline grain types, upon which we grow isopachous and syntaxial calcite cement types, respectively. We model two syntaxial cement shapes, compact and elongated, that approximate the geometries of typical rhombohedral calcite forms. Results demonstrate the effect of cement competition: an increasing proportion of monocrystalline grains creates stronger competition and a reduction in the impact of individual grains on final calcite cement volume and porosity. Isopachous cement is effective in closing pore throats and limiting permeability. We also show that the impact of syntaxial cement on porosity occlusion and therefore flow is highly dependent on monocrystalline grain location and the orientation of crystal axes. This demonstrates the importance of diagenetic overprint in controlling the evolution of rock properties, but also that this process can be essentially random. We also show that diagenesis alone can create notable heterogeneity in the permeability of carbonates. While Calcite3D is successful in modelling realistic changes in cement volumes and pore space morphology, modelled permeabilities (0.01 -30D) are above the range reported in reservoir grainstones due to the very high permeability of the initial synthetic sediment deposit (58.9D). Poroperm data generated by Calcite3D, however, exhibits a linear relationship between the logarithms of porosity and permeability with a high coefficient of determination, as observed in natural media.

  6. Evaluation of Effect of Brushite-Calcite and Two Indigenous Herbs in Removal of Fluoride from Water. (United States)

    Ramesh, Manumanthu Venkata; Naveenkumar, Puvvadi Gopalakrishna; Prashant, Gouder Manjunath; Sakeenabi, Basha; Allamaprabhu; Vijetha, Kothyala


    The acceptable concentration of fluoride in drinking water is 1.5mg/l. Excess fluoride in drinking water causes fluorosis. Fluorosis is an important public health problem in India. Several treatment technologies suggested in the past for removing excess fluoride generated and causes various chemical byproductswhich are hazardous to public. In recent years, there has been a resurgence of interest to use natural materials due to cost and associated health and environmental concerns of synthetic organic polymers and inorganic chemicals. The aim of this study was to evaluate and compare the defluoridating capability of the brushite-calcite with that of two indigenous herbs, tulsi and wheat grass. One gram of brushite-calcite combination, tulsi and wheat grass were separately added to 10 containers, each containing 1.0 l of prepared distilled water with a fluoride concentration of 5ppm and naturally fluoridated water at 2ppm. Half of the samples were boiled for one minute in a domestic electric kettle for one minute and allowed to cool. The remaining half of the samples was left un-boiled. Fluoride concentration in all the samples was assessed at the end of 30 minutes and 24 hours using fluoride ion selective electrode method. Data was analyzed using unpaired t-test and one-way ANOVA. For water with 2ppm and 5ppm fluoride, brushite-calcite had shown highest de-fluoridation capacity (p=0.001) at the end of both 30 minutes and 24 hours in boiled samples whereas tulsi (p=0.001) was most effective in un-boiled samples. The results of the study suggest that tulsi can be used for domestic water defluoridation as it is economic, safe and effective.

  7. The laws of fluorite and calcite habit formation in terms of the morphogenetic structural-chemical concept (United States)

    Kiryanova, E. V.; Glikin, A. E.


    Effects of solution components, pH, temperature and supersaturation on fluorite and calcite habits (the modern and formerly obtained data) were generalised. Fluorite was synthesised in 40 flux systems (350-1000°C), 7 hydrothermal systems (100-420°C), and about 30 aqueous systems at room temperatures. It is faced mostly by {1 0 0} and {1 1 1}; octahedron as well as rare faces {1 1 0} and {1 1 2} which are displayed preferably at higher temperatures and far from the neutrality. Calcite was synthesised in more than 50 aqueous systems at room temperatures. It is faced mostly by {1 0 1¯ 1}+{0 0 0 1}+{0 1 1¯ 2} (the cleavage rhombohedron type); strongly alkaline media containing sulphates and citrates cause {0 8¯ 8 1}+{0 0 0 1} (the sharpest rhombohedron type). Morphogenetic effectivenesses of the solution components at different conditions were estimated by the comparison of habit variations of these substances. These results were interpreted in terms of the structural-chemical concept of crystal habit formation. In general, the composition and structure of the adsorbed solvent film determining the faceting are deduced from the correlation between the morphodrome and phase diagram features as well as from the epitaxial adsorbate-substrate congruence. Specifically, water adsorbed on fluorite and calcite with help of Ca(OH) 2-layers, is characterised by the dominant morphogenetic effectiveness at the relatively low temperature range close to neutral media, causing cube and pinacoid on these minerals. The appearance of the other faces is connected with destruction of adsorbed Ca(OH) 2 complexes.

  8. The effect of dissolved magnesium on creep of calcite II: transition from diffusion creep to dislocation creep (United States)

    Xu, Lili; Renner, Jörg; Herwegh, Marco; Evans, Brian


    We extended a previous study on the influence of Mg solute impurity on diffusion creep in calcite to include deformation under a broader range of stress conditions and over a wider range of Mg contents. Synthetic marbles were produced by hot isostatic pressing (HIP) mixtures of calcite and dolomite powders for different intervals (2-30 h) at 850°C and 300 MPa confining pressure. The HIP treatment resulted in high-magnesian calcite aggregates with Mg content ranging from 0.5 to 17 mol%. Both back-scattered electron images and chemical analysis suggested that the dolomite phase was completely dissolved, and that Mg distribution was homogeneous throughout the samples at the scale of about two micrometers. The grain size after HIP varied from 8 to 31 μm, increased with time at temperature, and decreased with increasing Mg content (>3.0 mol%). Grain size and time were consistent with a normal grain growth equation, with exponents from 2.4 to 4.7, for samples containing 0.5-17.0 mol% Mg, respectively. We deformed samples after HIP at the same confining pressure with differential stresses between 20 and 200 MPa using either constant strain rate or stepping intervals of loading at constant stresses in a Paterson gas-medium deformation apparatus. The deformation tests took place at between 700 and 800°C and at strain rates between 10-6 and 10-3 s-1. After deformation to strains of about 25%, a bimodal distribution of large protoblasts and small recrystallized neoblasts coexisted in some samples loaded at higher stresses. The deformation data indicated a transition in mechanism from diffusion creep to dislocation creep. At stresses below 40 MPa, the strength was directly proportional to grain size and decreased with increasing Mg content due to the reductions in grain size. At about 40 MPa, the sensitivity of log strain rate to log stress, ( n), became greater than 1 and eventually exceeded 3 for stresses above 80 MPa. At a given strain rate and temperature, the stress at

  9. Stratigraphic implications of trace element and strontium-isotope analyses of Kimmeridgian shell calcite from the Lower Saxony Basin, Germany (United States)

    Zuo, Fanfan; Heimhofer, Ulrich; Huck, Stefan; Erbacher, Jochen; Bodin, Stephane


    Stratigraphic uncertainties due to the lack of open marine marker fossils (e.g. ammonites) hamper the precise age assignment and stratigraphic correlation of Kimmeridgian strata found in the Lower Saxony Basin of Northern Germany. Correlation of these deposits with the Jurassic standard ammonite zonation is still difficult, since the existing ostracod biostratigraphy is facies-controlled and of only limited stratigraphic precision. In this study, a chemostratigraphic approach has been chosen and biogenic shell material produced by brachiopods, oysters and lithiotids is evaluated for its reliability to act as proxy of the original Jurassic seawater strontium isotope composition. Low-Mg calcite shells have been collected from three stratigraphic sections accessible in open-cast quarries located in the Lower Saxony Basin of Northern Germany. In order to identify diagenetically altered shell calcite, trace element and stable isotope analysis of 227 calcite samples (oysters=101; brachiopods=60; Trichites=52) has been carried out. The geochemical results reveal that (1) concentration of different trace elements varies between the different groups of shell-forming organisms, which may be related to vital effects and (2) high strontium contents, low Mn and Fe contents and the lack of correlation between these elements indicate near-pristine calcite shells, and therefore shells are supposed to record the ambient sea water composition during the Late Jurassic. Strontium-isotope (87Sr/86Sr) analysis of diagenetically screened samples indicates an Early Kimmeridgian age of the studied deposits, which is in accordance with ostracod biostratigraphic data. An increasing trend in 87Sr/86Sr with stratigraphic height fits well with the global strontium-isotope curve. Besides, similar 87Sr/86Sr ratios derived from different organisms from a single stratigraphic level highlight the suitability of the shells for strontium-isotope stratigraphy. Despite the shallow-marine character of

  10. Seasonal dynamics of stable isotopes and element ratios in authigenic calcites during their precipitation and dissolution, Sacrower See (northeastern Germany

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    Full Text Available The seasonal evolution of chemical and physical water properties as well as particle fluxes was monitored in Sacrower See (northeastern Germany during two consecutive years (Oct 2003 - Oct 2005. Additonally, we measured δ18O and δ13C as well as Sr:Ca and Mg:Ca ratios of authigenic calcites that were collected in sequencing sediment traps in order to disentangle environmental and climatic factors controlling these parameters. In particular, our aim was to find out if element ratios and the isotopic composition of calcites reflect changes in water and air temperatures. Lake water is highly enriched in 18O (-1.3 to -2.5‰ VSMOW with an evaporative increase of 0.6‰ during summer. Values are 5-6‰ more positive than groundwater values and 4-5‰ more positive than long-term weighted annual means of precipitation. During spring and summer, high amounts of dissolved phosphate cause eutrophic conditions and calcite precipitation in isotopic disequilibrium. Measured values are depleted in 18O by 2 to 10‰ compared to calculated equilibrium values. Resuspension and partial dissolution of calcite in the water column contribute to this isotopic divergence in summer and autumn as δ18Oca and δ13C values increased in the hypolimnion during this time. Mg:Ca and Sr:Ca ratios are altered by dissolution as well. In the hypolimnion these ratios were higher than in the epilimnion. Another reason for the huge deviation between measured and theoretical δ18Oca values during summer is the occurrence of large amounts of Phacotus lenticularis in the carbonate fraction. High amounts of Phacotus lead to more negative δ18Oca and more positive δ13C values. Several characteristics of δ18Oca and δ13C are also reflected by Mg:Ca and Sr:Ca ratios and isotopic composition of oxygen and carbon were influenced by the onset and stability of stratification. Especially the earlier onset of stratification in 2005 caused higher sediment fluxes and more positive carbon and

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

    Energy Technology Data Exchange (ETDEWEB)

    Legens, Ch.


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

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

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


    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

  13. Controls on the precipitation of barite (BaSO 4) crystals in calcite travertine at Twitya Spring, a warm sulphur spring in Canada's Northwest Territories (United States)

    Bonny, Sandy M.; Jones, Brian


    Twitya Spring discharges warm (24 °C), anoxic, sulphide-, calcium- (65 ppm) and barium- (≥ 0.78 ppm) rich spring water to a steep flow path that is inhabited by streamer and mat-forming microbes ( Thiothrix, Beggiatoa, Oscillatoria, Spirulina, diatoms, rod shaped bacteria). Oxidation and CO 2 degassing drive precipitation of elemental sulphur, barite, opaline silica, and calcite. A mound of travertine at the base of the flow path, dominantly composed of bedded barium-enriched crystallographic and noncrystallographic dendritic calcite crystals and calcite cements, hosts three types of barite crystals: type 1 (T1) intergrown tabular crystals that formed in solution, type 2 (T2) tabular and rhombic crystals that nucleated on calcite, and type 3 (T3) subhedral and anhedral microcrystals that nucleated on microbial cell surfaces and in microbial extracellular polymeric substances. The formation and distribution of T1, T2, and T3 barite in the Twitya Spring flow path are controlled by physiochemical gradients, calcite precipitation rates, and adsorption of barium to microbial biomass, all of which vary seasonally and episodically at Twitya Spring. The complex physiochemical and biological controls on barite formation at Twitya Spring both suggest that the classification of biogenic or inorganic sedimentary barite on the basis of crystal size and morphology may be oversimplified. There is also the potential that primary and authigenic barite crystals hosted in carbonates may yield information about the microbial ecology and ambient physiochemistry of their depositional environments.

  14. Improvement Of The U-Th Method For Dating Of Impure Calcite Having A Large Amount Of Clay And Very Low Uranium Content

    Directory of Open Access Journals (Sweden)

    Samer Farkh


    Full Text Available Abstract The U-Th method also called series method of uranium is improved by a new experimental protocol and successfully applied to the impure calcite with uranium concentration 005 dpmg which was previously difficult to be dated accurately. Our experiments performed on 15 calcite samples taken from France and Morocco have highlighted the importance of this methodological improvement by enabling i the elimination of 100 of clay residues ii the reduction of calcite quantity necessary to the chemical manipulation from 20g to 5g iii the analysis of calcite samples poor in uranium and on the other hand rich with clay and iiii the reduction of the lower limit of the U-Th method from 10 Kyrs to 6 Kyrs. The optimization of U-Th method in this work provided a better dating of the accurate age of calcite. Thus this technique is important for the chemical analysis of stalagmite floors of different caves in the region of the Near East.

  15. Zircon-quartz-calcite segregations in carbonate-alkaline metasomatic rocks of the western Baikal region and their petrogenetic implications (United States)

    Savelyeva, V. B.; Bazarova, E. P.; Sharygin, V. V.; Karmanov, N. S.


    Fine-grained segregations up to 5 mm in size composed of graphic intergrowths of zircon, quartz, calcite and containing up to 0.8 wt % SrO have been found in albite-riebeckite and dolomite-biotite metasomatic rocks formed after alaskite granite. They contain magnetite, titanomagnetite (25.4 wt % TiO2), cerite-(Ce,Nd), rutile (up to 1.2 wt % Nb2O5), as well as rare micrograins of monazite-(Ce), bastnaesite-(Ce), and barite (up to 5.7 wt % SrO). The fine-grained structure of mineral aggregates suggests a metacolloidal nature. It is assumed that the zircon-quartz-calcite assemblage was formed due to exchange decomposition reaction between the salt phase of hydrothermal solution with predominant Na2CO3, elevated Zr and, to a lesser extent, Fe, Ti, LREE, Nb contents and dissolved calcium and silica compounds of a Na2SiO3 type.

  16. Stable calcium isotope composition of a pedogenic carbonate in forested ecosystem: the case of the needle fibre calcite (NFC). (United States)

    Milliere, Laure; Verrecchia, Eric; Gussone, Nikolaus


    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 δ44Ca signature of NFC and LCC crystals were used to determine possible differences of the precipitation rate during their formation. NFC and LCC have similar δ18O 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

  17. Tectonically driven organic fluid migration in the Dabashan Foreland Belt: Evidenced by geochemistry and geothermometry of vein-filling fibrous calcite with organic inclusions (United States)

    Li, Rongxi; Dong, Shuwen; Lehrmann, Dan; Duan, Lizhi


    Fibrous calcite veins with organic inclusions have been widely considered as indicators of oil and gas generation and migration under overpressure. Abundant fibrous calcite veins containing organic-bearing inclusions occur in faulted Lower Paleozoic through Triassic hydrocarbon source rocks in the Dabashan Foreland Belt (DBF). δ13CPDB and δ18OPDB values of the fibrous calcite range from -4.8‰ to -1.9‰ and -12.8‰ to -8.4‰ respectively, which is lighter than that of associated carbonate host rocks ranging from -1.7‰ to +3.1‰ and -8.7‰ to -4.5‰. A linear relationship between δ13CPDB and δ18OPDB indicates that the calcite veins were precipitated from a mixture of basinal and surface fluids. The fibrous calcite contains a variety of inclusions, such as solid bitumen, methane-bearing all-liquid inclusions, and vapor-liquid aqueous inclusions. Homogenization temperatures of aqueous inclusions range from 140 to 196 °C with an average of 179 °C. Salinities of aqueous inclusions average 9.7 wt% NaCl. Independent temperatures from bitumen reflectance and inclusion phase relationships of aqueous and methane-bearing inclusions were used to determine fluid pressures. Results indicate high pressures, elevated above typical lithostatic confining pressure, from 150 to 200 MPa. The elevated salinity and high temperature and pressure conditions of the fibrous calcite veins argue against an origin solely from burial overpressure resulting from clay transformation and dehydration reactions. Instead fluid inclusion P-T data and geochemistry results and regional geology indicate abnormally high pressures during fluid migration. These findings indicate that tectonic stress generated fracture and fault fluid pathways and caused migration of organic-bearing fluids from the DBF during the Yanshan orogeny.

  18. 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. (United States)

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


    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 (5-15 mol% mineral). These become cemented together by epitaxially oriented second stage very high Mg calcite (30-40 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. Copyright © 2011 S. Karger AG, Basel.

  19. The radiogenic and stable Sr isotope geochemistry of basalt weathering in Iceland: Role of hydrothermal calcite and implications for long-term climate regulation (United States)

    Andrews, M. Grace; Jacobson, Andrew D.


    Several studies have examined the geochemistry of Icelandic rivers to quantify the relationship between basalt weathering and long-term climate regulation. Recent research has suggested that the chemical weathering of hydrothermal and metamorphic calcite contributes significant quantities of HCO3- to the Icelandic riverine flux (Jacobson et al., 2015). Because the HCO3- derives from volcanic CO2 that was sequestered in mineral form prior to atmospheric injection, the strength of the basalt weathering feedback occurring in Iceland may be lower than previously realized. To test these hypotheses, we analyzed the radiogenic and stable Sr isotope composition (87Sr/86Sr and δ88/86Sr) of the same suite of water, rock, and mineral samples as examined in Jacobson et al. (2015), and we developed a simple model of the long-term C cycle that considers the transformation of volcanic CO2 to HCO3- during subsurface silicate weathering, which is a precursor to hydrothermal calcite formation. Interpretations based on 87Sr/86Sr and Ca/Sr ratios suggest that conservative, three-component mixing between basalt, calcite, and atmospheric deposition adequately explains river geochemistry. On average, the δ88/86Sr values of glacial and non-glacial rivers (0.414‰ and 0.388‰, respectively) are generally higher than those for basalt (0.276‰); however, calcite δ88/86Sr values (0.347‰) are also higher than those for basalt and span the range of riverine values. Thus, riverine δ88/86Sr values are also consistent three-component mixing between basalt, calcite, and atmospheric deposition. Isotopic fractionation is not required to explain riverine trends. Finally, model equations for the long-term C cycle demonstrate that subsurface silicate weathering reduces the magnitude of the volcanic CO2 degassing flux, which in turn causes the atmosphere to stabilize at lower pCO2 values compared to the case where no subsurface silicate weathering occurs. However, the proportion of the net

  20. Impacts of cave air ventilation and in-cave prior calcite precipitation on Golgotha Cave dripwater chemistry, southwest Australia (United States)

    Treble, Pauline C.; Fairchild, Ian J.; Griffiths, Alan; Baker, Andy; Meredith, Karina T.; Wood, Anne; McGuire, Elizabeth


    Speleothem trace element chemistry is an important component of multi-proxy records of environmental change but a thorough understanding of hydrochemical processes is essential for its interpretation. We present a dripwater chemistry dataset (PCO2, alkalinity, Ca, SIcc, Mg and Sr) from an eight-year monitoring study from Golgotha Cave, building on a previous study of hydrology and dripwater oxygen isotopes (Treble et al., 2013). Golgotha Cave is developed in Quaternary aeolianite and located in a forested catchment in the Mediterranean-type climate of southwest Western Australia. All dripwaters from each of the five monitored sites become supersaturated with respect to calcite during most of the year when cave ventilation lowers PCO2 in cave air. In this winter ventilation mode, prior calcite precipitation (PCP) signals of increased Mg/Ca and Sr/Ca in dripwater are attributed to stalactite deposition. A fast-dripping site displays less-evolved carbonate chemistry, implying minimal stalactite growth, phenomena which are attributed to minimal degassing because of the short drip interval (30 s). We employ hydrochemical mass-balance modelling techniques to quantitatively investigate the impact of PCP and CO2 degassing on our dripwater. Initially, we reverse-modelled dripwater solutions to demonstrate that PCP is dominating the dripwater chemistry at our low-flow site and predict that PCP becomes enhanced in underlying stalagmites. Secondly, we forward-modelled the ranges of solution Mg/Ca variation that potentially can be caused by degassing and calcite precipitation to serve as a guide to interpreting the resulting stalagmite chemistry. We predict that stalagmite trace element data from our high-flow sites will reflect trends in original dripwater solutes, preserving information on biogeochemical fluxes within our system. By contrast, stalagmites from our low-flow sites will be dominated by PCP effects driven by cave ventilation. Our poorly karstified system allows us

  1. Multi-proxy geochemical evidence for primary aragonite precipitation in a tropical-shelf 'calcite sea' during the Hirnantian glaciation (United States)

    Kimmig, Sara R.; Holmden, Chris


    A positive excursion in sedimentary δ26Mg values (2-3‰) is recorded in a mud dominated carbonate succession spanning the Hirnantian glaciation event in a tropical-shelf sea in Nevada. The increase is coincident with lithofacies and biofacies indicators of sea-level change, and previously reported changes in sedimentary δ13C and δ44/40Ca values in the same section. The synchronousness of the isotopic changes is inconsistent with differences in the oceanic residence times of Mg (13 Myr), Ca (0.5-1 Myr), and C (0.1 Myr), indicating that the isotopic trends cannot be attributed to perturbations in the oceanic cycling of these elements. Instead, a mixing analysis (δ26Mg vs. Ca/Mg) reveals that the stratigraphic shift in sedimentary δ26Mg values is an artifact of changing dolomite abundance in the carbonate succession, which increases by an average of ∼12 mol% during the glaciation. The mixing analysis also uncovers stratigraphic changes in end-member limestone δ26Mg values that are tentatively attributed to variations in aragonite abundance. The aragonite, which inverted to calcite during diagenesis, accumulated during the glacio-eustatically controlled sea-level lowstand in the study setting. Although this interpretation is vulnerable to diagenetic effects that are difficult to evaluate, it is strengthened by shifts to lower δ44/40Ca values and higher δ13C values in the same section. Experiments show that aragonite can precipitate in seawater with the chemistry of a 'calcite sea' at temperatures above 20-23 °C. Considering the warm climates of the early Paleozoic, temperatures above this range were likely common in low latitudes. This study shows that the isotopes of Mg, Ca, and C have the potential to fingerprint aragonite that has inverted to calcite in the rock record. It is important recognize carbonate successions where this has occurred so as to avoid misinterpreting facies-dependent changes in carbonate polymorph mineralogy as genuine records of

  2. Stable isotope composition of earthworm calcite granules: a new proxy to reconstruct paleoclimate during the Last Glacial in loess deposit (United States)

    Prud'homme, C.; Lécuyer, C.; Antoine, P.; Moine, O.; Hatte, C.; Fourel, F. P.; Martineau, F.; Rousseau, D. D.


    Fossil calcite granules have been found in loess sequences, in large amount in tundra gley horizons and in palaeosols. These granules, composed of rhomboedric calcite crystals and organized in a radial crystalline structure are produced by earthworms that released them in the first upper centimeters of the soil. Oxygen isotope compositions of earthworm calcite granules (ECG) from the Nussloch loess sequence (Rhine Valley, Germany) have already been used to reconstruct absolute mean soil and air temperatures during the warmest period of the Last Glacial interstadials. In this study, we explored, for the first time, the potential of this new bio-indicator as a climate proxy for precipitation. In loess sequences, palaeoprecipitation reconstructions are estimated from the δ13C of organic matter, which is not always well preserved in sedimentary sequences. ECG were extracted from the Nussloch loess sequence (17-m-thick) previously dated between 45 and 23 ka. 30 granules were selected from 3 tundra gley horizons and 2 brown soils. Carbon measurements were performed on each granule and duplicated. Throughout the studied section, δ13C values range from -15.4 to -10.3‰ for tundra gleys and from -14.9 to -9.5‰ for boreal brown soils. The isotopic fractionation factor between the carbon ingested by the earthworm and the carbon output in the granule is equal to -11.7±1.5‰. Thus, we estimated the δ13C of the plants with a mean of -24.3±2.4‰ for tundra gley horizons and -24.1±2.4‰ for brown soils. We used two independent methods to calculate the yearly amount of rainfall: 1) an empirical method based on the relationship between the δ13C of plants and that of biogenic carbonate and 2) the BIOME4 inverse model. The mean annual paleo-precipitation estimated by the empirical equation is higher in tundra gley horizons (365±124mm/yr) than in brown soils (304±115mm/yr). BIOME4 output suggests that the vegetation of tundra gley horizons was mainly shrub tundra whereas

  3. Temperature dependence of oxygen isotope fractionation in coccolith calcite: A culture and core top calibration of the genus Calcidiscus (United States)

    Candelier, Yaël; Minoletti, Fabrice; Probert, Ian; Hermoso, Michaël


    Reconstructions of seawater temperature based on measurement of oxygen isotopes in carbonates mostly derive from analyses of bulk sediment samples or manually picked foraminifera. The temperature dependence of 18O fractionation in biogenic calcite was first established in the 1950s and the objective of the present study is to re-evaluate this temperature dependence in coccolith calcite with a view to developing a robust proxy for reconstructing "vital effect"-free δ18O values. Coccoliths, the micron-sized calcite scales produced by haptophyte algae that inhabit surface mixed-layer waters, are a dominant component of pelagic sediments. Despite their small size, recent methodological developments allow species-specific separation (and thus isotopic analysis) of coccoliths from bulk sediments. This is especially the case for Calcidiscus spp. coccoliths that are relatively easy to separate out from other sedimentary carbonate grains including other coccolith taxa. Three strains of coccolithophores belonging to the genus Calcidiscus and characterised by distinct cell and coccolith diameters were grown in the laboratory under controlled temperature conditions over a range from 15 to 26 °C. The linear relationship that relates 18O fractionation to the temperature of calcification is here calibrated by the equation: T [°C] = -5.83 × (δ18OCalcidiscus - δ18Omedium) + 4.83 (r = 0.98). The slope of the regression is offset of ˜-1.1‰ from that of equilibrium calcite. This offset corresponds to the physiologically induced isotopic effect or "vital effect". The direction of fractionation towards light isotopic values is coherent with previous reports, but the intensity of fractionation in our dilute batch cultures was significantly closer to equilibrium compared to previously reported offset values. No significant isotopic difference was found between the three Calcidiscus coccolithophores, ruling out a control of the cell geometry on oxygen isotope fractionation within

  4. Calcium and strontium isotope fractionation in aqueous solutions as a function of temperature and reaction rate; I. Calcite (United States)

    AlKhatib, Mahmoud; Eisenhauer, Anton


    In order to study Strontium (Sr) partitioning and isotope fractionation of Sr and Calcium (Ca) in calcite we performed precipitation (T) experiments decoupling temperature and precipitation rate (R∗). Calcite was precipitated at 12.5, 25.0 and 37.5 °C by diffusing NH3 and CO2 gases into aqueous solutions closely following the experimental setup of Lemarchand et al. (2004). The precipitation rate (R∗) for every sample was determined applying the initial rate method and from the specific surface area of almost all samples for each reaction. The order of reaction with respect to Ca2+ ions was determined to be one and independent of T. However, the order of reaction with respect to HCO3- changed from three to one as temperature increases from 12.5, 25 °C and 37.5 °C. Strontium incorporated into calcite (expressed as DSr = [Sr/Ca]calcite/[Sr/Ca]solution) was found to be R∗ and T dependent. As a function of increasing R∗ the Δ88/86Sr-values become more negative and as temperature increases the Δ88/86Sr values also increase at constant R∗. The DSr and Δ88/86Sr-values are correlated to a high degree and depend only on R∗ being independent of temperature, complexation and varying initial ratios. Latter observation may have important implications for the study of diagenesis, the paleo-sciences and the reconstruction of past environmental conditions. Calcium isotope fractionation (Δ44/40Ca) was also found to be R∗ and T dependent. For 12.5 and 25.0 °C we observe a general increase of the Δ44/40Ca values as a function of R∗ (Lemarchand et al. type behavior, Lemarchand et al. (2004)). Whereas at 37.5 °C a significant decreasing Δ44/40Ca is observed relative to increasing R∗ (Tang et al. type behavior, Tang et al. (2008)). In order to reconcile the discrepant observations we suggest that the temperature triggered change from a Ca2+-NH3-aquacomplex covalent controlled bonding to a Ca2+-H2O-aquacomplex van-der-Waals controlled bonding caused the change

  5. The influence of environmental variability on the biogeography of coccolithophores and diatoms in the Great Calcite Belt (United States)

    Smith, Helen E. K.; Poulton, Alex J.; Garley, Rebecca; Hopkins, Jason; Lubelczyk, Laura C.; Drapeau, Dave T.; Rauschenberg, Sara; Twining, Ben S.; Bates, Nicholas R.; Balch, William M.


    The Great Calcite Belt (GCB) of the Southern Ocean is a region of elevated summertime upper ocean calcite concentration derived from coccolithophores, despite the region being known for its diatom predominance. The overlap of two major phytoplankton groups, coccolithophores and diatoms, in the dynamic frontal systems characteristic of this region provides an ideal setting to study environmental influences on the distribution of different species within these taxonomic groups. Samples for phytoplankton enumeration were collected from the upper mixed layer (30 m) during two cruises, the first to the South Atlantic sector (January-February 2011; 60° W-15° E and 36-60° S) and the second in the South Indian sector (February-March 2012; 40-120° E and 36-60° S). The species composition of coccolithophores and diatoms was examined using scanning electron microscopy at 27 stations across the Subtropical, Polar, and Subantarctic fronts. The influence of environmental parameters, such as sea surface temperature (SST), salinity, carbonate chemistry (pH, partial pressure of CO2 (pCO2), alkalinity, dissolved inorganic carbon), macronutrients (nitrate + nitrite, phosphate, silicic acid, ammonia), and mixed layer average irradiance, on species composition across the GCB was assessed statistically. Nanophytoplankton (cells 2-20 µm) were the numerically abundant size group of biomineralizing phytoplankton across the GCB, with the coccolithophore Emiliania huxleyi and diatoms Fragilariopsis nana, F. pseudonana, and Pseudo-nitzschia spp. as the most numerically dominant and widely distributed. A combination of SST, macronutrient concentrations, and pCO2 provided the best statistical descriptors of the biogeographic variability in biomineralizing species composition between stations. Emiliania huxleyi occurred in silicic acid-depleted waters between the Subantarctic Front and the Polar Front, a favorable environment for this species after spring diatom blooms remove silicic acid

  6. Structure and interactions of calcite spherulites with {alpha}-chitin in the brown shrimp (Penaeus aztecus) shell

    Energy Technology Data Exchange (ETDEWEB)

    Heredia, A. [Instituto de Ciencias Nucleares, Departamento de Quimica de Radiaciones y Radioquimica, UNAM, Circuito Exterior C.U. Apdo., Postal 70-543, 04510 Mexico, D.F. (Mexico); Physikalisches Institut and Center for Nanotechnology, Universitaet Muenster, Gievenbecker Weg 11, 48149 Muenster (Germany); Aguilar-Franco, M. [Instituto de Fisica, Depto de Fisicoquimica, UNAM, Circuito Exterior s/n, Ciudad Universitaria Apartado Postal 20-364 01000 Mexico D.F. (Mexico); Magana, C. [Instituto de Fisica, Depto de Estado Solido, UNAM, Circuito Exterior s/n, Ciudad Universitaria Apartado Postal 20-364 01000 Mexico D.F. (Mexico); Flores, C. [Instituto de Investigaciones en Materiales, Depto de Estado Solido, Laboratorio de Biomateriales, UNAM, Circuito Exterior C.U. S/N CP 04510 Mexico, D.F. (Mexico); Pina, C. [Instituto de Investigaciones en Materiales, Depto de Estado Solido, Laboratorio de Biomateriales, UNAM, Circuito Exterior C.U. S/N CP 04510 Mexico, D.F. (Mexico); Velazquez, R. [Centro de Fisica Aplicada Tecnologia Avanzada, UNAM, Km. 15 Carretera Queretaro-San Luis Potosi, C.P. 76230, Queretaro, Qro. (Mexico); Schaeffer, T.E. [Physikalisches Institut and Center for Nanotechnology, Universitaet Muenster, Gievenbecker Weg 11, 48149 Muenster (Germany); Bucio, L. [Instituto de Fisica, Depto de Estado Solido, UNAM, Circuito Exterior s/n, Ciudad Universitaria Apartado Postal 20-364 01000 Mexico D.F. (Mexico); Basiuk, V.A. [Instituto de Ciencias Nucleares, Departamento de Quimica de Radiaciones y Radioquimica, UNAM, Circuito Exterior C.U. Apdo., Postal 70-543, 04510 Mexico, D.F. (Mexico)


    White spots form in the brown shrimp (Penaeus aztecus, Decapoda) shell during frozen storage. The mineral formed consists of calcite incorporated into an amorphous {alpha}-chitin matrix. We studied mechanisms of interaction of amorphous {alpha}-chitin macromolecules with hkl crystal planes to form highly ordered structures, as well as the role of specific sites in the biopolymer, which can be related to nucleation and spheroidal crystal growth. We used low vacuum scanning electron microscopy (LVSEM), X-ray powder diffraction (XRD), atomic force microscopy (AFM), Fourier-transform infrared spectroscopy (FT-IR), and molecular mechanics modeling (MM+ method). AFM images showed fingerprint distances in the biopolymer and a highly layered structure in the crystalline material. The presence of {alpha}-chitin, with a specific spatial distribution of radicals, is thought to be responsible for nucleation and to thermodynamically stabilize ions to form the spherulite crystalline phase, which are usually oval to spherical (0.10 to 200 {mu}m in diameter). Our models of crystal-biopolymer interaction found high affinity of CO{sub 3} {sup 2-} anions in the (104) crystalline plane (the main plane in calcite monocrystals) to NH- groups of the biopolymer, as well as of the C=O in the biopolymer to Ca{sup 2+} cations in the crystalline structure. These interactions explain the spherical growth and inhibition in some planes. The specific physicochemical interactions (docking of groups depending on their geometrical distribution) suggest that the biomineral structure is controlled by the biopolymer on a local scale. This information is useful for further design and improvement of (hybrid) materials for versatile application, from nanotechnology to biomedicine and engineering.

  7. Reconciling disparate views of template-directed nucleation through measurement of calcite nucleation kinetics and binding energies. (United States)

    Hamm, Laura M; Giuffre, Anthony J; Han, Nizhou; Tao, Jinhui; Wang, Debin; De Yoreo, James J; Dove, Patricia M


    The physical basis for how macromolecules regulate the onset of mineral formation in calcifying tissues is not well established. A popular conceptual model assumes the organic matrix provides a stereochemical match during cooperative organization of solute ions. In contrast, another uses simple binding assays to identify good promoters of nucleation. Here, we reconcile these two views and provide a mechanistic explanation for template-directed nucleation by correlating heterogeneous nucleation barriers with crystal-substrate-binding free energies. We first measure the kinetics of calcite nucleation onto model substrates that present different functional group chemistries (carboxyl, thiol, phosphate, and hydroxyl) and conformations (C11 and C16 chain lengths). We find rates are substrate-specific and obey predictions of classical nucleation theory at supersaturations that extend above the solubility of amorphous calcium carbonate. Analysis of the kinetic data shows the thermodynamic barrier to nucleation is reduced by minimizing the interfacial free energy of the system, γ. We then use dynamic force spectroscopy to independently measure calcite-substrate-binding free energies, ΔGb. Moreover, we show that within the classical theory of nucleation, γ and ΔGb should be linearly related. The results bear out this prediction and demonstrate that low-energy barriers to nucleation correlate with strong crystal-substrate binding. This relationship is general to all functional group chemistries and conformations. These findings provide a physical model that reconciles the long-standing concept of templated nucleation through stereochemical matching with the conventional wisdom that good binders are good nucleators. The alternative perspectives become internally consistent when viewed through the lens of crystal-substrate binding.

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

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    Stephen Kershaw


    Based on the above evidence, our opinion is that B-CIC calcite is best explained as a later diagenetic feature unrelated to rapid Earth-surface environmental change associated with mass extinctions; thus a novel carbonate factory is highly unlikely.

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

    Nishio, Takashi; Naka, Kensuke


    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.

  10. Review: geological and experimental evidence for secular variation in seawater Mg/Ca (calcite-aragonite seas and its effects on marine biological calcification

    Directory of Open Access Journals (Sweden)

    J. B. Ries


    Full Text Available Synchronized transitions in the polymorph mineralogy of the major reef-building and sediment-producing calcareous marine organisms and abiotic CaCO3 precipitates (ooids, marine cements throughout Phanerozoic time are believed to have been caused by tectonically induced variations in the Mg/Ca ratio of seawater (molar Mg/Ca>2="aragonite seas", <2="calcite seas". Here, I assess the geological evidence in support of secular variation in seawater Mg/Ca and its effects on marine calcifiers, and review a series of recent experiments that investigate the effects of seawater Mg/Ca (1.0–5.2 on extant representatives of calcifying taxa that have experienced variations in this ionic ratio of seawater throughout the geologic past.

    Secular variation in seawater Mg/Ca is supported by synchronized secular variations in (1 the ionic composition of fluid inclusions in primary marine halite, (2 the mineralogies of late stage marine evaporites, abiogenic carbonates, and reef- and sediment-forming marine calcifiers, (3 the Mg/Ca ratios of fossil echinoderms, molluscs, rugose corals, and abiogenic carbonates, (4 global rates of tectonism that drive the exchange of Mg2+ and Ca2+ along zones of ocean crust production, and (5 additional proxies of seawater Mg/Ca including Sr/Mg ratios of abiogenic carbonates, Sr/Ca ratios of biogenic carbonates, and Br concentrations in marine halite.

    Laboratory experiments have revealed that aragonite-secreting bryopsidalean algae and scleractinian corals and calcite-secreting coccolithophores exhibit higher rates of calcification and growth in experimental seawaters formulated with seawater Mg/Ca ratios that favor their skeletal mineral. These results support the assertion that seawater Mg/Ca played an important role in determining which hypercalcifying marine organisms were the major reef-builders and sediment-producers throughout Earth history. The observation that primary

  11. Stable carbon isotopes and lipid biomarkers provide new insight into the formation of calcite and siderite concretions in organic-matter rich deposits (United States)

    Baumann, Lydia; Birgel, Daniel; Wagreich, Michael; Peckmann, Jörn


    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

  12. Ostracod calcite records the 18O/16O ratio of the bicarbonate and carbonate ions in water (United States)

    Devriendt, Laurent S.; McGregor, Helen V.; Chivas, Allan R.


    The δ18O of ostracod valves is widely used to infer water δ18O and temperature. However, ostracod δ18O appears sensitive to other environmental variables. In addition, there is species-dependent ostracod calcite 18O enrichment, relative to slowly precipitated inorganic calcite under the same conditions. Together these uncertainties complicate ostracod paleoclimate reconstructions. This study presents a new understanding of the causes of ostracod δ18O variations based on a global database of published ostracod δ18O values in lake, marine and coastal environments, and from culture experiments. The database includes associated field/experiment host water parameters including temperature (-1 to 32 °C), water δ18O (-13.2‰ to 4.3‰ VSMOW), pH (6.9-10.4), salinity (0-72 g/kg), calcite saturation states (0.6-26), and dissolved inorganic carbon concentration [DIC] (0.9-54.3 mmol/kg). The data show that: (1) the δ18O of marine and non-marine ostracods reflects the 18O/16O of the sum of host water CO32- and HCO3- ions. For example, at a given temperature, the δ18O of non-marine ostracods decreases by 4‰ to 6‰ as [CO32-]/[DIC] reaches 70%, depending on the ostracod species. In low [CO32-]/[DIC] settings (i.e. high HCO3-/CO32-), ostracod 18O/16O is close to the 18O/16O of HCO3- ions, which explains why on average ostracod δ18O is higher than the δ18O of inorganic calcite precipitated slowly under the same conditions. (2) Taxonomic offsets in ostracod δ18O vary with the host water [CO32-]/[DIC]. In environments where HCO3- ≫ CO32- (i.e. most freshwater lakes), the 18O/16O of Candonids is indistinguishable from the 18O/16O of HCO3- ions (difference of 0.10 ± 0.16‰) while the 18O/16O of Cyprids is lower than the 18O/16O of HCO3- ions by -0.77‰ to -0.32‰, Cytherids by -0.88 ± 0.29‰, and Limnocytherids by -1.12 ± 0.05‰. (3) The sensitivity of ostracod δ18O to [CO32-]/[DIC] also varies with taxonomy. For each percent increase in [CO32-]/[DIC

  13. Effects of increased pCO2 and geographic origin on purple sea urchin (Strongylocentrotus purpuratus) calcite elemental composition (United States)

    LaVigne, M.; Hill, T. M.; Sanford, E.; Gaylord, B.; Russell, A. D.; Lenz, E. A.; Hosfelt, J. D.; Young, M. K.


    Ocean acidification will likely have negative impacts on invertebrates producing skeletons composed of calcium carbonate. Skeletal solubility is partly controlled by the incorporation of "foreign" ions (such as Mg and Sr) into the crystal lattice of these skeletal structures, a process that is sensitive to a variety of biological and environmental factors. Here we explore the effects of life stage, oceanographic region of origin, and changes in the partial pressure of carbon dioxide in seawater (pCO2) on trace elemental composition in the purple sea urchin (Strongylocentrotus purpuratus). We show that, similar to other urchin taxa, adult purple sea urchins have the ability to precipitate skeleton composed of a range of biominerals spanning low to high magnesium calcites. Mg/Ca and Sr/Ca ratios were substantially lower in adult spines compared to adult tests. On the other hand, trace elemental composition was invariant among adults collected from four oceanographically distinct regions along the US west coast (Oregon, Northern California, Central California, and Southern California). Skeletons of newly settled juvenile urchins that originated from adults from the four regions exhibited intermediate Mg/Ca and Sr/Ca between adult spine and test endmembers, indicating that skeleton precipitated during early life stages is more soluble than adult spines and less soluble than adult tests. Mean skeletal Mg/Ca or Sr/Ca of juvenile skeleton did not vary with source region when larvae were reared under present-day, global-average seawater carbonate conditions (400 ppm; pH = 8.02 ± 0.03 1 SD; Ωcalcite = 3.3 ± 0.2 1 SD). However, when reared under elevated CO2 (900 ppm; pH = 7.72 ± 0.03; Ωcalcite = 1.8 ± 0.1), skeletal Sr/Ca in juveniles exhibited increased variance across the four regions. Although larvae from the northern populations (Oregon, Northern California, Central California) did not exhibit differences in Mg or Sr incorporation under elevated CO2 (Sr/Ca = 2

  14. The influence of environmental variability on the biogeography of coccolithophores and diatoms in the Great Calcite Belt

    Directory of Open Access Journals (Sweden)

    H. E. K. Smith


    Full Text Available The Great Calcite Belt (GCB of the Southern Ocean is a region of elevated summertime upper ocean calcite concentration derived from coccolithophores, despite the region being known for its diatom predominance. The overlap of two major phytoplankton groups, coccolithophores and diatoms, in the dynamic frontal systems characteristic of this region provides an ideal setting to study environmental influences on the distribution of different species within these taxonomic groups. Samples for phytoplankton enumeration were collected from the upper mixed layer (30 m during two cruises, the first to the South Atlantic sector (January–February 2011; 60° W–15° E and 36–60° S and the second in the South Indian sector (February–March 2012; 40–120° E and 36–60° S. The species composition of coccolithophores and diatoms was examined using scanning electron microscopy at 27 stations across the Subtropical, Polar, and Subantarctic fronts. The influence of environmental parameters, such as sea surface temperature (SST, salinity, carbonate chemistry (pH, partial pressure of CO2 (pCO2, alkalinity, dissolved inorganic carbon, macronutrients (nitrate + nitrite, phosphate, silicic acid, ammonia, and mixed layer average irradiance, on species composition across the GCB was assessed statistically. Nanophytoplankton (cells 2–20 µm were the numerically abundant size group of biomineralizing phytoplankton across the GCB, with the coccolithophore Emiliania huxleyi and diatoms Fragilariopsis nana, F. pseudonana, and Pseudo-nitzschia spp. as the most numerically dominant and widely distributed. A combination of SST, macronutrient concentrations, and pCO2 provided the best statistical descriptors of the biogeographic variability in biomineralizing species composition between stations. Emiliania huxleyi occurred in silicic acid-depleted waters between the Subantarctic Front and the Polar Front, a favorable environment for this species

  15. Experimental fractionation of stable carbon isotopes during degassing of carbon dioxide and precipitation of calcite from aqueous solutions (United States)

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


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

  16. Synthesis and characterization of CaCO3 (calcite) nano particles from cockle shells (Anadara granosa Linn) by precipitation method (United States)

    Widyastuti, Sri; Intan Ayu Kusuma, P.


    Calcium supplements can reduce the risk of osteoporosis, but they are not automatically absorbed in the gastrointestinal tract. Nanotechnology is presumed to have a capacity in resolving this problem. The preparation and characterization of calcium carbonate nano particle to improve the solubility was performed. Calcium carbonate nano particles were synthesized using precipitation method from cockle shells (Anadara granosa Linn). Samples of the cockle shells were dried in an oven at temperature of 50°C for 7 (seven) days and subsequently they were crushed and blended into fine powder that was sieved through 125-μm sieve. The synthesis of calcium carbonate nanocrystals was done by extracting using hydro chloride acid and various concentrations of sodium hydroxide were used to precipitate the calcium carbonate nano particles. The size of the nano particles was determined by SEM, XRD data, and Fourier transform infrared spectroscopy (FT-IR). The results of XRD indicated that the overall crystalline structure and phase purity of the typical calcite phase CaCO3 particles were approximately 300 nm in size. The method to find potential applications in industry to yield the large scale synthesis of aragonite nano particles by a low cost but abundant natural resource such as cockle shells is required.

  17. Porosity of natural stone and use of confocal laser scanning microscopy on calcitic marble aged in laboratory

    Directory of Open Access Journals (Sweden)

    Ana Mladenovič


    Full Text Available Porosity is one of the key characteristics of natural stone, which influences ondurability as well as functionality of stone as building material. Further, deterioration processes themselves are also characterized by change of porosity. Different direct and indirect techniques can be used for porosity determination. In the following paper overview of these methods, as well as their advantages and disadvantages, is given. Confocal laser scanning microscopy (CLSM is indirect (microscopic technique. Despite its numerous advantages, among which 3D visualizationof pore structure is of major importance, this technique is less known in the area of building materials. An example how CLSM can be applied for qualitative and quantitative evaluation of porosity of calcitic polygonal granoblastic marble is given in this paper. Studied marble has been, despite of its poor durability, often used as building material, especially in the case of claddings. It is shown that thermal hydric factors of deterioration can influence porosity significantly,especially formation of intergranular cracks.This kind of deterioration can be successfully evaluated with use of CLSM method, if samples are suitable prepared and if suitable image analysis tools are developed.

  18. A comparison of the low frequency electrical signatures of iron oxide versus calcite precipitation in granular zero valent iron columns. (United States)

    Wu, Yuxin; Slater, Lee; Versteeg, Roelof; LaBrecque, Douglas


    Geophysical methods have been proposed as technologies for non-invasively monitoring geochemical alteration in permeable reactive barriers (PRBs). We conducted column experiments to investigate the effect of mineralogy on the electrical signatures resulting from iron corrosion and mineral precipitation in Fe0 columns using (a) Na2SO4, and (b) NaHCO3 plus CaCl2 mixture, solutions. At the influent interface where the reactions were most severe, a contrasting time-lapse electrical response was observed between the two columns. Solid phase analysis confirmed the formation of corrosion halos and increased mineralogical complexity in the corroded sections of the columns compared to the minimal/non-corroded sections. We attribute the contrasting time-lapse signatures to the differences in the electrical properties of the mineral phases formed within the two columns. While newly precipitated/transformed polarizable and semi-conductive iron oxides (mostly magnetite and green rust) increase the polarization and conductivity of the sulfate column, the decrease of both parameters in the bicarbonate column is attributed to the precipitation of non-polarizable and non-conductive calcite. Our results show that precipitate mineralogy is an important factor influencing the electrical properties of the corroded iron cores and must be considered if electrical geophysical methods are to be developed to monitor PRB barrier corrosion processes in situ.

  19. Detecting Microbially Induced Calcite Precipitation in a Model Well-Bore Using Downhole Low-Field NMR. (United States)

    Kirkland, Catherine M; Zanetti, Sam; Grunewald, Elliot; Walsh, David O; Codd, Sarah L; Phillips, Adrienne J


    Microbially induced calcite precipitation (MICP) has been widely researched recently due to its relevance for subsurface engineering applications including sealing leakage pathways and permeability modification. These applications of MICP are inherently difficult to monitor nondestructively in time and space. Nuclear magnetic resonance (NMR) can characterize the pore size distributions, porosity, and permeability of subsurface formations. This investigation used a low-field NMR well-logging probe to monitor MICP in a sand-filled bioreactor, measuring NMR signal amplitude and T2 relaxation over an 8 day experimental period. Following inoculation with the ureolytic bacteria, Sporosarcina pasteurii, and pulsed injections of urea and calcium substrate, the NMR measured water content in the reactor decreased to 76% of its initial value. T2 relaxation distributions bifurcated from a single mode centered about approximately 650 ms into a fast decaying population (T2 less than 10 ms) and a larger population with T2 greater than 1000 ms. The combination of changes in pore volume and surface minerology accounts for the changes in the T2 distributions. Destructive sampling confirmed final porosity was approximately 88% of the original value. These results indicate the low-field NMR well-logging probe is sensitive to the physical and chemical changes caused by MICP in a laboratory bioreactor.

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

    Energy Technology Data Exchange (ETDEWEB)

    Lecocq, D


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

  1. Greenschist-Facies Pseudotachylytes and Gouge: a Microstructural Study of the Deformation Propagation at the Boundary Between Hp-Metabasite and Calcite Bearing Metasediments (United States)

    Crispini, L.; Scambelluri, M.; Capponi, G.


    Recent friction experiments on calcite-bearing systems reproduce pseudotachylyte structures, that are diagnostic of dinamic calcite recrystallization related to seismic slip in the shallow crust. Here we provide the study of a pseudotachylyte (PT) bearing low angle oblique-slip fault. The fault is linked to the exhumation of Alpine HP-ophiolites and it is syn- to post-metamorphic with respect to retrograde greenschist facies metamorphism. The observed microstructures developed at the brittle-ductile transition and suggest that seismic and interseismic slip was enhanced by interaction with fluids. The fault zone is in-between high-pressure eclogite-facies metabasites (hangingwall) and calcite bearing metasediments (footwall). The mafic rocks largely consist of upper greenschist facies hornblende, albite, chlorite, epidote with relict eclogitic garnet, Na-pyroxene and rutile; metasediments correspond to calcschist and micaschist with quartz, phengite, zoisite, chlorite, calcite and relics of garnet. Key features of the oucrop are: the thickness and geometry of the PT and gouge; the multiple production of PT characterized by overprinting plastic and brittle deformation; the occurrence in footwall metasediments of mm-thick bands of finely recrystallized calcite coeval with PT development in the hangingwall. The damage zone is ca. 2 m-thick and is characterized by two black, ultra-finegrained straight and sharp Principal Slip Zones (PSZ) marked by PT. The damage zone shows a variety of fault rocks (cataclasite and ultracataclasite, gouge and PT) with multiple crosscutting relationships. Within the two main PSZ, PT occurs in 10-20 cm thick layer, in small scale injection veins and in microfractures. In the mafic hanging wall, the PT is recrystallized and does not preserve glass: it shows flow structures with subrounded, embayed and rebsorbed quartz in a fine grained matrix composed of isotropic albite + chlorite + quartz + epidote + titanite, suggesting recrystallization

  2. Early diagenetic high-magnesium calcite and dolomite indicate that coal balls formed in marine or brackish water: Stratigraphic and paleoclimatic implications (United States)

    Raymond, Anne


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

  3. Calcite veining and feeding conduits in a hydrothermal system: Insights from a natural section across the Pleistocene Gölemezli travertine depositional system (western Anatolia, Turkey) (United States)

    Capezzuoli, Enrico; Ruggieri, Giovanni; Rimondi, Valentina; Brogi, Andrea; Liotta, Domenico; Alçiçek, Mehmet Cihat; Alçiçek, Hülya; Bülbül, Ali; Gandin, Anna; Meccheri, Marco; Shen, Chuan-Chou; Baykara, Mehmet Oruç


    Linking the architecture of structural conduits with the hydrothermal fluids migrating from the reservoir up to the surface is a key-factor in geothermal research. A contribution to this achievement derives from the study of spring-related travertine deposits, but although travertine depositional systems occur widely, their feeding conduits are only rarely exposed. The integrated study carried out in the geothermal Gölemezli area, nearby the well-known Pamukkale area (Denizli Basin, western Anatolia, Turkey), focused on onyx-like calcite veins (banded travertine) and bedded travertine well exposed in a natural cross-section allowing the reconstruction of the shallower part of a geothermal system. The onyx-like veins represent the thickest vein network (> 150 m) so far known. New field mapping and structural/kinematic analyses allowed to document a partially dismantled travertine complex (bedded travertine) formed by proximal fissure ridges and distal terraced/pools depositional systems. The banded calcite veins, WNW-trending and up to 12 m thick, developed within a > 200 m thick damaged rock volume produced by parallel fault zones. Th/U dating indicates a long lasting (middle-late Pleistocene) fluids circulation in a palaeo-geothermal system that, due to its location and chemical characteristics, can be considered the analogue of the nearby, still active, Pamukkale system. The isotopic characteristics of the calcite veins together with data from fluid inclusions analyses, allow the reconstruction of some properties (i.e. temperature, salinity and isotopic composition) and processes (i.e. temperature variation and intensity of degassing) that characterized the parent fluids and the relation between degassing intensity and specific microfabric of calcite crystals (elongated/microsparite-micrite bands), controlled by changes/fluctuations of the physico-chemical fluid characteristics.

  4. Modification of streaming potential by precipitation of calcite in a sand-water system: laboratory measurements pH range from 4 to 12


    Guichet, Xavier; Jouniaux, Laurence; Catel, Nicole


    The definitive version is available at; We acknowledge the Geophysical Journal International, the Royal Astronomical Society and Blackwell Publishing. Full bibliographic reference is : Guichet, X., L. Jouniaux, and N. Catel, Modification of streaming potential by precipitation of calcite in a sand-water system: laboratory measurements in the pH range from 4 to 12, Geophysical Journal International, 166, 445-460, doi:10.1111/j.1365-246X.2006.02922.x, 2006; Spontaneous...

  5. Structure in continuously cored, deep drill holes at Yucca Mountain, Nevada, with notes on calcite occurrence; Yucca Mountain Site Characterization Project

    Energy Technology Data Exchange (ETDEWEB)

    Carr, W.J. [Carr (Wilfred J.), Wheat Ridge, CO (United States)


    A study of more than 22,000 feet of core from five deep drill holes at Yucca Mountain, Nevada, provided data on the attitude and vertical distribution of faults and fractures, the sense of fault displacement, and the occurrence of calcite. The study was done mainly to look for evidence of fault flattening at depth, but no consistent downward decrease in dip of faults was found, and no increase in strata rotation was evident with increasing depth. In the two drill holes located near prominent faults that dip toward the holes (USW G-3 and G-2), an apparent increase in the frequency of faults occurs below the tuffs and lavas of Calico Hills. Some of this increase occurs in brittle lavas and flow breccias in the lower part of the volcanic section. In the two holes presumed to be relatively removed from the influence of important faults at depth, the vertical distribution of faults is relatively uniform. Calcite occurs mainly in two general zones, voids in welded portions of the Paintbrush Tuff, and in a deeper zone, mostly below 3,500 feet. Calcite is least abundant in USW G-4, which may reflect the fewer faults and fractures encountered in that drill hole.

  6. Diagenesis associated with subaerial exposure of Miocene strata, southeastern Spain: Implications for sea-level change and preservation of low-temperature fluid inclusions in calcite cement (United States)

    Goldstein, R.H.; Franseen, E.K.; Mills, M.S.


    Many ancient carbonate rocks contain calcite cements that precipitated from shallow, fresh groundwater that entered strata during events of subaerial exposure. Such low-temperature cementation may be difficult to interpret from fluid inclusion studies because some of the inclusions may reequilibrate during later thermal events. Miocene rocks of southeast Spain provide an example of the utility of fluid inclusion studies in rocks that have not been subjected to significant heating. In the Mesa Roldan area, one type of calcite cement occurs exclusively below a regional stratigraphic surface of enigmatic origin. The cement has petrographic characteristics indicative of cementation in the vadose zone (generally thought to be a zone of oxidation) but has cathodoluminescent bands containing reduced manganese and iron. Primary fluid inclusions contain mostly fresh water, have variable ratios of vapor to liquid, and are at one atmosphere of pressure. Our observations indicate that calcite precipitated from a freshwater vadose zone, which was subjected to local or repetitive saturation, and minor brackish water. The fluid inclusion data indicate that low-temperature fluid inclusions can be preserved in ancient sequences despite a later history of different pore fluids. This indication of subaerial diagenesis of distal slope deposits suggests a relative sea-level drop of at least 50-55 m during the Late Miocene. Similar petrographic and fluid inclusion observations can be used to interpret sea-level changes in other areas. ?? 1990.

  7. Omphacite-bearing calcite marble and associated coesite-bearing pelitic schist from the meta-ophiolitic belt of Chinese western Tianshan (United States)

    Lü, Zeng; Bucher, Kurt; Zhang, Lifei


    In the meta-ophiolitic belt of Chinese western Tianshan, marble (5-50 cm thick) is found interlayered with pelitic schist. The marble is mainly composed of calcite (>90% in volume) and accessory phases include omphacite, quartz, dolomite, albite, phengite, clinozoisite and titanite with or without rutile core. This is the first omphacite (Jd35-50) reported from marble of Chinese western Tianshan. It mainly occurs in the calcite matrix, rarely as inclusion in albite. The presence of omphacite suggests that the layered marble was subjected to eclogite-facies metamorphism, consistent with the occurrence of high-Si phengite (Si a.p.f.u. up to 3.7) and aragonite relic in albite. The associated pelitic schist consists of quartz, white mica (phengite + paragonite), garnet, albite, amphibole (barroisite ± glaucophane) and rutile/titanite, as well as minor amounts of dolomite, tourmaline and graphite. Coesite is optically recognized within porphyroblastic pelitic garnet and is further confirmed via Raman spectroscopy. Thermodynamic models support the UHP metamorphism of calcite marble, similar to the associated pelitic schist. Shared UHP-LT history of calcareous and pelitic rocks in Chinese western Tianshan suggests that the supracrustal carbon-rich sediments have been carried to depths of >90 km during fast subduction and thus are potential sources for carbon recycled into arc crust.

  8. Final report for DOE Grant No. DE-SC0006609 - Persistence of Microbially Facilitated Calcite Precipitation as an in situ Treatment for Strontium-90

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Robert W. [Univ. of Idaho, Idaho Falls, ID (United States); Fujita, Yoshiko [Idaho National Lab. (INL), Idaho Falls, ID (United States); Hubbard, Susan S. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)


    Subsurface radionuclide and 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 ions, such as the short-lived radionuclide 90Sr, is co-precipitation in calcite. We have previously found that nutrient addition can stimulate microbial ureolytic activity, that this activity accelerates calcite precipitation and co-precipitation of Sr, and that higher calcite precipitation rates can result in increased Sr partitioning. We have conducted integrated field, laboratory, and computational research to evaluate the relationships between ureolysis and calcite precipitation rates and trace metal partitioning under environmentally relevant conditions, and investigated the coupling between flow/flux manipulations and precipitate distribution. A field experimental campaign conducted at the Integrated Field Research Challenge (IFRC) site located at Rifle, CO was based on a continuous recirculation design; water extracted from a down-gradient well was amended with urea and molasses (a carbon and electron donor) and re-injected into an up-gradient well. The goal of the recirculation design and simultaneous injection of urea and molasses was to uniformly accelerate the hydrolysis of urea and calcite precipitation over the entire inter-wellbore zone. The urea-molasses recirculation phase lasted, with brief interruptions for geophysical surveys, for 12 days and was followed by long-term monitoring which continued for 13 months. A post experiment core located within the inter-wellbore zone was collected on day 321 and characterized with respect to cation exchange capacity, mineral carbonate content, urease activity, ureC gene abundance, extractable ammonium (a urea hydrolysis product) content, and the 13C isotopic composition of solid carbonates. It was also subjected to selective extractions for strontium and uranium. Result

  9. Multi-scale Geophysical Signatures of Biogenic Calcite and FeS Precipitation Using Rifle as a Model Site (United States)

    Wu, Y.; Ajo-Franklin, J.; Williams, K. H.; Hubbard, S. S.; Nico, P. S.


    In-situ remediation strategies are frequently considered for cleanup of DOE sites. However, the impact of induced biogeochemical transformations on remediation efficacy is not well understood. For example, the generation of remediation end-products, such as gas bubbles, precipitates, and biomass, can alter the porosity and permeability of the system, rendering it challenging to subsequently introduce amendments and/or altering the hydrobiogeochemical conditions favorable for sustained remediation. An understanding of how reaction processes modify the properties of the porous medium is critical to the design, execution, and interpretation of in-situ remediation approaches.Rent hydrogeophysical and biogeophysical studies have demonstrated the sensitivity of geophysical methods to hydrobiogeochemical processes and end products. Geophysical methods offer spatiotemporally dense geophysical data which, through combining with direct measurements, can provide a unique opportunity to better characterize biogeochemical processes/end products and their effects on the porous medium in multi-scale heterogeneous systems. Here, we present a study of synchrotron and column-based geophysical signatures of precipitates induced through biostimulation. Our experiments utilize material from the DOE Rifle, CO Integrated Field Research Challenge Site (IFC), where biostimulation experiments are underway to reduce and immobilize subsurface uranium contamination. At the Rifle IFC, calcite and iron sulfide are the two major end products during bioremediation. These two phases often precipitate simultaneously and are mixed together geometrically. We use two platforms to investigate the geophysical signatures of Rifle-based precipitates evolve in response to biostimulation. At the smallest scale, we conducted time-lapse synchrotron x-ray microtomography of Rifle sediments using Beamline 8.3.2 of the LBNL Advanced Light Source. The resolution of this approach permits investigation of pore

  10. Heavy metal incorporation in foraminiferal calcite: results from multi-element enrichment culture experiments with Ammonia tepida

    Directory of Open Access Journals (Sweden)

    G.-J. Reichart


    Full Text Available The incorporation of heavy metals into carbonate tests of the shallow water benthic foraminifer Ammonia tepida was investigated under controlled laboratory conditions. Temperature, salinity, and pH of the culture solutions were kept constant throughout the duration of this experiment, while trace metal concentrations were varied. Concentrations of Ni, Cu, and Mn were set 5-, 10-, and 20 times higher than levels found in natural North Sea water; for reference, a control experiment with pure filtered natural North Sea water was also analysed. The concentrations of Cu and Ni from newly grown chambers were determined by means of both μ-synchrotron XRF and Laser Ablation Inductively Coupled Plasma Mass Spectroscopy (LA-ICP-MS. The results of both independent analytical techniques agreed within the analytical uncertainty. In general, the concentration of the analysed elements in the tests increased in line with their concentration in the culture solutions. Potential toxic and/or chemical competition effects might have resulted in the decreased incorporation of Ni and Cu into the calcite of the specimens exposed to the highest elemental concentrations. Mn incorporation exhibited large variability in the experiment with the 20-fold increased element concentrations, potentially due to antagonistic effects with Cu. The partition coefficients of Cu and Ni were calculated to be 0.14 ± 0.02 and 1.0 ± 0.5, respectively, whereas the partition coefficient of Mn was estimated to be least 2.4. These partition coefficients now open the way for reconstructing past concentrations for these elements in sea water.

  11. Petrography, mineralogy, and chemistry of calcite-silica deposits at Exile Hill, Nevada, compared with local spring deposits

    Energy Technology Data Exchange (ETDEWEB)

    Vaniman, D.T.; Chipera, S.J.; Bish, D.L.


    Chemical, mineralogic, and petrographic analyses of siliceous calcretes from Exile Hill east of Yucca Mountain, Nevada, indicate that pedogenic processes alone account for the formation of the calcretes. These calcretes have been interpreted by some observers as evidence of seismically triggered eruptions of deep water. Such an origin could have important consequences if Yucca Mountain is developed as an unsaturated site for the disposal of high-level nuclear waste. At odds with this hypothesis are the absence of features that should be present at fault-fed springs (e.g., fissure-ridge mounds with microterraces) and the preservation within root casts of delicate pedogenic microfossils, such as calcified filaments and needle-fiber calcites. Mineral-chemical evidence of pedogenic origin is found in heavy-mineral concentrations, reflected in Fe and Sc enrichments. These concentrations, which occur in the most massive of the vein calcretes, require derivation of detritus from a mixture of weathered and eolian materials that occur in the overlying B soil horizons, as opposed to direct incorporation of adjacent unweathered bedrock. Carbonate and silica abundances and accumulation rates are well within the scope of pedogenic processes. Calcium is derived from rainwater or eolian sources, whereas silica is derived in part by dissolution of local volcanic glasses or from dissolution of unstable silica minerals that are abundant in the local tuffs. In contrast with local deposits that are of spring or seep origin, the siliceous calcretes at Yucca Mountain are pedogenic in origin as well as evolution and provide no evidence in support of conjectured spring activity.

  12. Constraining the subsoil carbon source to cave-air CO2 and speleothem calcite in central Texas (United States)

    Bergel, Shelly J.; Carlson, Peter E.; Larson, Toti E.; Wood, Chris T.; Johnson, Kathleen R.; Banner, Jay L.; Breecker, Daniel O.


    Canonical models for speleothem formation and the subsurface carbon cycle invoke soil respiration as the dominant carbon source. However, evidence from some karst regions suggests that belowground CO2 originates from a deeper, older source. We therefore investigated the carbon sources to central Texas caves. Drip-water chemistry of two caves in central Texas implies equilibration with calcite at CO2 concentrations (PCO2_sat) higher than the maximum CO2 concentrations observed in overlying soils. This observation suggests that CO2 is added to waters after they percolate through the soils, which requires a subsoil carbon source. We directly evaluate the carbon isotope composition of the subsoil carbon source using δ13C measurements on cave-air CO2, which we independently demonstrate has little to no contribution from host rock carbon. We do so using the oxidative ratio, OR, defined as the number of moles of O2 consumed per mole of CO2 produced during respiration. However, additional belowground processes that affect O2 and CO2 concentrations, such as gas-water exchange and/or diffusion, may also influence the measured oxidative ratio, yielding an apparent OR (ORapparent). Cave air in Natural Bridge South Cavern has ORapparent values (1.09 ± 0.06) indistinguishable from those expected for respiration alone (1.08 ± 0.06). Pore space gases from soils above the cave have lower values (ORapparent = 0.67 ± 0.05) consistent with respiration and gas transport by diffusion. The simplest explanation for these observations is that cave air in NB South is influenced by respiration in open-system bedrock fractures such that neither diffusion nor exchange with water influence the composition of the cave air. The radiocarbon activities of NB South cave-air CO2 suggest the subsoil carbon source is hundreds of years old. The calculated δ13C values of the subsoil carbon source are consistent with tree-sourced carbon (perhaps decomposing root matter), the δ13C values of which

  13. Uranium-Lead Ages of Lake Margin Tufa Calcite From the Middle Miocene Barstow Formation, Southern California (United States)

    Cole, J. M.; Rasbury, E. T.; Montañez, I. P.; Pedone, V. A.; Hemming, S. R.; Lanzirotti, A.; Becker, M. L.; Hanson, G. N.


    The Barstow Formation crops out in the Mud Hills near the city of Barstow in the Mojave Desert. The deposits consist mostly of sandstones and mudstones with intercalated ash and carbonate horizons. Localized deposits of well-laminated to spongy non-laminated limestone occur throughout the Barstow Formation and are referred to as tufa deposits. The Barstow Formation has excellent mammalian fossil preservation and represents the type section for the Barstovian North American Land Mammal Age. Ashes within the Barstow Formation have been dated by Ar-based techniques and constrain it to be middle Miocene. However, the ages of the carbonate layers have not previously been constrained by any radiometric technique. \\We collected carbonate samples from different horizons within the middle member of the Barstow Formation and focused on pristine calcite samples for U-Pb analyses. We characterized our samples on three different scales to determine which samples should provide the best U-Pb ages. Polished slabs from our hand samples were evaluated with phosphor imaging technology to identify areas of high radionuclide concentration. Using transmitted light, polarized light, and cathodoluminescence petrography we carefully selected samples that did not have a complicated alteration history. Fission-track analyses were used to help identify uranium incorporation on the thin section scale. Synchrotron-based techniques, such as x-ray florescence (XRF) mapping, helped us to see U and other trace element concentrations on the micron scale. Phosphor imaging proved to be the most helpful technique for sample selection. \\The tufa deposits are enriched in U, with up to about 170 ppm as measured by isotope dilution and over 500 ppm as measured by in situ XRF. Based on isotope dilution measurements, 238U/204Pb ratios range between 400 and 6500, making the tufa deposits excellent candidates for U-Pb dating. Our most precise age thus far is 16.36 +/- 0.16 Ma, giving a 2-sigma uncertainty

  14. Green technological approach to synthesis hydrophobic stable crystalline calcite particles with one-pot synthesis for oil-water separation during oil spill cleanup. (United States)

    Wu, Min-Nan; Maity, Jyoti Prakash; Bundschuh, Jochen; Li, Che-Feng; Lee, Chin-Rong; Hsu, Chun-Mei; Lee, Wen-Chien; Huang, Chung-Ho; Chen, Chien-Yen


    The process of separating oil and water from oil/water mixtures is an attractive strategy to answer the menace caused by industrial oil spills and oily wastewater. In addition, water coproduced during hydrocarbon exploitation, which can be an economic burden and risk for freshwater resources, can become an important freshwater source after suitable water-oil separation. For oil-water separation purposes, considerable attention has been paid to the preparation of hydrophobic-oleophilic materials with modified surface roughness. However, due to issues of thermodynamic instability, costly and complex methods as well as lack of ecofriendly compounds, most of hydrophobic surface modified particles are of limited practical application. The study presents a facile procedure, to synthesize crystalline particles of calcite, which is the most stable polymorph of CaCO 3 from industrial CaCO 3 using oleic acid as an additive in a one-pot synthesis method. The XRD results show that the synthesized particles were a well-crystallized form of calcite. The FTIR results reflect the appearance of the alkyl groups from the oleic acid in synthesized particles which promotes the production of calcite with 'rice shape' (1.64 μm) (aggregated by spherical nanoparticle of 19.56 nm) morphology with concomitant changes in its surface wettability from hydrophilic to hydrophobic. The synthesized particles exhibited near to super hydrophobicity with ∼99% active ratio and a contact angle of 143.8°. The synthesized hydrophobic calcite particles had an oleophilic nature where waste diesel oil adsorption capacity of synthesized calcium carbonate (HCF) showed a very high (>99%) and fast (7 s) oil removal from oil-water mixture. The functional group of long alkyl chain including of CO bounds may play critical roles for adsorption of diesel oils. Moreover, the thermodynamically stable crystalline polymorph calcite (compared to vaterite) exhibited excellent recyclability. The isothermal study

  15. Isotopic studies of authigenic sulfides, silicates and carbonates, and calcite and pyrite veinlets in the Creede Formation, San Juan Mountains, Southwest Colorado (United States)

    Bethke, Philip M.; Rye, Robert O.; Finkelstein, David B.


    Sulfur isotope analysis of authigenic pyrite in the Creede Formation documents its precipitation by the reaction between iron in the volcaniclastic sediments and H2S formed through bacteriogenic reduction of sulfate added to the lake during and immediately following repeated volcanic eruptions during sedimentation. Pyrite veinlets in the underlying Snowshoe Mountain Tuff were formed by the percolation of H2S-bearing pore waters into fractures in the tuff. Conventional analyses of bulk samples of authigenic pyrite range from -20.4% to 34.5% essentially equivalent to the range of -30% to 40% determined using SHRIMP microprobe techniques. Conventional analyses of bulk samples of pyrite from veinlets in the Snowshow Mountain Tiff range from -3.5% to 17.6% much more limited than the ranges of -23% to 111% and -15.6% to 67.0% determined by SHRIMP and laser ablation microbeam techniques, respectively. The extreme range of δ34S for the veinlets is interpreted to be the result of continued fractionation of the already 34S-depleted pore water. Oxygen isotope analysis of authigenic smectite, kaolinite, and K-feldspar together with fluid-inclusion temperatures and oxygen isotope analysis of calcite coexisting with kaolinite indicate that the smectites formed early during burial diagenesis, in accord with petrographic observations. The 40Ar/39Ar dating of K-feldspar, concorfance of K-feldspar, kaolinite, and calcite δ18O values, and fluid-inclusion temperatures in calcite, indicate that the sediments at core hole CCM-1 were subjected to a hydrothermal event at 17.6 Ma. The minerals formed oxygen-shifted meteoric waters with δ18O values of ~-9% Smecities at CCM-1 at least partially exchanged with these waters. Carbon and oxygen isotope analysis of authigenic calcites in the Creede Formation show that they formed over a wide range of temperatures from fluids having a wide range of isotopic composition, presumably over an extended period time. Some of the cements apparently

  16. Microstructural and rheological evolution of calcite mylonites during shear zone thinning: Constraints from the Mount Irene shear zone, Fiordland, New Zealand (United States)

    Negrini, Marianne; Smith, Steven A. F.; Scott, James M.; Tarling, Matthew S.


    Layers of calc-mylonite in the Mount Irene shear zone, Fiordland, New Zealand, show substantial variations in thickness due to deflection of the shear zone boundaries around wall rock asperities. In relatively thick parts (c. 2.6 m) of the shear zone, calcite porphyroclasts are internally strained, contain abundant subgrain boundaries and have a strong shape preferred orientation (SPO) and crystallographic preferred orientation (CPO), suggesting that deformation occurred mainly by dislocation creep involving subgrain-rotation recrystallization. In relatively thin parts (c. 1.5 m) of the shear zone, aggregates of fine-grained recrystallized calcite surrounding flattened porphyroclasts have a weak SPO and CPO, and contain polygonal calcite grains with low degrees of internal misorientation. The recrystallized aggregates also contain microstructures (e.g. grain quadruple junctions, randomized misorientation axes) similar to those reported for neighbor-switching processes during grain-boundary sliding. Comparison of subgrain sizes in the porphyroclasts to published grain-size differential-stress relationships indicates that stresses and strain rates were substantially higher in relatively thin parts of the shear zone. The primary microstructural response to higher stresses and strain rates was an increase in the amount of recrystallization to produce aggregates that deformed by grain-boundary sliding. However, even after the development of interconnected networks of recrystallized grains, dislocation creep by subgrain-rotation recrystallization continued to occur within porphyroclasts. This behavior suggests that the bulk rheology of shear zones undergoing thinning and thickening can be controlled by concomitant grain-size insensitive and grain-size sensitive mechanisms. Overall, our observations show that shear zone thickness variations at constant P-T can result in highly variable stresses and strain rates, which in turn modifies microstructure, deformation mechanism

  17. Atomic Resolution of Calcium and Oxygen Sublattices of Calcite in Ambient Conditions by Atomic Force Microscopy Using qPlus Sensors with Sapphire Tips. (United States)

    Wastl, Daniel S; Judmann, Michael; Weymouth, Alfred J; Giessibl, Franz J


    Characterization and imaging at the atomic scale with atomic force microscopy in biocompatible environments is an ongoing challenge. We demonstrate atomically resolved imaging of the calcite (101̅4) surface plane using stiff quartz cantilevers ("qPlus sensors", stiffness k = 1280 N/m) equipped with sapphire tips in ambient conditions without any surface preparation. With 10 atoms in one surface unit cell, calcite has a highly complex surface structure comprising three different chemical elements (Ca, C, and O). We obtain true atomic resolution of calcite in air at relative humidity ranging from 20% to 40%, imaging atomic steps and single atomic defects. We observe a great durability of sapphire tips with their Mohs hardness of 9, only one step below diamond. Depending on the state of the sapphire tip, we resolve either the calcium or the oxygen sublattice. We determine the tip termination by comparing the experimental images with simulations and discuss the possibility of chemical tip identification in air. The main challenges for imaging arise from the presence of water layers, which form on almost all surfaces and have the potential to dissolve the crystal surface. Frequency shift versus distance spectra show the presence of at least three ordered hydration layers. The measured height of the first hydration layer corresponds well to X-ray diffraction data and molecular dynamic simulations, namely, ∼220 pm. For the following hydration layers we measure ∼380 pm for the second and third layer, ending up in a total hydration layer thickness of at least 1 nm. Understanding the influence of water layers and their structure is important for surface segregation, surface reactions including reconstructions, healing of defects, and corrosion.

  18. Multiphase Calcite Cementation and Fluids Evolution of a Deeply Buried Carbonate Reservoir in the Upper Ordovician Lianglitag Formation, Tahe Oilfield, Tarim Basin, NW China


    Jiaqing Liu; Zhong Li; Lijuan Cheng; Jiawei Li


    Oil and gas have been found in the Upper Ordovician Lianglitag Formation carbonates in the Tahe Oilfield, Tarim Basin, NW China. This study documents the origin of diagenetic fluids by using a combination of petrology, SIMS, fluid inclusion, and radiogenic isotope analysis. Six stages of calcite cements were revealed. C1-C2 formed in marine to early burial environments. C3 has relatively low δ18OVPDB values (−8.45‰ to −6.50‰) and likely has a meteoric origin. Meteoric water probably fluxed in...

  19. Investigating the Basis of Biogenic Calcium Carbonate Formation from an Amorphous Precursor: Nature of the Transformation to Calcite on Hydroxyl Functionalized Surfaces (United States)

    Wang, D.; Lee, J. R.; Talley, C. E.; Murphy, K. E.; Han, T. Y.; Deyoreo, J. J.; Dove, P. M.


    Calcium carbonate biominerals are particularly significant because of their direct role in regulating the global carbon cycle, as well as their ubiquitous occurrence across earth environments. Biogenic carbonates are further distinguished by their broad phlyogenetic distribution; hence it has been suggested that unrelated eukaryotes must have used similar biochemical strategies to control mineralization. Recent studies have shown that an amorphous calcium carbonate (ACC) phase potentially plays a key role in the initial formation of carbonate minerals and in "shaping" them into complex morphologies widely seen in biominerals. Echinoderms, mollusks, and possibly many other organisms use ACC as a precursor phase that is first nucleated in cellularly controlled environments such as vesicles and subsequently transforms into a fully crystalline material. Recent studies on sea urchin embryos have shown that during transformation ACC develops short range that resembles calcite before fully crystallizing and serve as inspiration for our studies in synthetic systems. Self-assembled monolayers (SAM) on gold and silver have been used as simple model systems that approximate biological surfaces. Many studies have shown that thiol monolayers with hydroxyl termination stabilize a transitory ACC film that with prolonged exposure to aqueous solution transforms into calcite nucleated on {104} faces. Using Near Edge X-ray Absorption Fine Structure (NEXAFS) we studied SAM/mineral interactions with well ordered mercaptophenol monolayers showed that when these films are first exposed to calcium carbonate solutions, they become disordered and remain so after subsequent deposition of an ACC over-layer. Yet calcite nucleates and grows from the surface bound ACC with predominantly {104} orientation, which suggests a dynamic structural relationship between the SAMs and the mineral phase. While the monolayer/mineral phase interaction has been characterized, the mechanism for nucleating

  20. Origin and timing of siderite and calcite concretions in late Palaeogene non- to marginal-marine facies of the Te Kuiti Group, New Zealand (United States)

    Middleton, Heather A.; Nelson, Campbell S.


    The Late Eocene-earliest Miocene Te Kuiti Group represents an overall transgressive sequence of formations ranging upwards from non-marine coal measure facies through marginal-marine low-energy shoreline siliciclastic sediments to fully-marine mixed siliciclastic-carbonate deposits. Concretionary structures are common in the lowest formations of the group, being dominantly sideritic in the non-marine to brackish sediment facies (Waikato Coal Measures and Glen Afton Claystone) and calcitic in the more marine-influenced sediments (Rotowaro Siltstone). The geochemistry of the carbonate cements within these early diagenetic concretions records the change from carbonate precipitation from purely meteoric fluids to precipitation from marine fluids, and a shifting source of carbonate carbon across this transition. Siderite precipitation in the Waikato Coal Measures concretions and hardpans was initiated and often largely completed in the methanogenic zone, within the upper 20 m of the sediment pile over a period possibly lasting 100-300 ka. Precipitation continued at a reduced rate to burial depths of 300 m or more when septarian cracking occurred in some siderite concretions and was healed by calcite vein cements that probably derived carbonate from the oxidation of methane ascending from the maturing coal seams directly below. Siderite precipitation in the concretions and hardpans of the overlying brackish-marine Glen Afton Claystone was completed in the topmost few metres of sediment, possibly a few 10 ka. Stable-isotope values near zero support a marine carbonate carbon source, suggested to be from remobilised shell material as evidenced by the common occurrence of shell casts in the formation and the high degree of Mg and Ca substitution in the siderites. The overlying marginal-marine to low-energy marine Rotowaro Siltstone contains calcite concretions precipitated from pore waters enriched in bicarbonate derived from the sulphate-reduction zone, largely within the

  1. Late Pleistocene cryogenic calcite spherolites from the Malachitdom Cave (NE Rhenish Slate Mountains, Germany: Origin, unusual internal structure and stable C-O isotope composition.

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    Detlev Konrad Richter


    Full Text Available Cryogenic calcites yielded U-series ages in the range from 15.61±0.20 ka to 14.48±0.12 ka, which is the youngest age obtained so far for this type of cryogenic cave carbonates in Europe. Most of these particles of the Malachitdom Cave (NE Brilon, Sauerland, North Rhine-Westphalia are complex spherolites usually smaller than 1 cm. They show δ13C-values between –1 and –5 ‰ VPDB and δ18O-values ranging from –7 to –16 ‰ VPDB, the δ13C-values increase and the δ18O-values decrease from centre to border. The complex spherolites are interpreted to be formed in slowly freezing pools of residual water on ice, a situation that repeatedly occurred during the change of glacial to interglacial periods in the periglacial areas of Central Europe. After the melting of the cave-ice, the complex spherolites make up one type of cryogenic calcite particles in the arenitic to ruditic sediment.

  2. Composite Magnetite and Protein Containing CaCO3 Crystals. External Manipulation and Vaterite → Calcite Recrystallization-Mediated Release Performance. (United States)

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


    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.

  3. Electrolyte layering at the calcite(104)-water interface indicated by Rb+- and Se(VI) K-edge resonant interface diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Heberling, F.; Eng, P.; Denecke, M. A.; Lützenkirchen, J.; Geckeis, H. [Karlsruher; (Manchester); (UC)


    Calcite–water interface reactions are of major importance in various environmental settings as well as in industrial applications. Here we present resonant interface diffraction results on the calcite(104)–aqueous solution interface, measured in solutions containing either 10 mmol L-1 RbCl or 0.5 mmol L-1 Se(VI). Results indicate that Rb+ ions enter the surface adsorbed water layers and adsorb at the calcite(104)–water interface in an inner-sphere fashion. A detailed analysis based on specular and off-specular resonant interface diffraction data reveals three distinct Rb+ adsorption species: one 1.2 Å above the surface, the second associated with surface adsorbed water molecules 3.2 Å above the surface, and the third adsorbed in an outer-sphere fashion 5.6 Å above the surface. A peak in resonant amplitude between L = 1.5 and L = 3.0 is interpreted as signal from a layered electrolyte structure. The presence of a layered electrolyte structure seems to be confirmed by data measured in the presence of Se(VI).

  4. Paleoclimatic Inferences from a 120,000-Yr Calcite Record of Water-Table Fluctuation in Browns Room of Devils Hole, Nevada (United States)

    Szabo, B. J.; Kolesar, Peter T.; Riggs, A.C.; Winograd, I.J.; Ludwig, K. R.


    The petrographic and morphologic differences between calcite precipitated below, at, or above the present water table and uranium-series dating were used to reconstruct a chronology of water-table fluctuation for the past 120,000 yr in Browns Room, a subterranean air-filled chamber of Devils Hole fissure adjacent to the discharge area of the large Ash Meadows groundwater flow system in southern Nevada. The water table was more than 5 m above present level between about 116,000 and 53,000 yr ago, fluctuated between about +5 and +9 m during the period between about 44,000 and 20,000 yr ago, and declined rapidly from +9 to its present level during the past 20,000 yr. Because the Ash Meadows groundwater basin is greater than 12,000 km2 in extent, these documented water-table fluctuations are likely to be of regional significance. Although different in detail, water-level fluctuation recorded by Browns Room calcites generally correlate with other Great Basin proxy palcoclimatic data.

  5. Recombinant production of a shell matrix protein in Escherichia coli and its application to the biomimetic synthesis of spherulitic calcite crystals. (United States)

    Song, Wooho; Bahn, So Yeong; Cha, Hyung Joon; Pack, Seung Pil; Choi, Yoo Seong


    To overcome the limited production capability of shell matrix proteins and efficiently conduct in vitro CaCO3 biomineralization studies, a putative recombinant shell matrix protein was prepared and characterized. A glycine-rich protein (GRP_BA) was found in Pinctada fucata as a putative shell matrix protein (NCBI reference sequence; BAA20465). It was genetically redesigned for the production in Escherichia coli. The recombinant protein was obtained in a 400 ml shake-flask culture at approx. 30 mg l(-1) with a purity of >95 %. It efficiently formed a complex with Ca(2+). Ca(2+)-induced agglomeration was like other calcification-related proteins. Spherulitic calcite micro-particles, 20-30 µm diam. with rosette- and sphere-like structures were synthesized in the presence of the recombinant shell protein, which could be formed by stacking and/or aggregation of calcite nanograins and the bound protein. Recombinant production of a shell matrix protein could overcome potential difficulties associated with the limited amount of protein available for biomineralization studies and provide opportunities to fabricate biominerals in practical aspects.

  6. Multiphase Calcite Cementation and Fluids Evolution of a Deeply Buried Carbonate Reservoir in the Upper Ordovician Lianglitag Formation, Tahe Oilfield, Tarim Basin, NW China

    Directory of Open Access Journals (Sweden)

    Jiaqing Liu


    Full Text Available Oil and gas have been found in the Upper Ordovician Lianglitag Formation carbonates in the Tahe Oilfield, Tarim Basin, NW China. This study documents the origin of diagenetic fluids by using a combination of petrology, SIMS, fluid inclusion, and radiogenic isotope analysis. Six stages of calcite cements were revealed. C1-C2 formed in marine to early burial environments. C3 has relatively low δ18OVPDB values (−8.45‰ to −6.50‰ and likely has a meteoric origin. Meteoric water probably fluxed into aquifers during the Early Paleozoic and Late Paleozoic uplift. C4 has δ18OVPDB values typically 3‰ higher than those of C3, and probably formed during shallow burial. C5 displays relatively negative δ18OVPDB values (−8.26‰ to −5.12‰, and the moderate-to-high fluid-inclusion temperatures imply that it precipitated in burial environments. C6 shows homogenization temperatures (up to 200°C higher than the maximum burial and much lower salinities (<10.61 wt% NaCl, which may suggest that the fluid was deeply recycled meteoric water. The average 87Sr/86Sr ratios of fracture- and vug-filling calcite cements are much higher, indicative of incorporation of radiogenic Sr. Caves and fractures constitute the dominant reservoir spaces. A corresponding diagenesis-related reservoir evolution model was established that favors exploration and prediction.

  7. Dissolution Processes at Step Edges of Calcite in Water Investigated by High-Speed Frequency Modulation Atomic Force Microscopy and Simulation. (United States)

    Miyata, Kazuki; Tracey, John; Miyazawa, Keisuke; Haapasilta, Ville; Spijker, Peter; Kawagoe, Yuta; Foster, Adam S; Tsukamoto, Katsuo; Fukuma, Takeshi


    The microscopic understanding of the crystal growth and dissolution processes have been greatly advanced by the direct imaging of nanoscale step flows by atomic force microscopy (AFM), optical interferometry, and X-ray microscopy. However, one of the most fundamental events that govern their kinetics, namely, atomistic events at the step edges, have not been well understood. In this study, we have developed high-speed frequency modulation AFM (FM-AFM) and enabled true atomic-resolution imaging in liquid at ∼1 s/frame, which is ∼50 times faster than the conventional FM-AFM. With the developed AFM, we have directly imaged subnanometer-scale surface structures around the moving step edges of calcite during its dissolution in water. The obtained images reveal that the transition region with typical width of a few nanometers is formed along the step edges. Building upon insight in previous studies, our simulations suggest that the transition region is most likely to be a Ca(OH)2 monolayer formed as an intermediate state in the dissolution process. On the basis of this finding, we improve our understanding of the atomistic dissolution model of calcite in water. These results open up a wide range of future applications of the high-speed FM-AFM to the studies on various dynamic processes at solid-liquid interfaces with true atomic resolution.

  8. Constraints on Neogene deformation in the southern Terror Rift from calcite twinning analyses of veins within the ANDRILL MIS core, Victoria Land Basin, Antarctica (United States)

    Paulsen, T. S.; Demosthenous, C.; Wilson, T. J.; Millan, C.


    The ANDRILL MIS (McMurdo Ice Shelf) Drilling Project obtained over 1200 meters of Neogene sedimentary and volcanic rocks in 2006/2007. Systematic fracture logging of the AND-1B core identified 1,475 natural fractures, i.e. pre-existing fractures in the rock intersected by coring. The most abundant natural fractures are normal faults and calcite veins; reverse faults, brecciated zones, and sedimentary intrusions are also present. In order to better understand Neogene deformation patterns within the southern Terror Rift, we have been conducting strain analyses on mechanically twinned calcite within healed fractures in the drill core. Twinning strains using all of the data from each sample studied to date range from 2% to 10%. The cleaned data (20% of the largest magnitude deviations removed) typically show ≤30% negative expected values, consistent with a single deformation episode or multiple ~coaxial deformation episodes. The majority of the samples record horizontal extension, similar to strain patterns expected in a normal fault regime and/or vertical sedimentary compaction in a continental rift system. The morphology, width, and intensity of twins in the samples suggest that twinning typically occurred at temperatures <170° C. Twinning intensities suggest differential stress magnitudes that caused the twinning ranged from 216 to 295 MPa.

  9. Susceptibility of experimental faults to pore pressure increase: insights from load-controlled experiments on calcite-bearing rocks (United States)

    Spagnuolo, Elena; Violay, Marie; Nielsen, Stefan; Cornelio, Chiara; Di Toro, Giulio


    Fluid pressure has been indicated as a major factor controlling natural (e.g., L'Aquila, Italy, 2009 Mw 6.3) and induced seismicity (e.g., Wilzetta, Oklahoma, 2011 Mw 5.7). Terzaghi's principle states that the effective normal stress is linearly reduced by a pore pressure (Pf) increase σeff=σn(1 - αPf), where the effective stress parameter α, may be related to the fraction of the fault area that is flooded. A value of α =1 is often used by default, with Pf shifting the Mohr circle towards lower normal effective stresses and anticipating failure on pre-existing faults. However, within a complex fault core of inhomogeneous permeability, α may vary in a yet poorly understood way. To shed light on this problem, we conducted experiments on calcite-bearing rock samples (Carrara marble) at room humidity conditions and in the presence of pore fluids (drained conditions) using a rotary apparatus (SHIVA). A pre-cut fault is loaded by constant shear stress τ under constant normal stress σn=15 MPa until a target value corresponding roughly to the 80 % of the frictional fault strength. The pore pressure Pf is then raised with regular pressure and time steps to induce fault instability. Assuming α=1 and a threshold for instability τp_eff=μp σeff, the experiments reveal that an increase of Pf does not necessarily induce an instability even when the effective strength threshold is largely surpassed (e.g., τp_eff=1.3 μpσeff). This result may indicate that the Pf increase did not instantly diffuse throughout the slip zone, but took a finite time to equilibrate with the external imposed pressure increase due to finite permeability. Under our experimental conditions, a significant departure from α=1 is observed provided that the Pf step is shorter than about < 20s. We interpret this delay as indicative of the diffusion time (td), which is related to fluid penetration length l by l = √ κtd-, where κ is the hydraulic diffusivity on the fault plane. We show that a

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

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    Zavarin, M; Bruton, C J


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

  11. Chemical and physical evolution of dolomite precipitation at 180°C and 220°C from calcite and aragonite seeds (United States)

    Kell-Duivestein, Isaac; Dietzel, Martin; Mavromatis, Vasileios


    In this present study an experimental approach is taken to gain a better understanding of secondary dolomite formation under diagenetic hydrothermal conditions. A series of 60 experiments were set up in closed bomb reactors with Teflon inserts to simulate exposure of calcium carbonate materials of (i) aragonite and (ii) calcite to hydrothermal conditions. 30 reactors were prepared using calcite as a seed material and 30 using aragonite. In each experiment 330mg of the seed calcium carbonate was placed in 30mL of 0.2M MgCl2 solution along with 252mg NaHCO3 to balance charges. 15 of each the calcite and aragonite prepared reactors were placed in an oven at 180°C and 15 of each at 220°C. Samples were then progressively removed from the ovens beginning in short time intervals and increasing the time apart as the phase transformations became less rapid (ie. after 3, 6, 13, 21, 31, 56 days *ongoing*). Samples were separated into fluid and solid phases by filtration for separate analysis. Fluids were analysed by titration for alkalinity and ICP-OES for elemental concentrations of major cations to determine the migration of major cations between the calcium carbonate seed material and the reaction fluid. Solid samples were analysed with FTIR-spectroscopy and X-ray diffraction of powdered smears on glass loading slides to identify the present mineral phases. Rietveld analysis was conducted on the XRD patterns to quantify the mineral phases and to determine the stoichiometry and the superstructure of the formed magnesite and dolomite. Although experiments are still running, several trends have been identified. Transformation of the aragonite seed material occurs at a much faster rate than transformation of the calcite seed material, with each precursor material first transforming into a Ca-rich magnesite. With increased reaction time the Ca-rich magnesite recrystallizes to purer phases of magnesite, the Ca concentration of the fluid increases as the Ca is liberated into

  12. Origin and significance of postore dissolution collapse breccias cemented with calcite and barite at the Meikle gold deposit, Northern Carlin trend, Nevada (United States)

    Emsbo, P.; Hofstra, A.H.


    The final event in a complicated hydrothermal history at the Meikle gold deposit was gold deficient but caused extensive postore dissolution of carbonate, collapse brecciation, and precipitation of calcite and barite crystals in the resulting cavities. Although previously interpreted to be part of the Carlin-type hydrothermal system, crosscutting relationships and U-Th-Pb geochronology constrain this hydrothermal event to late Pliocene time (ca. 2 Ma), nearly 36 Ma after ore formation. Mineralogic, fluid inclusion, and stable isotope data indicate that postore hydrothermal fluids were reduced, H2S-rich, unevolved meteoric waters ((??18O = -17???) of low temperature (ca. 65??C). The ??18O values of barite and calcite indicate that these minerals were in isotopic equilibrium, requiring that barite SO4 was derived from the oxidation of reduced sulfur; however, preexisting sulfides in breccia cavities were not oxidized. The ??34S (15???) values of barite are higher than those of local bulk sulfide and supergene alunite indicating that SO4 was not derived from supergene oxidation of local sulfide minerals. The 15 per mil ??34S value suggests that the H2S in the fluids may have been leached from sulfur-rich organic matter in the local carbonaceous sedimentary rocks. A reduced H2S-rich fluid is also supported by the bright cathodoluminescence of calcite which indicates that it is Mn rich and Fe poor. Calcite has a narrow range of ??13C values (0.3-1.8???) that are indistinguishable from those of the host Bootstrap limestone, indicating that CO2 in the fluid was from dissolution of the local limestone. These data suggest that dissolution and brecciation of the Bootstrap limestone occurred where H2S-rich fluids encountered more oxidizing fluids and formed sulfuric acid (H2SO4). Intense fracturing in the mine area by previous structural and hydrothermal events probably provided conduits for the descent of oxidized surface water which mixed with the underlying H2S-rich waters

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

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    Mansour Rezaei Azizi


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

  14. Criteria for the recognition of pedogenic/supergene and nonpedogenic/hypogene deposits and their relationship to the origin of calcite/opal deposits at Yucca Mountain. Special report No. 14

    Energy Technology Data Exchange (ETDEWEB)

    Hill, C.A.; Schluter, C.M.; Monger, H.C.


    This study is part of the research program of the Yucca Mountain Project intended to provide the State of Nevada with a detailed assessment of the geology and geochemistry of Yucca Mountain and adjacent regions. The purpose of this report is to try and establish criteria for the recognition of pedogenic/supergene deposits of calcite/opal versus non-pedogenic/hypogene deposits of calcite/opal. Far from being of esoteric concern, this subject is of paramount importance to the pedogenic-hypogene debate which rages around the suitability of Yucca Mountain as a high-level radioactive waste repository site.

  15. Late-stage anhydrite-gypsum-siderite-dolomite-calcite assemblages record the transition from a deep to a shallow hydrothermal system in the Schwarzwald mining district, SW Germany (United States)

    Burisch, Mathias; Walter, Benjamin F.; Gerdes, Axel; Lanz, Maximilian; Markl, Gregor


    The majority of hydrothermal vein systems of economic interest occur at relatively shallow crustal levels, although many of them formed at significantly greater depths. Their present position is a consequence of uplift and erosion. Although, many aspects of their formation are well constrained, the temporal chemical evolution of such systems during uplift and erosion is still poorly understood. These vein minerals comprise calcite, dolomite-ankerite, siderite-magnesite, anhydrite and gypsum forming the last gangue assemblages in Jurassic and Tertiary sulphide-fluorite-quartz-barite veins of the Schwarzwald mining district, SW Germany. Mineral textures of samples from nine localities reveal that in these sequences, mineral precipitation follows a recurring pattern: early calcite is followed by anhydrite or gypsum, siderite and/or dolomite. This succession may repeat up to three times. In-situ (LA-ICP-MS) U-Pb age dating of 15 carbonates from three subsequent generations of the late-stage vein assemblage yield robust ages between 20 and 0.6 Ma. Each mineral sequence forms in a distinctive period of about 2-5 Ma. These ages clearly relate these late-stage mineral phases to the youngest geological episode of the Schwarzwald, which is associated with the Cenozoic Rhine Graben rifting and basement uplift. Based on thermodynamic modelling, the formation of the observed mineral assemblages required an deeply sourced Mg-, Fe- and SO4-rich fluid (b), which was episodically mixed with a shallow crustal HCO3-rich fluid (a). As a consequence of fluid mixing, concentrations of Mg, Fe and SO4 temporarily increased and initiated the formation of the observed sulphate-carbonate mineral sequences. This discontinuous large-scale vertical fluid mixing was presumably directly related to episodes of active tectonics associated with the Cenozoic strike-slip regime of the Upper Rhine Graben. Analogously, episodic fluid mixing is a major key in the formation of older (Jurassic to early

  16. Modification of calcite crystal morphology by designed phosphopeptides and primary structures and substrate specifities of the cysteine proteases mexicain and chymomexicain (United States)

    Lian, Zhirui

    In order to better understand the mechanism of biomineralization, we have undertaken to synthesize polypeptide model compounds of well-defined structure that can interact with specific faces of calcite and alter its crystal morphology. These peptides were designed based on the structure of alpha-helical winter flounder antifreeze polypeptide HPLC-6. In these peptides, from one to three of the threonine residues in HPLC-6 were substituted by phosphoserine or phosphotyrosine. CD spectra show that all the peptides have virtually the same alpha-helicity, i.e., about 90% at 4°C and 50% at 25°C. However, only peptides which contain at least two phosphate groups spaced 16.8-A apart can modify the crystal morphology of the calcite. The newly developed surface has been tentatively identified as the (001) basal face. Molecular modeling indicates that the spacing of phosphate groups allows for a good match with crystal lattice ions on the (001) plane. Another peptide, CBP-3D, in which the three threonine residues in HPLC-6 were substituted by aspartic acids, appears to bind only to {104} rhombohedral faces of calcite. These experiments suggest that conformation and orientation of the binding ligands in the peptide are important factors governing the mutual recognition of crystal surface and proteins. The complete amino acid sequences of the cysteine proteases mexicain and chymomexicain, isolated from the latex of the plant Pileus mexicanus , were determined by Edman degradation of proteolytic fragments. Mexicain and chymomexicain show-high sequence homology to the papain family of cysteine protease. Mexicain and chymomexicain are monomeric polypeptides, with molecular masses of 23,762 Da and 23,694 Da, respectively, and both contain three deduced disulfide bonds. The proteolytic substrate specificities of mexicain and chymomexicain were studied by digesting a series of synthetic peptides and analyzing the fragments by mass spectrometry. The two proteases showed virtually

  17. Evidence of a Biological Control over Origin, Growth and End of the Calcite Prisms in the Shells of Pinctada margaritifera (Pelecypod, Pterioidea

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    Jean-Pierre Cuif


    Full Text Available Consistently classified among the references for calcite simple prisms, the microstructural units that form the outer layer of the Pinctada margaritifera have been investigated through a series of morphological, crystallographical and biochemical characterizations. It is often said that the polygonal transverse shape of the prisms result from the competition for space between adjacent crystals. In contrast to this classical scheme the Pinctada prisms appear to be composed of four successive developmental stages from the concentrically growing disks on the internal side of the periostracum to the morphological, structural and compositional changes in both envelopes and mineral components at the end of the prisms. These latest structural and compositional changes predate nacre deposition, so that the end of prism growth is not caused by occurrence of nacre, but by metabolic changes in the secretory epithelium. This sequence makes obvious the permanent biological control exerted by the outer cell layer of the mantle in both organic envelopes and mineralizing organic phases.

  18. Pseudospherulitic fibrous calcite from the Quaternary shallow lacustrine carbonates of the Farafra Oasis, Western Desert, Egypt: A primary precipitate with possible bacterial influence (United States)

    Wanas, H. A.


    Pseudospherulitic fibrous calcite (PFC) has been found as a major constituent (85-90%) within thin massive limestone beds of the Quaternary mudflat-shallow lacustrine facies association (1.5-2 m thick) that forms part of combined facies associations of the Quaternary clastic-carbonate unit (25-30 m thick) at Bir-Karawein area in the Farafra Oasis, Western Desert, Egypt. The thin massive limestone beds (2-5 cm thick) are devoid of pedogenic features and marine fossils. They form a rhythmic cyclic succession with thin massive mudrocks (5-10 cm thick). The mudflat-shallow lacustrine facies association herein occurs within a depositional sequence of distal alluvial-floodplain (6-12 m thick) and palustrine (1.5-4.5 m thick) facies associations. The PFC is a composed of loosely packed rounded to sub-rounded single low-Mg-calcite crystals (150-250 μm-sized) with intracrystalline fibrous microfabric marked by fibers (150-250 μm long and 10-20 μm wide) radiating from the center of the individual crystals and displaying irregular internal growth with lobate pattern. The PFC crystals show non-planar to highly irregular intercrystalline boundaries. Under SEM, the individual crystal fibers group of PFC form ellipsoid to sub-globular bodies. Each PFC crystal exhibits successive zones of thick non-luminescence and thin brightly orange to dull luminescence. The matrix (10-15%) between the PFC crystals is mainly a honeycomb-like smectite. The PFC is postulated to be a primary precipitate. This concept is reached because the PFC: (i) does not display the criteria of typical Microcodium structures, root-calcification, speleothem structures, calcite spherulites of laminar calcretes, and calcitization of precursor dolomite or aragonite, (ii) possesses homogenous compositional and textural characteristics, and (iii) occurs within limestone beds that lie in between impermeable massive mudrock beds that dampen diagenesis. A role for possible bacterial contribution in crystallization of

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

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    Archambeau, C.


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

  20. Differential displacement and rotation in thrust fronts: A magnetic, calcite twinning and palinspastic study of the Jones Valley thrust, Alabama, US Appalachians (United States)

    Hnat, James S.; van der Pluijm, Ben A.; Van der Voo, Rob; Thomas, William A.


    To test whether a displacement gradient along a curved fault structure requires rotation, we studied the northeast-striking, northwest-verging, large-displacement Jones Valley thrust fault of the Appalachian thrust belt in Alabama. Paleomagnetism, anisotropy of magnetic susceptibility (AMS) and calcite twinning analysis, complemented by balanced cross-sections, were used to evaluate the presence and magnitude of any rotation. Remanence directions from the Silurian Red Mountain Formation reveal a prefolding magnetization acquired in the Pennsylvanian, whereas magnetic analysis shows a strong, bedding-parallel compaction fabric with a tectonic lineation. Paleomagnetic directions and magnetic lineations reveal no relative rotation between the hanging wall and footwall of the thrust fault. Rather than rotation, therefore, we interpret the Jones Valley thrust sheet as a structure that developed in a self-similar fashion, with lateral growth of the fault surface occurring coincident with growth into the foreland.

  1. Calcite raft geochemistry as a hydrological proxy for Holocene aquifer conditions in Hoyo Negro and Ich Balam (Sac Actun Cave System), Quintana Roo, Mexico (United States)

    Kovacs, Shawn E.; Reinhardt, Eduard G.; Chatters, James C.; Rissolo, Dominique; Schwarcz, Henry P.; Collins, Shawn V.; Kim, Sang-Tae; Nava Blank, Alberto; Luna Erreguerena, Pilar


    Two cores from calcite rafts deposits located in Cenote Ich Balam and Hoyo Negro were dated and analyzed for 87Sr/86Sr, δ18O, δ13C, Sr/Ca and Cl/Ca. The geochemical records show changing aquifer salinity spanning the last ∼ 8.5 cal kyrs BP and interrelationships with Holocene climate trends (wet and dry periods). During the wet mid-Holocene, the salinity of the meteoric Water Mass (WM; at 7.8-8.3 cal kyrs BP) was relatively high at 1.5-2.7 ppt and then became less saline (1.0-1.5 ppt) during the last ∼ 7000 yrs as climate became progressively drier. High salinity of the meteoric WM during the wet mid-Holocene is attributed to increased turbulent mixing between the meteoric and underlying marine WM. Increased precipitation, in terms of amount, frequency, and intensity (e.g. hurricanes) causes higher flow of meteoric water towards the coast and mixing at the halocline, a phenomenon recorded with recent instrumental monitoring of the aquifer. Conversely, during dry periods reduced precipitation and flow in the meteoric WM would result in lower salinity. Karst properties and Holocene sea-level rise also seem to have an effect on the aquifer. When the regionally extensive network of shallow cave passages (∼ 10-12 m water depth) are flooded at ∼ 8000 cal yrs BP, there is a rapid shift in salinity. This study demonstrates that calcite raft deposits can be used as paleo-environmental recorders documenting the effects of sea level and climate change on aquifer condition.

  2. Inversion of calcite twin data for paleostress orientations and magnitudes: A new technique tested and calibrated on numerically-generated and natural data (United States)

    Parlangeau, Camille; Lacombe, Olivier; Schueller, Sylvie; Daniel, Jean-Marc


    The inversion of calcite twin data is a powerful tool to reconstruct paleostresses sustained by carbonate rocks during their geological history. Following Etchecopar's (1984) pioneering work, this study presents a new technique for the inversion of calcite twin data that reconstructs the 5 parameters of the deviatoric stress tensors from both monophase and polyphase twin datasets. The uncertainties in the parameters of the stress tensors reconstructed by this new technique are evaluated on numerically-generated datasets. The technique not only reliably defines the 5 parameters of the deviatoric stress tensor, but also reliably separates very close superimposed stress tensors (30° of difference in maximum principal stress orientation or switch between σ3 and σ2 axes). The technique is further shown to be robust to sampling bias and to slight variability in the critical resolved shear stress. Due to our still incomplete knowledge of the evolution of the critical resolved shear stress with grain size, our results show that it is recommended to analyze twin data subsets of homogeneous grain size to minimize possible errors, mainly those concerning differential stress values. The methodological uncertainty in principal stress orientations is about ± 10°; it is about ± 0.1 for the stress ratio. For differential stresses, the uncertainty is lower than ± 30%. Applying the technique to vein samples within Mesozoic limestones from the Monte Nero anticline (northern Apennines, Italy) demonstrates its ability to reliably detect and separate tectonically significant paleostress orientations and magnitudes from naturally deformed polyphase samples, hence to fingerprint the regional paleostresses of interest in tectonic studies.

  3. δ13C signal of earthworm calcite granules: A new proxy for palaeoprecipitation reconstructions during the Last Glacial in western Europe (United States)

    Prud'homme, Charlotte; Lécuyer, Christophe; Antoine, Pierre; Hatté, Christine; Moine, Olivier; Fourel, François; Amiot, Romain; Martineau, François; Rousseau, Denis-Didier


    Quantification of paleoprecipitation during the Last Glacial is a key element to reconstruct palaeoclimates. Recently, fossil calcite granules have been identified in loess sequences with high contents in specific horizons. In this study, we explored for the first time the potential of this new bio-indicator as a climatic proxy for precipitation in western Europe during the Last Glacial. We extracted 30 granules from eleven samples belonging to three tundra gleys and two brown soils from the Nussloch loess sequence previously dated between 50 and 20 ka. Stable carbon isotope measurements were performed on each granule and duplicated. Throughout the studied section, δ13C values range from -15.4 to -10.3‰ for tundra gleys and from -14.9 to -9.5‰ for brown soils. By taking into account the fractionation factor between the carbon ingested by the earthworm and the carbon output of the granules, the δ13C values of these granules reflect the composition of the C3 plant vegetation cover. Thus, we estimated the δ13C of the plants with a mean value of -24.3 ± 0.9‰ for tundra gleys and -24.1 ± 0.9‰ for brown soils, which are in agreement with values obtained from organic matter preserved in sediments. Palaeoprecipitation range over both tundra gley horizons and brown soils were estimated at about 333[159-574] mm/yr by using an empirical relationship determined between present-day plant leaf isotopic discrimination and the mean annual precipitation. This original preliminary study highlights the potential of earthworm calcite granule δ13C measurements as a new proxy for paleoprecipitation during the Last Glacial interstadials in continental environments.

  4. Reconstruction of drip-water δ18O based on calcite oxygen and clumped isotopes of speleothems from Bunker Cave (Germany

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    T. Kluge


    Full Text Available The geochemical signature of many speleothems used for reconstruction of past continental climates is affected by kinetic isotope fractionation. This limits quantitative paleoclimate reconstruction and, in cases where the kinetic fractionation varies with time, also affects relative paleoclimate interpretations. In carbonate archive research, clumped isotope thermometry is typically used as proxy for absolute temperatures. In the case of speleothems, however, clumped isotopes provide a sensitive indicator for disequilibrium effects. The extent of kinetic fractionation co-varies in Δ47 and δ18O so that it can be used to account for disequilibrium in δ18O and to extract the past drip-water composition. Here we apply this approach to stalagmites from Bunker Cave (Germany and calculate drip-water δ18Ow values for the Eemian, MIS3, and the Holocene, relying on independent temperature estimates and accounting for disequilibrium. Applying the co-variation method to modern calcite precipitates yields drip-water δ18Ow values in agreement with modern cave drip-water δ18Ow of −7.9 ± 0.3‰, despite large and variable disequilibrium effects in both calcite δ18Oc and Δ47. Reconstructed paleo-drip-water δ18Ow values are lower during colder periods (e.g., MIS3: −8.6 ± 0.4‰ and the early Holocene at 11 ka: −9.7 ± 0.2‰ and show higher values during warmer climatic periods (e.g., the Eemian: −7.6 ± 0.2‰ and the Holocene Climatic Optimum: −7.2 ± 0.3‰. This new approach offers a unique possibility for quantitative climate reconstruction including the assessment of past hydrological conditions while accounting for disequilibrium effects.

  5. Effect of pH on the precipitation of synthetic CaCO3 polymorphs and determination of Mg/Ca ratios in synthetic low-magnesium calcite: An experimental investigation (United States)

    Gabitov, R. I.; Weremeichik, J. M.; Novak, A.; Sadekov, A.; Thirumalai, R. V. K. G.


    The intent of the work presented is to determine the effect which the Mg/Ca ratio in fluid has on the Mg partition coefficient (KMg) between synthetically precipitated low-magnesium calcite and solution. In nature, planktonic foraminifera produce low-magnesium calcite with distinct Mg/Ca that is typically found to be within the range of 1.4 to 10 mmol/mol (e.g. Regenberg et al., 2009; Sadekov et al., 2009). Our intent was to replicate Mg/Ca found in foraminifera by conducting experiments where low-Mg calcite was grown inorganically at a near-constant salinity and temperature. Synthetic low-Mg calcite was precipitated using a continuous pumping method whereby NaHCO3 and Mg-doped CaCl2 solutions were pumped into a NaCl solution. Continuous pumping allows for delivery of solutions to a reaction vessel at a constant rate while simultaneously maintaining fluid volume by removing fluid at a constant rate equal to the delivery rate. In order to vary the Mg/Ca ratio while keeping salinity near-constant, magnesium and calcium molar concentrations were varied but the sum of the concentrations was kept equal to the concentration of NaHCO3 or Na2CO3. Optical microscopy analysis of samples showed that the use of Na2CO3 as the carbonate ion source in experiments precipitated predominately aragonite with needle-like crystals whereas use of NaHCO3 yielded calcite with rhombohedral crystals. Powder XRD analysis of a sample collected from one of the Na2CO3 experiments confirmed that the dominant CaCO3 polymorph precipitated was aragonite. This suggests that aragonite is being produced at higher pH values using Na2CO3 and calcite is being produced at lower values of pH using NaHCO3. We intend use XRD, AAS, and ICP-MS to confirm that rhombohedral crystals are calcite and determine Mg/Ca of fluid and those crystals. ReferencesRegenberg et al. (2009) Earth Planet. Sci. Lett., 278, doi: 10.1016/j.epsl.2008.12.019. Sadekov et al. (2009) Paleoceanography, 24, doi: 10.1029/2008PA001664.

  6. The elemental composition of purple sea urchin (Strongylocentrotus purpuratus calcite and potential effects of pCO2 during early life stages

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    M. LaVigne


    Full Text Available Ocean acidification will likely have negative impacts on invertebrates producing skeletons composed of calcium carbonate. Skeletal solubility is partly controlled by the incorporation of "foreign" ions (e.g. magnesium into the crystal lattice of these skeletal structures, a process that is sensitive to a variety of biological and environmental factors. Here we explore effects of life stage, oceanographic region of origin, and changes in the partial pressure of carbon dioxide in seawater (pCO2 on trace elemental composition in the purple sea urchin (Strongylocentrotus purpuratus. We show that, similar to other urchin taxa, adult purple sea urchins have the ability to precipitate skeleton composed of a range of biominerals spanning low- to high-Mg calcites. Mg / Ca and Sr / Ca ratios were substantially lower in adult spines compared to adult tests. On the other hand, trace elemental composition was invariant among adults collected from four oceanographically distinct regions spanning a range of carbonate chemistry conditions (Oregon, Northern California, Central California, and Southern California. Skeletons of newly settled juvenile urchins that originated from adults from the four regions exhibited intermediate Mg / Ca and Sr / Ca between adult spine and test endmembers, indicating that skeleton precipitated during early life stages is more soluble than adult spines and less soluble than adult tests. Mean skeletal Mg / Ca or Sr / Ca of juvenile skeleton did not vary with source region when larvae were reared under present-day, global-average seawater carbonate conditions (400 μatm; pHT = 8.02 ± 0.03 1 SD; Ωcalcite = 3.3 ± 0.2 1 SD. However, when reared under elevated pCO2 (900 μatm; pHT = 7.73 ± 0.03; Ωcalcite = 1.8 ± 0.1, skeletal Sr / Ca in juveniles exhibited increased variance across the four regions. Although larvae from the northern populations (Oregon, Northern California, Central California did not exhibit differences in Mg or Sr

  7. The elemental composition of purple sea urchin (Strongylocentrotus purpuratus) calcite and potential effects of pCO2 during early life stages (United States)

    LaVigne, M.; Hill, T. M.; Sanford, E.; Gaylord, B.; Russell, A. D.; Lenz, E. A.; Hosfelt, J. D.; Young, M. K.


    Ocean acidification will likely have negative impacts on invertebrates producing skeletons composed of calcium carbonate. Skeletal solubility is partly controlled by the incorporation of "foreign" ions (e.g. magnesium) into the crystal lattice of these skeletal structures, a process that is sensitive to a variety of biological and environmental factors. Here we explore effects of life stage, oceanographic region of origin, and changes in the partial pressure of carbon dioxide in seawater (pCO2) on trace elemental composition in the purple sea urchin (Strongylocentrotus purpuratus). We show that, similar to other urchin taxa, adult purple sea urchins have the ability to precipitate skeleton composed of a range of biominerals spanning low- to high-Mg calcites. Mg / Ca and Sr / Ca ratios were substantially lower in adult spines compared to adult tests. On the other hand, trace elemental composition was invariant among adults collected from four oceanographically distinct regions spanning a range of carbonate chemistry conditions (Oregon, Northern California, Central California, and Southern California). Skeletons of newly settled juvenile urchins that originated from adults from the four regions exhibited intermediate Mg / Ca and Sr / Ca between adult spine and test endmembers, indicating that skeleton precipitated during early life stages is more soluble than adult spines and less soluble than adult tests. Mean skeletal Mg / Ca or Sr / Ca of juvenile skeleton did not vary with source region when larvae were reared under present-day, global-average seawater carbonate conditions (400 μatm; pHT = 8.02 ± 0.03 1 SD; Ωcalcite = 3.3 ± 0.2 1 SD). However, when reared under elevated pCO2 (900 μatm; pHT = 7.73 ± 0.03; Ωcalcite = 1.8 ± 0.1), skeletal Sr / Ca in juveniles exhibited increased variance across the four regions. Although larvae from the northern populations (Oregon, Northern California, Central California) did not exhibit differences in Mg or Sr

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

    Directory of Open Access Journals (Sweden)

    Arizzi, A.


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

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

  9. Controls on the long term earthquake behavior of an intraplate fault revealed by U-Th and stable isotope analyses of syntectonic calcite veins (United States)

    Williams, Randolph; Goodwin, Laurel; Sharp, Warren; Mozley, Peter


    U-Th dates on calcite precipitated in coseismic extension fractures in the Loma Blanca normal fault zone, Rio Grande rift, NM, USA, constrain earthquake recurrence intervals from 150-565 ka. This is the longest direct record of seismicity documented for a fault in any tectonic environment. Combined U-Th and stable isotope analyses of these calcite veins define 13 distinct earthquake events. These data show that for more than 400 ka the Loma Blanca fault produced earthquakes with a mean recurrence interval of 40 ± 7 ka. The coefficient of variation for these events is 0.40, indicating strongly periodic seismicity consistent with a time-dependent model of earthquake recurrence. Stochastic statistical analyses further validate the inference that earthquake behavior on the Loma Blanca was time-dependent. The time-dependent nature of these earthquakes suggests that the seismic cycle was fundamentally controlled by a stress renewal process. However, this periodic cycle was punctuated by an episode of clustered seismicity at 430 ka. Recurrence intervals within the earthquake cluster were as low as 5-11 ka. Breccia veins formed during this episode exhibit carbon isotope signatures consistent with having formed through pronounced degassing of a CO2 charged brine during post-failure, fault-localized fluid migration. The 40 ka periodicity of the long-term earthquake record of the Loma Blanca fault is similar in magnitude to recurrence intervals documented through paleoseismic studies of other normal faults in the Rio Grande rift and Basin and Range Province. We propose that it represents a background rate of failure in intraplate extension. The short-term, clustered seismicity that occurred on the fault records an interruption of the stress renewal process, likely by elevated fluid pressure in deeper structural levels of the fault, consistent with fault-valve behavior. The relationship between recurrence interval and inferred fluid degassing suggests that pore fluid pressure

  10. Microstructural analysis and calcite piezometry on hydrothermal veins: Insights into the deformation history of the Cocos Plate at Site U1414 (IODP Expedition 344) (United States)

    Brandstätter, Jennifer; Kurz, Walter; Rogowitz, Anna


    In this study we present microstructural data from hydrothermal veins in the sedimentary cover and the igneous basement recovered from Hole U1414A, Integrated Ocean Drilling Program (IODP) Expedition 344 (Costa Rica Seismogenesis Project), to constrain deformation mechanism operating in the subducting Cocos Plate. Cathodoluminescence studies, mechanical e-twin piezometry and electron backscatter diffraction (EBSD) analyses of carbonate veins were used to give insights into the deformation conditions and to help to understand the tectonic deformation history of the Cocos Plate offshore Costa Rica. Analyses of microstructures in the sedimentary rocks and in the basalt of the igneous basement reveal brittle deformation, as well as crystal-plastic deformation of the host rock and the vein material. Cathodoluminescence images showed that in the basalt fluid flow and related precipitation occurred over several episodes. The differential stresses, obtained from two different piezometers using the same parameter (twin density), indicate various mean differential stresses of 49 ± 11 and 69 ± 30 MPa and EBSD mapping of calcite veins reveals low-angle subgrain boundaries. Deformation temperatures are restricted to the range from 170°C to 220°C, due to the characteristics of the existing twins and the lack of high-temperature intracrystalline deformation mechanisms (>220°C). The obtained results suggest that deformation occurred over a period associated with changes of ambient temperatures, occurrence of fluids and hydrofracturing, induced differential stresses due to the bending of the plate at the trench, and related seismic activity.

  11. Kinematics of the Neogene Terror Rift: Constraints from calcite twinning strain in AND-1B core, McMurdo Ice Shelf (United States)

    Paulsen, T.; Wilson, T. J.; Demosthenous, C.; Millan, C.; Jarrard, R. D.; Laufer, A.


    Strain analyses of mechanically twinned calcite in veins and faults hosted by Neogene (13.6 Ma to 4.3 Ma) sedimentary and volcanic rocks recovered within the ANDRILL AND-1B drill core from the Terror Rift in the southern Ross Sea, Antarctica, yield prolate and oblate ellipsoids with principal shortening and extension strains ranging from 0.1% to 8.5%. The majority of samples show homogeneous coaxial strain predominantly characterized by subvertical shortening, which we attribute to lithostatic loading in an Andersonian normal faulting stress regime during sedimentary and ice sheet burial of the stratigraphic sequence. The overall paucity of a non-coaxial layer-parallel shortening signal in the AND-1B twin populations suggests that horizontal compressive stresses predicted by Neogene transtensional kinematic models for the rift system have been absent or of insufficient magnitude to cause a widespread noncoaxial strain overprint. Limited numbers of oriented samples yield a possible average ESE extension direction for the rift that is subparallel to other indicators of Neogene extension. The lack of horizontal shortening in the twin data suggests the Neogene Terror Rift system either lacks a strong longitudinal strike-slip component, or that spatial partitioning of strain controls the maximum shortening axes seen in rocks of this age.

  12. How well do we know VPDB? Variability of delta13C and delta18O in CO2 generated from NBS19-calcite. (United States)

    Brand, Willi A; Huang, Lin; Mukai, Hitoshi; Chivulescu, Alina; Richter, Jürgen M; Rothe, Michael


    In order to generate a local daughter scale from the material defining the international delta13C and delta18O stable isotope ratio scales (NBS19-calcite),1,2 the carbon and oxygen must be liberated to the gas phase, usually as CO2, using acid digestion of the calcite with H3PO4. It is during this conversion step that systematic errors can occur, giving rise to commonly observed discrepancies in isotopic measurements between different stable isotope laboratories. Scale consistency is of particular importance for air-CO2 isotope records where very small differences in isotopic composition have to be reliably compared between different laboratories and quantified over long time periods.3 The information is vital for estimating carbon budgets on regional and global scales and for understanding their variability under the conditions of climate change. Starting from this requirement a number of CO2 preparations from NBS19 were made at Environment Canada (EC) and analyzed in our laboratories together with Narcis II, a set of well-characterized CO2 samples in sealed tubes available from the National Institute for Environmental Studies (NIES).4,5 Narcis II is very homogeneous in delta13C and delta18O with the isotopic composition close to NBS19-CO2. Among our laboratories the results for delta13C agreed to within +/-0.004 per thousand. The same level of agreement in delta13C was obtained when CO2 was generated from NBS19-calcite using different experimental procedures and conditions in the other two laboratories. For delta18O, the corresponding data were +/-0.011 per thousand when using NBS19-CO2 produced at EC, but discrepancies were enhanced by almost one order of magnitude when NBS19-CO2 was prepared by the other laboratories using slightly different reaction conditions (range=0.13 per thousand).In a second series of experiments, larger amounts of CO2 prepared from NBS19 at the Max-Planck-Institut für Biogeochemie (MPI-BGC) were analyzed together with Narcis II and

  13. The effect of the Ca2+ to CO32- activity ratio on spiral growth at the calcite {1014} surface

    DEFF Research Database (Denmark)

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


    Variation in the Ca2+ to CO 2¿ activity ratio of natural waters is rarely considered in models intended to describe calcite 3 growth. Atomic force microscopy (AFM) and differential interference contrast (DIC) microscopy were used to examine spiral growth on calcite f10¿14g surfaces from solutions...... steps grow faster 3 than acute steps but this trend reverses at low activity ratios. This is reflected in the morphology of growth pyramids. The reversal in the inequivalent step growth velocity indicates that the hydrated carbonate ion preferentially incorporates at kink sites along the more...... structurally open obtuse step edges, whereas the hydrated calcium ion is more easily accommodated at the more confined acute step kink sites. Furthermore, the experimental data demonstrate that velocity is maximum for obtuse steps when the activities of Ca2+ and CO 2¿ are equal, whereas maximum acute step...

  14. The solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C, and an evaluation of the aqueous model for the system CaCO3-CO2-H2O (United States)

    Plummer, L. Niel; Busenberg, Eurybiades


    Calculations based on approximately 350 new measurements (CaT-PCO2) of the solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants KC, KA, and KV respectively, for the reaction CaCO3(s) = Ca2+ + CO2−3: 

  15. Manganese-calcium intermixing facilitates heteroepitaxial growth at the 101¯4 calcite-water interface

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.; Du, Yingge; Kovarik, Libor; Varga, Tamas; Arey, Bruce W.; Qafoku, Odeta; Kerisit, Sebastien


    In situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10-14) surface of calcite (CaCO3) single crystals following reaction with Mn2+-bearing aqueous solutions with a range of initial concentrations. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces and in situ time-sequenced measurements demonstrated that their growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2+-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO3) and calcite display a 10% lattice mismatch, based on the area of their (10-14) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals with calcite-equilibrated aqueous solutions with concentrations of up to 250 µM MnCl2 and analyzed to determine the composition of the surface precipitates. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO3 solid solution with a spatially complex composition atop the calcite surface, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO3 for the thickest coatings. These findings explain the measured growth rates (the effective lattice mismatch was much smaller than nominal mismatch) and highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.

  16. The Rf/φ and Fry methods applied to synthetic calcite `conglomerates' deformed under grain size-insensitive and grain size-sensitive regimes (United States)

    Edwards, A.; Covey-Crump, S. J.; Rutter, E. H.


    The rocks that make up the lithosphere are mostly polyphase, that is, composed of several constituents each having different mechanical properties. During the deformation of such materials the stresses and strains are commonly partitioned between the phases so that each phase experiences a different stress or strain than the others. Knowledge of the factors that control this partitioning is therefore important if we are to improve our understanding of the mechanical behaviour of the lithosphere. In order to explore this matter quantitatively, we have performed constant strain rate (3 x 10-4 s-1), axial compression experiments on hot-pressed calcite ‘conglomerates’ fabricated from randomly intermixed powders so as to contain 18 vol% polycrystalline clasts of Solnhofen limestone (mean clast size 78 µm, grain size 5.5 µm) in a matrix of pure calcite (grain size 18.5 µm). The experiments were performed at 550°C at which temperature both clast and matrix deformed by grain size-insensitive processes, and at 700°C where both matrix and clast deform in part by grain size-sensitive processes. Experiments were also performed on single phase samples at identical conditions. In each set of experiments the samples were deformed to three different strains in the bulk strain range 0 to 25%. The Rf/φ and Fry finite strain analysis techniques were applied to the deformed microstructures to obtain both the clast and matrix strains at each imposed bulk strain. The application of these techniques was first evaluated by applying them to the single phase samples at 550°C, and in each case the strains obtained using both techniques are in excellent agreement with the experimentally imposed strain. In the ‘conglomerates’ deformed at 550°C the strains obtained from the clasts and matrix are approximately the same as the bulk strain, that is, there is no strain partitioning between clast and matrix despite the large strength contrast between the phases. At 700°C, since a

  17. Microstructural analysis and calcite piezometry on hydrothermal veins: Insights into the deformation history of the Cocos Plate at Site U1414 (IODP Expedition 344). (United States)

    Brandstätter, Jennifer; Kurz, Walter; Rogowitz, Anna


    In this study we present microstructural data from hydrothermal veins in the sedimentary cover and the igneous basement recovered from Hole U1414A, Integrated Ocean Drilling Program (IODP) Expedition 344 (Costa Rica Seismogenesis Project), to constrain deformation mechanism operating in the subducting Cocos Plate. Cathodoluminescence studies, mechanical e-twin piezometry and electron backscatter diffraction (EBSD) analyses of carbonate veins were used to give insights into the deformation conditions and to help to understand the tectonic deformation history of the Cocos Plate offshore Costa Rica. Analyses of microstructures in the sedimentary rocks and in the basalt of the igneous basement reveal brittle deformation, as well as crystal-plastic deformation of the host rock and the vein material. Cathodoluminescence images showed that in the basalt fluid flow and related precipitation occurred over several episodes. The differential stresses, obtained from two different piezometers using the same parameter (twin density), indicate various mean differential stresses of 49 ± 11 and 69 ± 30 MPa and EBSD mapping of calcite veins reveals low-angle subgrain boundaries. Deformation temperatures are restricted to the range from 170°C to 220°C, due to the characteristics of the existing twins and the lack of high-temperature intracrystalline deformation mechanisms (>220°C). The obtained results suggest that deformation occurred over a period associated with changes of ambient temperatures, occurrence of fluids and hydrofracturing, induced differential stresses due to the bending of the plate at the trench, and related seismic activity.

  18. Solubility Measurements and Predictions of Gypsum, Anhydrite, and Calcite Over Wide Ranges of Temperature, Pressure, and Ionic Strength with Mixed Electrolytes (United States)

    Dai, Zhaoyi; Kan, Amy T.; Shi, Wei; Zhang, Nan; Zhang, Fangfu; Yan, Fei; Bhandari, Narayan; Zhang, Zhang; Liu, Ya; Ruan, Gedeng; Tomson, Mason B.


    Today's oil and gas production from deep reservoirs permits exploitation of more oil and gas reserves but increases risks due to conditions of high temperature and high pressure. Predicting mineral solubility under such extreme conditions is critical for mitigating scaling risks, a common and costly problem. Solubility predictions use solubility products and activity coefficients, commonly from Pitzer theory virial coefficients. However, inaccurate activity coefficients and solubility data have limited accurate mineral solubility predictions and applications of the Pitzer theory. This study measured gypsum solubility under its stable phase conditions up to 1400 bar; it also confirmed the anhydrite solubility reported in the literature. Using a novel method, the virial coefficients for Ca2+ and {{SO}}4^{2 - } (i.e., β_{{{{CaSO}}4 }}^{(0)} ,β_{{{{CaSO}}4 }}^{(2)} ,C_{{{{CaSO}}4 }}^{φ }) were calculated over wide ranges of temperature and pressure (0-250 °C and 1-1400 bar). The determination of this set of virial coefficients widely extends the applicable temperature and pressure ranges of the Pitzer theory in Ca2+ and SO 4 2- systems. These coefficients can be applied to improve the prediction of calcite solubility in the presence of high concentrations of Ca2+ and SO 4 2- ions. These new virial coefficients can also be used to predict the solubilities of gypsum and anhydrite accurately. Moreover, based on the derived β_{{{{CaSO}}4 }}^{(2)} values in this study, the association constants of {{CaSO}}4^{( 0 )} at 1 bar and 25 °C can be estimated by K_{{assoc}} = - 2β_{{{{CaSO}}4 }}^{(2)}. These values match very well with those reported in the literature based on other methods.

  19. Testing the Specificity of Primers to Environmental Ammonia Monooxygenase (amoA) Genes in Groundwater Treated with Urea to Promote Calcite Precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Freeman, S.; Reed, D.W.; Fujita, Y.


    Bacterial ammonia monooxygenase (amoA) genes in DNA isolated from microorganisms in groundwater were characterized by amplification of amoA DNA using polymerase chain reaction (PCR), Restriction Fragment Length Polymorphism (RFLP) analysis, and sequencing. The amoA gene is characteristic of ammonia oxidizing bacteria (AOB). The DNA extracts were acquired from an experiment where dilute molasses and urea were sequentially introduced into a well in the Eastern Snake River Plain Aquifer (ESRPA) in Idaho to examine whether such amendments could stimulate enhanced ureolytic activity. The hydrolysis of urea into ammonium and carbonate serves as the basis for a potential remediation technique for trace metals and radionuclide contaminants that can co-precipitate in calcite. The ammonium ion resulting from ureolysis can promote the growth of AOB. The goal of this work was to investigate the effectiveness of primers designed for quantitative PCR of environmental amoA genes and to evaluate the effect of the molasses and urea amendments upon the population diversity of groundwater AOB. PCR primers designed to target a portion of the amoA gene were used to amplify amoA gene sequences in the groundwater DNA extracts. Following PCR, amplified gene products were cloned and the clones were characterized by RFLP, a DNA restriction technique that can distinguish different DNA sequences, to gauge the initial diversity. Clones exhibiting unique RFLP patterns were subjected to DNA sequencing. Initial sequencing results suggest that the primers were successful at specific detection of amoA sequences and the RFLP analyses indicated that the diversity of detected amoA sequences in the ESRPA decreased with the additions of molasses and urea.

  20. Final report for DOE Grant No. DE-FG02-07ER64404 - Field Investigations of Microbially Facilitated Calcite Precipitation for Immobilization of Strontium-90 and Other Trace Metals in the Subsurface

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Robert W; Fujita, Yoshiko; Ginn, Timothy R; Hubbard, Susan S


    Subsurface radionuclide and 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 ions, such as the short-lived radionuclide 90Sr, is co-precipitation in calcite. We have previously found that that nutrient addition can stimulate microbial ureolytic activity that this activity accelerates calcite precipitation and co-precipitation of Sr, and that higher calcite precipitation rates can result in increased Sr partitioning. We have conducted integrated field, laboratory, and computational research to evaluate the relationships between ureolysis and calcite precipitation rates and trace metal partitioning under environmentally relevant conditions, and investigated the coupling between flow/flux manipulations and precipitate distribution. A field experimental campaign conducted at the Integrated Field Research Challenge (IFRC) site located at Rifle, CO was based on a continuous recirculation design; water extracted from a down-gradient well was amended with urea and molasses (a carbon and electron donor) and re-injected into an up-gradient well. The goal of the recirculation design and simultaneous injection of urea and molasses was to uniformly accelerate the hydrolysis of urea and calcite precipitation over the entire inter-wellbore zone. The urea-molasses recirculation phase lasted, with brief interruptions for geophysical surveys, for 12 days followed by long-term monitoring which continued for 13 months. Following the recirculation phase we found persistent increases in urease activity (as determined from 14C labeled laboratory urea hydrolysis rates) in the upper portion of the inter-wellbore zone. We also observed an initial increase (approximately 2 weeks) in urea concentration associated with injection activities followed by decreasing urea concentration and associated increases in ammonium and dissolved inorganic carbon

  1. Quartz: structural and thermodynamic analyses across the α ↔ β transition with origin of negative thermal expansion (NTE) in β quartz and calcite

    Energy Technology Data Exchange (ETDEWEB)

    Antao, Sytle M.


    The temperature variation,T, of the crystal structure of quartz, SiO2, from 298 to 1235 K was obtained with synchrotron powder X-ray diffraction data and Rietveld structure refinements. The polymorphic transformation fromP3221 (low-T, α quartz) toP6222 (high-T, β quartz) occurs at a transition temperature,Ttr= 847 K. TheTvariations of spontaneous strains and several structural parameters are fitted to an order parameter,Q, using Landau theory. The change in Si atom coordinate, Six, givesTtr-Tc= 0.49 K, which indicates an α ↔ β transition that is weakly first order and nearly tricritical in character (Q4T). Strains give higherTtr-Tcvalues (≃ 7 K). Other fitted parameters are the oxygen Ozcoordinate, Si—Si distance, Si—O—Si and φ angles, and intensity of the (111) reflection,I111. In α quartz, the Si—Si distance increases withTbecause of cation repulsion, so the Si—O—Si angle increases (and φ decreases) and causes the thermal expansion of the framework structure that consists of corner-sharing distorted rigid SiO4tetrahedra. The Si—Si distances contract withTand cause negative thermal expansion (NTE) in β quartz because of increasing thermal librations of the O atom in the Si—O—Si linkage that occur nearly perpendicular to the Si—Si contraction. In calcite, CaCO3, the short Ca—Ca distance expands withT, but the next-nearest Ca—Ca distance, which is of equal length to theaaxis, contracts withTand causes NTE along

  2. Sifat fisik hidroksiapatit sintesis kalsit sebagai bahan pengisi pada sealer saluran akar resin epoxy (Physical properties of calcite synthesized hydroxyapatite as the filler of epoxy-resin-based root canal sealer

    Directory of Open Access Journals (Sweden)

    Ema Mulyawati


    Full Text Available Background: The filler addition to resin based sealers will enhance the physical properties of the polymer. Because of its biological properties, the synthetic hydroxyapatite (HA has been proposed as filler for dental material such as composite resin. The calcite synthesized HA is the HA produced of calcite minerals that came from many Indonesian mining. Purpose: The aim of study was to determine the effect of different concentration of calcite synthesized HA as the filler of the epoxy-resin-based root canal sealer on the physical properties such as its contact angle, the film thickness and the microhardness. Methods: The crystal of the calcite synthesized hydroxyapatite with the size between 77.721-88.710 nm and the ratio of Ca/P 1.6886 were synthesized at Ceramic Laboratory, Mechanical Engineering, using wet method of hydrothermal microwave. The powders of the epoxy- resin were prepared by added the synthesized hydroxyapatite crystal in 5 different weight ratios (e.g.: HA-10%, HA-20%, HA-30%, HA-40% and HA-50%. Each of these was mixed with the paste of 3:1 ratio using spatula on a glass plate until homogen and then measuring the contact angle and the film thickness. Microhardness test was conducted after the mixture of experimental sealer was stored for 24 hrs at 37 oC to reach perfect polymerization. Results: All of contact angles were <90o and were not significantly different to each other (p= 0.510. All groups had a film thickness in accordance with ISO 6876 (<50 um and with no statistical difference (p= 0.858. In the HA of 10%, 20%, 30% seen that the microhardness were increased, while in the HA-50% was decreased and in the HA-40% has the same microhardness to the control groups (HA-0%. Conclusion: Calcite synthesized HA as the filler did not affect contact angle and film thickness of the sealer. Microhardness of the epoxy-resin based sealer could be increased using maximum 30% of the calcite synthesized HA as the filler.Latar belakang

  3. Final Technical Report for DOE Award DE-FG02-07ER64403 [Modeling of Microbially Induced Calcite Precipitation for the Immobilization of Strontium-90 Using a Variable Velocity Streamtube Ensemble

    Energy Technology Data Exchange (ETDEWEB)

    Ginn, Timothy R. [University of California, Davis; Weathers, Tess [University of California, Davis


    Biogeochemical modeling using PHREEQC2 and a streamtube ensemble approach is utilized to understand a well-to-well subsurface treatment system at the Vadose Zone Research Park (VZRP) near Idaho Falls, Idaho. Treatment involves in situ microbially-mediated ureolysis to induce calcite precipitation for the immobilization of strontium-90. PHREEQC2 is utilized to model the kinetically-controlled ureolysis and consequent calcite precipitation. Reaction kinetics, equilibrium phases, and cation exchange are used within PHREEQC2 to track pH and levels of calcium, ammonium, urea, and calcite precipitation over time, within a series of one-dimensional advective-dispersive transport paths creating a streamtube ensemble representation of the well-to-well transport. An understanding of the impact of physical heterogeneities within this radial flowfield is critical for remediation design; we address this via the streamtube approach: instead of depicting spatial extents of solutes in the subsurface we focus on their arrival distribution at the control well(s). Traditionally, each streamtube maintains uniform velocity; however in radial flow in homogeneous media, the velocity within any given streamtube is spatially-variable in a common way, being highest at the input and output wells and approaching a minimum at the midpoint between the wells. This idealized velocity variability is of significance in the case of ureolytically driven calcite precipitation. Streamtube velocity patterns for any particular configuration of injection and withdrawal wells are available as explicit calculations from potential theory, and also from particle tracking programs. To approximate the actual spatial distribution of velocity along streamtubes, we assume idealized radial non-uniform velocity associated with homogeneous media. This is implemented in PHREEQC2 via a non-uniform spatial discretization within each streamtube that honors both the streamtube’s travel time and the idealized

  4. Heterogeneous uptake of gaseous nitric acid on dolomite (CaMg(CO3)2) and calcite (CaCO3) particles: a Knudsen cell study using multiple, single, and fractional particle layers. (United States)

    Johnson, Elizabeth R; Sciegienka, Joanna; Carlos-Cuellar, Sofia; Grassian, Vicki H


    In this study, the heterogeneous uptake of gaseous nitric acid on dolomite, CaMg(CO3)2, and calcite, CaCO3, particles under dry conditions at 296 K was investigated. A Knudsen cell reactor was used to measure heterogeneous uptake coefficients for these reactions. Several different experiments were performed including those on many, single, and fractional layers of particles. For experiments using multiple particle layers, the Knudsen cell data were modeled to take into account gas diffusion into the underlying layers of the sample. From this analysis, initial heterogeneous uptake coefficients, gamma(o,t), were determined to be (5 +/- 2) x 10(-4) and (2 +/- 1) x 10(-3), for dolomite and calcite, respectively, at a nitric acid concentration of 6.5 x 10(10) molecules cm(-3). For experiments that employed single or fractional particle layers, the initial heterogeneous uptake coefficient was analyzed using a recent method described in the literature. Values of the initial heterogeneous uptake coefficient using this analysis were in agreement with the above analysis and determined to be (7 +/- 4) x 10(-4) and (2 +/- 0.4) x 10(-3) for CaMg(CO3)2 and CaCO3, respectively. In addition, these results are compared to previous literature values.

  5. First-principles calculations of typical anisotropic cubic and hexagonal structures and homogenized moduli estimation based on the Y-parameter: Application to CaO, MgO, CH and Calcite CaCO3 (United States)

    Fu, Jia; Bernard, Fabrice; Kamali-Bernard, Siham


    X-ray method to test the material properties and to obtain elastic constants is commonly based on the Reuss model and Kroner model. Y parameter has been turned out to be an effective method to estimate elastic properties of polycrystalline material. Since Y-parameters of cubic polycrystalline material based on the certain uniform stress (Reuss model) has not been given, our work aims to complete this part of the theoretical analysis, which can effectively compare elastic constants measured by the X-ray diffraction method. The structural and the elastic properties of cubic structures (CaO and MgO) and hexagonal structures (CH and Calcite CaCO3) are investigated by the density functional theory method. And then the credibility of Y parameters for determing elastic moduli of cubic structures is proved and elastic properties in typical crystallographic planes of [100], [110] and [111] are also calculated. Meanwhile, Young's moduli of CH and Calcite structure are 58.08 GPa and 84.549 GPa, which are all close to references. Elastic properties of cubic and hexagonal structures under various pressures are calculated and the surface constructions of elastic moduli are drawn, showing the anisotropy at various directions. The crystal structure investigated in this work are typical of some primary or secondary components of Hardened Cements Pastes and their homogenized elastic properties are needed in a hierarchical multi-scale modeling, such as the one developed by some of the authors of this paper.

  6. Evaluation of Surface and Transport Limitations to the Rate of Calcite Dissolution Using Pore Scale Modeling of a Capillary Tube Experiment at pCO2 4 bar (United States)

    Molins, S.; Trebotich, D.; Yang, L.; Ajo Franklin, J. B.; Ligocki, T.; Shen, C.; Steefel, C. I.


    Mineral trapping is generally considered to account for most of the long-term trapping of CO2 in the subsurface. Prediction of mineral trapping at the reservoir scale requires knowledge of continuum-scale mineral dissolution and precipitation rates. However, processes that take place at the pore scale (e.g., transport limitation to reactive surfaces) affect rates applicable at the continuum scale. To explore the pore scale processes that result in the discrepancy between rates measured in laboratory experiments and those calibrated from continuum-scale models, we have developed a high-resolution pore scale model of a capillary tube experiment. The capillary tube (L=0.7-cm, D=500-μm) is packed with crushed calcite (Iceland spar) and the resulting 3D pore structure is imaged by X-ray computed microtomography (XCMT) at Berkeley Lab's Advanced Light Source at a 0.899-μm resolution. A solution in equilibrium with a partial pressure of CO2 of 4 bars is injected at a rate of 5 microliter/min and the effluent concentrations of calcium are measured to ensure steady state conditions are achieved. A simulation domain is constructed from the XCMT image using implicit functions to represent the mineral surface locally on a grid. The pore-scale reactive transport model is comprised of high performance simulation tools and algorithms for incompressible Navier-Stokes flow, advective-diffusive transport and multicomponent geochemical reactions. Simulations are performed using 6,144 processors on NERSC's Cray XE6 Hopper to achieve a grid resolution of 2.32 μm. Equivalent continuum scale simulations are also performed to evaluate the effect of pore scale processes. Comparison of results is performed based on flux-averaged effluent calcium concentrations, which are used as indicator of effective rates in the capillary tube. Results from both pore- and continuum-scale simulations overestimate the calcium effluent concentrations, suggesting that the TST rate expression parameters

  7. Oxygen isotope analysis of carbonates in the calcite-dolomite-magnesite solid-solution by high-temperature pyrolysis: initial results. (United States)

    Crowley, Stephen F; Spero, Howard J; Winter, David A; Sloane, Hilary J; Croudace, Ian W


    Accurate and efficient measurement of the oxygen isotope composition of carbonates (delta(C) (18)O) based on the mass spectrometric analysis of CO(2) produced by reacting carbonate samples with H(3)PO(4) is compromised by: (1) uncertainties associated with fractionation factors (alpha(CO)(2)C) used to correct measured oxygen isotope values of CO(2)(delta(CO(2)(18)O) to delta(C) (18)O; and (2) the slow reaction rates of many carbonates of geological and environmental interest with H(3)PO(4). In contrast, determination of delta(C) (18)O from analysis of CO produced by high-temperature (>1400 degrees C) pyrolytic reduction, using an elemental analyser coupled to continuous-flow isotope-ratio mass spectrometry (TC/EA CF-IRMS), offers a potentially efficient alternative that measures the isotopic composition of total carbonate oxygen and should, therefore, theoretically be free of fractionation effects. The utility of the TC/EA CF-IRMS technique was tested by analysis of carbonates in the calcite-dolomite-magnesite solid-solution and comparing the results with delta(C) (18)O measured by conventional thermal decomposition/fluorination (TDF) on the same materials. Initial results show that CO yields are dependent on both the chemical composition of the carbonate and the specific pyrolysis conditions. Low gas yields (+0.2 per thousand) deviations in delta(C(TC/EA) (18)O compared with delta(C(TDF) (18)O. At a pyrolysis temperature of 1420 degrees C the difference between delta(C) (18)O measured by TC/EA CF-IRMS and TDF (Delta(C(TC/EA,TDF) (18)O) was found to be negatively correlated with gas yield (r = -0.785) and this suggests that delta(C) (18)O values (with an estimated combined standard uncertainty of +/-0.38 per thousand) could be derived by applying a yield-dependent correction. Increasing the pyrolysis temperature to 1500 degrees C also resulted in a statistically significant correlation with gas yield (r = -0.601), indicating that delta(C) (18)O values (with an


    Directory of Open Access Journals (Sweden)

    Denise Regina Macário


    >, respectively. Blood glucose averaged 86.20, 71.4, 58.87 and 77.22 mg/l after 1 hour and 75.4, 58.87 and 77.22 mg/ml after 8 hours, differing significantly at P=0.05. Blood urea values showed no significant difference between one and eight hour periods after intake. Values were 34.25, 37.77 and 31.55 mg/ml after one hour and 29.52, 34.42 and 27.85 mg/ml after eight hours. Results showed that CaCO3 changes ruminal pH and products of fermentation and blood metabolites.

    KEY-WORDS: Calcitic calcarium; ruminal pH.

  9. Calcite Dissolution Kinetics and Solubility in NaCl-CaCl2-MgCl2 Brines up to 1 bar pCO2 and 80\\deg C (United States)

    Gledhill, D. K.; Morse, J. W.


    Sedimentary basins can contain close to 20% by volume pore fluids that are commonly classified as brines. These fluids can become undersaturated with respect to calcite as a result of migration, dispersive mixing or by anthropogenic injection of CO2. Both the solubility of calcite and its dissolution kinetics are currently poorly constrained in these concentrated solutions. This study measured calcite solubility and dissolution rates in geologically relevant NaCl-CaCl2-MgCl2 synthetic brines (50,000 to 200,000 mg L-1 TDS). The EQPITZER calculated calcium carbonate ion activity product at steady-state was in reasonable agreement (\\pm10%) with Kcal in low concentration brines but systematically exceeded Kcal with increasing brine concentration. The deviation was most strongly correlated with calcium activity and was independent of magnesium concentration. This has been interpreted as an uncertainty in the carbonate ion activity coefficient perhaps related to errors in the calcium interaction parameters with the carbonic acid system under these conditions. The dissolution rate dependency on brine concentration, pCO2 (0.1 to 1 bar) and temperature (25\\deg C to 80\\deg C) was modeled using the empirical rate equation R=k(1-\\Omega) n. Relative to an apparent kinetic solubility it was found that n could be assumed to be first order over the range of degree of disequilibrium investigated (\\Omega = 0.2 to 1.0). Rates increased with increasing pCO2 as did the sensitivity to brine concentration. At 0.1 bar rates were independent of concentration (k = 9.0\\pm1.0\\times10-3 moles m-2 hr-1). However, at higher partial pressures rates were linearly correlated to TDS. At 1 bar pCO2 and 25\\deg C the rate constant can be described by the linear regression k(moles m-2 hr-1) = 0.053 - 1.7\\times10-7(TDS), R2 = 0.996. The specific effects of Ca2+, Mg2+ and ionic strength were tested in addition to the inhibitory effect of the presence of 1000 mg L-1 SO42-. A roughly three fold

  10. A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry. (United States)

    Goverapet Srinivasan, Sriram; Shivaramaiah, Radha; Kent, Paul R C; Stack, Andrew G; Riman, Richard; Anderko, Andre; Navrotsky, Alexandra; Bryantsev, Vyacheslav S


    Bastnäsite, a fluoro-carbonate mineral, is the single largest mineral source of light rare earth elements (REE), La, Ce and Nd. Enhancing the efficiency of separation of the mineral from gangue through froth flotation is the first step towards meeting an ever increasing demand for REE. To design and evaluate collector molecules that selectively bind to bastnäsite, a fundamental understanding of the structure and surface properties of bastnäsite is essential. In our earlier work (J. Phys. Chem. C, 2016, 120, 16767), we carried out an extensive study of the structure, surface stability and water adsorption energies of La-bastnäsite. In this work, we make a comparative study of the surface properties of Ce-bastnäsite, La-bastnäsite, and calcite using a combination of density functional theory (DFT) and water adsorption calorimetry. Spin polarized DFT+U calculations show that the exchange interaction between the electrons in Ce 4f orbitals is negligible and that these orbitals do not participate in bonding with the oxygen atom of the adsorbed water molecule. In agreement with calorimetry, DFT calculations predict larger surface energies and stronger water adsorption energies on Ce-bastnäsite than on La-bastnäsite. The order of stabilities for stoichiometric surfaces is as follows: [101[combining macron]0] > [101[combining macron]1] > [101[combining macron]2] > [0001] > [112[combining macron]2] > [101[combining macron]4] and the most favorable adsorption sites for water molecules are the same as for La-bastnäsite. In agreement with water adsorption calorimetry, at low coverage water molecules are strongly stabilized via coordination to the surface Ce3+ ions, whereas at higher coverage they are adsorbed less strongly via hydrogen bonding interaction with the surface anions. Due to similar water adsorption energies on bastnäsite [101[combining macron]1] and calcite [101[combining macron]4] surfaces, the design of collector molecules that selectively bind to

  11. Scientific results from the deepened Lopra-1 borehole, Faroe Islands: A reconnaissance study of fluid inclusions in fracture-filling quartz and calcite from the Lopra-1/1A well, Faroe Islands

    Directory of Open Access Journals (Sweden)

    Konnerup-Madsen, Jens


    Full Text Available Fracture-filling calcite and quartz from the Lopra-1/1A well (at 2380 m and 3543 m depth contains both aqueous low-salinity fluid inclusions and hydrocarbon-dominated fluid inclusions. Microthermometry indicates that the aqueous fluids contain 0.2 to 1.4 equivalent weight% NaCl and occasionally contain traces of hydrocarbons. Homogenisation to liquid occurred between 90°C and 150°C. Modelling based on these fluid inclusion observations indicates that during burial the basaltic section was subjected to temperatures of 160°C and 170°C, occasional pressures of 600–700 bars and the simultaneous percolation of aqueous and hydrocarbon fluids. These fluid conditions may also be relevant to the formation of zeolite observed in the Lopra-1/1A well.

  12. Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Stronthium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Robert W.; Fujita, Yoshiko


    Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) energy research and weapons complex. In situ containment and stabilization of these contaminants represents a cost-effective treatment strategy that minimizes workers’ exposure to hazardous substances, does not require removal or transport of contaminants, and generally does not generate a secondary waste stream. We have investigated an in situ bioremediation approach that immobilizes radionuclides or contaminant metals (e.g., strontium-90) by their microbially facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Calcite, a common mineral in many aquifers and vadose zones in the arid west, can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of a solid solution. Collaborative research undertaken by the Idaho National Laboratory (INL), University of Idaho, and University of Toronto as part of this Environmental Management Science Program project has focused on in situ microbially-catalyzed urea hydrolysis, which results in an increase in pH, carbonate alkalinity, ammonium, calcite precipitation, and co-precipitation of divalent cations. In calcite-saturated aquifers, microbially facilitated co-precipitation with calcium carbonate represents a potential long-term contaminant sequestration mechanism. Key results of the project include: **Demonstrating the linkage between urea hydrolysis and calcite precipitation in field and laboratory experiments **Observing strontium incorporation into calcite precipitate by urea hydrolyzers with higher distribution coefficient than in abiotic **Developing and applying molecular methods for characterizing microbial urease activity in groundwater including a quantitative PCR method for enumerating ureolytic bacteria **Applying the suite of developed molecular methods to assess the feasibility of the

  13. Ion microprobe assessment of the heterogeneity of Mg/Ca, Sr/Ca and Mn/Ca ratios in Pecten maximus and Mytilus edulis (bivalvia shell calcite precipitated at constant temperature

    Directory of Open Access Journals (Sweden)

    P. S. Freitas


    Full Text Available Small-scale heterogeneity of biogenic carbonate elemental composition can be a significant source of error in the accurate use of element/Ca ratios as geochemical proxies. In this study ion microprobe (SIMS profiles showed significant small-scale variability of Mg/Ca, Sr/Ca and Mn/Ca ratios in new shell calcite of the marine bivalves Pecten maximus and Mytilus edulis that was precipitated during a constant-temperature culturing experiment. Elevated Mg/Ca, Sr/Ca and Mn/Ca ratios were found to be associated with the deposition of elaborate shell features, i.e. a shell surface stria in P. maximus and surface shell disturbance marks in both species, the latter a common occurrence in bivalve shells. In both species the observed small-scale elemental heterogeneity most likely was not controlled by variable transport of ions to the extra-pallial fluid, but by factors such as the influence of shell organic content and/or crystal size and orientation, the latter reflecting conditions at the shell crystal-solution interface. In the mid and innermost regions of the P. maximus shell the lack of significant small-scale variation of Mg/Ca ratios, which is consistent with growth at constant temperature, suggest a potential application as a palaeotemperature proxy. Cross-growth band element/Ca ratio profiles in the interior of bivalve shells may provide more promising palaeo-environmental tools than sampling from the outer region of bivalve shells.

  14. Characterization of three antifungal calcite-forming bacteria, Arthrobacter nicotianae KNUC2100, Bacillus thuringiensis KNUC2103, and Stenotrophomonas maltophilia KNUC2106, derived from the Korean islands, Dokdo and their application on mortar. (United States)

    Park, Jong-Myong; Park, Sung-Jin; Ghim, Sa-Youl


    Crack remediation on the surface of cement mortar using microbiological calcium carbonate (CaCO3) precipitation (MICP) has been investigated as a microbial sealing agent on construction materials. However, MICP research has never acknowledged the antifungal properties of calcite-forming bacteria (CFB). Since fungal colonization on concrete surfaces can trigger biodeterioration processes, fungi on concrete buildings have to be prevented. Therefore, to develop a microbial sealing agent that has antifungal properties to remediate cement cracks without deteriorative fungal colonization, we introduced an antifungal CFB isolated from oceanic islands (Dokdo islands, territory of South Korea, located at the edge of the East Sea in Korea.). The isolation of CFB was done using B4 or urea-CaCl2 media. Furthermore, antifungal assays were done using the pairing culture and disk diffusion methods. Five isolated CFB showed CaCO3 precipitation and antifungal activities against deteriorative fungal strains. Subsequently, five candidate bacteria were identified using 16S rDNA sequence analysis. Crack remediation, fungi growth inhibition, and water permeability reduction of antifungal CFB-treated cement surfaces were tested. All antifungal CFB showed crack remediation abilities, but only three strains (KNUC2100, 2103, and 2106) reduced the water permeability. Furthermore, these three strains showed fungi growth inhibition. This paper is the first application research of CFB that have antifungal activity, for an eco-friendly improvement of construction materials.

  15. Using presence of calcite cap rock in shales to predict occurrence of reservoirs composed of leached secondary porosity in the geopressured zone. Annual report, June 1, 1980-October 31, 1980

    Energy Technology Data Exchange (ETDEWEB)

    Kaiser, W.R.; Magara, K.; Milliken, K.L.; Richmann, D.L.


    The distribution of high-resistivity shale in the Frio Formation between hydropressured and geopressured strata has been mapped along the Texas Gulf Coast. Two high-resistivity intervals more than 1000 ft thick have been mapped, one in Brazoria and Galveston Counties and the other in Kenedy County. They coincide with Frio delta systems and may be related to extraordinary quantities of CO/sub 2/ produced by deltaic sediments rich in woody and herbaceous matter. Beyond being calcareous, the nature of the high-resistivity interval is enigmatic and its relationship to deep secondary porosity problematic. Most of the contained carbonate is microscopically and isotopically skeletal in origin, revealing no evidence of diagenetic modification. Minor rhombs of iron-bearing carbonate tens of microns in size were identified. Detrital feldspar compositions are being established to test subsequent changes in feldspar composition resulting from progressive burial and albitization. Hydrolysis reactions for authigenic minerals and reactions between key pairs of minerals have been written. Thermodynamic functions for complex phyllosilicates at temperatures up to 200/sup 0/C have been calculated. From thermodynamic calculations it was predicted that ferroan calcite would be the favored authigenic carbonate in shales.

  16. Combined δ11B, δ13C, and δ18O analyses of coccolithophore calcite constrains the response of coccolith vesicle carbonate chemistry to CO2-induced ocean acidification (United States)

    Liu, Yi-Wei; Tripati, Robert; Aciego, Sarah; Gilmore, Rosaleen; Ries, Justin


    Coccolithophorid algae play a central role in the biological carbon pump, oceanic carbon sequestration, and in marine food webs. It is therefore important to understand the potential impacts of CO2-induced ocean acidification on these organisms. Differences in the regulation of carbonate chemistry, pH, and carbon sources of the intracellular compartments where coccolith formation occurs may underlie the diverse calcification and growth responses to acidified seawater observed in prior experiments. Here we measured stable isotopes of boron (δ11B), carbon (δ13C) and oxygen (δ18O) within coccolith calcite, and δ13C of algal tissue to constrain carbonate system parameters in two strains of Pleurochrysis carterae (P. carterae). The two strains were cultured under variable pCO2, with water temperature, salinity, dissolved inorganic carbon (DIC), and alkalinity monitored. Notably, PIC, POC, and PIC/POC ratio did not vary across treatments, indicating that P. carterae is able to calcify and photosynthesize at relatively constant rates irrespective of pCO2 treatment. The δ11B data indicate that mean pH at the site of coccolith formation did not vary significantly in response to elevated CO2. These results suggest that P. carterae regulates calcifying vesicle pH, even amidst changes in external seawater pH. Furthermore, δ13C and δ18O data suggest that P. carterae may utilize carbon from a single internal DIC pool for both calcification and photosynthesis, and that a greater proportion of dissolved CO2 relative to HCO3- enters the internal DIC pool under acidified conditions. These results suggest that P. carterae is able to calcifyand photosynthesize at relatively constant rates across pCO2 treatments by maintaining pH homeostasis at their site of calcification and utilizing a greater proportion of aqueous CO2.

  17. Nickel adsorption on chalk and calcite

    DEFF Research Database (Denmark)

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


    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...

  18. δ13C and δ18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite (United States)

    Revesz, Kinga M.; Landwehr, Jurate M.


    A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 ± 20 µg) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H3PO4/CaCO3) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H3PO4/CaCO3 reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 °C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was ≤0.1 and ≤0.2 per mill or ‰, respectively, although later analysis showed that materials from one specific standard required reaction time between 34 and 54 h for δ18O to achieve this level of precision. Aliquot screening methods were shown to further minimize the total error. The accuracy and precision of the new method were analyzed and confirmed by statistical analysis. The utility of the method was verified by analyzing calcite from Devils Hole, Nevada, for which isotope-ratio values had previously been obtained by the classical method. Devils Hole core DH-11 recently had been re-cut and re-sampled, and isotope-ratio values were obtained using the new method. The results were comparable with those obtained by the classical method with correlation = +0.96 for both isotope ratios. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, and two cutting errors that occurred during re-sampling then were confirmed independently. This result indicates that the new method is a viable alternative to the classical reaction method. In particular, the new method requires less sample material permitting finer resolution and allows

  19. Evolution of the isotope composition of C and O in the DIC in a water film during precipitation of calcite to the surface of a stalagmite in the presence of isotope exchange with the CO2 of the cave atmosphere and evaporation of the water (United States)

    Dreybrodt, Wolfgang; Romanov, Douchko


    In a thin water layer, super saturated with respect to calcite with pH of about 8, where the aqueous CO2 is in equilibrium with the pCO2 of the cave atmosphere, the following processes determine the temporal evolution of the isotope composition of carbon and oxygen in the dissolved inorganic carbon ( DIC). a) Precipitation of calcite driven by super saturation, whereby deposition rates Between the heavy and light isotopes are slightly different. b) Evaporation of water reducing the depth of the water layer and changing the isotope composition of oxygen in the water by Rayleigh-distillation. c) Isotope exchange between the CO2 in the cave atmosphere and the DIC for both carbon and oxygen. d) Isotope exchange between the oxygen in the water molecules and that in the DIC. All these processes can be described by a differential equation, which can be solved numerically. For small times a simple solution can be given. Δ_DIC(T_drip) = [ ( (⪉mbda + ɛ) C_eq/C0 - ɛ ) T_drip/τ + (δ^atm_eq - δ0 ) T_drip/τ^atm + (δ^water_eq-δ_0-ɛ_wT_drip/T_ev) T_drip/τ^water] Δ_DIC(T_drip) is the change of the δ13C and δ18O (given here as small numbers and not in the ‰ notation) after the drip time T_drip. ⪉mbda, ɛ are kinetic parameters of precipitation on the order of 10-2 and τ is the time scale of precipitation, typically about 1000 s. (δ^atm_eq - δ_0) and (δ^water_eq - δ_0) are the differences between the corresponding initial δ-value and that when DIC is in isotope equilibrium with the atmosphere or in the case of oxygen with the water. τ^atm and τ^water, both on the order of 10,000 s, are the time scales of the exchange reactions to approach isotope equilibrium. For carbon the last term (exchange with water) must be deleted. C_eq is the concentration of DIC in chemical equilibrium with the CO2 in the cave atmosphere and C0 is the initial concentration, when the water drips to the stalagmite. T_ev is the time needed to fully evaporate the water layer and

  20. Scale and corrosion control with combined dolomite/calcite filter. (United States)

    Log, T; Simpson, G; Hanssen, H K; Robinson, M; Hubble, J; Parsons, S A


    Water quality is a major operational issue for boiler operation and control. If the water is hard scale control is required and if it is soft then corrosion control is an issue. Here a two stream boiler test rig has been used to test the effect a fixed bed filter has on the scaling and corrosion properties of both hard and soft waters. The filter effectively controlled the pH, hardness and alkalinity of both waters leading to significant decreases in scale formation and effective control of corrosion.

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

    DEFF Research Database (Denmark)

    Schultz, Logan Nicholas

    coarsening – small grains coarsen by aggregation at high temperatures, followed by Ostwald ripening. Alginate, a model for the acidic polysaccharides produced by coccolithiphores, inhibited coarsening at a steady rate. A Pseudomonas aeruginosa biofilm preserved particles for at least 60 days before...

  2. Formation of Calcite Biocrystals; Structure and Formation of Matrix Glycoproteins

    National Research Council Canada - National Science Library

    Lennarz, William


    .... In these organisms, including the primitive skeleton (spicule) of the sea urchin embryo, the structural and functional role of these proteins either in the biomineralization process or in control of the structural features of the biocrystals is unclear...

  3. Isotopic and elemental proxies in mollusc and brachiopod calcite

    DEFF Research Database (Denmark)

    Ullmann, Clemens Vinzenz

    . Additional to environmental parameters, the composition of the shell is controlled by biological processes (i.e. vital effects), and post-depositional alteration. The chemical fingerprints of all the parameters influencing the shell composition need to be understood and ideally quantified in order to allow...

  4. Production Engineering for Growth of Synthetic Calcite Polarizer Material (United States)


    other optical devices. NOTICES Approved for public release, distribution not limited; mm This project has been accomplished as part of the...take place throughout the nutrient zone. It is not possible to obtain sintered CaC03 under atomos - Table I Main Impurities in Optical Grade...efforts were continued in this direction. It was felt that the temperature for sintering 100% CaOOj had for the most part been isolated

  5. Environmental controls on the Emiliania huxleyi calcite mass

    NARCIS (Netherlands)

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


    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

  6. U-Pb Dating of Calcite by LA-ICPMS (United States)

    Hacker, B. R.; Kylander-Clark, A. R.; Holder, R. M.; Nuriel, P.


    An emerging frontier area in geochronology is U-Pb dating of carbonate minerals by laser-ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The spate of papers over the last few years applying LA-ICPMS to carbonate dating stems from the capability of LA-ICPMS to deal with the variable, and often low, U/Pb ratios of carbonate. LA-ICPMS is an excellent tool for efficiently screening out samples with low U/Pb ratios and provides the ability to measure many spots with different U/Pb ratios and obtain dates free of assumptions about the composition of common Pb. Because this technique is in its infancy, important questions remain. What percentage of carbonate samples have high enough U/Pbc ratios that they can be dated? What percentage of samples yield isochronous datasets? What are the limits on precision and accuracy of carbonate U/Pb dates? What is the best analytical method in the absence of isotopically homogeneous reference materials? Through the generosity of our colleagues we have acquired 8 reference materials ranging in age from 3 to 250 Ma. We have analyzed 125 unknowns from a variety of locations using a 193 nm ns laser with an 80-100 μm spot and a Nu Plasma HR-ES. We measure 207Pb/206Pb using NIST 614 glass and then calculate a 206Pb/238U correction factor based on the measured vs. known ages of the reference materials. Sixty of these samples ( 50%) have high enough U/Pb ratios that they can be dated. There is great heterogeneity among the sample suites: some have no datable samples, whereas one suite of 68 samples yielded 53 datable rocks. Of the samples with high U/Pbc ratios, a majority yielded isochronous U-Pb data, indicating that the U-Pb system closed at a given time and was not subsequently disturbed.

  7. Ocean acidification: Towards a better understanding of calcite dissolution (United States)

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


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

  8. Measurement of delta13C and delta18O Isotopic Ratios of CaCO3 by a Thermoquest Finnigan GasBench II Delta Plus XL Continous Flow Isotope Ratio Mass Spectrometer with Application to Devils Hole Core DH-11 Calcite (United States)

    Revesz, Kinga M.; Landwehr, Jurate Maciunas; Keybl, Jaroslav Edward


    A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400?20 ?g) of calcium carbonate. This new method streamlines the classical phosphoric acid - calcium carbonate (H3PO4 - CaCO3) reaction method by making use of a Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. To obtain reproducible and accurate results, optimal conditions for the H3PO4 - CaCO3 reaction had to be determined. At the acid-carbonate reaction temperature suggested by the equipment manufacturer, the oxygen isotope ratio results were unsatisfactory (standard deviation () greater than 1.5 per mill), probably because of a secondary reaction. When the acid-carbonate reaction temperature was lowered to 26?C and the reaction time was increased to 24 hours, the precision of the carbon and oxygen isotope ratios for duplicate analyses improved to 0.1 and 0.2 per mill, respectively. The method was tested by analyzing calcite from Devils Hole, Nevada, which was formed by precipitation from ground water onto the walls of a sub-aqueous cavern during the last 500,000 years. Isotope-ratio values previously had been obtained by the classical method for Devils Hole core DH-11. The DH-11 core had been recently re-sampled, and isotope-ratio values were obtained using this new method. The results were comparable to those obtained by the classical method. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, a cutting error that was then independently confirmed. The reproducibility of the isotopic values is demonstrated by a correlation of approximately 0.96 for both isotopes, after correcting for an alignment offset. This result indicates that the new method is a viable alternative to the classical method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes

  9. Cold seeps in Monterey Bay, California: Geochemistry of pore waters and relationship to benthic foraminiferal calcite

    Energy Technology Data Exchange (ETDEWEB)

    Gieskes, Joris, E-mail: [Scripps Institution of Oceanography, IOD-0208, 9500 Gilman Drive, La Jolla, CA 92093-0208 (United States); Rathburn, Anthony E. [Scripps Institution of Oceanography, IOD-0208, 9500 Gilman Drive, La Jolla, CA 92093-0208 (United States)] [Indiana State University, Department of Earth and Environmental Systems, Terre Haute, IN 47809 (United States); Martin, Jonathan B. [University of Florida, Department of Geological Sciences, Gainesville, FL 32611-2120 (United States); Perez, M. Elena [Indiana State University, Department of Earth and Environmental Systems, Terre Haute, IN 47809 (United States)] [The Natural History Museum, Department of Palaeontology, Cromwell Road, London SW7 5BD (United Kingdom); Mahn, Chris [Scripps Institution of Oceanography, IOD-0208, 9500 Gilman Drive, La Jolla, CA 92093-0208 (United States); Bernhard, Joan M. [Woods Hole Oceanographic Institution, Geology and Geophysics Department, MS52, Woods Hole, MA 02543 (United States); Day, Shelley [University of Florida, Department of Geological Sciences, Gainesville, FL 32611-2120 (United States)


    Highlights: > We describe the geochemistry of pore waters in the Clam Flats area of Monterey Bay. > The geochemical data are compared with the {delta}{sup 13}C chemistry of benthic foraminifera. > Living foraminifera indicate little effects of pore water low {delta}{sup 13}C (DIC) in the clam bed. > This phenomenon and its implications are discussed in detail. > Implications with regards to paleo-methane seepage are discussed. - Abstract: An extensive geochemical and biogeochemical examination of CH{sub 4} seeps in the Clam Flats area of Monterey Bay provides insight into the character of relationships between seep geochemistry and benthic foraminiferal geochemistry. The area is characterized by sulfide-rich fluids. Sulfide increases are associated with large increases in alkalinity, as well as small decreases in dissolved Ca and Mg. In addition, only small increases in NH{sub 4} are observed, but values of {delta}{sup 13}C of dissolved inorganic C are as low as -60 per mille at shallow depths (<3 cm). These observations indicate that all these processes are related to the bacterial oxidation of CH{sub 4}, which is transported upward by slow seepage of pore fluids. The geochemistry of the pore fluids should be relevant to the geochemistry of the carbonate tests of living and dead foraminifera. However, a profound disequilibrium of approximately an order of magnitude occurs between the {delta}{sup 13}C values of stained (cytoplasm-containing) foraminiferal carbonate and the C isotope values of ambient pore water dissolved inorganic C. Reasons are unclear for this isotopic disequilibrium, but have important implications for interpretations of foraminiferal carbonate as a paleoenvironmental proxy. Much fine scale work is needed to fully understand the relationships between the biogeochemistry of benthic foraminifera and the geochemistry of the pore waters where they live.

  10. A study based on cosmogenic 10Be, Be and Al in marine calcite ...

    Indian Academy of Sciences (India)

    R. Narasimhan, Krishtel eMaging Solutions

    Scripps Institution of Oceanography, Geosciences Research Division, La Jolla, CA 92093. 1Lawrence Livermore National Laboratory, Center for Accelerator Mass Spectrometry, ..... 1.3 × 10−8. 8.6 × 10−6. (a) Approximate average of 0–5 cm samples in table 1. Table 3. Measured concentrations of Be and Al in diatom opal.

  11. Mechanical properties of anorthite based ceramics prepared from kaolin DD2 and calcite

    Energy Technology Data Exchange (ETDEWEB)

    Harabi, A.; Zaiou, S.; Guechi, A.; Foughali, L.; Harabi, E.; Karboua, N.-E.; Zouai, S.; Mezahi, F.-Z.; Guerfa, F., E-mail:, E-mail:, E-mail:, E-mail:, E-mail:, E-mail:, E-mail:, E-mail: [Ceramics Lab., Faculty of Exact Science, Physics Department, Mentouri University of Constantine (Algeria)


    Good quality ceramics costs a lot that has limited their use in developing countries. This work was devoted to prepare low-cost and good quality anorthite based ceramics. The proposed composition was 80 wt% kaolin (DD2 type) and 20 wt% calcium oxide (CaO). The choice of these raw materials was dictated by their natural abundance coupled with a modified milling system, as another interesting advantage. Previous studies have shown that a simple vibratory multidirectional milling system using bimodal distribution of highly resistant ceramic milling elements has been successfully applied for obtaining fine powders. The influence of the relatively lower sintering temperature, ranging from 800 to 1100 °C, on the porosity and the average pore size (APS) have been investigated. The APS and the porosity values of samples sintered at 950 °C were about 1 μm and 4%, respectively. The best Vickers microhardness and 3-point bending strength values for these sintered samples, using this proposed milling system, were 7.1 GPa and 203 MPa, respectively. Finally, the crystalline phase evolution during heat treatment was investigated by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy techniques. (author)

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

    Digital Repository Service at National Institute of Oceanography (India)

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

    proxy, Paleoceanogra- phy, 16(6), 669–671. Broecker, W. S., and E. Clark (2002), Carbonate ion concen- tration in glacial-age deep waters of the Caribbean Sea, Geo- chem. Geophys. Geosyst., 3(3), 1021, doi:10.1029/ 2001GC000231. Broecker, W. S., and E... in the western tropical Indian Ocean: A multiproxy approach, Geochem. Geophys. Geosyst., 8, Q08009, doi:10.1029/2007GC001615. 1. Introduction [2] Attempts to reconstruct the carbonate ion his- tory from sediments of the world oceans have yielded two important...

  13. Strontium stable isotope behaviour in foraminiferal calcite and the retrieval of marine records (United States)

    Stevenson, E.; Burton, K.; Rickaby, R.; Parkinson, I. J.; Anand, P.; Hathorne, E.


    The stable strontium (88Sr/86Sr) isotope composition of seawater recorded in sedimentary foraminifera potentially provides key information on variations in the composition of material delivered by continental weathering to the oceans and on changes in carbonate productivity over time. However, recent studies suggest a significant temperature dependent fractionation of Sr stable isotopes during the precipitation of calcium carbonate, which must be quantified before seawater records can be accurately retrieved [1, 2]. This study presents high-precision stable Sr isotope data (±10 ppm 2 s.d.) for core-top planktonic foraminifera from sites in the South Atlantic with a range of annual sea surface temperatures of 18 - 28°C, and preliminary data for quaternary marine foraminiferal records from the SE Indian Ocean. These results indicate that there is no signficiant variation in the stable isotope composition of an individual species across the temperature range studied here, but there are resolvable differences in the offset from seawater between species. In this case, seawater stable Sr isotope records can be reconstructed without the necessity of a temperature correction. The preliminary results for a glacial-interglacial planktonic foraminifera record indicate that there are no resolvable variations in the stable isotope ratios over this time interval, indicating that there are no significant variations in the Sr isotope composition of continental runoff or carbonate productivity in the oceans over this time interval. [1] Fietzke, J., Eisenhauer, A. (2006), Geochem. Geophys. Geosyst., 7, (8), 1-6 . [2] Ruggerburg, A., Fietzke, J., Liebetrau, V. Eisenhauer, A., Dullo, W-C., Freiwald, A. (2008). Earth Plan. Sci. Lett. 269, 570-575

  14. New developments in early diagenetic modeling : pH distributions, calcite dissolution and compaction

    NARCIS (Netherlands)

    Jourabchi, P.


    The goal of this thesis is to advance the modeling of physical, chemical, and biological transformations that define the early diagenetic processes in sediments. Early diagenetic models encompass the mathematical formulation and numerical solution of complex biogeochemical reaction systems, and thus

  15. New developments in early diagenetic modeling: pH distributions, calcite dissolution and compaction

    NARCIS (Netherlands)

    Jourabchi, P.


    The goal of this thesis is to advance the modeling of physical, chemical, and biological transformations that define the early diagenetic processes in sediments. Early diagenetic models encompass the mathematical formulation and numerical solution of complex biogeochemical reaction systems, and thus

  16. Possible factors that control calcite dissolution in the western tropical Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

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

    at Site SK199C/7 is due to this corrosive benthic fluff layer, we cal- culated the ΔCO = 3 interface – ΔCO = 3 bottom water gradient. We used the relationship from the core-top data of Broecker and Clark 11 for P. obliquiloculata shell weight...





    A bactéria Rhodococcus opacus foi avaliada como biorreagente para a flotação dos minerais da magnesita calcita e barita. As análises para determinar a conformação de parede o R. opacus estabelecem que é constituída por macromoléculas com características anfipáticas. O balanço entre grupos catiônicos e aniônicos da parede atribui um ponto isoelétrico equivalente de 3,2. Os resultados dos testes de aderência indicam que a bactéria R. opacus tem uma fort...

  18. Effect of some biotic factors on microbially-induced calcite precipitation in cement mortar. (United States)

    Al-Salloum, Yousef; Abbas, H; Sheikh, Q I; Hadi, S; Alsayed, Saleh; Almusallam, Tarek


    Sporosarcina pasteurii, a common soil bacterium has been tested for microbial treatment of cement mortar. The present study also seeks to investigate the effects of growth medium, bacterial concentration and different buffers concerning the preparation of bacterial suspensions on the compressive strength of cement mortar. Two growth media, six different suspensions and two bacterial concentrations were used in the study. The influence of growth medium on calcification efficiency of S. pasteurii was insignificant. Significant improvement in the compressive as well as the tensile strength of cement mortar was observed. Microbial mineral precipitation visualized by Scanning Electron Microscopy (SEM) shows fibrous material that increased the strength of cement mortar. Formation of thin strands of fillers observed through SEM micrographs improves the pore structure, impermeability and thus the compressive as well as the tensile strengths of the cement mortar. The type of substrate and its molarity have a significant influence on the strength of cement mortar.

  19. Mechanical properties of anorthite based ceramics prepared from kaolin DD2 and calcite

    Directory of Open Access Journals (Sweden)

    A. Harabi

    Full Text Available Abstract Good quality ceramics costs a lot that has limited their use in developing countries. This work was devoted to prepare low-cost and good quality anorthite based ceramics. The proposed composition was 80 wt% kaolin (DD2 type and 20 wt% calcium oxide (CaO. The choice of these raw materials was dictated by their natural abundance coupled with a modified milling system, as another interesting advantage. Previous studies have shown that a simple vibratory multidirectional milling system using bimodal distribution of highly resistant ceramic milling elements has been successfully applied for obtaining fine powders. The influence of the relatively lower sintering temperature, ranging from 800 to 1100 °C, on the porosity and the average pore size (APS have been investigated. The APS and the porosity values of samples sintered at 950 °C were about 1 μm and 4%, respectively. The best Vickers microhardness and 3-point bending strength values for these sintered samples, using this proposed milling system, were 7.1 GPa and 203 MPa, respectively. Finally, the crystalline phase evolution during heat treatment was investigated by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy techniques.

  20. Production, use and reuse of Dutch calcite in drinking water pellet softening

    NARCIS (Netherlands)

    Palmen, LJ; Schetters, M.J.A.; van der Hoek, J.P.; Kramer, O.J.I.; Kors, L.J.; Hofs, B; Koppers, H


    In The Netherlands, 50% of the drinking water is treated with pellet softening for various reasons: i) public health (heavy metal solubility), ii) costs (warm water device maintenance, energy and soap requirement), iii) environmental benefits (energy and soap requirement) and iv) customer comfort

  1. Laser-induced breakdown spectroscopy for elemental characterization of calcitic alterations on cave walls. (United States)

    Bassel, Léna; Motto-Ros, Vincent; Trichard, Florian; Pelascini, Frédéric; Ammari, Faten; Chapoulie, Rémy; Ferrier, Catherine; Lacanette, Delphine; Bousquet, Bruno


    Cave walls are affected by different kinds of alterations involving preservative issues in the case of ornate caves, in particular regarding the rock art covering the walls. In this context, coralloids correspond to a facies with popcorn-like aspect belonging to the speleothem family, mostly composed of calcium carbonate. The elemental characterization indicates the presence of elements that might be linked to the diagenesis and the expansion of the alterations as demonstrated by prior analyses on stalagmites. In this study, we report the use of laser-induced breakdown spectroscopy (LIBS) to characterize the elemental composition of one coralloid sample with a portable instrument allowing punctual measurements and a laboratory mapping setup delivering elemental images with spatial resolution at the micrometric scale, being particularly attentive to Mg, Sr, and Si identified as elements of interest. The complementarity of both instruments allows the determination of the internal structure of the coralloid. Although a validation based on a reference technique is necessary, LIBS data reveal that the external layer of the coralloid is composed of laminations correlated to variations of the LIBS signal of Si. In addition, an interstitial layer showing high LIBS signals for Fe, Al, and Si is interpreted to be a detrital clay interface between the external and the internal part of the coralloid. These preliminary results sustain a possible formation scenario of the coralloid by migration of the elements from the bedrock.

  2. Optimized sequential extraction for carbonates : Quantification and δ13C analysis of calcite, dolomite and siderite

    NARCIS (Netherlands)

    Morera-Chavarría, A.; Griffioen, J.; Behrends, T.


    Siderite is present in diverse types of rocks and sediments, but its quantification is cumbersome when present in relatively low contents. A new analytical method for the sequential separation of different carbonate phases is presented. The separation, quantification and characterization of the

  3. Unusual biogenic calcite structures in two shallow lakes, James Ross Island, Antarctica

    Czech Academy of Sciences Publication Activity Database

    Elster, Josef; Nedbalová, Linda; Vodrážka, R.; Láska, K.; Haloda, J.; Komárek, Jiří


    Roč. 13, č. 2 (2016), s. 535-549 ISSN 1726-4170 R&D Projects: GA MŠk ME 945 Institutional support: RVO:67985939 Keywords : James Ross Island * cyanobacteria * microalgae Subject RIV: EH - Ecology, Behaviour Impact factor: 3.851, year: 2016

  4. Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation (United States)

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


    Plankton, corals, and other organisms produce calcium carbonate skeletons that are integral to their survival, form a key component of the global carbon cycle, and record an archive of past oceanographic conditions in their geochemistry. A key aspect of the formation of these biominerals is the interaction between organic templating structures and mineral precipitation processes. Laboratory-based studies have shown that these atomic-scale processes can profoundly influence the architecture and composition of minerals, but their importance in calcifying organisms is poorly understood because it is difficult to measure the chemistry of in vivo biomineral interfaces at spatially relevant scales. Understanding the role of templates in biomineral nucleation, and their importance in skeletal geochemistry requires an integrated, multiscale approach, which can place atom-scale observations of organic-mineral interfaces within a broader structural and geochemical context. Here we map the chemistry of an embedded organic template structure within a carbonate skeleton of the foraminifera Orbulina universa using both atom probe tomography (APT), a 3D chemical imaging technique with Ångström-level spatial resolution, and time-of-flight secondary ionization mass spectrometry (ToF-SIMS), a 2D chemical imaging technique with submicron resolution. We quantitatively link these observations, revealing that the organic template in O. universa is uniquely enriched in both Na and Mg, and contributes to intraskeletal chemical heterogeneity. Our APT analyses reveal the cation composition of the organic surface, offering evidence to suggest that cations other than Ca2+, previously considered passive spectator ions in biomineral templating, may be important in defining the energetics of carbonate nucleation on organic templates. PMID:27794119

  5. Microbial community composition and endolith colonization at an Arctic thermal spring are driven by calcite precipitation (United States)

    Starke, Verena; Kirshtein, Julie; Fogel, Marilyn L.; Steele, Andrew


    Environmental conditions shape community composition. Arctic thermal springs provide an opportunity to study how environmental gradients can impose strong selective pressures on microbial communities and provide a continuum of niche opportunities. We use microscopic and molecular methods to conduct a survey of microbial community composition at Troll Springs on Svalbard, Norway, in the high Arctic. Microorganisms there exist under a wide range of environmental conditions: in warm water as periphyton, in moist granular materials, and in cold, dry rock as endoliths. Troll Springs has two distinct ecosystems, aquatic and terrestrial, together in close proximity, with different underlying environmental factors shaping each microbial community. Periphyton are entrapped during precipitation of calcium carbonate from the spring's waters, providing microbial populations that serve as precursors for the development of endolithic communities. This process differs from most endolith colonization, in which the rock predates the communities that colonize it. Community composition is modulated as environmental conditions change within the springs. At Troll, the aquatic environments show a small number of dominant operational taxonomic units (OTUs) that are specific to each sample. The terrestrial environments show a more even distribution of OTUs common to multiple samples.

  6. Calcite precipitation dominates the electrical signatures of zero valent iron columns under simulated field conditions

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Yuxin; Versteeg, R.; Slater, L.; LaBrecque, D.


    Calcium carbonate is a secondary mineral precipitate influencing zero valent iron (ZVI) barrier reactivity and hydraulic performance. We conducted column experiments to investigate electrical signatures resulting from concurrent CaCO{sub 3} and iron oxides precipitation under simulated field geochemical conditions. We identified CaCO{sub 3} as a major mineral phase throughout the columns, with magnetite present primarily close to the influent based on XRD analysis. Electrical measurements revealed decreases in conductivity and polarization of both columns, suggesting that electrically insulating CaCO{sub 3} dominates the electrical response despite the presence of electrically conductive iron oxides. SEM/EDX imaging suggests that the electrical signal reflects the geometrical arrangement of the mineral phases. CaCO{sub 3} forms insulating films on ZVI/magnetite surfaces, restricting charge transfer between the pore electrolyte and ZVI particles, as well as across interconnected ZVI particles. As surface reactivity also depends on the ability of the surface to engage in redox reactions via charge transfer, electrical measurements may provide a minimally invasive technology for monitoring reactivity loss due to CaCO{sub 3} precipitation. Comparison between laboratory and field data shows consistent changes in electrical signatures due to iron corrosion and secondary mineral precipitation.

  7. A novel salinity proxy based on Na incorporation into foraminiferal calcite

    NARCIS (Netherlands)

    Wit, J.C.; de Nooijer, L.J.; Wolthers, M.; Reichart, G.J.


    Salinity and temperature determine seawater density, and differences in both thereby control global thermohaline circulation. Whereas numerous proxies have been calibrated and applied to reconstruct temperature, a direct and independent proxy for salinity is still missing. Ideally, a new proxy for

  8. Treatment Of Metal-Mine Effluents By Limestone Neutralization And Calcite Co-Precipitation (United States)

    The U.S. Geological Survey - Leetown Science Center and the Colorado School of Mines have developed a remediation process for the treatment of metals in circumneutral mining influenced waters. The process involves treatment with a pulsed limestone bed (PLB) system, followed by c...

  9. Treatment Of Metal-Mine Effluents By Limestone Neutralization And Calcite Co-Precipitation (Presentation) (United States)

    The U.S. Geological Survey - Leetown Science Center and the Colorado School of Mines have developed a remediation process for the treatment of metals in circumneutral mining influenced waters. The process involves treatment with a pulsed limestone bed (PLB) system, followed by c...

  10. Sintering of anorthite based ceramics prepared from kaolin DD2 and calcite

    Energy Technology Data Exchange (ETDEWEB)

    Zaiou, S.; Harabi, A.; Harabi, E.; Guechi, A.; Karboua, N.; Benhassine, M.-T.; Zouai, S.; Guerfa, F., E-mail:, E-mail:, E-mail:, E-mail:, E-mail:, E-mail:, E-mail:, E-mail: [Ceramics Lab., Faculty of Exact Science, Physics Department, Mentouri University of Constantine (Algeria)


    In this work, the preparation of anorthite based ceramics using a modified milling system and 80 wt% kaolin (DD2 type) and 20 wt% calcium oxide extracted from CaCO{sub 3} is shown. The choice of these raw materials was dictated by their natural abundance. Previous studies have shown that a simple and vibratory multidirectional milling system using a bimodal distribution of highly resistant ceramics can be successfully used for obtaining fine powders. The prepared samples were sintered at different temperatures ranging between 800 and 1100 °C. It has been found that the relative density of samples sintered at 900 °C for 1 h with a heating rate of 5 °C/min was about 96% of the theoretical density of anorthite (2.75 g/cm{sup 3} ). Finally, the prepared samples were also characterized by scanning electron microscopy, X-ray diffraction and Raman spectroscopy. (author)

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

    DEFF Research Database (Denmark)

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


    -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...

  12. Calcite precipitation from aqueous solution: transformation from vaterite and role of solution stoichiometry

    NARCIS (Netherlands)

    Nehrke, G.


    The morphology of vaterite precipitated by bubbling CO2 through a CaCl2 solution is framboidal aggregates. It is not possible, even when using the identical experimental setup and conditions, to reproduce aggregates having identical morphology. The density of the aggregates and crystallite size can

  13. Strength, stability, and microstructure of simulated calcite faults sheared under laboratory conditions spanning the brittle-plastic transition

    NARCIS (Netherlands)

    Verberne, B.A.|info:eu-repo/dai/nl/357286405


    Destructive earthquakes are commonplace in tectonically-active carbonate-bearing terrains, often leading to severe economic damage and major loss of life (e.g. the Apennines, Italy). Efforts to improve seismic risk assessment in such terrains require a quantitative understanding of the slip

  14. The Influence of Calcite, Fluorite, and Rutile on the Fusion-Related Behavior of Metal Cored Coated Electrodes for Hardfacing (United States)

    Cruz-Crespo, Amado; Fuentes, Rafael Fernández; Scotti, Américo


    Coated electrodes for SMAW have exhibited their advantages for longer than one century. Means of boosting their performance, particularly for hardfacing, would be a raise in the alloying transfer efficiency and a lowering of the dilution with the substrate, without losing the production capacity. In this study, an evaluation about the operational behavior of a new conception of electrodes for hardfacing is described, i.e., metal cored coated electrodes. Experimental electrodes were produced using metal cored technique to obtain the rods. FeCrMn was used as alloying material at two grain sizes. Using the Mc Lean Anderson experimental design approach, the content ratio of CaCO3:CaF2:TiO2 in the coating was varied. The effect of the coating composition and granulometry of the filling alloying material on the formation a cannon-like end was assessed. Fusion and metal transfer behaviors were evaluated through measurements of fusion and deposition rates, deposition efficiency, and duration and frequencies of short-circuiting. Based on a balance of performances, the most appropriate composition for the coating was determined. It was also observed that a coarser FeCrMn presented better performance.

  15. Variability in calcitic Mg/Ca and Sr/Ca ratios in clones of the benthic foraminifer

    NARCIS (Netherlands)

    de Nooijer, L.J.; Hathorne, E.C.; Reichart, G.J.; Langer, G.; Bijma, J.


    Biological activity introduces variability in element incorporation during calcification and thereby decreases the precision and accuracy when using foraminifera as geochemical proxies in paleoceanography. This so-called 'vital effect' consists of organismal and environmental components. Whereas

  16. Fine Formation During Brine-Crude Oil-Calcite Interaction in Smart Water Enhanced Oil Recovery for Caspian Carbonates

    DEFF Research Database (Denmark)

    Chakravarty, Krishna Hara; Fosbøl, Philip Loldrup; Thomsen, Kaj


    Modified sea water has been shown to affect the oil recovery fraction considerably during secondary and tertiary waterfloods. Available soluble potential ions (i.e. Ca2+, Mg2+ & SO42-) in the interacting waterflood (ITW) are suggested to play a key role in increasing the displacement efficiency...

  17. Cryogenic fracturing of calcite flowstone in caves: theoretical considerations and field observations in Kents Cavern, Devon, UK

    Directory of Open Access Journals (Sweden)

    Lundberg Joyce


    Full Text Available Several caves in Devon, England, have been noted for extensive cracking of substantial flowstone floors. Conjectural explanations have included earthquake damage, local shock damage from collapsing cave passages, hydraulic pressure, and cryogenic processes. Here we present a theoretical model to demonstrate that frost-heaving and fracture of flowstone floors that overlie wet sediments is both a feasible and likely consequence of unidirectional air flow or cold-air ponding in caves, and argue that this is the most likely mechanism for flowstone cracking in caves located in Pleistocene periglacial environments outside of tectonically active regions. Modeled parameters for a main passage in Kents Cavern, Devon, demonstrate that 1 to 6 months of -10 to -15° C air flow at very modest velocities will result in freezing of 1 to 3 m of saturated sediment fill. The resultant frost heave increases with passage width and depth of frozen sediments. In the most conservative estimate, freezing over one winter season of 2 m of sediment in a 6-m wide passage could fracture flowstone floors up to ~13 cm thick, rising to ~23 cm in a 12-m wide passage. Natural flaws in the flowstone increase the thickness that could be shattered. These numbers are quite consistent with the field evidence.

  18. Soft interactions, solid results : nucleation of calcite on organic monolayers and knowledge creation in a University Research Institute

    NARCIS (Netherlands)

    Travaille, A.M.


    While knowledge creation lies at the heart of scientific research, the role of knowledge typically remains implicit in studies of the practices and the management of that research. This paper examines which critical success factors (CSF's) define successful research. Based on Nonaka's knowledge

  19. Formation of Anhydrite due to Interaction Between Water Soluble CO2 (aq) and Calcite Mineral During Enhanced Oil Recovery

    DEFF Research Database (Denmark)

    Chakravarty, Krishna Hara; Fosbøl, Philip Loldrup; Thomsen, Kaj


    place during CO2 injection in limestone reservoirs. At reservoir conditions, a considerable fraction of the injected CO2 becomes soluble in sea water. This dissolved CO2 causes dissolution of CaCO3 from the mineral surface and releases Ca2+ ions into the pore space. Excess Ca2+ ions form anhydrite fines......In the Low Salinity based EOR method, formation and migration of fines have proved to have profound effect on the displacement efficiency of residual oil. Salinity variations of injected brines have also been shown to affect oil recovery for WAG-CO2 processes. But the effect of fines in EOR during...... simulations were conducted over a temperature range of 50°C to 250°C and a pressure range of 5 bars to 500 bars. The amounts of fines formation taking place for different LSWAG-CO2 processes were correlated to the described oil recovery. It is observed that significant amounts of fines formation can take...

  20. Evaluating Zeta Potential and the Calcite/Aragonite Ratio as Potential Success Indicators for Magnetic Water Treatment

    National Research Council Canada - National Science Library

    Lambert, Kevin


    The potential benefits of anti-scale magnetic treatment (AMT) are not realized or reliably predicted because the factors measuring performance of magnetic treatment have either not been identified or are poorly defined...

  1. Production, oxygen respiration rates, and sinking velocity of copepod fecal pellets: Direct measurements of ballasting by opal and calcite

    DEFF Research Database (Denmark)

    Ploug, H.; Iversen, M.H.; Koski, Marja


    Production, oxygen uptake, and sinking velocity of copepod fecal pellets egested by Temora longicornis were measured using a nanoflagellate (Rhodomonas sp.), a diatom (Thalassiosira weissflogii), or a coccolithophorid (Emiliania huxleyi) as food sources. Fecal pellet production varied between 0.......8 pellets ind(-1) h(-1) and 3.8 pellets ind(-1) h(-1) and was significantly higher with T. weissflogii than with the other food sources. Average pellet size varied between 2.2 X 10(5) mu m(3) and 10.0 X 10(5) mu m(3). Using an oxygen microsensor, small-scale oxygen fluxes and microbial respiration rates...... were measured directly with a spatial resolution of 2 mu m at the interface of copepod fecal pellets and the surrounding water. Averaged volume-specific respiration rates were 4.12 fmol O-2 mu m(-3) d(-1), 2.86 fmol O-2 mu m(-3) d(-1), and 0.73 fmol O-2 mu m(-3) d(-1) in pellets produced on Rhodomonas...

  2. Physical and nanomechanical properties of the synthetic anhydrous crystalline CaCO3 polymorphs: vaterite, aragonite and calcite

    Czech Academy of Sciences Publication Activity Database

    Ševčík, Radek; Šašek, Petr; Viani, Alberto


    Roč. 53, č. 6 (2018), s. 4022-4033 ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LO1219; GA ČR(CZ) GA17-05030S Keywords : X-ray-diffraction * thermal expansion * mechanical characterization * relative-humidity * carbonates * mortars Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 2.599, year: 2016 and -nanomechanical-properties-of-the-synthetic-anhydrou/15290962

  3. Adsorption mechanism of alkyl polyglucoside (APG) on calcite nanoparticles in aqueous medium at varying pH (United States)

    Suh, Seokjin; Choi, Kyeong-Ok; Yang, Seung-Chul; Kim, Yeong Eun; Ko, Sanghoon


    In this study, adsorption mechanism of alkyl polyglucoside (APG) on calcium carbonate (CaCO3) nanoparticles (CCNPs) in aqueous medium at varying pH was identified. An initial adsorption of APG on CCNP surface seemed to be occurred due to the van der Waals force. An initial surface charge influenced determination of a major driving force, which resulted in hydrogen bonds (pH 7) and the hydrophobic interaction (pH 10) as a main sources of adsorption of APG on the CCNP surface. Even if the initial surface charge of CCNPs had little effect on a quantitative adsorption of APG on CCNPs, eventually, it influence on the definitive adsorption structure between APG and CCNPs and improvement of dispersion stability of CCNPs in water. In conclusion, it was revealed that 0.39% APG aqueous solution was most appropriate to improve the dispersion stability of CCNPs, which is postulated to be used effectively in food and pharmaceutical fields.

  4. Predicting Calcite (CaCO3) Requirements of Sphagnum Peat Moss from pH Titration Curves (United States)

    Liming materials are required to neutralize acidity in peat moss to make it a suitable substrate for growing container crops. A series of time-consuming incubations of peat:lime mixtures are typically used to determine the liming rate to achieve a desired pH. Our objective was to evaluate the util...

  5. Atomic Force Microscopy of Coccoliths: Implications for Biomineralisation and Diagenesis

    DEFF Research Database (Denmark)

    Henriksen, Karen; Young, Jette F.; Bown, P.R.


    geochemistry, diagenesis, coccoliths, biomineralization, biological calcite, atomic force microscopy......geochemistry, diagenesis, coccoliths, biomineralization, biological calcite, atomic force microscopy...

  6. EBSD analysis of heterogeneous microstructures in experimentally deformed calcite: development of core and mantle subgrains, grain boundary bulges and recrystallised grains. Geologica Ultraiectina (289)

    NARCIS (Netherlands)

    Valcke, S.L.A.|info:eu-repo/dai/nl/304833452


    Geodynamic processes such as subduction and rifting are mainly controlled by high temperature plastic deformation of rocks. It is known that elements of the microstructure in plastically deformed rocks, such as subgrains and recrystallised grains, are potentially useful as indicators of past

  7. Quantification of loss of calcite, pyrite, and organic matter due to weathering of Toarcian black shales and effects on kerogen and bitumen characteristics (United States)

    Littke, R.; Klussmann, U.; Krooss, B.; Leythaeuser, D.


    Comparison of geochemical data on Posidonia Shale (Early Toarcian) from a shallow unweathered core and from adjacent weathered exposures of the same fades was performed. Results revealed that quantitatively the most affected petrographic constituent is pyrite and that organic matter and carbonate were also altered by weathering. Due to this process of weathering, the bulk composition of organic matter, especially the molecular composition of soluble organic matter and the fluorescence colour of organic particles, are changed. Estimates of weathering rates reveal that the annual release of sulphur and organic carbon from black shales may significantly add to anthropogenic pollution.

  8. Quantification of loss of calcite, pyrite, and organic matter due to weathering of Toarcian black shales and effects on kerogen and bitumen characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Littke, R.; Klussmann, U.; Krooss, B.; Leythaeuser, D. (Inst. fuer Erdoel und organische Geochemie, Juelich (West Germany))


    Comparison of geochemical data on Posidonia Shale (Early Toarcian) from a shallow unweathered core and from adjacent weathered exposures of the same facies was performed. Results revealed that quantitatively the most affected petrographic constituent is pyrite and that organic matter and carbonate were also altered by weathering. Due to this process of weathering, the bulk composition of organic matter, especially the molecular composition of soluble organic matter and the fluorescence color of organic particles, are changed. Estimates of weathering rates reveal that the annual release of sulfur and organic carbon from black shales may significantly add to anthropogenic pollution.

  9. Genesis and distribution pattern of carbonate cements in lacustrine deep-water gravity-flow sandstone reservoirs in the third member of the Shahejie Formation in the Dongying Sag, Jiyang Depression, Eastern China

    DEFF Research Database (Denmark)

    Yang, Tian; Cao, Yingchang; Friis, Henrik


    deep-water gravity-flow sandstone reservoirs. The sandstones are mainly lithic arkose with an average framework composition of Q43F33L24. The carbonate cements are dominated by calcite, ferroan calcite, ankerite and a small amount of dolomite. The calcite and ferroan calcite are mainly poikilotopic...

  10. Impact of seawater pCO2 on calcification and Mg/Ca and Sr/Ca ratios in benthic foraminifera calcite: results from culturing experiments with Ammonia tepida

    NARCIS (Netherlands)

    Dissard, D.; Nehrke, G.; Reichart, G.-J.; Bijma, J.


    Evidence of increasing concentrations of dissolved carbon dioxide, especially in the surface ocean and its associated impacts on calcifying organisms, is accumulating. Among these organisms, benthic and planktonic foraminifera are responsible for a large amount of the globally precipitated calcium

  11. Characterization of Three Antifungal Calcite-Forming Bacteria, Arthrobacter nicotianae KNUC2100, Bacillus thuringiensis KNUC2103, and Stenotrophomonas maltophilia KNUC2106, Derived from the Korean Islands, Dokdo and Their Application on Mortar

    National Research Council Canada - National Science Library

    Jong Myong Park; ; Sung Jin Park; Sa Youl Ghim


    ... prevented. Therefore, to develop a microbial sealing agent that has antifungal properties to remediate cement cracks without deteriorative fungal colonization, we introduced an antifungal CFB isolated from oceanic islands...

  12. Microaccretionary and Accretionary Carbonate Spherules of the Chicxulub Impact Event from Brazos River, Texas, and Bass River, New Jersey (United States)

    Guillemette, R. N.; Yancey, T. E.


    Small accretionary carbonate spherules of low-Mg calcite and clay are common in deposits of the Chicxulub impact. These form as primary calcite in the vapor plume, indicating much carbonate was preserved as particles and not as carbon dioxide.

  13. Why did the UV-A-induced photoluminescent blue-green glow in trilobite eyes and exoskeletons not cause problems for trilobites?


    Schoenemann, Brigitte; Clarkson, Euan N. K.; Horváth, Gábor


    The calcitic lenses in the eyes of Palaeozoic trilobites are unique in the animal kingdom, although the use of calcite would have conveyed great advantages for vision in aquatic systems. Calcite lenses are transparent, and due to their high refractive index they would facilitate the focusing of light. In some respects, however, calcite lenses bear evident disadvantages. Birefringence would cause double images at different depths, but this is not a problem for trilobites since the difference i...

  14. Why did the UV-A-induced photoluminescent blue–green glow in trilobite eyes and exoskeletons not cause problems for trilobites?


    Brigitte Schoenemann; Clarkson, Euan N. K.; Gábor Horváth


    The calcitic lenses in the eyes of Palaeozoic trilobites are unique in the animal kingdom, although the use of calcite would have conveyed great advantages for vision in aquatic systems. Calcite lenses are transparent, and due to their high refractive index they would facilitate the focusing of light. In some respects, however, calcite lenses bear evident disadvantages. Birefringence would cause double images at different depths, but this is not a problem for trilobites since the difference i...

  15. Technical comment on Kroeker et al. (2010) Meta-analysis reveals negative yet variable effects of ocean acidification on marine organisms. Ecology Letters, 13, 1419-1434. (United States)

    Andersson, Andreas J; Mackenzie, Fred T


    Meta-analysis of experimental results has been interpreted to imply that the calcification response of organisms depositing high Mg-calcite is more resilient to ocean acidification than organisms depositing aragonite/calcite. This conclusion might be biased by inadequate recognition and categorisation of high Mg-calcite according to mineral solubility. © 2011 Blackwell Publishing Ltd/CNRS.

  16. Effect of Filler Loading on the Molecular Movement of Benzene and ...

    African Journals Online (AJOL)

    The sorption behaviour of the solvents – benzene and toluene in calcite-filled low density polyethylene composite samples at 40oC and 65oC were investigated using gravimetric sorption method. The effect of calcite loading on the molecular movement of benzene and toluene through the calcite-filled LDPE composites ...

  17. Calcium carbonate precipitation in the Cueva di Watapana on Bonaire, Netherlands Antilles

    NARCIS (Netherlands)

    Meer Mohr, van der C.G.


    Calcium carbonate precipitates as low Mg-calcite and aragonite in slightly brackish water in a cave in the Pleistocene Middle Terrace of southern Bonaire. The calcium carbonate precipitates at the atmosphere-water interface forming floating calcite scales (calcite ice). Aragonite crystals frequently

  18. Demonstration of Regenerable, Large-Scale Ion Exchange System Using WBA Resin in Rialto, CA (Drinking Water Treatment - Pilot Scale) (United States)


    Calcite Contactor Treated Water Figure 4. Process Configuration for Capital and O&M Cost Analyses. CO2 Filter Neutralization LiquiCel Membrane ...10,000 Equipment Quantity Unit Total Cost Ion exchange vessels 2 10 ft dia. $ 200,000 Calcite contactor 1 100 gpm $ 30,000 LiquiCel Membranes 6 3...varying the pH and using a combination of air/ membrane stripping and calcite contacting. Treated water had a Langelier Saturation Index (LSI) near zero

  19. Perchlorate Removal, Destruction and Field Monitoring Demonstration (Groundwater RemediationPilot-Scale) (United States)


    Series Calcite Contactor Treated Water Figure 4. Process Configuration for Capital and O&M Cost Analyses. CO2 Filter Neutralization LiquiCel Membrane ...1 60 $ 10,000 Equipment Quantity Unit Total Cost Ion exchange vessels 2 10 ft dia. $ 200,000 Calcite contactor 1 100 gpm $ 30,000 LiquiCel Membranes varying the pH and using a combination of air/ membrane stripping and calcite contacting. Treated water had a Langelier Saturation Index (LSI

  20. Sandblaster 2 Support of See-Through Technologies for Particulate Brownout (United States)


    particles. Photomicrographs of the YPG and Iraq soils are shown in Figure 14. Particle size and shape characteristics of the two test soils are similar...Both Yuma and Iraq soils showed an abundance of calcite, but the formations differed. Calcite in the Yuma dust occurs as discrete clasts . the Iraq dust occurs as very fine-grained coatings on monomineralic clasts and as aggregates mixed with other fine-grained phases. In the Iraq

  1. Soil Stabilization for Roadways and Airfields (United States)


    calcining calcite or dolomite , respectively. The controlled addition of water to quicklime can produce three types of hydrated lime: (1) high-calcium, Ca(OH...Stabilization: ’ a. Lime. All classes of quicklime and hydrated lime, both calcitic-(high calcium) and dolomitic (ASTM C-593). b. Lime-Modified Soils...calcium and magnesium. There are various types of commercial lime. Calcitic quicklime (CaO) and dolomitic quicklime (CaO + MgO) are produced by

  2. Grout for Closure of the Demonstration Vault at the US DOE Hanford Facility (United States)


    Calcined Natural Pozzolan for Use as a Mineral Admixture in Portland Cement Concrete." k. Designation C 939-87. "Standard Test Method for Flow of Grout...ettringite or CACH11 were identified. Calcite and dolomite probably from Lhe palygorskite, were present in the wasteform material. The cold-cap...C2S) - minor Dolomite - minor (C) Material on Contact - Waste Side (D) Interface - Waste Side Quartz Calcite Albite Quartz Calcite Aragonite Hematite

  3. Limnology of Eifel maar lakes

    National Research Council Canada - National Science Library

    Scharf, Burkhard W; Björk, Sven


    ... & morphometry - Physical & chemical characteristics - Calcite precipitation & solution in Lake Laacher See - Investigations using sediment traps in Lake Gemundener Maar - Phytoplankton of Lake Weinfelder Maar...

  4. Department of Defense Enhanced Particulate Matter Surveillance Program (EPMSP) (United States)


    kaolinite, illite, motmorillonite, and palygorskite Dolomite Calcium magnesium carbonate mineral Evaporites Water-soluble mineral sediments (salts...contained in carbonate minerals such as calcite and dolomite . ........................................ 42 Figure 4-25. Trace element compositions...MgO. The last two components are contained in the carbonate minerals calcite and dolomite and were found in higher concentrations at the UAE and Al

  5. Diagenesis of Holocene reef and associated beachrock of certain ...

    Indian Academy of Sciences (India)

    (a) Well developed dog-tooth cementation in the coral reef skeleton, (b) Neomorphic calcite (NC) filled the thick wall of coral skeletal structure, (c) Meteoric diagenesis developed the neomorphic calcite (NC) above the well precipitated marine aragonite cements (MAC). (d) The occurrence of internal sediments within the ...

  6. Independent impacts of calcium and carbonate ion concentration on Mg and Sr incorporation in cultured benthic foraminifera

    NARCIS (Netherlands)

    Duenas-Bohorquez, A.; Raitzsch, M.; Nooijer, L.J. de; Reichart, G.-J.


    concentration ([CO3 2−]), and thereby calcite saturation state (Ω), on Mg and Sr incorporation into calcite of two species of shallow-water benthic foraminifera: Ammonia tepida and Heterostegina depressa. Impact on Mg and Sr incorporation by increased seawater [CO3 2−] and thereby higher Ω is

  7. River water quality in weathered limestone: A case study in upper ...

    Indian Academy of Sciences (India)

    Stromatolitic limestone and calcareous shale belonging to Chattisgarh Supergroup of Proterozoic age dominate the upper part of the Mahanadi river basin.X-ray diffractogram (XRD)of limestone rocks show presence of a significant amount of calcite,dolomite and ankerite.Shales of various colours contain calcite and ...

  8. Formation of methane-related authigenic carbonates in a highly dynamic biogeochemical system in the Krishna–Godavari Basin, Bay of Bengal

    Digital Repository Service at National Institute of Oceanography (India)

    Kocherla, M.; Teichert, B.M.A.; Pillai, S.; Satyanarayan, M.; Ramamurty, P.B.; Patil, D.J.; Rao, A.N.

    We report the abundant occurrence of authigenic Fe-rich carbonate, high Mg-calcite (HMC) and low Mg-calcite from 11 cores recovered from the Krishna–Godavari Basin (K–G Basin), Bay of Bengal. The cores were collected as part of the Indian gas...


    African Journals Online (AJOL)

    Preferred Customer

    viz-a-viz the removal of heavy metals and especially Pb(II) from aqueous solutions. ... heavy metals using calcite as the adsorbent [9-15]. ... outer sphere adsorption on the surface of calcite combined with co-precipitation of discrete Pb2+.

  10. Removal of Pb(II) from aqueous solution by natural and synthetic ...

    African Journals Online (AJOL)

    A comparative evaluation of the adsorption capacity and kinetics of Pb(II) uptake by both synthetic and natural calcites has been undertaken using batch equilibration technique. The originality of the calcite materials was confirmed by XRD and elemental composition by XRF. The point of zero charge values of 9.57 and 8.20 ...

  11. Evaluation of aqueous geochemistry of fluoride enriched groundwater: A case study of the Patan district, Gujarat, Western India

    Directory of Open Access Journals (Sweden)

    Pankaj Kumar


    Saturation index for selected minerals suggests that most of the samples are oversaturated with calcite and undersaturated with fluorite. Calcite precipitation leads to the removal of Ca2+ from solution thus allowing more fluorite to dissolve. These released Ca2+ ions combine with CO32− ions to further enhance the precipitation of CaCO3.

  12. Untitled

    Indian Academy of Sciences (India)

    (211) planes of calcite, namely 3:03 A.U.. Figs. 3a, b, c and d in Plate XXXIII reproduce a series of four Laue photographs obtained with a thin and perfectly flawless cleavage plate of calcite. The X-rays from a molybdenum target tube run at 45000 peak voltage and 12 milliamperes were employed, the beam emerging from a.

  13. Biomineralization of carbonate and phosphate by moderately halophilic bacteria

    NARCIS (Netherlands)

    Sánchez-Román, Mónica; Rivadeneyra, Maria A.; Vasconcelos, Crisogono; McKenzie, Judith A.

    We investigated the precipitation of carbonate and phosphate minerals by 19 species of moderately halophilic bacteria using media with variable Mg 2+/Ca2+ ratios. The precipitated minerals were calcite, magnesium (Mg) calcite, and struvite (MgNH4PO4· 6H2O) in variable proportions depending on the

  14. Biogeochemical implications of comparative growth rates of Emiliania huxleyi and Coccolithus species (United States)

    Daniels, C. J.; Sheward, R. M.; Poulton, A. J.


    Coccolithophores, a diverse group of phytoplankton, make important contributions to pelagic calcite production and export, yet the comparative biogeochemical role of species other than the ubiquitous Emiliania huxleyi is poorly understood. The contribution of different coccolithophore species to total calcite production is controlled by inter-species differences in cellular calcite, growth rate and relative abundance within a mixed community. In this study we examined the relative importance of E. huxleyi and two Coccolithus species in terms of daily calcite production. Culture experiments compared growth rates and cellular calcite content of E. huxleyi (Arctic and temperate strains), Coccolithus pelagicus (novel Arctic strain) and Coccolithus braarudii (temperate strain). Despite assumptions that E. huxleyi is a fast-growing species, growth rates between the three species were broadly comparable (0.16-0.85 d-1) under identical temperature and light conditions. Emiliania huxleyi grew only 12% faster on average than C. pelagicus, and 28% faster than C. braarudii. As the cellular calcite content of C. pelagicus and C. braarudii is typically 30-80 times greater than E. huxleyi, comparable growth rates suggest that Coccolithus species have the potential to be major calcite producers in mixed populations. To further explore these results we devised a simplistic model comparing daily calcite production from Coccolithus and E. huxleyi across a realistic range of relative abundances and a wide range of relative growth rates. Using the relative differences in growth rates from our culture studies, we found that C. pelagicus would be a larger source of calcite if abundances of E. huxleyi to C. pelagicus were below 34:1. Relative abundance data collected from North Atlantic field samples (spring and summer 2010) suggest that, with a relative growth rate of 88%, C. pelagicus dominated calcite production at 69% of the sites sampled. With a more extreme difference in growth

  15. Biomineralization

    DEFF Research Database (Denmark)

    Sand, K. K.; Pedersen, C. S.; Sjöberg, S.


    step edges. Adsorption, even at extremely low concentrations (0.5 μg/mL), results in decreased growth rate and dramatic morphology changes during growth and dissolution. The experimental results are complemented with surface complexation modeling for adsorption of components of polysaccharide from......Our results demonstrate that in addition to being used for controlling morphology during calcite growth, polysaccharide (PS) that has been designed for biomineralization is also extremely robust, influencing calcite reactions even after millions of years. We investigated calcite (CaCO3) behavior...... in solutions with very small concentrations of PS that was produced ∼70 Ma ago by coccolithophorids. We used atomic force microscopy (AFM) and the constant composition method to monitor calcite growth in the presence of this ancient PS. The ancient PS is still very active and has a high affinity for calcite...

  16. Occurrence and genesis of Quaternary microbialitic tufa at Hammam Al Ali, Oman (United States)

    Khalaf, Fikry I.


    Remnants of late Quaternary microbialitic tufa occurs within a shallow depression in the Hammam Al Ali hot spring area, which is located approximately 14.5 km to the southwest of Muscat, Oman. The tufa precipitated from hot spring water supersaturated with respect to calcium carbonate and is mostly of a porous phytogenic type, with occasional detrital and stromatolitic types. Microscopic and nanoscopic examination revealed that the tufa deposits developed through two successive processes of calcite precipitation, biotic and abiotic, preceded by limited precipitation of unstable aragonite. It is suggested that biologically mediated precipitation results in the construction of incomplete skeletal calcite crystals. The latter provide a base for classical physiochemical precipitation and, eventually, the development of complete sparry calcite crystals. The initiation of dendritic calcite crystals in the stromatolitic tufa as incomplete biogenic skeletal crystals and their characteristic growth pattern indicates that the tufa represents a clear example of hot spring calcitic microbialite.

  17. Why did the UV-A-induced photoluminescent blue-green glow in trilobite eyes and exoskeletons not cause problems for trilobites? (United States)

    Schoenemann, Brigitte; Clarkson, Euan N K; Horváth, Gábor


    The calcitic lenses in the eyes of Palaeozoic trilobites are unique in the animal kingdom, although the use of calcite would have conveyed great advantages for vision in aquatic systems. Calcite lenses are transparent, and due to their high refractive index they would facilitate the focusing of light. In some respects, however, calcite lenses bear evident disadvantages. Birefringence would cause double images at different depths, but this is not a problem for trilobites since the difference in the paths of the ordinary and extraordinary rays is less than the diameter of the receptor cells. Another point, not discussed hitherto, is that calcite fluoresces when illuminated with UV-A. Here we show experimentally that calcite lenses fluoresce, and we discuss why fluorescence does not diminish the optical quality of these lenses and the image formed by them. In the environments in which the trilobites lived, UV-A would not have been a relevant factor, and thus fluorescence would not have disturbed or confused their visual system. We also argue that whatever the reason that calcite was never again used successfully in the visual systems of aquatic arthropods, it was not fluorescence.

  18. Why did the UV-A-induced photoluminescent blue–green glow in trilobite eyes and exoskeletons not cause problems for trilobites?

    Directory of Open Access Journals (Sweden)

    Brigitte Schoenemann


    Full Text Available The calcitic lenses in the eyes of Palaeozoic trilobites are unique in the animal kingdom, although the use of calcite would have conveyed great advantages for vision in aquatic systems. Calcite lenses are transparent, and due to their high refractive index they would facilitate the focusing of light. In some respects, however, calcite lenses bear evident disadvantages. Birefringence would cause double images at different depths, but this is not a problem for trilobites since the difference in the paths of the ordinary and extraordinary rays is less than the diameter of the receptor cells. Another point, not discussed hitherto, is that calcite fluoresces when illuminated with UV-A. Here we show experimentally that calcite lenses fluoresce, and we discuss why fluorescence does not diminish the optical quality of these lenses and the image formed by them. In the environments in which the trilobites lived, UV-A would not have been a relevant factor, and thus fluorescence would not have disturbed or confused their visual system. We also argue that whatever the reason that calcite was never again used successfully in the visual systems of aquatic arthropods, it was not fluorescence.

  19. Self-diffusion of carbon and oxygen in dolomite. (United States)

    Anderson, T. F.


    Self-diffusion of carbon and oxygen in dolomite was measured by isotopic exchange with CO2 at 645-785 C at 120-935 bars pressure. Several runs were also made with calcite under comparable experimental conditions. The principal findings of this study are that (1) the self-diffusion coefficients of both carbon and oxygen in dolomite are approximately 100 times larger than the values in calcite over the temperature range investigated and (2) oxygen self-diffusion in calcite is accelerated by high CO2 pressure.

  20. Nano sized clay detected on chalk particle surfaces

    DEFF Research Database (Denmark)

    Skovbjerg, Lone; Hassenkam, Tue; Makovicky, Emil


    adsorption takes place, are largely unknown. In this study, we have used atomic force microscopy (AFM) to show that the grain surfaces in offshore and onshore chalk are more heterogeneous than previously assumed. The particles are not simply calcite surfaces but are partially covered by clay that is only 1...... that in calcite saturated water, both the polar and the nonpolar functional groups adhere to the nano sized clay particles but not to calcite. This is fundamentally important information for the development of conceptual and chemical models to explain wettability alterations in chalk reservoirs...

  1. Late Quaternary palaeoenvironmental reconstruction from Lakes Ohrid and Prespa (Macedonia/Albania border using stable isotopes

    Directory of Open Access Journals (Sweden)

    M. J. Leng


    Full Text Available Here we present stable isotope data from three sediment records from lakes that lie along the Macedonian-Albanian border (Lake Prespa: 1 core, and Lake Ohrid: 2 cores. The records only overlap for the last 40 kyr, although the longest record contains the MIS 5/6 transition (Lake Ohrid. The sedimentary characteristics of both lakes differ significantly between the glacial and interglacial phases. At the end of MIS 6 Lake Ohrid's water level was low (high δ18Ocalcite and, although productivity was increasing (high calcite content, the carbon supply was mainly from inorganic catchment rock sources (high δ13Ccarb. During the last interglacial, calcite and TOC production and preservation increased, progressively lower δ18Ocalcite suggest increase in humidity and lake levels until around 115 ka. During ca. 80 ka to 11 ka the lake records suggest cold conditions as indicated by negligible calcite precipitation and low organic matter content. In Lake Ohrid, δ13Corg are complacent; in contrast, Lake Prespa shows consistently higher δ13Corg suggesting a low oxidation of 13C-depleted organic matter in agreement with a general deterioration of climate conditions during the glacial. From 15 ka to the onset of the Holocene, calcite and TOC begin to increase, suggesting lake levels were probably low (high δ18Ocalcite. In the Holocene (11 ka to present enhanced productivity is manifested by high calcite and organic matter content. All three cores show an early Holocene characterised by low δ18Ocalcite, apart from the very early Holocene phase in Prespa where the lowest δ18Ocalcite occurs at ca. 7.5 ka, suggesting a phase of higher lake level only in (the more sensitive Lake Prespa. From 6 ka, δ18Ocalcite suggest progressive aridification, in

  2. Characterization of Precipitated CaCO3 Synthesized from Dolomite (United States)

    Arifin, Zaenal; Fitria Apriliani, Nurul; Zainuri, Mochamad; Darminto, dan


    The precipitated CaCO3 has successfully been synthesized from dolomite. The influence of various temperature and carbonation rate on the morphology, crystal size, phase and structure of the carbonation products were studied. The particles resulted from this process have the crystal size 400-800 nm. The calcite phase wasformed inthe synthesis at 30°C with carbonation rate of 2 and 7 SCFH, and synthesis at 80 °C and 2 SCFH also produces calcite phase. Observations by SEM shows morphology of calcite as so-called schalenohedral.

  3. Basalts of the Khodzhirbulak Suite and Assessment their Feasibility for Basalt Fiber (Surkhantau Mountains, Southwestern Shoots of the Hissar Ridge

    Directory of Open Access Journals (Sweden)

    N. M. Khakberdyev


    Full Text Available The results of preliminary assessment of basalt of the Khodzhirbulakskoy Suite of Surkhantau Mountains for the basalt fiber production are presented. According to petrographic study, the rocks are described as basalts of amygdaloidal structure. On the base of content of the amount of glassy form and nodular calcite, three groups of basalts were identified. The inverse relationship between the bulk content of the volcanic rock and the content of calcite: the greater volume of volcanic rocks, the less content of calcite, and vice versa. The basalt material demonstrates average pH module of 3.52.

  4. The Vein-type Zn-(Pb, Cu, As, Hg) mineralization at Fedj Hassène orefield, North-Western Tunisia: Mineralogy, Trace Elements, Sulfur Isotopes and Fluid Inclusions

    National Research Council Canada - National Science Library

    Bejaoui, J; Bouhlel, S; Barca, D; Braham, A


    .... LA-ICP-MS analyses in sphalerites show mean contents of 0,84 wt% Fe, 0,14 wt% Cd and 0,02 wt% Mn Ore. Fluid inclusions study in calcite and sphalerite reveals one mineralizing fluid characterized...

  5. Effect of calcifying bacteria on permeation properties of concrete structures. (United States)

    Achal, V; Mukherjee, A; Reddy, M S


    Microbially enhanced calcite precipitation on concrete or mortar has become an important area of research regarding construction materials. This study examined the effect of calcite precipitation induced by Sporosarcina pasteurii (Bp M-3) on parameters affecting the durability of concrete or mortar. An inexpensive industrial waste, corn steep liquor (CSL), from starch industry was used as nutrient source for the growth of bacteria and calcite production, and the results obtained with CSL were compared with those of the standard commercial medium. Bacterial deposition of a layer of calcite on the surface of the specimens resulted in substantial decrease of water uptake, permeability, and chloride penetration compared with control specimens without bacteria. The results obtained with CSL medium were comparable to those obtained with standard medium, indicating the economization of the biocalcification process. The results suggest that calcifying bacteria play an important role in enhancing the durability of concrete structures.

  6. Authigenic Gypsum in Gas-Hydrate Associated Sediments from the East Coast of India (Bay of Bengal)

    Digital Repository Service at National Institute of Oceanography (India)

    Kocherla, M.

    Authigenic gypsum crystals, along with pyrite and carbonate mineralization, predominantly calcites were noticed in distinct intervals in a 32 m long piston core, collected in the gas hydrate-bearing sediments in the northern portion of the Krishna...

  7. Potential of bacteria-based repair solution as healing agent for porous network concrete

    NARCIS (Netherlands)

    Wiktor, V.A.C.; Sangadji, S.; Jonkers, H.M.; Schlangen, H.E.J.G.


    Bacterially induced calcium carbonate precipitation has received considerable attention for its potential application in enforcing or repairing construction material. The mechanism of bacterially mediated calcite precipitation in those studies is primarily based on the enzymatic hydrolysis of urea.

  8. Planktic foraminifera form their shells via metastable carbonate phases. (United States)

    Jacob, D E; Wirth, R; Agbaje, O B A; Branson, O; Eggins, S M


    The calcium carbonate shells of planktic foraminifera provide our most valuable geochemical archive of ocean surface conditions and climate spanning the last 100 million years, and play an important role in the ocean carbon cycle. These shells are preserved in marine sediments as calcite, the stable polymorph of calcium carbonate. Here, we show that shells of living planktic foraminifers Orbulina universa and Neogloboquadrina dutertrei originally form from the unstable calcium carbonate polymorph vaterite, implying a non-classical crystallisation pathway involving metastable phases that transform ultimately to calcite. The current understanding of how planktic foraminifer shells record climate, and how they will fare in a future high-CO2 world is underpinned by analogy to the precipitation and dissolution of inorganic calcite. Our findings require a re-evaluation of this paradigm to consider the formation and transformation of metastable phases, which could exert an influence on the geochemistry and solubility of the biomineral calcite.

  9. Interpretação do mecanismo de difusão no processo gás-sólido da reação de dessulfurização

    Directory of Open Access Journals (Sweden)

    Daniela Andresa Mortari


    Full Text Available The present paper aims to interpret the SO2 diffusion mechanism process for two different limestones: a calcite and a dolomite. In previous study, the apparent activation energies for sulfation reaction were between 3.03 and 4.45 kJ mol-1 for the calcite, and 11.24 kJ mol-1 for the dolomite. Using nitrogen porosimetry it was possible to observe that the dolomite presents mesopores of 0.03 μm, while the calcite presents mesopores of 0.01 μm. The evaluation of limestones porous structure together with their kinetic parameters, allowed concluding that the diffusion mechanism follows Fick law and Knudsen law for dolomite and calcite, respectively.

  10. Phosphorus retention in calcareous soils and the effect of organic matter on its mobility

    National Research Council Canada - National Science Library

    von Wandruszka, Ray


    A survey of the interactions between phosphorus (P) species and the components of calcareous soils shows that both surface reactions and precipitation take place, especially in the presence of calcite and limestone...

  11. Epibiotic community on the acorn barnacle (Balanus amphitrite) from a monsoon-influenced tropical estuary

    Digital Repository Service at National Institute of Oceanography (India)

    Sahoo, G.; Khandeparker, L.

    of the barnacle Balanus amphitrite: calcite crystal growth in a hydrogel. Crystal Growth & Design, 11(11), 5122-5130. 12   Khandeparker, L., A. Anil, S. Raghukumar (2003) Barnacle larval destination: piloting possibilities by bacteria and lectin interaction...

  12. Study of Factors Related to Magnetic Treatment of Calcium Carbonate Saturated Water

    National Research Council Canada - National Science Library

    Lambert, Kevin


    ..., calcium carbonate concentration and number of magnetic device attached. XRD of crystals gave relative proportions of calcite and aragonite present and XRF measured transition metals and elements known to substitute for calcium in scale...

  13. Interactions of Eu(III) with biogenic CaCO{sub 3} studied with TRLFS

    Energy Technology Data Exchange (ETDEWEB)

    Johnstone, Erik V.; Schmidt, Moritz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Surface Processes; Cherkouk, Andrea [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Biogeochemistry


    The interactions of Eu(III) with CaCO{sub 3} arising from biogenic origin was investigated by Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS). Biologically-induced precipitation via ureolysis was studied with the bacteria Sporosarcina pasteurii in the presence of Eu(III). Biomineralization occurred forming mixed phases of vaterite and calcite after one day that transformed over two weeks to pure calcite. Eu(III) was quantitatively removed from solution during mineral formation. TRLFS results show that after one day the Eu{sup 3+} is located in the vaterite phase. After one week, the Eu{sup 3+} was found primarily in the vaterite, despite calcite now being the predominant mineral, and a transition species was also formed. In the calcite two incorporated Eu{sup 3+} species were present: one substitutes at the Ca{sup 2+} site in the crystal lattice and the other is speculated to be associated with the organicmineral matrix.

  14. Light rare earth element systematics as a tool for investigating the petrogenesis of phoscorite-carbonatite associations, as exemplified by the Phalaborwa Complex, South Africa (United States)

    Milani, Lorenzo; Bolhar, Robert; Frei, Dirk; Harlov, Daniel E.; Samuel, Vinod O.


    In-situ trace element analyses of fluorapatite, calcite, dolomite, olivine, and phlogopite have been undertaken on representative phoscorite and carbonatite rocks of the Palaeoproterozoic Phalaborwa Complex. Textural and compositional characterization reveals uniformity of fluorapatite and calcite among most of the intrusions, and seems to favor a common genetic origin for the phoscorite-carbonatite association. Representing major repositories for rare earth elements (REE), fluorapatite and calcite exhibit tightly correlated light REE (LREE) abundances, suggesting that partitioning of LREE into these rock forming minerals was principally controlled by simple igneous differentiation. However, light rare earth element distribution in apatite and calcite cannot be adequately explained by equilibrium and fractional crystallization and instead favors a complex crystallization history involving mixing of compositionally distinct magma batches, in agreement with previously reported mineral isotope variability that requires open-system behaviour.

  15. Bioremediation of strontium (Sr) contaminated aquifer quartz sand based on carbonate precipitation induced by Sr resistant Halomonas sp. (United States)

    Achal, Varenyam; Pan, Xiangliang; Zhang, Daoyong


    Contamination of aquifers or sediments by radioactive strontium ((90)Sr) is a significant environmental problem. In the present study, microbially induced calcite precipitation (MICP) was evaluated for its potential to remediate strontium from aquifer quartz sand. A Sr resistant urease producing Halomonas sp. was characterized for its potential role in bioremediation. The bacterial strain removed 80% of Sr from soluble-exchangeable fraction of aquifer quartz sand. X-ray diffraction detected calcite, vaterite and aragonite along with calcite-strontianite (SrCO(3)) solid solution in bioremediated sample with indications that Sr was incorporated into the calcite. Scanning electron micrography coupled with energy-dispersive X-ray further confirmed MICP process in remediation. The study showed that MICP sequesters soluble strontium as biominerals and could play an important role in strontium bioremediation from both ecological and greener point of view. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Franconite, a new hydrated Na-Nb oxide mineral from Montreal Island, Quebec

    National Research Council Canada - National Science Library

    Jambor, J L; Sabina, A P; Roberts, A C; Bonardi, M; Ramik, R A; Sturman, B D


    The new mineral species franconite occurs as white 150-mu m globules on crystals of weloganite, calcite and quartz in vugs in a dawsonite-bearing sill in the Francon limestone quarry, Montreal, Quebec...

  17. Durability improvement assessment in different high strength ...

    Indian Academy of Sciences (India)

    -concrete can be constructed using microbial application that is able to precipitate the calcite. A new technique based on bio-mineralization process by which living organisms can produce minerals to harden or stiffen the existing tissues to ...