WorldWideScience

Sample records for calcite

  1. Nickel adsorption on chalk and calcite

    DEFF Research Database (Denmark)

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

    2014-01-01

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

  2. Interaction of alcohols with the calcite surface

    DEFF Research Database (Denmark)

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

    2015-01-01

    A clearer understanding of calcite interactions with organic molecules would contribute to a range of fields including harnessing the secrets of biomineralisation where organisms produce hard parts, increasing oil production from spent reservoirs, remediating contaminated soils and drinking water...

  3. Microbially Induced Calcite Precipitation Employing Environmental Isolates

    OpenAIRE

    Gunjo Kim; Heejung Youn

    2016-01-01

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

  4. Do organic ligands affect calcite dissolution rates?

    Science.gov (United States)

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

    2011-04-01

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

  5. Structural point defects in 'Iceland spar' calcite

    International Nuclear Information System (INIS)

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

  6. Carbon isotope fractionation in synthetic magnesian calcite

    Science.gov (United States)

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

    2006-03-01

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

  7. in situ Calcite Precipitation for Contaminant Immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Yoshiko Fujita; Robert W. Smith

    2009-08-01

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

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

    NARCIS (Netherlands)

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

    2012-01-01

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

  9. Molecular ordering of ethanol at the calcite surface

    DEFF Research Database (Denmark)

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

    2012-01-01

    dynamics (MD) simulations, the structuring on calcite of a layer of the simplest carbon chain molecule that contains an OH group, ethanol (CH 3-CH2-OH). We found evidence that EtOH forms a highly ordered structure at the calcite surface, where the first layer molecules bond with calcite. The ethanol...

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

    Science.gov (United States)

    Reddy, Michael M.

    2012-01-01

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

  11. Oxygen isotope fractionation in synthetic magnesian calcite

    Science.gov (United States)

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

    2004-08-01

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

  12. Magnesian calcite sorbent for carbon dioxide capture

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

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

  13. Recovery of crystallinity in ground calcite

    Energy Technology Data Exchange (ETDEWEB)

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

    1976-01-01

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

  14. Zinc isotope fractionation during adsorption on calcite

    Science.gov (United States)

    Dong, S.; Wasylenki, L. E.

    2013-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-02-01

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

  16. Global calcite cycling constrained by sediment preservation controls

    Science.gov (United States)

    Dunne, John P.; Hales, Burke; Toggweiler, J. R.

    2012-09-01

    We assess the global balance of calcite export through the water column and burial in sediments as it varies regionally. We first drive a comprehensive 1-D model for sediment calcite preservation with globally gridded field observations and satellite-based syntheses. We then reformulate this model into a simpler five-parameter box model, and combine it with algorithms for surface calcite export and water column dissolution for a single expression for the vertical calcite balance. The resulting metamodel is optimized to fit the observed distributions of calcite burial flux. We quantify the degree to which calcite export, saturation state, organic carbon respiration, and lithogenic sedimentation modulate the burial of calcite. We find that 46% of burial and 88% of dissolution occurs in sediments overlain by undersaturated bottom water with sediment calcite burial strongly modulated by surface export. Relative to organic carbon export, we find surface calcite export skewed geographically toward relatively warm, oligotrophic areas dominated by small, prokaryotic phytoplankton. We assess century-scale projected impacts of warming and acidification on calcite export, finding high sensitive to inferred saturation state controls. With respect to long-term glacial cycling, our analysis supports the hypothesis that strong glacial abyssal stratification drives the lysocline toward much closer correspondence with the saturation horizon. Our analysis suggests that, over the transition from interglacial to glacial ocean, a resulting ˜0.029 PgC a-1decrease in deep Atlantic, Indian and Southern Ocean calcite burial leads to slow increase in ocean alkalinity until Pacific mid-depth calcite burial increases to compensate.

  17. Origin of calcite in the glacigenic Virttaankangas complex

    Directory of Open Access Journals (Sweden)

    Nina M. Kortelainen

    2007-01-01

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

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

    OpenAIRE

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

    2005-01-01

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

  19. Sorption and desorption of arsenate and arsenite on calcite

    DEFF Research Database (Denmark)

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

    2008-01-01

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

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

    OpenAIRE

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

    2012-01-01

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

  1. Single-contact pressure solution creep on calcite monocrystals

    CERN Document Server

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

    2005-01-01

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

  2. The role of silicate surfaces on calcite precipitation kinetics

    DEFF Research Database (Denmark)

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

    2014-01-01

    , labradorite, olivine, basaltic glass and peridotite rock. Calcite saturation was achieved by mixing a CaCl2-rich aqueous solution with a NaHCO3-Na2CO3 aqueous buffer in mixed-flow reactors containing 0.5-2g of mineral, rock, or glass seeds. This led to an inlet fluid calcite saturation index of 0.6 and a p......H equal to 9.1. Although the inlet fluid composition, flow rate, and temperature were identical for all experiments, the onset of calcite precipitation depended on the identity of the seeds present in the reactor. Calcite precipitated instantaneously and at a constant rate in the presence of calcite...

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

    International Nuclear Information System (INIS)

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

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

    DEFF Research Database (Denmark)

    Schultz, Logan Nicholas

    In a saturated solution, submicrometer calcite (CaCO3) crystals recrystallize and coarsen to minimize surface area. The thermodynamic driving force is described by the Gibbs-Thomson equation, but the rates and mechanism are poorly understood. Calcite grain coarsening has many implications...... grain diameter: The small particle size was similar to coccolith elements in chalk. Calcite was aged in saturated solutions for up to 261 days at temperatures up to 200 °C. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and BET surface area data showed fundamental insight into grain...

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

    Science.gov (United States)

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

    2012-11-21

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

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

    Science.gov (United States)

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

    2012-04-01

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

  7. On the complex conductivity signatures of calcite precipitation

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-11-01

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

  8. Monoclinic deformation of calcite crystals at ambient conditions

    Science.gov (United States)

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

    2016-09-01

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

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

    Science.gov (United States)

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

    2011-10-01

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

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

    DEFF Research Database (Denmark)

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

    2014-01-01

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

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

    OpenAIRE

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

    2012-01-01

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

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

    Science.gov (United States)

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

    2016-03-01

    We have used density functional theory with the COSMO-RS implicit solvent model to predict the pKa for the deprotonation of bicarbonate to carbonate, i.e. HCO3- CO32- + H+, when HCO3- is included in, and adsorbed on, a calcite surface. We have used cluster models (80-100 atoms) to represent the flat {10.4} surface, acute steps, obtuse steps, two types of kinks on the acute step and two types of kinks on the obtuse steps. Based on the predicted pKa values, which range from -6.0 to 2.4 depending on the surface site, we conclude that bicarbonate deprotonates to carbonate when it is in calcite even when pH in solution is very low. This is true for all surface sites, even for solutions where 2.4 pH pH units lower than in aqueous solution, 10.35. This means that adsorbed carbonate is stable even when the concentration of dissolved CO32- is several orders of magnitude lower. This has a significant effect on surface charge and thus the behaviour of the calcite surface. Our results help explain the potential determining behaviour of the carbonate species in calcite-water systems, particularly in the pH range where the bicarbonate species dominates in water and where the carbonate species dominates at the surface, i.e. when 7.5 pH high temperature and pressure.

  13. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    DEFF Research Database (Denmark)

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

    1996-01-01

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

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

    Science.gov (United States)

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2016-09-01

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

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

    Science.gov (United States)

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

    2016-06-01

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

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

    Science.gov (United States)

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

    2015-07-01

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

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

    Science.gov (United States)

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

    2015-09-01

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

  19. Growth rate controlled barium partitioning in calcite and aragonite

    Science.gov (United States)

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

    2016-04-01

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

  20. Fracture-aperture alteration induced by calcite precipitation

    Science.gov (United States)

    Jones, T.; Detwiler, R. L.

    2013-12-01

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

  1. Tuning hardness in calcite by incorporation of amino acids

    Science.gov (United States)

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

    2016-08-01

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

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

    Science.gov (United States)

    Herwegh, Marco; Xiao, Xiaohui; Evans, Brian

    2003-07-01

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

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

    Directory of Open Access Journals (Sweden)

    G. J. van der Zwaan

    2007-07-01

    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.

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

    Directory of Open Access Journals (Sweden)

    L. J. de Nooijer

    2007-04-01

    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 calculated partition coefficient (0.1–0.4 was constant to within experimetnal 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.

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

    OpenAIRE

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

    2008-01-01

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

  6. Arsenite sorption and co-precipitation with calcite

    CERN Document Server

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

    2008-01-01

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

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

    Science.gov (United States)

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

    2016-07-01

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

  8. Earthworm-produced calcite granules: A new terrestrial palaeothermometer?

    Science.gov (United States)

    Versteegh, Emma A. A.; Black, Stuart; Canti, Matthew G.; Hodson, Mark E.

    2013-12-01

    In this paper we show for the first time that calcite granules, produced by the earthworm Lumbricus terrestris, and commonly recorded at sites of archaeological interest, accurately reflect temperature and soil water δ18O values. Earthworms were cultivated in an orthogonal combination of two different (granule-free) soils moistened by three types of mineral water and kept at three temperatures (10, 16 and 20 °C) for an acclimatisation period of three weeks followed by transfer to identical treatments and cultivation for a further four weeks. Earthworm-secreted calcite granules were collected from the second set of soils. δ18O values were determined on individual calcite granules (δ18Oc) and the soil solution (δ18Ow). The δ18Oc values reflect soil solution δ18Ow values and temperature, but are consistently enriched by 1.51 (± 0.12)‰ in comparison to equilibrium in synthetic carbonates. The data fit the equation 1000 ln α = [20.21 ± 0.92] (103 T-1) - [38.58 ± 3.18] (R2 = 0.95; n = 96; p < 0.0005). As the granules are abundant in modern soils, buried soils and archaeological contexts, and can be dated using U-Th disequilibria, the developed palaeotemperature relationship has enormous potential for application to Holocene and Pleistocene time intervals.

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

    Science.gov (United States)

    Naidu, Sonia; Scherer, George W

    2014-12-01

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

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

    Directory of Open Access Journals (Sweden)

    Vučinić Dušica R.

    2012-01-01

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

  11. 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

    2010-03-01

    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

  12. 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.

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

    Directory of Open Access Journals (Sweden)

    L. Beaufort

    2008-08-01

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

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

    Science.gov (United States)

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

    2008-08-01

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

  15. Study of Biomass Calcite as Fine Aggregate of Concrete

    Institute of Scientific and Technical Information of China (English)

    WANG Jian; YU Yan

    2012-01-01

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

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

    DEFF Research Database (Denmark)

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

    2016-01-01

    , 10.35. This means that adsorbed carbonate is stable even when the concentration of dissolved CO32− is several orders of magnitude lower. This has a significant effect on surface charge and thus the behaviour of the calcite surface. Our results help explain the potential determining behaviour...... even when pH in solution is very low. This is true for all surface sites, even for solutions where 2.4 ... and constrain surface complexation modelling and are especially useful for predicting behaviour in systems where experiments are difficult or impossible, such as at high temperature and pressure....

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

    Science.gov (United States)

    Mkhonto, D.; Sahai, N.

    2008-12-01

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

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

    Science.gov (United States)

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

    2000-10-01

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

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

    Science.gov (United States)

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

    2009-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-01-01

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

  1. Molecular simulation of oligomer inhibitors for calcite scale

    Institute of Scientific and Technical Information of China (English)

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

    2012-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Bakke, N.E.

    1996-12-31

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

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

    Science.gov (United States)

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

    2016-09-01

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

  4. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-09-02

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

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

    Science.gov (United States)

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

    2006-01-01

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

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

    Science.gov (United States)

    Breecker, D.

    2015-12-01

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

  7. 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.

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

    International Nuclear Information System (INIS)

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

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

    DEFF Research Database (Denmark)

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

    2011-01-01

    The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3h) and low concentrations of phosphate (⩽50μM). Sorption of phosphate on calcite was stud....... 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...

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

    CERN Document Server

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

    2016-01-01

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

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

    International Nuclear Information System (INIS)

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

  12. Uranium isotope fractionation during coprecipitation with aragonite and calcite

    Science.gov (United States)

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

    2016-09-01

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

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

    Science.gov (United States)

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

    2013-12-01

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

  14. 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

    2014-08-01

    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.

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

    Science.gov (United States)

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

    2016-04-15

    Zeta potential is a physicochemical parameter of particular importance in describing the surface electrical properties of charged porous media. However, the zeta potential of calcite is still poorly known because of the difficulty to interpret streaming potential experiments. The Helmholtz-Smoluchowski (HS) equation is widely used to estimate the apparent zeta potential from these experiments. However, this equation neglects the influence of surface conductivity on streaming potential. We present streaming potential and electrical conductivity measurements on a calcite powder in contact with an aqueous NaCl electrolyte. Our streaming potential model corrects the apparent zeta potential of calcite by accounting for the influence of surface conductivity and flow regime. We show that the HS equation seriously underestimates the zeta potential of calcite, particularly when the electrolyte is diluted (ionic strength ⩽ 0.01 M) because of calcite surface conductivity. The basic Stern model successfully predicted the corrected zeta potential by assuming that the zeta potential is located at the outer Helmholtz plane, i.e. without considering a stagnant diffuse layer at the calcite-water interface. The surface conductivity of calcite crystals was inferred from electrical conductivity measurements and computed using our basic Stern model. Surface conductivity was also successfully predicted by our surface complexation model.

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

    Science.gov (United States)

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

    2011-09-01

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

  17. Low-magnesium uranium-calcite with high degree of crystallinity and gigantic luminescence emission

    Energy Technology Data Exchange (ETDEWEB)

    Valle-Fuentes, Francisco-Jose [Instituto de Ceramica y Vidrio, CSIC. Cantoblanco, 28049 Madrid (Spain); Garcia-Guinea, Javier [Museo Nacional Ciencias Naturales, CSIC, 28006 Madrid (Spain)]. E-mail: guinea@mncn.csic.es; Cremades, Ana [Departmento Fisica de Materiales, Facultad de Fisicas, University Complutense de Madrid, 28040 Madrid (Spain); Correcher, Virgilio [CIEMAT, Laboratory Dosimetria de Radiaciones, 28040 Madrid (Spain); Sanchez-Moral, Sergio [Museo Nacional Ciencias Naturales, CSIC, 28006 Madrid (Spain); Gonzalez-Martin, Rafael [Museo Nacional Ciencias Naturales, CSIC, 28006 Madrid (Spain); Sanchez-Munoz, Luis [CIEMAT, Laboratory Dosimetria de Radiaciones, 28040 Madrid (Spain); Lopez-Arce, Paula [Getty Conservation Institute, 1200 Getty Center Drive, Suite 700, Los Angeles, CA 90049 (United States)

    2007-01-15

    Cabrera (Madrid) low-Mg calcites exhibit: (i) an unusual twofold elevation in X-ray diffraction pattern intensity; (ii) a 60-fold elevation of luminescence emission, compared to six common natural calcites selected for comparison purposes; (iii) a natural relatively high radiation level of circa 200 nSv h{sup -1} not detected in 1300 other calcites from the Natural History Museum of Madrid. Calcites were analysed by the X-ray diffraction powder method (XRD), cathodo-luminescence spectroscopy in scanning electron microscopy (CL-SEM), thermoluminescence (TL), differential thermal analysis (DTA), X-ray fluorescence spectrometry (XRF) and particle size distribution (PSD). The Cabrera calcite study shows: (i) helicoidally distributed steps along the (0 0 0 1) orientation; (ii) protuberance defects onto the (0 0 0 1) surface, observed by SEM; (iii) XRF chemical contents of 0.03% MgO, 0.013% of Y{sub 2}O{sub 3}, and 0.022% of U{sub 3}O{sub 8}, with accessory amounts of rare earth elements (REE); (iv) DTA dissociation temperature of 879 {sup o}C; (v) TL maxima peaks at 233 and 297 {sup o}C whose areas are 60 times compared to other calcites; (vi) spectra CL-SEM bands at 2.0 and 3.4 eV in the classic structure of Mn{sup 2+} activators; (vii) a twofold XRD pattern explained given that sample is a low-Mg calcite. The huge TL and CL emissions of the Cabrera calcite sample must be linked with the uranyl group presence. This intense XRD pattern in low-Mg calcites could bring into being analytical errors.

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

    Directory of Open Access Journals (Sweden)

    C. Neal

    2001-01-01

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

  19. Effect of Second-phase Particles on Static Adjustment of Calcite Grain Boundaries in Carbonate Mylonites

    Science.gov (United States)

    Ree, J.; Lee, S.; Jung, H.

    2010-12-01

    Static adjustment of grain boundaries during the waning stage of deformation with sustained heat (e.g. at the end of an orogeny) has not been studied much, although it is important for the interpretation of microstructural status during the main stage of deformation. We report here that static adjustment of calcite grain boundaries is dependent on second-phase particles in carbonate mylonites from the Geounri Shear Zone in the Taebaeksan Basin of South Korea. The carbonate mylonites consist of relic (porphyroclastic) calcites (120-400 μm) and dynamically recrystallized calcites (30-35 μm) with second-phase particles (15-20 μm) of quartz and phyllosilicates. Both calcite grains contain mechanical twins and the twins are wider (10-20 μm thick) in the relic calcites than in the dynamically recrystallized ones (1-3 μm thick). In the layers of carbonate mylonite with less than 3% of second phases, grain boundaries of calcites are straight with triple junctions. In contrast, calcite grain boundaries are lobate to wavy in the layers with more than 3% of second phases, suggesting dynamic grain boundary migration. Calcite grains in both layers show a strong lattice preferred orientation indicating dominant slip system of basal with minor one of rhomb . We interpret that the foam texture of calcite in the mylonite layers with less than 3% of second phases was produced during the waning stage of the main deformation with a sustained heat since both syntectonic and posttectonic chloritoid porphyroblasts occur in adjacent phyllonite layers in the shear zone. 3% volume fraction of second-phase particles might be a critical value above which deformation microstructures of the main phase were ‘frozen’ without static adjustment in our carbonate mylonites.

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

    Science.gov (United States)

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

    2010-04-01

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

  1. Distribution of Minor Elements in Calcite From the Unsaturated Zone at Yucca Mountain, Nevada

    Science.gov (United States)

    Marshall, B. D.; Whelan, J. F.

    2001-12-01

    Calcite is sporadically distributed in fractures and cavities in the volcanic rocks that form the 500- to 700-m-thick unsaturated zone at Yucca Mountain. Previous work has shown that the calcite precipitated from water moving downward through the unsaturated zone since the volcanic rocks were emplaced approximately 13 Ma. Calcite thus serves as a proxy for the chemistry and amounts of past percolation, two parameters that are important in predictions of the future behavior of the potential radioactive waste repository at Yucca Mountain. Latest calcite, which began forming between approximately 5 and 2 Ma, typically displays fine-scale growth zoning defined by distributions of Mn (inferred from cathodoluminescence), Mg, and Sr. Electron microprobe (EPMA) mapping of outermost calcite reveals Mg growth zoning1 and higher overall concentrations of Mg in late calcite than in older calcite. Micro X-ray fluorescence (micro-XRF) maps were obtained by slow rastering of the samples over a 100-watt X-ray source collimated through a final aperture of 100 μ m. Although the spatial resolution of the micro-XRF mapping is much less than that of EPMA, this technique reveals distributions of some elements to which EPMA is less sensitive. Micro-XRF maps show that Sr is spatially correlated with Mg; Sr concentrations range to 500 μ g/g at the resolution of the 100-μ m collimator. Because both Mg and Sr have similar calcite-water distribution coefficients much less than one, the Mg/Sr in calcite reflects the Mg/Sr of the water that precipitated the calcite. The distribution coefficient for Mn is greater than one and variations in Mn are not correlated with Mg and Sr. Covariation of Mg and Sr in the percolating water may be explained by reactions that affect the rate of uptake of chemical constituents from the overlying rock and soil, and/or evaporation. Late calcite has lower δ 13C values, probably due to a regional change from wetter to drier climate conditions. The higher Mg and

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

    Science.gov (United States)

    Andreassen, Kim Hovgaard; Sloth Osther, Palle Jörn

    2016-01-01

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

  3. Comparison of galvanic displacement and electroless methods for deposition of gold nanoparticles on synthetic calcite

    Indian Academy of Sciences (India)

    Chamarthi K Srikanth; P Jeevanandam

    2012-11-01

    Gold nanoparticles have been deposited on synthetic calcite substrate by galvanic displacement reaction and electroless deposition methods. A comparative study has shown that electroless deposition is superior compared to galvanic displacement reaction for uniform deposition of gold nanoparticles on calcite. Characterization of the samples, prepared by two different deposition methods, was carried out by X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy (FE–SEM) and diffuse reflectance spectroscopy (DRS) measurements. FE–SEM studies prove that smaller nanoparticles of gold are deposited uniformly on calcite if electroless deposition method was employed and DRS measurements show the characteristic surface plasmon resonance of gold nanoparticles.

  4. Calcium sulfoaluminate (Ye'elimite) hydration in the presence of gypsum, calcite, and vaterite

    Energy Technology Data Exchange (ETDEWEB)

    Hargis, Craig W. [Department of Civil and Environmental Engineering, University of California, Berkeley, CA (United States); Telesca, Antonio [School of Engineering, University of Basilicata, Potenza (Italy); Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu [Department of Civil and Environmental Engineering, University of California, Berkeley, CA (United States)

    2014-11-15

    Six calcium sulfoaluminate-based cementitious systems composed of calcium sulfoaluminate, calcite, vaterite, and gypsum were cured as pastes and mortars for 1, 7, 28 and 84 days. Pastes were analyzed with X-ray diffraction, thermogravimetric and differential thermal analyses. Mortars were tested for compressive strength, dimensional stability and setting time. Furthermore, pastes with a water/cementitious material mass ratio of 0.80 were tested for heat evolution during the first 48 h by means of isothermal conduction calorimetry. It has been found that: (1) both calcite and vaterite reacted with monosulfoaluminate to give monocarboaluminate and ettringite, with vaterite being more reactive; (2) gypsum lowered the reactivity of both carbonates; (3) expansion was reduced by calcite and vaterite, irrespective of the presence of gypsum; and (4) both carbonates increased compressive strength in the absence of gypsum and decreased compressive strength less in the presence of gypsum, with vaterite's action more effective than that of calcite.

  5. Phase transformation of Mg-calcite to aragonite in active-forming hot spring travertines

    Science.gov (United States)

    Greer, Heather F.; Zhou, Wuzong; Guo, Li

    2015-08-01

    A travertine specimen collected from the western part of Yunnan Province of China was subjected to microstructural analysis by powder X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. A new formation mechanism was proposed whereby polycrystalline rhombohedral particles of magnesium-containing calcite underwent a phase transformation into sheaf-like clusters of aragonite microrods. It is proposed that a high concentration of magnesium ions and embedded biological matter poisoned the growth of calcite and therefore instigated the phase transformation of the core of the rhombohedral calcite particles to an aragonite phase with a higher crystallinity. The single crystalline aragonite microrods with a higher density than the Mg-calcite nanocrystallites grew at the expense of the latter to generate sheaf-like clusters. This newly discovered formation mechanism is expected to enhance previous knowledge on this geologically important phase transformation from a morphology point of view.

  6. (U-Th)/He dating and He diffusion in calcite from veins and breccia

    Science.gov (United States)

    Gautheron, C.; Cros, A.; Pagel, M.; Berthet, P.; Tassan-Got, L.; Douville, E.; Pinna-Jamme, R.; Sarda, P.

    2013-12-01

    Knowledge of He retention in crystalline calcite is mandatory to estimate the possibility of (U-Th)/He dating of calcite. To this aim, fault-filling calcite crystals from the Eocene/Oligocene Gondrecourt graben, Paris Basin, Eastern France, have been sampled, based on their relatively old, Eocene-Oligocene, precipitation age and cold thermal history (agreement with the He-retentive character of calcite as determined by Copeland et al. (2007), and these ages were obtained for the most recently precipitated crystals. To better understand the large He-age scatter and why calcites precipitated earlier show younger ages, He diffusion experiments have been conducted on 10 Gondrecourt calcite fragments from 3 samples with He ages of 0.2 to 6 Ma. In addition, a crystallographic investigation by X-Ray Diffraction (XRD) performed on similar samples reveals that the crystal structure evolves with increasing temperature, showing with micro-cracks and cleavage opening. These XRD results indicate that, in fault-filling calcite, He retention is controlled by multiple diffusion domains (MDD, Lovera et al., 1991) with various sizes, and therefore, evolves through time with strong consequences on (U-Th)/He age. We thus interpret the Gondrecourt calcite (U-Th)/He age scatter of older samples as a consequence of cleavage opening due to a succession of calcite crystallization phases related to the deformation history. Finally, we propose that the crystallization age of a calcite crystal with a known thermal history can nevertheless be retrieved by the (U-Th)/He method provided the He diffusion pattern can be measured by careful step-heating degassing analysis. Copeland, P., Watson, E.B., Urizar, S.C., Patterson, D., Lapen, T.J., 2007. Alpha thermochronology of carbonates. Geochim. Cosmochim. Acta, 71: 4488-4511. Cros, A. Gautheron, C., Pagel, M., Berthet, P., Tassan-Got, L., Douville, E., Pinna-Jamme, R., Sarda, P., submitted GCA, He behavior in calcite filling viewed by (U

  7. Low-Temperature Plasticity of Naturally Deformed Calcite Rocks

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Optical, cathodoluminescence and transmission electron microscope (TEM) analyses were conducted onfour groups of calcite fault rocks, a cataclastic limestone, cataclastic coarse-grained marbles from two fault zones, and afractured mylonite. These fault rocks show similar microstructural characteristics and give clues to similar processes ofrock deformation. They are characterized by the structural contrast between macroscopic cataclastic (brittle) andmicroscopic mylonitic (ductile) microstructures. Intragranular deformation microstructures (i.e. deformation twins, kinkbands and microfractures) are well preserved in the deformed grains in clasts or in primary rocks. The matrix materials areof extremely fine grains with diffusive features. Dislocation microstructures for co-existing brittle deformation andcrystalline plasticity were revealed using TEM. Tangled dislocations are often preserved at the cores of highly deformedclasts, while dislocation walls form in the transitions to the fine-grained matrix materials and free dislocations, dislocationloops and dislocation dipoles are observed both in the deformed clasts and in the fine-grained matrix materials. Dynamicrecrystallization grains from subgrain rotation recrystallization and subsequent grain boundary migration constitute themajor parts of the matrix materials. Statistical measurements of densities of free dislocations, grain sizes of subgrains anddynamically recrystallized grains suggest an unsteady state of the rock deformation. Microstructural andcathodoluminescence analyses prove that fluid activity is one of the major parts of faulting processes. Low-temperatureplasticity, and thereby induced co-existence of macroscopic brittle and microscopic ductile microstmctures are attributedto hydrolytic weakening due to the involvement of fluid phases in deformation and subsequent variation of rock rheology.During hydrolytic weakening, fluid phases, e.g. water, enhance the rate of dislocation slip and climb, and

  8. Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein*

    OpenAIRE

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

    2011-01-01

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called “calcite and aragonite seas.” Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, so...

  9. Accurate measurement of the main refractive indices and thermo-optical coefficients of the calcite crystal

    Institute of Scientific and Technical Information of China (English)

    Shuang Zhao; Fuquan Wu; Haifeng Wang; Weigang Zhong; Xiuzhen Li; Hengjing Tang; Meng Shi; Hongyan Deng

    2007-01-01

    The main refractive indices of calcite crystal are measured by the means of auto-collimation, and the thermo-optical coefficients are calculated. The coefficient expression of Sellmeier equation is obtained by solving Sellmeier equation strictly and the refractive indices of different wavelengths are calculated, which accord with experimental esultsery well. The measured main refractive indices of calcite at 488-nm wavelength are identical with the values obtained by Sellmeier equation.

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

    Directory of Open Access Journals (Sweden)

    S. Bindschedler

    2014-01-01

    Full Text Available Calcitic nanofibres are ubiquitous habits of secondary calcium carbonate (CaCO3 accumulations observed in calcareous vadose environments. Despite their widespread occurrence, the origin of these nanofeatures remains enigmatic. Three possible mechanisms fuel the debate: (i purely physicochemical processes, (ii mineralization of rod-shaped bacteria, and (iii crystal precipitation on organic templates. Nanofibres can be either mineral (calcitic or organic in nature. They are very often observed in association with Needle Fibre Calcite (NFC, another typical secondary CaCO3 habit in terrestrial environments. This association has contributed to some confusion between both habits, however they are truly two distinct calcitic features and their recurrent association is likely to be an important fact to help understanding the origin of nanofibres. In this manuscript the different hypotheses that currently exist to explain the origin of calcitic nanofibres are critically reviewed. In addition to this, a new hypothesis for the origin of nanofibres is proposed based on the fact that current knowledge attributes a fungal origin to NFC. As this feature and nanofibres are recurrently observed together, a possible fungal origin for nanofibres which are associated with NFC is investigated. Sequential enzymatic digestion of the fungal cell wall of selected fungal species demonstrates that the fungal cell wall can be a source of organic nanofibres. The obtained organic nanofibres show a striking morphological resemblance when compared to their natural counterparts, emphasizing a fungal origin for part of the organic nanofibres observed in association with NFC. It is further hypothesized that these organic nanofibres may act as templates for calcite nucleation in a biologically-influenced mineralization process, generating calcitic nanofibres. This highlights the possible involvement of Fungi in CaCO3 biomineralization processes, a role still poorly documented at

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

    Directory of Open Access Journals (Sweden)

    Agus Haris Widayat

    2015-12-01

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

  12. Molecular dynamics simulation of adsorption of an oil-water-surfactant mixture on calcite surface

    Institute of Scientific and Technical Information of China (English)

    Lu Guiwu; Zhang Xuefen; Shao Changjin; Yang Hong

    2009-01-01

    An interface super molecular structure model for oil-water-surfactant mixture and calcite was established. By using a molecular dynamics method, the effects of rhamnolipid, sodium dodecyl benzene sulfonate and sodium hexadecyl sulfonate on the interface adsorption behavior of oil molecules were investigated. It was found that these three surfactants could reduce oil-calcite interface binding energy, and play a role of oil-displacing agent.

  13. Origin of sulfate in barite and calcite cements in the Jebel Madar salt dome (Oman)

    Science.gov (United States)

    Vandeginste, V.; John, C. M.; Gilhooly, W. P.

    2012-12-01

    Jebel Madar is a 500-m high mountain rising in the desert at the Oman Foothills. The Jebel consists of Triassic to Cretaceous carbonate host rocks forming the carapace of a salt dome. Halokinesis caused major fracturing and faulting at Jebel Madar, and the resulting structures acted as the main pathways for fluids that generated diagenetic cements composed of both barite and calcite. The spatial distribution of calcite and barite occurrences shows that calcite is formed in large abundance along the three main faults, whereas barite is more concentrated along faults further away from the three main ones. The stable carbon and oxygen isotope composition of calcite and fluid inclusion data from both calcite and barite show a distinct evolution of the fluid with a highly saline component towards more mixing with meteoric water. This is in agreement with clumped isotopes data on calcite cements indicating an evolution towards lower temperatures, consistent with doming of the Jebel and greater input of lower-temperature descending meteoric fluids. Here, we present sulphur and oxygen isotopic data on barite that suggest a link between the barite formation and the Precambrian salt underlying Jebel Madar. The average δ34S measured in barite is 33‰ CDT (1σ = 5‰; n = 33), which falls at the lower end of the δ34S range reported for the Ara Group anhydrite. The average δ18O in the same barite samples is 23‰ VSMOW (1σ = 2‰; n = 33). Data from the barite will be compared with sulphur isotopes from the carbonate-associate sulfate in the calcite cements. The overall goal of our research is to gain a better insight in the formation process of barite and calcite in Jebel Madar and its link with salt tectonics. We would like to acknowledge the financial support of QCCSRC (funded jointly by Qatar Petroleum, Shell and the Qatar Science & Technology Park) and the GSA Laubach fund for this study.

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

    DEFF Research Database (Denmark)

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

    2010-01-01

    adsorption on calcite relative to OH from water and the consequences of the differences in interaction on crystal growth and dissolution. A combination of atomic force microscopy (AFM) and molecular dynamics (MD) simulations showed that EtOH attachment on calcite is stronger than HOH binding...... transport to and from the mineral surface, confining it to specific locations, thus providing the organism with control for biomineral morphology....

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

    Science.gov (United States)

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

    2012-11-01

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

  16. NMR characterization of hydrocarbon adsorption on calcite surfaces: a first principles study.

    Science.gov (United States)

    Bevilaqua, Rochele C A; Rigo, Vagner A; Veríssimo-Alves, Marcos; Miranda, Caetano R

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca(2+). Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for (43)Ca, (13)C, and (17)O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  17. NMR characterization of hydrocarbon adsorption on calcite surfaces: a first principles study.

    Science.gov (United States)

    Bevilaqua, Rochele C A; Rigo, Vagner A; Veríssimo-Alves, Marcos; Miranda, Caetano R

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca(2+). Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for (43)Ca, (13)C, and (17)O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated. PMID:25429955

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

    Indian Academy of Sciences (India)

    E Venkateshwar Rao; M Ramakrishna Murthy

    2008-04-01

    Experimental investigations on the defect sub-structure and surface modifications, brought about by He+ ion-bombardment of calcite cleavages (100), have been carried out. Optical and scanning electron microscopic investigations revealed drastic modifications on the surface morphology, local symmetry and defect concentration. Additional structural defects on ion-bombardment of calcite surfaces also have been observed. Changes in shape and form of chemical etch pits are found to be a function of ion-beam energy, as studied by optical microscopy. Radiation damage in calcite has been attributed mainly due to desorption of CO$^{-2}_{3}$ ions from the calcite surfaces, on irradiation. Measurements of surface conductivity on irradiated calcite surfaces have been made employing a four-probe technique. Enhancement of surface conductivity has been considered to be due to an increase in concentration of CO$^{-2}_{3}$ ions formed, on ion irradiation and subsequent thermal stimulation. Planar plastic anisotropy has been studied on irradiated calcite cleavages by measurement of microhardness.

  19. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    Energy Technology Data Exchange (ETDEWEB)

    Bevilaqua, Rochele C. A.; Miranda, Caetano R. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Rigo, Vagner A. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Universidade Tecnológica Federal do Paraná, UTFPR, Cornélio Procópio, PR (Brazil); Veríssimo-Alves, Marcos [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Departamento de Física, ICEx, Universidade Federal Fluminense, UFF, Volta Redonda, RJ (Brazil)

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca{sup 2+}. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO{sub 3} (101{sup ¯}4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for {sup 43}Ca, {sup 13}C, and {sup 17}O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  20. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    International Nuclear Information System (INIS)

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca2+. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for 43Ca, 13C, and 17O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated

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

    Science.gov (United States)

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

    2009-04-01

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

  2. Tropical Silurian Paleotemperatures from Clumped Isotope Analysis of Coexisting Dolomite and Calcite

    Science.gov (United States)

    Winkelstern, I. Z.; Lohmann, K. C.

    2013-12-01

    In many instances, pervasive diagenetic alteration of original material prevents the use of quantitative climate proxies on Paleozoic or older rocks. As an inherently diagenetic phase, dolomite may provide a more resilient paleotemperature resource. The Δ47 carbonate clumped isotope thermometer has been shown to be an accurate paleothermometer and, in a limited way, has been shown to be applicable to dolomites. The shallow water carbonates of the Pipe Creek Jr. Reef in central Indiana offer an opportunity to test the viability of the technique in ancient dolomite. After formation in the late Silurian, a sea level drop resulted in a diagenetic sequence of meteoric phreatic alteration of marine cement and biotic components, which included precipitation of dolomite cements inter-grown within the meteoric phreatic calcite cement. This was post-dated by a coarse void filling calcite spar formed at burial temperatures of ~100°C (based on fluid inclusion analysis). Preliminary analyses of coexisting dolomite and calcite suggest that near-surface temperatures are preserved in dolomites despite having experienced elevated thermal diagenetic effects.. In contrast, co-existing early-formed calcites exhibit resetting of earth surface temperatures to elevated values. Δ47 measurements in dolomites yield temperatures around 30°C using the Guo et al., (2009) theoretical calibration. This contrasts with analyses of early (original) and late (hydrothermal) calcites, which record temperatures greater than ~80°C using the Δ47-calcite calibration of Dennis and Schrag (2010). These data support the hypothesis that dolomite can be a more resilient paleotemperature proxy relative to calcite in deep-time studies. Temperatures from dolomites compare reasonably with other late Silurian paleoclimate studies, and offer insight into regional-scale paleoclimate.

  3. The influence of final repository relevant electrolyte on the interaction of trivalent lanthanides and actinides with calcite; Der Einfluss endlagerrelevanter Elektrolyte auf die Wechselwirkung dreiwertiger Lanthanide und Actinide mit Calcit

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, Sascha

    2015-10-21

    Calcite, a naturally occurring and very abundant mineral, is considered a potential retentive geochemical barrier regarding nuclear waste disposal. In this work, the reactivity of calcite towards trivalent Ln and An has been determined by spectroscopic, microscopic and X-ray scattering techniques. This, in connection with the use of luminescent probes Eu(III) and Cm(III), allowed for the understanding of electrolyte influences on the retention potential of calcite.

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

    Science.gov (United States)

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

    2002-11-26

    Shifts in the MgCa ratio of seawater driven by changes in midocean ridge spreading rates have produced oscillations in the mineralogy of nonskeletal carbonate precipitates from seawater on time scales of 10(8) years. Since Cambrian time, skeletal mineralogies of anatomically simple organisms functioning as major reef builders or producers of shallow marine limestones have generally corresponded in mineral composition to nonskeletal precipitates. Here we report on experiments showing that the ambient MgCa ratio actually governs the skeletal mineralogy of some simple organisms. In modern seas, coralline algae produce skeletons of high-Mg calcite (>4 mol % MgCO(3)). We grew three species of these algae in artificial seawaters having three different MgCa ratios. All of the species incorporated amounts of Mg into their skeletons in proportion to the ambient MgCa ratio, mimicking the pattern for nonskeletal precipitation. Thus, the algae calcified as if they were simply inducing precipitation from seawater through their consumption of CO(2) for photosynthesis; presumably organic templates specify the calcite crystal structure of their skeletons. In artificial seawater with the low MgCa ratio of Late Cretaceous seas, the algae in our experiments produced low-Mg calcite (MgCO(3)), the carbonate mineral formed by nonskeletal precipitation in those ancient seas. Our results suggest that many taxa that produce high-Mg calcite today produced low-Mg calcite in Late Cretaceous seas. PMID:12399549

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-12-01

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

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

    DEFF Research Database (Denmark)

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

    2012-01-01

    The competitive adsorption of arsenate and phosphate onto calcite was studied in batch experiments using calcite-equilibrated solutions. The solutions had circum-neutral pH (7–8.3) and covered a wide span in the activity of Ca2+ and View the MathML source. The results show that the adsorption...... that adsorption of arsenate onto calcite is of minor importance in most groundwater aquifers, as phosphate is often present at concentration levels sufficient to significantly reduce arsenate adsorption. The CD-MUSIC model for calcite was used successfully to model adsorption of arsenate and phosphate separately...

  7. Strontium isotope evolution of pore water and calcite in the Topopah Spring Tuff, Yucca Mountain, Nevada

    International Nuclear Information System (INIS)

    Pore water in the Topopah Spring Tuff has a narrow range of (delta)87Sr values that can be calculated from the (delta)87Sr values of the rock considering advection through and reaction with the overlying nonwelded tuffs of the PTn. This model can be extended to estimate the variation of (delta)87Sr in the pore water through time; this approximates the variation of (delta)87Sr measured in calcite fracture coatings. In samples of calcite where no silica can be dated by other methods, strontium isotope data may be the only method to determine ages. In addition, other Sr-bearing minerals in the calcite and opal coatings, such as fluorite, may be dated using the same model

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Jones, B. [Univ. of Alberta, Edmonton, Alberta (Canada). Dept. of Earth and Atmospheric Sciences; Renault, R.W. [Univ. of Saskatchewan, Saskatoon, Saskatchewan (Canada). Dept. of Geological Sciences

    1998-09-01

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

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

    Science.gov (United States)

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

    2016-08-01

    Coccolithophore contributions to the global marine carbon cycle are regulated by the calcite content of their scales (coccoliths) and the relative cellular levels of photosynthesis and calcification rates. All three of these factors vary between coccolithophore species and with response to the growth environment. Here, water samples were collected in the northern basin of the South China Sea (SCS) during summer 2014 in order to examine how environmental variability influenced species composition and cellular levels of calcite content. Average coccolithophore abundance and their calcite concentration in the water column were 11.82 cells mL-1 and 1508.3 pg C mL-1, respectively, during the cruise. Water samples can be divided into three floral groups according to their distinct coccolithophore communities. The vertical structure of the coccolithophore community in the water column was controlled by the trophic conditions, which were regulated by mesoscale eddies across the SCS basin. The evaluation of coccolithophore-based calcite in the surface ocean also showed that three key species in the SCS (Emiliania huxleyi, Gephyrocapsa oceanica, Florisphaera profunda) and other larger, numerically rare species made almost equal contributions to total coccolith-based calcite in the water column. For Emiliania huxleyi biometry measurements, coccolith size positively correlated with nutrients (nitrate, phosphate), and it is suggested that coccolith length is influenced by light and nutrients through the regulation of growth rates. Larger-sized coccoliths were also linked statistically to low pH and calcite saturation states; however, it is not a simple cause and effect relationship, as carbonate chemistry was strongly co-correlated with the other key environmental factors (nutrients, light).

  11. Determination of aragonite trace element partition coefficients from speleothem calcite-aragonite transitions

    Science.gov (United States)

    Wassenburg, Jasper A.; Scholz, Denis; Jochum, Klaus Peter; Cheng, Hai; Oster, Jessica; Immenhauser, Adrian; Richter, Detlev K.; Haeger, Tobias; Hoffmann, Dirk; Breitenbach, Sebastian F. M.

    2016-04-01

    Speleothem trace element variability has often been linked to environmental changes. While research has focused on element incorporation into speleothem calcite, our current knowledge of trace element variability in speleothem aragonite is limited to a few studies only. Here we present, to our knowledge, for the first time quantitative estimates of distribution coefficients for speleothem aragonite (DMg, DBa, DSr, and DU). These were derived from ten calcite-to-aragonite transitions from seven speleothems from Morocco, Germany, Spain, France and India. Our calculations indicate the following distribution coefficients: DMg = 1.01E-04 ± 9.0E-05, DBa(Ar) = 0.91 ± 0.53, DSr(Ar) = 1.38 ± 0.53, and DU(Ar) = 6.26 ± 4.53. These results are discussed in the context of speleothem growth rates, Rayleigh distillation effects, temperature, drip water elemental composition and drip water pH. We conclude that speleothem aragonite DMg(Ar) is below one, DSr(Ar) is close to unity, and DU(Ar) is above one. For DBa(Ar), such a conclusion is difficult. Speleothem growth rate may affect aragonite DSr in samples forming at a growth rate lower than 20 μm/a. Our results also indicate that calcite DSr and calcite DBa are affected by the Mg content of calcite. This has important implications for studies attempting to quantify processes like prior calcite precipitation. In particular, DSr and DBa cannot be transferred from caves developed within a limestone host rock to caves developed within a dolostone host rock.

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

    Institute of Scientific and Technical Information of China (English)

    Danhua Lou; Fengjiu Sun; Lijuan Li

    2007-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Hristova E.

    2003-01-01

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

  14. U and Sr Isotopes in ground water and calcite, Yucca Mountain, Nevada: Evidence against upwelling water

    Science.gov (United States)

    Stuckless, J.S.; Peterman, Z.E.; Muhs, D.R.

    1991-01-01

    Hydrogenic calcite and opaline silica deposits in fault zones at Yucca Mountain, Nevada, have created considerable public and scientific controversy because of the possible development of a high-level nuclear waste repository at this location. Strontium and uranium isotopic compositions of hydrogenic materials were used to test whether the veins could have formed by upwelling of deep-seated waters. The vein deposits are isotopically distinct from ground water in the two aquifers that underlie Yucca Mountain, indicating that the calcite could not have precipitated from ground water. The data are consistent with a surficial origin for the hydrogenic deposits.

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

    DEFF Research Database (Denmark)

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

    2010-01-01

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

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

    DEFF Research Database (Denmark)

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

    2014-01-01

    We have used density functional theory to predict the ion exchange energies for divalent cations Ni(2+), Sr(2+), Cd(2+), and Pb(2+) into a calcite {10.4} surface in equilibrium with water. Exchange energies were calculated for substitution into the topmost surface layer, at the mineral-fluid inte......We have used density functional theory to predict the ion exchange energies for divalent cations Ni(2+), Sr(2+), Cd(2+), and Pb(2+) into a calcite {10.4} surface in equilibrium with water. Exchange energies were calculated for substitution into the topmost surface layer, at the mineral...

  17. Not all calcite ballast is created equal: differing effects of foraminiferan and coccolith calcite on the formation and sinking of aggregates

    Directory of Open Access Journals (Sweden)

    K. Schmidt

    2013-09-01

    Full Text Available Correlation between particulate organic carbon (POC and calcium carbonate sinking through the deep ocean has led to the idea that ballast provided by calcium carbonate is important for the export of POC from the surface ocean. While this idea is certainly to some extent true, it is worth considering in more nuance, for example, examining the different effects on the aggregation and sinking of POC of small, non-sinking calcite particles like coccoliths and large, rapidly sinking calcite like planktonic foraminiferan tests. We have done that here in a simple experiment carried out in roller tanks that allow particles to sink continuously without being impeded by container walls. Coccoliths were efficiently incorporated into aggregates that formed during the experiment, increasing their sinking speed compared to similarly sized aggregates lacking added calcite ballast. The foraminiferan tests, which sank as fast as 700 m d−1, became associated with only very minor amounts of POC. In addition, when they collided with other, larger, foraminferan-less aggregates, they fragmented them into two smaller, more slowly sinking aggregates. While these effects were certainly exaggerated within the confines of the roller tanks, they clearly demonstrate that calcium carbonate ballast is not just calcium carbonate ballast- different forms of calcium carbonate ballast have notably different effects on POC aggregation, sinking, and export.

  18. Intra-skeletal calcite in a live-collected Porites sp.: Impact on environmental proxies and potential formation process

    Science.gov (United States)

    Lazareth, Claire E.; Soares-Pereira, Caroline; Douville, Eric; Brahmi, Chloé; Dissard, Delphine; Le Cornec, Florence; Thil, François; Gonzalez-Roubaud, Cécile; Caquineau, Sandrine; Cabioch, Guy

    2016-03-01

    Geochemical proxies measured in the carbonate skeleton of tropical coral Porites sp. have commonly been used to reconstruct sea surface temperature (SST) and more recently seawater pH. Nevertheless, both reconstructed SST and pH depend on the preservation state of the skeleton, here made of aragonite; i.e., diagenetic processes and its related effects should be limited. In this study, we report on the impact of the presence of intra-skeletal calcite on the skeleton geochemistry of a live-collected Porites sp. The Porites skeleton preservation state was analyzed using X-ray diffraction and scanning electron microscopy. Sr/Ca, Mg/Ca, U/Ca, Ba/Ca, Li/Mg, and B/Ca ratios were measured at a monthly and yearly resolution using quadrupole ICP-MS and multi-collector ICP-MS. The δ11B signatures and the calcite percentages were acquired at a yearly timescale. The coral colony presents two parts, one with less than 3% calcite (referred to as "no-calcite" skeleton), the other one, corresponding to the skeleton formed during the last 4 years of growth, with calcite percentages varying from 13% to 32% (referred to as "with calcite" skeleton). This intra-skeletal calcite replaces partly or completely numerous centers of calcification (COCs). All investigated geochemical tracers are significantly impacted by the presence of calcite. The reconstructed SST decreases by about 0.1 °C per calcite-percent as inferred from the Sr/Ca ratio. Such impact reaches up to 0.26 °C per calcite-percent for temperature deduced from the Li/Mg ratio. So, less than 5% of such intra-skeletal calcite does not prevent SST reconstructions using Sr/Ca ratio, but the percentage and type of calcite have to be determined before fine SST interpretation. Seawater pH reconstruction inferred from boron isotopes drop by about -0.011 pH-unit per calcite-percent. Such sensitivity to calcite presence is particularly dramatic for fine paleo-pH reconstructions. Here we suggest that after being brought to shallow

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

    Directory of Open Access Journals (Sweden)

    D. K. Richter

    2010-07-01

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

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

    Science.gov (United States)

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

    2013-08-01

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

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    , the present study aims to identify a broadly applicable precipitation modelling approach. The study uses two experimental platforms applied to calcite precipitating from synthetic aqueous solutions to identify and validate the model approach. Firstly, dynamic pH titration tests are performed to define...

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

    DEFF Research Database (Denmark)

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

    2010-01-01

    the starting configuration consists of a complete monolayer of water at the surface. The computational results are in good agreement with the results from atomic force microscopy experiments where it is observed that a layer of ethanol remains attached to the calcite surface, decreasing its ability to...

  3. Modelling how incorporation of divalent cations affects calcite wettability–implications for biomineralisation and oil recovery

    Science.gov (United States)

    Andersson, M. P.; Dideriksen, K.; Sakuma, H.; Stipp, S. L. S.

    2016-01-01

    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase. PMID:27352933

  4. Modelling how incorporation of divalent cations affects calcite wettability-implications for biomineralisation and oil recovery.

    Science.gov (United States)

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

    2016-01-01

    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase. PMID:27352933

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

    DEFF Research Database (Denmark)

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

    2008-01-01

    The use of calcite (CaCO3) as a substrate for a permeable reactive barrier (PRB) for removing fluoride from contaminated groundwater is proposed and is illustrated by application to groundwater contaminated by spent potliner leachate (SPL), a waste derived from the aluminium smelting process...

  6. Modelling how incorporation of divalent cations affects calcite wettability–implications for biomineralisation and oil recovery

    Science.gov (United States)

    Andersson, M. P.; Dideriksen, K.; Sakuma, H.; Stipp, S. L. S.

    2016-06-01

    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase.

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

    DEFF Research Database (Denmark)

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

    2008-01-01

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

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

    DEFF Research Database (Denmark)

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

    2009-01-01

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

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

    DEFF Research Database (Denmark)

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

    2009-01-01

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

  10. Unusual biogenic calcite structures in two shallow lakes, James Ross Island, Antarctica

    Science.gov (United States)

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

    2016-01-01

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

  11. 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...... in sorption edges, pKa’s and geometry of the two anions. The adsorption of arsenate and phosphate in the single sorbate systems was modelled successfully using either the constant capacitance model (CCM) for calcite or the CD-MUSIC model for calcite. Generally the models capture the variation in arsenate...

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

    Science.gov (United States)

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

    2016-01-01

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

  13. Ca-Mg inter-diffusion in synthetic polycrystalline dolomite-calcite aggregate at elevated temperatures and pressure

    Science.gov (United States)

    Huang, Wuu-Liang; Liu, Teh-Ching; Shen, Pouyan; Hsu, Allen

    2009-03-01

    This study measures the reaction rate of dolomite and aragonite (calcite) into Mg-calcite at 800, 850, and 900°C and 1.6 GPa. The dry synthetic dolomite-aragonite aggregate transformed very rapidly into dolomite-calcite polycrystalline aggregate while Mg-calcites formed at a relatively slow rate, becoming progressively richer in Mg with run time. We modeled the reaction progress semi-empirically by the first-order rate law. The temperature dependence of the overall transport rate of MgCO3 into calcite can be described by the kinetic parameters ( E = 231.7 kJ/mol and A o = 22.69 h-1). Extrapolation using the Arrhenius equation to the conditions during exhumation of UHPM rocks indicates that the reaction of dolomite with aragonite into Mg-saturated calcite can be completed as the P-T path enters the Mg-calcite stability field in a geologically short time period (340°C and >10 My). SEM-EDS analysis of individual calcite grains shows compositional gradients of Mg in the calcite grains. The Mg-Ca inter-diffusion coefficient at 850°C is around 1.68 × 10-14 m2/sec if diffusion is the major control of the reaction. The calculated closure temperatures for Ca-Mg inter-diffusion as a function of cooling rate and grain size reveal that Ca/Mg resetting in calcite in a dry polycrystalline carbonate aggregate (with grain size around 1 mm) may not occur at temperatures below 480°C at a geological cooling rate around 10°C/My, unless other processes, such as short-circuit interdiffusion along grain boundaries and dislocations, are involved.

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

    Science.gov (United States)

    Fein, Jeremy B.; Walther, John V.

    1987-06-01

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

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

    Science.gov (United States)

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2014-05-01

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

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

    Science.gov (United States)

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

    2010-02-01

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

  18. Environmental controls for the precipitation of different fibrous calcite cement fabrics

    Science.gov (United States)

    Ritter, Ann-Christine; Wiethoff, Felix; Neuser, Rolf D.; Richter, Detlev K.; Immenhauser, Adrian

    2016-04-01

    Abiogenic calcite cements are widely used as climate archives. They can yield information on environmental change and climate dynamics at the time when the sediment was lithified in a (marine) diagenetic environment. Radiaxial-fibrous (RFC) and fascicular-optic fibrous (FOFC) calcite cements are two very common and similar pore-filling cement fabrics in Palaeozoic and Mesozoic carbonate rocks (Richter et al., 2011) and in Holocene Mg-calcitic speleothems (Richter et al., 2015). Both fabrics are characterised by distinct crystallographic properties. Current research has shown that these fabrics are often underexplored and that a careful combination of conservative and innovative proxies allows for a better applicability of these carbonate archives to paleoenvironmental reconstructions (Ritter et al., 2015). A main uncertainty in this context is that it is still poorly understood which parameters lead to the formation of either RFC or FOFC and if differential crystallographic parameters affect proxy data from these fabrics. This study aims at a better understanding of the environmental factors that may control either RFC or FOFC precipitation. Therefore, suitable samples (a stalagmite and a Triassic marine cement succession), each with clearly differentiable layers of RFC and FOFC, were identified and analysed in high detail using a multi-proxy approach. Detailed thin section and cathodoluminescence analysis of the samples allowed for a precise identification of layers consisting solely of either RFC or FOFC. Isotopic (δ13C, δ18O) as well as trace elemental compositions have been determined and the comparison of data obtained from these different carbonate archives sheds light on changes in environmental parameters during RFC or FOFC precipitation. References: Richter, D.K., et al., 2011. Radiaxial-fibrous calcites: A new look at an old problem. Sedimentary Geology, 239, 26-36 Richter, D.K., et al., 2015. Radiaxial-fibrous and fascicular-optic Mg-calcitic cave

  19. Calibration of the calcite-water oxygen-isotope geothermometer at Devils Hole, Nevada, a natural laboratory

    Science.gov (United States)

    Coplen, T.B.

    2007-01-01

    The ??18O of ground water (-13.54 ?? 0.05 ???) and inorganically precipitated Holocene vein calcite (+14.56 ?? 0.03 ???) from Devils Hole cave #2 in southcentral Nevada yield an oxygen isotopic fractionation factor between calcite and water at 33.7 ??C of 1.02849 ?? 0.00013 (1000 ln ??calcite-water = 28.09 ?? 0.13). Using the commonly accepted value of ???(??calcite-water)/???T of -0.00020 K-1, this corresponds to a 1000 ln ??calcite-water value at 25 ??C of 29.80, which differs substantially from the current accepted value of 28.3. Use of previously published oxygen isotopic fractionation factors would yield a calcite precipitation temperature in Devils Hole that is 8 ??C lower than the measured ground water temperature. Alternatively, previously published fractionation factors would yield a ??18O of water, from which the calcite precipitated, that is too negative by 1.5 ??? using a temperature of 33.7 ??C. Several lines of evidence indicate that the geochemical environment of Devils Hole has been remarkably constant for at least 10 ka. Accordingly, a re-evaluation of calcite-water oxygen isotopic fractionation factor may be in order. Assuming the Devils Hole oxygen isotopic value of ??calcite-water represents thermodynamic equilibrium, many marine carbonates are precipitated with a ??18O value that is too low, apparently due to a kinetic isotopic fractionation that preferentially enriches 16O in the solid carbonate over 18O, feigning oxygen isotopic equilibrium.

  20. 3D Mapping of calcite and a demonstration of its relevance to permeability evolution in reactive fractures

    Science.gov (United States)

    Ellis, Brian R.; Peters, Catherine A.

    2016-09-01

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

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

    Science.gov (United States)

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

    2014-06-01

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

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

    DEFF Research Database (Denmark)

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

    2014-01-01

    asymmetric for the coccoliths and the synthetic calcite prepared using the carbonation method. It can be very well fitted by two peaks: a narrow Lorenzian at lower frequency and a broader Gaussian at higher frequency. These two samples both have a high specific surface area. Density functional theory...... broadening from macroscopic dielectric effects. We detect water adsorbed on the high surface area synthetic calcite, which permits observation of the chemistry of thin liquid films on calcite using transmission infrared spectroscopy. The combination of infrared spectroscopy and density functional theory also...

  3. Experimental Research on Microscopic Indicators of Temperature's Returning-to-Zero in Deformation of Calcite and Discussions of Correlation Problem

    Institute of Scientific and Technical Information of China (English)

    Yao Daquan; Zhai Hongtao

    2005-01-01

    In order to determine the degree of returning-to-zero of temperatures of deformed calcite, a series of rock-breaking experiments were designed to test calcite-rich limestone samples under fixed confining pressures and different temperatures. The consolidated deformed samples in their initial state were observed under a microscope and the microscopic indicators in different zero-returning states were put forward, thus providing a microscopic foundation for evaluation of reliability of dating values of deformation in calcite. At last, the correction of dating values of deformation for samples whose temperature has not yet returned to zero is discussed.

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

    Science.gov (United States)

    Busenberg, Eurybiades; Plummer, L. Niel

    1989-01-01

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

  5. Arsenic uptake by gypsum and calcite: Modeling and probing by neutron and x-ray scattering

    CERN Document Server

    Fernandez-Martinez, Alejandro; Roman-Ross, Gabriela; Johnson, Mark R; Bardelli, Fabrizio; Turrillas, Xavier; Charlet, Laurent

    2006-01-01

    Here we report on two structural studies performed on As-doped gypsum (CaSO4 2H2O) and calcite (CaCO3), using neutron (D20-ILL) and x-ray (ID11-ESRF) diffraction data and EXAFS (BM8-ESRF). The aim of this study is to determine whether As gets into the bulk of gypsum and calcite structures or is simply adsorbed on the surface. Different mechanisms of substitution are used as hypotheses. The combined Rietveld analysis of neutron and x-ray diffraction data shows an expansion of the unit cell volume proportional to the As concentration within the samples. DFT-based simulations confirm the increase of the unit cell volume proportional to the amount of carbonate or sulphate groups substituted. Interpolation of the experimental Rietveld data allows us to distinguish As substituted within the structure from that adsorbed on the surface of both minerals.

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

    Science.gov (United States)

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

    2001-01-01

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

  7. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers.

    Science.gov (United States)

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

    2016-01-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates. PMID:27302863

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

    Energy Technology Data Exchange (ETDEWEB)

    Marsili, E.; Beyenal, Haluk; Di Palma, L.; Merli, C.; Dohnalkova, Alice; Amonette, James E.; Lewandowski, Zbigniew

    2007-12-15

    Biofilms of sulfate-reducing bacteria Desulfovibrio desulfuricans G20 wereused 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.

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

    Science.gov (United States)

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

    2008-11-11

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

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

    Science.gov (United States)

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

    2016-04-01

    The composition of calcite and dolomite from several carbonatite complexes (including a large set of petrographically diverse samples from the Aley complex in Canada) was studied by electron-microprobe analysis and laser-ablation inductively-coupled-plasma mass-spectrometry to identify the extent of substitution of rare-earth and other trace elements in these minerals and the effects of different igneous and postmagmatic processes on their composition. Analysis of the newly acquired and published data shows that the contents of rare-earth elements (REE) and certain REE ratios in magmatic calcite and dolomite are controlled by crystal fractionation of fluorapatite, monazite and, possibly, other minerals. Enrichment in REE observed in some samples (up to ~2000 ppm in calcite) cannot be accounted for by coupled substitutions involving Na, P or As. At Aley, the REE abundances and chondrite-normalized (La/Yb)cn ratios in carbonates decrease with progressive fractionation. Sequestration of heavy REE from carbonatitic magma by calcic garnet may be responsible for a steeply sloping "exponential" pattern and lowered Ce/Ce* ratios of calcite from Magnet Cove (USA) and other localities. Alternatively, the low levels of Ce and Mn in these samples could result from preferential removal of these elements by Ce4+- and Mn3+-bearing minerals (such as cerianite and spinels) at increasing f(O2) in the magma. The distribution of large-ion lithophile elements (LILE = Sr, Ba and Pb) in rock-forming carbonates also shows trends indicative of crystal fractionation effects (e.g., concomitant depletion in Ba + Pb at Aley, or Sr + Ba at Kerimasi), although the phases responsible for these variations cannot be identified unambiguously at present. Overall, element ratios sensitive to the redox state of the magma and its complexing characteristics (Eu/Eu*, Ce/Ce* and Y/Ho) are least variable and in both primary calcite and dolomite, approach the average chondritic values. In consanguineous

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

    Science.gov (United States)

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

    2011-12-23

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

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

    Science.gov (United States)

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

    2015-09-01

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

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

    OpenAIRE

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

    2013-01-01

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

  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.

    2011-01-01

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

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    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......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...

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

    OpenAIRE

    Jin, X. B.; C. L. Liu; Poulton, A. J.; M. H. Dai; X.H. Guo

    2016-01-01

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

  17. Rapid changes in water hardness and alkalinity: Calcite formation is lethal to Daphnia magna.

    Science.gov (United States)

    Bogart, Sarah J; Woodman, Samuel; Steinkey, Dylan; Meays, Cindy; Pyle, Greg G

    2016-07-15

    There is growing concern that freshwater ecosystems may be negatively affected by ever-increasing anthropogenic inputs of extremely hard, highly alkaline effluent containing large quantities of Ca(2+), Mg(2+), CO3(2-), and HCO3(-) ions. In this study, the toxicity of rapid and extreme shifts in water hardness (38-600mg/L as CaCO3) and alkalinity (30-420mg/L as CaCO3) to Daphnia magna was tested, both independently and in combination. Within these ranges, where no precipitation event occurred, shifts in water hardness and/or alkalinity were not toxic to D. magna. In contrast, 98-100% of D. magna died within 96h after exposure to 600mg/L as CaCO3 water hardness and 420mg/L as CaCO3 alkalinity (LT50 of 60h with a 95% CI of 54.2-66.0h). In this treatment, a CaCO3 (calcite) precipitate formed in the water column which was ingested by and thoroughly coated the D. magna. Calcite collected from a mining impacted stream contained embedded organisms, suggesting field streams may also experience similar conditions and possibly increased mortality as observed in the lab tests. Although further investigation is required to determine the exact fate of aquatic organisms exposed to rapid calcite precipitation in the field, we caution that negative effects may occur more quickly or at lower concentrations of water hardness and alkalinity in which we observed effects in D. magna, because some species, such as aquatic insects, are more sensitive than cladocerans to changes in ionic strength. Our results provide evidence that both calcite precipitation and the major ion balance of waters should be managed in industrially affected ecosystems and we support the development of a hardness+alkalinity guideline for the protection of aquatic life.

  18. Rapid changes in water hardness and alkalinity: Calcite formation is lethal to Daphnia magna.

    Science.gov (United States)

    Bogart, Sarah J; Woodman, Samuel; Steinkey, Dylan; Meays, Cindy; Pyle, Greg G

    2016-07-15

    There is growing concern that freshwater ecosystems may be negatively affected by ever-increasing anthropogenic inputs of extremely hard, highly alkaline effluent containing large quantities of Ca(2+), Mg(2+), CO3(2-), and HCO3(-) ions. In this study, the toxicity of rapid and extreme shifts in water hardness (38-600mg/L as CaCO3) and alkalinity (30-420mg/L as CaCO3) to Daphnia magna was tested, both independently and in combination. Within these ranges, where no precipitation event occurred, shifts in water hardness and/or alkalinity were not toxic to D. magna. In contrast, 98-100% of D. magna died within 96h after exposure to 600mg/L as CaCO3 water hardness and 420mg/L as CaCO3 alkalinity (LT50 of 60h with a 95% CI of 54.2-66.0h). In this treatment, a CaCO3 (calcite) precipitate formed in the water column which was ingested by and thoroughly coated the D. magna. Calcite collected from a mining impacted stream contained embedded organisms, suggesting field streams may also experience similar conditions and possibly increased mortality as observed in the lab tests. Although further investigation is required to determine the exact fate of aquatic organisms exposed to rapid calcite precipitation in the field, we caution that negative effects may occur more quickly or at lower concentrations of water hardness and alkalinity in which we observed effects in D. magna, because some species, such as aquatic insects, are more sensitive than cladocerans to changes in ionic strength. Our results provide evidence that both calcite precipitation and the major ion balance of waters should be managed in industrially affected ecosystems and we support the development of a hardness+alkalinity guideline for the protection of aquatic life. PMID:27060657

  19. Effects of surface conductivity on the apparent zeta potential at the calcite-water interface

    OpenAIRE

    Li, Shuai; Leroy, Philippe; Devau, Nicolas

    2015-01-01

    International audience Carbonates are very reactive minerals that are used in many engineering applications like substance remediation and CO2 geological storage. Surface complexation reactions on calcite have significant effects on transport processes in carbonates. Zeta potential is a critical parameter to characterize the mineral surface electrochemical properties. The zeta potential is defined as the electrical potential at the shear plane between quasi immobile and mobile water at the...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-02-13

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

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

    Science.gov (United States)

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

    2013-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-12-31

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Randich, E.; Acton, R.U.

    1983-09-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Jones, B. [Univ. of Alberta, Edmonton, Alberta (Canada). Dept. of Earth and Atmospheric Sciences; Renaut, R.W. [Univ. of Saskatchewan, Saskatoon, Saskatchewan (Canada). Dept. of Geological Sciences

    1996-01-01

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

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

    Science.gov (United States)

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

    2013-07-01

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

  6. Textural properties of synthetic nano-calcite produced by hydrothermal carbonation of calcium hydroxide

    CERN Document Server

    Montes-Hernandez, German; Charlet, L; Tisserand, Delphine; Renard, F

    2008-01-01

    The hydrothermal carbonation of calcium hydroxide (Ca(OH)2) at high pressure of CO2 (initial PCO2 1/4 55 bar) and moderate to high temperature (30 and 90 1C) was used to synthesize fine particles of calcite. This method allows a high carbonation efficiency (about 95% of Ca(OH)2-CaCO3 conversion), a significant production rate (48 kg/m3 h) and high purity of product (about 96%). However, the various initial physicochemical conditions have a strong influence on the crystal size and surface area of the synthesized calcite crystals. The present study is focused on the estimation of the textural properties of synthesized calcite (morphology, specific surface area, average particle size, particle size distribution and particle size evolution with reaction time), using Rietveld refinements of X-ray diffraction (XRD) spectra, Brunauer-Emmett-Teller (BET) measurements, and scanning electron microscope (SEM) and transmission electron microscope (TEM) observations. This study demonstrate that the pressure, the temperatu...

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

    Directory of Open Access Journals (Sweden)

    Wen-Tien Tsai

    2013-08-01

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

  8. Calcite production by Coccolithophores in the South East Pacific Ocean: from desert to jungle

    Directory of Open Access Journals (Sweden)

    L. Beaufort

    2007-09-01

    Full Text Available BIOSOPE cruise achieved an oceanographic transect from the Marquise Islands to the Peru-Chili upwelling (PCU via the centre of the South Pacific Gyre (SPG. 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 are usually low and reach maxima west of the PCU. The coccoliths of Emiliania huxleyi, Gephyrocapsa spp. and Crenalithus spp. (Order Isochrysidales represent 50% of all the suspended calcite particles detected in the size range 0.1–46 μm (21% of PIC in term of the calcite weight. The latter species are found to grow preferentially in the Chlorophyll maximum zone. In the SPG their maximum concentrations was found to occur between 150 and 200 m, which is very deep for these taxa. The weight and size of coccoliths and coccospheres are correlated. Large and heavy coccoliths and coccospheres are found in the regions with relative higher fertility in the Marquises Island and in the PCU. Small and light coccoliths and coccospheres are found west of the PCU. This distribution may correspond to that of the concentration of calcium and carbonate ions.

  9. Calcite production by Coccolithophores in the South East Pacific Ocean: from desert to jungle

    Science.gov (United States)

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

    2007-09-01

    BIOSOPE cruise achieved an oceanographic transect from the Marquise Islands to the Peru-Chili upwelling (PCU) via the centre of the South Pacific Gyre (SPG). 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 are usually low and reach maxima west of the PCU. The coccoliths of Emiliania huxleyi, Gephyrocapsa spp. and Crenalithus spp. (Order Isochrysidales) represent 50% of all the suspended calcite particles detected in the size range 0.1-46 μm (21% of PIC in term of the calcite weight). The latter species are found to grow preferentially in the Chlorophyll maximum zone. In the SPG their maximum concentrations was found to occur between 150 and 200 m, which is very deep for these taxa. The weight and size of coccoliths and coccospheres are correlated. Large and heavy coccoliths and coccospheres are found in the regions with relative higher fertility in the Marquises Island and in the PCU. Small and light coccoliths and coccospheres are found west of the PCU. This distribution may correspond to that of the concentration of calcium and carbonate ions.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-07-01

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

  11. A simplified methodology to approach the complexity of foraminiferal calcite oxygen-isotope data - model comparison

    Science.gov (United States)

    Roche, Didier; Waelbroeck, Claire

    2016-04-01

    Since the pioneering work of Epstein (Epstein et al., 1953), numerous calcite isotopic records from the ocean have been used to attempt reconstructing paleoclimatic information. Additional to the well known complexity brought by the fact that foraminiferal calcite records both temperature and isotopic composition of the surrounding oceanic waters, an additional effect for surface - dwelling foraminifers is the fact that two different species do not have the same habitat and may thus record different signals. This is obvious when comparing paleoclimatic records where different species have been measured for the isotopic composition of the calcite. The difference in habitat produces a three dimensional spatial complexity (a foraminifera living in preferred climatic conditions at a specific location, but also at a specific depth, sometimes far from the surface) but also a temporal uncertainty (foraminifers generally live for only a few weeks and their growth season may be evolving through time with climate change). While the different species habitats potentially contain a wealth of information that could be used to better understand the sequences of climate change, this has seldom been used in modeling studies, most models deriving calcite isotopic signal from surface and annual mean conditions (e.g. Roche et al., 2014). In the present work, we propose a reduced complexity approach to compute the calcite for several planktonic foraminifers from climate model simulations under pre-industrial conditions. We base our approach on simple functions describing the temperature dependence of the different species growth rates (Lombard et al., 2009) and on probability of presence based on the physical variables computed in the climate model. We present a comparison to available sediment traps and core tops data as a validation of the methodology, focusing on the possibility for future applicability towards inversion of the signal measured in oceanic sediment cores. References

  12. Calcite precipitation on glass substrates and active stalagmites in Katerloch Cave (Austria): Constraints from environmental monitoring

    Science.gov (United States)

    Sakoparnig, Marlene; Boch, Ronny; Wang, Xianfeng; Lin, Ke; Spötl, Christoph; Leis, Albrecht; Gollowitsch, Anna; Dietzel, Martin

    2016-04-01

    Located near Graz at the SE-rim of the Alps Katerloch is well-known for its impressive dripstone decoration, e.g. several metres tall and relatively fast growing (0.2-0.7 mm/yr on average) candle-stick-type stalagmites. In the course of an ongoing multi-annual and partially high-resolution cave monitoring program we study modern (active) sites of carbonate deposition focusing on the site-specific growth dynamics and connection of modern regional and cave environmental conditions with petrographic, chemical and stable isotopic information captured in the speleothems. Fresh calcite precipitates on artificial (glass) substrates underneath active drip sites were collected continuously from 2006 to 2014 (eight years!). The samples (up to 7 mm thick) represent cave sections of different temperature and drip sites of partially different characteristics (e.g. drip rate). We also recovered short drill cores (up to 3 cm length, 1 cm diameter) from the top of active stalagmites probably representing the last decades to centuries of calcite crystallization. Moreover, an actively growing stalagmite (K10) comprising both modern and past calcite deposition was collected. 238U-234U-230Th dating using MC-ICP-MS of K10 (71 cm long) revealed several distinct growth intervals (separated by growth interruptions) starting at 129.1 ±1.2 kyr BP (Last Interglacial) up to now, mostly reflecting warm and humid climate intervals. High-resolution (100 μm) isotope profiles micromilled from the multi-annual modern calcite precipitates on artificial substrates revealed low δ13C values of -12.8 to -8.3 ‰ (VPDB) and relatively high δ18O of -6.9 to -4.9 ‰Ṫhe δ18O curves from all collection sites (different growth rate) record a pronounced decrease during their most recent growth period most likely corresponding to a significant decrease towards lower oxygen isotope values observed in drip waters collected in the year 2014 compared with samples from 2005 to 2007. Drip water δ2H /δ18O

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

    Directory of Open Access Journals (Sweden)

    A. Wackerbarth

    2012-11-01

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-01-01

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

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

    Institute of Scientific and Technical Information of China (English)

    Wei Chen; Weiqi Zhang; Antonio Simonetti; Shaoyong Jiang

    2016-01-01

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

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

    DEFF Research Database (Denmark)

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

    1997-01-01

    The Campanian-Maastrichtian limestones in the south of the Netherlands are well-sorted fine-grained mudstones and silt- to fine sand-sized bioclastic grainstones. These limestones show a distinct lithological cyclicity manifested by fining-upward grain-size cycles with calcite-cemented layers or ...... 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.......The Campanian-Maastrichtian limestones in the south of the Netherlands are well-sorted fine-grained mudstones and silt- to fine sand-sized bioclastic grainstones. These limestones show a distinct lithological cyclicity manifested by fining-upward grain-size cycles with calcite-cemented layers...... and differences in the degree of early diagenesis. Cemented layers and hardgrounds are the result of differential early marine calcite cementation. In these limestones early calcite cementation cannot be explained by the supply of cementing materials from saturated seawater, An alternative model for early marine...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-08-01

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

  18. Comparison of isotopic composition of different forms of calcite precipitated from fresh water

    International Nuclear Information System (INIS)

    In the karst area of NW Yugoslavia calcite is precipitated from fresh water in the form of speleothems in karst caves, as lacustrine deposits in river beds (tufa or travertine), and as lake sediments. The isotopic compositions of these forms of calcite were compared to determine conditions for calcite precipitation, i.e. whether precipitation takes place under isotopic equilibrium or not. The content of stable isotopes of carbon (13C) and oxygen (18O), as well as radiocarbon (14C) activity, were measured in calcite samples. Speleothems formed under various physicochemical conditions were collected in the Slovenian karst area, while most tufa samples and lake sediments were collected in the Plitvice Lakes area, Croatia. The δ18O of investigated young speleothems varies from -5 per mille to -7 per mille PDB and that of recent tufa and lake sediment from -8.5 to -10 per mille. The observed variations of δ13C content are much higher: δ13C of speleothems varies between -6.5 and -11 per mille, and that of tufa between -10 and -2 per mille PDB. However, the most frequent δ13C values of speleothems and tufa samples are very similar, indicating similar conditions of calcite formation. Higher δ13C values can be explained by the escape of isotopically lighter CO2 from water and by exchange with atmospheric CO2. It was observed that δ18O and δ13C values were higher for tufa deposits that were precipitated at waterfalls than those of sediments or tufa formed in lakes or under steady water flow conditions. More pronounced differences between tufa and speleothems were found in oxygen isotopic composition. The δ18O values of tufa are significantly more negative than the δ18O of speleothems owing to the different isotopic composition of water from which the calcite was precipitated. Tufa is precipitated from water with mean annual δ18O values of -10.7 per mille SMOW, while speleothems are formed from water with mean annual 6180 of -8.6 per mille (samples from caves

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-07-01

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

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

    Science.gov (United States)

    Reddy, Michael M.; Leenheer, Jerry

    2011-01-01

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

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

    Science.gov (United States)

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

    2012-12-01

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

  3. Texture evolution in calcite gouge formed at sub-seismic slip

    Science.gov (United States)

    Delle Piane, Claudio; Luzin, Vladimir; Timms, Nick E.; Ben Clennell, M.; Giwelli, Ausama

    2016-04-01

    Carbonate rocks are abundant in the upper crust and are notoriously seismogenic with Mw>6 earthquakes nucleating in fault zones in carbonate dominated units around the world. Field observations describe fault zones as characterised by a narrow principal slip zone at their core, containing fine, granular wear material referred to as fault gouge, produced during cumulative slip. The current literature on the link between texture and frictional properties of calcite gouges is very limited and somewhat contradictory: based on the study of a natural calcite gouge a link has been proposed between the presence of a crystallographic preferred orientation (CPO) and past seismic activity on the gouge hosting fault zone. However, similar features in terms of CPO were also identified on gouges experimentally generated at slip velocities well below the seismic ones, therefore questioning their interpretation as diagnostic of past seismic events. We studied the evolution of friction coefficient and texture on calcite gouges experimentally produced by means of high pressure direct shear experiments on large, water saturated, intact blocks of travertine (calcite 99 % wt.). Several blocks were deformed at room temperature up to different amounts of maximum displacements (20 mm, 70 mm and 120 mm) under an imposed sub-seismic slip rate of approximately 0.1 microns/s. Microstructural characterization of the deformed blocks was subsequently carried out on samples representing the highest strained portion s of each blocks (i.e. gouge zones). Local and bulk texture of the original and deformed materials was studied by means of electron backscattered diffraction (EBSD) and neutron diffraction, respectively. Direct shear experiments consistently indicate an evolution of the friction coefficient stabilizing at around values of 0.6 after 15 mm of slip. Macroscopic observations on the deformed blocks indicate that deformation is localised in a narrow band of extreme grain size reduction

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-01-01

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

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

    Science.gov (United States)

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

    2002-03-01

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

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Science.gov (United States)

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

    2016-09-01

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

  8. Graphitic carbon formation through calcite reduction in blueschist metasediments from Alpine Corsica (France)

    Science.gov (United States)

    Galvez, M.; Beyssac, O.; Martinez, I.; Benzerara, K.; Malvoisin, B.

    2012-04-01

    The geochemistry of reduced carbon in subduction zones is strongly affected by mineral equilibria. We study here the geochemistry of carbon in siliceous-marbles at the direct contact with serpentinites in the Alpine eclogitic meta-ophiolithic units of northern Corsica (France). We have combined petrology, Raman spectroscopy and carbon isotopy to provide a description of both the organic and carbonate components of the rocks across a reaction front where the reaction CaCO3+SiO2+2H2=CaSiO3+C+2H2O is evidenced. The continuous reaction zone is composed by a centimeter thick pale nephrite layer at the contact with the serpentinites, followed by a thin wollastonite layer and a 5 to 20 cm thick dark zone composed of wollastonite, carbonaceous material (CM), quartz but no carbonates. There is a sharp transition to the overlying original metasediment composed of calcite+quartz which is significantly less rich in CM. Raman spectroscopy shows that CM is much more graphitic in the reaction zone than in the original sediment. Significant isotopic differences are observed apart the reaction front with δ13C (CM) and δ13C (calcite) around -15‰ and 1.3‰ respectively in the original rock far from the reaction zone, whereas δ13C (CM) is around -1‰ in the reaction zone. We interpret the graphitic CM in the reaction zone as formed from the destabilization and reduction of calcite due to the diffusion of reducing fluids from the underlying serpentinite unit. Mass balance calculations support this hypothesis and show that a complete reduction of carbonates might have occurred. The timing of this abiotic macromolecular and graphitic C formation is discussed. We show that the combined study of isotopic geochemistry and structure of inorganic and organic carbon in metamorphic rocks might be suited to reveal with great fidelity redox gradients in subduction zones.

  9. Influence of temperature and CO2 on the strontium and magnesium composition of coccolithophore calcite

    Directory of Open Access Journals (Sweden)

    M. N. Müller

    2013-10-01

    Full Text Available Marine calcareous sediments provide a fundamental basis for paleoceanographic studies aiming to reconstruct past oceanic conditions and understand key biogeochemical element cycles. Calcifying unicellular phytoplankton (coccolithophores are a major contributor to both carbon and calcium cycling by photosynthesis and the production of calcite (coccoliths in the euphotic zone and the subsequent long-term deposition and burial into marine sediments. Here we present data from controlled laboratory experiments on four coccolithophore species and elucidate the relation between the divalent cation (Sr, Mg and Ca partitioning in coccoliths and cellular physiology (growth, calcification and photosynthesis. Coccolithophores were cultured under different seawater temperature and carbonate chemistry conditions. The partition coefficient of strontium (DSr was positively correlated with both carbon dioxide (pCO2 and temperature but displayed no coherent relation to particulate organic and inorganic carbon production rates. Furthermore, DSr correlated positively with cellular growth rates when driven by temperature but no correlation was present when changes in growth rates were pCO2-induced. The results demonstrate the complex interaction between environmental forcing and physiological control on the strontium partitioning in coccolithophore calcite. The partition coefficient of magnesium (DMg displayed species-specific differences and elevated values under nutrient limitation. No conclusive correlation between coccolith DMg and temperature was observed but pCO2 induced a rising trend in coccolith DMg. Interestingly, the best correlation was found between coccolith DMg and chlorophyll a production suggesting that chlorophyll a and calcite associated Mg originate from the same intracellular pool. These results give an extended insight into the driving factors that lead to variations in the coccolith Mg / Ca ratio and can be used for Sr / Ca and Mg / Ca

  10. Microstructure and thermal change of texture of calcite crystals in ostrich eggshell Struthio camelus

    Energy Technology Data Exchange (ETDEWEB)

    Heredia, A. [Instituto de Ciencias Nucleares, UNAM. Circuito Exterior, Ciudad Universitaria, Coyoacan C.P. 04510 Mexico D.F. (Mexico) and Instituto de Fisica, UNAM. Apartado Postal 20-364, 01000 Mexico D.F. (Mexico)]. E-mail: heredia@fisica.unam.mx; Rodriguez-Hernandez, A.G. [Instituto de Fisica, UNAM. Apartado Postal 20-364, 01000 Mexico D.F. (Mexico); Lozano, L.F. [Instituto de Fisica, UNAM. Apartado Postal 20-364, 01000 Mexico D.F. (Mexico); Pena-Rico, M.A. [Instituto de Fisica, UNAM. Apartado Postal 20-364, 01000 Mexico D.F. (Mexico); Velazquez, R. [Instituto de Fisica, UNAM. Apartado Postal 20-364, 01000 Mexico D.F. (Mexico); Basiuk, V.A. [Instituto de Ciencias Nucleares, UNAM. Circuito Exterior, Ciudad Universitaria, Coyoacan C.P. 04510 Mexico D.F. (Mexico); Bucio, L. [Instituto de Fisica, UNAM. Apartado Postal 20-364, 01000 Mexico D.F. (Mexico)

    2005-01-01

    Eggshell from ostrich Struthio camelus, pristine and thermally treated in the range from room temperature to 550 deg. C, was investigated with low vacuum scanning electron microscopy (LVSEM), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray powder diffractometry (XRD). Different zones of the eggshell were analysed, including the protein-related, non-crystalline, inner organic membrane. After the high-temperature treatment (>500 deg. C), only crystallised calcite phase was found showing two main textures depending on the shell zone and the treatment temperature. In the crystal layer of the untreated samples, nanosized calcite crystals are organized with their c crystallographic axes highly aligned normal to eggshell surface (a very sharp gaussian angular distribution, {sigma}=0.14, was obtained by using the Rietveld method to model the preferred orientation function in the X-ray powder diffraction pattern). Elemental analysis revealed more Mg{sup 2+} in the crystal layer than in cone layer of the eggshell. A high nitrogen content in the organic membrane is associated to a proteinaceous phase. The cone and palisade layers are composed of needle-shaped calcite crystals, which are more crystallized than in the crystal layer and in average with their c crystallographic axes oriented in all directions except for the one perpendicular to the eggshell surface. Due to the complex structure and the amorphous/crystal phase interactions, the heating at about 500 deg. C texturizes the crystals orienting them mainly along the c-axes normal to the inner eggshell surface.

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

    Science.gov (United States)

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

    2012-09-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-12-01

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

  13. DECARBONATION AND ATTRITION OF CALCITE IN A PLASMA SPOUTED BED REACTOR

    OpenAIRE

    G. Flamant; Chraibi, M. (Mohamede); Vallbona, G.; Bertrand, C

    1990-01-01

    The mechanical power and the thermal energy for the processing of calcite are the main part of the energy consumption in cement industry. Experimental results about particle size reduction and calcination of CaCO3 in a plasma spouted bed reactor are presented in this paper. The main parameter seems to be the specific enthalpy of the plasma jet, it ranges between 3 kWh.m-3 20 kWh.m-3. The variations of the attrition rate, decomposition rate and particle size distribution are discussed.

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

    DEFF Research Database (Denmark)

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

    2012-01-01

    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...... by hydrogen bonds almost doubles. Comparison between radiated and non-radiated areas of the same samples demonstrate that these effects are induced only by radiation and not caused by aging. These observations contribute to establishing a time limit for synchrotron experiments involving fluid...

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

    Energy Technology Data Exchange (ETDEWEB)

    Asperger, R.G.

    1982-08-01

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

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Science.gov (United States)

    Spalding, Jennifer; Schneider, David

    2016-04-01

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

  18. Preservation state of metastable magnesian calcite in periplatform sediments from the Caribbean Sea over the last million years

    Science.gov (United States)

    Sepulcre, Sophie; Tachikawa, Kazuyo; Vidal, Laurence; Thouveny, Nicolas; Bard, Edouard

    2009-11-01

    Carbonate-rich periplatform sediments represent an active carbon reservoir containing metastable aragonite and magnesian calcite (Mg-calcite, > 4 mol % MgCO3). Since Mg-calcite is highly soluble, the preservation state of this mineral provides information on past carbonate systems at water depths shallower than the lysocline. The mineralogy and geochemistry of the carbonate-rich fine fraction (MgCO3) during interglacials. Glacial Mg/Ca ratios were approximately 8 mol % MgCO3 for the period from 940 ka to 400 ka, and approximately 10 mol % MgCO3 for the last 400 ka. The Mg/Ca shift is concomitant with a preferential loss of Mg-calcite relative to aragonite. The preservation state of Mg-calcite revealed that the bottom water mass of the studied site was slightly more corrosive for the earlier period, possibly relating to a composition change in intermediate water and/or to the ventilation rate in the Atlantic Ocean.

  19. Calcite Supersaturation and Precipitation Kinetics in the Lower Colorado River, Ail-American Canal and East Highline Canal

    Science.gov (United States)

    Suarez, D. L.

    1983-06-01

    In situ pH determinations and analysis of major ions in solution indicated that the lower Colorado River is supersaturated with respect to calcite throughout the entire daily cycle, in both winter and summer. Although the ion activity product was 4 to 6 times greater than the calcite solubility product, there was no detectable precipitation. Chemical analyses of water samples taken along 350 km of the river and canals from Parker Dam to the Salton Sea also revealed no evidence of calcium carbonate precipitation despite the inflow of saline and highly supersaturated irrigation return flows. Laboratory kinetic studies indicated that calcite crystal growth rates with Colorado River water are about 30% of the rate for pure Ca-HCO3 waters and about 70% of that for synthetic Colorado River water. Calcite precipitation by crystal growth in the river is limited by the combination of short residence times and unavailability of reactive calcite. Critical supersaturation levels necessary for heterogeneous nucleation do not occur; a high suspended load limits algal photosynthesis and thus prevents large decreases in daytime H2CO3 levels.

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

    International Nuclear Information System (INIS)

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-15

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

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

    Science.gov (United States)

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

    2016-04-01

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

  3. Characterization of Shock Effects in Calcite by Raman Spectroscopy: Results of Experiments

    Science.gov (United States)

    Bell, M. S.

    2016-01-01

    Carbonates comprise approx. 20% by volume of present day Earth's sedimentary rocks and store most of the terrestrial CO2 inventory. Some of the oldest meta-sedimentary rocks found on Earth contain abundant carbonate from which impact-induced release of CO2 could have played a role in the formation and evolution of the atmosphere. Carbonates are also present in the target materials for approx. 30% of all terrestrial impact structures including large impacts such as Chicxulub which happened to occur at a location with extraordinarily thick platform carbonate 3-6 km deep. The impact release of CO2 from carbonates can cause global warming as a result of the well-known greenhouse effect and have subsequent effects on climate and biota. Therefore, the shock behavior of calcite is important in understanding the Cretaceous-Paleogene event and other impacts with carbonate-bearing sediments in their target(s) such as Mars and some asteroids. A comprehensive survey utilizing a variety of techniques to characterize the effects manifest in Calcite (Iceland Spar) experimentally shocked to 60.8 GPa has been completed. Results of analysis by Raman Spectroscopy are reported here.

  4. Continuous 500,000-year climate record from vein calcite in Devils Hole, Nevada

    International Nuclear Information System (INIS)

    Oxygen-18 (δ18O) variations in a 36-centimeter-long core (DH-11) of vein calcite from Devils Hole, Nevada, yield an uninterrupted 500,000-year paleotemperature record that closely mimics all major features in the Vostok (Antarctica) paleotemperature and marine δ18O ice-volume records. The chronology for this continental record is based on 21 replicated mass-spectrometric uranium-series dates. Between the middle and latest Pleistocene, the duration of the last four glacial cycles recorded in the calcite increased from 80,000 to 130,000 years; this variation suggests that major climate changes were aperiodic. The timing of specific climatic events indicates that orbitally controlled variations in solar insolation were not a major factor in trigering deglaciations. Interglacial climates lasted about 20,000 years. Collectively, these observations are inconsistent with the Milankovitch hypothesis for the origin of the Pleistocene glacial cycles but they are consistent with the thesis that these cycles originated from internal nonlinear feedbacks within the atmosphere-ice sheet-ocean system

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-09-05

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

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

    Science.gov (United States)

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

    2014-09-01

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

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

    Institute of Scientific and Technical Information of China (English)

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

    2006-01-01

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

  8. Two-dimensional X-ray diffraction as a tool for the rapid, nondestructive detection of low calcite quantities in aragonitic corals

    Science.gov (United States)

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

    2015-10-01

    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 advantage of 2-D-XRD over convenient 1-D-XRD methods is the nondestructive and rapid detection of calcite with relatively high spatial resolution directly on coral 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 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-10-01

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

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

    Science.gov (United States)

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

    2012-12-01

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

    Science.gov (United States)

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

    2014-09-01

    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

  12. An 8.1Ma calcite record of Asian summer monsoon evolution on the Chinese central Loess Plateau

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Carbonates in loess-red clay sequences consist mainly of calcite and dolomite. The EDTA analysis of carbonates in different size fractions and magnetic susceptibility reveal that calcite is a sensitive index of summer monsoon. The chemical analysis of carbonates and calcite from an 8.1 Ma loess-red clay sequence at Chaona on the Chinese central Loess Plateau shows that the evolution of the Asian summer monsoon experienced four stages, namely 8.1―5.5 Ma, 5.5―2.8 Ma, 2.8―1.5 Ma and 1.5―0 Ma, with increasing intensification and fluctuation, suggesting a possible combining impacts of uplift of the Tibetan Plateau and global changes on the Asian summer monsoon.

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

    Science.gov (United States)

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

    1987-01-01

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

  14. Empirical calibration of the clumped isotope paleothermometer using calcites of various origins

    Science.gov (United States)

    Wacker, Ulrike; Fiebig, Jens; Tödter, Julian; Schöne, Bernd R.; Bahr, André; Friedrich, Oliver; Tütken, Thomas; Gischler, Eberhard; Joachimski, Michael M.

    2014-09-01

    We present the first universal calibration of the clumped isotope thermometer for calcites of various mineralizing types. These are an eggshell of an ostrich, a tropical bivalve, a brachiopod shell, cold seep carbonate, and three foraminifera samples that grew between 9 and 38 °C. CaCO3 was digested at 90 °C using a common acid bath. Considering a difference in phosphoric acid fractionation factors between reaction at 25 and 90 °C of 0.069‰ (Guo et al., 2009), the function between growth temperature T and the excess of 13C-18O bonds in the evolved CO2 is expressed by a linear regression between 1/T2 and absolute Δ47 (R2 = 0.9915): Δ47=0.0327(±0.0026)× 106/T2+0.3030(±0.0308) (with Δ47 in ‰ and T in K). Both the slope and intercept of our regression line deviate significantly from the first experimental calibration based on synthetic calcites digested at 25 °C (Ghosh et al., 2006a) and from several other studies having confirmed this pioneering calibration (i.e., Came et al., 2007; Tripati et al., 2010; Thiagarajan et al., 2011; Grauel et al., 2012; Saenger et al., 2012; Zaarur et al., 2013). However, our relationship between temperature and absolute Δ47 values is indistinguishable from that determined by Henkes et al. (2013) if the same difference in phosphoric acid fractionation factors between 25 and 90 °C is applied to both datasets. Our study and that of Henkes et al. (2013) have in common that data were primarily projected onto the absolute scale proposed by Dennis et al. (2011) - a reference frame that allows comparison of clumped isotope data measured in different laboratories. Furthermore, at any T, our regression line lies within 0.006‰ of the theoretical calcite calibration of Guo et al. (2009). The observation that both empirical calibrations are indistinguishable from each other implies that clumped isotope data can be directly compared between laboratories and referenced to a unique temperature calibration if (1) the phosphoric acid

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

    Directory of Open Access Journals (Sweden)

    Pichard C.

    2006-11-01

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

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

    DEFF Research Database (Denmark)

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

    2001-01-01

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

  17. Dating historical calcite mortar by blue OSL: results from known age samples

    International Nuclear Information System (INIS)

    The study investigates whether blue OSL, known as a dating tool for partially bleached materials, can also be used for dating calcite mortar from young constructions. Starting from samples of known age the aim of the study is to determine appropriate evaluation methods for dose distributions. Using a model-calculation we first try to answer the question of how far a mortar sample can possibly be bleached during the manufacturing process. We then deal with the question of optimizing the analytical process, especially in view of the most suitable grain size. In the focus of our investigations we have tested several methods of evaluating frequency distributions based on single aliquot/multiple grain measurements. Depending on grain size, two methods have proved sufficiently successful; optimal equivalent doses may be obtained either from radial plots or from maxima of weighted histograms. The comparison is based on measurements of 14 mortar samples from the last millennium

  18. Study of Pickering emulsions stabilized by mixed particles of silica and calcite

    Institute of Scientific and Technical Information of China (English)

    Sha Wang; Yongjun He; Yong Zou

    2010-01-01

    Picketing emulsions were prepared using mixed particles of silica and calcite as emulsifiers.The effects of the silica content in the mixed particles on the stability and the drop size of the Pickering emulsions were investigated.The results showed that the Pickering emulsions were of the oil-in-water type.With increasing silica content in the mixed particles,the stability and the drop size of the Pickering emulsions decreased.Larger silica particles had more influence on the stability of the emulsions,while smaller ones had more influence on the drop size of the emulsions.The effect of the silica particles on the emulsions was attributed to their adsorptive behavior at the oil-water interfaces of the Pickering emulsions.

  19. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

    Science.gov (United States)

    Kimball, J.; Tripati, R. E.; Dunbar, R.

    2015-12-01

    Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near constant temperature, salinity and pH, and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop "clumped" isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly-substituted isotopologue 13C18O16O2 in carbonate minerals, analyzed in CO2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ47 values. We analyzed Δ47 in live-collected aragonitic scleractinian (Enallopsammia sp.) and calcitic gorgonian (Isididae and Coralliidae) deep-sea corals, and compared results to published data for other aragonitic scleractinian taxa. Measured Δ47 values were compared to in situ temperatures and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than calcitic gorgonian corals and the two groups of coral produce statistically different relationship between Δ47-temperature calibrations. These data are significant in the interpretation of all carbonate "clumped" isotope calibration data as they show that distinct Δ47-temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the

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

    Energy Technology Data Exchange (ETDEWEB)

    Gates, Ian [University of Calgary (Canada)

    2011-07-01

    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. Determination of aragonite trace element distribution coefficients from speleothem calcite-aragonite transitions

    Science.gov (United States)

    Wassenburg, J. A.; Scholz, D.; Jochum, K. P.; Cheng, H.; Oster, J.; Immenhauser, A.; Richter, D. K.; Häger, T.; Jamieson, R. A.; Baldini, J. U. L.; Hoffmann, D.; Breitenbach, S. F. M.

    2016-10-01

    The processes that govern the incorporation of (trace) elements into speleothems can often be linked to environmental changes. Although element incorporation into speleothem calcite is now reasonably well understood, current knowledge regarding trace element variability in speleothem aragonite is very limited. Of particular interest is whether trace element distribution coefficients are above or below one in order to assess the extent to which prior aragonite precipitation has affected speleothem aragonite trace element records. This study uses nine calcite-to-aragonite transitions in seven speleothems from diverse environmental settings to derive the first quantitative estimates of the distribution coefficients for several elements in speleothem aragonite: DMg(Ar) = 9.7E-5 ± 9.01E-5, DBa(Ar) = 0.91 ± 0.88, DSr(Ar) = 1.38 ± 0.53, and DU(Ar) = 6.26 ± 4.54 (1σ SD). For one speleothem from western Germany, the distribution coefficients are generally higher, which is potentially related to the very low growth rates (negative correlation with growth rate when growth rate is below 20 μm/year. In summary, our results demonstrate that speleothem aragonite DMg(Ar) is below one, DU(Ar) is considerably above one, and DSr(Ar) is above one or close to unity. For DBa(Ar), reaching a similar conclusion is difficult due to the relatively high uncertainty. Enhanced prior aragonite precipitation will thus result in lower U and higher Mg concentrations in speleothem aragonite, although in many cases Mg in speleothem aragonite is most likely dominated by other processes. This result suggests that U concentrations in aragonitic stalagmites could serve as a very effective proxy for palaeo-rainfall.

  2. First-principles study of boron speciation in calcite and aragonite

    Science.gov (United States)

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

    2016-11-01

    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.

  3. Impact of Montmorillonite and Calcite on Release and Adsorption of Cyanobacterial Fatty Acids at Ambient Temperature

    Institute of Scientific and Technical Information of China (English)

    Liu Deng; Yang Xiaofen; Wang Hongmei; Li Jihong; Su Nian

    2008-01-01

    Minerals might act as important sorbents of sedimentary organic matter and reduce biodegradation, which favors the formation of hydrocarbon source rocks in the earth's history. Since most organic matter is degraded during the sinking process, at ambient temperature, it is important to investigate the adsorption capacity of different minerals during this process, to assess the organic loss from primary productivity to sedimentary organic matter. In this study, montmorillonite and calcite have been selected to study the impact of different minerals on the release, adsorption, and deposition of cyanobacterial (Synechococcus elonpata) fatty acids (FAs) at ambient temperature. Gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS) have been utilized to detect the variation in fatty acids. Primary results suggest that minerals have a different impact on dissolved organic matter. Montmorillonite can specifically enhance the release of fatty acids from cyanobacterial cells by lowering the pH values of the solution. The adsorption of the dissolved organic matter by montmorillonite will also be enhanced under a lower pH value. Conjunction of fatty acids with montmorillonite to form a complex will favor the sinking and preservation of these organics. Selective adsorption is observed among fatty acids with different carbon numbers. In contrast, calcite does not show any impact on the release and adsorption of organic matter even though it is reportedly capable of acting as a catalyst during the transformation of organic matter at high temperature. The primary data bridge a link between primary productivity and sedimentary organic matter, suggesting the relative importance of claystoncs in the formation of hydrocarbon source rocks in the earth's history.

  4. Separation of deviatoric stress tensors from heterogeneous calcite twin data using a statistical mixture model

    Science.gov (United States)

    Yamaji, Atsushi

    2016-04-01

    It is essential for the techniques of paleostress analysis to separate stresses from heterogeneous data (e.g., Tikoff et al., 2013). A statistical mixture model is shown in this paper to be effective for calcite twinning paleopiezometry: Given the orientations of twinned e-planes and their gliding directions, the present inverse method based on the mixture model determines not only deviatoric stress tensors, but also estimates the number of tensors that should be read from a data set using Bayesian information criterion. The present method is based on the fact that mechanical twinning occurs on an e-plane if the resolved shear stress along its gliding direction, τ, is greater than a critical value, τc (e.g., Lacombe, 2010). The orientation data from e-planes corresponds to points on a 5-dimensional unit sphere, a spherical cap on which indicates a deviatoric stress tensor. The twinning condition, τ > τc, is identical with the condition that the points corresponding to the orientation data are distributed upon the spherical cap (Yamaji, 2015a). It means that the paleostress analysis of calcite twins comes down to the problem of fitting a spherical cap to data points on the sphere (Yamaji, 2015b). Given a heterogeneous data set, two or more spherical caps should be fitted to the data point on the sphere. A statistical mixture model is employed for this fitting in the present work. Such a statistical model enables us to evaluate the number of stresses recorded in the data set. The present method was tested with artificial data sets and a natural data set obtained from a Miocene graben in central Japan. From the former type of data sets, the method determined the deviatoric stress tensors that were assumed to generate the data sets. The natural data were inverted to give two stresses that appeared appropriate for the tectonic setting of the area where the data were obtained.

  5. Evaluation of meteoric calcite cements as a proxy material for mass-47 clumped isotope thermometry

    Science.gov (United States)

    Defliese, William F.; Lohmann, Kyger C.

    2016-01-01

    Meteoric diagenetic cements are ubiquitous throughout geologic history, affecting most carbonate exposures worldwide. They can often be difficult to interpret, as it is usually difficult to separate the influences of water δ18O and temperature on isotopic signals contained within the carbonate rock body. Despite this difficulty in interpretation, meteoric phreatic cements can potentially be a useful proxy material, as they form slowly in equilibrium at mean annual temperature and are not affected by any biogenic effects that can bias other proxy materials. We applied the mass-47 clumped isotope paleothermometer to Pleistocene and Holocene carbonates from Bermuda and Barbados in order to investigate the effects of meteoric diagenesis on Δ47 signals, and to determine their suitability as a paleotemperature proxy. Phreatic calcite cements are found to record the same temperatures as unaltered carbonate sediments, while any sample exhibiting vadose characteristics is biased towards unreasonably hot apparent formation temperatures. Burial heating and re-equilibration are not geologically viable explanations for the anomalously hot temperatures recorded in vadose cements, as neither Bermuda or Barbados has any burial history. Instead, it is likely that precipitation in the vadose zone occurs on timescales quicker than isotopic equilibrium can be achieved, driven by a combination of CO2 degassing and evaporation, which have been previously shown to cause problems in speleothems and pedogenic carbonates. We conclude by suggesting that meteoric phreatic calcites may be an ideal phase for paleotemperature reconstruction, as they accurately record mean annual temperatures and form under equilibrium conditions, while also being resistant to further mineral driven diagenesis. Vadose cements, and any sample likely affected by processes similar to vadose diagenesis, should be avoided for climate reconstructions using the mass-47 clumped isotope thermometer.

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

    Institute of Scientific and Technical Information of China (English)

    YU BingSong; DONG HaiLiang; RUAN Zhuang

    2008-01-01

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

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

    Science.gov (United States)

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

    2008-10-15

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

  8. Origin of epigenetic calcite in coal from Antarctica and Ohio based on isotope compositions of oxygen, carbon and strontium

    International Nuclear Information System (INIS)

    This study discusses the conditions of formation and provenance of calcite cleats in coal deposits of Antarctica and Ohio, based on their isotope compositions of oxygen, carbon and strontium. The paper gives some data of the relative radioisotope abundance of 87Sr. (Auth.)

  9. Heterogeneous growth of calcite at aragonite {001}- and vaterite {001}-melt interfaces: A molecular dynamics simulation study

    Science.gov (United States)

    Nada, Hiroki; Nishimura, Tatsuya; Sakamoto, Takeshi; Kato, Takashi

    2016-09-01

    Crystal growth at the interface between a calcium carbonate (CaCO3) crystal and its melt at a high temperature of 1500 K is investigated by means of a molecular dynamics simulation. The simulation is performed for the interfaces of a calcite {104} plane, aragonite {001}, {100}, and {010} planes, and vaterite {001}, {110}, and {100} planes. The growth from a pure melt and that from a melt containing Mg2+ are examined. Calcite growth occurs on the calcite {104} plane, aragonite growth occurs on the aragonite {100}, and {010} planes, and vaterite growth occurs on the vaterite {110} and {100} planes. However, the heterogeneous growth of calcite occurs on the {001} plane of aragonite and vaterite, irrespective of the presence of Mg2+. The results advance our understanding of geological processes that occur at high temperature, such as the formation of CaCO3 crystals from carbonatite magma and the formation of marble. Moreover, the results provide useful information for the control of CaCO3 crystal formation in material design.

  10. Palaeotemperature reconstruction during the Last Glacial from δ18O of earthworm calcite granules from Nussloch loess sequence, Germany

    Science.gov (United States)

    Prud'homme, Charlotte; Lécuyer, Christophe; Antoine, Pierre; Moine, Olivier; Hatté, Christine; Fourel, François; Martineau, François; Rousseau, Denis-Didier

    2016-05-01

    The Nussloch loess-palaeosol sequence (Rhine Valley, Germany) is considered to be one of the most complete records of the last glacial period in Western Europe due to its very high sedimentation rate and its good chronological control. This sequence is therefore a good framework in which to develop new proxies for palaeoenvironmental reconstructions. In this study, we explore, for the first time, the potential of earthworm calcite granules as a new bio-indicator and climatic proxy of absolute air and soil temperature in the context of Last Glacial loess. These granules are composed of rhomboedric calcite crystals, organized in a radial crystalline structure. As these granules are individually generated by earthworms at a relative fast rate, they are expected to record intra-annual variations in the available sources of oxygen: percolating waters of meteoric origin. We extracted thirty earthworm calcite granules from 11 of 5 cm layers thick from tundra gley and brown soil horizons previously, dated at 45 to 23 ka. Oxygen isotope ratios were measured on each individual granule. The δ18O of calcite granules and interlinked transfer functions between water cycle, air and soil temperatures allowed us to estimate air temperatures ranging from 10 to 12 ± 4°C, which most likely reflect the warm periods of the year when earthworms were the most active.

  11. 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;

    2008-01-01

    sp., T. weissflogii, and E. huxleyi, respectively. The average carbon-specific respiration rate was 0.15 d(-1) independent on diet (range: 0.08-0.21 d(-1)). Because of ballasting of opal and calcite, sinking velocities were significantly higher for pellets produced on T. weissflogii (322 +/- 169 m d...

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

    Institute of Scientific and Technical Information of China (English)

    XU Cheng; HUANG Zhi-long

    2008-01-01

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

  13. Direct Experimental Evidence for Differing Reactivity Alterations of Minerals following Irradiation: The Case of Calcite and Quartz

    Science.gov (United States)

    Pignatelli, Isabella; Kumar, Aditya; Field, Kevin G.; Wang, Bu; Yu, Yingtian; Le Pape, Yann; Bauchy, Mathieu; Sant, Gaurav

    2016-01-01

    Concrete, used in the construction of nuclear power plants (NPPs), may be exposed to radiation emanating from the reactor core. Until recently, concrete has been assumed immune to radiation exposure. Direct evidence acquired on Ar+-ion irradiated calcite and quartz indicates, on the contrary, that, such minerals, which constitute aggregates in concrete, may be significantly altered by irradiation. More specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, calcite only experiences random rotations, and distortions of its carbonate groups. As a result, irradiated quartz shows a reduction in density of around 15%, and an increase in chemical reactivity, described by its dissolution rate, similar to a glassy silica. Calcite however, shows little change in dissolution rate - although its density noted to reduce by ≈9%. These differences are correlated with the nature of bonds in these minerals, i.e., being dominantly ionic or covalent, and the rigidity of the mineral’s atomic network that is characterized by the number of topological constraints (nc) that are imposed on the atoms in the network. The outcomes have major implications on the durability of concrete structural elements formed with calcite or quartz bearing aggregates in nuclear power plants.

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

    Directory of Open Access Journals (Sweden)

    Gebrehiwet Tsigabu A

    2012-01-01

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

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

    Directory of Open Access Journals (Sweden)

    D. K. Richter

    2010-11-01

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

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

  16. Origin of epigenetic calcite in coal from Antarctica and Ohio based on isotope compositions of oxygen, carbon and strontium

    Science.gov (United States)

    Faure, G.; Botoman, G.

    1984-01-01

    Isotopic compositions of oxygen, carbon and strontium of calcite cleats in coal seams of southern Victoria Land, Antarctica, and Tuscarawas County, Ohio, contain a record of the conditions a the time of their formation. The Antarctic calcites (?? 18O(SMOW) = +9.14 to +11.82%0) were deposited from waters enriched in 16O whose isotopic composition was consistent with that of meteoric precipitation at low temperature and high latitude. The carbon of the calcite cleats (?? 13C(PDB) = -15.6 to -16.9%0) was derived in part from the coal (?? 13C(PDB) = -23.5 to -26.7%0) as carbon dioxide and by oxidation of methane or other hydrocarbon gases. The strontium ( 87Sr 86Sr = 0.71318-0.72392) originated primarily from altered feldspar grains in the sandstones of the Beacon Supergroup. Calcite cleats in the Kittaning No. 6 coal seam of Ohio (?? 18O(SMOW) = +26.04 to +27.79%0) were deposited from waters that had previously exchanged oxygen, possibly with marine carbonate at depth. The carbon (?? 13C(PDB) = 0.9 to +2.4%0) is enriched in 13C even though that cleats were deposited in coal that is highly enriched in 12C and apparently originated from marine carbonates. Strontium in the cleats ( Sr 87 0.71182-0.71260) is not of marine origin but contains varying amounts of radiogenic 87Sr presumably derived from detrital Rb-bearing minerals in the adjacent sedimentary rocks. The results of this study suggest that calcite cleats in coal of southern Victoria Land, Antarctica, were deposited after the start of glaciation in Cenozoic time and that those in Ohio precipitated from formation waters derived from the underlying marine carbonate rocks, probably in the recent geologic past. ?? 1984.

  17. Calcite Twins, a Tool for Tectonic Studies in Thrust Belts and Stable Orogenic Forelands Les macles de la calcite, un outil pour les études tectoniques dans les chaînes plissées et les avant-pays peu déformés des orogènes

    OpenAIRE

    Lacombe O.

    2010-01-01

    Calcite twins have been used for a long time as indicators of stress/strain orientations and magnitudes. Recent developments during the last 15 years point toward significant improvements of existing techniques as well as new applications of calcite twin analysis in thrust belts and forelands. This paper summarizes the principles of the most common techniques in this tectonic field and illustrates some aspects of the use of calcite twins to constrain not only stress/strain orientations a...

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

    Science.gov (United States)

    Mbamba, Christian Kazadi; Batstone, Damien J; Flores-Alsina, Xavier; Tait, Stephan

    2015-01-01

    Process simulation models used across the wastewater industry have inherent limitations due to over-simplistic descriptions of important physico–chemical reactions, especially for mineral solids precipitation. As part of the efforts towards a larger Generalized Physicochemical Modelling Framework, the present study aims to identify a broadly applicable precipitation modelling approach. The study uses two experimental platforms applied to calcite precipitating from synthetic aqueous solutions to identify and validate the model approach. Firstly, dynamic pH titration tests are performed to define the baseline model approach. Constant Composition Method (CCM) experiments are then used to examine influence of environmental factors on the baseline approach. Results show that the baseline model should include precipitation kinetics (not be quasi-equilibrium), should include a 1st order effect of the mineral particulate state (Xcryst) and, for calcite, have a 2nd order dependency (exponent n = 2.05 ± 0.29) on thermodynamic supersaturation (σ). Parameter analysis indicated that the model was more tolerant to a fast kinetic coefficient (kcryst) and so, in general, it is recommended that a large kcryst value be nominally selected where insufficient process data is available. Zero seed (self nucleating) conditions were effectively represented by including arbitrarily small amounts of mineral phase in the initial conditions. Both of these aspects are important for wastewater modelling, where knowledge of kinetic coefficients is usually not available, and it is typically uncertain which precipitates are actually present. The CCM experiments confirmed the baseline model, particularly the dependency on supersaturation. Temperature was also identified as an influential factor that should be corrected for via an Arrhenius-style correction of kcryst. The influence of magnesium (a common and representative added impurity) on kcryst was found to be significant but was considered

  19. Two-dimensional X-ray diffraction as a tool for the rapid, nondestructive detection of low calcite quantities in aragonitic corals

    Science.gov (United States)

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

    2015-10-01

    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 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.

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

    Directory of Open Access Journals (Sweden)

    Shopov Yavor Y.

    2000-01-01

    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.

  1. Thermoluminescence studies of calcite extracted from natural sand used in making roasted chickpea

    International Nuclear Information System (INIS)

    In this study, thermoluminescence (TL) properties of the calcite extracted from natural sand which is used in making roasted chickpeas were investigated. And also the effects of different thermal treatments on thermoluminescence glow curve were observed. Two distinct TL peaks were observed at ∼130 °C and ∼230 °C. The annealing of sample, especially at 900 °C, causes a huge enhancement in sensitization of TL. Linearity in dose response is observed for the values up to 0.6 kGy and above 0.6 kGy linearity is not preserved and dose response becomes sublinear. The best reproducibility is obtained when the samples are annealed between 400°C and 600 °C. - Highlights: • The natural sand sample used in making roasted chickpea shows thermoluminescence properties. • Annealing at 900 °C for about 15 min gives best TL output. • A good sensitization of about 70 factor was observed in annealed samples when they were compared with no annealed samples. • At doses lower than 0.6 kGy, dose response is linear and sublinear at doses higher than 0.6 kGy. • The best reproducibility is obtained when the samples are annealed between 400 °C and 600 °C

  2. Heavy metal uptake in foraminiferal calcite: results of multi-element culture experiments

    Directory of Open Access Journals (Sweden)

    D. Munsel

    2010-02-01

    Full Text Available The incorporation of heavy metals into the test of the shallow water benthic foraminifer Ammonia tepida was investigated under controlled laboratory conditions. Except for the concentrations of the trace elements, all other culture conditions such as pH, temperature and salinity were kept constant. In the experiments, the concentrations of Ni, Cu and Mn were 5, 10, and 20 times higher than those in natural North Sea water, whereas in a control experiment foraminifera were cultured in filtered natural North Sea water. 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. Both independent analytical approaches agreed within the analytical uncertainty intervals. The calculated partition coefficients were 0.17±0.09 and 1.3±0.7 for Cu and Ni, respectively. Potential toxic and/or chemical competition effects might have lead to a decreasing incorporation rate of Cu and Ni into the calcite of the specimens of the tank with the highest chemical concentrations. Mn showed great scattering in the aquarium with the 20-fold higher element concentrations potentially due to antagonism effects with Cu. Nevertheless, the established partition coefficients now open the way for reconstructing past concentrations for these elements in sea water.

  3. Controls by saturation state on etch pit formation during calcite dissolution

    Science.gov (United States)

    Teng, H. Henry

    2004-01-01

    Dissolution experiments were conducted on {101¯4} cleavage faces of calcite at various under-saturations to determine how the saturation state controls etch pit formation. Experimental observations were made by using in situ fluid cell Atomic Force Microscopy. Three dissolution modes were observed. When the saturation index Ω > 0.541, no etch pit formation was seen and dissolution primarily occurred at existing steps. When Ω decreased to Ω c = 0.541-0.410, the first visible pits appeared and continuous reduction in saturation state slowly increased the pit density on terraces while dissolution simultaneously proceeded at step edges. Finally, when the saturation state fell below Ω max = ˜0.007, a precipitous increase in pit density took place that sharply contrasted to the ordered fashion of pit formation observed at saturation conditions above this level. These observations are interpreted to be two-dimensional and unassisted pit formation at Ω 0.541. The values of Ω c are in good agreement with the dislocation theory's predicted critical under-saturations for pit formation at line dislocations. The occurrence of Ω max is not directly predicted but is a logical consequence of dissolution thermodynamics. These findings suggest that (1) dissolution near and far from equilibrium (i.e., Ω > Ω c, Ω unassisted pit nucleation at Ω ˜ Ω max is not predicted by the current dissolution rate equations. This suggests that an accurate 'general' rate law describing universal dissolution processes has yet to be developed.

  4. Coccolithophores and calcite saturation state in the Baltic and Black Seas

    Directory of Open Access Journals (Sweden)

    T. Tyrrell

    2007-10-01

    Full Text Available The Baltic and Black Seas are both brackish, that is to say both have salinities intermediate between freshwater and seawater. The coccolithophore Emiliania huxleyi is abundant in one, the Black Sea, but absent from the other, the Baltic Sea. Here we present summertime coccolithophore measurements confirming this difference, as well as data on the calcium carbonate saturation state of the Baltic Sea. We find that the Baltic Sea becomes undersaturated (or nearly so in winter, with respect to both the aragonite and calcite mineral forms of CaCO3. Data for the Black Sea are more limited, but it appears to remain strongly supersaturated year-round. The absence of E. huxleyi from the Baltic Sea could therefore potentially be explained by dissolution of their coccoliths in winter, suggesting that minimum annual (wintertime saturation states could be most important in determining future ocean acidification impacts. In addition to this potential importance of winter saturation state, alternative explanations are also possible, either related to differences in salinity or else to differences in silicate concentrations.

  5. Thermoluminescence studies of calcite extracted from natural sand used in making roasted chickpea

    Energy Technology Data Exchange (ETDEWEB)

    Toktamiş, Hüseyin, E-mail: toktamis@gantep.edu.tr; Toktamiş, Dilek; Necmeddin Yazici, A.

    2014-09-15

    In this study, thermoluminescence (TL) properties of the calcite extracted from natural sand which is used in making roasted chickpeas were investigated. And also the effects of different thermal treatments on thermoluminescence glow curve were observed. Two distinct TL peaks were observed at ∼130 °C and ∼230 °C. The annealing of sample, especially at 900 °C, causes a huge enhancement in sensitization of TL. Linearity in dose response is observed for the values up to 0.6 kGy and above 0.6 kGy linearity is not preserved and dose response becomes sublinear. The best reproducibility is obtained when the samples are annealed between 400°C and 600 °C. - Highlights: • The natural sand sample used in making roasted chickpea shows thermoluminescence properties. • Annealing at 900 °C for about 15 min gives best TL output. • A good sensitization of about 70 factor was observed in annealed samples when they were compared with no annealed samples. • At doses lower than 0.6 kGy, dose response is linear and sublinear at doses higher than 0.6 kGy. • The best reproducibility is obtained when the samples are annealed between 400 °C and 600 °C.

  6. Pyrite-pyrrhotite intergrowths in calcite marble from Bistriški Vintgar, Slovenia

    Science.gov (United States)

    Zavašnik, J.

    2016-02-01

    Roman marble quarry in Bistrica gorge in southern Pohorje Mt. (north-eastern Slovenia) is situated in a 20 m thick lens of layered marble, at the contact zone between granodiorite and metamorphites. Grey and yellowish non-homogenous calcite marble is heavily included by mica, quartz, feldspars, zoisite, pyrite and amphiboles. In the present research, we have studied numerous pyrite (FeS2) crystals associated with yellowish-bronze non-stoichiometric pyrrhotite (Fe1-xS), not previously reported from this locality. SEM investigation revealed unusual sequence of crystallisation: primary skeletal pyrrhotite matrix is sparsely overgrown by well-crystalline pyrite, both being overgrown by smaller, well-developed hexagonal pyrrhotite crystals of the second generation. With TEM we identify the pyrrhotite as 5T-Fe1-xS phase, where x is about 0.1 and is equivalent to Fe9S10. The pyrite-pyrrhotite coexistence allows us a construction of fO2-pH diagram of stability fields, which reflects geochemical conditions at the time of marble re-crystallisation.

  7. Carbon and oxygen isotopes of hydrothermal calcite associated with the 'Lavas Ocoiticas' between Copiapo and Illapel

    International Nuclear Information System (INIS)

    In northern Chile, between latitudes 27o and 33oS, the Lower Cretaceous is characterized by an arc / back-arc basin system (Mpodozis and Ramos, 1989). In its first stage (Late Jurassic to Early Cretaceous) the arc was part of an island arc system of weakly continental character, which evolved into a continental arc (Vergara et al., 1995). The volcanic arc was associated with a marginal back-arc which terminated its development in the Aptian to Albian times (Vergara and Nystrom, 1996; Cisternas et al., 1999a). A sequence of porphyritic lavas, know as the 'Lavas Ocoiticas' extruded at the end of the Neocomian. In the area of Copiapo the 'Lavas Ocoiticas' host numerous metallic deposits and occurrences and has been designated as the Metallotect 'Ocoita Pabellon' (Cisternas et al., 1999b). This metallotect is characterized by the occurrence of 'migrabitumen' (both in veinlets and in vesicles) and copper sulfides. The genesis of the deposits in the Metallotect 'Ocoita Pabellon' has been studied by Cisternas et al. (1999b).and Hermosilla (2001). They conclude that hydrothermal fluid events mobilized and emplaced both the hydrocarbons and the metallic contents in the lavas. In this communications we presents new C and S isotope data obtained from hydrothermal calcite in both the norhtern area (Copiapo), where it is associated with bitumen; and in the southern area (Illapel) where hydrothermal alteration or metamorphism seems to have obliterated the bitumen (au)

  8. The role of microorganisms in the formation of calcitic moonmilk deposits and speleothems in Altamira Cave

    Science.gov (United States)

    Sanchez-Moral, S.; Portillo, M. C.; Janices, I.; Cuezva, S.; Fernández-Cortés, A.; Cañaveras, J. C.; Gonzalez, J. M.

    2012-02-01

    Bacteria are able to induce carbonate precipitation although the participation of microbial or chemical processes in speleothem formation remains a matter of debate. In this study, the origin of carbonate depositions such as moonmilk, an unconsolidated microcrystalline formation with high water content, and the consolidation of carbonate precipitates into hard speleothems were analyzed. The utilized methods included measurements of the composition of stable isotopes in these precipitates, fluorimetric determinations of RNA/DNA ratios and respirometric estimations in Altamira Cave. Results from isotope composition showed increases of the δ 18O and δ 13C ratios from moonmilk in the very first stages of formation toward large speleothems. Estimates of RNA/DNA ratios suggested an inactivation of microorganisms from incipient moonmilk toward consolidated deposits of calcium carbonate. Respiratory activity of microorganisms also showed a significant decrease in samples with accumulated calcite. These results suggest that bacterial activity induces the conditions required for calcium carbonate precipitation, initiating the first stages of deposition. Progressive accumulation of carbonate leads towards a less favorable environment for the development of bacteria. On consolidated speleothems, the importance of bacteria in carbonate deposition decreases and chemical processes gain importance in the deposition of carbonates.

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

    Directory of Open Access Journals (Sweden)

    Bjørnstad T.

    2013-05-01

    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.

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

    Science.gov (United States)

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

    1988-01-01

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

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    .1% of the enzyme product (corresponding to 0.002-0.005% protein). Likewise, proteases could also improve wettability, although the effect was not consistent and was dependent on impurities. Other enzymes had no effect on the wettability of calcite at the concentration studied. The main mechanism of enzymatic...... 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...... and adhesion behaviour tests. Comparative studies with a surfactant, protein, purified enzyme, enzyme stabiliser using n-decane (as a model for the oil) have also been carried out in order to verify experimental results. The enzymes that have the highest effect on the wettability have been identified. Those...

  12. Soluble organic matrices of the calcitic prismatic shell layers of two Pteriomorphid bivalves. Pinna nobilis and Pinctada margaritifera.

    Science.gov (United States)

    Dauphin, Yannicke

    2003-04-25

    The calcitic prisms of the shells of two bivalves, Pinna and Pinctada, are considered simple prisms according to some morphological and mineralogical characteristics. Scanning electron microscopic and atomic force microscopic studies show that the microstructures and nanostructures of these two shells are different. Pinna prisms are monocrystalline, whereas Pinctada prisms are not. Moreover, intraprismatic membranes are present only in the Pinctada prisms. The soluble organic matrices extracted from these prisms are acidic, but their bulk compositions differ. Ultraviolet and infrared spectrometries, fluorescence, high pressure liquid chromatography, and electrophoresis show that the sugar-protein ratios and the molecular weights are different. Sulfur is mainly associated with acidic sulfated sugars, not with amino acids, and the role of acidic sulfated sugars is still underestimated. Thus, the simple prism concept is not a relevant model for the biomineralization processes in the calcitic prismatic layer of mollusk shells.

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

    Science.gov (United States)

    Xu, Hong; Zhang, Jing; Gao, Yiming

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

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

    Science.gov (United States)

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

    2016-10-01

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

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

    Science.gov (United States)

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

    2016-04-01

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

  16. Biomineralisation in the Palaeozoic oceans: evidence for simultaneous crystallisation of high and low magnesium calcite by phacopine trilobites

    OpenAIRE

    Lee, M.; Torney, C.; Owen, A. W.

    2012-01-01

    The chemical composition and microstructure of the calcite cuticles of eleven species of phacopine trilobites have been investigated by electron beam imaging, diffraction, and microanalysis, and results reveal that the lenses of their schizochroal eyes differed significantly in chemical composition from the rest of the cuticle in vivo. Apart from the eye lenses, most cuticles are inferred to have escaped extensive recrystallisation because their constituent crystals are sub-micrometre in size ...

  17. Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands)

    Science.gov (United States)

    Lazzerini, Nicolas; Lécuyer, Christophe; Amiot, Romain; Angst, Delphine; Buffetaut, Eric; Fourel, François; Daux, Valérie; Betancort, Juan Francisco; Flandrois, Jean-Pierre; Marco, Antonio Sánchez; Lomoschitz, Alejandro

    2016-10-01

    Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ18Ocalc and δ13Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ18Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in 18O relative to 16O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ18Ocalc value of eggshell calcite to the δ18Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ13Ccalc and δ18Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ13Ccalc and high δ18Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions.

  18. Strength, stability, and microstructure of simulated calcite faults sheared under laboratory conditions spanning the brittle-plastic transition

    OpenAIRE

    Verberne, B.A.

    2015-01-01

    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 behaviour of faults in carbonate rocks. In this thesis I report the results of an experimental investigation of the mechanisms controlling slip of simulated fault rocks composed of calcite (CaCO3). Shear (...

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Science.gov (United States)

    Demény, Attila; Kele, Sándor; Siklósy, Zoltán

    2010-12-30

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

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

    Energy Technology Data Exchange (ETDEWEB)

    De La Pierre, Marco, E-mail: cedric.carteret@univ-lorraine.fr, E-mail: marco.delapierre@unito.it; Maschio, Lorenzo; Orlando, Roberto; Dovesi, Roberto [Dipartimento di Chimica, Università di Torino and NIS (Nanostructured Interfaces and Surfaces) Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Carteret, Cédric, E-mail: cedric.carteret@univ-lorraine.fr, E-mail: marco.delapierre@unito.it; André, Erwan [Laboratoire de Chimie Physique et Microbiologie pour l’Environnement (LCPME), UMR 7564, Université de Lorraine-CNRS, 405 rue de Vandoeuvre, 54601 Villers-lès-Nancy (France)

    2014-04-28

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

  2. Investigation of the Potential for 90Sr Immobilization in INTEC Perched Water via Microbially Facilitated Calcite Precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Yoshiko Fujita; Karen E. Wright; William A. Smith

    2006-10-01

    The goal of this work is to evaluate the applicability of a biogeochemical sequestration approach for remediation of 90Sr contamination in perched water zones underlying the Idaho Nuclear Technology and Engineering Center (INTEC). The approach is based on the accelerated co-precipitation of the contaminant in calcite, where the acceleration is catalyzed by the microbial urea hydrolysis. We have previously demonstrated the potential for this remediation mechanism to immobilize strontium. Urea hydrolysis promotes calcite precipitation (and trace metal co-precipitation) by increasing groundwater pH and alkalinity. Ureolysis is catalyzed by the urease enzyme, which is produced by many environmental microorganisms. In the Snake River Plain Aquifer, which is saturated with respect to calcite, any co-precipitated 90Sr should be effectively sequestered over the long-term, even after return to pre-manipulation conditions. Another advantage of the ureolysis approach is that the NH4+ ions produced by the reaction can exchange with cations sorbed to subsurface minerals, thereby enhancing the availability of the radionuclides for re-capture via a more stable mechanism (co-precipitation rather than adsorption).

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

    Directory of Open Access Journals (Sweden)

    Florea Lee J.

    2011-07-01

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-12-15

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

  5. Endolithic Microbial Communities in Fractures: Insights Gleaned from Mineralized Filaments in Cretaceous-age Calcite Veins in Serpentinized Peridotites, Iberia Abyssal Plain

    Science.gov (United States)

    Milliken, K. L.

    2001-03-01

    The occurrence of diverse mineralized microbial features in calcitized fractures in serpentinized peridotite, Iberia Abyssal Plain, suggests that mineralized fractures are of particular interest in the search for fossil or extant life on Mars.

  6. Growth rate effects on Mg/Ca and Sr/Ca ratios constrained by belemnite calcite

    Science.gov (United States)

    Vinzenz Ullmann, Clemens

    2016-04-01

    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.

  7. Numerical investigation of microbially induced calcite precipitation as a leakage mitigation technology

    Science.gov (United States)

    Hommel, Johannes; Cunningham, Alfred; Helmig, Rainer; Ebigbo, Anozie; Class, Holger

    2013-04-01

    One of the key issues of carbon capture and storage (CCS) is the long term security of the storage site, i.e. the permanent enclosure of the stored carbon dioxide (CO2) in the target reservoir. Amongst the different storage mechanisms, cap rock integrity is crucial for preventing leakage of CO2. Leakage to shallower regions or back to the atmosphere would reduce the efficiency and pose a threat to the environment, for example to groundwater resources or human residence areas. Ureolysis-driven microbially induced calcite precipitation (MICP) is one of the technologies in the current focus of research aiming at mitigation of potential leakage by sealing high permeability zones in cap rocks. In our current work, a numerical model has been developed and validated using MICP experiments in sand filled columns under atmospheric pressure conditions [1]. Based on new experimental data under reservoir pressure conditions in sandstone rock cores [2] the model will be improved and optimized. The focus is on extending the model to 3-D radial flow and the validation of the model under conditions relevant for field scale CCS. The improved numerical model will be used to design field scale MICP experiments and evaluate the results of those experiments to get a better understanding of the potential of MICP as a sealing technology. [1] Ebigbo A., Phillips A., Gerlach R., Helmig R., Cunningham A.B., Class H., and Spangler L. H. (2012), Darcy-scale modeling of microbially induced carbonate mineral precipitation in sand columns, Water Resour. Res., 48 [2] Phillips A., Lauchnor E., Eldring J., Esposito R., Mitchell A.C., Gerlach R., Cunningham A.B., and Spangler L. H. (2013), Potential CO2 leakage reduction through biofilm-induced calcium carbonate precipitation, Environ. Sci. Technol., 47(1)

  8. Estimation of unknown parameters to improve modeling of Microbially Induced Calcite Precipitation

    Science.gov (United States)

    Hommel, Johannes; Cunningham, Alfred B.; Helmig, Rainer; Ebigbo, Anozie; Class, Holger

    2014-05-01

    One of the key issues of underground gas storage is the long-term security of the storage site. Amongst the different storage mechanisms, cap-rock integrity is crucial for preventing leakage of the stored gas due to buoyancy into shallower aquifers or, ultimately, the atmosphere. This leakage would reduce the efficiency of underground gas storage and pose a threat to the environment. Ureolysis-driven, Microbially Induced Calcite Precipitation (MICP) is one of the technologies in the current focus of current research aiming at mitigation of potential leakage by sealing high-permeability zones in cap rocks. Previously, a numerical model, capable of simulating two-phase flow and MICP processes, was developed and validated against MICP experiments [1]. The model has been improved based on new experimental findings of our collaborators at MSU with respect to the microbial ureolysis kinetics as well as the impact of biomineralization on permeability. The number of fitting parameters used in the model has been reduced and the remaining ones have been refitted by inverse modeling. With the improved implementation of those processes relevant for modeling MICP, simulation results are expected to better match the observed features of a variety of MICP experiments in different porous media, flow regimes and under varying injection schemes conducted by our collaborators at MSU. References [1] A. Ebigbo, A.J. Phillips, R. Gerlach, R. Helmig, A.B. Cunningham, H. Class, L.H. Spangler. Darcy-scale modeling of microbially induced carbonate mineral precipitation in sand columns. Water Resources Research, 48, (2012)

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

    Directory of Open Access Journals (Sweden)

    J. C. Wit

    2013-10-01

    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.

  10. Species-specific coccolith calcite chemistry response to monsoonal upwelling (northwestern Indian Ocean)

    Science.gov (United States)

    Ziveri, P.; Kroon, D.; Stoll, H.; Ganssen, G.; Brummer, G.-J.

    2003-04-01

    The chemistry of coccoliths serves both as a record of changes in the chemistry of the ocean and as a record of environmental and biological conditions like temperature and productivity. It documents different information than that of foraminiferal carbonate because coccolithophorids, unlike foraminifers, are primary producers. Recently, a breakthrough in the separation of monospecific coccolith assemblages enabled detailed work on stable isotope composition and minor and trace elements of individual coccolith species in sediment trap and sediment samples. Culture studies indicate different nonequilibrium effects in the oxygen isotope fractionations in different species of coccolithophorids. Interest in nonequilibrium effects is also increasing as new studies reveal that these effects may provide useful new indicators for paleoceanographic studies. In the case of coccolithophorids, nonequilibrium effects appear to reflect changing ecological and physiological responses of the organisms. We discuss the calibration of the new proxies (mainly δ 18O, δ 3C, and Sr/Ca ratios in coccolith calcite) in material from a time series sediment trap located in a region with high seasonal production variability We present results on the response of species-specific coccolith chemistry in a NIOP-JGOFS sediment trap site in the NW Indian Ocean. The sediment trap was deployed off NE Somalia to intercept particle fluxes throughout both the SW and NE monsoon and the inter-monsoon period for nine months (7 June 1992 to 21 February 1993). It was found that coccolithophorids responded rapidly to the SW and NE monsoon with changes in productivity, species composition, and CaCO3 production.

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

    Directory of Open Access Journals (Sweden)

    John P. Craddock

    2016-02-01

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

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

    Science.gov (United States)

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

    2014-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-04-01

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

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

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

  16. Correcting for initial Th in speleothems to obtain the age of calcite nucleation after a growth hiatus

    Science.gov (United States)

    Richards, D. A.; Nita, D. C.; Moseley, G. E.; Hoffmann, D. L.; Standish, C. D.; Smart, P. L.; Edwards, R.

    2013-12-01

    In addition to the many U-Th dated speleothem records (δ18O δ13C, trace elements) of past environmental change based on continuous phases of calcite growth, discontinuous records also provide important constraints for a wide range of past states of the Earth system, including sea levels, permafrost extent, regional aridity and local cave flooding. Chronological information about human activity or faunal evolution can also be obtained where calcite can be seen to overlie cave art or mammalian bones, for example. Among the important considerations when determining the U-Th age of calcite that nucleates on an exposed surface are (1) initial 230Th/232Th, which can be elevated and variable in some settings, and (2) growth rate and sub-sample density, where extrapolation is required. By way of example, we present sea level data based on U-Th ages of vadose speleothems (i.e. formed above the water table and distinct from 'phreatic' examples) from caves of the circum-Caribbean , where calcite growth was interrupted by rising sea levels and then reinitiated after regression. These estimates demand large corrections and derived sea level constraints are compared with alternative data from coral reef terraces, phreatic overgrowths on speleothems or indirect, proxy evidence from oxygen isotopes to constrain rates of ice volume growth. Flowstones from the Bahamas provide useful sea level constraints because they present the longest and most continuous records in such settings (a function of preservation potential in addition to hydrological routing) and also earliest growth post-emergence after sea level fall. We revisit estimates for sea level regression at the end of MIS 5 at ~ 80 ka (Richards et al, 1994; Lundberg and Ford, 1994) and make corrections for non-Bulk Earth initial Th contamination (230Th/232Th activity ratio > 10), based on isochron analysis of alternative stalagmites from the same settings and recent high resolution analysis. We also present new U-Th ages for

  17. New inversion of calcite twin data for paleostress tested and calibrated on numerically-generated and natural data

    Science.gov (United States)

    Parlangeau, Camille; Lacombe, Olivier; Schueller, Sylvie; Daniel, Jean-Marc

    2016-04-01

    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 of inversion of calcite twin data, which allows reconstructing the 5 parameters of the deviatoric stress tensor. In order to determine the applicability domain of the technique as well as to estimate the uncertainties on the reconstructed stress tensors, we first carried out tests on numerically generated calcite twin data and tested the separability of superimposed stress tensors with various degrees of similarity and the influence of optical bias, heterogeneities and occurrence of different grain size classes as met in natural samples. For monophase datasets with homogeneous grain size, the errors on the different stress parameters (orientation of principal stress axes, stress ratio and differential stresses) are negligible except for the differential stress (error of 5%). In cases displaying distinct grain sizes, misfits remain negligible but may reach 20% for the differential stress if the differential stress applied is greater than 60-65 MPa. Incorporation of optical bias slightly increases uncertainties up to 25% for the differential stress, 5% for the stress ratio and 8° for the orientation of the principal stress axes. For polyphase datasets with homogeneous grain size, the misfit on the orientation of the principal stress axes increases up to 10°, the stress ratio remains well constrained and the misfit on differential stress reaches 20% (applied differential stress > 70 MPa). Incorporation of optical bias increases the misfit of the orientation of the principal stress axes (average misfit: 6-8°; maximum: 17°), the misfit on stress ratio (average misfit: 2%; maximum: 26%) and the misfit on the differential stress (average misfit: 15%; maximum: 30%) These tests demonstrate that it is better to analyze twin data from subsets of

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

    Science.gov (United States)

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

    2016-04-01

    We present laboratory experiments aiming to understand the processes affecting the δ13C and δ18O values of speleothems during precipitation of calcite from a thin layer of solution. In particular, we determined the precipitation rates and the isotope fractionation factors in dependence of several parameters, such as temperature, cave pCO2 and supersaturation with respect to calcite. The experiments were performed in a climate box in order to simulate cave conditions and to control them during the experiments[1]. In the experiments, a thin film of a CaCO3-CO2-H2O-solution supersaturated with respect to calcite flew down an inclined marble surface or a sand-blasted borosilicate glass plate, and the drip water was sampled at different distances and, thus, residence times on the plate. Subsequently, pH, electrical conductivity and the δ13C and δ18O values of the dissolved inorganic carbon (DIC) as well as the precipitated CaCO3 were determined. In addition, we determined the stable isotope values of the drip water and the atmosphere inside the box during the experiments. This enabled the identification of carbon and oxygen isotope fractionation factors between all carbonate species. The experiments were conducted at 10, 20 and 30 ° C, a pCO2 of 1000 and 3000 ppmV and with a Ca2+ concentration of 2 and 5 mmol/l. We observed an exponential decay of conductivity with increasing distance of flow documenting progressive precipitation of calcite confirming previous observations[2]. The corresponding time constants of precipitation range from 180 to 660 s. Both the δ13C and δ18O values show a progressive increase along the flow path. The enrichment of the δ13C values seems to be strongly influenced by kinetic isotope fractionation, whereas the δ18O values are in the range of isotopic equilibrium. The fractionation between the precipitated CaCO3 and DIC is between -1 and - 6.5 ‰ for carbon isotopes (13ɛ) and between -1.5 and -3 ‰ for oxygen isotopes (18ɛ). The

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

    Science.gov (United States)

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

    2016-04-01

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

  20. Evaluation of Effect of Brushite-Calcite and Two Indigenous Herbs in Removal of Fluoride from Water

    Science.gov (United States)

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

    2016-01-01

    Introduction 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. Aim 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. Materials and Methods 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. Results 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. Conclusion The results of the study suggest that tulsi can be used for domestic water defluoridation as it is economic, safe and effective. PMID:27504417

  1. Origin of gem corundum in calcite marble: The Revelstoke occurrence in the Canadian Cordillera of British Columbia

    Science.gov (United States)

    Dzikowski, Tashia J.; Cempírek, Jan; Groat, Lee A.; Dipple, Gregory M.; Giuliani, Gaston

    2014-06-01

    The calcite marble-hosted gem corundum (ruby, sapphire) occurrence near Revelstoke, British Columbia, Canada, occurs in the Monashee Complex of the Omineca Belt of the Canadian Cordillera. Corundum occurs in thin, folded and stretched layers with green muscovite + Ba-bearing K-feldspar + anorthite (An0.85-1) ± phlogopite ± Na-poor scapolite. Other silicate layers within the marble are composed of: (1) diopside + tremolite ± quartz and (2) garnet (Alm0.7-0.5Grs0.2-0.4) + Na-rich scapolite + diopside + tremolite + Na,K-amphiboles. Non-silicate layers in the marble are either magnetite- or graphite-bearing. Predominantly pink (locally red or purple) opaque to transparent corundum crystals have elevated Cr2O3 (≤ 0.21 wt.%) and variable amounts of TiO2; rare blue rims on the corundum crystals contain higher amounts of TiO2 (≤ 0.53 wt.%) and Fe2O3 (≤ 0.07 wt.%). The associated micas have elevated Cr, V, Ti, and Ba contents. Petrography of the silicate layers show that corundum formed from muscovite at the peak of metamorphism (~ 650-700 °C at 8.5-9 kbar). Because the marble is almost pure calcite (dolomite is very rare), the corundum was preserved because it did not react with dolomite to spinel + calcite during decompression. The scapolite-bearing assemblages formed during or after decompression of the rock at ~ 650 °C and 4-6 kbar. Gem-quality corundum crystals formed especially on borders of the mica-feldspar layers in an assemblage with calcite. Whole rock geochemistry data show that the corundum-bearing silicate (mica-feldspar) layers formed by mechanical mixing of carbonate with the host gneiss protolith; the bulk composition of the silicate layers was modified by Si and Fe depletion during prograde metamorphism. High element mobility is supported by the homogenization of δ18O and δ13C values in carbonates and silicates for the marble and silicate layers. The silicate layers and the gneiss contain elevated contents of Cr and V due to the volcanoclastic

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

    Directory of Open Access Journals (Sweden)

    Bernd ZOLITSCHKA

    2009-08-01

    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

  3. Polygenetic Karsted Hardground Omission Surfaces in Lower Silurian Neritic Limestones: a Signature of Early Paleozoic Calcite Seas

    Science.gov (United States)

    James, Noel P.; Desrochers, André; Kyser, Kurt T.

    2015-04-01

    Exquisitely preserved and well-exposed rocky paleoshoreline omission surfaces in Lower Silurian Chicotte Formation limestones on Anticosti Island, Quebec, are interpreted to be the product of combined marine and meteoric diagenesis. The different omission features include; 1) planar erosional bedding tops, 2) scalloped erosional surfaces, 3) knobs, ridges, and swales at bedding contacts, and 4) paleoscarps. An interpretation is proposed that relates specific omission surface styles to different diagenetic-depositional processes that took place in separate terrestrial-peritidal-shallow neritic zones. Such processes were linked to fluctuations in relative sea level with specific zones of diagenesis such as; 1) karst corrosion, 2) peritidal erosion, 3) subtidal seawater flushing and cementation, and 4) shallow subtidal deposition. Most surfaces are interpreted to have been the result of initial extensive shallow-water synsedimentary lithification that were, as sea level fell, altered by exposure and subaerial corrosion, only to be buried by sediments as sea level rose again. This succession was repeated several times resulting in a suite of recurring polyphase omission surfaces through many meters of stratigraphic section. Synsedimentary cloudy marine cements are well preserved and are thus interpreted to have been calcitic originally. Aragonite components are rare and thought to have to have been dissolved just below the Silurian seafloor. Large molluscs that survived such seafloor removal were nonetheless leached and the resultant megamoulds were filled with synsedimentary calcite cement. These Silurian inner neritic-strandline omission surfaces are temporally unique. They are part of a suite of marine omission surfaces that are mostly found in early Paleozoic neritic carbonate sedimentary rocks. These karsted hardgrounds formed during a calcite-sea time of elevated marine carbonate saturation and extensive marine cement precipitation. The contemporaneous greenhouse

  4. Cobalt incorporation in calcite: thermochemistry of (Ca,Co)CO3 solid solutions from density functional theory simulations

    Science.gov (United States)

    González-López, Jorge; Ruiz-Hernández, Sergio E.; Fernández-González, Ángeles; Jiménez, Amalia; de Leeuw, Nora H.; Grau-Crespo, Ricardo

    2015-04-01

    The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. Atomistic computer simulations, which allow the evaluation of thermodynamic properties without the interference of unknown kinetic factors, have been increasingly used in recent years for the investigation of the thermodynamics of mixing and impurity incorporation in carbonate. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. The solvus and spinodal lines in the phase diagram using a sub-regular solution model has been also calculated, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. The strong non-ideality of this solid solution has an important effect on the solid solution / aqueous solution thermodynamic partitioning: the equilibrium level of substitutional impurities in the endmember solids is always low, regardless of the composition of the aqueous

  5. Origin of authigenic calcite and aragonite in pelagic sediments of the Mendeleev Ridge (Arctic Ocean) and their paleoceanographicimplications

    Science.gov (United States)

    Woo, K. S.; Ji, H. S.; Nam, S.; Stein, R. H.; Mackensen, A.; Matthiessen, J. J.

    2013-12-01

    Carbonate minerals were discovered from the giant box core (PS72/410-1) of the pelagic sediments recovered from the Canadian Arctic across the central Mendeleev Ridge (Station location= Lat. 80°30.37"N, Long. 175°44.38"W) during the Arctic cruise by Polarstern in 2008. The core was 39 cm long and was collected from the water depth of 1802 meters. The sediments show various colours from grey to brown as previously reported in other Arctic pelagic sediments. The sediments include planktonic foraminifers together with carbonate minerals. The contents of planktonic foraminifers and carbonate minerals vary with core depth, however these carbonate minerals are present through the whole sequence except for a few centimetres. After wet sieving, coarse fractions were texturally examined with binocular microscope and SEM, and stable isotope and trace element contents were obtained. Mineralogy of carbonate minerals were determined using crystal shapes and qualitative Sr contents by EDAX together with trace element analysis. The carbonates are composed of high Mg-calcite, low Mg-calcite and aragonite. Aragonite crystals show (1) radiating fibrous texture, (2) randomly oriented fibrous texture, (3) spherulitic fibrous texture, and (4) bladed texture, and calcite crystals show (1) foliated texture, (2) randomly bladed texture, (3) spherulitic fibrous texture, and (4) equant texture. Various crystal shapes of aragonite and calcite together with clear growth shapes of the crystals suggest that they are inorganic in origin. Highly enriched carbon isotope compositions (δ13C = 0 ~ +5‰ vs. PDB) strongly indicate that they formed in methanogenic zone below sediment/water interface by the reaction between anoxic pore fluids and host sediments induced by methanogenic bacteria. However, a wide range of oxygen isotope values (δ18O = -5 ~ +5‰ vs. PDB) may indicate that porewater has been changed due to reaction between residual seawater and volcanic sediments. Four types of stable

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

    Energy Technology Data Exchange (ETDEWEB)

    Legens, Ch.

    1997-12-03

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

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

    Science.gov (United States)

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

    2010-12-01

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

  8. 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

    2015-01-01

    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.

  9. Reliability of stable carbon and oxygen isotope compositions of pedogenic needle fibre calcite as environmental indicators: examples from Western Europe.

    Science.gov (United States)

    Millière, Laure; Spangenberg, Jorge E; Bindschedler, Saskia; Cailleau, Guillaume; Verrecchia, Eric P

    2011-09-01

    Stable carbon and oxygen isotope analyses were conducted on pedogenic needle fibre calcite (NFC) from seven sites in areas with roughly similar temperate climates in Western Europe, including the Swiss Jura Mountains, eastern and southern France, northern Wales, and north-eastern Spain. The δ(13)C values (-12.5 to-6.8 ‰ Vienna Pee Dee Belemnite (VPDB)) record the predominant C(3) vegetation cover at the sites. A good correlation was found between mean monthly climatic parameters (air temperature, number of frost days, humidity, and precipitation) and δ(18)O values (-7.8 to-3.4‰ VPDB) of all the NFC. Similar seasonal variations of δ(18)O values for monthly NFC samples from the Swiss sites and those of mean monthly δ(18)O values of local precipitation and meteorological data point out precipitation and preferential growth/or recrystallisation of the pedogenic needle calcite during dry seasons. These covariations indicate the potential of stable isotope compositions of preserved NFC in fossil soil horizons as a promising tool for palaeoenvironmental reconstructions.

  10. Determination of the tectonic evolution from fractures, faults, and calcite twins on the southwestern margin of the Indochina Block

    Science.gov (United States)

    Arboit, Francesco; Amrouch, Khalid; Collins, Alan S.; King, Rosalind; Morley, Christopher

    2015-08-01

    In polyphase tectonic zones, integrating a study of fault and fracture with calcite twin analysis can determine the evolving paleostress magnitudes and principle stress directions that affected the area. This paper presents the results of the analyses of fractures, striated faults, and calcite twins collected within the Khao Khwang Fold-Thrust Belt in central Thailand (SE Asia). Here we attempt to reconstruct the orientation of the principal stresses that developed during the tectonic evolution of this highly deformed, polyphase orogen. Tectonic data were collected in the Permian carbonates of the Khao Khad Formation of the Saraburi Group, and five successive tectonic stages are determined that are interpreted to have developed before, during, and after, the Triassic Indosinian Orogeny. The first three stages predate the main deformation event: the first stage is interpreted as a pre-Indosinian N-S extensional stage, the second stage described a N-S strike-slip and compressional regime, largely perpendicular to the fold axes of the main structures, while the third stage is associated with an E-W compressional strike-slip phase. A further two stages took place after, or during, the main folding event and correspond to N-S compression and to an E-W composite strike-slip/contractional stage, the latter which is interpreted to represent Cenozoic deformation related to the India-Asia collision.

  11. TO STUDY THE MECHANICAL BEHAVIOUR OF CHANGE IN CONCENTRATION OF CALCITE FLUORIDE OF METAL CORED WELDING ELECTRODES

    Directory of Open Access Journals (Sweden)

    Sandeep

    2012-07-01

    Full Text Available Mild steels are the most common type of steels used in various engineering applications. Mild steels are widely used in various structural and fabrication applications like Bridges, buildings, machineries etc. Being very common and general purpose structural steel, it is widely applied to welding all over the world. A variety of electrodes are available globally for welding of mild steel, but the development of new electrodes is always a necessity.Dissertation aims to find out the mechanical behavior of change in concentration of Calcite Fluoride in the flux composition on the various characteristics of metal cored coated electrodes for the purpose of developing efficient and better rutile electrodes for structural mild steel. The information about the effects of CaF2 on the electrodes characteristics is scarce in international welding literature. In this work five rutile metal cored coated electrodes were prepared by increasing Calcium Fluoride (CaF2, at the expense of cellulose and Si-bearing components like Mica and Calcite in the fluxes. Various mechanical properties like micro hardness, tensileproperties and Impact toughness were measured and metallographic studies were undertaken. Qualitative measurements of operational properties like porosity, slag detachability, arc stability and smoke level were also carried out.

  12. Occlusion of Sulfate-Based Diblock Copolymer Nanoparticles within Calcite: Effect of Varying the Surface Density of Anionic Stabilizer Chains

    Science.gov (United States)

    2016-01-01

    Polymerization-induced self-assembly (PISA) offers a highly versatile and efficient route to a wide range of organic nanoparticles. In this article, we demonstrate for the first time that poly(ammonium 2-sulfatoethyl methacrylate)-poly(benzyl methacrylate) [PSEM–PBzMA] diblock copolymer nanoparticles can be prepared with either a high or low PSEM stabilizer surface density using either RAFT dispersion polymerization in a 2:1 v/v ethanol/water mixture or RAFT aqueous emulsion polymerization, respectively. We then use these model nanoparticles to gain new insight into a key topic in materials chemistry: the occlusion of organic additives into inorganic crystals. Substantial differences are observed for the extent of occlusion of these two types of anionic nanoparticles into calcite (CaCO3), which serves as a suitable model host crystal. A low PSEM stabilizer surface density leads to uniform nanoparticle occlusion within calcite at up to 7.5% w/w (16% v/v), while minimal occlusion occurs when using nanoparticles with a high PSEM stabilizer surface density. This counter-intuitive observation suggests that an optimum anionic surface density is required for efficient occlusion, which provides a hitherto unexpected design rule for the incorporation of nanoparticles within crystals. PMID:27509298

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

    Science.gov (United States)

    Anderson, Lesleigh

    2011-01-01

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

  14. X-ray dose response of calcite-A comprehensive analysis for optimal application in TL dosimetry

    Science.gov (United States)

    Kalita, J. M.; Wary, G.

    2016-09-01

    The effect of various annealing treatments on dosimetric characteristics of orange calcite (CaCO3) mineral has been studied in detail. Quantitative analysis on the dose response shows that the 573 K annealed sample showed sublinear dose response from 10 mGy to 1 Gy. The fading and reproducibility of this sample are also good enough for dosimetric application. However, a specific annealing treatment after irradiation shows some significant improvements in the dosimetric characteristics of the sample. The 773 K pre-annealed sample, after X-ray irradiation post-annealing at 340 K for 6 min provides linear dose response from 10 mGy to 3.60 Gy, very less fading and good reproducibility. Moreover, this sample after post-annealing at 380 K for 6 min shows linear dose response from 10 mGy to 5.40 Gy when analyzed from the ∼408 K thermoluminescence (TL) glow peak. Analysis of TL glow curves confirmed that the 1.30 eV trap center in calcite crystal is the most effective trapping site for dosimetric application.

  15. Elucidating low-frequency vibrational dynamics in calcite and water with time-resolved third-harmonic generation spectroscopy.

    Science.gov (United States)

    Wang, Liang; Liu, Weimin; Fang, Chong

    2015-07-14

    Low-frequency vibrations are foundational for material properties including thermal conductivity and chemical reactivity. To resolve the intrinsic molecular conformational dynamics in condensed phase, we implement time-resolved third-harmonic generation (TRTHG) spectroscopy to unravel collective skeletal motions in calcite, water, and aqueous salt solution in situ. The lifetime of three Raman-active modes in polycrystalline calcite at 155, 282 and 703 cm(-1) is found to be ca. 1.6 ps, 1.3 ps and 250 fs, respectively. The lifetime difference is due to crystallographic defects and anharmonic effects. By incorporating a home-built wire-guided liquid jet, we apply TRTHG to investigate pure water and ZnCl2 aqueous solution, revealing ultrafast dynamics of water intermolecular stretching and librational bands below 500 cm(-1) and a characteristic 280 cm(-1) vibrational mode in the ZnCl4(H2O)2(2-) complex. TRTHG proves to be a compact and versatile technique that directly uses the 800 nm fundamental laser pulse output to capture ultrafast low-frequency vibrational motion snapshots in condensed-phase materials including the omnipresent water, which provides the important time dimension to spectral characterization of molecular structure-function relationships.

  16. The equilibrium between diagenetic calcites and dolomites and its impact on reservoir quality in the sandstone reservoir of Kela 2 gas field

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Based on the equilibrium theory of chemical reactions between water and rocks, this paper establishes a thermodynamic phase relationship diagram among calcites, dolomites and water solution under the condition of diagenesis based on the thermodynamic database of related minerals and fluids and dolomite's degree of order parameters. It has been discovered that the equilibrium between calcites and dolomites in the diagenetic environment is strongly impacted by temperature and the Ca/Mg ratios in groundwater, and that the dolomite's degree of order in the diagenetic environment is a function of crystallization temperature and time, not controlled by water solution. Hereby, the authors make a further analysis of the close relationship of chemical reaction between carbonate cements and pore water in the sandstone reservoirs of Kala 2 gas field in Kuche sag. It can be seen that there are different impacts on sandstone reservoir quality among the equilibrium system of calcites, dolomites and pore water at different depths of reservoirs.

  17. Initial responses of carbonate-rich shelf sediments to rising atmospheric pCO2 and “ocean acidification”: Role of high Mg-calcites

    Science.gov (United States)

    Morse, John W.; Andersson, Andreas J.; Mackenzie, Fred T.

    2006-12-01

    Carbonate-rich sediments at shoal to shelf depths (MgCO 3. The only valid relationship that one can provisionally use for the metastable stabilities for Mg-calcite based on composition is that for the synthetically produced phases where metastable equilibrium has been achieved from both under- and over-saturation. Biogenic Mg-calcites exhibit a large offset in solubility from that of abiotic Mg-calcite and can also exhibit a wide range of solubilities for biogenic Mg-calcites of similar Mg content. This indicates that factors other than the Mg content can influence the solubility of these mineral phases. Thus, it is necessary to turn to observations of natural sediments where changes in the saturation state of surrounding waters occur in order to determine their likely responses to the changing saturation state in upper oceanic waters brought on by increasing pCO 2. In the present study, we investigate the responses of Mg-calcites to rising pCO 2 and "ocean acidification" by means of a simple numerical model based on the experimental range of biogenic Mg-calcite solubilities as a function of Mg content in order to bracket the behavior of the most abundant Mg-calcite phases in the natural environment. In addition, observational data from Bermuda and the Great Bahama Bank are also presented in order to project future responses of these minerals. The numerical simulations suggest that Mg-calcite minerals will respond to rising pCO 2 by sequential dissolution according to mineral stability, progressively leading to removal of the more soluble phases until the least soluble phases remain. These results are confirmed by laboratory experiments and observations from Bermuda. As a consequence of continuous increases in atmospheric CO 2 from burning of fossil fuels, the average composition of contemporary carbonate sediments could change, i.e., the average Mg content in the sediments may slowly decrease. Furthermore, evidence from the Great Bahama Bank indicates that the

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

    Science.gov (United States)

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

    2007-12-01

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

  19. Temperature dependence of oxygen isotope fractionation in coccolith calcite: A culture and core top calibration of the genus Calcidiscus

    Science.gov (United States)

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

    2013-01-01

    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

  20. Orientation with a Viking sun-compass, a shadow-stick, and two calcite sunstones under various weather conditions.

    Science.gov (United States)

    Bernáth, Balázs; Blahó, Miklós; Egri, Adám; Barta, András; Kriska, György; Horváth, Gábor

    2013-09-01

    It is widely accepted that Vikings used sun-compasses to derive true directions from the cast shadow of a gnomon. It has been hypothesized that when a cast shadow was not formed, Viking navigators relied on crude skylight polarimetry with the aid of dichroic or birefringent crystals, called "sunstones." We demonstrate here that a simple tool, that we call "shadow-stick," could have allowed orientation by a sun-compass with satisfying accuracy when shadows were not formed, but the sun position could have reliably been estimated. In field tests, we performed orientation trials with a set composed of a sun-compass, two calcite sunstones, and a shadow-stick. We show here that such a set could have been an effective orientation tool for Vikings only when clear, blue patches of the sky were visible.

  1. Calcite Twins, a Tool for Tectonic Studies in Thrust Belts and Stable Orogenic Forelands Les macles de la calcite, un outil pour les études tectoniques dans les chaînes plissées et les avant-pays peu déformés des orogènes

    Directory of Open Access Journals (Sweden)

    Lacombe O.

    2010-10-01

    Full Text Available Calcite twins have been used for a long time as indicators of stress/strain orientations and magnitudes. Recent developments during the last 15 years point toward significant improvements of existing techniques as well as new applications of calcite twin analysis in thrust belts and forelands. This paper summarizes the principles of the most common techniques in this tectonic field and illustrates some aspects of the use of calcite twins to constrain not only stress/strain orientations and magnitudes, but also to some extent paleotemperature or paleoburial in orogenic forelands. This review is based in a large part on the studies that I conducted in various geological settings such as the forelands of Taiwan, Pyrenees, Zagros, Rockies and Albanides orogens. The contribution of calcite twin analysis to the understanding of the intraplate stress transmission away from plate boundaries is also emphasized. Les macles de la calcite sont utilisees depuis longtemps comme indicateurs de paleocontraintes et comme marqueurs de la deformation finie, en orientations comme en grandeurs. Au cours des 15 dernieres annees, des ameliorations importantes des methodes d’analyses existantes ont ete realisees et ont donne lieu a de nouvelles applications dans les chaines plissees et les avant-pays peu deformes des orogenes. Cet article resume le principe des methodes les plus utilisees en tectonique et illustre quelques apports de l’analyse des macles de la calcite pour la caracterisation non seulement des orientations et des grandeurs des paleocontraintes et de la deformation finie, mais egalement dans une certaine mesure de la paleotemperature et du paleoenfouissement. Cette revue se fonde en grande partie sur les etudes regionales que j’ai effectuees dans des contextes geologiques varies, comme les avant-pays des chaines de Taiwan, des Pyrenees, du Zagros, des Rocheuses et des Albanides. Cet article discutera egalement la contribution de l’etude des

  2. 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)

    2007-01-15

    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.

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

    Science.gov (United States)

    Nishio, Takashi; Naka, Kensuke

    2015-06-01

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

  4. The impact of seawater calcite saturation state by modifying Ca ion concentrations on Mg and Sr incorporation in cultured benthic foraminifera

    Directory of Open Access Journals (Sweden)

    M. Raitzsch

    2009-12-01

    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. The dependency of Mg incorporation on seawater [Ca2+] in low-Mg species shows the need

  5. 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

    2010-09-01

    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

  6. Stable carbon isotopes and lipid biomarkers provide new insight into the formation of calcite and siderite concretions in organic-matter rich deposits

    Science.gov (United States)

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

    2015-04-01

    Carbonate concretions from two distinct settings have been studied for their petrography, stable carbon and oxygen isotopes, and lipid biomarker content. Carbonate concretions are in large part products of microbial degradation of organic matter, as for example by sulfate-reducing bacteria, iron-reducing bacteria, and methanogenic archaea. For these prokaryotes certain lipid biomarkers such as hopanoids, terminally-branched fatty acids (bacteria) and isoprenoids (archaea) are characteristic. Two different types of concretions were studied: a) Upper Miocene septarian calcite concretions of the southern Vienna Basin embedded in brackish sediments represented by partly bituminous calcareous sands, silts and clays; b) Paleocene-Eocene siderite concretions enclosed in marine, sandy to silty turbidites with varying carbonate contents and marl layers from the Upper Gosau Subgroup in northern Styria. Calcite concretions consist of abundant calcite microspar (80-90 vol.%), as well as detrital minerals and iron oxyhydroxides. The septarian cracks show beginning cementation with dog-tooth calcite to varying degrees. Framboidal pyrite occurs in some of the calcite concretions, pointing to bacterial sulfate reduction. Siderite concretions consist of even finer carbonate crystals, mainly siderite (40-70 vol.%) but also abundant ferroan calcite, accompanied by iron oxyhydroxides and detrital minerals. The δ13C values of the calcite concretions (-6.8 to -4.1o ) most likely reflect a combination of bacterial organic matter oxidation and input of marine biodetrital carbonate. The δ18O values range from -8.9 to -7.8o agreeing with a formation within a meteoric environment. The surrounding host sediment shows about 1-2o higher δ13C and δ18O values. The siderite δ13C values (-11.1 to -7.5o ) point to microbial respiration of organic carbon and the δ18O values (-3.5 to +2.2o ) agree with a marine depositional environment. In contrast to the calcite concretions, the stable isotope

  7. The influence of normal stress and sliding velocity on the frictional behaviour of calcite at room temperature: insights from laboratory experiments and microstructural observations

    Science.gov (United States)

    Carpenter, B. M.; Collettini, C.; Viti, C.; Cavallo, A.

    2016-04-01

    The presence of calcite in and near faults, as the dominant material, cement, or vein fill, indicates that the mechanical behaviour of carbonate-dominated material likely plays an important role in shallow- and mid-crustal faulting. To better understand the behaviour of calcite, under loading conditions relevant to earthquake nucleation, we sheared powdered gouge of Carrara Marble, >98 per cent CaCO3, at constant normal stresses between 1 and 100 MPa under water-saturated conditions at room temperature. We performed slide-hold-slide tests, 1-3000 s, to measure the amount of static frictional strengthening and creep relaxation, and velocity-stepping tests, 0.1-1000 μm s-1, to evaluate frictional stability. We observe that the rates of frictional strengthening and creep relaxation decrease with increasing normal stress and diverge as shear velocity is increased from 1 to 3000 μm s-1 during slide-hold-slide experiments. We also observe complex frictional stability behaviour that depends on both normal stress and shearing velocity. At normal stresses less than 20 MPa, we observe predominantly velocity-neutral friction behaviour. Above 20 MPa, we observe strong velocity-strengthening frictional behaviour at low velocities, which then evolves towards velocity-weakening friction behaviour at high velocities. Microstructural analyses of recovered samples highlight a variety of deformation mechanisms including grain size reduction and localization, folding of calcite grains and fluid-assisted diffusion mass transfer processes promoting the development of calcite nanograins in the highly deformed portions of the experimental fault. Our combined analyses indicate that calcite fault gouge transitions from brittle to semi-brittle behaviour at high normal stress and slow sliding velocities. This transition has important implications for earthquake nucleation and propagation on faults in carbonate-dominated lithologies.

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

    Science.gov (United States)

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

    2015-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-06-15

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

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

    International Nuclear Information System (INIS)

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

  11. Mesozoic (Lower Jurassic) red stromatactis limestones from the Southern Alps (Arzo, Switzerland): calcite mineral authigenesis and syneresis-type deformation

    Science.gov (United States)

    Neuweiler, Fritz; Bernoulli, Daniel

    2005-02-01

    The Broccatello lithological unit (Lower Jurassic, Hettangian to lower parts of Upper Sinemurian) near the village of Arzo (southern Alps, southern Switzerland) is a mound-shaped carbonate deposit that contains patches of red stromatactis limestone. Within the largely bioclastic Broccatello unit, the stromatactis limestone is distinguished by its early-diagenetic cavity system, a relatively fine-grained texture, and an in-situ assemblage of calcified siliceous sponges (various demosponges and hexactinellids). A complex shallow subsurface diagenetic pathway can be reconstructed from sediment petrography in combination with comparative geochemical analysis (carbon and oxygen isotopes; trace and rare earth elements, REE + Y). This pathway includes organic matter transformation, aragonite and skeletal opal dissolution, patchy calcification and lithification, sediment shrinkage, sagging and collapse, partial REE remobilization, and multiple sediment infiltration. These processes occurred under normal-marine, essentially oxic conditions and were independent from local, recurring syn-sedimentary faulting. It is concluded that the stromatactis results from a combination of calcite mineral authigenesis and syneresis-type deformation. The natural stromatactis phenomenon may thus be best explained by maturation processes of particulate polymer gels expected to form in fine-grained carbonate sediments in the shallow subsurface. Conditions favorable for the evolution of stromatactis appear to be particularly frequent during drowning of tropical or subtropical carbonate platforms.

  12. The effects of atmospheric [CO2] on carbon isotope fractionation and magnesium incorporation into biogenic marine calcite

    Science.gov (United States)

    Vieira, Veronica

    1997-01-01

    The influences of atmospheric carbon dioxide on the fractionation of carbon isotopes and the magnesium incorporation into biogenic marine calcite were investigated using samples of the calcareous alga Amphiroa and benthic foraminifer Sorites grown in the Biosphere 2 Ocean system under variable atmospheric CO2 concentrations (approximately 500 to 1200 ppm). Carbon isotope fractionation was studied in both the organic matter and the skeletal carbonate. Magnesium analysis was to be performed on the carbonate removed during decalcification. These data have not been collected due to technical problems. Carbon isotope data from Amphiroa yields a linear relation between [CO2] and Delta(sup 13)C(sub Corg)values suggesting that the fractionation of carbon isotopes during photosynthesis is positively correlated with atmospheric [CO2]. [CO2] and Delta(sup 13)C(sub Corg) values for Sorites produce a relation that is best described by a hyperbolic function where Delta(sup 13)C(sub Corg) values increase between 300 and 700 ppm and decrease from 700 to 1200 ppm. Further investigation of this relation and Sorites physiology is needed.

  13. The Influence Of Calcite On The Ash Flow Temperature For Semi-Anthracite Coal From Donbas District

    Directory of Open Access Journals (Sweden)

    Čarnogurská Mária

    2014-12-01

    Full Text Available This paper presents the results of research focused on the lowering of ash flow temperature at semianthracite coal from Donbas district by means of additive (calcite dosing. Ash fusion temperatures were set for two coal samples (A, B and for five various states (samples of ash without any additives, with 1%, with 3%, with 5% and with 7% of the additive in total. The macroscopicphotographic method was used for identifying all specific temperatures. Obtained outputs prove that A type coal has a lower value of sphere temperature than B type coal in the whole scope of percentage representation of the additive. The flow temperature dropped in total from 1489 °C to 1280 °C, i.e. by 14% during the test of coal of type A with 7% of the additive; while it was near 10% for coal of type B (from 1450 °C to 1308 °C. Numerical simulations of the process showed that it is not effective to add an additive with a grain size lower than 280 μm by means of wastevapour burners.

  14. Overview of calcite/opal deposits at or near the proposed high-level nuclear waste site, Yucca Mountain, Nevada, USA: Pedogenic, hypogene, or both?

    Science.gov (United States)

    Hill, C. A.; Dublyansky, Y. V.; Harmon, R. S.; Schluter, C. M.

    1995-09-01

    Calcite/opal deposits (COD) at Yucca Mountain were studied with respect to their regional and field geology, petrology and petrography, chemistry and isotopic geochemistry, and fluid inclusions. They were also compared with true pedogenic deposits (TPD), groundwater spring deposits (GSD), and calcite vein deposits (CVD) in the subsurface. Some of the data are equivocal and can support either a hypogene or pedogenic origin for these deposits. However, Sr-, C-, and O-isotope, fluid inclusion, and other data favor a hypogene interpretation. A hypothesis that may account for all currently available data is that the COD precipitated from warm, CO2-rich water that episodically upwelled along faults during the Pleistocene, and which, upon reaching the surface, flowed downslope within existing alluvial, colluvial, eluvial, or soil deposits. Being formed near, or on, the topographic surface, the COD acquired characteristics of pedogenic deposits. This subject relates to the suitability of Yucca Mountain as a high-level nuclear waste site.

  15. Deformation and magnetization of the Hudson Valley, eastern New York: Results of a study of calcite twinning and anisotropy of magnetic remanence in the Onondaga Limestone

    Science.gov (United States)

    Sierra, F.; Schedl, A.; McCabe, C.; Robbins, D. R.

    1993-01-01

    Results of a study of calcite-twin analysis and anisotropy of anhysteretic remanent magnetization (AARM) for the Onondaga Limestone in the Hudson Valley Fold and Thrust belt (HVB), raise questions about the deformation history of this area and the nature of AARM. Two bedding parallel shortening directions are inferred from calcite twinning: one normal to HVB fold axes, NW-SE to ENE-WSW, and the other at high angles to this direction, NNE-SSW to N-S. Two hypotheses are put forward to explain the inconsistent shortening direction: (1) even during the initial stages of folding and thrusting in the HVB, deformation was three-dimensional in character; (2) the HVB developed synchronous with Main phase Alleghanian deformation. AARM results are consistent with the magnetic anisotropy being in part caused by the deformation associated with folding and thrusting. This is a surprising result because the magnetization is presumably of diagenetic origin, and it was acquired after folding.

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

    Science.gov (United States)

    Raymond, Anne

    2016-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Lecocq, D

    2002-12-15

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

  18. Petrographic description of calcite/opal samples collected on field trip of December 5-9, 1992. Special report No. 7

    International Nuclear Information System (INIS)

    This study is part of the research program of the Yucca Mountain Project intended to provide the State of Nevada with a detailed analysis and assessment of the water-deposited minerals of Yucca Mountain and adjacent regions. Forty-three separate stops were made and 203 samples were collected during the five days of the field trip. This report describes petrographic observations made on the calcite/opal samples

  19. The difference between surface ocean carbonate chemistry and calcite dissolution in deep sea sediments as observed in tests of Globorotalia menardii

    Science.gov (United States)

    Russo, M.; Mekik, F.

    2010-12-01

    The Globorotalia menardii Fragmentation Index (MFI) was developed to trace deep sea calcite dissolution within sediments. While this proxy has a multi-basin core top calibration ranging the tropical and subtropical world ocean, the effect of the surface ocean [CO32-] on thickness of whole G. menardii shells has not been previously tested. If the size-normalized shell weight (SNSW) of G. menardii tests were affected by the [CO32-] of ambient habitat waters, this would put constraints on the applicability of MFI as a reliable bulk sediment calcite dissolution proxy. We present new SNSW data from G. menardii shells within core tops in the eastern equatorial Pacific where there is both a strong gradient to surface ocean [CO32-] and calcite dissolution in the sediments. We compare our G.menardii SNSW data with that of other species in the region, such as Neogloboquadrina dutertrei and Pulleniatina obliquiloculata. While SNSW of both N. dutertrei and P. obliquiloculata have clear relationships with surface ocean [CO32-], we do not find a similar relationship between G. menardii SNSW and surface ocean parameters, particularly [CO32-]. This bolsters our confidence in the reliability of MFI as a deep sea carbonate dissolution tracer.

  20. Inversion of calcite twin data, paleostress reconstruction and multiphase weak deformation in cratonic interior - Evidence from the Proterozoic Cuddapah basin, India

    Science.gov (United States)

    Tripathy, Vikash; Saha, Dilip

    2015-08-01

    Paleostress orientations from mechanically twinned calcite in carbonate rocks and veins in the neighborhood of large faults were investigated to comment on the nature of weak upper crustal stresses affecting sedimentary successions within the Proterozoic Cuddapah basin, India. Application of Turner's P-B-T method and Spang's Numerical dynamic analysis on Cuddapah samples provided paleostress orientations comparable to those derived from fault-slip inversion. Results from the neighborhood of E-W faults cutting through the Paleoproterozoic Papaghni and Chitravati groups and the Neoproterozoic Kurnool Group in the western Cuddapah basin, reveal existence of multiple deformation events - (1) NE-SW σ3 in strike-slip to extensional regime along with an additional event having NW-SE σ3, for lower Cuddapah samples; (2) compressional/transpressional event with ESE-WNW or NNE-SSW σ1 mainly from younger Kurnool samples. Integrating results from calcite twin data inversion, fault-slip analysis and regional geology we propose that late Mesoproterozoic crustal extension led to initial opening of the Kurnool sub-basin, subsequently influenced by weak compressional deformation. The dynamic analysis of calcite twins thus constrains the stress regimes influencing basin initiation in the southern Indian cratonic interior and subsequent basin inversion in relation to craton margin mobile belts and plausible global tectonic events in the Proterozoic.

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

    Institute of Scientific and Technical Information of China (English)

    Stephen Kershaw; Li Guo

    2016-01-01

    This paper reassesses published interpretation that beef and cone-in-cone (B-CIC) fibrous calcite cements were precipitated contemporaneously just below the sea floor in uncon-solidated sediment, in limestones associated with the end-Permian (P/T) and end-Triassic (T/J) mass extinctions. That interpretation introduced the concept of a sub-seafloor car-bonate factory associated with ocean acidification by raised carbon dioxide driven by volcanic eruption, coinciding with mass extinction. However, our new fieldwork and petrographic analysis, with literature comparison, reveals several problems with this concept. Two key points based on evidence in the T/J transition of the UK are:(1) that B-CIC calcite deposits form thin scattered layers and lenses at several horizons, not a distinct deposit associated with volcanic activity; and (2) B-CIC calcite is more common in Early Jurassic sediments after the extinction and after the end of the Central Atlantic Magmatic Province volcanism proposed to have supplied the carbon dioxide required. Our samples from Late Triassic, Early Jurassic and Early Cretaceous limestones in southern UK show that B-CIC calcite occurs in both marine and non-marine sediments, therefore ocean processes are not mandatory for its formation. There is no proof that fibrous calcite was formed before lithification, but our Early Jurassic samples do prove fibrous calcite formed after compaction, thus interpretation of crystal growth in uncon-solidated sediment is problematic. Furthermore, B-CIC crystals mostly grew both upwards and downwards equally, contradicting the interpretation of the novel carbonate factory that they grew preferentially upwards in soft sediment. Finally, Early Jurassic and Early Cretaceous examples are not associated with mass extinction. Three further key points derived from the literature include: (1) B-CIC calcite is wide-spread geographically and stratigraphically, not clustered around mass extinctions or the Paleocene

  2. 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 [University of Idaho; Fujita, Yoshiko [Idaho National Laboratory

    2013-11-15

    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 Sr-90, 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 C-13 isotopic composition of solid carbonates. It was also subjected to selective extractions for strontium and uranium. Result of the core

  3. Nyctemeral variations of magnesium intake in the calcitic layer of a Chilean mollusk shell ( Concholepas concholepas, Gastropoda)

    Science.gov (United States)

    Lazareth, Claire E.; Guzman, Nury; Poitrasson, Franck; Candaudap, Frederic; Ortlieb, Luc

    2007-11-01

    Mollusk shells are increasingly used as records of past environmental conditions, particularly for sea-surface temperature (SST) reconstructions. Many recent studies tackled SST (and/or sea-surface salinity) tracers through variations in the elementary (Mg and Sr) or stable isotope (δ 18O) composition within mollusk shells. But such attempts, which sometimes include calibration studies on modern specimens, are not always conclusive. We present here a series of Mg and Sr analyses in the calcitic layer of Concholepas concholepas (Muricidae, Gastropoda) with a very high time-resolution on a time window covering about 1 and a half month of shell formation, performed by Laser Ablation Inductively-Coupled Plasma Mass Spectrometry (LA-ICP-MS) and electron probe micro-analysis (EPMA). The selected specimen of this common Chilean gastropod was grown under controlled environmental conditions and precise weekly time-marks were imprinted in the shell with calcein staining. Strontium variations in the shell are too limited to be interpreted in terms of environmental parameter changes. In contrast, Mg incorporation into the shell and growth rate appear to change systematically between night and day. During the day, Mg is incorporated at a higher rate than at night and this intake seems positively correlated with water temperature. The nightly reduced Mg incorporation is seemingly related to metabolically controlled processes, formation of organic-rich shell increments and nocturnal feeding activity of the animals. The nyctemeral Mg changes in the C. concholepas shell revealed in this study might explain at least part of the discrepancies observed in previous studies on the use of Mg as a SST proxy in mollusk shells. In the case of C. concholepas, Mg cannot be used straightforwardly as a SST proxy.

  4. 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

    2010-08-01

    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.

  5. Early Paleogene variations in the calcite compensation depth: new constraints using old boreholes across Ninetyeast Ridge in the Indian Ocean

    Directory of Open Access Journals (Sweden)

    B. S. Slotnick

    2014-08-01

    Full Text Available Major variations in global carbon cycling occurred between 62 and 48 Ma. To better constrain the cause and magnitude of these changes, the community needs early Paleogene carbon isotope and carbonate accumulation records from widely separated deep-sea sediment sections, especially including the Indian Ocean. With the potential for renewed scientific drilling in the Indian Ocean, we examine lithologic, nannofossil assemblage, carbon isotope, and carbonate content records for late Paleocene – early Eocene sediment recovered at three existing sites spanning Ninetyeast Ridge: Deep Sea Drilling Project (DSDP Sites 213 (deep, east, 214 (shallow, central, and 215 (deep, west. The sediment sections are not ideal, because they were recovered in single holes using rotary coring methods. Site 214 was very shallow during the late Paleocene, when it received significant amounts of neritic carbonate. The δ13C records at Sites 213 and 215 are similar to those generated at several locations in the Atlantic and Pacific. The prominent high in δ13C across the Paleocene carbon isotope maximum (PCIM occurs at Site 215, and the prominent low in δ13C across the early Eocene Climatic Optimum (EECO occurs at both Site 213 and Site 215. The Paleocene–Eocene thermal maximum (PETM and the K/X event are found at Site 213 but not at Site 215, presumably because of coring gaps. Carbonate content at both Sites 213 and 215 drops to Discoaster lodoensis and the early Eocene rise in δ13C (~ 52 Ma. This reflects a rapid shoaling of the calcite compensation depth (CCD, and likely a major decrease in the net flux of 13C-depleted carbon to the ocean. Our work further constrains knowledge of the early Paleogene CCD, but more importantly suggests that excellent early Paleogene carbonate accumulation records might be recovered from the central Indian Ocean with future scientific drilling.

  6. Vital effects in coccolith calcite: Cenozoic climate-pCO2 drove the diversity of carbon acquisition strategies in coccolithophores?

    Science.gov (United States)

    Bolton, Clara T.; Stoll, Heather M.; Mendez-Vicente, Ana

    2012-12-01

    Coccoliths, calcite plates produced by the marine phytoplankton coccolithophores, have previously shown a large array of carbon and oxygen stable isotope fractionations (termed "vital effects"), correlated to cell size and hypothesized to reflect the varying importance of active carbon acquisition strategies. Culture studies show a reduced range of vital effects between large and small coccolithophores under high CO2, consistent with previous observations of a smaller range of interspecific vital effects in Paleocene coccoliths. We present new fossil data examining coccolithophore vital effects over three key Cenozoic intervals reflecting changing climate and atmospheric partial pressure of CO2 (pCO2). Oxygen and carbon stable isotopes of size-separated coccolith fractions dominated by different species from well preserved Paleocene-Eocene thermal maximum (PETM, ˜56 Ma) samples show reduced interspecific differences within the greenhouse boundary conditions of the PETM. Conversely, isotope data from the Plio-Pleistocene transition (PPT; 3.5-2 Ma) and the last glacial maximum (LGM; ˜22 ka) show persistent vital effects of ˜2‰. PPT and LGM data show a clear positive trend between coccolith (cell) size and isotopic enrichment in coccolith carbonate, as seen in laboratory cultures. On geological timescales, the degree of expression of vital effects in coccoliths appears to be insensitive topCO2 changes over the range ˜350 ppm (Pliocene) to ˜180 ppm (LGM). The modern array of coccolith vital effects arose after the PETM but before the late Pliocene and may reflect the operation of more diverse carbon acquisition strategies in coccolithophores in response to decreasing Cenozoic pCO2.

  7. 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)

    Stephanie Freeman; David Reed; Yoshiko Fujita

    2006-12-01

    The diversity of bacterial ammonia monooxygenase (amoA) genes in DNA isolated from microorganisms in groundwater was 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 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.

  8. 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.

    1995-12-01

    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.

  9. Potentials and Limitations of calcite Speleothems to chart the Secular Variation of the Earth's magnetic field during the Holocene.

    Science.gov (United States)

    Camps, P. C.; Poidras, T.; Audra, P.; Carvallo, C.; Bosch, D.; Goupil, A.

    2015-12-01

    This study addresses several issues of using calcite speleothems as a high temporal resolution archive of the directional fluctuations of the Earth's magnetic field. This was achieved by collecting 3 stalagmites in the Theoreticians' cave (St Benoît, French Alps). This cave, although hardly accessible, presents two advantages. First, there are recent speleothems as evidenced by their still active growth. Thus the remanent magnetization can be directly compared with a secular variation model such as ARCH.3k. Second, the cave is carved in lutetian limestones that are directly overlain by iron-sulfide-rich priabonian marlstones. So potentially, drip water can contain iron that is a major asset for a magnetic study. We estimated by means of various rock magnetic experiments that the remanent magnetization is carried by single-domain magnetite. The recent age of the stalagmites is confirmed with U/Th dating suggesting that our sampling covers the last 3 millennia. These ages yield a mean growing rate of about 0.1 mm/yr. Remanent magnetization measurements are carried out with a 2G cryogenic magnetometer. The challenging issue is to measure samples of small size (cylinder of 1 inch in diameter and about 2 mm in height, i.e. a sample of about 1 gram). We worked on improving measurement protocols as well as on the development of a new type of sample holder. Before each series of measurements, the magnetometer must be perfectly tuned in order to have the lowest possible baseline and a minimum drift. In the best conditions, encountered during the nights or during the weekends, the background noise is around 1x10-12 Am2. Such conditions are necessary to measure the NRM that is characterized in most cases by intensity less than 1x10-8 Am2/kg (i.e one order of magnitude above the sensitivity limit of our magnetometer). With such NRM intensities, the major challenge is to determine the direction of the ChRM by stepwise AF treatment. The results obtained are very encouraging in

  10. Pore fluid in experimental calcite-bearing faults: Abrupt weakening and geochemical signature of co-seismic processes

    Science.gov (United States)

    Violay, M.; Nielsen, S.; Spagnuolo, E.; Cinti, D.; Di Toro, G.; Di Stefano, G.

    2013-01-01

    While it is widely recognized that fluids influence fault strength and earthquake nucleation, propagation and arrest, their effects on co-seismic sliding friction are only conjectured. To shed light on these effects, 55 high velocity (>1 m s-1) friction experiments were conducted at room temperature on Carrara marble samples in the presence of pore fluid (up to 15 MPa pore pressure), room-humidity and "vacuum" (10-4 mbar) conditions. In all the experiments, the friction coefficient evolved from a peak value of 0.6-0.8 to a steady-state value of 0.1 in about 1-1.5 m of slip. However, experiments performed in the presence of pore fluid had a large and more abrupt decrease in friction at the initiation of sliding (65% after 20 mm of slip), whereas experiments performed under vacuum and room humidity conditions showed initial velocity-strengthening behavior followed by a more gradual reduction in friction. This indicates that calcite-bearing rocks are more prone to slip in the presence of water. Under room-humidity conditions, CO2 was detected during the entire duration of the experiment. In the presence of pore fluid, HCO3- and Ca2+ were detected for slips >0.1 m. The lack of decarbonation products (HCO3- and Ca2+) in pore fluid experiments for slip <0.1 m implies that the abrupt weakening is not related to decarbonation (or that the abundance of the reaction products is below the resolution of the analytical methods). Given the modest thermal expansion of water, the estimated thermal pressurization during the abrupt weakening appears to be negligible. Instead, we suggest that abrupt weakening is due to subcritical crack-growth, hydrolytic weakening and brittle failure of the asperities on the sliding surfaces. Modeling shows that the occurrence in nature of co-seismic (water-present) decarbonation reactions similar to those triggered in the laboratory could yield sufficient reaction product to be detected in aquifers located in the proximity of active faults.

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

    Science.gov (United States)

    Plummer, L. Neil; Sundquist, Eric T.

    1982-01-01

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

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

    Indian Academy of Sciences (India)

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

    2001-06-01

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

  13. 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

    2008-07-01

    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.

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

    Science.gov (United States)

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

    2015-09-30

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Zavarin, M; Bruton, C J

    2004-12-17

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

  16. Sorption of the Rare Earth Elements and Yttrium (REE-Y) in calcite: the mechanism of a new effective tool in identifying paleoearthquakes on carbonate faults

    Science.gov (United States)

    Moraetis, Daniel; Mouslopoulou, Vasiliki; Pratikakis, Alexandros

    2015-04-01

    A new tool for identifying paleoearthquakes on carbonate faults has been successfully tested on two carbonate faults in southern Europe (the Magnola Fault in Italy and the Spili Fault in Greece): the Rare Earth Element and Yttrium (REE-Y) method (Manighetti et al., 2010; Mouslopoulou et al., 2011). The method is based on the property of the calcite in limestone scarps to absorb the REE and Y from the soil during its residence beneath the ground surface (e.g. before its exhumation due to earthquakes). Although the method is established, the details of the enrichment mechanism are poorly investigated. Here we use published data together with new information from pot-experiments to shed light on the sorption mechanism and the time effectiveness of the REE-Y method. Data from the Magnola and Spili faults show that the average chemical enrichment is ~45%, in REE-Y while the denudation rate of the enriched zones is ~1% higher every 400 years due to exposure of the fault scarp in weathering. They also show that the chemical enrichment is significant even for short periods of residence time (e.g., ~100 years). To better understand the enrichment mechanism, we performed a series of pot experiments, where carbonate tiles extracted from the Spili Fault were buried into soil collected from the hanging-wall of the same fault. We irrigated the pots with artificial rain that equals 5 years of rainfall in Crete and at temperatures of 15oC and 25oC. Following, we performed sorption isotherm, kinetic and pH-edge tests for the europium (Eu), the cerium (Ce) and the ytterbium (Yt) that occur in the calcite minerals. The processes of adsorption and precipitation in the batch experiments are simulated by the Mineql software. The pot experiments indicate incorporation of the REE and Y into the surface of the carbonate tile which is in contact with the soil. The pH of the leached solution during the rain application range from 7.6 to 8.3. Nutrient release like Ca is higher in the leached

  17. Chemical and physical evolution of dolomite precipitation at 180°C and 220°C from calcite and aragonite seeds

    Science.gov (United States)

    Kell-Duivestein, Isaac; Dietzel, Martin; Mavromatis, Vasileios

    2016-04-01

    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

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

    Directory of Open Access Journals (Sweden)

    Mansour Rezaei Azizi

    2015-04-01

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

  19. Paleostress reconstruction from calcite twin and fault-slip data using the multiple inverse method in the East Walanae fault zone: Implications for the Neogene contraction in South Sulawesi, Indonesia

    Science.gov (United States)

    Jaya, Asri; Nishikawa, Osamu

    2013-10-01

    A new approach for paleostress analysis using the multiple inverse method with calcite twin data including untwinned e-plane was performed in the East Walanae fault (EWF) zone in South Sulawesi, Indonesia. Application of untwinned e-plane data of calcite grain to constrain paleostress determination is the first attempt for this method. Stress states caused by the collision of the south-east margin of Sundaland with the Australian microcontinents during the Pliocene were successfully detected from a combination of calcite-twin data and fault-slip data. This Pliocene NE-SW-to-E-W-directed maximum compression activated the EWF as a reverse fault with a dextral component of slip with pervasive development of secondary structures in the narrow zone between Bone Mountain and Walanae Depression.

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

    Energy Technology Data Exchange (ETDEWEB)

    Archambeau, C.

    1994-08-01

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

  1. 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

    2014-12-01

    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.

  2. Mechanism of O and C isotope fractionation in magnesian calcite skeletons of Octocorallia corals and an implication on their calcification response to ocean acidification

    Directory of Open Access Journals (Sweden)

    T. Yoshimura

    2015-01-01

    Full Text Available Coral calcification is strongly dependent on both the pH and the dissolved inorganic carbon (DIC of the calcifying fluid. Skeletal oxygen and carbon isotope fractionation of high-Mg calcite skeletons of \\textit{Octocorallia} corals directly record the biological manipulation on sources of DIC in response to environmental changes. The coral skeletons were enriched in light isotopes (16O and 12C relative to the expected values based on habitat environmental parameters and Mg/Ca of the skeletons. The differences between the expected and observed values ranged from −4.66 to −1.53 for δ18O and from −7.34 to −1.75 for δ13C. The large variability cannot be explained by the ambient environment, the contribution of metabolic carbon, or the precipitation rate of the skeleton. Therefore, the most plausible explanation for the observed O and C isotope differences in high-Mg calcite coral skeletons is the existence of two carbon sources, aqueous carbon dioxide in the calcifying fluid and dissolved inorganic carbon in seawater. Positive correlations of B/Ca with δ18O and δ13C suggest that skeletal isotopic compositions are enriched in light isotopes when conditions are less alkaline. Therefore, the relative contribution of isotopically heavy DIC from seawater through the skeleton and pericellular channels decreases under the reduced pH of the extracytoplasmic calcifying fluid. Our data suggest an even stronger biological effect under lower pH. Skeletal δ18O and δ13C values record the response of the sources of DIC in the coral calcifying fluids to ambient seawater pH. These changes give insight into how ocean acidification impacts the physiological mechanisms as well as the pH offset between calcifying fluid and seawater in response to ocean acidification.

  3. Reconstruction of drip-water δ18O based on calcite oxygen and clumped isotopes of speleothems from Bunker Cave (Germany

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    T. Kluge

    2013-02-01

    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.

  4. Reconstruction of drip-water δ18O based on calcite oxygen and clumped isotopes of speleothems from Bunker Cave (Germany

    Directory of Open Access Journals (Sweden)

    A. Wackerbarth

    2012-07-01

    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, Marine Isotope Stage (MIS 3, 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., MIS 3: −8.5 ± 0.4‰ and the early Holocene at 11 kyr: −9.3 ± 0.1‰ and show higher values during warmer climatic periods (e.g., the Eemian: −7.5 ± 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. Unusual carbon and oxygen isotropic ratios of ostracodal calcite from last interglacial (Sangamon episode) lacustrine sediment in Raymond Basin, Illinois, USA

    Science.gov (United States)

    Curry, B. Brandon; Anderson, T.F.; Lohmann, K.C.

    1997-01-01

    The stable isotopic records of ostracode valves deposited during the last interglaciation in Raymond Basin, Illinois, have ??13C and ??18O values as high as +16.5??? and +9.2??? respectively, the highest values yet reported from continental ostracodal calcite. Located in south-central Illinois, Raymond, Pittsburgh, Bald Knob, and Hopwood Farm basins collectively have yielded important long pollen and ostracode records that date from about 130 000 years ago to the present. Although fossils from the present-day interglaciation are not well preserved, these records constitute the only described, conformable, fossiliferous successions of this age from the interior of glaciated North America. The high ??13C values from Raymond Basin are attributed to the residual effects of methane loss either by ebullition or by emission through the stems of senescent emergent aquatic vegetation. A mass balance model suggests that an increase in ??13C of dissolved inorganic carbon on the order of +15??? is possible within a few hours given modest rates of methanogenesis of about 0.02 mol m-2 d-1. The ??13C records from other studies of ostracode valves have values approaching, but not exceeding about +14??? suggesting a limiting value to ???13C enrichment due to simultaneous inputs and outputs of dissolved inorganic carbon. Values of ??18O in ostracodal calcite are quite variable (-4 to +9???) in sediment from the late Sangamon subepisode. A model of isotopic enrichment in a desiccating water body implies that a reduction in reservoir volume of 20% could produce this range of isotopic values. High humidity and evaporation probably account for most of the ??18O variability.

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

    Science.gov (United States)

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

    2010-01-01

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

  7. The elemental composition of purple sea urchin (Strongylocentrotus purpuratus) calcite and potential effects of pCO2 during early life stages

    Science.gov (United States)

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

    2013-06-01

    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. Geochemistry of sapphirine-apatite-calcite-bearing gabbroic dykes from the Finero Phlogopite Peridotite (Ivrea-Verbano Zone): evidence for multistage interaction with the ambient peridotite

    Science.gov (United States)

    Tommaso, Giovanardi; Alberto, Zanetti; Maurizio, Mazzucchelli; Tomoaki, Morishita; Antonio, Langone

    2016-04-01

    The Finero Phlogopite-Peridotite (FPP) is a mantle unit outcropping in the northernmost tip of the Ivrea-Verbano Zone (IVZ, Southern Alps). It shows a virtually complete recrystallization due to pervasive to channelled melt migration. The pervasive metasomatism formed a main lithologic association constituted by phlogopite harzburgites associated to phlogopite pyroxenites (mainly olivine-websterites, websterites and orthopyroxenites). These lithologies are also rich in amphibole and do not show significant chemical gradients among them (Zanetti et al., 1999). The channelled migration stages formed dunite bodies, which sometimes contain stratiform chromitites and, more rarely, pyroxenite layers similar to those associated to phlogopite harzburgite. The FPP also shows a discrete number of other, subordinate rock-types, which are characterised by the presence of apatite usually associated to carbonates (i.e. calcite or dolomite) and exhibit marked modal and chemical gradients with respect to the host phlogopite harzburgite. Examples of these lithologies are apatite-dolomite-bearing wehrlites and harzburgites (e.g. Zanetti et al. 1999; Morishita et al., 2008), apatite-calcite zircon-syenites and hornblendites. Ar-Ar amphibole analysis and U-Pb zircon and apatite data return Triassic ages for these rocks, which have been considered to document the time of melt/fluid injection. Notwithstanding the apparent mineralogical and chemical differences with the main lithologic sequences, apatite-carbonates-bearing rocks have been frequently interpreted as cogenetic to phlogopite harzburgites. To debate the petrogenesis of these rocks, a detailed field, petrological and geochemical investigation has been carried out on a swarm of apatite-calcite-bearing gabbroic veins that randomly cut the main lithologic association. Preliminary investigation evidenced as these veins show complex metasomatic haloes and a symmetric internal layering, characterised by crystallisation of magmatic

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

    Directory of Open Access Journals (Sweden)

    Arizzi, A.

    2012-06-01

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

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

  10. U-series Dating of Syntectonic Calcite Veins Constrains the Time Scales of the Elements of the Seismic Cycle in an Intraplate Normal Fault

    Science.gov (United States)

    Goodwin, L. B.; Williams, R. T.; Mozley, P.; Sharp, W. D.

    2015-12-01

    The link between fluid overpressure and the earthquake cycle has been documented through previous studies of vein arrays associated with faults and carefully designed experimental work. In the interseismic period, elevated pore fluid pressure (overpressure) will reduce the effective fault-normal stress, weakening the fault and promoting seismic rupture. Fractures produced during faulting will serve as fluid migration pathways until they are sealed by either collapse or precipitation of cement. Following sealing, pore fluid pressure is inferred to progressively increase until it reaches a level sufficient to start the cycle again. Though the rock record of this overpressure-driven seismic cycle is clear, the timescales of the different elements of the cycle have not been quantified. We have addressed this problem by dating calcite veins in the hanging wall damage zone of the Loma Blanca fault zone of the Socorro Basin, Rio Grande rift, New Mexico. These veins exhibit crack-seal microstructures that record repeated episodes of fracture opening, fluid migration, and fracture sealing, suggesting a prolonged history of recurrent seismicity and post-failure fluid migration. Stable isotope analyses of these veins reveal distinct fluid chemistries associated with individual fluid migration events. Carbon isotope values as high as +6.00‰ suggest depressurization and degassing of CO2 charged fluids, supporting the interpretation that fracturing was associated with fault slip. Preliminary U-series dating of calcite veins show a well-defined periodicity of fault slip and fracture formation, with a slip recurrence interval of approximately 73 ± 17 ka, consistent with previous studies of other faults in the Rio Grande rift. Analyses of cements deposited during single crack-seal events record sealing times of approximately 16 ± 4 ka. These results suggest that the time required to re-establish sufficient pore fluid pressure for failure following sealing of damage zone

  11. An ˜1500 year history of El Niño Southern Oscillation rainfall anomalies and land use for the Isthmus of Panama from speleothem calcite

    Science.gov (United States)

    Lachniet, M. S.; Burns, S. J.; Piperno, D. R.; Asmerom, Y.; Polyak, V. P.

    2003-12-01

    The history of the El Niño Southern Oscillation (ENSO) over the past two millennia remains poorly constrained. To document further the tropical paleoclimatic response to ENSO, we present a precisely-dated (180 B.C. to 1310 A.D.), high-resolution ( ˜3 yr / sample), cave calcite isotopic time series from the Isthmus of Panama, a region that experiences ENSO-forced rainfall anomalies. We show evidence for rapid and dramatic rainfall variation in southern Central America, as inferred from stalagmite δ 18O isotope stratigraphy. Isthmian convective rainfall from 550 A.D. to 1300 A.D. was both less intense and more variable than the period 180 B.C. to 550 A.D. Speleothem growth spanned the interval of the Classic Maya Collapse (750 - 950 A.D.), and provides additional evidence for dry anomalies at this time. Carbon isotopes document changing vegetation from native rainforest to grasslands and/or maize, a period of soil erosion associated with pre-Colombian agriculture, and final forest recovery. We suggest that ENSO-forced sea surface temperature anomalies in the eastern equatorial Pacific Ocean resulted in isthmian rainfall anomalies over much of the past two millennia. Our data suggest that El Niño events are associated with decreased isthmian rainfall, and that increased ENSO activity results in generally drier and more variable conditions.

  12. Fingerprinting stress: stylolite and calcite twinning paleopiezometry reveal the complexity of stress distribution during the growth of the Monte Nero anticline (Apennines, Italy).

    Science.gov (United States)

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

    2016-04-01

    This contribution presents for the first time how quantitative stress estimates can be derived by combining calcite twinning and stylolite roughness stress fingerprinting techniques in a structure part of a complex fold and thrust belts. We report a high-resolution deformation and stress history that was experienced by Meso-Cenozoic limestone strata in the overturned Monte Nero Anticline during its late Miocene-Pliocene growth in the Umbria-Marche Arcuate Ridge (northern Apennines, Italy). New methodological development enables an easier use for the inversion technique of sedimentary and tectonic stylolite roughness. A stylolite-fracture network developed during layer-parallel shortening (LPS), as well as syn- and post-folding. Stress fingerprinting shows how stress builds up in the sedimentary strata during LPS with variations of differential stress before folding around a value of 50 MPa. The stress regime oscillated between strike-slip and compressional during LPS and became transiently extensional in limbs of developing fold due to a coeval increase of vertical stress related to local burial and decrease of maximum horizontal stress related to hinge development, before ultimately becoming strike-slip again during late stage fold tightening. Our case study shows that stress fingerprinting is possible and that this novel method can be used to unravel complex temporal relationships that relate to local variations within evolving regional orogenic stresses. Beyond regional implication, this study validates our approach as a new exciting toolbox to high-resolution stress fingerprinting in basins and orogens.

  13. First-principles calculations of structural, electronic, optical and elastic properties of magnesite MgCO 3 and calcite CaCO 3

    Science.gov (United States)

    Brik, M. G.

    2011-02-01

    Detailed ab initio calculations of the structural, electronic, optical and elastic properties of two crystals - magnesite (MgCO 3) and calcite (CaCO 3) - are reported in the present paper. Both compounds are important natural minerals, playing an important role in the carbon dioxide cycling. The optimized crystal structures, band gaps, density of states diagrams, elastic constants, optical absorption spectra and refractive indexes dependence on the wavelength all have been calculated and compared, when available, with literature data. Both crystals are indirect band compounds, with calculated band gaps of 5.08 eV for MgCO 3 and 5.023 eV for CaCO 3. Both values are underestimated by approximately 1.0 eV with respect to the experimental data. Although both crystals have the same structure, substitution of Mg by Ca ions leads to certain differences, which manifest themselves in noticeable change in the electronic bands profiles and widths, shape of the calculated absorption spectra, and values of the elastic constants. Response of both crystals to the applied hydrostatic pressure was analyzed in the pressure range of phase stability, variations of the lattice parameters and characteristic interionic distances were considered. The obtained dependencies of lattice constants and calculated band gap on pressure can be used for prediction of properties of these two hosts at elevated pressures that occur in the Earth's mantle.

  14. Rhombohedral calcite precipitation from CO2-H2O-Ca(OH)2 slurry under supercritical and gas CO2 media

    CERN Document Server

    Montes-Hernandez, German; Geoffroy, Nicolas; Charlet, Laurent; Pironon, Jacques

    2008-01-01

    The formation of solid calcium carbonate (CaCO3) from aqueous solutions or slurries containing calcium and carbon dioxide (CO2) is a complex process of considerable importance in the ecological, geochemical and biological areas. Moreover, the demand for powdered CaCO3 has increased considerably recently in various fields of industry. The aim of this study was therefore to synthesize fine particles of calcite with controlled morphology by hydrothermal carbonation of calcium hydroxide at high CO2 pressure (initial PCO2=55 bar) and at moderate and high temperature (30 and 90 degrees C). The morphology of precipitated particles was identified by transmission electron microscopy (TEM/EDS) and scanning electron microscopy (SEM/EDS). In addition, an X-ray diffraction analysis was performed to investigate the carbonation efficiency and purity of the solid product. Carbonation of dispersed calcium hydroxide in the presence of supercritical (PT=90 bar, T=90 degrees C) or gaseous (PT=55 bar, T=30 degrees C) CO2 led to t...

  15. An AFM investigation of the interaction of chiral amino acids with the {l_brace}104{r_brace} face of calcite

    Energy Technology Data Exchange (ETDEWEB)

    Orme, C A; Noy, A; McBride, M T; DeYoreo, J J

    2000-10-01

    In biomineralized tissue, Nature often uses a single crystal system to form tools with widely varied form and functionality. To accomplish this, organisms have developed methods to deterministically modify and control crystal habit, commonly creating shapes with lower symmetry than is possessed by the pure crystal. In this paper we use atomic force microscopy to investigate the effect of chiral amino acids on calcite growth. We show that the atomic steps and resultant macroscopic shape exhibit a lower symmetry that reflects the chirality of the amino acid. We use this result to constrain the possible stereospecific binding sites. We argue that the change in morphology is not due to the incorporation of the amino acid, but rather that it acts like a surfactant changing the energetics of the interface. These results suggest that the conventional paradigm for understanding the geometrical and chemical aspects of biomineralization in terms of stereochemical recognition should be expanded to capture the energetic controls that determine the mechanisms of mineral modification by biomolecules.

  16. How well do we know VPDB? Variability of delta13C and delta18O in CO2 generated from NBS19-calcite.

    Science.gov (United States)

    Brand, Willi A; Huang, Lin; Mukai, Hitoshi; Chivulescu, Alina; Richter, Jürgen M; Rothe, Michael

    2009-03-01

    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

  17. Inferring surface water equilibrium calcite δ18O during the last deglacial period from benthic foraminiferal records: Implications for ocean circulation

    Science.gov (United States)

    Amrhein, Daniel E.; Gebbie, Geoffrey; Marchal, Olivier; Wunsch, Carl

    2015-11-01

    The ocean circulation modifies mixed layer (ML) tracer signals as they are communicated to the deep ocean by advection and mixing. We develop and apply a procedure for using tracer signals observed "upstream" (by planktonic foraminifera) and "downstream" (by benthic foraminifera) to constrain how tracer signals are modified by the intervening circulation and, by extension, to constrain properties of that circulation. A history of ML equilibrium calcite δ18O (δ18Oc) spanning the last deglaciation is inferred from a least-squares fit of eight benthic foraminiferal δ18Oc records to Green's function estimated for the modern ocean circulation. Disagreements between this history and the ML history implied by planktonic records would indicate deviations from the modern circulation. No deviations are diagnosed because the two estimates of ML δ18Oc agree within their uncertainties, but we suggest data collection and modeling procedures useful for inferring circulation changes in future studies. Uncertainties of benthic-derived ML δ18Oc are lowest in the high-latitude regions chiefly responsible for ventilating the deep ocean; additional high-resolution planktonic records constraining these regions are of particular utility. Benthic records from the Southern Ocean, where data are sparse, appear to have the most power to reduce uncertainties in benthic-derived ML δ18Oc. Understanding the spatiotemporal covariance of deglacial ML δ18Oc will also improve abilities of δ18Oc records to constrain deglacial circulation.

  18. Hydrologic and climatic implications of stable isotope and minor element analyses of authigenic calcite silts and gastropod shells from a mid-Pleistocene pluvial lake, Western Desert, Egypt

    Science.gov (United States)

    Kieniewicz, Johanna M.; Smith, Jennifer R.

    2007-11-01

    Authigenic calcite silts at Wadi Midauwara in Kharga Oasis, Egypt, indicate the prolonged presence of surface water during the Marine Isotope Stage 5e pluvial phase recognized across North Africa. Exposed over an area of ˜ 4.25 km 2, these silts record the ponding of water derived from springs along the Libyan Plateau escarpment and from surface drainage. The δ 18O values of these lacustrine carbonates (- 11.3‰ to - 8.0‰ PDB), are too high to reflect equilibrium precipitation with Nubian aquifer water or water of an exclusively Atlantic origin. Mg/Ca and Sr/Ca of the silts have a modest negative covariance with silt δ 18O values, suggesting that the water may have experienced the shortest residence time in local aquifers when the water δ 18O values were highest. Furthermore, intra-shell δ 18O, Sr/Ca, and Ba/Ca analyses of the freshwater gastropod Melanoides tuberculata are consistent with a perennially fresh water source, suggesting that strong evaporative effects expected in a monsoonal climate did not occur, or that dry season spring flow was of sufficient magnitude to mute the effects of evaporation. The input of a second, isotopically heavier water source to aquifers, possibly Indian Ocean monsoonal rain, could explain the observed trends in δ 18O and minor element ratios.

  19. Highly Zn, Mn-rich calcite in calcareous tufa from the Qixiashan Pb-Zn Mine, Nanjing: a possible candidate for Zn-Mn removal from mining impacted waters

    Institute of Scientific and Technical Information of China (English)

    LIU Ting; WANG RuCheng; LU XianCai; LI Juan; HU Huan

    2009-01-01

    The exploitation of metallic mines may cause serious environmental problems.The removal of the heavy metals from the contaminated mining environments has become an urgent issue.In this paper,the occurrence and distribution of heavy metals in the calcareous tufa collected from the mining laneway of the Qixiashan Pb-Zn Mine in Nanjing were investigated by using multiple mineralogical techniques.Examination by X-ray diffraction spectrum (XRD) shows that calcite is the major compo-nent of the calcareous tufa.Several heavy metals such as Mn,Zn,Mg,Fe and Pb are detected in calcite by means of electron microprobe analysis.Although the heavy metal contents in the hostrock and the formation water are significantly low,the contents of Mn,Zn,Mg,Fe and Pb in the tufa calcite are as high as 23.65 wt%,9.6 wt%,0.76 wt%,4.44 wt% and 0.66 wt%,respectively.The back-scattered elec-tron image shows complex compositional zoning texture in the tufa,which is linked directly to varia-tions in heavy metals,particularly in Mn and Zn.In addition,we also observed floccule and helical pre-cipitations,which may be derived from the metabolism of the microbe.It is deduced that the occur-rence and high concentration of heavy metals in tufa may be controlled by the activities of microbes.The results presented in this work suggest that calcite will be an important candidate for the remedia-tion of the heavy metal contamination in mining areas.

  20. 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

    Science.gov (United States)

    Plummer, L. Niel; Busenberg, Eurybiades

    1982-01-01

    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: 

  1. Neutralization of calcite in mineral aerosols by acidic sullur species collected in China and Japan studied by ca K-edge X-ray absorption near-edge structure.

    Science.gov (United States)

    Takahashi, Yoshio; Miyoshi, Takuro; Higashi, Masayuki; Kamioka, Hikari; Kanai, Yutaka

    2009-09-01

    Calcium species in mineral aerosols collected simultaneously in Aksu (near the Taklimakan Desert), Qingdao (eastern China), and Tsukuba (Japan) during dust and nondust periods were determined using Ca K-edge X-ray absorption near-edge structure (XANES). From the fitting of XANES spectra, it was found that (i) calcite and gypsum were the main Ca species in the aerosol samples, and (ii) the gypsum fraction versus total Ca minerals [Gyp]/[Ca2+]t increased progressively in the order Aksu aerosols for all the samples except for that taken in Aksu during the dust period. The decrease of the [Gyp]/[Ca2+]t ratio with an increase in particle size showed that the neutralization effect proceeds from the particle surface. For the Aksu sample in the dust period, however, (i) the [Gyp]/[Ca2+]t ratios obtained by XANES measured in the fluorescence (FL; regarded as bulk analysis) and CEY modes were similar and (ii) size dependence was not found, showing that neutralization is not important for the sample because of the large supply of mineral aerosol with little neutralization effect in Aksu. It was also found that the pH of the aerosol and the ratio of (NH4)2SO4 to gypsum were positively and negatively correlated with the Ca (or calcite) content, respectively. The speciation of Ca by XANES revealed the neutralization processes of acidic sulfur species by calcite during the long-range transport of mineral aerosols. PMID:19764213

  2. Exploring the influence of loading geometry on the plastic flow properties of geological materials: Results from combined torsion + axial compression tests on calcite rocks

    Science.gov (United States)

    Covey-Crump, S. J.; Xiao, W. F.; Mecklenburgh, J.; Rutter, E. H.; May, S. E.

    2016-07-01

    For technical reasons, virtually all plastic deformation experiments on geological materials have been performed in either pure shear or simple shear. These special case loading geometries are rather restrictive for those seeking insight into how microstructure evolves under the more general loading geometries that occur during natural deformation. Moreover, they are insufficient to establish how plastic flow properties might vary with the 3rd invariant of the deviatoric stress tensor (J3) which describes the stress configuration, and so applications that use those flow properties (e.g. glaciological and geodynamical modelling) may be correspondingly compromised. We describe an inexpensive and relatively straightforward modification to the widely used Paterson rock deformation apparatus that allows torsion experiments to be performed under simultaneously applied axial loads. We illustrate the performance of this modification with the results of combined stress experiments performed on Carrara marble and Solnhofen limestone at 500°-600 °C and confining pressures of 300 MPa. The flow stresses are best described by the Drucker yield function which includes J3-dependence. However, that J3-dependence is small. Hence for these initially approximately isotropic calcite rocks, flow stresses are adequately described by the J3-independent von Mises yield criterion that is widely used in deformation modelling. Loading geometry does, however, have a profound influence on the type and rate of development of crystallographic preferred orientation, and hence of mechanical anisotropy. The apparatus modification extends the range of loading geometries that can be used to investigate microstructural evolution, as well as providing greater scope for determining the shape of the yield surface in plastically anisotropic materials.

  3. Test Research on Beneficiation of Calcite Type Fluorite Ore in Hu'nan%湖南某方解石型萤石选矿试验研究

    Institute of Scientific and Technical Information of China (English)

    胡瑞彪; 吉红; 陈典助; 荆正强

    2013-01-01

    The CaF 2 grade of calcite type fluorite ore from Hu'nan is reaching up to 56 .72%,regard as high-grades fluorite ore .According to the mineralogical characteristic of the ore ,the fluorite was studied,Using sodium carbonate as pH adjusting agent ,sodium silicate and starch as depressant ,so-dium oleate as collector , closed -circuit test were carried out in the condition that the roughing grinding fineness was -0 .074 mm 65%.The grade and recovery of the fluorite concentrate were 97.16%and 80.38%respectively,and the content of SiO2 and CaCO3 meet the national standards . The results showed that concentrate were obtained by swept one rougher -five cleaners-one scav-enging and coarse concentrate regrinding closed -circuit process .%湖南某方解石型萤石矿原矿含CaF256.72%,属高品位萤石矿。结合该矿石的工艺矿物学特性,采用碳酸钠为pH调整剂、水玻璃+淀粉为抑制剂、油酸钠为捕收剂进行浮选试验研究。闭路试验在粗选磨矿细度-0.074 mm占65%的情况下,通过一粗五精一扫-粗精矿再磨的工艺流程,可以获得品位97.16%、回收率80.38%的萤石精矿,且萤石精矿中含SiO21.20%、CaCO30.65%,达到国家萤石粉F97C的质量标准。

  4. First-principles calculations of structural, electronic, optical and elastic properties of magnesite MgCO{sub 3} and calcite CaCO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Brik, M.G., E-mail: brik@fi.tartu.e [Institute of Physics, University of Tartu, Riia 142, Tartu 51014, Tartu (Estonia)

    2011-02-15

    Detailed ab initio calculations of the structural, electronic, optical and elastic properties of two crystals - magnesite (MgCO{sub 3}) and calcite (CaCO{sub 3}) - are reported in the present paper. Both compounds are important natural minerals, playing an important role in the carbon dioxide cycling. The optimized crystal structures, band gaps, density of states diagrams, elastic constants, optical absorption spectra and refractive indexes dependence on the wavelength all have been calculated and compared, when available, with literature data. Both crystals are indirect band compounds, with calculated band gaps of 5.08 eV for MgCO{sub 3} and 5.023 eV for CaCO{sub 3}. Both values are underestimated by approximately 1.0 eV with respect to the experimental data. Although both crystals have the same structure, substitution of Mg by Ca ions leads to certain differences, which manifest themselves in noticeable change in the electronic bands profiles and widths, shape of the calculated absorption spectra, and values of the elastic constants. Response of both crystals to the applied hydrostatic pressure was analyzed in the pressure range of phase stability, variations of the lattice parameters and characteristic interionic distances were considered. The obtained dependencies of lattice constants and calculated band gap on pressure can be used for prediction of properties of these two hosts at elevated pressures that occur in the Earth's mantle. -- Research highlights: {yields} Ab initio calculations of physical properties of MgCO{sub 3} and CaCO{sub 3} were performed. {yields} Changes of the calculated properties with replacement of Mg by Ca were followed. {yields} Pressure dependence of the structural and electronic properties was analyzed. {yields} Good agreement with experimental data was demonstrated.

  5. Trace Metals in Groundwater & Vadose Zone Calcite: In Situ Containment & Stabilization of 90Strontium & Other Divalent Metals & Radionuclides at Arid West DOE Sites

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-06-01

    Radionuclide and metal contaminants such as 90Sr are present beneath U.S. Department of Energy (DOE) lands in both the groundwater (e.g., 100-N area at Hanford, WA) and vadose zone (e.g., Idaho Nuclear Technology and Engineering Center (INTEC) at the Idaho National Engineering and Environmental Laboratory). In situ containment and stabilization of these contaminants is a cost-effective treatment strategy. However, implementing in situ containment and stabilization approaches requires definition of the mechanisms that control contaminant sequestration. We are investigating the in situ immobilization of radionuclides or contaminant metals (e.g., 90Sr) by their facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Our facilitated approach, shown schematically in Figure 1, relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity. Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface urea hydrolyzing microorganisms. Because the precipitation process tends to be irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from the aqueous phase over the long-term. Another advantage of the ureolysis approach is that the ammonium ions produced by the reaction can exchange with radionuclides sorbed to subsurface minerals, thereby enhancing the availability of the radionuclides for re-capture in a more stable solid phase (co-precipitation rather than adsorption).

  6. Trace Metals in Groundwater and the Vadose Zone Calcite: In Situ Containment and Stabilization of Strontium-90 and Other Divalent Metals and Radionuclides at Arid West DOE

    International Nuclear Information System (INIS)

    Radionuclide and metal contaminants such as strontium-90 are present beneath U.S. Department of Energy (DOE) lands in both the groundwater (e.g., 100-N area at Hanford, WA) and vadose zone (e.g., Idaho Nuclear Technology and Engineering Center at the Idaho National Engineering and Environmental Laboratory). In situ containment and stabilization of these contaminants is a cost-effective treatment strategy. However, implementing in situ containment and stabilization approaches requires definition of the mechanisms that control contaminant sequestration. We are investigating the in situ immobilization of radionuclides or contaminant metals (e.g., strontium-90) by their facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Our facilitated approach, shown schematically in Figure 1, relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity. Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface urea hydrolyzing microorganisms. Because the precipitation process tends to be irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from the aqueous phase over the long-term. Another advantage of the ureolysis approach is that the ammonium ions produced by the reaction can exchange with radionuclides sorbed to subsurface minerals, thereby enhancing the availability of the radionuclides for re-capture in a more stable solid phase (co-precipitation rather than adsorption)

  7. Quantitative analyse of trace elements with HR-ICP-MS Element2 : an example of application in calcite shell of the Great Scallop Pecten Maximus.

    Science.gov (United States)

    Richard, M.; Chauvaud, L.; Benoit, M.; Thebault, J.; L'Helguen, S.; Hemond, C.; Maguer, J.; Sinquin, G.

    2008-12-01

    Carbonate minerals are abundant on the Earth's surface, and they are produced by a number of processes, including precipitation from hydrothermal fluids or synthesis by organisms like coral, foraminifera, molluscs, or bacteria. Consequently, they are found in a large variety of environments. Their isotopic compositions (Sr, C, or O ) and trace element concentrations are widely used to understand or reconstruct biological, geological or biogeochimical processes. A large scientific community define the elemental composition of bivalve shells a promising tool as a recorder of environmental parameters like sea surface temperature, salinity and primary productivity. But we have compile evidences that trace elements variation within shells can be species dependant or change in a complex network of environmental interactions. In this context, a better understanding of the incorporation of elements from seawater into biogenic carbonate is necessary to generalize the use of these proxies. Daily shell growth in the calcitic bivalve Pecten maximus has been extensively measured and these daily growth marks can be used to date each subsequent sample of calcium carbonate. In this study, micro- sampling of carbonate powder along the shell was carried out with a high-resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS, Finnigan Element2). This method led to a quantitative detection of trace element in biocaronates and to the accurate reconstruction of ontogenetic profiles of elemental ratios with a 3-day temporal resolution. Repeated analyses of different growth layers sections on the same valve showed that the trace elements are homogeneously distributed along the shell. Mo concentration was reproducible for several scallop individuals from a same location over different years and from different coastal temperate environments. Each profile was characterised by a background level punctuated by sharp episodic peaks occurring in spring (may). Some hypotheses will be

  8. Individual and interacting effects of pCO2 and temperature on Emiliania huxleyi calcification: study of the calcite production, the coccolith morphology and the coccosphere size

    Science.gov (United States)

    de Bodt, C.; van Oostende, N.; Harlay, J.; Sabbe, K.; Chou, L.

    2010-05-01

    The impact of ocean acidification and increased water temperature on marine ecosystems, in particular those involving calcifying organisms, has been gradually recognised. We examined the individual and combined effects of increased pCO2 (180 ppmV CO2, 380 ppmV CO2 and 750 ppmV CO2 corresponding to past, present and future CO2 conditions, respectively) and temperature (13 °C and 18 °C) during the exponential growth phase of the coccolithophore E. huxleyi using batch culture experiments. We showed that cellular production rate of Particulate Organic Carbon (POC) increased from the present to the future CO2 treatments at 13 °C. A significant effect of pCO2 and of temperature on calcification was found, manifesting itself in a lower cellular production rate of Particulate Inorganic Carbon (PIC) as well as a lower PIC:POC ratio at future CO2 levels and at 18 °C. Coccosphere-sized particles showed a size reduction with both increasing temperature and CO2 concentration. The influence of the different treatments on coccolith morphology was studied by categorizing SEM coccolith micrographs. The number of well-formed coccoliths decreased with increasing pCO2 while temperature did not have a significant impact on coccolith morphology. No interacting effects of pCO2 and temperature were observed on calcite production, coccolith morphology or on coccosphere size. Finally, our results suggest that ocean acidification might have a larger adverse impact on coccolithophorid calcification than surface water warming.

  9. 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.

    2006-01-01

    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.

  10. 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

    2012-10-12

    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

  11. 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.

    2016-04-01

    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

  12. The mineralizing fluid property reflected by gochemical characteristics of calcite in polymetallic deposit%多金属矿床中方解石的地球化学特征反映的成矿流体性质

    Institute of Scientific and Technical Information of China (English)

    邹明亮; 王琦; 李剑; 梁永东; 李冉

    2012-01-01

    利用多金属矿床中不同阶段形成的方解石Fe,Mn,Sr的质量分数及C,O,Sr的同位素特征探讨成矿过程中的流体性质,并尝试对成矿机制及其过程进行定量模拟.分析表明:①成矿期形成的方解石中Fe,Mn的质量分数明显增高,大部分Mn的质量分数高于1%,是岩浆期后热液作用的反映,利用阴极发光强度可区分不同期次沉淀的方解石;②d(13C)和δ(18O)的联合变化趋势可定性判别方解石的沉淀机制,结合流体中碳氧同位素背景值可对方解石及与之伴生的多金属矿物沉淀过程进行定量模拟;③不同成矿区具有特定的87Sr/86 Sr值区间,该值可作为区分不同端元流体的有利依据.Sr-87Sr/86 Sr体系可用于蚀变-成矿体系中的流体/岩石值以及不同来源流体中Sr贡献度的定量计算;④成矿过程均伴随有放射性成因锶加入,古老铝硅酸盐是成矿物质的主要母源.%This paper tries to discuss the mineralizing fluid property during mineralization and simulate metallogenetic mechanism and process quantitatively on basis of characteristics of Fe, Mn, Sr content and C, O, Sr isotope value of calcite from polymetallic deposit. The analysis indicate that 1) the intensity of cathodoluminescence could be used to distinguish calcite of different stages and the content of Fe and Mn increase obviously in calcite during the metallizing phase and the majority content of Mn was more than one percent that is the reflection of postmagmatic hydrothermal activity; 2) The precipitation mechanism of calcite could been distinguished qualitatively based on the conjuncture variational tendency of δ13C and δ18O value and combined with the δ13 C and δ18 O value in fluid precipitation process of calcite and polymetallic minerals associaed with the calcite could been simulated quantitatively; 3) each metallogenic provinces have specific 87Sr/86Sr value range which is the basis for distinguishing the end fluid. The Sr

  13. 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

    2013-12-01

    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

  14. 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

    2013-08-26

    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

  15. 华庆地区长6油层组方解石胶结物特征%Characteristics of calcite cements of Chang 6 oil reservoir set in Huaqing area

    Institute of Scientific and Technical Information of China (English)

    张莹莹; 黄思静

    2012-01-01

    The Triassic Chang 6 oil reservoir set in Huaqing area is the main hydrocarbon reservoir and producing formation of Mesozoic in Ordao Basin.The cementation of calcite cements is a major factor for the tight reservoir.The analyses on thin section,cathodoluminescence,elemental composition and carbon isotope show that most of the calcites cemented in granular and poecilitic texture,and a few cemented in micrite texture which are the matrix of syndepositional lake facies.There are several different genetic mechanisms for the granular and poecilitic calcite cements formed during post sedimentary stages,and the calcite cements deposited during the early diagenetic A stage are in connection with the hydration of aluminum silicate minerals,metamorphic rocks and magmatic rocks.The ferrocalcite cements filled not only in the primary pore,but also in secondary pores.The formation of ferrocalcite cements are closely related to the aluminum silicate minerals and the transformation of clay mineral and occurred during the early diagenetic B stage.The most cementation of the calcites and ferrocalcite are disadvantageous for the reservoir properties.%华庆地区长6油层组是鄂尔多斯盆地中生界主要的油气储层和产层,方解石胶结物是导致储层致密的重要因素之一。薄片、扫描电镜、阴极发光、元素组分及碳、氧同位素分析表明,方解石胶结物除常见的粒状胶结物和嵌晶式胶结物外,还存在较少泥微晶结构方解石。泥微晶结构方解石是同沉积的湖相内杂基;沉积期后形成的粒状和嵌晶式方解石胶结物具多种成因机制,其中在早成岩阶段A期沉淀的方解石胶结物与铝硅酸盐矿物和变质岩、岩浆岩岩屑的水化作用有关;铁方解石胶结物充填于原生孔隙的同时,还充填于骨架颗粒溶蚀形成的次生孔隙中,其形成与有机酸对长石等铝硅酸盐矿物的溶蚀作用和黏土矿物的转化作用有关,为早成岩阶段B期沉淀

  16. 自修复混凝土中微生物矿化方解石的形成机理%Mechanism of Microbially Induced Calcite Precipitation in Self-healing Concrete

    Institute of Scientific and Technical Information of China (English)

    钱春香; 罗勉; 潘庆峰; 李瑞阳

    2013-01-01

    分别从矿化产物、pH值、O2、底物4个方面对用于混凝土裂缝自修复的微生物矿化形成方解石机理进行了研究.结果表明:混凝土裂缝自修复细菌矿化产物为方解石型CaCO3,矿化过程需要O2参与;细菌生长过程中pH值从7.0逐渐升高到8.3,碱性环境在细菌矿化过程中起重要作用;CaCO3不是由底物在胞外酶作用下直接分解而得,而是需要经过细菌一系列代谢转换,代谢过程中产生CO2,底物既提供矿化所需的Ca2+源,也提供CO2=来源,其他有机营养物质也可提供CO32-.同时,对该菌株的矿化机理进行了分析,结果表明:细菌生长繁殖过程中创造碱性环境,产生CO2,细菌细胞表面带负电荷,能够吸附Ca2+并作为成核位点,在碱性环境下CO2与Ca2+反应形成CaCO3晶体.%The process of microbially induced calcite precipitation was investigated via the control of mineralization production, pH value, O2 and substrate, respectively. The experimental results show that the mineral precipitation induced by bacteria is calcite crystal, and the mineralization process needs O2. The pH value of bacteria liquid increased from 7.0 to 8.3 gradually when the bacteria grew, which plays an important role in the bacteria mineralization process. Calcite was formed due to the bacterial metabolic conversions rather than the direct decomposition of substrate under the action of extracellular enzymes. The metabolic process produced CO2, the substrate provided Ca2+ and CO32-, and other organic nutrients could also provide CO32-. The possible mechanism of bacterial induced mineral precipitation was analyzed. The results show that the growth of bacteria creates an alkaline environment and produces CO2 through various physiological activities. The cell wall of bacteria was negatively charged, affecting calcium carbonate precipitation by acting as sites of nucleation or calcium enrichment. The produced CO2 molecules reacted with Ca2+ to form calcite

  17. 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

    2006-07-01

    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.

  18. Ages of sediment-hosted Himalayan Pb-Zn-Cu-Ag polymetallic deposits in the Lanping basin, China: Re-Os geochronology of molybdenite and Sm-Nd dating of calcite

    Science.gov (United States)

    Zhang, Jinrang; Wen, Hanjie; Qiu, Yuzhuo; Zhang, Yuxu; Li, Chao

    2013-09-01

    The Lanping basin is a significant Pb-Zn-Cu-Ag mineralization belt of the Sanjiang Tethyan metallogenic province in China. Over 100 thrust-controlled, sediment-hosted, Himalayan base metal deposits have been discovered in this basin, including the largest sandstone-hosted Pb-Zn deposit in the world (Jinding), and several Cu ± Ag ± Co deposits (Baiyangping, Baiyangchang and Jinman). These deposits, with total reserves of over 16.0 Mt Pb + Zn, 0.6 Mt Cu, and 7000 t Ag, are mainly hosted in Meso-Cenozoic mottled clastic rocks, and strictly controlled by two Cenozoic thrust systems developed in the western and eastern segments of the Lanping basin. To define the metallogenic history of the study area, we dated nine calcite samples associated with copper sulfides from the Jinman Cu deposit by the Sm-Nd method and five molybdenite samples from the Liancheng Cu-Mo deposit by the Re-Os method. The calcite Sm-Nd age for the Jinman deposit (58 ± 5 Ma) and the molybdenite Re-Os age for the Liancheng deposit (48 ± 2 Ma), together with previously published chronological data, demonstrate (1) the Cu-Ag mineralization in the western Lanping basin mainly occurred in three episodes (i.e., ∼56-54, 51-48, and 31-29 Ma), corresponding to the main- and late-collisional stages of the Indo-Asian orogeny; and (2) the Pb-Zn-Ag (±Cu) mineralization in the eastern Lanping basin lacked precise and direct dating, however, the apatite fission track ages of several representative deposits (21 ± 4 Ma to 32 ± 5 Ma) may offer some constraints on the mineralization age.

  19. Reciclagem do resíduo da serragem de calcário laminado para produção de blocos cerâmicos Recycling of laminated calcite tile sawing waste for the production of ceramic bricks

    Directory of Open Access Journals (Sweden)

    Romualdo R. Menezes

    2010-12-01

    Full Text Available As indústrias da mineração e beneficiamento de calcário laminado representam um importante segmento econômico do Estado do Ceará, entretanto produzem uma grande quantidade de resíduos, que poluem e agridem o meio ambiente. Assim, esse trabalho tem por objetivo a caracterização do resíduo da serragem da Pedra Cariri e a avaliação de sua aplicabilidade como matéria-prima cerâmica alternativa para a produção de telhas e blocos cerâmicos. O resíduo foi caracterizado através da determinação de sua composição química e mineralógica, por difração de raios X, análise térmica diferencial, distribuição de tamanho de partículas e análise morfológica por microscopia eletrônica de varredura. Foram formuladas composições contendo o resíduo e confeccionados corpos-de-prova por prensagem. Os corpos-de-prova foram queimados e, em seguida, foram determinados a absorção de água e o módulo de ruptura à flexão. Pode-se concluir que o resíduo é constituído por calcita e dolomita, que apresenta elevada finura e que é possível a incorporação de até 10% de resíduo em formulações para a produção de telhas e blocos cerâmicos.The mining and processing industries of laminated calcite tile are an important economic sector in the State of Ceará. However, they generate a large amount of wastes, which are a source of contamination and environmental pollution. This study aimed to characterize the laminated calcite tile sawing waste and evaluate its suitability as an alternative ceramic raw material for the production of bricks and roof tiles. The waste was characterized by chemical composition determination, X-ray diffraction, differential thermal analyses, particle size distribution determination, and morphological analysis by electronic scanning microscopy. Several formulations were prepared and sample bodies were prepared by uniaxial pressing. The sample bodies were fired at different temperatures. Sintered samples

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

    Institute of Scientific and Technical Information of China (English)

    梁冰; 陈楠; 姜利国

    2011-01-01

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

  1. A 500 year seasonally resolved δ18O and δ13C, layer thickness and calcite fabric record from a speleothem deposited in equilibrium of the Han-sur-Lesse cave, Belgium

    Directory of Open Access Journals (Sweden)

    M. Van Rampelbergh

    2014-10-01

    Full Text Available Speleothem δ18O and δ13C signals have already proven to enable climate reconstructions at high resolution. However, seasonally resolved speleothem records are still scarce and often difficult to interpret in terms of climate due to the multitude of factors that can affect the proxy signals. In this paper, a fast growing (up to 2 mm yr−1 seasonally laminated speleothem from the Han-sur-Lesse cave (Belgium is analyzed for its δ18O and δ13C values, layer thickness and changes in calcite fabric. The studied part of the speleothem covers the most recent 500 years as indicated by layer counting and confirmed by 20 U/Th-ages. Epikarst recharge occurs mainly in winter and lesser during spring and fall. a good correlation can be established between lower winter temperatures and lower winter precipitation (DJF based on the measured data by the Belgian meteorological institute since 1833 indicating that a dry winter is also a cold winter. Colder and dryer winters cause lower winter recharge and generally drier conditions in the cave. Lower winter recharge decreases the amount of isotopically light (δ18O winter precipitation added to the epikarst in comparison to the heavier spring and fall waters, which leads to a net increase in δ18O value of the water in the epikarst. Increased δ18O values in the Proserpine are consequently interpreted to reflect colder and dryer winters. Higher δ13C signals are interpreted to reflect increased prior calcite precipitation (PCP due to colder and dryer winters, when recharge is lower. Thinner layers and darker calcite relate to slower growth and occur when drip rates are low and when the drip water calcium ion concentration is low due to increased PCP, both caused by lower recharge during periods with colder and dryer winters. Exceptionally cold and dry winters cause the drip discharge to decrease under a certain threshold value inducing anomalies in the measured proxy records. Such anomalies occur from 1565 to

  2. Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Strontium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

    International Nuclear Information System (INIS)

    Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) 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

  3. 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

    2007-11-07

    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

  4. 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.

    1981-01-01

    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.

  5. 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.

    Science.gov (United States)

    Park, Jong-Myong; Park, Sung-Jin; Ghim, Sa-Youl

    2013-09-28

    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.

  6. 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

    2009-07-01

    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.

  7. Combined δ11B, δ13C, and δ18O analyses of coccolithophore calcite constrains the response of coccolith vesicle carbonate chemistry to CO2-induced ocean acidification

    Science.gov (United States)

    Liu, Yi-Wei; Tripati, Robert; Aciego, Sarah; Gilmore, Rosaleen; Ries, Justin

    2016-04-01

    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.

  8. 构造驱动大巴山前陆烃类流体排泄:含烃包裹体纤维状方解石脉证据%Tectonically Driven Organic Fluid Flow in Dabashan Foreland Belt:Recorded by fibrous calcite veins contained hydrocarbon-bearing inclusions

    Institute of Scientific and Technical Information of China (English)

    李荣西; 董树文; 丁磊; 施炜

    2013-01-01

    含烃包裹体纤维状方解石脉被认为是超高压下油气流体形成和排泄的标志.大巴山前陆构造带一些断裂和下古生界黑色泥岩和泥灰岩烃源岩微裂隙中分布有含烃包裹体纤维状方解石脉,成分分析表明其为低镁方解石.纤维状方解石脉δ13CVPDB和δ18OVPDB比围岩碳酸盐岩的明显变轻,前者δ13CVPDB和δ18OVPDB变化范围分别为-1.9% ~-4.8‰和-8.4%~-12.8‰,后者分别为-1.7%~+3.1‰和-8.7%~-4.5‰,且δ13C与δ18O具有明显的线性关系,反映出纤维状方解石脉具有成岩有机流体与浅部流体混合的流体特征.纤维状方解石脉含有共生的固体沥青包裹体、含甲烷液相包裹体和气液二相盐水包裹体等多相态包裹体,其中沥青包裹体为油气运移的残余沥青.气液二相盐水包裹体均一温度主要位于140℃和196℃之间(峰值为179℃),盐度较高(平均为9.7wt% NaCl).分别应用盐水包裹体和甲烷包裹体等溶线P—T相图确定出含烃包裹体纤维状方解石脉形成的流体压力为150 ~200 MPa,属于异常超高压流体.地质和地球化学特征分析认为,大巴山含烃包裹体纤维状方解石脉不具有泥岩因压实成岩作用而形成的超高压流体特征.结合沉积和构造演化历史分析认为,印支碰撞造山运动和燕山前陆构造作用导致大巴山褶皱隆起并伴随天然气藏破坏和改造,挤压环境下的超高压构造应力驱动天然气流体排泄,大巴山前陆构造带含烃包裹体纤维状方解石脉就是超高压构造应力驱动天然气排泄的产物.%Fibrous calcite veins with organic inclusions were considered as indication to oil/gas generation and expelling under overpressure.Abundant fibrous calcite veins contained hydrocarbon-bearing inclusions filled in fractures were found in lower Paleozoic hydrocarbon source of black mudstone,clay shale and limestone as well as some faults in Dabashan Foreland Belt

  9. 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

    Science.gov (United States)

    Revesz, Kinga M.; Landwehr, Jurate M.

    2002-01-01

    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

  10. 碳酸钡单晶微米锥阵列在方解石(104)面上的外延生长%Epitaxial Growth of Single-Crystalline Barium Carbonate Microcone Arrays on (104) Face of Calcite

    Institute of Scientific and Technical Information of China (English)

    吴威克; 张玉哲; 李斌; 马玉荣

    2015-01-01

    Heteroepitaxial growth of single-crystal ine witherite (BaCO3) microcone arrays on the (104) face of calcite (CaCO3) was realized, by the interface-coupled dissolution-precipitation reaction in water/ethanol at room temperature. The witherite microcone long axis was parallel to the [001] direction of witherite and [001] direction of the calcite substrate. The top of the microcones appeared as uniform tri-symmetrical hexagons while the long axis of the witherite microcones was parallel to the electron beam. The witherite microcones increased in size and decreased in length:diameter ratio with extending crystallization time. The size and morphology of the epitaxially grown witherite could be tuned by changing the water:ethanol volume ratio, or the Ba(NO3)2 concentration of the precursor solution. Increasing the water:ethanol volume ratio or Ba(NO3)2 concentration yielded smal er, denser witherite single-crystal ine microstructures. The witherite microcone arrays were thought to form by the synergetic epitaxial growth of witherite and dissolution of calcite. Carbonate crystals of witherite and calcite contained middle-high misfits on calcite (104) and (001) faces. Witherite microcones may have grown epitaxially on these two calcite faces, according to the Volmer-Weber model.%通过液固界面上的溶解-沉淀耦合反应在Ba(NO3)2乙醇-水溶液中实现了毒重石晶型的碳酸钡在方解石(CaCO3)晶体基底上的外延生长,得到碳酸钡的单晶微米锥阵列。碳酸钡微米锥的长轴平行于毒重石晶体的[001]方向,同时也与方解石基底[001]晶向相同,其俯视图为六边形,具有近似的六方对称性。随反应时间的增加,外延生长形成的碳酸钡微米锥的尺寸增加,但其轴径比逐渐减小。通过改变乙醇-水混合溶剂中的乙醇含量或者Ba(NO3)2浓度也能调控碳酸钡晶体的尺寸和形貌。随着混合溶剂中乙醇含量与Ba(NO3)2浓度的提高,溶液中BaCO3的过饱

  11. Geochemistry and Sm-Nd age of calcites from the Sandaogou Pb-Zn-Ag deposit in Luanchuan, western Henan Province%河南栾川三道沟铅锌银矿床方解石地球化学特征及Sm-Nd年龄研究

    Institute of Scientific and Technical Information of China (English)

    曹华文; 裴秋明; 张寿庭; 向辉; 张林奎; 唐利

    2016-01-01

    三道沟铅锌银矿床位于华北陆块南缘栾川多金属矿集区西部。受断裂控制的薄脉状矿体赋存于新元古界栾川群南泥湖组碎屑岩、碳酸盐岩地层中。本文在矿床地质特征和矿物学研究的基础上,对早、中、晚3个成矿阶段的9件热液方解石进行微量元素、稀土元素和 Sm-Nd同位素测年研究。结果表明方解石的稀土元素总量(REE)为6.42~216μg/g,富集重稀土元素, HREE/LREE比值为1.47~5.94;δEu =0.62~2.71,具弱Ce异常;强烈亏损Nb和Zr,富集Pb。从成矿早阶段到晚阶段,∑REE值、LREE/HREE比值和δEu值逐渐减小。Y/Ho-La/Ho 图解和 Tb/Ca-Tb/La 图解均指示该矿床方解石为热液成因。方解石147Sm/144Nd 和143Nd/144Nd同位素比值具有良好的线性关系,等时线年龄为(138.3±2.6) Ma (2σ, MSWD =2.3)。结合矿集区内成岩-成矿年代学资料,认为三道沟矿床与区内最晚阶段的花岗质岩浆活动(136~142 Ma)有关,属于栾川Mo-W-Pb-Zn- Ag多金属成矿系统中的热液脉型铅锌银矿床。%The Sandaogou hydrothermal Pb-Zn-Ag deposit is located in the western part of the Luanchuan polymetallic ore district on the southern margin of the North China Block. Vein-shaped ore bodies occur in clastic and carbonate strata of the Nannihu Formation of the Neoproterozoic Luanchuan Group. Based on the study of the geological setting and mineralogy of the deposit, we performed trace element analysis and Sm-Nd isotopic dating on 9 hydrothermal calcites from three ore-forming stages. The results show that the calcites are enriched in heavy rare-earth elements with the total REE contents (∑REE) of 6.42~216μg/g and a HREE/LREE ratio of 1.47~5.94 (δEu = 0.62~2.71). The calcites show a slight Ce anomaly, but are strongly depleted in Nb and Zr and enriched in Pb.REE, LREE/HREE andδEu decrease gradually from the early stage to the late stage of mineralization. The calcites show that they are of hydrothermal genesis

  12. Precipitation kinetics of calcite in the system CaCO 3H2OC02: The conversion to CO 2 by the slow process H ++HCO 3- → CO 2+H 2O as a rate limiting step

    Science.gov (United States)

    Dreybrodt, W.; Eisenlohr, L.; Madry, B.; Ringer, S.

    1997-09-01

    Precipitation rates of CaCO 3 from supersaturated solutions in the H 2OCO 2CaCO 3 system are controlled by three rate-determining processes: the kinetics of precipitation at the mineral surface, mass transport of the reaction species involved to and from the mineral surface, and the slow kinetics of the overall reaction HCO 3-+H + → CO 2+H 2O. A theoretical model by Buhmann and Dreybrodt (1985a,b) taking these processes into account predicts that, due to the slow kinetics of this reaction, precipitation rates to the surface of CaC0 3 minerals depend critically on the ratio V/A of the volume V of the solution to the surface area A of the mineral in contact with it, for both laminar and turbulent flow. We have performed measurements of precipitation rates in a porous medium of sized particles of marble, limestone, and synthetic calcite, with V/A ratios ranging from 3·10 -4 to 1.2·10 -2 cm at 10°C. Calcite was precipitated from supersaturated solutions with [Ca 2+] ≈ 4 mmol/L and an initial PCO2 of 5·10 -3 or 1·10 -3 atm, respectively, using experimental conditions which prevented exchange of CO 2 with the atmosphere, i.e., closed system. The results are in qualitative agreement with the theoretical predictions. Agreement with the observed data, however, is obtained by modifying the rate law of Plummer et al. (1978) to take into account surface-controlled inhibition effects. Experiments with supersaturated solutions containing carbonic anhydrase, an enzyme which enhances the conversion of HCO 3- into CO 2, yield rates increased by a factor of up to 15. This provides for the first time unambiguous experimental evidence that this reaction is rate limiting. We have also measured precipitation rates in batch experiments, stirring sized mineral particles in a solution with V/A ranging from 0.03 to 0.75 cm. These experiments also give clear evidence on the importance of the conversion of HCO 3- into CO 2 as rate limiting step. Taken together our experiments

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-06-15

    Radionuclide and metal contaminants such as 90Sr are present beneath U.S. Department of Energy (DOE) lands in both the groundwater (e.g., 100-N area at Hanford, WA) and vadose zone (e.g., Idaho Nuclear Technology and Engineering Center at the Idaho National Engineering and Environmental Laboratory). In situ containment and stabilization of these contaminants is a cost-effective treatment strategy. However, implementing in situ containment and stabilization approaches requires definition of the mechanisms that control contaminant sequestration. We are investigating the in situ immobilization of radionuclides or contaminant metals (e.g., 90Sr) by their facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Our facilitated approach, shown schematically in Figure 1, relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity. Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface urea hydrolyzing microorganisms. Because the precipitation process tends to be irreversible and many western aquifers are saturated with respect to calcite, the coprecipitated metals and radionuclides will be effectively removed from the aqueous phase over the long-term. Another advantage of the ureolysis approach is that the ammonium ions produced by the reaction can exchange with radionuclides sorbed to subsurface minerals, thereby enhancing the availability of the radionuclides for re-capture in a more stable solid phase (co-precipitation rather than adsorption).

  14. 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....... C and O isotope trends from high southern palaeo-latitudes as well as Sr/Ca ratios of seawater were reconstructed using Permian to Jurassic fossils from New Zealand and New Caledonia. A study on Sr/Ca ratios in ostreoids and belemnites was conducted to provide the first high resolution Sr/Ca curve...

  15. ESR experiments on quaternary calcites and bones for dating purposes

    International Nuclear Information System (INIS)

    A series of experiments and measurements regarding sample preparation, peak intensity estimation, annealing, signal identification, dose determination and dose-rate estimation was carried out in order to explore the technique of ESR for dating speleothemes and bones. Anthropological remains from a cave were used for this study. The results indicate the existence of four peaks, two organic and two radiation induced ones. The bone samples were found to have absorbed large amounts of uranium from the environment making their dating impossible. A range of ages 20-45x103 years was calculated for the travertines of the cave. (author) 15 refs.; 10 figs

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

    Science.gov (United States)

    Orme, Christine

    2002-03-01

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

  17. 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

    Science.gov (United States)

    Revesz, Kinga M.; Landwehr, Jurate Maciunas; Keybl, Jaroslav Edward

    2001-01-01

    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

  18. Evidence of a bacterial carbonate coating on plaster samples subjected to the Calcite Bioconcept biomineralization technique

    OpenAIRE

    Anne, Séverinne; Rozenbaum, Olivier; Andreazza, Pascal; Rouet, Jean-Louis

    2010-01-01

    International audience Degradation of historical buildings is mainly due to the intrusion of water which is the main vector of pollutants. Different types of surface treatment have been proposed to avoid or limit this effect. One alternative to chemical treatments is the use of the carbonatogenesis property of some bacteria. This bacterial production has been evidenced on concrete and on limestone samples in an aqueous environment. However, the carbonate production was measured indirectly ...

  19. Unusual biogenic calcite structures in two shallow lakes, James Ross Island, Antarctica

    OpenAIRE

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

    2015-01-01

    The floors of two shallow endorheic lakes, located on volcanic surfaces on James Ross Island, are covered with calcareous organosedimentary structures. Their biological and chemical composition, lake water characteristics, and seasonal variability of the thermal regime are introduced. The lakes are frozen down to the bottom eight-nine months per year and their water chemistry is characterized by low conductivity and neutral to slightly alkaline pH. The photosynthetic microbi...

  20. A kinetic study of the replacement of calcite marble by fluorite

    Science.gov (United States)

    Trindade Pedrosa, Elisabete; Boeck, Lena; Putnis, Christine V.; Putnis, Andrew

    2016-04-01

    Replacement reactions are relevant in any situation that involves the reequilibration between a solid and an aqueous fluid phase and are commonly controlled by an interface-coupled dissolution-precipitation mechanism (Putnis and Putnis, 2007). These reactions control many large-scale Earth processes whenever aqueous fluids are available, such as during metamorphism, metasomatism, and weathering. An important consequence of coupled dissolution-precipitation is the generation of porosity in the product phase that then allows the infiltration of the fluid within the mineral being replaced. Understanding the mechanism and kinetics of the replacement of carbonates by fluorite has application in earth sciences and engineering. Fluorite (CaF2) occurs in all kinds of rocks (igneous, sedimentary, and metamorphic) and its origin is commonly associated with hydrothermal fluids. Moreover, calcium carbonate has been suggested as a successful seed material for the sequestration of fluoride from contaminated waters (Waghmare and Arfin, 2015). The aim of the present work is to investigate aspects of the replacement of calcium carbonate by fluorite to better understand the mechanism and kinetics of this reaction. Small cubes (˜ 3 × 3 × 3 mm) of Carrara marble (CaCO3 > 99 %) were cut and reacted with a 4 M ammonium fluoride (NH4F) solution for different times (1 to 48 hours) and temperatures (60, 80, 100, and 140 ° C). The microstructure of the product phases was analysed using SEM. The kinetics of replacement was monitored from the Rietveld analysis of X-ray powder diffraction patterns of the products as a function of temperature and reaction time. After reaction, all samples preserved their size and external morphology (a pseudomorphic replacement) and the product phase (fluorite) was highly porous. The activation energy Ea (kJ/mol) of the replacement reaction was empirically determined by both model-fitting and model-free methods. The isoconversional method yielded an empirical activation energy of 41 kJ/mol, and a statistical approach applied to the model-fitting method revealed that the replacement of Carrara marble by fluorite is better fitted to a diffusion-controlled process. This is consistent with ion diffusion through the fluid phase. These results suggest that the replacement reaction is dependent on the fluid migration rate through the newly formed porosity. Putnis, A., Putnis C.V., 2007. The mechanism of reequilibration of solids in the presence of a fluid phase. Journal of Solid State Chemistry, 180, 1783-1786. Waghmare, S.S., Arfin, T. (2015). Fluoride removal from water by calcium materials: A state-of-the-art review. Int. J. Innov. Res. Sci. Eng. Technol. 4, 8090-8102.

  1. 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.

    water CO sub(3) sup (=*) concentrations. This variability is attributed to shell calcification, and shell weights are controlled by CO sub(3) sup(=) concentration in the surface waters. Further, surface water CO sub(3) sup(=) concentrations override...

  2. A New foodweb based on microbes in calcitic caves: The Cansiliella (Beetles) case in Northern Italy

    OpenAIRE

    Paoletti Maurizio G.; Beggio Mattia; Dreon Angelo Leandro; Pamio Alberto; Gomiero Tiziano; Brilli Mauro; Dorigo Luca; Concheri Giuseppe; Squartini Andrea; Summers Engel Annette

    2011-01-01

    The troglobitic beetle, Cansiliella servadeii (Leptodirini), has specialized mouthparts modified for browsing and feeding under percolating water on moonmilk, a speleothem formation in Grotta della Foos, Italy. Results from analyses of stable isotopes of carbon and nitrogen suggest thatacquires and assimilates dissolved allochthonous organic carbon, inorganic nitrogen, and possibly phosphorus and other nutrients from the microbial fauna associated with moonmilk.

  3. New developments in early diagenetic modeling: pH distributions, calcite dissolution and compaction

    NARCIS (Netherlands)

    Jourabchi, P.

    2007-01-01

    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

  4. New developments in early diagenetic modeling : pH distributions, calcite dissolution and compaction

    NARCIS (Netherlands)

    Jourabchi, P.

    2007-01-01

    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

  5. 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.

    2013-01-01

    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 s

  6. Microbial community composition and endolith colonization at an Arctic thermal spring are driven by calcite precipitation.

    Science.gov (United States)

    Starke, Verena; Kirshtein, Julie; Fogel, Marilyn L; Steele, Andrew

    2013-10-01

    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. PMID:24115614

  7. Sulphate reduction and calcite precipitation in relation to internal eutrophication of groundwater fed alkaline fens

    NARCIS (Netherlands)

    Cirkel, D.G.; Beek, van C.G.E.M.; Witte, J.P.M.; Zee, van der S.E.A.T.M.

    2014-01-01

    Although in Europe atmospheric deposition of sulphur has decreased considerably over the last decades, groundwater pollution by sulphate may still continue due to pyrite oxidation in the soil as a result of excessive fertilisation. Inflowing groundwater rich in sulphate can change biogeochemical cyc

  8. Treatment Of Metal-Mine Effluents By Limestone Neutralization And Calcite Co-Precipitation (Presentation)

    Science.gov (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

    Science.gov (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. 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: jgieskes@ucsd.edu [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)

    2011-05-15

    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.

  11. 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.

    and Figure 1. Map showing core top locations in the tropical Indian Ocean along with GEOSECS stations used in the calculation of CO = 3 concentrations. Solid circles indicate core top locations and stars indicate GEOSECS stations with numbers. SCIENTIFIC... CORRESPONDENCE CURRENT SCIENCE, VOL. 95, NO. 1, 10 JULY 2008 23 Table 1. Shell weights (μg) of foraminifera species Pulleniatina obliquiloculata. CO = 3 (μmol/kg) calculated using the program developed by Takahashi; pressure-normalized carbonate ion...

  12. The role of microorganisms in the formation of calcitic moonmilk deposits and speleothems in Altamira Cave

    OpenAIRE

    Sánchez-Moral, Sergio; Portillo Guisado, María del Carmen; Janices, Inés; Cuezva, Soledad; Fernández Cortés, A.; Cañaveras, Juan Carlos; González Grau, Juan Miguel

    2011-01-01

    Bacteria are able to induce carbonate precipitation although the participation of microbial or chemical processes in speleothem formation remains a matter of debate. In this study, the origin of carbonate depositions such as moonmilk, an unconsolidated microcrystalline formation with high water content, and the consolidation of carbonate precipitates into hard speleothems were analyzed. The utilized methods included measurements of the composition of stable isotopes in these precipitates, flu...

  13. Shear zone nucleation and deformation transient: effect of heterogeneities and loading conditions in experimentally deformed calcite

    Science.gov (United States)

    Morales, L. F. G.; Rybacki, E.; Dresen, G. H.; Kilian, R.

    2015-12-01

    In the Earth's middle to lower crust, strain is frequently localized along ductile shear zones, which commonly nucleate at structural and material heterogeneities. To investigate shear zone nucleation and development due to heterogeneities, we performed constant strain-rate (CSR) and constant stress (CS) simple shear (torsion) deformation experiments on Carrara marble samples containing weak (limestone) inclusions. The experiments were conducted in a Paterson-type gas deformation apparatus at 900 °C temperature and 400 MPa confining pressure and maximum bulk shear strains of 3. Peak shear stress was about 20 MPa for all the samples, followed by smooth weakening and steady state behavior. The strain is predominantly localized in the host marble within the process zone in front of the inclusion, defined by a zone of intense grain size reduction due to dynamic recrystallization. In CS tests a narrow shear zone developed in front of the inclusion, whereas in CSR experiments the deformation is more heterogeneously distributed, up to g=3.. In the later, secondary foliations oblique to the process zone and alternating thin, high-strain layers are common. In samples deformed at the same shear strain (g=1), the average recrystallized grain size in the process zone is similar for CS and CSR conditions. Crystallographic preferred orientation (CPO) measurements shows that different grain sizes have slightly different CPO patterns. CPO strength varies for different grain sizes, with a CPO strength peak between 40-50 μm, decreasing progressively within smaller grain size, but with secondary peaks for different coarse-grained sizes. Our observations suggest that the initial formation and transient deformation of shear zones is strongly affected by loading conditions.

  14. Strength, stability, and microstructure of simulated calcite faults sheared under laboratory conditions spanning the brittle-plastic transition

    NARCIS (Netherlands)

    Verberne, B.A.

    2015-01-01

    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 behaviou

  15. Detection limit improvement for Mg in marine foraminiferal calcite by using helium induced X-ray emission

    International Nuclear Information System (INIS)

    New efforts focus on tools which enable the reconstruction of past climates. For example, the Mg/Ca atomic ratio in marine Foraminifera starts to be used as a proxy for ocean water mass temperature. Because both, Mg content is very low (3 samples by using helium ions instead of protons to induce X-ray emission. We determine the Mg/Ca concentration ratio of standard CaCO3 powders and Globigerinoides ruber Foraminifera collected in the Equatorial Atlantic Ocean. The results show a decrease in the Mg/Ca ratio with the water depth indicating that the temperature record is partially altered by dissolution processes which should be taken into account in a future calibration model

  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

    2015-01-01

    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. 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.

    The Oxygen Minimum Zone (OMZ) is a potential source of CO2 to the atmosphere, and the extensive OMZ spread to 1.37 × 106 km2 in the Northern Arabian Sea would be an important contributor to the CO2 budget...

  18. Anti-cyclonic eddy imprint on calcite geochemistry of several planktonic foraminiferal species in the Mozambique Channel

    NARCIS (Netherlands)

    Steinhardt, J.; Cléroux, C.; Ullgren, J.; de Nooijer, L.; Durgadoo, J. V.; Brummer, G.-J.; Reichart, G.-J.

    2014-01-01

    Hydrographic conditions in the Mozambique Channel are dominated by the passing of large anticyclonic eddies, propagating poleward into the upstreamAgulhas area. Further south, these eddies have been found to control the shedding of Agulhas rings into theAtlantic ocean, thereby playing a key role in

  19. Dissolution of calcite in the twilight zone: bacterial control of dissolution of sinking planktonic carbonates is unlikely.

    Directory of Open Access Journals (Sweden)

    Andrew Bissett

    Full Text Available We investigated the ability of bacterial communities to colonize and dissolve two biogenic carbonates (Foraminifera and oyster shells. Bacterial carbonate dissolution in the upper water column is postulated to be driven by metabolic activity of bacteria directly colonising carbonate surfaces and the subsequent development of acidic microenvironments. We employed a combination of microsensor measurements, scanning electron microscopy (SEM, confocal laser scanning microscopy (CLSM and image analysis and molecular documentation of colonising bacteria to monitor microbial processes and document changes in shell surface topography. Bacterial communities rapidly colonised shell surfaces, forming dense biofilms with extracellular polymeric substance (EPS deposits. Despite this, we found no evidence of bacterially mediated carbonate dissolution. Dissolution was not indicated by Ca²⁺ microprofiles, nor was changes in shell surface structure related to the presence of colonizing bacteria. Given the short time (days settling carbonate material is actually in the twilight zone (500-1000 m, it is highly unlikely that microbial metabolic activity on directly colonised shells plays a significant role in dissolving settling carbonates in the shallow ocean.

  20. Rare Earth Element Geochemistry of Calcite from the World-class Huize Pb-Zn Deposits, Yunnan Province, China

    Institute of Scientific and Technical Information of China (English)

    HUANG Zhi-long; ZHOU Mei-fu; LI Xiao-biao; LI Wen-bo; JIN Zhong-guo

    2008-01-01

    @@ The world-class Huize Pb-Zn deposits of Yunnan province, China, is located in the center of the Sichuan-Yun-nan-Guizhou Pb-Zn polymetallic metallogenic province, has Pb+Zn reserves of more than 5 million tons at Pb+Zn grade of higher than 25% and contains abundant metals, such as Ag, Ge, Cd, and Ga.

  1. TO STUDY THE MECHANICAL BEHAVIOUR OF CHANGE IN CONCENTRATION OF CALCITE FLUORIDE OF METAL CORED WELDING ELECTRODES

    OpenAIRE

    Sandeep; Rajesh Kuamr

    2012-01-01

    Mild steels are the most common type of steels used in various engineering applications. Mild steels are widely used in various structural and fabrication applications like Bridges, buildings, machineries etc. Being very common and general purpose structural steel, it is widely applied to welding all over the world. A variety of electrodes are available globally for welding of mild steel, but the development of new electrodes is always a necessity.Dissertation aims to find out the mechanical ...

  2. 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

    2012-07-01

    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.

  3. C and S isotope characteristics of bitumen, calcite, Fe and Cu sulfides in the metallogenic analysis of the Ocoita metallotec

    International Nuclear Information System (INIS)

    As a result of a significant increase in the rate of convergence of the Phoenix and South American plates during the Early Cretaceous (120 -100 Ma.), a basin, defined by Aberg et al., (1984) as an 'Aborted Marginal Basin', developed in Central Chile. In the late stages of this back-arc marine basin, submarine lava flows extruded through the thinned continental crust underlying the bottom of the shallow sea. The porphyritic lavas of the Pabellon Formation are the northernmost units of this event and are very similar to those of the Ocoa member in the Veta Negra Formation (Cisternas et al. 1999). The lava sequence lies conformably above calcareous rocks of the Pabellon Formation (Barremian-Aptian) and average 70 meters of thickness. The whole sequence dips to the east with a north-south directed strike. A notable characteristic of these lavas are the abundant (>40%) centimeter-size plagioclase phenocrysts, which can be associated with the 'lavas ocoiticas' or 'ocoitas' of the Ocoa member in the Veta Negra Formation of Central Chile. Geochemical analysis of the Pabellon formation lavas indicates that these lavas were derived from K-rich calc-alkaline to transitional magmas, typical of a continental margin subduction, however with an important component of intra-plate contamination (Galindo 1998; Cisternas et al., 1999). The basal rocks are cut by intrusives (119-93 ma.), the same age as the lavas. These intrusives are believed to be the source of heat needed for the thermal maturation of organic matter in the underlying beds. The organic matter rich limestones of the Nantoco formation are the most probable source of the hydrocarbons, which were mobilized by hydrothermal fluids and deposited in veinlets and voids in the lavas (au)

  4. Predicting Calcite (CaCO3) Requirements of Sphagnum Peat Moss from pH Titration Curves

    Science.gov (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. 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

    2015-01-01

    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 durin...

  6. Early Paleogene variations in the calcite compensation depth : New constraints using old borehole sediments from across Ninetyeast Ridge, central Indian Ocean

    NARCIS (Netherlands)

    Slotnick, B. S.; Lauretano, V.; Backman, J.; Dickens, G. R.; Sluijs, A.; Lourens, L.

    2015-01-01

    Major variations in global carbon cycling occurred between 62 and 48 Ma, and these very likely related to changes in the total carbon inventory of the ocean-atmosphere system. Based on carbon cycle theory, variations in the mass of the ocean carbon should be reflected in contemporaneous global ocean

  7. 使用碳酸钙防治阿巴拉契亚煤田煤肺病技术可行性讨论%Feasibility study to use calcite in mitigating black lung problems in Appalachian coal fields

    Institute of Scientific and Technical Information of China (English)

    Yi Luo; Xi Huang

    2014-01-01

    煤肺病是世界煤炭工业最严重的职业病.通常煤肺病的成因取决于工作环境中可吸尘浓度及工人吸尘时间.一项最近的研究表明,煤尘的毒性由煤的化学成份浃定.化学成分的差异是导致美国东部煤田煤肺病的发病率高于美国西部煤田的主要原因.在阿巴拉契亚(东部)煤成份中,生物可用铁(bio-available iron,BAI)和石英成分是导致煤肺病的两大直接因素.美国西部煤所含碳酸钙有效地阻止了煤中的铁向生物可用铁的转化过程,从而减少了西部煤田煤肺发病率,此发现能合理地解释阿巴拉契亚与西部煤田煤肺发病率的巨大区域差别.根据该发现,我们提议除继续使用传统的降尘技术外,应把减少及消除煤尘的毒性作为开发防治煤肺病技术的新方向.为了遏制并扭转阿巴拉契亚煤田近期煤肺发病率回升的趋势,作者提出了将碳酸钙引入含生物可用铁的煤或煤尘的区域性非传统防煤尘新技术并对其进行了可行性讨论.

  8. Reciclagem do resíduo da serragem de calcário laminado para produção de blocos cerâmicos Recycling of laminated calcite tile sawing waste for the production of ceramic bricks

    OpenAIRE

    Menezes, Romualdo R.; Luiz Ronaldo L. Melo; Francisco Antonio Santos Fonsêca; Pollyane M. Souto; Gelmires A. Neves; Lisiane N. L. Santana

    2010-01-01

    As indústrias da mineração e beneficiamento de calcário laminado representam um importante segmento econômico do Estado do Ceará, entretanto produzem uma grande quantidade de resíduos, que poluem e agridem o meio ambiente. Assim, esse trabalho tem por objetivo a caracterização do resíduo da serragem da Pedra Cariri e a avaliação de sua aplicabilidade como matéria-prima cerâmica alternativa para a produção de telhas e blocos cerâmicos. O resíduo foi caracterizado através da determinação de sua...

  9. 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.

    2010-01-01

    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 c

  10. Impact of seawater pCO2 changes on calcification and on Mg/Ca and Sr/Ca in benthic foraminifera calcite (Ammonia tepida: results from culturing experiments

    Directory of Open Access Journals (Sweden)

    J. Bijma

    2009-04-01

    Full Text Available Evidence is accumulating of increasing concentrations of dissolved carbon dioxide in the ocean and associated acidification impacts on calcifying organisms. Among these organisms, benthic and planktonic foraminifera are responsible for a large amount of the globally precipitated calcium carbonate. Therefore, their response to an acidifying ocean may have important consequences for future inorganic carbon cycling. To assess the sensitivity of benthic foraminifera to changing carbon dioxide levels and subsequent alteration in seawater carbonate chemistry, we cultured specimens of the shallow water species Ammonia tepida at two concentrations of atmospheric CO2 (120 and 2000 ppm and two temperatures (10°C and 15°C. Shell weights and elemental compositions were determined. Results indicate that shell weights decrease with decreasing [CO32−], and increase with decreasing temperature. Changes in [CO32−] or total dissolved inorganic carbon do not affect the Mg partition coefficient. On the contrary, Sr incorporation is enhanced under increasing [CO32−]. Implications of these results for the paleoceanographic application of foraminifera are also discussed.

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

    Science.gov (United States)

    Dreybrodt, Wolfgang; Hansen, Maximilian; Scholz, Denis

    2016-02-01

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

  12. Dune associated calcretes, Rhizoliths and Paleosols from the western continental shelf of India

    Digital Repository Service at National Institute of Oceanography (India)

    Rao, V.P.; Thamban, M.

    diameter, interpreted as vascular cylinders of the root tissues are typical. Radial fibrous calcite and spar calcite with inclusions indicate neomorphic cements. Reddish brown mudstones contain calcified root-hair sheaths, micrite glaebules and reworked...

  13. Potential of bacteria-based repair solution as healing agent for porous network concrete

    OpenAIRE

    Wiktor, V.A.C.; Sangadji, S.; Jonkers, H.M.; Schlangen, H.E.J.G.

    2013-01-01

    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. Besides calcite precipitation, this reaction mechanism leads also to the production of ammonium ions which may result in excessive environmental pressure. More recently, bacterially mediated calcit...

  14. FORWARD AND INVERSE BIO-GEOCHEMICAL MODELING OF MICROBIALLY INDUCED PRECIPITATION IN 0.5M COLUMNAR EXPERIMENTS

    Energy Technology Data Exchange (ETDEWEB)

    Tammer Barkouki; Brian Martinez; Brina Mortensen; Tess Weathers; Jason DeJong; Nic Spycher; Tim Ginn; Yoshiko Fujita; Robert Smith

    2009-09-01

    Microbial ureolysis-induced calcite precipitation may offer an in situ remediation for heavy metal and radionuclide contamination, as well as an alternative to traditional soil strengthening techniques. A microbially mediated calcite precipitation model was built in TOUGHREACT v2 and calibrated to batch and columnar experimental data. Kinetic ureolysis and calcite precipitation-rate expressions were parameterized by coupling TOUCHREACT with UCODE.

  15. Aspartic Acid-rich Proteins in Insoluble Orgaic Matrix Play a Key Role in the Growth of Calcitic Sclerites in Alcyonarian Coral%不溶性基质中天冬氨酸丰富的蛋白在珊瑚的钙质骨片形成中的重要作用

    Institute of Scientific and Technical Information of China (English)

    M. Azizur Rahman; Tamotsu Oomori

    2008-01-01

    一般认为,酸性蛋白在控制矿物的形成和发展中发挥重要作用.因此,在不溶性有机基质中鉴定酸性蛋白对于理解珊瑚中个体蛋白的功能是非常重要的一步.在短指多型软珊瑚(sinularia polydactyla)的可溶性和不溶性基质层中分析蛋白组分表明,在不溶性基质和可溶性基质层中天冬氨酸的含量分别是61%和29%.利用体外分析法发现,基质蛋白诱导碳酸钙形成非晶态析出相先于其形成钙质的结晶态.利用X-射线衍射来鉴定骨片上结晶态的碳酸钙,结果表明钙质的多晶态呈现强反射.傅利叶变换红外光谱分析表明珊瑚基质中富含天冬氨酸的蛋白和多醣的结构.在不溶性基质组分中用钙离子结合分析显示一个分子量为109 kD的蛋白质可以与形成骨片的钙离子结合,这一过程对骨片形成非常重要.在对生物钙化过程中起重要作用的碳酸酐酶的分析中显示了此酶的新颖的活性.以上结果显示珊瑚中不溶性基质内的富含天冬氨酸的蛋白在生物矿化调控过程中起重要作用.

  16. Application of Fluid Inclusions and Mineral Textures in Exploration for Epithermal Precious Metals Deposits

    OpenAIRE

    Moncada de la Rosa, Jorge Daniel

    2008-01-01

    Fluid inclusion and mineralogical features indicative of boiling have been characterized in 855 samples from epithermal precious metals deposits along the Veta Madre at Guanajuato, Mexico. Features associated with boiling that have been identified at Guanajuato include colloform texture silica, plumose texture silica, moss texture silica, ghost-sphere texture silica, lattice-bladed calcite, lattice-bladed calcite replaced by quartz and pseudo-acicular quartz after calcite and coexisting liqu...

  17. Texture asymmetries as shear sense indicators in naturally deformed mono- and polyphase carbonate rocks

    OpenAIRE

    Leiss, B.; Siegesmund, S.; Weber, K.

    1999-01-01

    The microstructural and quantitative texture analyses of a naturally deformed calcite mylonite, a dolomite mylonite and a dolomitic calcite mylonite reveal different texture asymmetries for comparable deformation conditions. Calcite shows a c-axis maximum rotated against the shear sense with regard to the main shear plane. In contrast, the dolomite shows a c-axis maximum rotated with the shear sense. In accordance with the experimental and simulated textures from the literature, this differen...

  18. Extended chronologies of aqueous alteration in the CM2 carbonaceous chondrites: evidence from carbonates in Queen Alexandra Range 93005

    OpenAIRE

    Lee, M.; Lindgren, P.; Sofe, M.; Alexander, C.; Wang, J.

    2012-01-01

    The Antarctic CM2 carbonaceous chondrite QUE 93005 contains four compositionally distinct carbonates, namely breunnerite, calcite, dolomite and a Ca-poor dolomite. These carbonates can form monomineralic grains, or may be intergrown as bimineralic grains consisting of dolomite plus breunnerite and dolomite plus calcite, or polymineralic grains containing an intergrowth of breunnerite, Ca-poor dolomite and calcite. Carbonates in all grain types have inclusions of Fe,Ni sulphides and/or Mg-Fe p...

  19. Diagenesis of the Lisburne Group, northeastern Brooks Range, Alaska

    Energy Technology Data Exchange (ETDEWEB)

    Carlson, R.C.; Goldstein, R.H.; Enos, P. [and others

    1995-05-01

    Petrographic cathodoluminescence studies of the cement stratigraphy of the Lisburne Group yield insights on its diagenetic history. Crosscutting relationships between features of subaerial exposure and calcite cements show that early generations of nonferroan, nonluminescent and multibanded-luminescent calcites are synchronous with or postdated by subaerial exposure surfaces within the Lisburne. Surfaces of subaerial exposure occur at 18 horizons within the Lisburne and are distinguished by features as laminated crusts, rhizoliths, autoclastic breccia, fissure fills, mud cracks, and erosional surfaces. Crosscutting relationships also occur between calcite cements and clasts in karst breccias and conglomerates that formed along the sub-Permian unconformity at the top of the Lisburne. The sub-Permian unconformity postdates later generations of calcite cement. These cements formed in the following sequence: nonferroan to low-ferroan, dully luminescent calcite; ferroan, very-dully luminescent calcite; and second generation of nonferroan, multibanded calcite. The crosscutting relationships not only constrain the timing of cement precipitation, but also suggest that the cements probably were precipitated from meteoric groundwaters introduced during subaerial exposure of the Lisburne platform. Late cements in the Lisburne postdate the Permian Echooka Formation. These cements are low-ferroan, moderately-bright to dully luminescent calcite, followed by a second generation of ferroan, very-dully luminescent calcite. Features of compaction and pressure solution are coincident with the precipitation of the late ferroan calcite and further constrain its timing to deep burial of the Lisburne. The youngest phase of calcite cement precipitated in the Lisburne Group is nonferroan, very-dully luminescent calcite. It commonly fills tectonically-induced shear fractures, indicating precipitation after the onset of Cretaceous (and/or Cenozoic) tectonism in the northeastern Brooks Range.

  20. Differential dissolution of a Pleistocene reef in the groundwater mixing zone of coastal Yucatan, Mexico.

    Science.gov (United States)

    Back, W.; Hanshaw, B.B.; Herman, J.S.; Van Driel, J. N.

    1986-01-01

    Mixing of fresh groundwater with subterranean Caribbean seawater generates a highly reactive geochemical zone that enhances aragonite and calcite dissolution and permits neomorphism of aragonite.-from Authors

  1. Effects Of Various Parameters On The Thickening Of Softening Plant Sludges

    DEFF Research Database (Denmark)

    Peters, Günther H.J.; Baumann, E. R.; Larson, M. A.

    1989-01-01

    Spectroscopic and thermal data for sludges from full-scale softening plants showed calcium and magnesium precipitated as calcite and an amorphous hydrated hydroxide, respectively. Magnesium ions were not incorporated into the calcium lattice to form a magnesian calcite. Scanning electron photomic......Spectroscopic and thermal data for sludges from full-scale softening plants showed calcium and magnesium precipitated as calcite and an amorphous hydrated hydroxide, respectively. Magnesium ions were not incorporated into the calcium lattice to form a magnesian calcite. Scanning electron...... by the magnesium hydroxide. The settling rate of the sludges is related to the CSD. Higher fluxes were achieved with an upflow contact clarifier....

  2. Profiling planktonic foraminiferal crust formation

    NARCIS (Netherlands)

    Steinhardt, Juliane; de Nooijer, Lennart; Brummer, Geert Jan; Reichart, Gert Jan

    2015-01-01

    Planktonic foraminifera migrate vertically through the water column during their life, thereby growing and calcifying over a range of depth-associated conditions. Some species form a calcite veneer, crust, or cortex at the end of their lifecycle. This additional calcite layer may vary in structure,

  3. Profiling planktonic foraminiferal crust formation

    NARCIS (Netherlands)

    Steinhardt, J.; de Nooijer, L.J.; Brummer, G.-J.A.; Reichart, G.J.

    2015-01-01

    Planktonic foraminifera migrate vertically through the water column during their life, therebygrowing and calcifying over a range of depth-associated conditions. Some species form a calcite veneer,crust, or cortex at the end of their lifecycle. This additional calcite layer may vary in structure, co

  4. Mineralogical analyses in Peştera Polovragi (Olteţului Gorges and Peştera Muierii (Galbenului Gorges, Gorj County

    Directory of Open Access Journals (Sweden)

    Ştefan Marincea

    2008-01-01

    Full Text Available Following a series of cave mineralogy researches in Peştera Polovragi and Peştera Muierii, Gorj county, we evidence an association made up of hydroxylapatite, taranakite, calcite and secondarily of quartz and illite and respectively, of hydroxylapatite, brushite, calcite and aragonite, and secondarily of α-quartz and illite.

  5. Nano sized clay detected on chalk particle surfaces

    DEFF Research Database (Denmark)

    Skovbjerg, Lone; Hassenkam, Tue; Makovicky, Emil;

    2012-01-01

    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...

  6. Stable carbon and oxygen isotope investigation in historical lime mortar and plaster - Results from field and experimental study

    Energy Technology Data Exchange (ETDEWEB)

    Kosednar-Legenstein, B. [Institute of Applied Geosciences, Graz University of Technology, Rechbauerstrasse 12, A-8010 Graz (Austria); Dietzel, M. [Institute of Applied Geosciences, Graz University of Technology, Rechbauerstrasse 12, A-8010 Graz (Austria)], E-mail: martin.dietzel@tugraz.at; Leis, A. [Institute of Water Resources Management, Hydrogeology and Geophysics, Joanneum Research, Elisabethstrasse 16/II, A-8010 Graz (Austria); Stingl, K. [Institute of Applied Geosciences, Graz University of Technology, Rechbauerstrasse 12, A-8010 Graz (Austria)

    2008-08-15

    Lime mortar and plaster were sampled from Roman, medieval and early modern buildings in Styria. The historical lime mortar and plaster consist of calcite formed in the matrix during setting and various aggregates. The stable C and O isotopic composition of the calcite matrix was analyzed to get knowledge about the environmental conditions during calcite formation. The {delta}{sup 13}C{sub matrix} and {delta}{sup 18}O{sub matrix} values range from -31 to 0 per mille and -26 to -3 per mille (VPDB), respectively. Obviously, such a range of isotope values does not represent the local natural limestone assumed to be used for producing the mortar and plaster. In an ideal case, the calcite matrix in lime mortar and plaster is isotopically lighter in the exterior vs. the interior mortar layer according to the relationship {delta}{sup 18}O{sub matrix} = 0.61 . {delta}{sup 13}C{sub matrix} - 3.3 (VPDB). Calcite precipitation by uptake of gaseous CO{sub 2} into alkaline Ca(OH){sub 2} solutions shows a similar relationship, {delta}{sup 18}O{sub calcite} = 0.67 . {delta}{sup 13}C{sub calcite} - 6.4 (VPDB). Both relationships indicate that the {sup 13}C/{sup 12}C and {sup 18}O/{sup 16}O values of the calcite reflect the setting behaviour of the lime mortar and plaster. Initially, CO{sub 2} from the atmosphere is fixed as calcite, which is accompanied by kinetic isotope fractionation mostly due to the hydroxylation of CO{sub 2} ({delta}{sup 13}C{sub matrix} {approx} -25 per mille and {delta}{sup 18}O{sub matrix} {approx} -20 per mille ). As calcite formation continued the remaining gaseous CO{sub 2} is subsequently enriched in {sup 13}C and {sup 18}O causing later formed calcite to be isotopically heavier along the setting path in the matrix. Deviations from such an ideal isotopic behaviour may be due to the evolution of H{sub 2}O, e.g. evaporation, the source of CO{sub 2}, e.g. from biogenic origin, relicts of the natural limestone, and secondary effects, such as

  7. Depressing effect of phenoxyl acetic acids on flotation of minerals containing Ca2+/Mg2+ gangues

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Phenoxyl acetic acids were applied to determine their depressing effect on minerals containing Ca2+/Mg2+ gangues. Calcite,mixture of calcite and fluorite, and nickel ore were used in the flotation. And the depression mechanism was studied by the determination of contact angle, zeta potential, adsorptive capacity of collector, and IR analysis as well. It is found that 0.1 mmol/L of phenoxyl acetic acid derived from pyrogallol or gallic acid exhibits strong depressing ability on calcite in almost zero yields at pH value of 9.8, and calcite can be depressed in the flotation of calcite/fluorite mixture for approximate 87% yield of fluorite. The flotation result of practical nickel ore containing serpentine indicates that these two depressants may also show better depression performance to serpentine than traditional depressants such as sodium fluosilicate and carboxylmethyl cellulose. Analysis for the depression mechanism reveals that there exists strong chemical interaction between the depressants and minerals.

  8. Selective silicification of fossils by syntaxial overgrowths on quartz sand, Oriskany Sandstone (Lower Devonian), New York

    Science.gov (United States)

    Maliva, Robert G.

    1992-07-01

    Some fossil fragments in the Oriskany Sandstone (Lower Devonian) of New York were partially replaced by syntaxial quartz overgrowths. These replacive overgrowths are significant in that they provide insights into the mechanism and controls of quartz replacement of calcite. The susceptibility of the different calcite types of quartz replacement was governed by their microstructural complexity. Fossil fragments with finely crystalline microstructures, such as brachiopods, ostracods, and bryozoans, were partially replaced by quartz, whereas echinoderm ossicles, which consist of single large calcite crystals, were not replaced. Calcite cement was also immune to replacement. Brachiopod, bryozoan, and ostracod bioclasts (with minor exceptions) underwent partial replacement by quartz (with its concomitant shell calcite dissolution) only where the shell fragments were in contact with detrital quartz grains. Proximity to authigenic crystal nucleation sites (i.e., quartz sand grains) was thus the prime control over whether host mineral dissolution occurred, which is a situation unique to the force of crystallization-driven replacement mechanism.

  9. Influence of clay and silica on permeability and capillary entry pressure of chalk reservoirs in the North Sea

    DEFF Research Database (Denmark)

    Røgen, Birte; Fabricius, Ida Lykke

    2002-01-01

    specific surface area. Fifty-nine Tor and Ekofisk Formation chalk samples from five North Sea chalk reservoirs were investigated. All contain quartz and clay minerals, most commonly kaolinite and smectite, with trace amounts of illite. The contents of calcite and quartz are inversely correlated and both...... are independent of the content of clays. We thus infer that the main part of the silica is of biogenic origin. The specific surface area of the chalk is mainly controlled by clay content. The specific surface area of calcite is determined by the individual calcite crystal size and is not dependent...... on stratigraphic variations in fossil size. The specific surface area of calcite increases with increasing content of quartz and clays. These constituents may inhibit recrystallization of calcite and thus preserve high 2 specific surface area. Our data accord with the following specific surface areas (m(2) g(-1...

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

    Science.gov (United States)

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

    2014-12-01

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

  11. Oxygen isotope fractionation in travertine-depositing pools at Baishuitai, Yunnan, SW China: Effects of deposition rates

    Science.gov (United States)

    Sun, Hailong; Liu, Zaihua; Yan, Hao

    2014-05-01

    Travertine δ18O values can be used to reconstruct paleo-temperatures if the oxygen isotope fractionation factors between travertine and water are accurately understood. For this purpose, the δ18O values of pool travertine and its parent water, and the deposition rates of the calcite were investigated at Baishuitai (Yunnan, SW China) over the course of the full hydrological year, April 23 2006-April 25 2007. The results show that the travertine-water isotope fractionation factors are close to the commonly accepted equilibrium line of Kim and O'Neil (1997). This differs from the results obtained by Yan et al. (2012) who found that the oxygen isotope fractionation factors in the travertine-depositing pools were close to the line suggested as equilibrium relationship by Coplen (2007). The average calcite deposition rate (2.30 mg cm-2 d-1) in the present study is six times larger than that (0.38 mg cm-2 d-1) in Yan et al. (2012). If slower calcite precipitation leads to equilibrium oxygen isotopic fractionation, then the results of this study support the results of Coplen (2007) that indicate that the equilibrium fractionation factor may be greater than the commonly accepted one derived by Kim and O'Neil (1997). The relationship between oxygen isotope fractionation factor and calcite deposition rate in our study also agrees with the results of Dietzel et al. (2009) who found that the kinetic-isotope effect favors preferential incorporation of 16O in solid calcite as the calcite deposition rate increases. There was a threshold for calcite precipitation rate control on oxygen isotopic equilibrium. In our case of travertine-depositing pools, when the calcite deposition rate was lower than 0.38 mg cm-2 d-1, oxygen isotopic equilibrium between calcite and water was attained. Therefore, calcite deposition rate is a potentially important consideration when using δ18O in natural carbonates as a proxy for terrestrial and ocean temperature.

  12. Diagenesis and Its Effect on Reservoir Quality of Silurian Sandstones, Tabei Area, Tarim Basin, China

    Institute of Scientific and Technical Information of China (English)

    Zhang Jinliang; Jia Ying; Du Guilin

    2007-01-01

    The diagenetic processes of the Tabei sandstones in the Tarim Basin include compaction, cementation (quartz overgrowths, calcite, clay minerals and a minor amount of pyrite), and dissolution of the feldspar and calcite cement.Porosity was reduced by compaction from an assumed original 40% to about 22.1%. Cementation reduced porosity to 26.6%. The Tabei sandstones lost a little more porosity by compaction than by cementation. Quartz cementation,especially syntaxial quartz overgrowth, is a major cause of porosity-loss in many reservoirs in moderately to deeply buried sandstone. Calcite cementation played a key role in the porosity evolution of sandstones. At the early stage of burial, the early calcite cement occupied most of the pore spaces resulting in significant porosity. On the other hand, some primary porosity has been preserved due to incomplete filling or the presence of scattered patches of calcite cement. In addition to calcite, several clay minerals, including illite and chlorite occurred as pore-filling and pore-lining cements.The pore-lining chlorite may have helped in retaining the porosity by preventing the precipitation of syntaxial quartz overgrowths. Illite, which largely occurred as hair-like rims around the grains and bridges on the pore throats, caused a substantial deterioration of penetrability of the reservoir. Calcite cement dissolution was extensive and contributed significantly to the development of secondary porosity.

  13. The 2008 Emiliania huxleyi bloom along the Patagonian Shelf: Ecology, biogeochemistry, and cellular calcification

    Science.gov (United States)

    Poulton, Alex J.; Painter, Stuart C.; Young, Jeremy R.; Bates, Nicholas R.; Bowler, Bruce; Drapeau, Dave; Lyczsckowski, Emily; Balch, William M.

    2013-12-01

    blooms are significant contributors to the global production and export of calcium carbonate (calcite). The Patagonian Shelf is a site of intense annual coccolithophore blooms during austral summer. During December 2008, we made intensive measurements of the ecology, biogeochemistry, and physiology of a coccolithophore bloom. High numbers of Emiliania huxleyi cells and detached coccoliths (>1 × 103 mL-1 and >10 × 103 mL-1, respectively), high particulate inorganic carbon concentrations (>10 mmol C m-2), and high calcite production (up to 7.3 mmol C m-2 d-1) all characterized bloom waters. The bloom was dominated by the low-calcite-containing B/C morphotype of Emiliania huxleyi, although a small (30%, similar to estimates for E. huxleyi and indicative of a significant role for this diatom in bloom biogeochemistry. Cell-normalized calcification rates, when corrected for a high number of nonactive cells, were relatively high and when normalized to estimates of coccolith calcite indicate excessive coccolith production in the declining phase of the bloom. We find that low measures of calcite and calcite production relative to other blooms in the global ocean indicate that the dominance of the B/C morphotype may lead to overall lower calcite production. Globally, this suggests that morphotype composition influences regional bloom inventories of carbonate production and export and that climate-induced changes in morphotype biogeography could affect the carbon cycle.

  14. Reassessing the dissolution of marine carbonates: I. Solubility

    Science.gov (United States)

    Gehlen, M.; Bassinot, F. C.; Chou, L.; McCorkle, D.

    2005-08-01

    We studied the solubility of the [63-150 μm] and the greater than 150 μm size fractions of sediments from two bathymetric transects in the eastern tropical Atlantic (Sierra Leone rise and Cape Verde Plateau). Both fractions are made mainly of foraminiferal shells and fragments. We determined the calcite crystallinity (full width at half maximum of XRD (104) calcite peak) of the >150 μm size fraction. Equilibration experiments were carried out in artificial seawater (20 °C, pCO 2=3100 ppm) for up to 57 days starting from undersaturation with respect to calcite and supersaturation with respect to aragonite. Experiments starting from supersaturation yielded concentration products close to aragonite solubility for sediments from the shallowest stations, suggesting the presence of trace levels of aragonite in these samples. Concentration products computed for the deeper stations were intermediate between aragonite and calcite solubility. Our results indicate the formation of a high-Mg coating. The equilibration period was too short to allow the complete recrystallization of these Mg-rich overgrowths. Experiments initiated from undersaturation yield concentration products that are between 4% and 24% higher than the reported stoichiometric concentration product of synthetic calcite. These differences between estimates of calcite stoichiometric solubility products are explained in terms of variations in experimental conditions (artificial versus natural seawater) and related choices of carbonic acid dissociation constants. They do not reflect a true difference in solubility between biogenic and synthetic calcite. The thinning of the foraminiferal calcite (104) XRD peak from 0.168°( 2θ) to 0.148°( 2θ) along the depth transects is interpreted as reflecting an improvement in calcite crystallinity. This and the change in specific surface area are consistent with the progressive change of the carbonate assemblage. The evolution of the bulk composition of the carbonate

  15. The chemical evolution of a travertine-depositing stream: geochemical processes and mass transfer reactions

    Science.gov (United States)

    Lorah, M.M.; Herman, J.S.

    1988-01-01

    Focuses on quantiatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virgina. The processes of CO2 outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall. -from Authors

  16. Late Quaternary palaeoenvironmental reconstruction from Lakes Ohrid and Prespa (Macedonia/Albania border using stable isotopes

    Directory of Open Access Journals (Sweden)

    M. J. Leng

    2010-10-01

    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

  17. Skeletal mineralogy of bryozoans: Taxonomic and temporal patterns

    Science.gov (United States)

    Smith, Abigail M.; Key, Marcus M., Jr.; Gordon, Dennis P.

    2006-10-01

    Skeletal carbonate mineralogy of 1183 specimens of marine bryozoans from the literature was examined for phylogenetic patterns in order to elucidate the effects of bryozoan mineralogy on geochemical and paleoenvironmental analysis. Colonies are composed of calcite (66% of specimens), aragonite (17% of specimens) or various mixtures of the two (17% specimens) (phylum mean = 72.9 wt.% calcite, n = 1051). When calcite is present, it ranges from 0.0 to 13.7 wt.% MgCO 3 (mean = 5.0 wt.% MgCO 3, n = 873). Most (61%) calcitic specimens are formed of intermediate-Mg calcite (4 to 8 wt.% MgCO 3), others (28%) of low-Mg calcite (0 to 4 wt.% MgCO 3), and few of high-Mg calcite (> 8 wt.% MgCO 3). The phylum occupies at least 63% of the theoretical mineralogical "space" available to biomineralisation. Most of this variation occurs in the class Gymnolaemata, order Cheilostomata, suborder Neocheilostomata. Fossil and Recent stenolaemate taxa are generally low- to intermediate-Mg calcite (mean = 99.7 wt.% calcite, 2.6 wt.% MgCO 3, 17% of available biomineral space). Variability among families is related in a general way to first appearance datum: families younger than 100 Ma display greater mineralogical complexity than older ones. The cheilostome infraorder Flustrina includes unusual free-living aragonitic families, dual-calcite skeletons (mainly low-Mg calcite, but with secondary high-Mg calcite), and some genera with considerable mineralogical variability. Families (e.g., Membraniporidae and Phidoloporidae) and species (e.g., Schizoporella unicornis) with the highest degree of variability have potential for environmental correlations with mineralogy, paleoenvironmental interpretation, and possibly molecular investigation for potential cryptic species. Stenolaemate families, genera and species with low variability, on the other hand, are well-suited for geochemical work such as stable isotope analysis. Variability in the skeletal mineralogy of bryozoans suggests that they may be

  18. Late Quaternary palaeoenvironmental reconstruction from Lakes Ohrid and Prespa (Macedonia/Albania border using stable isotopes

    Directory of Open Access Journals (Sweden)

    M. J. Leng

    2010-05-01

    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 till 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 agreement

  19. Study of fluid inclusion from uranium deposit No.302 in north Guangdong

    International Nuclear Information System (INIS)

    The temperature of fluid inclusions in gangue minerals such as calcite, quartz, fluorite was measured and carbon isotope composition of Calcite was studied for uranium deposit No.302 in north Guangdong in this paper. It shows that the homogeneous temperature and salinity decreased from the early ore-forming period to late ore-forming period, and the early ore-forming period had at least two-staged fluid process with medium-high temperature and salinity. The carbon isotopic composition of δ13CPDB of calcites of different stages are: -0.614%--0.971% which indicates that the carbon maybe came from deep crust. (authors)

  20. Interpretação do mecanismo de difusão no processo gás-sólido da reação de dessulfurização

    OpenAIRE

    Daniela Andresa Mortari; Paula Manoel Crnkovic; Ivonete Ávila; Fernando Eduardo Milioli

    2010-01-01

    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 togeth...

  1. 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.

    2013-01-01

    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.

  2. Contributions to Th-230/U-234 dating of speleothems; comparison of the results with those of other absolute dating methods

    International Nuclear Information System (INIS)

    Calcite speleothems, e.g. stalagmites, have been investigated by α-spectrometry using Si-surface boundary layer detectors after radiochemical separation. The findings are compared with those of other physical/chemical/nuclear physics techniques. (HP)

  3. Enhanced rates of particulate organic matter remineralization by microzooplankton are diminished by added ballast minerals

    Directory of Open Access Journals (Sweden)

    F. A. C. Le Moigne

    2013-02-01

    Full Text Available To examine the potentially competing influences of microzooplankton and calcite mineral ballast on organic matter remineralization, we incubated diatoms in darkness in rolling tanks with and without added calcite minerals (coccoliths and microzooplankton (rotifers. Concentrations of particulate organic matter (POM, suspended or in aggregates, of dissolved organic matter (DOM, and of dissolved inorganic nutrients were monitored over 8 days. The presence of rotifers enhanced the remineralization of ammonium and phosphate, but not dissolved silicon, from the biogenic material, up to 40% of which became incorporated into aggregates early in the experiment. Added calcite resulted in rates of excretion of ammonium and phosphate by rotifers that were depressed by 67% and 36%, respectively, demonstrating the potential for minerals to inhibit the destruction of POM in the water column by zooplankton. Lastly, the presence of the rotifers and added calcite minerals resulted in more rapid kinetics of aggregation, although not a greater overall amount of aggregation during the experiment.

  4. Belemnite-based strontium, carbon and oxygen isotope stratigraphy of the type area of the Maastrichtian Stage

    NARCIS (Netherlands)

    Vonhof, H.B.; Jagt, J.W.M.; Immenhauser, A.; Smit, J.; Berg, Y.W. van den; Saher, M.; Keutgen, N.; Reijmer, J.J.G.

    2011-01-01

    Belemnitellid cephalopods from the Maastrichtian stratotype area (southeast Netherlands) are shown to be comparatively well preserved. Although partial diagenetic alteration has been observed, micromilling techniques have permitted the extraction of pristine belemnite calcite, suitable for the recon

  5. 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...

  6. GEOCHEMISTRY

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    <正>20101501 Dou Chuanwei (State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002, China); Lian Bin Microbial Weathering of Calcite by Rock-Inhabiting Fungi, biogenic processes

  7. Interpretação do mecanismo de difusão no processo gás-sólido da reação de dessulfurização

    Directory of Open Access Journals (Sweden)

    Daniela Andresa Mortari

    2010-01-01

    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.

  8. Evaluation of Speleothem Oxygen Isotope Fractionation from a Tropical Cave on the Island of Guam

    Science.gov (United States)

    Moore, M. W.; Hardt, B. F.; Banner, J. L.; Jenson, J. W.

    2013-12-01

    Recent studies in the tropics apply oxygen isotope variations in speleothems as proxies for changes in past hydroclimate, yet little work has been done to study the modern tropical cave environment. Oxygen isotope time series in speleothems are commonly used to interpret past climate based on the assumption of equilibrium fractionation. When re-constructing paleoclimate, there are limited tools available to assess potential non-equilibrium isotope effects. One approach is to test for agreement of oxygen isotope values between parallel-milled tracks from a stalagmite. A stalagmite collected from Jinapsan Cave on the island of Guam supports the argument for equilibrium as multiple overlapping transects along the growth axis show consistent replication. However, to fully evaluate the fractionation processes relating to calcite growth, we have also studied the relationship between modern drip water and modern speleothem calcite. To accomplish this, we collected monthly dripwater samples and deployed artificial substrates under active drips to measure calcite growth rates and to assess the state of isotopic equilibrium between speleothem calcite and drip water. We evaluate the processes controlling the δ18O values of calcite formed on substrates relative to values for the dripwater feeding the site of the speleothem in Jinapsan Cave. The studied drip site shows seasonal variability in dripwater δ18O of ~1‰, with more negative composition occurring during the wet season. The δ18O of the substrate calcite sampled at the point of first growth (analogous to the growth axis in a speleothem) also shows a seasonal cycle of about 1‰, yet the values are more positive than predicted by the equilibrium equation of Kim & O'Neil 1997. In addition, carbon and oxygen isotopic composition between substrates strongly covary. Correlation of carbon and oxygen isotopes between substrates at the point of first growth may be explained by prior calcite precipitation. Carbon isotope

  9. Mineralogical Evidence for the Palaeohydrogeological Stability of a Deep Groundwater System in Fractured Rock, in West Cumbria, Northwest England

    Science.gov (United States)

    Milodowski, A. E.; Gillespie, M. R.; Chenery, S. R. N.; Naden, J.; Shaw, R. P.

    2014-12-01

    An important requirement of the safety assessment for a geological disposal facility (GDF) for radioactive waste is to be able to demonstrate the long-term chemical stability of the groundwater system at repository depth over the long period of time during which the waste will be a hazard, typically up to one million years. Of particular concern in the UK is the potential for oxidising groundwater to penetrate to repository depth during periods of glaciation, thereby increasing the mobility of some transuranic radionuclides.Between 1990 and 1998, United Kingdom Nirex Limited carried out geological investigations into the suitability of a potential site in the Sellafield area of NW England, for a GDF for L/ILW. As part of these investigations, detailed petrological analysis of fracture mineralisation in 23 deep boreholes identified a complex sequence of mineralisation events referred to as ME1-ME9. The distribution of the ME9 calcite mineralisation correlates closely with present-day groundwater flows. The ME9 calcite has been studied in more detail to understand the evolution of the deep groundwater system. The morphology and growth zoning characteristics of the calcites reflects the groundwater chemistry. Freshwater calcites display c-axis flattened to equant crystals, and are non-ferroan and strongly zoned with Mn-rich and Mn-free bands. Deeper saline-zone calcites display c-axis elongated crystals, with high Mn:Fe and low Mn:Fe growth zones. Calcite in the transition zone between the saline and fresh groundwater display saline-type cores overgrown by freshwater-type calcite, indicating a small depression of the position of the transition zone during the growth of the calcites. Sr isotope ratios and fluid inclusion chemistry confirm a link between ME9 calcite and the present regional groundwater system. Modelling of the oxygen isotope data indicates that some growth zones in the ME9 calcite precipitated from groundwater potentially containing a significant

  10. Hydrothermal carbonate chimneys from a continental rift (Afar Rift): Mineralogy, geochemistry, and mode of formation

    OpenAIRE

    Dekov, V. M.; Egueh, N. M.; Kamenov, G.D.; Bayon, G.; Lalonde, S. V.; Schmidt, Mark; Liebetrau, Volker; Munnik, F.; Fouquet, Y.; Tanimizu, M.; Awaleh, M. O.; Guirreh, I.; Le Gall, B.

    2014-01-01

    International audience Carbonate chimney-like deposits up to 60 m high are scattered or arranged in rows at the shores of a desiccating hypersaline and alkaline lake from a continental rift setting (Lake Abhé, Afar Rift, Djibouti). The chimneys formed sub-aqueously in the lake water body at a higher water level than observed today. Alternating calcite and low-Mg calcite + silica concentric layers compose the chimney structures. Mineralogical and geochemical investigations of the chimneys, ...

  11. Characterization, feasibility and optimization of Agaricus subrufescens growth based on chemical elements on casing layer

    OpenAIRE

    Cunha Zied, D.; Pardo-Giménez, A.; de Almeida Minhoni, M.T.; R.L. Villas Boas; Alvarez-Orti, M.; Pardo-González, J.E.

    2012-01-01

    The aim of this study was to analyze yields, biological efficiency, earliness (expressed as days to first harvest), and precociousness and establish models for the mushroom growing according to these parameters. The experiment followed a double factorial design with four sources of calcium (calcitic limestone, calcitic limestone + gypsum, dolomitic limestone and dolomitic limestone + gypsum) and 2 application times (25 days before casing and at the moment of casing), with 4 replicates for eac...

  12. Annually laminated speleotherms : a review

    OpenAIRE

    Baker, Andy; Smith, Claire; Jex, Catherine; Fairchild, I. J.; Genty, Dominique; Fuller, Lisa

    2008-01-01

    This review of annually laminated speleothems firstly considers the four types of annual laminae found within speleothems: fluorescent laminae formed by annual variations in organic matter flux; visible or petrographic laminae, formed by annual variations in calcite texture or fabric; calcite-aragonite couplets; and finally trace element laminae. The methods available to confirm the annual nature, or otherwise, of lamina deposition are reviewed. We consider the use of annual laminae ...

  13. Enhanced rates of particulate organic matter remineralization by microzooplankton are diminished by added ballast minerals

    OpenAIRE

    Moigne, F. A. C.; Gallinari, M.; Laurenceau, E.; Rocha, C L

    2013-01-01

    International audience; To examine the potentially competing influences of microzooplankton and calcite mineral ballast on organic matter remineralization, we incubated diatoms in darkness in rolling tanks with and without added calcite minerals (coccoliths) and microzooplankton (rotifers). Concentrations of particulate organic matter (POM in suspension or in aggregates), of dissolved organic matter (DOM), and of dissolved inorganic nutrients were monitored over 8 days. The presence of rotife...

  14. Lithologic characteristics and diagenesis of the Devonian Jauf sandstone at Ghawar Field, Eastern Saudi Arabia

    Energy Technology Data Exchange (ETDEWEB)

    Al Ramadan, K.A.; Hussain, M. [King Fahd Univ. of Petroleum and Minerals, Dhahran (Saudi Arabia). Dept. of Earth Sciences; Imam, B. [Dhaka Univ. (Bangladesh). Dept. of Geology; Saner, S. [King Fahd Univ. of Petroleum and Minerals, Dhahran (Saudi Arabia). Research Inst.

    2004-12-01

    The Lower Devonian Jauf Formation in Saudi Arabia is an important hydrocarbon reservoir. However, in spite of its importance as a reservoir, published studies on the Jauf Formation more specifically on the reservoir quality (including diagenesis), are very few. This study, which is based on core samples from two wells in the Ghawar Field, northeastern Saudi Arabia, reports the lithologic and diagenetic characteristics of this reservoir. The Jauf reservoir is a fine to medium-grained, moderate to well-sorted quartz arenite. The diagenetic processes recognized include compaction, cementation (calcite, clay minerals, quartz overgrowths, and a minor amount of pyrite), and dissolution of the calcite cements and of feldspar grains. The widespread occurrences of early calcite cement suggest that the Jauf reservoir lost a significant amount of primary porosity at a very early stage of its diagenetic history. Early calcite cement, however, prevented the later compaction of the sandstone, thus preserving an unfilled part of the primary porosity. Based on the framework grain-cement relationships, precipitation of the early calcite cement was either accompanied or followed by the development of part of the pore-lining and pore-bridging clay cement. Secondary porosity development occurred due to partial to complete dissolution of early calcite cements and feldspar. Late calcite cement occurs as isolated patches, and has little impact on reservoir quality of the sandstones. In addition to calcite, several different clay minerals including illite and chlorite occur as pore-filling and pore-lining cements. While the pore-filling illite and chlorite resulted in a considerable loss of porosity, the pore-lining chlorite may have helped in retaining the porosity by preventing the precipitation of syntaxial quartz overgrowths. Illite, which largely occurs as hair-like rims around the grains and bridges on the pore throats, caused a substantial deterioration to permeability of the

  15. Morphology, Absorptivity and Viscoelastic Properties of Mineralized PVP-CMC Hydrogel

    OpenAIRE

    Saha, Nabanita; Shah, Rushita; Vyroubal, Radek; Kitano, Takeshi; Sáha, Petr

    2013-01-01

    A simple liquid diffusion mineralization technique was applied for the incorporation of calcium carbonate (CaCO3) in PVP-CMC hydrogel. The hydrogel was prepared 6.5 mm thick to achieve around 1 mm thick sample after mineralization of hydrogel matrix with calcite. The calcite crystals were round shaped and organized as building blocks inside the porous three dimensional cross linked structure of the PVP-CMC hydrogel. The present study was designed to evaluate the properties of mineralized (cal...

  16. Carbonatite tuffs in the Laetolil Beds of Tanzania and the Kaiserstuhl in Germany

    Science.gov (United States)

    Hay, R.L.; O'Neil, J.R.

    1983-01-01

    Carbonatite lava and tephra are now well known. The only modern eruptive carbonatites, from Oldoinyo Lengai, Tanzania, are of alkali carbonatite, whereas all of the pre-modern examples are of calcite or dolomite. Chemical and stable isotope analyses were made of separate phases of Pliocene carbonatite tuffs of the Laetolil Beds in Tanzania and of Miocene carbonatite tuffs of the Kaiserstuhl in Germany in order to understand the reasons for this major difference. The Laetolil Beds contain numerous carbonatite and melilitite-carbonatite tuffs. It is proposed that the carbonatite ash was originally of alkali carbonate composition and that the alkali component was dissolved, leaving a residuum of calcium carbonate. The least recrystallized melilitite-carbonatite tuff contains early-deposited calcite cement and calcite pseudomorphs after nyerereite (?) that have contents of strontium and barium and ??18O and ??13C values suggestive of incomplete chemical and isotopic exchange during alteration and replacement of alkali carbonatite ash. Carbonatite tuffs of the Kaiserstuhl contain globules composed of calcite phenocrysts and microphenocrysts in a groundmass of calcite with a small amount of clay, apatite, and magnetite. The SrO contents of phenocrysts, microphenocrysts, and groundmass calcite average 0.90, 1.42, and 0.59 percent, respectively. The average ??18O and ??13C values of globules (+14.3 and -9.0, respectively) fall between those of coarse-grained intrusive Kaiserstuhl carbonatite (avg. +6.6, -5.8) and those of low-temperature calcite cement in the carbonatite tuffs (+21.8, -14.9). The phenocrysts and microphenocrysts are primary magmatic calcite, but several features indicate that the groundmass has been recrystallized and altered in contact with meteoric water, resulting in weathering of silicate to clay, leaching of strontium, and isotopic exchange. The weight of evidence favors an original high content of alkali carbonatite in the groundmass, with

  17. Kinetical and thermodynamical parametars of crystallization of iPP nucleated with mixed α-nucleators

    OpenAIRE

    Janevski, Aco; Bogoeva-Gaceva, Gordana

    2013-01-01

    It is well known that the presence of a solid surface (substrate) in contact with thermoplastic polymers during the crystallization from the melt, generally favors the heterogeneous nucleation. Isothermal and nonisothermal crystallization of isotactic polypropylene (iPP) nucleated with 0.1 %wt. talc (average dimension of 20 µ) (assign. PPT), 0.1 %wt. calcite (average dimension of 5µ) (assign. PPC) and polymer nucleated with 0.1 %wt. talc plus 0.1 % wt. calcite (assign. PPTC), were studied...

  18. From nanometer aggregates to micrometer crystals

    DEFF Research Database (Denmark)

    Schultz, Logan Nicholas; Dideriksen, Knud; Lakshtanov, Leonid;

    2014-01-01

    and crystal shapes. Grain coarsening of calcite, CaCO3, is relevant for biomineralization and commercial products and is an important process in diagenesis of sediments to rock during geological time. We investigated coarsening of pure, synthetic calcite powder of sub-micrometer diameter crystals and...... one growth mechanism to the other. This has been poorly described by mean field coarsening models and offers predictive power to grain coarsening models. © 2014 American Chemical Society....

  19. High-purity limestone assessment : from mine to market

    OpenAIRE

    Mitchell, Clive

    2009-01-01

    High-purity limestone can be defined as carbonate rock that contains greater than 97% calcium carbonate (CaCO3, typically as calcite); it is often referred to as high-calcium or highly-calcitic limestone. Limestone has by far the largest number of commercial uses of all the industrial minerals; including construction (aggregate, cement and dimension stone), mineral fillers (for paper, paint, plastic, rubber and pharmaceuticals), adhesives, abrasives, fertilisers and soil conditioners, the pro...

  20. Resonant laser-SNMS of boron for analysis of paleoceanographic samples

    OpenAIRE

    Vering, G.; Crone, C; Kathers, P.; Bijma, Jelle; Arlinghaus, H. F.

    2006-01-01

    Calcite shells of foraminifera, which are accumulated in the ocean sediment, are an important object of paleoceanographic studies to reconstruct environmental parameters of the past. Foraminifera are unicellular organisms living in almost all parts of the ocean during the entire paleoceanographic time scale. The isotope ratio of boron incorporated in the calcite shell provides information about the pH-value of the ocean at the time the shell was formed. Since the boron fraction of such a shel...

  1. Microbial isotopic signatures in calcareous tufa from Punta Mita coastal vents, Mexico

    Science.gov (United States)

    Canet, C.; Prol-Ledesma, R. M.; Melgarejo, J. C.; Reyes, A.

    2002-12-01

    Numerous small calcareous mounds accompanied by Ba, Hg and Tl mineralization occur in shallow submarine hydrothermal manifestations on the sea bottom, at 10 m depth, in Punta Mita (Western coast of Mexico). The formation of calcite mounds in these coastal vents provides an uncommon example of calcareous tufa deposits in a submarine hydrothermal environment. The hydrothermal activity consists in water and gas (essentially nitrogen and methane) venting at 85°C, through a 100 m fissure hosted in basaltic rocks and partially covered by unconsolidated sediments. The mounds consist of travertine-like metre-sized calcite aggregates that develop around the main submarine hot springs. Barite, sulphides (mostly pyrite and cinnabar) and phosphates (carbonate-hydroxylapatite) are also present in these mounds. Two main calcite types are texturally distinguished: firstly an earlier radial-fibrous generation, and a later fine-grained calcite generation that cements the detrital grains and fills the pore spaces. Stable isotope analyses were performed in calcite from these mounds. The δ13C measured values show a strong depletion in 13C, with values as low as -39.2 per mil (PDB). These values agree with a microbially mediated calcite mineralization process, by means of bacterial oxidation of vent derived methane. In contrast to most known cases of microbial methane oxidation, in Punta Mita this process took place under hydrothermal conditions.

  2. 大安寨石灰岩的成岩作用与成岩圈闭

    Institute of Scientific and Technical Information of China (English)

    强子同

    1981-01-01

    Daanzhai limestone in the Szechuan Basin consists of biosparite, biomicrite and micrite, with intercalations of black shales. Daanthai limestone is of lake origin and known as oil reservoir rocks. There are five layers of reservoir rocks, of which D-3 is the most important in Shuangsijiao oil field. Stained thin sections were studied for 250 limestone samples from the oil field. In addition to non-ferrous calcite, three phases of ferrous calcite were identified in Daanzhai limestone, which are ferrous calcite Ⅰ (0.5 to 1.5% FeO), ferrous calcite Ⅱ (1.5 to 2.5% FeO) and ferrous calcite Ⅲ (2.5 to 3.5% FeO). Shuangsijiao off field belongs to diagenetic trap type. It has been confirmed that the non.ferrous sparry calcite cementation and solution (vug) of the second period control the distribution of commercial oil wells, which are located in southeastern part of the structure trap.

  3. Carbonate clumped isotope bond reordering and geospeedometry

    Science.gov (United States)

    Passey, Benjamin H.; Henkes, Gregory A.

    2012-10-01

    Carbonate clumped isotope thermometry is based on the preference of 13C and 18O to form bonds with each other. At elevated temperatures such bond ordering is susceptible to resetting by diffusion of C and O through the solid mineral lattice. This type of bond reordering has the potential to obscure primary paleoclimate information, but could also provide a basis for reconstructing shallow crustal t