Sample records for subglacially precipitated calcite

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

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


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

  2. in situ Calcite Precipitation for Contaminant Immobilization

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    Yoshiko Fujita; Robert W. Smith


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

  3. On the complex conductivity signatures of calcite precipitation

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


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

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

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


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

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

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


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

  6. Geochemical processes leading to the precipitation of subglacial carbonate crusts at Bossons glacier, Mont Blanc Massif (French Alps) (United States)

    Thomazo, Christophe; Buoncristiani, Jean-Francois; Vennin, Emmanuelle; Pellenard, Pierre; Cocquerez, Theophile; Mugnier, Jean L.; Gérard, Emmanuelle


    Cold climate carbonates can be used as paleoclimatic proxies. The mineralogy and isotopic composition of subglacially precipitated carbonate crusts provide insights into the subglacial conditions and processes occurring at the meltwater-basement rock interface of glaciers. This study documents such crusts discovered on the lee side of a gneissic roche moutonnée at the terminus of the Bossons glacier in the Mont Blanc Massif area (France). The geological context and mineralogical investigations suggest that the Ca used for the precipitation of large crystals of radial fibrous sparite observed in these crusts originated from subglacial chemical weathering of Ca-bearing minerals of the local bedrock (plagioclase and amphibole). Measurements of the carbon and oxygen isotope compositions in the crusts indicate precipitation at, or near to, equilibrium with the basal meltwater under open system conditions during refreezing processes. The homogeneous and low carbonate δ13C values (ca. -11.3‰) imply a large contribution of soil organic carbon to the Bossons subglacial meltwater carbon reservoir at the time of deposition. In addition, organic remains trapped within the subglacially precipitated carbonate crusts give an age of deposition around 6500 years cal BP suggesting that the Mid-Holocene climatic and pedological optima are archived in the Bossons glacier carbonate crusts.

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

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    Iris Heine


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

  8. The role of silicate surfaces on calcite precipitation kinetics

    DEFF Research Database (Denmark)

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


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

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

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


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

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

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    Francesco G. Offeddu


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

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

    DEFF Research Database (Denmark)

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


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

  12. Geochemical Processes Leading to the Precipitation of Subglacial Carbonate Crusts at Bossons Glacier, Mont Blanc Massif (French Alps

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    Christophe Thomazo


    Full Text Available Cold climate carbonates can be used as paleoclimatic proxies. The mineralogy and isotopic composition of subglacially precipitated carbonate crusts (SPCCs provide insights into the subglacial conditions and processes occurring at the meltwater-basement rock interface of glaciers. This study documents such crusts discovered on the lee side of a gneissic roche moutonnée at the terminus of the Bossons glacier in the Mont Blanc Massif area (France. The geological context and mineralogical investigations suggest that the Ca used for the precipitation of large crystals of radial fibrous sparite observed in these crusts originated from subglacial chemical weathering of Ca-bearing minerals of the local bedrock (plagioclase and amphibole. Measurements of the carbon and oxygen isotope compositions in the crusts indicate precipitation at, or near to, equilibrium with the basal meltwater under open system conditions during refreezing processes. The homogeneous and low carbonate δ13C values (ca. −11.3‰ imply a large contribution of soil organic carbon to the Bossons subglacial meltwater carbon reservoir at the time of deposition. In addition, organic remains trapped within the SPCCs give an age of deposition around 6,500 years cal BP suggesting that the Mid-Holocene climatic and pedological optima are archived in the Bossons glacier carbonate crusts.

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

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    C. Neal


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



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


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

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

    Zhang, Chonghong; Li, Fuchun; Lv, Jiejie


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

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

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


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

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

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


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

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

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    Agus Haris Widayat


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

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

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


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

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


    Tokarenko, Olga Grigorievna; Zippa, E. V.


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

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

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    DePaolo, D.


    A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R{sub p}) to the gross forward precipitation rate (R{sub f}), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R{sub p} has been experimentally measured under varying conditions, but the magnitude of R{sub f} is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R{sub f} can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R{sub b} or k{sub b}), since at equilibrium R{sub f} = R{sub b}, and R{sub p} = 0. Hence it can be inferred that R{sub f} {approx} R{sub p} + R{sub b}. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R{sub p} (= R{sub f} - R{sub b}) << R{sub b}. For precipitation rates high enough that R{sub p} >> R{sub b}, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R{sub p} {approx} R{sub b} for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R{sub f} for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R{sub p

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

    Lokier, Stephen; Krieg Dosier, Ginger


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

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

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


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

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

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


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


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    Heriansyah ePutra


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

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

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


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

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

    Achal, Varenyam; Pan, Xiangliang


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

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

    Paquette, Jeanne; Vali, Hojatollah; Mucci, Alfonso


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

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

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    Animesh Sharma


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

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

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    S.A. Abo-El-Enein


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

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


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


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

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

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


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

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

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


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

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

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    Huifang Xu


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

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

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


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

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

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


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

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

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

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

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


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

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

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


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

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

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


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

  1. Calcite precipitation dominates the electrical signatures of zero valent iron columns under simulated field conditions

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    Wu, Yuxin; Versteeg, R.; Slater, L.; LaBrecque, D.


    Calcium carbonate is a secondary mineral precipitate influencing zero valent iron (ZVI) barrier reactivity and hydraulic performance. We conducted column experiments to investigate electrical signatures resulting from concurrent CaCO{sub 3} and iron oxides precipitation under simulated field geochemical conditions. We identified CaCO{sub 3} as a major mineral phase throughout the columns, with magnetite present primarily close to the influent based on XRD analysis. Electrical measurements revealed decreases in conductivity and polarization of both columns, suggesting that electrically insulating CaCO{sub 3} dominates the electrical response despite the presence of electrically conductive iron oxides. SEM/EDX imaging suggests that the electrical signal reflects the geometrical arrangement of the mineral phases. CaCO{sub 3} forms insulating films on ZVI/magnetite surfaces, restricting charge transfer between the pore electrolyte and ZVI particles, as well as across interconnected ZVI particles. As surface reactivity also depends on the ability of the surface to engage in redox reactions via charge transfer, electrical measurements may provide a minimally invasive technology for monitoring reactivity loss due to CaCO{sub 3} precipitation. Comparison between laboratory and field data shows consistent changes in electrical signatures due to iron corrosion and secondary mineral precipitation.

  2. Calcite precipitation from aqueous solution: transformation from vaterite and role of solution stoichiometry

    NARCIS (Netherlands)

    Nehrke, G.


    The morphology of vaterite precipitated by bubbling CO2 through a CaCl2 solution is framboidal aggregates. It is not possible, even when using the identical experimental setup and conditions, to reproduce aggregates having identical morphology. The density of the aggregates and crystallite size can

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

    Bonny, Sandy M.; Jones, Brian


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

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

    Widyastuti, Sri; Intan Ayu Kusuma, P.


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

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

    Kimmig, Sara R.; Holmden, Chris


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

  6. Effect of some biotic factors on microbially-induced calcite precipitation in cement mortar. (United States)

    Al-Salloum, Yousef; Abbas, H; Sheikh, Q I; Hadi, S; Alsayed, Saleh; Almusallam, Tarek


    Sporosarcina pasteurii, a common soil bacterium has been tested for microbial treatment of cement mortar. The present study also seeks to investigate the effects of growth medium, bacterial concentration and different buffers concerning the preparation of bacterial suspensions on the compressive strength of cement mortar. Two growth media, six different suspensions and two bacterial concentrations were used in the study. The influence of growth medium on calcification efficiency of S. pasteurii was insignificant. Significant improvement in the compressive as well as the tensile strength of cement mortar was observed. Microbial mineral precipitation visualized by Scanning Electron Microscopy (SEM) shows fibrous material that increased the strength of cement mortar. Formation of thin strands of fillers observed through SEM micrographs improves the pore structure, impermeability and thus the compressive as well as the tensile strengths of the cement mortar. The type of substrate and its molarity have a significant influence on the strength of cement mortar.

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

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


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

  8. Microbial community composition and endolith colonization at an Arctic thermal spring are driven by calcite precipitation (United States)

    Starke, Verena; Kirshtein, Julie; Fogel, Marilyn L.; Steele, Andrew


    Environmental conditions shape community composition. Arctic thermal springs provide an opportunity to study how environmental gradients can impose strong selective pressures on microbial communities and provide a continuum of niche opportunities. We use microscopic and molecular methods to conduct a survey of microbial community composition at Troll Springs on Svalbard, Norway, in the high Arctic. Microorganisms there exist under a wide range of environmental conditions: in warm water as periphyton, in moist granular materials, and in cold, dry rock as endoliths. Troll Springs has two distinct ecosystems, aquatic and terrestrial, together in close proximity, with different underlying environmental factors shaping each microbial community. Periphyton are entrapped during precipitation of calcium carbonate from the spring's waters, providing microbial populations that serve as precursors for the development of endolithic communities. This process differs from most endolith colonization, in which the rock predates the communities that colonize it. Community composition is modulated as environmental conditions change within the springs. At Troll, the aquatic environments show a small number of dominant operational taxonomic units (OTUs) that are specific to each sample. The terrestrial environments show a more even distribution of OTUs common to multiple samples.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


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

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


    Guichet, Xavier; Jouniaux, Laurence; Catel, Nicole


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

  12. High surface area calcite (United States)

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


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

  13. Chemical and physical evolution of dolomite precipitation at 180°C and 220°C from calcite and aragonite seeds (United States)

    Kell-Duivestein, Isaac; Dietzel, Martin; Mavromatis, Vasileios


    the fluid and the Mg concentration decreases as it is taken up by the solid. With further reaction time dolomite formation begins as non-stoichiometric dolomite (57-54 mol% CaCO3) with poor cation ordering within the superstructure. The rate of initial dolomite formation tends to be relatively rapid (changing with seed material and temperature) and then becomes increasingly slower as more dolomite precipitates. Reactions at 220°C show a rapid change in the stoichiometry of the dolomite being formed with the calcite reactors reaching approximately ideal stoichiometry (CaMgCO3) within 21 days reaction time, dolomite precipitated at 220°C from the aragonite seed material reaches a stoichiometry of ~51.2 mol% CaCO3 rapidly (within 6 days) however plateaus and does not change notably with further reaction time. In each reaction the cation ordering within the superstructure increases linearly with reaction time and reached the same degree of ordering at approximately equal reaction times (ie. 0.45-0.52 within 21 days, 0.60-0.65 within 31 days) suggesting a strong kinetic control on superstructure. Future experiments through mixed-flow reactors will see an increase in CO2 pressure and decrease in temperature. A multi-proxy isotopic study will be conducted measuring δ13C, δ18O, δ26/24Mg, δ44/40Ca, δ88/86Sr and clumped isotope (Δ47) fractionation throughout the process of dolomitization to gain a better understanding of the isotopic proxies within the Ca-Mg-CO2-H2O system.

  14. Pseudospherulitic fibrous calcite from the Quaternary shallow lacustrine carbonates of the Farafra Oasis, Western Desert, Egypt: A primary precipitate with possible bacterial influence (United States)

    Wanas, H. A.


    Pseudospherulitic fibrous calcite (PFC) has been found as a major constituent (85-90%) within thin massive limestone beds of the Quaternary mudflat-shallow lacustrine facies association (1.5-2 m thick) that forms part of combined facies associations of the Quaternary clastic-carbonate unit (25-30 m thick) at Bir-Karawein area in the Farafra Oasis, Western Desert, Egypt. The thin massive limestone beds (2-5 cm thick) are devoid of pedogenic features and marine fossils. They form a rhythmic cyclic succession with thin massive mudrocks (5-10 cm thick). The mudflat-shallow lacustrine facies association herein occurs within a depositional sequence of distal alluvial-floodplain (6-12 m thick) and palustrine (1.5-4.5 m thick) facies associations. The PFC is a composed of loosely packed rounded to sub-rounded single low-Mg-calcite crystals (150-250 μm-sized) with intracrystalline fibrous microfabric marked by fibers (150-250 μm long and 10-20 μm wide) radiating from the center of the individual crystals and displaying irregular internal growth with lobate pattern. The PFC crystals show non-planar to highly irregular intercrystalline boundaries. Under SEM, the individual crystal fibers group of PFC form ellipsoid to sub-globular bodies. Each PFC crystal exhibits successive zones of thick non-luminescence and thin brightly orange to dull luminescence. The matrix (10-15%) between the PFC crystals is mainly a honeycomb-like smectite. The PFC is postulated to be a primary precipitate. This concept is reached because the PFC: (i) does not display the criteria of typical Microcodium structures, root-calcification, speleothem structures, calcite spherulites of laminar calcretes, and calcitization of precursor dolomite or aragonite, (ii) possesses homogenous compositional and textural characteristics, and (iii) occurs within limestone beds that lie in between impermeable massive mudrock beds that dampen diagenesis. A role for possible bacterial contribution in crystallization of

  15. Effect of pH on the precipitation of synthetic CaCO3 polymorphs and determination of Mg/Ca ratios in synthetic low-magnesium calcite: An experimental investigation (United States)

    Gabitov, R. I.; Weremeichik, J. M.; Novak, A.; Sadekov, A.; Thirumalai, R. V. K. G.


    The intent of the work presented is to determine the effect which the Mg/Ca ratio in fluid has on the Mg partition coefficient (KMg) between synthetically precipitated low-magnesium calcite and solution. In nature, planktonic foraminifera produce low-magnesium calcite with distinct Mg/Ca that is typically found to be within the range of 1.4 to 10 mmol/mol (e.g. Regenberg et al., 2009; Sadekov et al., 2009). Our intent was to replicate Mg/Ca found in foraminifera by conducting experiments where low-Mg calcite was grown inorganically at a near-constant salinity and temperature. Synthetic low-Mg calcite was precipitated using a continuous pumping method whereby NaHCO3 and Mg-doped CaCl2 solutions were pumped into a NaCl solution. Continuous pumping allows for delivery of solutions to a reaction vessel at a constant rate while simultaneously maintaining fluid volume by removing fluid at a constant rate equal to the delivery rate. In order to vary the Mg/Ca ratio while keeping salinity near-constant, magnesium and calcium molar concentrations were varied but the sum of the concentrations was kept equal to the concentration of NaHCO3 or Na2CO3. Optical microscopy analysis of samples showed that the use of Na2CO3 as the carbonate ion source in experiments precipitated predominately aragonite with needle-like crystals whereas use of NaHCO3 yielded calcite with rhombohedral crystals. Powder XRD analysis of a sample collected from one of the Na2CO3 experiments confirmed that the dominant CaCO3 polymorph precipitated was aragonite. This suggests that aragonite is being produced at higher pH values using Na2CO3 and calcite is being produced at lower values of pH using NaHCO3. We intend use XRD, AAS, and ICP-MS to confirm that rhombohedral crystals are calcite and determine Mg/Ca of fluid and those crystals. ReferencesRegenberg et al. (2009) Earth Planet. Sci. Lett., 278, doi: 10.1016/j.epsl.2008.12.019. Sadekov et al. (2009) Paleoceanography, 24, doi: 10.1029/2008PA001664.

  16. Testing the Specificity of Primers to Environmental Ammonia Monooxygenase (amoA) Genes in Groundwater Treated with Urea to Promote Calcite Precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Freeman, S.; Reed, D.W.; Fujita, Y.


    Bacterial ammonia monooxygenase (amoA) genes in DNA isolated from microorganisms in groundwater were characterized by amplification of amoA DNA using polymerase chain reaction (PCR), Restriction Fragment Length Polymorphism (RFLP) analysis, and sequencing. The amoA gene is characteristic of ammonia oxidizing bacteria (AOB). The DNA extracts were acquired from an experiment where dilute molasses and urea were sequentially introduced into a well in the Eastern Snake River Plain Aquifer (ESRPA) in Idaho to examine whether such amendments could stimulate enhanced ureolytic activity. The hydrolysis of urea into ammonium and carbonate serves as the basis for a potential remediation technique for trace metals and radionuclide contaminants that can co-precipitate in calcite. The ammonium ion resulting from ureolysis can promote the growth of AOB. The goal of this work was to investigate the effectiveness of primers designed for quantitative PCR of environmental amoA genes and to evaluate the effect of the molasses and urea amendments upon the population diversity of groundwater AOB. PCR primers designed to target a portion of the amoA gene were used to amplify amoA gene sequences in the groundwater DNA extracts. Following PCR, amplified gene products were cloned and the clones were characterized by RFLP, a DNA restriction technique that can distinguish different DNA sequences, to gauge the initial diversity. Clones exhibiting unique RFLP patterns were subjected to DNA sequencing. Initial sequencing results suggest that the primers were successful at specific detection of amoA sequences and the RFLP analyses indicated that the diversity of detected amoA sequences in the ESRPA decreased with the additions of molasses and urea.

  17. Final report for DOE Grant No. DE-FG02-07ER64404 - Field Investigations of Microbially Facilitated Calcite Precipitation for Immobilization of Strontium-90 and Other Trace Metals in the Subsurface

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Robert W; Fujita, Yoshiko; Ginn, Timothy R; Hubbard, Susan S


    Subsurface radionuclide and metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE's greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent ions, such as the short-lived radionuclide 90Sr, is co-precipitation in calcite. We have previously found that that nutrient addition can stimulate microbial ureolytic activity that this activity accelerates calcite precipitation and co-precipitation of Sr, and that higher calcite precipitation rates can result in increased Sr partitioning. We have conducted integrated field, laboratory, and computational research to evaluate the relationships between ureolysis and calcite precipitation rates and trace metal partitioning under environmentally relevant conditions, and investigated the coupling between flow/flux manipulations and precipitate distribution. A field experimental campaign conducted at the Integrated Field Research Challenge (IFRC) site located at Rifle, CO was based on a continuous recirculation design; water extracted from a down-gradient well was amended with urea and molasses (a carbon and electron donor) and re-injected into an up-gradient well. The goal of the recirculation design and simultaneous injection of urea and molasses was to uniformly accelerate the hydrolysis of urea and calcite precipitation over the entire inter-wellbore zone. The urea-molasses recirculation phase lasted, with brief interruptions for geophysical surveys, for 12 days followed by long-term monitoring which continued for 13 months. Following the recirculation phase we found persistent increases in urease activity (as determined from 14C labeled laboratory urea hydrolysis rates) in the upper portion of the inter-wellbore zone. We also observed an initial increase (approximately 2 weeks) in urea concentration associated with injection activities followed by decreasing urea concentration and associated increases in ammonium and dissolved inorganic carbon

  18. Arsenic uptake in bacterial calcite (United States)

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


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

  19. Arsenic uptake in bacterial calcite

    Energy Technology Data Exchange (ETDEWEB)

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


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

  20. Final Technical Report for DOE Award DE-FG02-07ER64403 [Modeling of Microbially Induced Calcite Precipitation for the Immobilization of Strontium-90 Using a Variable Velocity Streamtube Ensemble

    Energy Technology Data Exchange (ETDEWEB)

    Ginn, Timothy R. [University of California, Davis; Weathers, Tess [University of California, Davis


    Biogeochemical modeling using PHREEQC2 and a streamtube ensemble approach is utilized to understand a well-to-well subsurface treatment system at the Vadose Zone Research Park (VZRP) near Idaho Falls, Idaho. Treatment involves in situ microbially-mediated ureolysis to induce calcite precipitation for the immobilization of strontium-90. PHREEQC2 is utilized to model the kinetically-controlled ureolysis and consequent calcite precipitation. Reaction kinetics, equilibrium phases, and cation exchange are used within PHREEQC2 to track pH and levels of calcium, ammonium, urea, and calcite precipitation over time, within a series of one-dimensional advective-dispersive transport paths creating a streamtube ensemble representation of the well-to-well transport. An understanding of the impact of physical heterogeneities within this radial flowfield is critical for remediation design; we address this via the streamtube approach: instead of depicting spatial extents of solutes in the subsurface we focus on their arrival distribution at the control well(s). Traditionally, each streamtube maintains uniform velocity; however in radial flow in homogeneous media, the velocity within any given streamtube is spatially-variable in a common way, being highest at the input and output wells and approaching a minimum at the midpoint between the wells. This idealized velocity variability is of significance in the case of ureolytically driven calcite precipitation. Streamtube velocity patterns for any particular configuration of injection and withdrawal wells are available as explicit calculations from potential theory, and also from particle tracking programs. To approximate the actual spatial distribution of velocity along streamtubes, we assume idealized radial non-uniform velocity associated with homogeneous media. This is implemented in PHREEQC2 via a non-uniform spatial discretization within each streamtube that honors both the streamtube’s travel time and the idealized

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

    NARCIS (Netherlands)

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


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

  2. Modeling Subglacial Permafrost Evolution (United States)

    Koutnik, M. R.; Marshall, S.


    Permanently frozen ground was present both beneath and peripheral to the Quaternary ice sheets. In areas where the ice sheet grew or advanced over permafrost, the ice sheet insulated the ground, leading to subglacial permafrost degradation. This has created distinct signatures of ice sheet occupation in the Canadian north and in Alaska during the last glacial period, with greatly diminished permafrost thickness in regions that were ice covered for an extended period. In contrast, areas peripheral to the ice sheet, including the Midwest United States, were cooled by the glacial climate conditions and the regional cooling influence of the ice sheet, leading to permafrost growth. We have developed a sub- and proglacial diffusion based permafrost model that utilizes a logarithmic grid transformation to more efficiently track the changing depth of permafrost with time. This model is coupled with the ice sheet thermodynamic model of Marshall and Clarke [1997a] to explore the geologic signatures of the last glacial cycle in North America. This offers the potential for new constraints on modeled ice sheet history. Preliminary model runs show that the overlying ice sheet has a significant effect on the underlying and peripheral permafrost degradation and formation. Subglacial permafrost is also important because its evolution influences the basal temperature of the ice sheet, critical for evolution of subglacial hydrology and fast flow instabilities (e.g. ice streams). We present results of permafrost conditions under the last glacial maximum ice sheet and the effect of permafrost on basal temperature evolution through the last glacial cycle in North America. Marshall, S. J. and G. K. C. Clarke, 1997a. J. Geophys. Res., 102 (B9), 20,599-20,614.

  3. Immobilization of nanoparticles by occlusion into microbial calcite

    DEFF Research Database (Denmark)

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


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

  4. Subglacial till formation: Microscale processes within the subglacial shear zone (United States)

    Hart, Jane K.


    This was a study of subglacial deformation till genesis from a modern temperate glacier, at Skálafellsjökull, Iceland. Detailed microscale properties of till samples (from Scanning Electron Microscope [SEM] and thin section analysis) were examined from a glacial site with in situ subglacial process monitoring and an exposed subglacial surface in the foreland. Two lithofacies were examined, a grey sandy till derived from the ash and basalt, and a silty reddish brown till derived from oxidized paleosols and/or tephra layers. These also represented a clay-content continuum from low (0.3%) to high (22.3%). The evolution from debris to subglacial till was investigated. This included a reduction in grain-size (21% for grey lithology, 13% reddish brown lithology), and reduction in rounding (RA) (32% for the grey lithology, 26% for the reddish brown lithology), and the quantification and analysis of the different grain erosion/comminution processes in the resultant till. It was shown that the microstructures within a till were dependent on shear strain and glaciological conditions (deformation history). The low clay content tills were dominated by linear structures (lineations and boudins, and anisotropic microfabric) whilst the higher clay content tills were dominated by rotational structures (turbates and plaster, and isotropic microfabric). These results are important in our understanding of the formation of both modern and Quaternary tills and informs our reconstruction of past glacial dynamics.

  5. Exploration of Subglacial Lake Ellsworth (United States)

    Ross, N.


    Antarctic subglacial lakes are thought to be extreme habitats for microbial life and may contain important records of ice sheet history within their lake-floor sediments. To find if this is true, and to answer the science questions that would follow, direct measurement and sampling of these environments is required. Ever since the water depth of Vostok Subglacial Lake in East Antarctica was shown to be >500 m, attention has been given to how these unique, ancient and pristine subglacial environments may be entered without contamination and adverse disturbance. Several organizations have offered guidelines on the desirable cleanliness and sterility requirements for direct sampling experiments, including the US National Academy of Sciences and the Scientific Committee on Antarctic Research. The aims, design and implementation of subglacial lake access experiments have direct relevance for the exploration of extra-terrestrial ice-covered bodies (e.g. Europa) and the search for microbial life elsewhere in the Solar System. This presentation summarizes the scientific protocols and methods being developed for the exploration of Ellsworth Subglacial Lake in West Antarctica, and provides an up-to-date summary of the status of the project. The proposed exploration, planned for December 2012, involves accessing the lake using a hot-water drill and deploying a sampling probe and sediment corer to allow in situ measurement and sample collection. Details are presented on how this can be undertaken with minimal environmental impact that maximizes scientific return without compromising the environment for future experiments. The implications of this experiment for the search for extra-terrestrial life will be discussed.

  6. 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)


    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

  7. Ion microprobe assessment of the heterogeneity of Mg/Ca, Sr/Ca and Mn/Ca ratios in Pecten maximus and Mytilus edulis (bivalvia shell calcite precipitated at constant temperature

    Directory of Open Access Journals (Sweden)

    P. S. Freitas


    Full Text Available Small-scale heterogeneity of biogenic carbonate elemental composition can be a significant source of error in the accurate use of element/Ca ratios as geochemical proxies. In this study ion microprobe (SIMS profiles showed significant small-scale variability of Mg/Ca, Sr/Ca and Mn/Ca ratios in new shell calcite of the marine bivalves Pecten maximus and Mytilus edulis that was precipitated during a constant-temperature culturing experiment. Elevated Mg/Ca, Sr/Ca and Mn/Ca ratios were found to be associated with the deposition of elaborate shell features, i.e. a shell surface stria in P. maximus and surface shell disturbance marks in both species, the latter a common occurrence in bivalve shells. In both species the observed small-scale elemental heterogeneity most likely was not controlled by variable transport of ions to the extra-pallial fluid, but by factors such as the influence of shell organic content and/or crystal size and orientation, the latter reflecting conditions at the shell crystal-solution interface. In the mid and innermost regions of the P. maximus shell the lack of significant small-scale variation of Mg/Ca ratios, which is consistent with growth at constant temperature, suggest a potential application as a palaeotemperature proxy. Cross-growth band element/Ca ratio profiles in the interior of bivalve shells may provide more promising palaeo-environmental tools than sampling from the outer region of bivalve shells.

  8. Landscape evolution by subglacial quarrying

    DEFF Research Database (Denmark)

    Ugelvig, Sofie Vej; Egholm, D.L.; Iverson, Neal R.

    of sliding and erosion is not well supported when considering models for quarrying of rock blocks from the bed. Iverson (2012) introduced a new subglacial quarrying model that operates from the theory of adhesive wear. The model is based on the fact that cavities, with a high level of bedrock differential...... to a model for glacial hydrology. In order to also include the effects of cavitation on the subglacial sliding rate, we use a sliding law proposed by Schoof (2005), which includes an upper limit for the stress that can be supported at the bed. Computational experiments show that the combined influence...... evolution models. Geology, v. 40, no. 8, 679-682 (2012). Schoof, C. The effect of cavitation on glacier sliding. Proc. R. Soc. A , 461, 609-627 (2005). Jaeger, J.C., and Cook, N.G.W. Fundamentals of rock mechanics: New York, Chapman and Hall, 593 p. (1979)...

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

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


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

  10. Subglacial biochemical weathering and transport drove fertilization in the Southern Ocean during Antarctic temperature maxima and NH Heinrich events (United States)

    Frisia, S.; Augustinus, P. M.; Hellstrom, J.; Borsato, A.; Drysdale, R.; Weyrich, L.; Cooper, A.; Johnston, V. E.; Cotte, M.


    Changes in bioproductivity in the subantarctic region have been observed to coincide with episodes of significant iceberg discharge in the North Atlantic (Heinrich events), thus linking iron delivery to the Southern Ocean (SO) with abrupt climate changes in the Northern Hemisphere. Whilst upwelling has been proposed as a likely source of bioavailable iron during Heinrich events, it is well known that, today, subglacial metabolic pathways under limited carbon supply may accumulate divalent iron, which could have been mobilized and delivered to the SO during full glacial conditions. This alternative hypothesis remains largely untested for the SO because of the difficulties in accessing palaeoenvironmental archives from beneath the Antarctic ice sheets. We present a record of the subglacial production and fate of nutrients from calcite crusts formed beneath a tributary of the Rennick outlet glacier (East Antarctic Ice Sheet, EAIS) during the Last Glacial Maximum. Chemistry, stratigraphy and preliminary ancient DNA characterization of the microbial consortium of 27- to 17-kyr-old calcites suggest that bioweathering released iron in hypoxic pools of local basal meltwater. Anaerobic methane oxidising microbes released bicarbonate and sulfuric acid in the isolated pockets, which facilitated local weathering of the amphibolite rock. During episodes of channelized flow, identified by clast-rich microsparites, and which have ages near-commensurate with Antarctic Isotope Maximum2 (AIM2) and Heinrich event 2, ferrous iron may have been mobilized and transported subglacially to the ice shelf. The calcites formed during this phase preserve evidence of microbes using sulfite dehydrogenase, which explains the accumulation of sulfate in the calcite. Our data thus indicate that subglacial processes contributed to SO productivity increases at the time of Heinrich event 2, ultimately leading to drawdawn of atmospheric carbon dioxide at millennial scale.

  11. The influence of Antarctic subglacial volcanism on the global iron cycle during the Last Glacial Maximum (United States)

    Frisia, Silvia; Weyrich, Laura S.; Hellstrom, John; Borsato, Andrea; Golledge, Nicholas R.; Anesio, Alexandre M.; Bajo, Petra; Drysdale, Russell N.; Augustinus, Paul C.; Rivard, Camille; Cooper, Alan


    Marine sediment records suggest that episodes of major atmospheric CO2 drawdown during the last glacial period were linked to iron (Fe) fertilization of subantarctic surface waters. The principal source of this Fe is thought to be dust transported from southern mid-latitude deserts. However, uncertainty exists over contributions to CO2 sequestration from complementary Fe sources, such as the Antarctic ice sheet, due to the difficulty of locating and interrogating suitable archives that have the potential to preserve such information. Here we present petrographic, geochemical and microbial DNA evidence preserved in precisely dated subglacial calcites from close to the East Antarctic Ice-Sheet margin, which together suggest that volcanically-induced drainage of Fe-rich waters during the Last Glacial Maximum could have reached the Southern Ocean. Our results support a significant contribution of Antarctic volcanism to subglacial transport and delivery of nutrients with implications on ocean productivity at peak glacial conditions.

  12. Origin of calcite in the glacigenic Virttaankangas complex

    Directory of Open Access Journals (Sweden)

    Nina M. Kortelainen


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

  13. Unveiling the Antarctic subglacial landscape. (United States)

    Warner, Roland; Roberts, Jason


    Better knowledge of the subglacial landscape of Antarctica is vital to reducing uncertainties regarding prediction of the evolution of the ice sheet. These uncertainties are associated with bedrock geometry for ice sheet dynamics, including possible marine ice sheet instabilities and subglacial hydrological pathways (e.g. Wright et al., 2008). Major collaborative aerogeophysics surveys motivated by the International Polar Year (e.g. ICECAP and AGAP), and continuing large scale radar echo sounding campaigns (ICECAP and NASA Ice Bridge) are significantly improving the coverage. However, the vast size of Antarctica and logistic difficulties mean that data gaps persist, and ice thickness data remains spatially inhomogeneous. The physics governing large scale ice sheet flow enables ice thickness, and hence bedrock topography, to be inferred from knowledge of ice sheet surface topography and considerations of ice sheet mass balance, even in areas with sparse ice thickness measurements (Warner and Budd, 2000). We have developed a robust physically motivated interpolation scheme, based on these methods, and used it to generate a comprehensive map of Antarctic bedrock topography, using along-track ice thickness data assembled for the BEDMAP project (Lythe et al., 2001). This approach reduces ice thickness biases, compared to traditional inverse distance interpolation schemes which ignore the information available from considerations of ice sheet flow. In addition, the use of improved balance fluxes, calculated using a Lagrangian scheme, eliminates the grid orientation biases in ice fluxes associated with finite difference methods (Budd and Warner, 1996, Le Brocq et al., 2006). The present map was generated using a recent surface DEM (Bamber et al., 2009, Griggs and Bamber, 2009) and accumulation distribution (van de Berg et al., 2006). Comparing our results with recent high resolution regional surveys gives confidence that all major subglacial topographic features are

  14. Antarctic Subglacial Lake Classification Inventory, Version 1 (United States)

    National Aeronautics and Space Administration — This data set is an Antarctic radar-based subglacial lake classification collection, which focuses on the radar reflection properties of each given lake.

  15. Elastic constants of calcite (United States)

    Peselnick, L.; Robie, R.A.


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

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


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


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

  17. Geoethical Approach to Antarctic Subglacial Lakes Exploration (United States)

    Talalay, Pavel; Markov, Alexey; Sysoev, Mikhail


    Antarctic subglacial aquatic environment have become of great interest to the science community because they may provide unique information about microbial evolution, the past climate of the Earth, and the formation of the Antarctic ice sheet. Nowadays it is generally recognized that a vast network of lakes, rivers, and streams exists thousands of meters beneath Antarctic Ice Sheets. Up to date only four boreholes accessed subglacial aquatic system but three of them were filled with high-toxic drilling fluid, and the subglacial water was contaminated. Two recent exploration programs proposed by UK and USA science communities anticipated direct access down to the lakes Ellsworth and Whillans, respectively, in the 2012/2013 Antarctic season. A team of British scientists and engineers engaged in the first attempt to drill into Lake Ellsworth but failed. US research team has successfully drilled through 800 m of Antarctic ice to reach a subglacial lake Whillans and retrieve water and sediment samples. Both activities used hot-water drilling technology to access lakes. Hot water is considered by the world science community as the most clean drilling fluid medium from the present point of view but it cannot solve environmental problems in total because hot-water even when heated to 90 °C, filtered to 0.2 μm, and UV treated at the surface could pick up microorganisms from near-surface snow and circulate them in great volume through the borehole. Another negative impact of hot-water circulation medium is thermal pollution of subglacial water. The new approach to Antarctic subglacial lakes exploration is presented by sampling technology with recoverable autonomous sonde which is equipped by two hot-points with heating elements located on the bottom and top sides of the sonde. All down-hole sonde components will be sterilized by combination of chemical wash, HPV and UV sterilization prior using. At the beginning of the summer season sonde is installed on the surface of the

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

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


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

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

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


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

  20. Evolution of the isotope composition of C and O in the DIC in a water film during precipitation of calcite to the surface of a stalagmite in the presence of isotope exchange with the CO2 of the cave atmosphere and evaporation of the water (United States)

    Dreybrodt, Wolfgang; Romanov, Douchko


    In a thin water layer, super saturated with respect to calcite with pH of about 8, where the aqueous CO2 is in equilibrium with the pCO2 of the cave atmosphere, the following processes determine the temporal evolution of the isotope composition of carbon and oxygen in the dissolved inorganic carbon ( DIC). a) Precipitation of calcite driven by super saturation, whereby deposition rates Between the heavy and light isotopes are slightly different. b) Evaporation of water reducing the depth of the water layer and changing the isotope composition of oxygen in the water by Rayleigh-distillation. c) Isotope exchange between the CO2 in the cave atmosphere and the DIC for both carbon and oxygen. d) Isotope exchange between the oxygen in the water molecules and that in the DIC. All these processes can be described by a differential equation, which can be solved numerically. For small times a simple solution can be given. Δ_DIC(T_drip) = [ ( (⪉mbda + ɛ) C_eq/C0 - ɛ ) T_drip/τ + (δ^atm_eq - δ0 ) T_drip/τ^atm + (δ^water_eq-δ_0-ɛ_wT_drip/T_ev) T_drip/τ^water] Δ_DIC(T_drip) is the change of the δ13C and δ18O (given here as small numbers and not in the ‰ notation) after the drip time T_drip. ⪉mbda, ɛ are kinetic parameters of precipitation on the order of 10-2 and τ is the time scale of precipitation, typically about 1000 s. (δ^atm_eq - δ_0) and (δ^water_eq - δ_0) are the differences between the corresponding initial δ-value and that when DIC is in isotope equilibrium with the atmosphere or in the case of oxygen with the water. τ^atm and τ^water, both on the order of 10,000 s, are the time scales of the exchange reactions to approach isotope equilibrium. For carbon the last term (exchange with water) must be deleted. C_eq is the concentration of DIC in chemical equilibrium with the CO2 in the cave atmosphere and C0 is the initial concentration, when the water drips to the stalagmite. T_ev is the time needed to fully evaporate the water layer and

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

    DEFF Research Database (Denmark)

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


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

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

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


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

  3. Penicillium mycobiota in Arctic subglacial ice

    DEFF Research Database (Denmark)

    Sonjak, S.; Frisvad, Jens Christian; Gunde-Cimerman, N.


    to be inhabited exclusively by heterotrophic bacteria. In this study we report on the very high occurrence (up to 9000 CFU L-1) and diversity of filamentous Penicillium spp. in the sediment-rich subglacial ice of three different polythermal Arctic glaciers (Svalbard, Norway). The dominant species was P. crustosum......, representing on the average half of all isolated strains from all three glaciers. The other most frequently isolated species were P. bialowiezense, P. chrysogenum, P. thomii, P. solitum, P. palitans, P. echinulatum, P. polonicum, P. commune, P. discolor, P. expansum, and new Penicillium species (sp. 1). Twelve...... more Penicillium species were occasionally isolated. The fungi isolated produced consistent profiles of secondary metabolites, not different from the same Penicillium species from other habitats. This is the first report on the presence of large populations of Penicillium spp. in subglacial sediment...

  4. Numerical Modeling of Subglacial Sediment Deformation

    DEFF Research Database (Denmark)

    Damsgaard, Anders


    may cause mass loss in the near future to exceed current best estimates. Ice flow in larger ice sheets focuses in fast-moving streams due to mechanical non-linearity of ice. These ice streams often move at velocities several magnitudes larger than surrounding ice and consequentially constitute...... glaciers move by deforming their sedimentary beds. Several modern ice streams, in particular, move as plug flows due to basal sediment deformation. An intense and long-winded discussion about the appropriate description for subglacial sediment mechanics followed this discovery, with good reason...... velocities previously associated with elastic or viscous ice deformation. If a glacier dominated by subglacial creep experiences prolonged events of strong surface melt or increased driving stresses, the plastic strength limit can cause rapid acceleration downslope due to imbalance of stresses....

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

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


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

  6. Calcite Dissolution Kinetics (United States)

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


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

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

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


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

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


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


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

  9. Seawater-softening process through formation of calcite ooids

    Directory of Open Access Journals (Sweden)

    A.A. Bakr


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

  10. Calcium carbonate precipitation in the Cueva di Watapana on Bonaire, Netherlands Antilles

    NARCIS (Netherlands)

    Meer Mohr, van der C.G.


    Calcium carbonate precipitates as low Mg-calcite and aragonite in slightly brackish water in a cave in the Pleistocene Middle Terrace of southern Bonaire. The calcium carbonate precipitates at the atmosphere-water interface forming floating calcite scales (calcite ice). Aragonite crystals frequently

  11. Physiography and tectonic setting of the subglacial lake district between Vostok and Belgica subglacial highlands (Antarctica) (United States)

    Tabacco, I. E.; Cianfarra, P.; Forieri, A.; Salvini, F.; Zirizotti, A.


    We present the interpretation of 11 radio echo-sounding (RES) missions carried out over the Vostok-Dome Concordia region during the Italian Antarctic expeditions in the period 1995-2001. The extension and the density of the radar data in the surveyed area allowed to reconstruct a reliable subglacial morphology and to identify four relevant morphological structures namely: the Aurora trench, the Concordia trench, the Concordia ridge and the South Hills. These structures show evidence compatible with the presence of tectonic features. Morphological considerations indicate their development in Cenozoic time. Hybrid cellular automata (HCA)-based numerical modelling allowed to justify a possible role played by the tectonics of the Aurora and Concordia trench evolution. This was accomplished by matching the bed profiles along opportunely projected sections with the modelled surfaces as derived by the activity of normal faults with variable surfaces within the continental crust. The Vostok-Dome C region is characterized by a large number of subglacial lakes. From the analysis of basal reflected power echo, we identified 14 new lakes and obtained information about their physiography as well as their possible relations with tectonics. We propose a grouping of subglacial lakes on the base of their physiography and geological setting, namely relief lakes, basin lakes and trench lakes. Relief lakes located in the Belgica subglacial highlands and are characterized by sharp and steep symmetric edges, suggesting a maximum water depth of the order of 100 m. Their origin may well relate to localized, positive geothermal flux anomalies. Basin lakes located in the Vincennes subglacial basin and are characterized by wider dimension that allow the development of well-defined, flat ice surface anomalies. Trench lakes characterize the Aurora and Concordia trenches as the possible effect of normal fault activity.

  12. Subglacial discharge at tidewater glaciers revealed by seismic tremor (United States)

    Bartholomaus, Timothy C.; Amundson, Jason M.; Walter, Jacob I.; O'Neel, Shad; West, Michael E.; Larsen, Christopher F.


    Subglacial discharge influences glacier basal motion and erodes and redeposits sediment. At tidewater glacier termini, discharge drives submarine terminus melting, affects fjord circulation, and is a central component of proglacial marine ecosystems. However, our present inability to track subglacial discharge and its variability significantly hinders our understanding of these processes. Here we report observations of hourly to seasonal variations in 1.5–10 Hz seismic tremor that strongly correlate with subglacial discharge but not with basal motion, weather, or discrete icequakes. Our data demonstrate that vigorous discharge occurs from tidewater glaciers during summer, in spite of fast basal motion that could limit the formation of subglacial conduits, and then abates during winter. Furthermore, tremor observations and a melt model demonstrate that drainage efficiency of tidewater glaciers evolves seasonally. Glaciohydraulic tremor provides a means by which to quantify subglacial discharge variations and offers a promising window into otherwise obscured glacierized environments.

  13. 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.

  14. Probe technologies for clean sampling and measurement of subglacial lakes. (United States)

    Mowlem, Matt; Saw, Kevin; Brown, Robin; Waugh, Edward; Cardwell, Christopher L; Wyatt, James; Magiopoulos, Iordanis; Keen, Peter; Campbell, Jon; Rundle, Nicholas; Gkritzalis-Papadopoulos, Athanasios


    It is 4 years since the subglacial lake community published its plans for accessing, sampling, measuring and studying the pristine, and hitherto enigmatic and very different, Antarctic subglacial lakes, Vostok, Whillans and Ellsworth. This paper summarizes the contrasting probe technologies designed for each of these subglacial environments and briefly updates how these designs changed or were used differently when compared to previously published plans. A detailed update on the final engineering design and technical aspects of the probe for Subglacial Lake Ellsworth is presented. This probe is designed for clean access, is negatively buoyant (350 kg), 5.2 m long, 200 mm in diameter, approximately cylindrical and consists of five major units: (i) an upper power and communications unit attached to an optical and electrical conducting tether, (ii)-(iv) three water and particle samplers, and (v) a sensors, imaging and instrumentation pack tipped with a miniature sediment corer. To date, only in Subglacial Lake Whillans have instruments been successfully deployed. Probe technologies for Subglacial Lake Vostok (2014/15) and Lake Ellsworth (2012/13) were not deployed for technical reasons, in the case of Lake Ellsworth because hot-water drilling was unable to access the lake during the field season window. Lessons learned and opportunities for probe technologies in future subglacial access missions are discussed. © 2015 The Author(s).

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

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


    Carbon and oxygen isotopes measured on natural calcite crystals provide a record of paleo-environment conditions. Despite the importance of measuring stable isotopes in calcite for paleo-environment reconstructions, there is neither a general theory nor an experimental data set that fully separates the effects of pH, temperature, and precipitation rate on isotope discrimination during calcite growth. Many stable isotope studies of calcite have focused on either carbon or oxygen isotope compositions individually, but few have measured both carbon and oxygen isotope uptake in the same set of crystals. We are precipitating inorganic calcite across a range in temperature, pH, and precipitation rate to guide the development of a general theory for combined carbon and oxygen isotope uptake into calcite crystals grown on laboratory timescales. In our experiments, dissolved inorganic carbon (DIC) is added to an aqueous solution (15 mM CaCl2 + 5 mM NH4Cl) by CO2 bubbling. Once a critical supersaturation is reached, calcite crystals nucleate spontaneously and grow on the beaker walls. A key aspect of this experimental approach is that the δ13C of DIC is relatively constant throughout the crystal growth period, because there is a continuous supply of DIC from the CO2-bearing bubbles. Carbonic anhydrase, an enzyme promoting rapid equilibration of isotopes between DIC and water, was added to ensure that the solution remained isotopically equilibrated during calcite growth. We have conducted experiments at T = 25°C and pH = 8.3 - 9.0. We observe that the fractionation of oxygen isotopes between calcite and water decreases with increasing pH, consistent with available data from experiments in which the enzyme carbonic anhydrase was used. Our results for carbon isotopes extend the available data set, which previously ranged from pH 6.62 to 7.75, to higher pH. At pH 8.3, we observe that calcite is isotopically heavier than DIC with respect to carbon isotopes by about 0.25‰. At

  16. Drumlins, subglacial meltwater floods, and ocean responses (United States)

    Shaw, John


    Drumlins and erosional marks in bedrock give evidence for broad, subglacial meltwater floods that have discharge-rate estimates of about 106 m3/s. Similar discharge rates are obtained for other late glacial catastrophic floods. The total volume of meltwater that is thought to have formed the Livingstone Lake, Saskatchewan, drumlin field is estimated at 8.4 x 104 km3. This volume is equivalent to a eustatic rise of 0.23 m in global sea level. Meltwater release and roughly contemporaneous formation of drumlin fields in North America and Europe could have involved several metres of sea-level rise in a few years. The implications of such floods for the generation of myths and the interpretation of the oxygen isotopic record of the oceans are discussed. High meltwater discharges are of potential importance to the generation of a lid of cold, fresh water over the North Atlantic and its effects on late glacial climate.

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

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


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

  18. Antarctic Active Subglacial Lake Inventory from ICESat Altimetry, Version 1 (United States)

    National Aeronautics and Space Administration — This data set contains lake boundaries, volume changes, and gridded elevations for 124 active subglacial lakes beneath the Antarctic ice sheet. Lakes were identified...

  19. 88Sr/86Sr fractionation and calcite accumulation rate in the Sea of Galilee (United States)

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


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

  20. Rock comminution as a source of hydrogen for subglacial ecosystems (United States)

    Telling, J.; Boyd, E. S.; Bone, N.; Jones, E. L.; Tranter, M.; Macfarlane, J. W.; Martin, P. G.; Wadham, J. L.; Lamarche-Gagnon, G.; Skidmore, M. L.; Hamilton, T. L.; Hill, E.; Jackson, M.; Hodgson, D. A.


    Substantial parts of the beds of glaciers, ice sheets and ice caps are at the pressure melting point. The resulting water harbours diverse subglacial microbial ecosystems capable of affecting global biogeochemical cycles. Such subglacial habitats may have acted as refugia during Neoproterozoic glaciations. However, it is unclear how life in subglacial environments could be supported during glaciations lasting millions of years because energy from overridden organic carbon would become increasingly depleted. Here we investigate the potential for abiogenic H2 produced during rock comminution to provide a continual source of energy to support subglacial life. We collected a range of silicate rocks representative of subglacial environments in Greenland, Canada, Norway and Antarctica and crushed them with a sledgehammer and ball mill to varying surface areas. Under an inert atmosphere in the laboratory, we added water, and measured H2 production with time. H2 was produced at 0 °C in all silicate-water experiments, probably through the reaction of water with mineral surface silica radicals formed during rock comminution. H2 production increased with increasing temperature or decreasing silicate rock grain size. Sufficient H2 was produced to support previously measured rates of methanogenesis under a Greenland glacier. We conclude that abiogenic H2 generation from glacial bedrock comminution could have supported life and biodiversity in subglacial refugia during past extended global glaciations.

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

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


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

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

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


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

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

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


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

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

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  6. Height changes over subglacial Lake Vostok, East Antarctica: Insights from GNSS observations

    National Research Council Canada - National Science Library

    Richter, Andreas; Popov, Sergey V; Fritsche, Mathias; Lukin, Valery V; Matveev, Alexey Yu; Ekaykin, Alexey A; Lipenkov, Vladimir Ya; Fedorov, Denis V; Eberlein, Lutz; Schröder, Ludwig; Ewert, Heiko; Horwath, Martin; Dietrich, Reinhard


    Height changes of the ice surface above subglacial Lake Vostok, East Antarctica, reflect the integral effect of different processes within the subglacial environment and the ice sheet. Repeated GNSS...

  7. Seismic Tremor Reveals Subglacial Discharge at Tidewater Glaciers (United States)

    Bartholomaus, T. C.; Larsen, C. F.; O'Neel, S.; West, M. E.; Amundson, J. M.; Walter, J. I.; Catania, G. A.; Stearns, L. A.; Walker, R. T.; Sutherland, D.; Shroyer, E.; Nash, J. D.


    Subglacial discharge from the termini of tidewater glaciers drives submarine terminus melting, influences fjord circulation, erodes and redeposits subglacial sediment, and is a central component of proglacial marine ecosystems. The timing and variability of subglacial discharge can also exert a strong influence on the upstream flow of tidewater glaciers through hydrology-mediated changes in basal motion. However, a lack of observations of subglacial discharge at the ice-ocean interface hinders progress in understanding these processes and contributes to some of the largest uncertainties in sea level rise projections. Here we demonstrate that passive seismic observations collected adjacent to glaciers can meet this observational need. At tidewater and lake-terminating glaciers in Alaska and Greenland, we observe hourly to seasonal variations in low-amplitude, background seismic noise, termed glacio-hydraulic tremor. Variations in tremor amplitude correlate with discharge during the drainage of a glacially-dammed lake and reveal increases in discharge efficiency over the course of the melt season. Recordings of glacio-hydraulic tremor across a range of settings suggest widespread utility for our method. Reliable prediction of future sea level rise requires observations of subglacial discharge that elicit physical insight and can validate models. Our findings provide a platform for new understanding of ice-ocean interactions and related oceanographic, geologic, and ecological disciplines.

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

    NARCIS (Netherlands)

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


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

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

    NARCIS (Netherlands)

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


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


    Directory of Open Access Journals (Sweden)

    G. I. Leychenkov


    Full Text Available In early February 2012, the drill hole at the Vostok Station encountered theLakeVostokwater. This step is important to study the lake composition including possible microbial life and to model subglacial environments however, the next ambitious target of the Vostok Drilling Project is sampling of bottom sediments, which contain the unique record of ice sheet evolution and environmental changes in centralAntarcticafor millions of years. In this connection, the forecast of sedimentary succession based on existing geophysical data, study of mineral inclusions in the accretion ice cores and tectonic models is important task. Interpretation of Airborne geophysical data suggests thatLakeVostokis the part of spacious rift system, which exists at least from Cretaceous. Reflection and refraction seismic experiments conducted in the southern part ofLakeVostokshow very thin (200–300 m stratified sedimentary cover overlying crystalline basement with velocity of 6.0–6.2 km/s. At present, deposition in southernLakeVostokis absent and similar conditions occurred likely at least last3 m.y. when ice sheet aboveLakeVostokchanged insignificantly. It can be also inferred that from the Late Miocene the rate of deposition inLakeVostokwas extremely low and so the most of sedimentary section is older being possibly of Oligocene to early to middle Miocene age when ice sheet oscillated and deposition was more vigorous. If so, the sampling of upper few meters of this condensed section is very informative in terms of history of Antarctic glaciation. Small thickness of sedimentary cover raises a question about existence of lake (rift depression during preglacial and early glacial times.

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

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


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

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

    DEFF Research Database (Denmark)

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


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

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

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


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

  14. Calcium carbonate precipitation by different bacterial strains ...

    African Journals Online (AJOL)

    Bacteria are capable of performing metabolic activities which thereby promote precipitation of calcium carbonate in the form of calcite. In this study, it is shown that microbial mineral precipitation was a result of metabolic activities of some specific microorganisms. Concrete microorganisms were used to improve the overall ...

  15. Advances in modelling subglacial lakes and their interaction with the Antarctic ice sheet. (United States)

    Pattyn, Frank; Carter, Sasha P; Thoma, Malte


    Subglacial lakes have long been considered hydraulically isolated water bodies underneath ice sheets. This view changed radically with the advent of repeat-pass satellite altimetry and the discovery of multiple lake discharges and water infill, associated with water transfer over distances of more than 200 km. The presence of subglacial lakes also influences ice dynamics, leading to glacier acceleration. Furthermore, subglacial melting under the Antarctic ice sheet is more widespread than previously thought, and subglacial melt rates may explain the availability for water storage in subglacial lakes and water transport. Modelling of subglacial water discharge in subglacial lakes essentially follows hydraulics of subglacial channels on a hard bed, where ice sheet surface slope is a major control on triggering subglacial lake discharge. Recent evidence also points to the development of channels in deformable sediment in West Antarctica, with significant water exchanges between till and ice. Most active lakes drain over short time scales and respond rapidly to upstream variations. Several Antarctic subglacial lakes exhibit complex interactions with the ice sheet due to water circulation. Subglacial lakes can therefore-from a modelling point of view-be seen as confined small oceans underneath an imbedded ice shelf. © 2015 The Author(s).

  16. Geology and environments of subglacial Lake Vostok. (United States)

    Leitchenkov, German L; Antonov, Anton V; Luneov, Pavel I; Lipenkov, Vladimir Ya


    The reconstruction of the geological (tectonic) structure and environments of subglacial Lake Vostok is based on geophysical surveys and the study of mineral particles found in cores of accreted ice and frozen lake water (sampled after the lake was unsealed). Seismic reflection and refraction investigations conducted in the southern part of Lake Vostok show very thin (200-300 m) sedimentary cover overlying a crystalline basement. Most of this thin veneer is thought to have been deposited during temperate-glacial conditions in Oligocene to Middle Miocene time (ca 34-14 Ma). The composition of the lake-bottom sediments can be deduced from mineral inclusions found in cores of accreted ice. Inclusions are represented by soft aggregates consisting mainly of clay-mica minerals and micrometre-sized quartz grains. Some of these inclusions contain subangular to semi-rounded rock clasts (siltstones and sandstones) ranging from 0.3 to 8 mm in size. In total, 31 zircon grains have been identified in two rock clasts and dated using SHRIMP-II. The ages of the studied zircons range from 0.6 to 2.0 Ga with two distinct clusters between 0.8 and 1.15 Ga and between 1.6 and 1.8 Ga. Rock clasts obviously came from the western lake shore, which is thus composed of terrigenous strata with an age of not older than 600 Ma. The sedimentary nature of the western lake shore is also confirmed by seismic refraction data showing seismic velocities there of 5.4-5.5 km s(-1) at the bedrock surface. After Lake Vostok was unsealed, its water (frozen and sampled next season) was also studied with scanning electron microscopy and X-ray microprobe analysis. This study showed the existence of calcium carbonate and silica microparticles (10-20 μm across) in frozen water. © 2015 The Author(s).

  17. Interaction of alcohols with the calcite surface

    DEFF Research Database (Denmark)

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


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

  18. Ice thickness, volume and subglacial topography of Urumqi Glacier ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Earth System Science; Volume 123; Issue 3. Ice thickness, volume and subglacial topography of Urumqi Glacier No. 1, Tianshan mountains, central Asia, by ground penetrating radar survey. Puyu Wang Zhongqin Li Shuang Jin Ping Zhou Hongbing Yao Wenbin Wang. Volume 123 Issue 3 April ...

  19. Lake Vostok: From a Continental Margin to a Subglacial Lake (United States)

    Studinger, M.; Bell, R. E.; KArner, G. D.; Tikku, A. A.; Levin, V.; Raymond, C. A.; Lerner-Lam, A.


    Subglacial ecosystems, in particular subglacial lakes, represent the most oligothrophic environments on Earth. The geologic origin of Lake Vostok is a critical boundary condition for both the stability of the lake and energy fluxes into the lake. Microbial life may use geothermal energy, similar to life discovered at deep sea hydrothermal vents. Significant geothermal anomalies are often associated with active faulting. The topographic depression which forms the craddle for Lake Vostok is part of a regional tectonic structure ranging from the Gamburtsev Subglacial Mountains to the Aurora Subglacial Basin. This geologic boundary was formed by emplacement of a thrust sheet from the east over a pre-existing passive continental margin beneath the present-day Lake Vostok. No data exist to directly date either the timing of passive margin formation or the subsequent crustal shortening. Minor extensional reactivation of the thrust sheet explains a simple mechanism to explain the formation of the Lake Vostok basin. The steep slopes bounding this depression are likley being fault-controlled. Our recent discovery of microseismic activity suggest that this faults might be active and could act as conduits for convecting fluids. The tectonic processes can have an important influence on the ecosystem within the lake.

  20. A wireless subglacial probe for deep ice applications

    NARCIS (Netherlands)

    Smeets, C.J.P.P.|info:eu-repo/dai/nl/191522236; Boot, W.; Hubbard, A.; Pettersson, R.; Wilhelms, F.; van den Broeke, M.R.|info:eu-repo/dai/nl/073765643; van de Wal, R.S.W.|info:eu-repo/dai/nl/101899556


    We present the design and first results from two experiments using a wireless subglacial sensor system (WiSe) that is able to transmit data through 2500m thick ice. Energy consumption of the probes is minimized, enabling the transmission of data for at least 10 years. In July 2010 the first

  1. Incorporating modelled subglacial hydrology into inversions for basal drag

    Directory of Open Access Journals (Sweden)

    C. P. Koziol


    Full Text Available A key challenge in modelling coupled ice-flow–subglacial hydrology is initializing the state and parameters of the system. We address this problem by presenting a workflow for initializing these values at the start of a summer melt season. The workflow depends on running a subglacial hydrology model for the winter season, when the system is not forced by meltwater inputs, and ice velocities can be assumed constant. Key parameters of the winter run of the subglacial hydrology model are determined from an initial inversion for basal drag using a linear sliding law. The state of the subglacial hydrology model at the end of winter is incorporated into an inversion of basal drag using a non-linear sliding law which is a function of water pressure. We demonstrate this procedure in the Russell Glacier area and compare the output of the linear sliding law with two non-linear sliding laws. Additionally, we compare the modelled winter hydrological state to radar observations and find that it is in line with summer rather than winter observations.

  2. Modeling of subglacial hydrological development following rapid supraglacial lake drainage (United States)

    Dow, C. F.; Kulessa, B.; Rutt, I. C.; Tsai, V. C.; Pimentel, S.; Doyle, S. H.; van As, D.; Lindbäck, K.; Pettersson, R.; Jones, G. A.; Hubbard, A.


    The rapid drainage of supraglacial lakes injects substantial volumes of water to the bed of the Greenland ice sheet over short timescales. The effect of these water pulses on the development of basal hydrological systems is largely unknown. To address this, we develop a lake drainage model incorporating both (1) a subglacial radial flux element driven by elastic hydraulic jacking and (2) downstream drainage through a linked channelized and distributed system. Here we present the model and examine whether substantial, efficient subglacial channels can form during or following lake drainage events and their effect on the water pressure in the surrounding distributed system. We force the model with field data from a lake drainage site, 70 km from the terminus of Russell Glacier in West Greenland. The model outputs suggest that efficient subglacial channels do not readily form in the vicinity of the lake during rapid drainage and instead water is evacuated primarily by a transient turbulent sheet and the distributed system. Following lake drainage, channels grow but are not large enough to reduce the water pressure in the surrounding distributed system, unless preexisting channels are present throughout the domain. Our results have implications for the analysis of subglacial hydrological systems in regions where rapid lake drainage provides the primary mechanism for surface-to-bed connections.

  3. Diffusion of Ca and Mg in Calcite

    Energy Technology Data Exchange (ETDEWEB)

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


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

  4. Subglacial sediment mechanics investigated by computer simulation of granular material (United States)

    Damsgaard, A.; Egholm, D. L.; Tulaczyk, S. M.; Piotrowski, J. A.; Larsen, N. K.; Siegfried, M. R.; Beem, L.; Suckale, J.


    The mechanical properties of subglacial sediments are known to directly influence the stability of ice streams and fast-moving glaciers, but existing models of granular sediment deformation are poorly constrained. In addition, upscaling to generalized mathematical models is difficult due to the mechanical nonlinearity of the sediment, internal porosity changes during deformation, and associated structural and kinematic phase transitions. In this presentation, we introduce the Discrete Element Method (DEM) for particle-scale granular simulation. The DEM is fully coupled with fluid dynamics. The numerical method is applied to better understand the mechanical properties of the subglacial sediment and its interaction with meltwater. The computational approach allows full experimental control and offers insights into the internal kinematics, stress distribution, and mechanical stability. During confined shear with variable pore-water pressure, the sediment changes mechanical behavior, from stick, to non-linear creep, and unconstrained failure during slip. These results are contrary to more conventional models of plastic or (non-)linear viscous subglacial soft-bed sliding. Advection of sediment downstream is pressure dependent, which is consistent with theories of unstable bed bump growth. Granular mechanics prove to significantly influence the geometry and hydraulic properties of meltwater channels incised into the subglacial bed. Current models assume that channel bed erosion is balanced by linear-viscous sediment movement. We demonstrate how channel flanks are stabilized by the sediment frictional strength. Additionally, sediment liquefaction proves to be a possible mechanism for causing large and episodic sediment transport by water flow. Though computationally intense, our coupled numerical method provides a framework for quantifying a wide range of subglacial sediment-water processes, which are a key unknown in our ability to model the future evolution of ice

  5. Clean access, measurement, and sampling of Ellsworth Subglacial Lake: A method for exploring deep Antarctic subglacial lake environments (United States)

    Siegert, Martin J.; Clarke, Rachel J.; Mowlem, Matt; Ross, Neil; Hill, Christopher S.; Tait, Andrew; Hodgson, Dominic; Parnell, John; Tranter, Martyn; Pearce, David; Bentley, Michael J.; Cockell, Charles; Tsaloglou, Maria-Nefeli; Smith, Andy; Woodward, John; Brito, Mario P.; Waugh, Ed


    Antarctic subglacial lakes are thought to be extreme habitats for microbial life and may contain important records of ice sheet history and climate change within their lake floor sediments. To find whether or not this is true, and to answer the science questions that would follow, direct measurement and sampling of these environments are required. Ever since the water depth of Vostok Subglacial Lake was shown to be >500 m, attention has been given to how these unique, ancient, and pristine environments may be entered without contamination and adverse disturbance. Several organizations have offered guidelines on the desirable cleanliness and sterility requirements for direct sampling experiments, including the U.S. National Academy of Sciences and the Scientific Committee on Antarctic Research. Here we summarize the scientific protocols and methods being developed for the exploration of Ellsworth Subglacial Lake in West Antarctica, planned for 2012-2013, which we offer as a guide to future subglacial environment research missions. The proposed exploration involves accessing the lake using a hot-water drill and deploying a sampling probe and sediment corer to allow sample collection. We focus here on how this can be undertaken with minimal environmental impact while maximizing scientific return without compromising the environment for future experiments.

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

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


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

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

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


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

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

    Directory of Open Access Journals (Sweden)

    M. Raitzsch


    Full Text Available We investigated the effect of the calcium concentration in seawater and thereby the calcite saturation state (Ω on the magnesium and strontium incorporation into benthic foraminiferal calcite under laboratory conditions. For this purpose individuals of the shallow-water species Heterostegina depressa (precipitating high-Mg calcite, symbiont-bearing and Ammonia tepida (low-Mg calcite, symbiont-barren were cultured in media under a range of [Ca2+], but similar Mg/Ca ratios. Trace element/Ca ratios of newly formed calcite were analysed with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS and normalized to the seawater elemental composition using the equation DTE=(TE/Cacalcite/(TE/Caseawater. The culturing study shows that DMg of A. tepida significantly decreases with increasing Ω at a gradient of −4.3×10−5 per Ω unit. The DSr value of A. tepida does not change with Ω, suggesting that fossil Sr/Ca in this species may be a potential tool to reconstruct past variations in seawater Sr/Ca. Conversely, DMg of H. depressa shows only a minor decrease with increasing Ω, while DSr increases considerably with Ω at a gradient of 0.009 per Ω unit. The different responses to seawater chemistry of the two species may be explained by a difference in the calcification pathway that is, at the same time, responsible for the variation in the total Mg incorporation between the two species. Since the Mg/Ca ratio in H. depressa is 50–100 times higher than that of A. tepida, it is suggested that the latter exhibits a mechanism that decreases the Mg/Ca ratio of the calcification fluid, while the high-Mg calcite forming species may not have this physiological tool. If the dependency of Mg incorporation on seawater [Ca2+] is also valid for deep

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

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


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

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

    Lüttge, Andreas; Conrad, Pamela G


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

  11. Calcite Biohybrids as Microenvironment for Stem Cells

    Directory of Open Access Journals (Sweden)

    Razi Vago


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

  12. Two-phase flow and calcite deposition

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Kwiatkowski, Kamil; Szymczak, Piotr; Jarosiński, Marek


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

  14. Microbial sulfur transformations in sediments from Subglacial Lake Whillans

    Directory of Open Access Journals (Sweden)

    Alicia M Purcell


    Full Text Available Diverse microbial assemblages inhabit subglacial aquatic environments. While few of these environments have been sampled, data reveal that subglacial organisms gain energy for growth from reduced minerals containing nitrogen, iron, and sulfur. Here we investigate the role of microbially mediated sulfur transformations in sediments from Subglacial Lake Whillans (SLW, Antarctica, by examining key genes involved in dissimilatory sulfur oxidation and reduction. The presence of sulfur transformation genes throughout the top 34 cm of SLW sediments changes with depth. SLW surficial sediments were dominated by genes related to known sulfur-oxidizing chemoautotrophs. Sequences encoding the adenosine-5’-phosphosulfate (APS reductase gene, involved in both dissimilatory sulfate reduction and sulfur oxidation, were present in all samples and clustered into 16 distinct OTUs. The majority of APS reductase sequences (74% clustered with known sulfur oxidizers including those within the Sideroxydans and Thiobacillus genera. Reverse-acting dissimilatory sulfite reductase (rDSR and 16S rRNA gene sequences further support dominance of Sideroxydans and Thiobacillus phylotypes in the top 2 cm of SLW sediments. The SLW microbial community has the genetic potential for sulfate reduction which is supported by experimentally measured low rates (1.4 pmol cm-3d-1 of biologically mediated sulfate reduction and the presence of APS reductase and DSR gene sequences related to Desulfobacteraceae and Desulfotomaculum. Our results also infer the presence of sulfur oxidation, which can be a significant energetic pathway for chemosynthetic biosynthesis in SLW sediments. The water in SLW ultimately flows into the Ross Sea where intermediates from subglacial sulfur transformations can influence the flux of solutes to the Southern Ocean.

  15. A confined-unconfined aquifer model for subglacial hydrology (United States)

    Beyer, Sebastian; Kleiner, Thomas; Humbert, Angelika


    Modeling the evolution of subglacial channels underneath ice sheets is an urgent need for ice sheet modellers, as channels affect sliding velocities and hence ice discharge. Owing to very limited observations of the subglacial hydraulic system, the development of physical models is quite restricted. Subglacial hydrology models are currently taking two different approaches: either modeling the development of a network of individual channels or modeling an equivalent porous layer where the channels are not resolved individually but modeled as a diffusive process, adjusted to reproduce the characteristic of an efficient system. Here, we use the latter approach, improving it by using a confined-unconfined aquifer model (CUAS), that allows the system to run dry in absence of sufficient water input. This ensures physical values for the water pressure. Channels are represented by adjusting the permeability and storage of the system according to projected locations of channels. The evolution of channel positions is governed by a reduced complexity model that computes channel growths according to simple rules (weighted random walks descending the hydraulic potential). As a proof of concept we present the results of the evolution of the hydrological system over time for a simple artificial glacier geometry.

  16. Constraining local subglacial bedrock erosion rates with cosmogenic nuclides (United States)

    Wirsig, Christian; Ivy-Ochs, Susan; Christl, Marcus; Reitner, Jürgen; Reindl, Martin; Bichler, Mathias; Vockenhuber, Christof; Akcar, Naki; Schlüchter, Christian


    The constant buildup of cosmogenic nuclides, most prominently 10Be, in exposed rock surfaces is routinely employed for dating various landforms such as landslides or glacial moraines. One fundamental assumption is that no cosmogenic nuclides were initially present in the rock, before the event to be dated. In the context of glacially formed landscapes it is commonly assumed that subglacial erosion of at least a few meters of bedrock during the period of ice coverage is sufficient to remove any previously accumulated nuclides, since the production of 10Be ceases at a depth of 2-3 m. Insufficient subglacial erosion leads to overestimation of surface exposure ages. If the time since the retreat of the glacier is known, however, a discordant concentration of cosmogenic nuclides delivers information about the depth of subglacial erosion. Here we present data from proglacial bedrock at two sites in the Alps. Goldbergkees in the Hohe Tauern National Park in Austria and Gruebengletscher in the Grimsel Pass area in Switzerland. Samples were taken inside as well as outside of the glaciers' Little Ice Age extent. Measured nuclide concentrations are analyzed with the help of a MATLAB model simulating periods of exposure or glacial cover of user-definable length and erosion rates.

  17. Subglacial discharge-driven renewal of tidewater glacier fjords (United States)

    Carroll, Dustin; Sutherland, David A.; Shroyer, Emily L.; Nash, Jonathan D.; Catania, Ginny A.; Stearns, Leigh A.


    The classic model of fjord renewal is complicated by tidewater glacier fjords, where submarine melt and subglacial discharge provide substantial buoyancy forcing at depth. Here we use a suite of idealized, high-resolution numerical ocean simulations to investigate how fjord circulation driven by subglacial plumes, tides, and wind stress depends on fjord width, grounding line depth, and sill height. We find that the depth of the grounding line compared to the sill is a primary control on plume-driven renewal of basin waters. In wide fjords the plume exhibits strong lateral recirculation, increasing the dilution and residence time of glacially-modified waters. Rapid drawdown of basin waters by the subglacial plume in narrow fjords allows for shelf waters to cascade deep into the basin; wide fjords result in a thin, boundary current of shelf waters that flow toward the terminus slightly below sill depth. Wind forcing amplifies the plume-driven exchange flow; however, wind-induced vertical mixing is limited to near-surface waters. Tidal mixing over the sill increases in-fjord transport of deep shelf waters and erodes basin stratification above the sill depth. These results underscore the first-order importances of fjord-glacier geometry in controlling circulation in tidewater glacier fjords and, thus, ocean heat transport to the ice.

  18. What controls the explosivity of subglacial rhyolite in Iceland? (United States)

    Owen, J.; Tuffen, H.; McGarvie, D. W.


    The eruption controls of subglacial rhyolite are poorly understood but this is of key importance in mitigating hazards. In subaerial rhyolite eruptions the pre-eruptive volatile content and degassing path are considered to be the primary controls of explosivity, but is this also the case when rhyolitic eruptions occur under ice? We present the first pre-eruptive volatile content and degassing path data for subglacial rhyolite eruptions, comparing three edifices of contrasting eruption style from the Torfajökull complex in South Iceland[1]. Volatile concentrations were measured using infra-red spectroscopy (FTIR) and Secondary Ion Mass Spectroscopy (SIMS). SE Rauðfossafjöll is a large volume (~1 km3) explosively erupted tuya, Dalakvísl (~0.2 km3) is an entirely subglacial edifice that has both explosive and effusive deposits and Bláhnúkur is a small volume (Bull Vol. [3] Tuffen et al. (2007) Ann Glac, 45(1): 87-94

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

    Jones, Brian


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

  20. Predictive modelling of (palaeo-)subglacial lake locations and their meltwater drainage routeways (United States)

    Livingstone, S. J.; Clark, C.; Tarasoff, L.; Woodward, J.


    There is increasing recognition that subglacial lakes act as key components within the ice sheet system, capable of influencing ice-sheet topography, ice volume and ice flow. At present, much glaciological research is concerned with the role of modern subglacial lake systems in Antarctica. Another approach to the exploration of subglacial lakes involves identification of the geological record of subglacial lakes that once existed beneath ice sheets of the last glaciation. Investigation of such palaeo-subglacial lakes offers significant advantages because we have comprehensive information about the bed properties, they are much more accessible and we can examine and sample the sediments with ease. However, their identification in the geological record remains controversial. We therefore present a simple diagnostic approach based on the Shreve equation, for predicting and investigating likely (palaeo-)subglacial lake locations. Data on the current topography and seafloor bathymetry, and elevation models of the ice and ground surface topography from data-calibrated glaciological modelling are used to calculate the hydraulic potential surface at the ice-sheet bed. Meltwater routing algorithms and the flooding of local hydraulic minima allow us to predict subglacial routeways and lakes respectively. Discovered subglacial lakes beneath the Antarctic Ice Sheet present an opportunity to verify the model using the BEDMAP2 dataset. Using a lake threshold of 5 km2 we identify 12,767 subglacial lakes occurring over 4% of the grounded bed and are able to recover >60% of the discovered subglacial lakes. Applying the same approach to the Greenland Ice Sheet produces 1,607 potential subglacial lakes, covering 1.3% of the bed. These lake localities will make suitable targets for radar surveys attempting to find subglacial lakes. Finally, we apply the Shreve equation to the North American Ice Sheet to try and predict likely palaeo-subglacial lake locations. Given that specific ice

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


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

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

    NARCIS (Netherlands)

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


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

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

    Directory of Open Access Journals (Sweden)

    Volodymyr Ivanov


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

  5. Structure, morphology and water flux of a subglacial drainage system, Midtdalsbreen, Norway

    NARCIS (Netherlands)

    Willis, I.C.; Fitzsimmons, C.D.; Melvold, K.; Andreassen, L.M.; Giesen, R.H.|info:eu-repo/dai/nl/304831603


    Digital elevation models of the surface and bed of Midtdalsbreen, Norway are used to calculate subglacial hydraulic potential and infer drainage system structure for a series of subglacial water pressure assumptions ranging from atmospheric to ice overburden. A distributed degree-day model is used

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

    Reddy, Michael M.


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

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

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


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

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

    Wirth, Stefanie; Gilli, Adrian


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

  9. Exploring Explanations of Subglacial Bedform Sizes Using Statistical Models.

    Directory of Open Access Journals (Sweden)

    John K Hillier

    Full Text Available Sediments beneath modern ice sheets exert a key control on their flow, but are largely inaccessible except through geophysics or boreholes. In contrast, palaeo-ice sheet beds are accessible, and typically characterised by numerous bedforms. However, the interaction between bedforms and ice flow is poorly constrained and it is not clear how bedform sizes might reflect ice flow conditions. To better understand this link we present a first exploration of a variety of statistical models to explain the size distribution of some common subglacial bedforms (i.e., drumlins, ribbed moraine, MSGL. By considering a range of models, constructed to reflect key aspects of the physical processes, it is possible to infer that the size distributions are most effectively explained when the dynamics of ice-water-sediment interaction associated with bedform growth is fundamentally random. A 'stochastic instability' (SI model, which integrates random bedform growth and shrinking through time with exponential growth, is preferred and is consistent with other observations of palaeo-bedforms and geophysical surveys of active ice sheets. Furthermore, we give a proof-of-concept demonstration that our statistical approach can bridge the gap between geomorphological observations and physical models, directly linking measurable size-frequency parameters to properties of ice sheet flow (e.g., ice velocity. Moreover, statistically developing existing models as proposed allows quantitative predictions to be made about sizes, making the models testable; a first illustration of this is given for a hypothesised repeat geophysical survey of bedforms under active ice. Thus, we further demonstrate the potential of size-frequency distributions of subglacial bedforms to assist the elucidation of subglacial processes and better constrain ice sheet models.

  10. Physiological ecology of microorganisms in Subglacial Lake Whillans

    Directory of Open Access Journals (Sweden)

    Trista J Vick-Majors


    Full Text Available Subglacial microbial habitats are widespread in glaciated regions of our planet. Some of these environments have been isolated from the atmosphere and from sunlight for many thousands of years. Consequently, ecosystem processes must rely on energy gained from the oxidation of inorganic substrates or detrital organic matter. Subglacial Lake Whillans (SLW is one of more than 400 subglacial lakes known to exist under the Antarctic ice sheet; however, little is known about microbial physiology and energetics in these systems. When it was sampled through its 800 m thick ice cover in 2013, the SLW water column was shallow (~2 m deep, oxygenated, and possessed sufficient concentrations of C, N, and P substrates to support microbial growth. Here, we use a combination of physiological assays and models to assess the energetics of microbial life in SLW. In general, SLW microorganisms grew slowly in this energy-limited environment. Heterotrophic cellular carbon turnover times, calculated from 3H-thymidine and 3H-leucine incorporation rates, were long (60 to 500 days while cellular doubling times averaged 196 days. Inferred growth rates (average ~0.006 d-1 obtained from the same incubations were at least an order of magnitude lower than those measured in Antarctic surface lakes and oligotrophic areas of the ocean. Low growth efficiency (8% indicated that heterotrophic populations in SLW partition a majority of their carbon demand to cellular maintenance rather than growth. Chemoautotrophic CO2-fixation exceeded heterotrophic organic C-demand by a factor of ~1.5. Aerobic respiratory activity associated with heterotrophic and chemoautotrophic metabolism surpassed the estimated supply of oxygen to SLW, implying that microbial activity could deplete the oxygenated waters, resulting in anoxia. We used thermodynamic calculations to examine the biogeochemical and energetic consequences of environmentally imposed switching between aerobic and anaerobic metabolisms

  11. Physiological Ecology of Microorganisms in Subglacial Lake Whillans (United States)

    Vick-Majors, Trista J.; Mitchell, Andrew C.; Achberger, Amanda M.; Christner, Brent C.; Dore, John E.; Michaud, Alexander B.; Mikucki, Jill A.; Purcell, Alicia M.; Skidmore, Mark L.; Priscu, John C.


    Subglacial microbial habitats are widespread in glaciated regions of our planet. Some of these environments have been isolated from the atmosphere and from sunlight for many thousands of years. Consequently, ecosystem processes must rely on energy gained from the oxidation of inorganic substrates or detrital organic matter. Subglacial Lake Whillans (SLW) is one of more than 400 subglacial lakes known to exist under the Antarctic ice sheet; however, little is known about microbial physiology and energetics in these systems. When it was sampled through its 800 m thick ice cover in 2013, the SLW water column was shallow (~2 m deep), oxygenated, and possessed sufficient concentrations of C, N, and P substrates to support microbial growth. Here, we use a combination of physiological assays and models to assess the energetics of microbial life in SLW. In general, SLW microorganisms grew slowly in this energy-limited environment. Heterotrophic cellular carbon turnover times, calculated from 3H-thymidine and 3H-leucine incorporation rates, were long (60 to 500 days) while cellular doubling times averaged 196 days. Inferred growth rates (average ~0.006 d−1) obtained from the same incubations were at least an order of magnitude lower than those measured in Antarctic surface lakes and oligotrophic areas of the ocean. Low growth efficiency (8%) indicated that heterotrophic populations in SLW partition a majority of their carbon demand to cellular maintenance rather than growth. Chemoautotrophic CO2-fixation exceeded heterotrophic organic C-demand by a factor of ~1.5. Aerobic respiratory activity associated with heterotrophic and chemoautotrophic metabolism surpassed the estimated supply of oxygen to SLW, implying that microbial activity could deplete the oxygenated waters, resulting in anoxia. We used thermodynamic calculations to examine the biogeochemical and energetic consequences of environmentally imposed switching between aerobic and anaerobic metabolisms in the SLW

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

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


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

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

    Prabhakar, Sanjay; Liu, Jian; Pantelides, Sokrates

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

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

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


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

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

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


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

  16. Characterization of Precipitated CaCO3 Synthesized from Dolomite (United States)

    Arifin, Zaenal; Fitria Apriliani, Nurul; Zainuri, Mochamad; Darminto, dan


    The precipitated CaCO3 has successfully been synthesized from dolomite. The influence of various temperature and carbonation rate on the morphology, crystal size, phase and structure of the carbonation products were studied. The particles resulted from this process have the crystal size 400-800 nm. The calcite phase wasformed inthe synthesis at 30°C with carbonation rate of 2 and 7 SCFH, and synthesis at 80 °C and 2 SCFH also produces calcite phase. Observations by SEM shows morphology of calcite as so-called schalenohedral.

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

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


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

  18. Direct observations of evolving subglacial drainage beneath the Greenland Ice Sheet. (United States)

    Andrews, Lauren C; Catania, Ginny A; Hoffman, Matthew J; Gulley, Jason D; Lüthi, Martin P; Ryser, Claudia; Hawley, Robert L; Neumann, Thomas A


    Seasonal acceleration of the Greenland Ice Sheet is influenced by the dynamic response of the subglacial hydrologic system to variability in meltwater delivery to the bed via crevasses and moulins (vertical conduits connecting supraglacial water to the bed of the ice sheet). As the melt season progresses, the subglacial hydrologic system drains supraglacial meltwater more efficiently, decreasing basal water pressure and moderating the ice velocity response to surface melting. However, limited direct observations of subglacial water pressure mean that the spatiotemporal evolution of the subglacial hydrologic system remains poorly understood. Here we show that ice velocity is well correlated with moulin hydraulic head but is out of phase with that of nearby (0.3-2 kilometres away) boreholes, indicating that moulins connect to an efficient, channelized component of the subglacial hydrologic system, which exerts the primary control on diurnal and multi-day changes in ice velocity. Our simultaneous measurements of moulin and borehole hydraulic head and ice velocity in the Paakitsoq region of western Greenland show that decreasing trends in ice velocity during the latter part of the melt season cannot be explained by changes in the ability of moulin-connected channels to convey supraglacial melt. Instead, these observations suggest that decreasing late-season ice velocity may be caused by changes in connectivity in unchannelized regions of the subglacial hydrologic system. Understanding this spatiotemporal variability in subglacial pressures is increasingly important because melt-season dynamics affect ice velocity beyond the conclusion of the melt season.

  19. Calculating the balance between atmospheric CO2 drawdown and organic carbon oxidation in subglacial hydrochemical systems (United States)

    Graly, Joseph A.; Drever, James I.; Humphrey, Neil F.


    In order to constrain CO2 fluxes from biogeochemical processes in subglacial environments, we model the evolution of pH and alkalinity over a range of subglacial weathering conditions. We show that subglacial waters reach or exceed atmospheric pCO2 levels when atmospheric gases are able to partially access the subglacial environment. Subsequently, closed system oxidation of sulfides is capable of producing pCO2 levels well in excess of atmosphere levels without any input from the decay of organic matter. We compared this model to published pH and alkalinity measurements from 21 glaciers and ice sheets. Most subglacial waters are near atmospheric pCO2 values. The assumption of an initial period of open system weathering requires substantial organic carbon oxidation in only 4 of the 21 analyzed ice bodies. If the subglacial environment is assumed to be closed from any input of atmospheric gas, large organic carbon inputs are required in nearly all cases. These closed system assumptions imply that order of 10 g m-2 y-1 of organic carbon are removed from a typical subglacial environment—a rate too high to represent soil carbon built up over previous interglacial periods and far in excess of fluxes of surface deposited organic carbon. Partial open system input of atmospheric gases is therefore likely in most subglacial environments. The decay of organic carbon is still important to subglacial inorganic chemistry where substantial reserves of ancient organic carbon are found in bedrock. In glaciers and ice sheets on silicate bedrock, substantial long-term drawdown of atmospheric CO2 occurs.

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

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


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

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

    Dong, S.; Wasylenki, L. E.


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

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

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


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

  3. Subglacial lake and meltwater flow predictions of the last North American and European Ice Sheets (United States)

    Livingstone, S. J.; Clark, C. D.; Tarasov, L.


    There is increasing recognition that subglacial lakes act as key components within the ice sheet system, capable of influencing ice-sheet topography, ice volume and ice flow. The subglacial water systems themselves are recognised as being both active and dynamic, with large discharges of meltwater capable of flowing down hydrological pathways both between lakes and to the ice-sheet margins. At present, much glaciological research is concerned with the role of modern subglacial lake systems in Antarctica. Another approach to the exploration of subglacial lakes involves identification of the geological record of subglacial lakes that once existed beneath ice sheets of the last glaciation. Investigation of such palaeo-subglacial lakes offers significant advantages because we have comprehensive information about the bed properties, they are much more accessible and we can examine and sample the sediments with ease. If we can find palaeo-subglacial lakes then we have the potential to advance understanding with regard to the topographic context and hydrological pathways that the phenomena form a part of; essentially we gain spatial and sedimentological information in relation to investigations of contemporary subglacial lakes and lose out on the short-time dynamics. In this work we present predictions of palaeo-subglacial lakes and meltwater drainage pathways under the former European and North American ice sheets during the last glaciation. We utilise data on the current topography and seafloor bathymetry, and elevation models of the ice and ground surface topography (interpolated to a 5 km grid) to calculate the hydraulic potential surface at the ice-sheet bed. Meltwater routing algorithms and the flooding of local hydraulic minima allow us to predict subglacial channels and lakes respectively. Given that specific ice-surface and bed topographies are only known from modelled outputs, and thus contain significant uncertainty, we utilise many such outputs to examine

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

    Catalli, K. C.; Williams, Q.


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

  5. A reassessment of the englacial and subglacial drainage system of Storglaciären in northern Sweden - How much did climate warming change the drainage system? (United States)

    Dahlke, H. E.; Rosqvist, G. N.; Jansson, P.; Lyon, S. W.


    Storglaciären glacier, located in the sub-arctic Tarfala catchment, in northern Sweden is one of the world's longest continuously monitored glaciers which provides a unique research platform for the long-term assessment of climate change impacts on mountain glacier systems. In the presented study we assess signals of climate-induced change in the englacial and subglacial drainage system of the lower ablation area of Storglaciären. Flow velocities and dispersive characteristics of the englacial and subglacial hydraulic system were re-investigated in the 2012 summer melt season using fluorescent dye-tracing tests and compared to previous assessments of from the 1980s and 1990s. Historical hydro-climatic records from Tarfala catchment indicate that there have been significant increases in the cold season air temperature (0.76 °C/decade, 1965-2009) and a doubling of summer event precipitation over the past four decades. These changes contributed to the consistently negative glacier net balance of Storglaciären and significant positive trends in both the mean summer discharge and flood magnitudes over the past 45 years. Six of the eight largest annual maximum flood events occurred during the last decade and meltwater contributions from Storglaciären to the Tarfalajokken stream increased by 15% during the same period. These hydro-climatic trends in conjunction with an isotopic hydrograph separation of present-day samplings indicate that high magnitude rainfall events receive an increasing role in the runoff generation in Tarfala catchment and the glacier systems. This shift towards a greater rainwater contribution to catchment streamflow and glacier runoff indicates fundamental changes in the pathways that water takes through the glacier. The isotopic data suggests that the transit of rainwater via the englacial drainage system is increasing. However, in contrast to the 1980s assessment, dye-tracing tests conducted in 2012 indicate that the majority of meltwater


    Directory of Open Access Journals (Sweden)

    S. A. Bulat


    Full Text Available The objective was to estimate the genuine microbial content of ice samples from refrozen water (accretion ice from the subglacialLakeVostok(Antarctica buried beneath the 4-km thick East Antarctic ice sheet as well as surface snow nearby Vostok station. The lake ice samples were extracted by heavy deep ice drilling from3764 mbelow the surface reaching the depth3769.3 mby February 2011 (lake entering. High pressure, an ultra low carbon and chemical content, isolation, complete darkness and the probable excess of oxygen in water for millions of years characterize this extreme environment. A decontamination protocol was first applied to samples selected for the absence of cracks to remove the outer part contaminated by handling and drilling fluid. Preliminary indications showed the accretion ice samples to be almost gas free with the very low impurity content. Flow cytometry showed the very low unevenly distributed biomass in both accretion (0–19 cells per ml and glacier (0–24 cells per ml ice and surface snow (0–0.02 cells per ml as well while repeated microscopic observations were unsuccessful meaning that the whole Central East Antarctic ice sheet seems to be microbial cell-free.We used strategies of Ancient DNA research that include establishing contaminant databases and criteria to validate the amplification results. To date, positive results that passed the artifacts and contaminant databases have been obtained for a few bacterial phylotypes only in accretion ice samples featured by some bedrock sediments. Amongst them are the chemolithoautotrophic thermophile Hydrogenophilus thermoluteolus of beta-Proteobacteria, the actinobacterium rather related (95% to Ilumatobacter luminis and one unclassified phylotype distantly related (92% to soil-inhabiting uncultured bacteria. Combined with geochemical and geophysical considerations, our results suggest the presence of a deep biosphere, possibly thriving within some active faults of the bedrock

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

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


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


    Directory of Open Access Journals (Sweden)

    G. V. Kazko


    Full Text Available Different ways of defining the characteristics of Antarctic subglacialLakeVostokcirculation are considered. The disadvantages of hydrodynamic models using the hydrostatic approximation exposed to analysis. Differential equations and boundary conditions of three-dimensional nonhydrostatic model in terms vorticity–vector potential, specially developed for the modelling of the lake circulation are presented. 3D model passed through the testing by means simulations of convective currents in the simple-form reservoirs. On the basis of the seismic data on the thickness of a glacier and bathimetry of the lake the computational domain approximating a water body ofLakeVostokis constructed. Some results of modeling of the convective processes in the lake, obtained at the initial stage of circulation evolution using finite-difference grid with a spatial resolution of 8000 × 1500 ×30 mare shown.

  9. Subglacial sediment mechanics investigated by computer simulation of granular material

    DEFF Research Database (Denmark)

    Damsgaard, Anders; Egholm, David Lundbek; Tulaczyk, Slawek

    to the mechanical nonlinearity of the sediment, internal porosity changes during deformation, and associated structural and kinematic phase transitions. In this presentation, we introduce the Discrete Element Method (DEM) for particle-scale granular simulation. The DEM is fully coupled with fluid dynamics....... The numerical method is applied to better understand the mechanical properties of the subglacial sediment and its interaction with meltwater. The computational approach allows full experimental control and offers insights into the internal kinematics, stress distribution, and mechanical stability. During...... by linear-viscous sediment movement. We demonstrate how channel flanks are stabilized by the sediment frictional strength. Additionally, sediment liquefaction proves to be a possible mechanism for causing large and episodic sediment transport by water flow. Though computationally intense, our coupled...

  10. Microbial Community Structure of Subglacial Lake Whillans, West Antarctica. (United States)

    Achberger, Amanda M; Christner, Brent C; Michaud, Alexander B; Priscu, John C; Skidmore, Mark L; Vick-Majors, Trista J


    Subglacial Lake Whillans (SLW) is located beneath ∼800 m of ice on the Whillans Ice Stream in West Antarctica and was sampled in January of 2013, providing the first opportunity to directly examine water and sediments from an Antarctic subglacial lake. To minimize the introduction of surface contaminants to SLW during its exploration, an access borehole was created using a microbiologically clean hot water drill designed to reduce the number and viability of microorganisms in the drilling water. Analysis of 16S rRNA genes (rDNA) amplified from samples of the drilling and borehole water allowed an evaluation of the efficacy of this approach and enabled a confident assessment of the SLW ecosystem inhabitants. Based on an analysis of 16S rDNA and rRNA (i.e., reverse-transcribed rRNA molecules) data, the SLW community was found to be bacterially dominated and compositionally distinct from the assemblages identified in the drill system. The abundance of bacteria (e.g., Candidatus Nitrotoga, Sideroxydans, Thiobacillus, and Albidiferax) and archaea (Candidatus Nitrosoarchaeum) related to chemolithoautotrophs was consistent with the oxidation of reduced iron, sulfur, and nitrogen compounds having important roles as pathways for primary production in this permanently dark ecosystem. Further, the prevalence of Methylobacter in surficial lake sediments combined with the detection of methanogenic taxa in the deepest sediment horizons analyzed (34-36 cm) supported the hypothesis that methane cycling occurs beneath the West Antarctic Ice Sheet. Large ratios of rRNA to rDNA were observed for several operational taxonomic units abundant in the water column and sediments (e.g., Albidiferax, Methylobacter, Candidatus Nitrotoga, Sideroxydans, and Smithella), suggesting a potentially active role for these taxa in the SLW ecosystem. Our findings are consistent with chemosynthetic microorganisms serving as the ecological foundation in this dark subsurface environment, providing new

  11. Stress Redistribution Explains Anti-correlated Subglacial Pressure Variations

    Directory of Open Access Journals (Sweden)

    Pierre-Marie Lefeuvre


    Full Text Available We used a finite element model to interpret anti-correlated pressure variations at the base of a glacier to demonstrate the importance of stress redistribution in the basal ice. We first investigated two pairs of load cells installed 20 m apart at the base of the 210 m thick Engabreen glacier in Northern Norway. The load cell data for July 2003 showed that pressurisation of a subglacial channel located over one load cell pair led to anti-correlation in pressure between the two pairs. To investigate the cause of this anti-correlation, we used a full Stokes 3D model of a 210 m thick and 25–200 m wide glacier with a pressurised subglacial channel represented as a pressure boundary condition. The model reproduced the anti-correlated pressure response at the glacier bed and variations in pressure of the same order of magnitude as the load cell observations. The anti-correlation pattern was shown to depend on the bed/surface slope. On a flat bed with laterally constrained cross-section, the resulting bridging effect diverted some of the normal forces acting on the bed to the sides. The anti-correlated pressure variations were then reproduced at a distance >10–20 m from the channel. In contrast, when the bed was inclined, the channel support of the overlying ice was vertical only, causing a reduction of the normal stress on the bed. With a bed slope of 5 degrees, the anti-correlation occurred within 10 m of the channel. The model thus showed that the effect of stress redistribution can lead to an opposite response in pressure at the same distance from the channel and that anti-correlation in pressure is reproduced without invoking cavity expansion caused by sliding.

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

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


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

  13. Greenland subglacial drainage evolution regulated by weakly connected regions of the bed. (United States)

    Hoffman, Matthew J; Andrews, Lauren C; Price, Stephen A; Catania, Ginny A; Neumann, Thomas A; Lüthi, Martin P; Gulley, Jason; Ryser, Claudia; Hawley, Robert L; Morriss, Blaine


    Penetration of surface meltwater to the bed of the Greenland Ice Sheet each summer causes an initial increase in ice speed due to elevated basal water pressure, followed by slowdown in late summer that continues into fall and winter. While this seasonal pattern is commonly explained by an evolution of the subglacial drainage system from an inefficient distributed to efficient channelized configuration, mounting evidence indicates that subglacial channels are unable to explain important aspects of hydrodynamic coupling in late summer and fall. Here we use numerical models of subglacial drainage and ice flow to show that limited, gradual leakage of water and lowering of water pressure in weakly connected regions of the bed can explain the dominant features in late and post melt season ice dynamics. These results suggest that a third weakly connected drainage component should be included in the conceptual model of subglacial hydrology.

  14. Subglacial water drainage, storage, and piracy beneath the Greenland ice sheet (United States)

    Lindbäck, K.; Pettersson, R.; Hubbard, A. L.; Doyle, S. H.; As, D.; Mikkelsen, A. B.; Fitzpatrick, A. A.


    Meltwater drainage across the surface of the Greenland ice sheet (GrIS) is well constrained by measurements and modeling, yet despite its critical role, knowledge of its transit through the subglacial environment remains limited. Here we present a subglacial hydrological analysis of a land-terminating sector of the GrIS at unprecedented resolution that predicts the routing of surface-derived meltwater once it has entered the basal drainage system. Our analysis indicates the probable existence of small subglacial lakes that remain undetectable by methods using surface elevation change or radar techniques. Furthermore, the analysis suggests transient behavior with rapid switching of subglacial drainage between competing catchments driven by seasonal changes in the basal water pressure. Our findings provide a cautionary note that should be considered in studies that attempt to relate and infer future response from surface temperature, melt, and runoff from point measurements and/or modeling with measurements of proglacial discharge and ice dynamics.

  15. Predicting subglacial lakes and meltwater drainage pathways beneath the Antarctic and Greenland ice sheets (United States)

    Livingstone, S. J.; Clark, C. D.; Woodward, J.


    In this paper we use the Shreve hydraulic potential equation to predict subglacial lakes and meltwater drainage pathways beneath the Antarctic and Greenland ice sheets. For the Antarctic Ice Sheet we are able to predict known subglacial lakes with a >70% success rate, which demonstrates the validity of this method. Despite the success in predicting known subglacial lakes the calculations produce two-orders of magnitude more lakes than are presently identified, covering 4% of the ice-sheet bed. The difference is thought to result from our poor knowledge of the bed (which has resulted in artefacts associated with the interpolation method), intrinsic errors associated with the simplified modelling approach and because thousands of subglacial lakes, particularly smaller ones, remain to be found. Applying the same modelling approach to the Greenland Ice Sheet predicts only 90 lakes under the present-day ice-sheet configuration, covering 0.2% of the bed. The paucity of subglacial lakes in Greenland is thought to be a function of steeper overall ice-surface gradients. As no lakes have currently been located under Greenland, model predictions will make suitable targets for radar surveys of Greenland to identify subglacial lakes. During deglaciation from the Last Glacial Maximum both ice sheets had more subglacial lakes at their beds, though many of these lakes have persisted to present conditions. These lakes, inherited from past ice-sheet configurations would not form under current surface conditions, suggesting a retreating ice-sheet will have many more subglacial lakes than an advancing ice sheet. This hysteresis effect has implications for ice-stream formation and flow, bed lubrication and meltwater drainage. The lake model also allows modelling of the drainage pathways of the present-day and former Greenland and Antarctic ice sheets. Significantly, key sectors of the ice sheets, such as the Siple Coast (Antarctica) and NE Greenland Ice Stream system, are shown to have

  16. Potential subglacial lake locations and meltwater drainage pathways beneath the Antarctic and Greenland ice sheets (United States)

    Livingstone, S. J.; Clark, C. D.; Woodward, J.; Kingslake, J.


    We use the Shreve hydraulic potential equation as a simplified approach to investigate potential subglacial lake locations and meltwater drainage pathways beneath the Antarctic and Greenland ice sheets. We validate the method by demonstrating its ability to recall the locations of >60% of the known subglacial lakes beneath the Antarctic Ice Sheet. This is despite uncertainty in the ice-sheet bed elevation and our simplified modelling approach. However, we predict many more lakes than are observed. Hence we suggest that thousands of subglacial lakes remain to be found. Applying our technique to the Greenland Ice Sheet, where very few subglacial lakes have so far been observed, recalls 1607 potential lake locations, covering 1.2% of the bed. Our results will therefore provide suitable targets for geophysical surveys aimed at identifying lakes beneath Greenland. We also apply the technique to modelled past ice-sheet configurations and find that during deglaciation both ice sheets likely had more subglacial lakes at their beds. These lakes, inherited from past ice-sheet configurations, would not form under current surface conditions, but are able to persist, suggesting a retreating ice-sheet will have many more subglacial lakes than advancing ones. We also investigate subglacial drainage pathways of the present-day and former Greenland and Antarctic ice sheets. Key sectors of the ice sheets, such as the Siple Coast (Antarctica) and NE Greenland Ice Stream system, are suggested to have been susceptible to subglacial drainage switching. We discuss how our results impact our understanding of meltwater drainage, basal lubrication and ice-stream formation.

  17. Reconstruction of a Palaeo-Subglacial Lake Network in Alberta, Canada (United States)

    Livingstone, S. J.; Utting, D.; Clark, C.; Ruffell, A.; Pawley, S. M.; Atkinson, N.; Mallon, G.


    Subglacial lakes have been widely documented since first being identified beneath the Antarctic Ice Sheet in the 1960s and comprise a significant component of the subglacial hydrological system (Wright & Siegert, 2011). However, their investigation is largely limited to contemporary ice masses despite critical information that could be gleaned from palaeo-subglacial lake studies, including: (i) their influence on meltwater drainage, ice flow and ice streams; (ii) details about how they relate to palaeo-floods, ice dynamics and sub-Milankovitch-scale climate events; and (iii) as archives of long-term Quaternary climate change. They are also readily available, we can sample the sediments and maps the landforms with ease and we have comprehensive information on the lake-bed properties. Output from numerical ice sheet models and the simple Shreve equation approach has been used to diagnose where subglacial lakes are likely to have occurred in the geological record (Livingstone et al. 2013). However, their identification remains controversial due to the difficulty in distinguishing their signature from proglacial lake deposits (see Livingstone et al. 2012). Here, we present new geomorphological, geophysical and sedimentological evidence for the existence of a palaeo-subglacial lake network beneath the suture zone of the former Cordilleran and Laurentide ice sheets. These relatively small (~1 km diameter) palaeo-subglacial lakes manifest as flat-spots in a drumlin field and are perched in upland areas behind small ridges. The flat-spots, which comprise basins in-filled with diamicton, are associated with subglacial meltwater channels and eskers that we interpret to document lake drainage events. References: Livingstone, S.J., et al., 2012. Quaternary Science Reviews,55, 88-110. Livingstone, S.J., et al., 2013. Earth and Planetary Science Letters, 375, 13-33. Wright A.P., Siegert M.J. 2011. In: Siegert, M.J., Kennicutt, C., Bindschadler, B. (Eds.). Subglacial Antarctic

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

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


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

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

    Heberling, Frank; Brendebach, Boris; Bosbach, Dirk


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

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

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


    of critical importance for inheritance of different elements. The volume of solution is controlled by (1) the discharge of water passing through the sample and (2) the lapse time between aragonite dissolution and calcite precipitation. Hydrology and hydrochemistry of the interacting solution, together with the mineralogy and texture of the speleothem are the essential controls for the diagenesis of the speleothem. Recrystallization of aragonite speleothems does not follow stratigraphical levels of the sample but occurs along sites with preferential flow paths in any sector of the speleothem. In these cases the relationship between age and distance from base is not preserved. However, alternation of periods of recrystallization with periods of aragonite precipitation causing speleothem accretion can result in recrystallized speleothems with coherent distance from the base-age relationship. Thus, early diagenesis of speleothems affected by seasonal or inter-annual oscillation of drip waters supersaturated and subsaturated in aragonite may provide best-scenario conditions for dating and preservation of paleoenvironmental records along recrystallized speleothems. However, even in this scenario, the variable discharge and the diagenetic rate control the geochemical inheritance from the primary aragonite crystals.

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

    NARCIS (Netherlands)

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


    Calcite–water interactions are important not only in carbon sequestration and the global carbon cycle, but also in contaminant behaviour in calcite-bearing host rock and in many industrial applications. Here we quantify the effect of variations in surface structure on calcite surface reactivity.

  2. Automatic detection of subglacial lakes in radar sounder data acquired in Antarctica (United States)

    Ilisei, Ana-Maria; Khodadadzadeh, Mahdi; Dalsasso, Emanuele; Bruzzone, Lorenzo


    Subglacial lakes decouple the ice sheet from the underlying bedrock, thus facilitating the sliding of the ice masses towards the borders of the continents, consequently raising the sea level. This motivated increasing attention in the detection of subglacial lakes. So far, about 70% of the total number of subglacial lakes in Antarctica have been detected by analysing radargrams acquired by radar sounder (RS) instruments. Although the amount of radargrams is expected to drastically increase, from both airborne and possible future Earth observation RS missions, currently the main approach to the detection of subglacial lakes in radargrams is by visual interpretation. This approach is subjective and extremely time consuming, thus difficult to apply to a large amount of radargrams. In order to address the limitations of the visual interpretation and to assist glaciologists in better understanding the relationship between the subglacial environment and the climate system, in this paper, we propose a technique for the automatic detection of subglacial lakes. The main contribution of the proposed technique is the extraction of features for discriminating between lake and non-lake basal interfaces. In particular, we propose the extraction of features that locally capture the topography of the basal interface, the shape and the correlation of the basal waveforms. Then, the extracted features are given as input to a supervised binary classifier based on Support Vector Machine to perform the automatic subglacial lake detection. The effectiveness of the proposed method is proven both quantitatively and qualitatively by applying it to a large dataset acquired in East Antarctica by the MultiChannel Coherent Radar Depth Sounder.

  3. Dissolution phases of carbonate in Chinese loess deposits: a new proxy of monsoon precipitation intensity (United States)

    Meng, X.; Ji, J.; Zhao, W.


    Carbonate minerals are common in many soil and sedimentary deposits and they are also particularly sensitive to climate change because their dissolution, migration and leaching loss is strongly influenced by climatic factors (e.g. precipitation). Calcite and detrital dolomite are the two most common types of carbonate minerals in soils. Dolomite of detrital origin in soil can help indicate the intensity of carbonate dissolution and leaching processes. Using Fourier Transform infrared spectroscopy we generated dolomite and calcite content from modern surficial soils and eight sections spanning the last 130 kyr on the Chinese Loess Plateau. Dolomite and calcite contents of the surficial soils and eight sections range from 0 4.7% and 0 31.6%, respectively. The dolomite and calcite contents systematically vary and decrease gradually from the northwest to the southeast in surficial soils and eight sections. In addition, the variations in the dolomite and calcite contents of loess-paleosol sequences on the CLP are influenced mainly by pedogenesis (e.g. precipitation) rather than changing provenance. The precipitation of depletion of dolomite and calcite in surficial soils are 610 mm and 690 mm , respectively. Based on the relative abundance of calcite and dolomite, four dissolution phases of carbonate minerals related to East Asian Summer Monsoon precipitation variations are identified as follows: (1) coexistence of dolomite and calcite indicating a very weak monsoon with a mean annual precipitation (MAP) 725mm. The future application of our methodology has great potential to explore monsoon precipitation information recorded in carbonate-rich paleosols in the other areas and eras. This study was funded by National Science Foundation of China through grants 41273111, 41230526, and 41321062

  4. Subglacial sediment provenance and transport in West Antarctica from micropaleontologic analysis of Subglacial Lake Whillans and the upstream sectors of the Whillans and Kamb ice streams (United States)

    Scherer, Reed; Coenen, Jason; Warny, Sophie


    The WISSARD (Whillans Ice Stream Subglacial Access Research Drilling) project recovered sediment cores from Subglacial Lake Whillans (SLW) in West Antarctica. We report preliminary micropaleontological analyses of SLW sediments, augmented by analysis of sediments previously recovered from beneath the upstream camps of the Whillans Ice Stream (WIS) and Kamb Ice Stream (KIS). Microfossils in these sediments (notably diatoms, sponge spicules, and organic-walled palynomorphs), include information regarding sediment transport, subglacial physical processes and ice sheet history. Absolute abundance (particles per gram dry sediment) of identifiable diatoms and diatom fragments in different size classes were calculated to compare and contrast each environment. Sponge spicules are being analyzed for taphonomic effects from subglacial transport and shearing. Palynomorphs are analyzed for abundance, diversity, and source rock ages. In SLW the upper 30 cm is softer and more water-rich than the underlying sediments. However, no statistically significant variation in microfossil and fragment abundance or taphonomy is noted in these diamictons, which is in agreement with the stratigraphic homogeneity evident from geochemical and geological analyses performed to date. SLW contains 1.52x106 to 1.13x107 diatom fragments per gram, compared with 6.43x106 to 4.63x108 at upstream WIS and 6.13 107 to 1.58x108 at KIS. Whole diatoms are orders of magnitude lower in concentration. Low abundance and poor preservation of diatoms and spicules at SLW suggests relatively long distance transport from their marine sediment source, with evidence of high shear strain, following the subglacial shearing index of Scherer et al. (2004). Upper Miocene diatoms dominate all samples analyzed, though older and younger diatoms are noted as well. The WIS samples exhibit the highest diversity of diatoms, including Paleogene freshwater diatoms. KIS sediments have the highest abundance of whole diatoms, but they

  5. 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


    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.


    Directory of Open Access Journals (Sweden)

    S. V. Popov


    Full Text Available The results of the remote sensing which carried out in the LakeVostokarea are discussed in the paper. A.P. Kapitsa and O.G. Sorokhtin started the geophysical researches in this area in 1950s. Satellite altimetry data, which analyzed in 1990s yielded to the discovering of the LakeVostok. After that, PMGE and RAE started the systematic studying of this natural phenomenon by seismic and radio-echo sounding. Total, 318 seismic soundings and 5190 kmof the radio-echo profiles has been collected by 2008. Special precise measurements which carried out in the 5G-1 borehole vicinity are resulted in the ice thickness over Vostok Station is 3760±30 mby seismic and 3775±15 mby radio-echo sounding. Thus, the error of geophysical measurements is less than 0.3%. The Russian investigations are resulted in definition the border of the lake, the discovering of 56 subglacial water caves around the lake and compilation the maps including ice thickness, ice base and bedrock topography and the depth of the lake. Average depth of the LakeVostokis about 400 m; water volume is 6100 km3. After 2008, the remote sensing works have been concentrated to the studying of the bottom sediments by refraction seismic technique. The firsts result shown that the bottom sediments thickness varies from 400 to1200 m.

  7. Molecular ordering of ethanol at the calcite surface

    DEFF Research Database (Denmark)

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


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

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

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


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

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

    Directory of Open Access Journals (Sweden)

    A. Wackerbarth


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

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

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

  10. Subglacial bedforms and conditions associated with the 1991 surge of Skeidarárjökull, Iceland

    NARCIS (Netherlands)

    Waller, R.I.; Dijk, T. van; Knudson, O.


    Much previous research at surge-type glaciers has sought to identify features diagnostic of surge-type behaviour. However, in comparatively little work have subglacial landform-sediment characteristics been used to reconstruct changing basal processes and conditions during surge events. Subglacial

  11. An isotopic model for basal freeze-on associated with subglacial upward flow of pore water (United States)

    Souchez, R.; Samyn, D.; Lorrain, R.; Pattyn, F.; Fitzsimons, S.


    Subglacial freezing in polar glaciers can have a significant dynamical effect. Recent studies have shown that freezing of pore water flowing upward through subglacial fine-grained sediments at the freezing interface and progression of this freezing front downward are responsible for fast ice flow stoppage in ice streams. The upward pore water flow leads to the formation of debris-bearing basal ice layers. A model for stable isotope composition, both in δD and δ18O, is developed for predicting the isotopic composition of the ice segregated by such a mechanism. The development of this isotopic model for water films present along the grains of the subglacial sediment predicts the absence of apparent fractionation for the ice formed. This prediction is tested against two East Antarctic outlet glaciers by studying the δD-δ18O relationships in the basal ice layers of these glaciers.

  12. Actively evolving subglacial conduits and eskers initiate ice shelf channels at an Antarctic grounding line (United States)

    Drews, R.; Pattyn, F.; Hewitt, I. J.; Ng, F. S. L.; Berger, S.; Matsuoka, K.; Helm, V.; Bergeot, N.; Favier, L.; Neckel, N.


    Ice-shelf channels are long curvilinear tracts of thin ice found on Antarctic ice shelves. Many of them originate near the grounding line, but their formation mechanisms remain poorly understood. Here we use ice-penetrating radar data from Roi Baudouin Ice Shelf, East Antarctica, to infer that the morphology of several ice-shelf channels is seeded upstream of the grounding line by large basal obstacles indenting the ice from below. We interpret each obstacle as an esker ridge formed from sediments deposited by subglacial water conduits, and calculate that the eskers' size grows towards the grounding line where deposition rates are maximum. Relict features on the shelf indicate that these linked systems of subglacial conduits and ice-shelf channels have been changing over the past few centuries. Because ice-shelf channels are loci where intense melting occurs to thin an ice shelf, these findings expose a novel link between subglacial drainage, sedimentation and ice-shelf stability.

  13. Actively evolving subglacial conduits and eskers initiate ice shelf channels at an Antarctic grounding line. (United States)

    Drews, R; Pattyn, F; Hewitt, I J; Ng, F S L; Berger, S; Matsuoka, K; Helm, V; Bergeot, N; Favier, L; Neckel, N


    Ice-shelf channels are long curvilinear tracts of thin ice found on Antarctic ice shelves. Many of them originate near the grounding line, but their formation mechanisms remain poorly understood. Here we use ice-penetrating radar data from Roi Baudouin Ice Shelf, East Antarctica, to infer that the morphology of several ice-shelf channels is seeded upstream of the grounding line by large basal obstacles indenting the ice from below. We interpret each obstacle as an esker ridge formed from sediments deposited by subglacial water conduits, and calculate that the eskers' size grows towards the grounding line where deposition rates are maximum. Relict features on the shelf indicate that these linked systems of subglacial conduits and ice-shelf channels have been changing over the past few centuries. Because ice-shelf channels are loci where intense melting occurs to thin an ice shelf, these findings expose a novel link between subglacial drainage, sedimentation and ice-shelf stability.

  14. A new methodology to simulate subglacial deformation of water saturated granular material

    DEFF Research Database (Denmark)

    Damsgaard, Anders; Egholm, David Lundbek; Piotrowski, Jan A.


    can cause variations in the pore-fluid pressure. The pressure variations weaken or strengthen the granular phase, and in turn influence the distribution of shear strain with depth. In permeable sediments the strain distribution is governed by the grain-size distribution and effective normal stress...... of subglacial sediment to the shear stress of an overriding glacier. In this study, we present a new methodology designed to simulate subglacial deformation using a coupled numerical model for computational experiments on grain-fluid mixtures. The granular phase is simulated on a per-grain basis by the discrete......The dynamics of glaciers are to a large degree governed by processes operating at the ice-bed interface, and one of the primary mechanisms of glacier flow over soft unconsolidated sediments is subglacial deformation. However, it has proven difficult to constrain the mechanical response...

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

    Directory of Open Access Journals (Sweden)

    Zhiyong Gao


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

  16. Study of calcium carbonate and sulfate co-precipitation

    KAUST Repository

    Zarga, Y.


    Co-precipitation of mineral based salts in scaling is still not well understood and/or thermodynamically well defined in the water industry. This study focuses on investigating calcium carbonate (CaCO3) and sulfate mixed precipitation in scaling which is commonly observed in industrial water treatment processes including seawater desalination either by thermal-based or membrane-based processes. Co-precipitation kinetics were studied carefully by monitoring several parameters simultaneously measured, including: pH, calcium and alkalinity concentrations as well as quartz microbalance responses. The CaCO3 germination in mixed precipitation was found to be different than that of simple precipitation. Indeed, the co-precipitation of CaCO3 germination time was not anymore related to supersaturation as in a simple homogenous precipitation, but was significantly reduced when the gypsum crystals appeared first. On the other hand, the calcium sulfate crystals appear to reduce the energetic barrier of CaCO3 nucleation and lead to its precipitation by activating heterogeneous germination. However, the presence of CaCO3 crystals does not seem to have any significant effect on gypsum precipitation. IR spectroscopy and the Scanning Electronic Microscopy (SEM) were used to identify the nature of scales structures. Gypsum was found to be the dominant precipitate while calcite and especially vaterite were found at lower proportions. These analyses showed also that gypsum crystals promote calcite crystallization to the detriment of other forms. © 2013 Elsevier Ltd.

  17. Long-term subglacial sliding patterns based on a sliding law with cavitation

    DEFF Research Database (Denmark)

    Ugelvig, Sofie Vej; Egholm, D.L.

    In ice-sheet models and glacial landscape evolution models, subglacial sliding rates are often related to basal shear stress by a power-law. However, the power-law relationship implies that the subglacial bed can provide unlimited levels of basal drag as sliding rates increases, which is recogniz...... of cavitation on glacier sliding. Proc. R. Soc. A , 461, 609-627 (2005). Egholm et al. Modeling the flow of glaciers in steep terrains: The integrated second-order shallow ice approximation (iSOSIA). Journal of Geophysical Research, 116, F02012 (2011)....

  18. Feedbacks between subglacial dynamics and long-term glacial landscape evolution

    DEFF Research Database (Denmark)

    Brædstrup, Christian; Egholm, D.L.; Ugelvig, Sofie Vej

    computational experiments with a higher-order ice sheet model (Egholm et al., 2009) capable of simulating the long-term evolution of subglacial dynamics at a high spatial resolution. The orientation and magnitude of subglacial stress components depend not only on ice thickness and ice surface gradients...... associated to the level of cavitation (Iverson, 2012). The highly non-linear computational experiments are made possible by new and very efficient GPU-accelerated multigrid algorithms. The computational experiments show that higher-order stress effects associated with local changes to the bed gradient...

  19. Microbial Activity and Precipitation at Solution-Solution Mixing Zones in Porous Media -- Subsurface Biogeochemical Research

    Energy Technology Data Exchange (ETDEWEB)

    Colwell, Frederick [Oregon State Univ., Corvallis, OR (United States); Wildenschild, Dorthe [Oregon State Univ., Corvallis, OR (United States); Wood, Brian [Oregon State Univ., Corvallis, OR (United States); Gerlach, Robin [Montana State Univ., Bozeman, MT (United States); Mitchell, Andrew [Montana State Univ., Bozeman, MT (United States); Redden, George [Idaho National Lab. (INL), Idaho Falls, ID (United States)


    The goal for this research was to understand how best to add compounds to receptive microbial communities in porous media in order to achieve optimal calcite precipitation in a volumetrically significant space and to understand the physiological health of the cells that are responsible for the calcite precipitation. The specific objectives were to: (1) develop better tools for visually examining biofilms in porous media and calcium carbonate precipitation being mediated by microbes in porous media, and (2) demonstrate the effectiveness of using that tool within a flow cell model system.

  20. Refined broad-scale sub-glacial morphology of Aurora Subglacial Basin, East Antarctica derived by an ice-dynamics-based interpolation scheme

    Directory of Open Access Journals (Sweden)

    J. L. Roberts


    Full Text Available Ice thickness data over much of East Antarctica are sparse and irregularly distributed. This poses difficulties for reconstructing the homogeneous coverage needed to properly assess underlying sub-glacial morphology and fundamental geometric constraints on sea level rise. Here we introduce a new physically-based ice thickness interpolation scheme and apply this to existing ice thickness data in the Aurora Subglacial Basin region. The skill and robustness of the new reconstruction is demonstrated by comparison with new data from the ICECAP project. The interpolated morphology shows an extensive marine-based ice sheet, with considerably more area below sea-level than shown by prior studies. It also shows deep features connecting the coastal grounding zone with the deepest regions in the interior. This has implications for ice sheet response to a warming ocean and underscores the importance of obtaining additional high resolution data in these marginal zones for modelling ice sheet evolution.

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

    Larsen, M J; Pearce, E I F


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

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

    Hosa, Aleksandra; Wood, Rachel


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

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

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


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

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

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


    Raman spectroscopy was used to characterize and differentiate the two minerals calcite and dolomite and the bands related to the mineral structure. The (CO3)(2-) group is characterized by four prominent Raman vibrational modes: (a) the symmetric stretching, (b) the asymmetric deformation, (c) asymmetric stretching and (d) symmetric deformation. These vibrational modes of the calcite and dolomite were observed at 1440, 1088, 715 and 278 cm(-1). The significant differences between the minerals calcite and dolomite are observed by Raman spectroscopy. Calcite shows the typical bands observed at 1361, 1047, 715 and 157 cm(-1), and the special bands at 1393, 1098, 1069, 1019, 299, 258 and 176 cm(-1) for dolomite are observed. The difference is explained on the basis of the structure variation of the two minerals. Calcite has a trigonal structure with two molecules per unit cell, and dolomite has a hexagonal structure. This is more likely to cause the splitting and distorting of the carbonate groups. Another cause for the difference is the cation substituting for Mg in the dolomite mineral. Copyright © 2013 Elsevier B.V. All rights reserved.

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

    Diler, Songül Budak; Ergene, Serap


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

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

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    Songül Budak Diler


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

  7. Subglacial lake matters: piracy on a divide between thawed and frozen bed (United States)

    Carter, S. P.; Bougamont, M. H.; Christoffersen, P.; Fricker, H. A.; Lipscomb, W. H.; Price, S. F.


    The two most populated active subglacial lake districts in Antarctica, upper Kamb Ice Stream and lower Whillans Ice Stream, occur along boundaries between where temperature models predict net basal freezing and net basal accretion. This occurs in part due to a basal traction contrast, which creates a ridge in the ice surface and creates a pressure seal; this impedes the downstream movement of water until a subglacial lake flood occurs. Here we use a model for basal water routing, which incorporates subglacial floods and a realistic term for effective pressure, to explore the ability of these floods to provide water to areas of net basal accretion and thus maintain basal lubrication. We hypothesize that these floods can distribute sufficient water to most of the regions experiencing net basal freezing; the exception being those nearest to the lakes themselves, Discharge in these regions likely occurs via narrow subglacial conduits. Over time this will cause ice downstream of the dam to thicken and pre-flood lake levels to increase until water ultimately exits the lake via an alternate route i.e. water piracy. Once piracy occurs, water is no longer supplied along the former flowpath and ice stream shutdown accelerates. We conclude that the formation and quasi-periodic flooding of lakes at the basal melt/ basal freezing boundary is a critical process in accelerating ice stream shutdown.

  8. A balanced water layer concept for subglacial hydrology in large-scale ice sheet models

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    S. Goeller


    Full Text Available There is currently no doubt about the existence of a widespread hydrological network under the Antarctic Ice Sheet, which lubricates the ice base and thus leads to increased ice velocities. Consequently, ice models should incorporate basal hydrology to obtain meaningful results for future ice dynamics and their contribution to global sea level rise. Here, we introduce the balanced water layer concept, covering two prominent subglacial hydrological features for ice sheet modeling on a continental scale: the evolution of subglacial lakes and balance water fluxes. We couple it to the thermomechanical ice-flow model RIMBAY and apply it to a synthetic model domain. In our experiments we demonstrate the dynamic generation of subglacial lakes and their impact on the velocity field of the overlaying ice sheet, resulting in a negative ice mass balance. Furthermore, we introduce an elementary parametrization of the water flux–basal sliding coupling and reveal the predominance of the ice loss through the resulting ice streams against the stabilizing influence of less hydrologically active areas. We point out that established balance flux schemes quantify these effects only partially as their ability to store subglacial water is lacking.

  9. A balanced water layer concept for subglacial hydrology in large scale ice sheet models (United States)

    Goeller, S.; Thoma, M.; Grosfeld, K.; Miller, H.


    There is currently no doubt about the existence of a wide-spread hydrological network under the Antarctic ice sheet, which lubricates the ice base and thus leads to increased ice velocities. Consequently, ice models should incorporate basal hydrology to obtain meaningful results for future ice dynamics and their contribution to global sea level rise. Here, we introduce the balanced water layer concept, covering two prominent subglacial hydrological features for ice sheet modeling on a continental scale: the evolution of subglacial lakes and balance water fluxes. We couple it to the thermomechanical ice-flow model RIMBAY and apply it to a synthetic model domain inspired by the Gamburtsev Mountains, Antarctica. In our experiments we demonstrate the dynamic generation of subglacial lakes and their impact on the velocity field of the overlaying ice sheet, resulting in a negative ice mass balance. Furthermore, we introduce an elementary parametrization of the water flux-basal sliding coupling and reveal the predominance of the ice loss through the resulting ice streams against the stabilizing influence of less hydrologically active areas. We point out, that established balance flux schemes quantify these effects only partially as their ability to store subglacial water is lacking.

  10. Clean hot water drilling for exploration of the Antarctic deep subglacial environment (United States)

    Makinson, K.; Pearce, D.; Hodgson, D.; Bentley, M.; Smith, A.; Tranter, M.; Rose, M. C.; Ross, N.; Mowlem, M. C.; Parnell, J.; Siegert, M. J.


    Overlain by several kilometres of ice, the subglacial environments deep beneath the Antarctic Ice Sheet are regarded as extreme habitats for microbial life and repositories of important paleoclimate records. Of significant scientific interest, yet remaining largely unexplored, accessing and sampling these environments presents several challenges to existing drilling technologies. With over half of the ice sheet believed to be resting on a wet bed, much of it part of a hydrological drainage network, accessing of this environment must conform to international environmental contamination protocols. This makes hot water drilling the most viable option for clean, fast, access through thick ice. After two decades of planning, involving the development of drilling techniques for subglacial access, instrument design and logistics set up, significant progress has been made in attempts to directly access, measure, and sample subglacial lakes and sediments. Combining the experiences from the notable setbacks and successes, as well as recent field testing for this drilling technique, the most practical technical options and operational procedures for future clean entry into Subglacial Lake Ellsworth and other deep (>3000 m) access targets will be presented.

  11. Viable cold-tolerant iron-reducing microorganisms in geographically diverse subglacial environments (United States)

    Nixon, Sophie L.; Telling, Jon P.; Wadham, Jemma L.; Cockell, Charles S.


    Subglacial environments are known to harbour metabolically diverse microbial communities. These microbial communities drive chemical weathering of underlying bedrock and influence the geochemistry of glacial meltwater. Despite its importance in weathering reactions, the microbial cycling of iron in subglacial environments, in particular the role of microbial iron reduction, is poorly understood. In this study we address the prevalence of viable iron-reducing microorganisms in subglacial sediments from five geographically isolated glaciers. Iron-reducing enrichment cultures were established with sediment from beneath Engabreen (Norway), Finsterwalderbreen (Svalbard), Leverett and Russell glaciers (Greenland), and Lower Wright Glacier (Antarctica). Rates of iron reduction were higher at 4 °C compared with 15 °C in all but one duplicated second-generation enrichment culture, indicative of cold-tolerant and perhaps cold-adapted iron reducers. Analysis of bacterial 16S rRNA genes indicates Desulfosporosinus were the dominant iron-reducing microorganisms in low-temperature Engabreen, Finsterwalderbreen and Lower Wright Glacier enrichments, and Geobacter dominated in Russell and Leverett enrichments. Results from this study suggest microbial iron reduction is widespread in subglacial environments and may have important implications for global biogeochemical iron cycling and export to marine ecosystems.

  12. Recent technical developments at the IMAU: A new generation of AWS and wireless subglacial measurements

    NARCIS (Netherlands)

    Smeets, C.J.P.P.; Boot, W.; van den Broeke, M.R.; van de Wal, R.S.W.


    Two technical developments are presented: a new generation of AWS and a wireless subglacial measurement system. Both systems build on the experience of the IMAU in developing GPS systems (Den Ouden et al., 2010). Combining methods to minimize energy consumption and wireless communication form the

  13. Paleo ice flow and subglacial meltwater dynamics in Pine Island Bay, West Antarctica

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    F. O. Nitsche


    Full Text Available Increasing evidence for an elaborate subglacial drainage network underneath modern Antarctic ice sheets suggests that basal meltwater has an important influence on ice stream flow. Swath bathymetry surveys from previously glaciated continental margins display morphological features indicative of subglacial meltwater flow in inner shelf areas of some paleo ice stream troughs. Over the last few years several expeditions to the eastern Amundsen Sea embayment (West Antarctica have investigated the paleo ice streams that extended from the Pine Island and Thwaites glaciers. A compilation of high-resolution swath bathymetry data from inner Pine Island Bay reveals details of a rough seabed topography including several deep channels that connect a series of basins. This complex basin and channel network is indicative of meltwater flow beneath the paleo-Pine Island and Thwaites ice streams, along with substantial subglacial water inflow from the east. This meltwater could have enhanced ice flow over the rough bedrock topography. Meltwater features diminish with the onset of linear features north of the basins. Similar features have previously been observed in several other areas, including the Dotson-Getz Trough (western Amundsen Sea embayment and Marguerite Bay (SW Antarctic Peninsula, suggesting that these features may be widespread around the Antarctic margin and that subglacial meltwater drainage played a major role in past ice-sheet dynamics.

  14. Precipitous Birth

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    Jennifer Yee


    Full Text Available Audience: This scenario was developed to educate emergency medicine residents on the management of a precipitous birth in the emergency department (ED. The case is also appropriate for teaching of medical students and advanced practice providers, as well as reviewing the principles of crisis resource management, teamwork, and communication. Introduction: Patients with precipitous birth require providers to manage two patients simultaneously with limited time and resources. Crisis resource management skills will be tested once baby is delivered, and the neonate will require assessment for potential neonatal resuscitation. Objectives: At the conclusion of the simulation session, learners will be able to manage women who have precipitous deliveries, as well as perform neonatal assessment and management. Method: This session was conducted using high-fidelity simulation, followed by a debriefing session and lecture on precipitous birth management and neonatal evaluation.

  15. TCA precipitation. (United States)

    Koontz, Laura


    Trichloroacetic acid (TCA) precipitation of proteins is commonly used to concentrate protein samples or remove contaminants, including salts and detergents, prior to downstream applications such as SDS-PAGE or 2D-gels. TCA precipitation denatures the protein, so it should not be used if the protein must remain in its folded state (e.g., if you want to measure a biochemical activity of the protein). © 2014 Elsevier Inc. All rights reserved.


    McKenzie, T.R.


    A process is given for improving the precipitation of strontium from an aqueous phosphoric-acid-containing solution with nickel or cobalt ferrocyanide by simultaneously precipitating strontium or calcium phosphate. This is accomplished by adding to the ferrocyanide-containing solution calcium or strontium nitrate in a quantity to yield a concentration of from 0.004 to 0.03 and adjusting the pH of the solution to a value of above 8.

  17. Modelling subglacial drainage and its role in ice-ocean interaction (United States)

    Hewitt, Ian; Dallaston, Michael; Wells, Andrew


    Melting at the ice-ocean interface, both beneath ice shelves and at near-vertical tidewater margins, is strongly influenced by discharge of meltwater from beneath the grounded ice. The fresh water source can help to initiate a buoyant plume that rises up the ice face, entraining heat from the ocean to melt the ice. When the subglacial discharge is spatially and temporally variable, it can cause spatial and temporal variations in the melting rate, which in turn may influence ocean circulation in the cavity and ice flow within the shelf. Recent observations of channelized ice shelf bases may have their origin in variable subglacial discharge from beneath the grounded ice. In this work, we use physically-based models of the subglacial drainage system to examine the likely mode of melt water delivery across the grounding line. We find that if subglacial channels (Rothlisberger channels) exist they can be expected to `trumpet' out as the ocean is approached, due to a lack of confining stress to counteract wall melting. This causes a reduction in horizontal momentum in the water and can lead to pronounced localized melting around channel termini. This may lead to increased propensity for calving at such locations. We also examine the effect of subglacial discharge variations on the evolution of a downstream floating ice shelf. We find that lateral variations in the flow across the grounding line can result in variations in plume-driven melting which evolve to create basal channels in the shelf aligned with the flow. The preferred spacing of the channels is controlled by a balance between buoyancy-driven acceleration and turbulent mixing in the ocean layer.

  18. Recharge of a subglacial lake by surface meltwater in northeast Greenland. (United States)

    Willis, Michael J; Herried, Bradley G; Bevis, Michael G; Bell, Robin E


    In a warming climate, surface meltwater production on large ice sheets is expected to increase. If this water is delivered to the ice sheet base it may have important consequences for ice dynamics. For example, basal water distributed in a diffuse network can decrease basal friction and accelerate ice flow, whereas channelized basal water can move quickly to the ice margin, where it can alter fjord circulation and submarine melt rates. Less certain is whether surface meltwater can be trapped and stored in subglacial lakes beneath large ice sheets. Here we show that a subglacial lake in Greenland drained quickly, as seen in the collapse of the ice surface, and then refilled from surface meltwater input. We use digital elevation models from stereo satellite imagery and airborne measurements to resolve elevation changes during the evolution of the surface and basal hydrologic systems at the Flade Isblink ice cap in northeast Greenland. During the autumn of 2011, a collapse basin about 70 metres deep and about 0.4 cubic kilometres in volume formed near the southern summit of the ice cap as a subglacial lake drained into a nearby fjord. Over the next two years, rapid uplift of the floor of the basin (which is approximately 8.4 square kilometres in area) occurred as surface meltwater flowed into crevasses around the basin margin and refilled the subglacial lake. Our observations show that surface meltwater can be trapped and stored at the bed of an ice sheet. Sensible and latent heat released by this trapped meltwater could soften nearby colder basal ice and alter downstream ice dynamics. Heat transport associated with meltwater trapped in subglacial lakes should be considered when predicting how ice sheet behaviour will change in a warming climate.

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

    Milliere, Laure; Verrecchia, Eric; Gussone, Nikolaus


    Calcium (Ca), carbon (C) and oxygen (O) are important elements in terrestrial environment, as their biogeochemical cycles are directly related to the storage of atmospheric carbon. Nevertheless, contrarily to C and O, Ca isotope composition has been only poorly studied in the terrestrial carbonates. Needle Fibre Calcite (NFC) is one of the most common pedogenic carbonates, unless its origin is still under debate. Recent studies explain its formation by precipitation inside fungal hyphae. Due to this possible biogenic origin, NFC can be considered as a potential bridge between the biochemistry (precipitation inside organic structure) and geochemistry (pedogenic carbonate related to soil conditions) of the Ca. Thus, the study of the Ca isotope composition of NFC seem to be of first interest in order to shed light on the behaviour of Ca in terrestrial environment, especially when precipitation of secondary carbonates is involved. The sampling site is situated in the Swiss Jura Mountains and has been chosen due to a previous complete study of the C and O isotope composition of NFC in relation to the ecosystem, which represent a good precondition for the understanding of the NFC Ca isotope signatures in this context. In this study, the implication of the fungi in the origin of NFC is investigated, by comparing the Ca isotope composition of NFC and a purely physicochemical calcite cement (LCC), both precipitated in the same environment. The δ44Ca signature of NFC and LCC crystals were used to determine possible differences of the precipitation rate during their formation. NFC and LCC have similar δ18O composition and are supposed to precipitate at the same temperature (Milliere et al., 2011a). Thus the study of Ca isotope composition of NFC seems to demonstrate that the elongated shape of the calcite needle can be explained by different precipitation processes than the rhombohedric calcite crystals precipitated in the same environment; and more precisely, the specific

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

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


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

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

    Cloud, P; Lajoie, K R


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

  2. The Wilkes subglacial basin eastern margin electrical conductivity anomaly (United States)

    Rizzello, Daniele; Armadillo, Egidio; Ferraccioli, Fausto; Caneva, Giorgio


    We have analyzed the deep conductivity structure at the transition between the Transantarctic Mountains (TAM) and the eastern margin of the WSB in NVL, by means of the GDS (Geomagnetic Deep Sounding) technique, in order to constrain the geodynamical interpretation of this antarctic sector. The TAM form the uplifted flank of the Mesozoic and Cenozoic West Antarctic Rift System. Structure of the TAM rift flank has been partially investigated with different geophysical approaches.The Wilkes Subglacial Basin is a broad depression over 400 km wide at the George V Coast and 1200 km long. Geology, lithospheric structure and tectonics of the Basin are only partially known because the Basin is buried beneath the East Antarctic Ice Sheet and is located in a remote region which makes geophysical exploration logistically challenging. Different authors have proposed contrasting hypothesis regarding the origin of the WSB: it could represent a region of rifted continental crust, or it may have a flexural origin or might represent an "extended terrane". Recently aerogeophysical investigations have demonstrated a strong structural control on the margin. Magnetovariational studies carried out at high geomagnetic latitudes are often hampered by source effects, mainly due to the closeness to the Polar Electrojet currents systems (PEJ). Its presence, in fact, makes the uniform magnetic field assumption, on which the magnetovariational methods are based on, often invalid, which outcome is a bias in the GDS transfer functions and to compromise the reliability of the inverted models. Data from the aforementioned campaigns have been then processed under the ISEE project (Ice Sheet Electromagnetic Experiment), aimed at evaluate and mitigate the bias effect of the PEJ on geomagnetic an magnetotelluric transfer functions at high geomagnetic latitudes, by means of suitable processing algorithms, developed upon a statistical analysis study on PEJ effects (Rizzello et al. 2013). Recent results

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

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    Yuki Kezuka


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

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

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


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

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

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


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

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

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    Florea Lee J.


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

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

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


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

  8. Global Catalogue of the Martian Valley Networks: Evidences for Fluvial, Sapping and Subglacial Processes on Early Mars (United States)

    Grau Galofre, A.; Jellinek, A. M.


    We use erosion models and statistical morphometry schemes to show quantitative evidence for fluvial, glacial, groundwater sapping and subglacial erosion on the Noachian highlands, to then build a global map of valley network origin and distribution.

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

    NARCIS (Netherlands)

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


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

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

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


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

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

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


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

  12. Treatment Of Metal-Mine Effluents By Limestone Neutralization And Calcite Co-Precipitation (United States)

    The U.S. Geological Survey - Leetown Science Center and the Colorado School of Mines have developed a remediation process for the treatment of metals in circumneutral mining influenced waters. The process involves treatment with a pulsed limestone bed (PLB) system, followed by c...

  13. Treatment Of Metal-Mine Effluents By Limestone Neutralization And Calcite Co-Precipitation (Presentation) (United States)

    The U.S. Geological Survey - Leetown Science Center and the Colorado School of Mines have developed a remediation process for the treatment of metals in circumneutral mining influenced waters. The process involves treatment with a pulsed limestone bed (PLB) system, followed by c...

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

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


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

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

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


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

  16. Rapid Submarine Melting Driven by Subglacial Discharge, LeConte Glacier, Alaska (United States)

    Motyka, R. J.; Dryer, W. P.; Amundson, J. M.; Truffer, M.; Fahnestock, M. A.


    Submarine melting impacts the stability of tidewater glaciers worldwide, but the connections between the ocean, a warming climate, and retreat of outlet glaciers are poorly known. Clearly warm seawater plays an important role, but the tremendous heat potential resident in oceans and fjords must first be brought into contact with outlet glacier termini in order to affect them. We show here that for many glaciers, the principal process driving high rates of submarine melting is subglacial discharge of freshwater. This buoyant discharge draws in warm seawater, entraining it in a turbulent upwelling convective flow along the submarine face that melts glacier ice. To capture the effect of changing subglacial discharge on submarine melting, we conducted four days of hydrographic transects during late summer 2012 at LeConte Glacier, Alaska. A major rainstorm allowed us to directly measure the influence of large changes in subglacial discharge. We found strong submarine melt rates that increased from 9.0×1.0 to 16.8×1.3 m/d (ice face equivalent frontal ablation) as subglacial discharge increased from 130 to 440 m^3/s over a four day period. This subglacial discharge drove influx of warm seawater (thermal forcing ~ 8° C) to the terminus with fluxes increasing from 1800 to 4000 m3/s. Our ice equivalent frontal ablation rates due to submarine melting are two to three times values found for Greenland glaciers, where thermal forcing is substantially lower (~ 1 - 4 °C) and termini are wider. Together, these studies confirm the importance of submarine melting at grounded glaciers. At LeConte, the total frontal ablation rate (calving flux plus submarine melting) is ~ 3.0 x10^6 m^3/d w.e., which far surpasses surface ablation. One-half to two-thirds of the frontal ablation during September 2012 can be attributed to submarine melting. A two-layer model driven by a buoyant plume of subglacial discharge has been previously invoked to describe the proglacial fjord circulation

  17. Prospects of obtaining samples of bottom sediments from subglacial lake Vostok

    Directory of Open Access Journals (Sweden)

    Н. И. Васильев


    Full Text Available The paper proves the timeliness of obtaining and examining bottom sediments from subglacial Lake Vostok. Predictive geological section of Lake Vostok and information value of bottom sediments have been examined. Severe requirements towards environmental security of lake examinations and sampling of bottom sediments rule out the use of conventional drilling technologies, as they would pollute the lake with injection liquid from the borehole. In order to carry out sampling of bottom sediments from the subglacial lake, it is proposed to use a dynamically balanced tool string, which enables rotary drilling without any external support on borehole walls to transmit counter torque.     A theoretical analysis has been carried out to assess the operation of the tool string, which is a two-mass oscillatory electromechanical system of reciprocating and rotating motion (RRM with two degrees of freedom.

  18. Manganese-calcium intermixing facilitates heteroepitaxial growth at the 101¯4 calcite-water interface

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.; Du, Yingge; Kovarik, Libor; Varga, Tamas; Arey, Bruce W.; Qafoku, Odeta; Kerisit, Sebastien


    In situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10-14) surface of calcite (CaCO3) single crystals following reaction with Mn2+-bearing aqueous solutions with a range of initial concentrations. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces and in situ time-sequenced measurements demonstrated that their growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2+-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO3) and calcite display a 10% lattice mismatch, based on the area of their (10-14) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals with calcite-equilibrated aqueous solutions with concentrations of up to 250 µM MnCl2 and analyzed to determine the composition of the surface precipitates. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO3 solid solution with a spatially complex composition atop the calcite surface, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO3 for the thickest coatings. These findings explain the measured growth rates (the effective lattice mismatch was much smaller than nominal mismatch) and highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.

  19. Geomorphological evidence of channelized subglacial meltwater drainage under the Scandinavian Ice Sheet (United States)

    Adamczyk, Aleksander; Wysota, Wojciech; Sobiech, Marcin; Piotrowski, Jan A.


    The impact of subglacial meltwater erosion on shaping glacial landscapes is contentious and often difficult to constrain due to the lack of unequivocal diagnostic criteria. The same holds for the role of subglacial meltwater in glacier movement processes and sediment transport and deposition. Here we present new evidence of widespread channelized erosion under the southern, soft-bedded fringe of the last Scandinavian Ice Sheet (SIS) based on high-resolution terrain analysis with LiDAR imagery. We identify several tens of sites with "glacial curvilineation" landscapes first recognized by Lesemann et al. (2010, 2014) and considered as evidence of erosion by turbulent meltwater flows at the ice/bed interface. The "glacial curvilineation" landscapes mapped here consist of sets of parallel, winding ridges typically several metres high and up to several kilometres long occupying glacial overdeepenings and tunnel valleys. The ridges are aligned approximately perpendicular to the past ice sheet margins and they are composed of various deposits often pre-dating the last ice advance. We interpret them as erosional remnants of older landscapes dissected by high-energy subglacial meltwater flows. These findings suggest that the palaeoglaciological significance of meltwater drainage under the southern portion of SIS may have been grossly underestimated. References Lesemann, J.-E., Piotrowski, J.A. and Wysota, W., 2010. „Glacial curvilineations": New glacial landforms produced by longitudinal vortices in subglacial meltwater flows. Geomorphology 120, 153-161. Lesemann, J.-E., Piotrowski, J.A. and Wysota, W., 2014. Genesis of the "glacial curvilineation" landscape by meltwater processes under the former Scandinavian Ice Sheet, Poland. Sedimentary Geology 312, 1-18.

  20. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph (United States)

    Harrold, Zoë R.; Skidmore, Mark L.; Hamilton, Trinity L.; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E.


    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O32−), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O32− that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO42−) several orders of magnitude higher than those of S2O32−. Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O32−, CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O32− as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O32−-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O32− by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment. PMID:26712544

  1. Subglacial discharges create fluctuating foraging hotspots for sea birds in tidewater glacier bays (United States)

    Urbanski, Jacek Andrzej; Stempniewicz, Lech; Węsławski, Jan Marcin; Dragańska-Deja, Katarzyna; Wochna, Agnieszka; Goc, Michał; Iliszko, Lech


    Although the processes occurring at the front of an ice face in tidewater glacier bays still await thorough investigation, their importance to the rapidly changing polar environment is spurring a considerable research effort. Glacier melting, sediment delivery and the formation of seabird foraging hotspots are governed by subglacial discharges of meltwater. We have combined the results of tracking black-legged kittiwakes Rissa tridactyla equipped with GPS loggers, analyses of satellite images and in situ measurements of water temperature, salinity and turbidity in order to examine the magnitude and variability of such hotspots in the context of glacier bay hydrology. Small though these hotspots are in size, foraging in them appears to be highly intensive. They come into existence only if the subglacial discharge reaches the surface, if the entrainment velocity at a conduit is high and if there is sufficient macroplankton in the entrainment layer. The position and type of subglacial discharges may fluctuate in time and space, thereby influencing glacier bay hydrology and the occurrence of foraging hotspots. PMID:28266602

  2. Self-affine subglacial roughness: consequences for radar scattering and basal water discrimination in northern Greenland (United States)

    Jordan, Thomas M.; Cooper, Michael A.; Schroeder, Dustin M.; Williams, Christopher N.; Paden, John D.; Siegert, Martin J.; Bamber, Jonathan L.


    Subglacial roughness can be determined at a variety of length scales from radio-echo sounding (RES) data either via statistical analysis of topography or inferred from basal radar scattering. Past studies have demonstrated that subglacial terrain exhibits self-affine (power law) roughness scaling behaviour, but existing radar scattering models do not take this into account. Here, using RES data from northern Greenland, we introduce a self-affine statistical framework that enables a consistent integration of topographic-scale roughness with the electromagnetic theory of radar scattering. We demonstrate that the degree of radar scattering, quantified using the waveform abruptness (pulse peakiness), is topographically controlled by the Hurst (roughness power law) exponent. Notably, specular bed reflections are associated with a lower Hurst exponent, with diffuse scattering associated with a higher Hurst exponent. Abrupt waveforms (specular reflections) have previously been used as a RES diagnostic for basal water, and to test this assumption we compare our radar scattering map with a recent prediction for the basal thermal state. We demonstrate that the majority of thawed regions (above pressure melting point) exhibit a diffuse scattering signature, which is in contradiction to the prior approach. Self-affine statistics provide a generalised model for subglacial terrain and can improve our understanding of the relationship between basal properties and ice-sheet dynamics.

  3. Preliminary Analysis of Life within a Former Subglacial Lake Sediment in Antarctica

    Directory of Open Access Journals (Sweden)

    Gavin Burns


    Full Text Available Since the first descriptions of Antarctic subglacial lakes, there has been a growing interest and awareness of the possibility that life will exist and potentially thrive in these unique and little known environments. The unusual combination of selection pressures, and isolation from the rest of the biosphere, might have led to novel adaptations and physiology not seen before, or indeed to the potential discovery of relic populations that may have become extinct elsewhere. Here we report the first microbiological analysis of a sample taken from a former subglacial lake sediment in Antarctica (Lake Hodgson, on the Antarctic Peninsula. This is one of a number of subglacial lakes just emerging at the margins of the Antarctic ice sheet due to the renewed onset of deglaciation. Microbial diversity was divided into 23.8% Actinobacteria, 21.6% Proteobacteria, 20.2% Planctomycetes and 11.6% Chloroflexi, characteristic of a range of habitat types ( Overall, common sequences were neither distinctly polar, low temperature, freshwater nor marine. Twenty three percent of this diversity could only be identified to “unidentified bacterium”. Clearly these are diverse ecosystems with enormous potential.

  4. Subglacial discharges create fluctuating foraging hotspots for sea birds in tidewater glacier bays (United States)

    Urbanski, Jacek Andrzej; Stempniewicz, Lech; Węsławski, Jan Marcin; Dragańska-Deja, Katarzyna; Wochna, Agnieszka; Goc, Michał; Iliszko, Lech


    Although the processes occurring at the front of an ice face in tidewater glacier bays still await thorough investigation, their importance to the rapidly changing polar environment is spurring a considerable research effort. Glacier melting, sediment delivery and the formation of seabird foraging hotspots are governed by subglacial discharges of meltwater. We have combined the results of tracking black-legged kittiwakes Rissa tridactyla equipped with GPS loggers, analyses of satellite images and in situ measurements of water temperature, salinity and turbidity in order to examine the magnitude and variability of such hotspots in the context of glacier bay hydrology. Small though these hotspots are in size, foraging in them appears to be highly intensive. They come into existence only if the subglacial discharge reaches the surface, if the entrainment velocity at a conduit is high and if there is sufficient macroplankton in the entrainment layer. The position and type of subglacial discharges may fluctuate in time and space, thereby influencing glacier bay hydrology and the occurrence of foraging hotspots.

  5. Potential Activity of Subglacial Microbiota Transported to Anoxic River Delta Sediments

    DEFF Research Database (Denmark)

    Cameron, Karen A.; Stibal, Marek; Olsen, Nikoline S.


    The Watson River drains a portion of the SW Greenland ice sheet, transporting microbial communities from subglacial environments to a delta at the head of Søndre Strømfjord. This study investigates the potential activity and community shifts of glacial microbiota deposited and buried under layers...... shift in predominant community members and a decline in diversity and cell abundance. These results highlight the need for further investigations into the fate of subglacial microbiota within downstream environments.......The Watson River drains a portion of the SW Greenland ice sheet, transporting microbial communities from subglacial environments to a delta at the head of Søndre Strømfjord. This study investigates the potential activity and community shifts of glacial microbiota deposited and buried under layers...... of sediments within the river delta. A long-term (12-month) incubation experiment was established using Watson River delta sediment under anaerobic conditions, with and without CO2/H2 enrichment. Within CO2/H2-amended incubations, sulphate depletion and a shift in the microbial community to a 52% predominance...

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

    DEFF Research Database (Denmark)

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


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

  7. Numerical modelling of esker formation in semi-circular subglacial channels (United States)

    Beaud, Flavien; Flowers, Gwenn E.; Venditti, Jeremy G.


    Eskers hold valuable information about past subglacial hydraulic conditions in their spatial organization, geometry, and sedimentary structures. The relations between hydraulic conditions and esker properties are nevertheless intricate as the formation of eskers has been mainly inferred from descriptive theories, about which a consensus has yet to be reached. Eskers are prevalent in areas of rigid bed and thin till cover and their formation is thought to be predominantly controlled by either water or sediment availability. In this study, we develop a 1-D numerical model of sediment transport in semi-circular bedrock-floored channels to explore the physical processes leading to esker formation. The model encompasses channel evolution by melt-opening created by the viscous heat dissipated as water flows, the creep closure of the ice walls, and changes in cross-sectional area due to sediment accumulation and removal. We find that a bottleneck in sediment transport close to the terminus is an inherent characteristic of subglacial channels. Creep closure is reduced as the ice thins towards the terminus and hydraulic potential gradients decline, thus reducing shear stresses. This bottleneck is accentuated when water discharge drops in a well established channel. We find the conditions most conducive to sediment deposition are low ice-surface slopes within several kilometres of the terminus and water discharge fluctuations over a few to several weeks. The model also produces shear stresses large enough to transport boulders under typical melt-season conditions. Our results thus suggest that incipient eskers form toward the end of the melt season, provided water input and sediment supply are sufficient. Overall these findings corroborate the theory that eskers are formed progressively during the waning stage of an ice sheet, although we suggest that eskers are a natural manifestation of the subglacial hydraulic system in the presence of an adequate trade-off between

  8. Investigating the hydrological origins of Blood Falls - geomicrobiological insights into a briny subglacial Antarctic aquifer (United States)

    Mikucki, J.; Tulaczyk, S. M.; Purcell, A. M.; Dachwald, B.; Lyons, W. B.; Welch, K. A.; Auken, E.; Dugan, H. A.; Walter, J. I.; Pettit, E. C.; Doran, P. T.; Virginia, R. A.; Schamper, C.; Foley, N.; Feldmann, M.; Espe, C.; Ghosh, D.; Francke, G.


    Subglacial waters tend to accumulate solutes from extensive rock-water interactions, which, when released to the surface, can provide nutrients to surface ecosystems providing a 'hot spot' for microbial communities. Blood Falls, an iron-rich, saline feature at the terminus of Taylor Glacier in the McMurdo Dry Valleys, Antarctica is a well-studied subglacial discharge. Here we present an overview of geophysical surveys, thermomechanical drilling exploration and geomicrobiological analyses of the Blood Falls system. A helicopter-borne transient electromagnetic system (SkyTEM) flown over the Taylor Glacier revealed a surprisingly extensive subglacial aquifer and indicates that Blood Falls may be the only surface manifestation of this extensive briny groundwater. Ground-based temperature sensing and GPR data combined with the helicopter-borne TEM data enabled targeted drilling into the englacial conduit that delivers brine to the surface. During the 2014-15 austral summer field season, we used a novel ice-melting drill (the IceMole) to collect englacial brine for geomicrobiological analyses. Results from previously collected outflow and more recent samples indicate that the brine harbors a metabolically active microbial community that persists, despite cold, dark isolation. Isotope geochemistry and molecular analysis of functional genes from BF suggested that a catalytic or 'cryptic' sulfur cycle was linked to iron reduction. Recent metagenomic analysis confirms the presence of numerous genes involved in oxidative and reductive sulfur transformations. Metagenomic and metabolic activity data also indicate that subglacial dark CO2 fixation occurs via various pathways. Genes encoding key steps in CO2 fixation pathways including the Calvin Benson Basham and Wood Ljungdahl pathway were present and brine samples showed measureable uptake of 14C-labeled bicarbonate. These results support the notion that, like the deep subsurface, subglacial environments are chemosynthetic

  9. Geophysical investigations of subglacial Antarctic lakes: identifying drill sites for lake access (United States)

    Woodward, J.; Tulaczyk, S. M.; Smith, A.; Walter, J.; Ross, N.; Fricker, H. A.; Siegert, M. J.; Pettersson, R.; Thoma, M.; Corr, H.; King, E. C.; Vaughan, D.


    Subglacial lakes are regarded as viable habitats for novel microbial life forms and may contain sedimentary palaeo-environmental records which would provide critical insights into the glacial history of Antarctica. In-situ sampling and analysis is the only way to explore these lake environments. In order to successfully plan access programs detailed geophysical investigations, in particular seismic measurements of water depth, are required to identify suitable drill sites. Prior to the austral summer of 2006/07 measurements of water depths only existed for Subglacial Lake Vostok, and spatial coverage was limited due to the size of the lake. More recently, active source seismic experiments have been carried out over three subglacial lakes, South Pole Lake, Subglacial Lake Ellsworth (SLE) and Subglacial Lake Whillans (SLW). With drilling programs now funded for SLW (access planned for 2011/12) and SLE (access planned for 2012/13) we present results from the geophysical experiments at SLE and SLW to allow the identification of primary drill sites. The two lakes are very different. Geophysical results from SLE suggest that the lake is over 155 m deep and has been a stable system for much of the Holocene. We propose that in order to optimize the chances of successful access and sampling, the entry site should be located in an area with a melting interface near the centre of the lake where water depths are in the order of 100 m. This is away from the down-lake end which shows a higher possibility for basal freezing, with the consequent risk to equipment deployment and retrieval. In contrast, SLW is characterized by dynamic filling and draining over short (2-3 year periods) and most likely has a shallow water column (currently estimated to be in the order of 5-10 m). We suggest that the most suitable location for access will be the centre of the elevation change anomaly recorded over the lake. This point is near equidistant from the lake shoreline features identified from

  10. Implications of sediment transport by subglacial water flow for interpreting contemporary glacial erosion rates (United States)

    Beaud, Flavien; Flowers, Gwenn E.; Venditti, Jeremy G.


    The role of glaciers in landscape evolution is central to the interactions between climate and tectonic forces at high latitudes and in mountainous regions. Sediment yields from glacierized basins are used to quantify contemporary erosion rates on seasonal to decadal timescales, often under the assumption that subglacial water flow is the main contributor to these yields. Two recent studies have furthermore used such sediment fluxes to calibrate a glacial erosion rule, where erosion rate scales with ice sliding speed raised to a power greater than one. Subglacial sediment transport by water flow has however seldom been studied, thus the controls on sediment yield from glacierized basins remain enigmatic. To bridge this gap, we develop a 1-D model of morphodynamics in semi-circular bedrock-floored subglacial channels. We adapt a sediment conservation law from the fluvial literature, developed for both mixed bedrock / alluvial and alluvial conditions, to subglacial channels. Channel evolution is a function of the traditional melt-opening due to viscous heat dissipation from the water flow, and creep closure of the overlying ice, to which we add the closure or enlargement due to sediment deposition or removal, respectively. Using a simple ice geometry representing a land-terminating glacier, we find that the shear stresses produced by the water flow on the bed decrease significantly near the terminus. As the ice thins, creep closure decreases and large hydraulic potential gradients cannot be sustained. The resulting gradients in sediment transport lead to a bottleneck, and sediment accumulates if the sediment supply is adequate. A similar bottleneck occurs if a channel is well established and water discharge drops. Whether such constriction happens in space of time, in the presence of a sufficiently large sediment supply sediment accumulates temporarily near the terminus, followed shortly thereafter by enhanced sediment transport. Reduction in the cross-sectional area

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

    Directory of Open Access Journals (Sweden)

    G. J. van der Zwaan


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

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

    Middleton, Heather A.; Nelson, Campbell S.


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    DEFF Research Database (Denmark)

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


    We have used density functional theory with the COSMO-RS implicit solvent model to predict the pKa for the deprotonation of bicarbonate to carbonate, i.e. HCO3− CO32− + H+, when HCO3− is included in, and adsorbed on, a calcite surface. We have used cluster models (80–100 atoms) to represent...... the flat {10.4} surface, acute steps, obtuse steps, two types of kinks on the acute step and two types of kinks on the obtuse steps. Based on the predicted pKa values, which range from −6.0 to 2.4 depending on the surface site, we conclude that bicarbonate deprotonates to carbonate when it is in calcite...... even when pH in solution is very low. This is true for all surface sites, even for solutions where 2.4 bicarbonate is adsorbed on calcite, the predicted pKa for deprotonation is 7.5, which is ∼3 pH units lower than in aqueous solution...

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

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


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

  16. Rate of radiocarbon retention onto calcite by isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Directory of Open Access Journals (Sweden)

    Vučinić Dušica R.


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

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

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


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

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

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


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

  20. The Subglacial Access and Fast Ice Research Experiment (SAFIRE): 1. Borehole-based englacial and subglacial measurements from a rapidly-moving tidewater glacier: Store Glacier, Greenland (United States)

    Hubbard, Bryn; Doyle, Samuel; Christoffersen, Poul; Young, Tun Jan; Hofstede, Coen; Hubbard, Alun; Box, Jason; Todd, Joe; Bougamont, Marion


    As part of the Subglacial Access and Fast Ice Research Experiment (SAFIRE) pressurised hot water was used to drill four 603-616 m-long boreholes to the bed of the Greenland Ice Sheet at a site located 30 km from the calving front of fast-flowing, marine-terminating Store Glacier (70 degrees N, ~1000 m elevation). Four wired sensor strings were successfully installed in three of the boreholes. These included a thermistor string to obtain the englacial temperature profile installed in the same borehole as a string of tilt sensors to measure borehole deformation, and two sets of combined water pressure, electrical conductivity and turbidity sensors installed just above the bed in separate, adjacent boreholes. The boreholes made a strong hydrological connection to the bed during drilling, draining rapidly to ~80 m below the ice surface. The connection of subsequent boreholes was observed as a perturbation in water pressure and temperature recorded in neighbouring boreholes, indicating an effective hydrological connection between them. The sensors, which were wired to data-loggers at the surface, operated for between ~30 and >80 days from late summer into autumn before the cables stretched and snapped, with the lowermost sensors failing first. The records obtained from these sensors reveal (i) subglacial water pressures that were close to overburden but which generally increased through the period of measurement and varied diurnally by ~0.3 m, (ii) a minimum englacial temperature of -21 degrees C underlain by a zone of temperate ice, some tens of m thick, located immediately above the bed, and (iii) high rates of internal deformation and strain that increased towards the bed. These borehole observations are complemented by GPS measurements of ice motion, meteorological data, and seismic and radar surveys.

  1. Coupling autotrophic sulfide mineral weathering with dolomite dissolution in a subglacial ecosystem (United States)

    Boyd, E. S.; Hamilton, T. L.; Havig, J. R.; Lange, R.; Murter, E.; Skidmore, M. L.; Peters, J.; Shock, E.


    Evidence in the rock record suggests that glaciers have been present and covered a significant portion of the Earth's surface since the putative Mozaan Glaciation (circa 2.9 Ga) and were demonstrated recently to host active microbial communities that impact local and global biogeochemical cycles. In the present study, we applied a microcosm-based radioisotopic biocarbonate tracer approach to quantify rates of inorganic carbon assimilation in sediments sampled from beneath Robertson Glacier (RG), Alberta, Canada at 4°C. Rates of inorganic carbon assimilation were stimulated by the addition of ammonium and phosphate, suggesting that these nutrients might be of limited supply in the subglacial environment or, in the case of ammonia, might be serving as a source of reductant fueling inorganic carbon fixation. Geochemical analyses were used to assess the potential redox couples that might be fueling autotrophic activity. The difference in the concentration of sulfate (2.4 mM) in unamended microcosm fluids when compared to fluids sampled from killed controls following 180 days incubation suggests that inorganic carbon assimilation in microcosms is driven by microbial populations involved in the oxidation of mineral sulfides, most likely pyrite. Amendment of microcosms with 1 mM ammonia led to near stoichiometric production of nitrate (~890 μM) and lower production of sulfate (~1.5 mM), indicating that the enhanced activity observed in ammonia treated microcosms is likely due to the stimulation of autotrophic ammonia oxidizing populations. The isotopic composition of dissolved organic carbon in subglacial meltwaters ranged was -24.40 ‰ versus VPDB, which is consistent with a source for this organic carbon via the activity of autotrophs that use the Calvin cycle of inorganic carbon fixation. Quantification and sequencing of transcripts of Calvin cycle biomarker genes (ribulose-1,5 bisphosphate carboxylase/oxygenase, encoded by cbbL) suggest the presence of a ubiquitous

  2. The use of magmatic water to reconstruct palaeo-ice thicknesses during subglacial rhyolitic eruptions (United States)

    Owen, Jacqueline; Tuffen, Hugh; McGarvie, Dave; Pinkerton, Harry; Wilson, Lionel


    Magma degassing patterns can potentially be used to reconstruct ice thicknesses during subglacial eruptions, as the pressure dependence of water solubility in silicate melts is reasonably well constrained. The amount of water remaining in the quenched bulk glasses should record the quenching pressure, which, in a subglacial setting, will be dependent on the pressure of overlying ice and/or meltwater that was present. This reconstruction technique has been applied to several basaltic volcanoes[1]. In one study the dissolved water contents was seen to vary as a function of altitude, consistent with the presence of an ice sheet[2]. Similar techniques have been applied to a rhyolitic volcano, as described below. Bláhnúkur is a small-volume rhyolitic, subglacial volcano at Torfajökull volcano, southern Iceland[3] that erupted at ~95 ka[4]. 45 glassy lava samples were collected from a variety of elevations and lithofacies types. These samples were analysed for water content using infra-red spectroscopy (FTIR), and pressure-solubility relationships were calculated using VolatileCalc[5]. The results reveal a general decrease in water concentration with elevation, consistent with the presence of an ice sheet with a surface elevation of ~1,050 m a.s.l.. This corresponds with an ice thickness of ~450 m, consistent with the field evidence from tuyas of a similar age within the same region[6]. Furthermore, the results suggest an eruptive temperature of 850°C and 0 ppm CO2. However, not all samples agree with this overall trend. We suggest that samples with anomalously low water contents could have formed in regions where there was meltwater drainage which lowered the quenching pressure[7]. By contrast, water-rich samples could reflect intrusive formation resulting in loading by rock as well as ice[8]. Crucially though, the anomalous values are all from the same locations, suggesting that there are processes that are specifically affecting certain localities. In order to use

  3. Culturable bacteria in subglacial sediments and ice from two Southern Hemisphere glaciers. (United States)

    Foght, J; Aislabie, J; Turner, S; Brown, C E; Ryburn, J; Saul, D J; Lawson, W


    Viable prokaryotes have been detected in basal sediments beneath the few Northern Hemisphere glaciers that have been sampled for microbial communities. However, parallel studies have not previously been conducted in the Southern Hemisphere, and subglacial environments in general are a new and underexplored niche for microbes. Unfrozen subglacial sediments and overlying glacier ice samples collected aseptically from the Fox Glacier and Franz Josef Glacier in the Southern Alps of New Zealand now have been shown to harbor viable microbial populations. Total direct counts of 2-7 x 10(6) cells g(-1) dry weight sediment were observed, whereas culturable aerobic heterotrophs ranged from 6-9 x 10(5) colony-forming units g(-1) dry weight. Viable counts in the glacier ice typically were 3-4 orders of magnitude smaller than in sediment. Nitrate-reducing and ferric iron-reducing bacteria were detected in sediment samples from both glaciers, but were few or below detection limits in the ice samples. Nitrogen-fixing bacteria were detected only in the Fox Glacier sediment. Restriction fragment analysis of 16S rDNA amplified from 37 pure cultures of aerobic heterotrophs capable of growth at 4 degrees C yielded 23 distinct groups, of which 11 were identified as beta-Proteobacteria. 16S rDNA sequences from representatives of these 11 groups were analyzed phylogenetically and shown to cluster with bacteria such as Polaromonas vacuolata and Rhodoferax antarcticus, or with clones obtained from permanently cold environments. Chemical analysis of sediment and ice samples revealed a dilute environment for microbial life. Nevertheless, both the sediment samples and one ice sample demonstrated substantial aerobic mineralization of 14C-acetate at 8 degrees C, indicating that sufficient nutrients and viable psychrotolerant microbes were present to support metabolism. Unfrozen subglacial sediments may represent a significant global reservoir of biological activity with the potential to

  4. Seismicity and Subglacial Hydrological Processes During Early Melt Season, Engabreen, Norway (United States)

    Moore, P. L.; Winberry, J.; Christianson, K.; Iverson, N. R.; Anandakrishnan, S.; Jackson, M.; Cohen, D. O.


    A broad array of mechanical and seismic instrumentation was deployed during May 2011 in subglacial tunnels beneath Engabreen, an outlet glacier of the Svartisen ice cap in northern Norway. Following a warm spell, increased melt supply to the glacier bed prompted several episodes of transient ice uplift and establishment of a more efficient basal hydraulic system. In each event, hydrological adjustment was accompanied by three distinct seismic sources, two of which have not been previously documented in glacial environments. High-frequency impulsive events with dominant Rayleigh-wave energy increased their rate-of-occurrence immediately prior to an abrupt change in basal water pressure and normal stress. These events are inferred represent propagation of water-filled crevasses permitting meltwater access to the bed. Ultra-long period (ULP, hydraulic jacking. During recovery of basal water pressure, vertical ULP deflections were correlated with increases in basal water flux and doubling of local subglacial seismic noise. The increase in seismic noise may represent turbulent flow and bedload sediment transport through newly-opened subglacial meltwater passages. The vertical ULP signal therefore likely reflects meltwater-forced uplift of ice. Surprisingly, although there was direct evidence that jacking activated frictional slip at the bed, there was no clear seismic expression of slip. Thus, broadband seismometers appear to have captured the transit of meltwater through crevasses, into isolated pockets at the glacier bed and then, by promoting ice uplift, draining though newly-established meltwater passages along the bed. Similar seismic sources could be detected elsewhere with strategically-located broadband seismic instrumentation, providing a means of remotely monitoring the hydrological processes that control ice motion.

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

    Kimball, Justine; Eagle, Robert; Dunbar, Robert


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

  6. Utilization of calcite produced in Turkey for paper coating

    Directory of Open Access Journals (Sweden)

    Hüdaverdi Eroğlu


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

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

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


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

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

    Directory of Open Access Journals (Sweden)

    Leif Erik Walther

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

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

    Directory of Open Access Journals (Sweden)

    L. Beaufort


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

  10. Small scale high resolution LiDAR measurements of a subglacial conduit (United States)

    Mankoff, K. D.; Gulley, J.


    We present direct measurements of surface roughness in a sub-glacial conduit system underneath the Rieperbreen Glacier, Svalbard, Norway. Data was collected with a low-cost (129 USD) Microsoft Kinect video game device used as a LIDAR sensor. Surface roughness is a primary control on water flow in rivers, channels, and cave conduit systems and understanding the effects of surface roughness on water flow has been problematic due to lack of direct measurements of roughness in natural systems. We use the ice scallop dimensions to derive flow velocity and explore implications of the changing roughness parameters as the cave grows and shrinks.

  11. Photogrammetric recognition of subglacial drainage channels during glacier lake outburst events (United States)

    Schwalbe, Ellen; Koschitzki, Robert


    In recent years, many glaciers all over the world have been distinctly retreating and thinning. One of the consequences of this is the increase of so called glacier lake outburst flood events (GLOFs): Lakes that have been dammed by a glacier spontaneously start to drain through a subglacial channel underneath the glacier due to their outweighing hydrostatic pressure. In a short period of time, the lake water drains under the glacier and causes floods in downstream valleys. In many cases the latter become hazardous for people and their property. Due to glacier movement, the tunnel will soon collapse, and the glacier lake refills, thus starting a new GLOF cycle. The mechanisms ruling GLOF events are yet still not fully understood by glaciologists. Thus, there is a demand for data and measurement values that can help to understand and model the phenomena. In view of the above, we will show how photogrammetric image sequence analysis can be used to collect data which allows for drawing conclusions about the location and development of a subglacial channel. The work is a follow-up on earlier work on a photogrammetric GLOF early warning system (Mulsow et. al., 2013). For the purpose of detecting the subglacial tunnel, a camera has been installed in a pilot study to observe the area of the Colonia glacier (Northern Patagonian ice field) where it dams the lake Lago Cachet II. To verify the hypothesis, that the course of the subglacial tunnel is indicated by irregular surface motion patterns during its collapse, the camera acquired image sequences of the glacier surface during several GLOF events. Applying LSM-based tracking techniques to these image sequences, surface feature motion trajectories could be obtained for a dense raster of glacier points. Since only a single camera has been used for image sequence acquisition, depth information is required to scale the trajectories. Thus, for scaling and georeferencing of the measurements a GPS-supported photogrammetric network

  12. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    DEFF Research Database (Denmark)

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


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

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

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


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

  14. Biologically mediated phosphorus precipitation in wastewater treatment with microalgae. (United States)

    Larsdotter, K; La Cour Jansen, J; Dalhammar, G


    A lab-scale continuous microalgal culture was grown on sterile-filtered wastewater in order to clarify the phosphorus removing mechanisms in a microalgal treatment step that treats residual phosphorus from a hydroponic wastewater treatment pilot plant. The phosphorus assimilation was dependent on algal biomass production, whereas the chemical precipitation was dependent on phosphorus load, i.e. an increase in average precipitation rate with decreased hydraulic retention time was observed. The chemical precipitation was mainly a result of the increased pH, which was biologically mediated by the photosynthesising algae. The precipitate was composed of a calcium phosphate with magnesium included, magnesium hydroxide and calcite. A significant nitrogen removal was also experienced, which implies that the microalgal wastewater treatment is appropriate both for phosphorus and nitrogen removal.

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

    Energy Technology Data Exchange (ETDEWEB)

    Bakke, N.E.


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

  16. Bioremediation of strontium (Sr) contaminated aquifer quartz sand based on carbonate precipitation induced by Sr resistant Halomonas sp. (United States)

    Achal, Varenyam; Pan, Xiangliang; Zhang, Daoyong


    Contamination of aquifers or sediments by radioactive strontium ((90)Sr) is a significant environmental problem. In the present study, microbially induced calcite precipitation (MICP) was evaluated for its potential to remediate strontium from aquifer quartz sand. A Sr resistant urease producing Halomonas sp. was characterized for its potential role in bioremediation. The bacterial strain removed 80% of Sr from soluble-exchangeable fraction of aquifer quartz sand. X-ray diffraction detected calcite, vaterite and aragonite along with calcite-strontianite (SrCO(3)) solid solution in bioremediated sample with indications that Sr was incorporated into the calcite. Scanning electron micrography coupled with energy-dispersive X-ray further confirmed MICP process in remediation. The study showed that MICP sequesters soluble strontium as biominerals and could play an important role in strontium bioremediation from both ecological and greener point of view. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

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


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

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

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


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

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

    Directory of Open Access Journals (Sweden)

    J. B. Ries


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

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

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

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

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


    composition of the host sediment differs significantly from the siderite concretions. The δ13C values of the Gosau host sediment reflect marine conditions, whereas the oxygen isotope values are best explained by meteoric overprint. Lipid biomarkers have been extracted before and after dissolution of the concretions in order to assess their authenticity and to exclude recent surface contamination. In the following, only the biomarkers extracted after dissolution are discussed, since they are thought to be related to concretion formation. The calcite concretions comprise abundant plant wax derived long-chain n-alkanes, reflecting high terrestrial input. Bacterial, terminally-branched fatty acids were found, but in overall low abundance. The siderite concretions did not yield biomarkers due to their high maturity. No archaeal biomarkers were found in any of the concretions. Considering the presence of framboidal pyrite, the moderately low δ13C values, and the biomarker inventory, bacterial sulfate reduction apparently contributed to the formation of the calcite concretions in a brackish environment. In contrast, ongoing sulfate reduction and resultant hydrogen sulfide production inhibit siderite precipitation. Therefore, the low δ13C values of the siderite concretions are best explained by bacterial iron reduction.

  1. Subglacial hydrological modelling of a rapid lake drainage event on the Russell Glacier catchment, SW Greenland (United States)

    Dow, C. F.; Pimentel, S.; Doyle, S. H.; Booth, A. D.; Fitzpatrick, A.; Jones, G. A.; Kulessa, B.; Hubbard, A.


    We use local-scale subglacial hydrological models to assess the development of the basal drainage system in response to a rapid lake-tapping event on the Russell Glacier catchment, SW Greenland. Water inputs to the model are constrained by in-situ records of the lake drainage rate. Subglacial conditions are estimated from active seismic line analysis including basal topography and substrate characteristics. A borehole slug test model is used to determine the radial flux of water from the drainage input point. Water flowing in the downstream direction is used to drive a 1-D flowband model, which allows development of interacting channelised and distributed drainage systems. The simulated basal water pressures are applied to an elastic beam model to assess vertical uplift at the lake drainage site. Modelled uplift outputs are compared with results from GPS stations located next to the lake. Initial modelling results suggest that channels are necessary for evacuation of water from rapid lake drainage events, even with the presence of a sediment-based bed, the latter of which is usually associated with distributed drainage.

  2. In-Situ Observations of a Subglacial Outflow Plume in a Greenland Fjord (United States)

    Mankoff, K. D.; Straneo, F.; Singh, H.; Das, S. B.


    We present oceanographic observations collected in and immediately outside of a buoyant, fresh, sediment-laden subglacial outflow plume rising up the marine-terminating front of Sarqardleq Glacier, Greenland (68.9 N, 50.4 W). Subglacial outflow plumes, associated with the discharge at depth of upstream glacial surface melt, entrain the relatively warm fjord waters and are correlated with enhanced submarine melt and increased calving. Few in-situ observations exist due to the challenges of making measurements at the calving front of glaciers. Our data were collected using a small boat, a helicopter, and a JetYak (a remote-controlled jet-ski-powered kayak). Temperature and salinity profiles in, around, and far from the plume are used to described its oceanographic properties, spatial extent, and temporal variability. This plume rises vertically up the ice front expanding laterally and away from the ice, over-shoots its stable isopycnal and reaches the surface. Its surface expression is identified by colder, saltier, sediment-laden water flowing at ~5 m/s away from the ice face. Within ~300 m from the ice it submerges as it seeks buoyant stability.

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

    Directory of Open Access Journals (Sweden)

    Bjørnstad T.


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

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

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


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

  5. A lander mission to probe subglacial water on Saturn's moon Enceladus for life (United States)

    Konstantinidis, Konstantinos; Flores Martinez, Claudio L.; Dachwald, Bernd; Ohndorf, Andreas; Dykta, Paul; Bowitz, Pascal; Rudolph, Martin; Digel, Ilya; Kowalski, Julia; Voigt, Konstantin; Förstner, Roger


    The plumes discovered by the Cassini mission emanating from the south pole of Saturn's moon Enceladus and the unique chemistry found in them have fueled speculations that Enceladus may harbor life. The presumed aquiferous fractures from which the plumes emanate would make a prime target in the search for extraterrestrial life and would be more easily accessible than the moon's subglacial ocean. A lander mission that is equipped with a subsurface maneuverable ice melting probe will be most suitable to assess the existence of life on Enceladus. A lander would have to land at a safe distance away from a plume source and melt its way to the inner wall of the fracture to analyze the plume subsurface liquids before potential biosignatures are degraded or destroyed by exposure to the vacuum of space. A possible approach for the in situ detection of biosignatures in such samples can be based on the hypothesis of universal evolutionary convergence, meaning that the independent and repeated emergence of life and certain adaptive traits is wide-spread throughout the cosmos. We thus present a hypothetical evolutionary trajectory leading towards the emergence of methanogenic chemoautotrophic microorganisms as the baseline for putative biological complexity on Enceladus. To detect their presence, several instruments are proposed that may be taken aboard a future subglacial melting probe. The "Enceladus Explorer" (EnEx) project funded by the German Space Administration (DLR), aims to develop a terrestrial navigation system for a subglacial research probe and eventually test it under realistic conditions in Antarctica using the EnEx-IceMole, a novel maneuverable subsurface ice melting probe for clean sampling and in situ analysis of ice and subglacial liquids. As part of the EnEx project, an initial concept study is foreseen for a lander mission to Enceladus to deploy the IceMole near one of the active water plumes on the moon's South-Polar Terrain, where it will search for

  6. Were kinetics of Archean calcium carbonate precipitation related to oxygen concentration? (United States)

    Sumner, D. Y.; Grotzinger, J. P.


    Archean carbonates commonly contain decimetre- to metre-thick beds consisting entirely of fibrous calcite and neomorphosed fibrous aragonite that precipitated in situ on the sea floor. The fact that such thick accumulations of precipitated carbonate are rare in younger marine carbonates suggests an important change in the modes of calcium carbonate precipitation through time. Kinetics of carbonate precipitation depend on the concentration of inhibitors to precipitation that reduce crystallization rates and crystal nuclei formation, leading to kinetic maintenance of supersaturated solutions. Inhibitors also affect carbonate textures by limiting micrite precipitation and promoting growth of older carbonate crystals on the sea floor. Fe2+, a strong calcite-precipitation inhibitor, is thought to have been present at relatively high concentrations in Archean seawater because oxygen concentrations were low. The rise in oxygen concentration at 2.2-1.9 Ga led to the removal of Fe2+ from seawater and resulted in a shift from Archean facies, which commonly include precipitated beds, to Proterozoic facies, which contain more micritic sediment and only rare precipitated beds.

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

    Vinzenz Ullmann, Clemens


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

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

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


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

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

    AlKhatib, Mahmoud; Eisenhauer, Anton


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

  10. Rapidly changing subglacial hydrological pathways at a tidewater glacier revealed through simultaneous observations of water pressure, supraglacial lakes, meltwater plumes and surface velocities (United States)

    How, Penelope; Benn, Douglas I.; Hulton, Nicholas R. J.; Hubbard, Bryn; Luckman, Adrian; Sevestre, Heïdi; van Pelt, Ward J. J.; Lindbäck, Katrin; Kohler, Jack; Boot, Wim


    Subglacial hydrological processes at tidewater glaciers remain poorly understood due to the difficulty in obtaining direct measurements and lack of empirical verification for modelling approaches. Here, we investigate the subglacial hydrology of Kronebreen, a fast-flowing tidewater glacier in Svalbard during the 2014 melt season. We combine observations of borehole water pressure, supraglacial lake drainage, surface velocities and plume activity with modelled run-off and water routing to develop a conceptual model that thoroughly encapsulates subglacial drainage at a tidewater glacier. Simultaneous measurements suggest that an early-season episode of subglacial flushing took place during our observation period, and a stable efficient drainage system effectively transported subglacial water through the northern region of the glacier tongue. Drainage pathways through the central and southern regions of the glacier tongue were disrupted throughout the following melt season. Periodic plume activity at the terminus appears to be a signal for modulated subglacial pulsing, i.e. an internally driven storage and release of subglacial meltwater that operates independently of marine influences. This storage is a key control on ice flow in the 2014 melt season. Evidence from this work and previous studies strongly suggests that long-term changes in ice flow at Kronebreen are controlled by the location of efficient/inefficient drainage and the position of regions where water is stored and released.

  11. Rapidly changing subglacial hydrological pathways at a tidewater glacier revealed through simultaneous observations of water pressure, supraglacial lakes, meltwater plumes and surface velocities

    Directory of Open Access Journals (Sweden)

    P. How


    Full Text Available Subglacial hydrological processes at tidewater glaciers remain poorly understood due to the difficulty in obtaining direct measurements and lack of empirical verification for modelling approaches. Here, we investigate the subglacial hydrology of Kronebreen, a fast-flowing tidewater glacier in Svalbard during the 2014 melt season. We combine observations of borehole water pressure, supraglacial lake drainage, surface velocities and plume activity with modelled run-off and water routing to develop a conceptual model that thoroughly encapsulates subglacial drainage at a tidewater glacier. Simultaneous measurements suggest that an early-season episode of subglacial flushing took place during our observation period, and a stable efficient drainage system effectively transported subglacial water through the northern region of the glacier tongue. Drainage pathways through the central and southern regions of the glacier tongue were disrupted throughout the following melt season. Periodic plume activity at the terminus appears to be a signal for modulated subglacial pulsing, i.e. an internally driven storage and release of subglacial meltwater that operates independently of marine influences. This storage is a key control on ice flow in the 2014 melt season. Evidence from this work and previous studies strongly suggests that long-term changes in ice flow at Kronebreen are controlled by the location of efficient/inefficient drainage and the position of regions where water is stored and released.

  12. Influence of calcium sources on microbially induced calcium carbonate precipitation by Bacillus sp. CR2. (United States)

    Achal, Varenyam; Pan, Xiangliang


    Stimulation of microbially induced calcium carbonate precipitation (MICCP) is likely to be influenced by calcium sources. In order to study such influences, we performed MICCP using Bacillus sp. CR2 in nutrient broth containing urea, supplemented with different calcium sources (calcium chloride, calcium oxide, calcium acetate and calcium nitrate). The experiment lasted 7 days, during which bacterial growth, urease activity, calcite production and pH were measured. Our results showed that calcium chloride is the better calcium source for MICCP process, since it provides higher urease activity and more calcite production. The influences of calcium sources on MICCP were further studied using Fourier transform-infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses. These analyses confirmed that the precipitate formed was CaCO3 and composed of predominantly calcite crystals with a little amount of aragonite and vaterite crystals. The maximum yield of calcite precipitation was achievable with calcium chloride followed by calcium nitrate as a calcium source. The results of present study may be applicable to media preparation during efficient MICCP process.

  13. Microscale evidence of liquefaction and its potential triggers during soft-bed deformation within subglacial traction tills (United States)

    Phillips, Emrys R.; Evans, David J. A.; van der Meer, Jaap J. M.; Lee, Jonathan R.


    Published conceptual models argue that much of the forward motion of modern and ancient glaciers is accommodated by deformation of soft-sediments within the underlying bed. At a microscale this deformation results in the development of a range of ductile and brittle structures in water-saturated sediments as they accommodate the stresses being applied by the overriding glacier. Detailed micromorphological studies of subglacial traction tills reveal that these polydeformed sediments may also contain evidence of having undergone repeated phases of liquefaction followed by solid-state shear deformation. This spatially and temporally restricted liquefaction of subglacial traction tills lowers the shear strength of the sediment and promotes the formation of "transient mobile zones" within the bed, which accommodate the shear imposed by the overriding ice. This process of soft-bed sliding, alternating with bed deformation, facilitates glacier movement by way of 'stick-slip' events. The various controls on the slip events have previously been identified as: (i) the introduction of pressurised meltwater into the bed, a process limited by the porosity and permeability of the till; and (ii) pressurisation of porewater as a result of subglacial deformation; to which we include (iii) episodic liquefaction of water-saturated subglacial traction tills in response to glacier seismic activity (icequakes), which are increasingly being recognized as significant processes in modern glaciers and ice sheets. As liquefaction operates only in materials already at very low values of effective stress, its process-form signatures are likely indicative of glacier sub-marginal tills.

  14. Subglacial bed conditions during Late Pleistocene glaciations and their impact on ice dynamics in the southern North Sea

    NARCIS (Netherlands)

    Passchier, S.; Laban, C.; Mesdag, C.S.; Rijsdijk, K.F.


    Changes in subglacial bed conditions through multiple glaciations and their effect on ice dynamics are addressed through an analysis of glacigenic sequences in the Upper Pleistocene stratigraphy of the southern North Sea basin. During Elsterian (MIS 12) ice growth, till deposition was subdued when

  15. Analysis of subglacial hydrodynamics and ice dynamics through combined terrestrial laser scanning and ground penetrating radar survey (United States)

    Gabbud, Chrystelle; Rüttimann, Sébastien; Micheletti, Natan; Irving, James; Lane, Stuart


    This study shows how high resolution surveys of subglacial channel morphology combined with high resolution terrestrial laser scanner survey of an Alpine glacier help to understand subglacial hydrological forcing of ice dynamics. The study area is the Haut Glacier d'Arolla in Switzerland, an Alpine valley glacier for which subglacial drainage system has been well studied. A new generation of terrestrial laser scanners was used to investigate glacier surface ablation and other elements of glacial hydrodynamics at exceptionally high spatial and temporal resolution. The LiDAR RIEGL VZ-6000 scanner, with a laser 3B specifically designed for measurements of snow and ice cover surfaces, was tested at seasonal and daily scales. The data revealed spatial variations in the patterns of surface melt, controlled by both aspect and differential debris cover at the seasonal scale, and controlled by ogive-related differences in ice surface debris content at the daily scale. More tentatively, intra-daily scale measurements pointed to possible hydraulic jacking of the glacier associated with short-term water pressure rises at the downstream part of the glacier. A ground-penetrating radar (GPR) field campaign was conducted a year later in the location where possible hydraulic jacking had been detected previously. The aims of this campaign were (i) to assess GPR usage for subglacial channel detection; (ii) identify more precisely the channel morphology; and (iii) investigate further the hydraulic jacking hypothesis. 100 MHz antennas were used to map a 240 x 34 m area near the glacier snout where the ice thickness did not exceed 50 m. The corresponding data, after processing, allowed reconstruction of the bed topography and the morphology of subglacial channels in 3D, showing two of the latter in this area. One channel was followed for approximately 20 m upglacier and corresponding morphology estimates were performed. These data allowed for 3D reconstructions of both the bed

  16. Tracking seasonal subglacial drainage evolution of alpine glaciers using radiogenic Nd and Sr isotope systematics: Lemon Creek Glacier, Alaska (United States)

    Clinger, A. E.; Aciego, S.; Stevenson, E. I.; Arendt, C. A.


    The transport pathways of water beneath a glacier are subject to change as melt seasons progress due to variability in the balance between basal water pressure and water flux. Subglacial hydrology has been well studied, but the understanding of spatial distribution is less well constrained. Whereas radiogenic isotopic tracers have been traditionally used as proxies to track spatial variability and weathering rates in fluvial and riverine systems, these techniques have yet to be applied extensively to the subglacial environment and may help resolve ambiguity in subglacial hydrology. Research has shown the 143Nd/144Nd values can reflect variation in source provenance processes due to variations in the age of the continental crust. Correlating the 143Nd/144Nd with other radiogenic isotope systematics such as strontium (87Sr/86Sr) provides important constraints on the role of congruent and incongruent weathering processes. Our study presents the application of Nd and Sr systematics using isotopic ratios to the suspended load of subglacial meltwater collected over a single melt season at Lemon Creek Glacier, USA (LCG). The time-series data show an average ɛNd ~ -6.83, indicating a young bedrock (~60 MYA). Isotopic variation helps track the seasonal expansion of the subglacial meltwater channels and subsequent return to early season conditions due to the parabolic trend towards less radiogenic Nd in June and towards more radiogenic Nd beginning in mid-August. However, the high variability in July and early August may reflect a mixture of source as the channels diverge and derive sediment from differently aged lithologies. We find a poor correlation between 143Nd/144Nd and 87Sr/86Sr (R2= 0.38) along with a slight trend towards more radiogenic 87Sr/86Sr values with time ((R2= 0.49). This may indicate that, even as the residence time decreases over the melt season, the LCG subglacial system is relatively stable and that the bedrock is congruently weathered. Our study

  17. Observations and modelling of subglacial discharge and heat transport in Godthåbsfjord (Greenland, 64 °N) (United States)

    Bendtsen, Jørgen; Mortensen, John; Rysgaard, Søren


    Subglacial discharge from tidewater outlet glaciers forms convective bouyant freshwater plumes ascending close the glacier face, and entrainment of ambient bottom water increases the salinity of the water until the plume reaches its level of neutral buoyancy at sub-surface levels or reaches the surface. Relatively warm bottom water masses characterize many fjords around Greenland and therefore entrainment would also increase the temperature in the plumes and, thereby, impact the heat transport in the fjords. However, relatively few oceanographic measurements have been made in or near plumes from subglacial discharge and, therefore, the potential for subglacial discharge for increasing heat transport towards the tidewater outlet glaciers are poorly understood. We present the first direct hydrographic measurements in a plume from subglacial discharge in Godthåbsfjord (located on the western coast of Greenland) where a XCTD was launched from a helicopter directly into the plume. Measurements of the surface salinity showed that the plume only contained 7% of freshwater at the surface, implying a large entrainment with a mixing ratio of 1:13 between outflowing meltwater and saline fjord water. These observations are analyzed together with seasonal observations of ocean heat transport towards the tidewater outlet glaciers in Godthåbsfjord and we show that subglacial discharge only had modest effects on the overall heat budget in front of the glacier. These results were supported from a high-resolution three-dimensional model of Godthåbsfjord. The model explicitly considered subglacial freshwater discharge from three tidewater outlet glaciers where entrainment of bottom water was taken into account. Model results showed that subglacial discharge only affected the fjord circulation relatively close ( 10 km) to the glaciers. Thus, the main effect on heat transport was due to the freshwater discharge itself whereas the subsurface discharge and associated entrainment only

  18. Promotion and nucleation of carbonate precipitation during microbial iron reduction. (United States)

    Zeng, Z; Tice, M M


    Iron-bearing early diagenetic carbonate cements are common in sedimentary rocks, where they are thought to be associated with microbial iron reduction. However, little is yet known about how local environments around actively iron-reducing cells affect carbonate mineral precipitation rates and compositions. Precipitation experiments with the iron-reducing bacterium Shewanella oneidensis MR-1 were conducted to examine the potential role of cells in promoting precipitation and to explore the possible range of precipitate compositions generated in varying fluid compositions. Actively iron-reducing cells induced increased carbonate mineral saturation and nucleated precipitation on their poles. However, precipitation only occurred when calcium was present in solution, suggesting that cell surfaces lowered local ferrous iron concentrations by adsorption or intracellular iron oxide precipitation even as they locally raised pH. Resultant precipitates were a range of thermodynamically unstable calcium-rich siderites that would likely act as precursors to siderite, calcite, or even dolomite in nature. By modifying local pH, providing nucleation sites, and altering metal ion concentrations around cell surfaces, iron-reducing micro-organisms could produce a wide range of carbonate cements in natural sediments. © 2014 John Wiley & Sons Ltd.

  19. Antarctic subglacial lakes drain through sediment-floored canals: theory and model testing on real and idealized domains (United States)

    Carter, Sasha P.; Fricker, Helen A.; Siegfried, Matthew R.


    Over the past decade, satellite observations of ice surface height have revealed that active subglacial lake systems are widespread under the Antarctic Ice Sheet, including the ice streams. For some of these systems, additional observations of ice-stream motion have shown that lake activity can affect ice-stream dynamics. Despite all this new information, we still have insufficient understanding of the lake-drainage process to incorporate it into ice-sheet models. Process models for drainage of ice-dammed lakes based on conventional R-channels incised into the base of the ice through melting are unable to reproduce the timing and magnitude of drainage from Antarctic subglacial lakes estimated from satellite altimetry given the low hydraulic gradients along which such lakes drain. We have developed an alternative process model, in which channels are mechanically eroded into the underlying deformable subglacial sediment. When applied to the known active lakes of the Whillans-Mercer ice-stream system, the model successfully reproduced both the inferred magnitudes and recurrence intervals of lake-volume changes, derived from Ice, Cloud and land Elevation Satellite (ICESat) laser altimeter data for the period 2003-2009. Water pressures in our model changed as the flood evolved: during drainage, water pressures initially increased as water flowed out of the lake primarily via a distributed system, then decreased as the channelized system grew, establishing a pressure gradient that drew water away from the distributed system. This evolution of the drainage system can result in the observed internal variability of ice flow over time. If we are correct that active subglacial lakes drain through canals in the sediment, this mechanism also implies that active lakes are typically located in regions underlain by thick subglacial sediment, which may explain why they are not readily observed using radio-echo-sounding techniques.

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

    Indian Academy of Sciences (India)


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

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

    Directory of Open Access Journals (Sweden)

    Ayomadewa Mercy Adesola


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

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

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


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

  3. The Subglacial Access and Fast Ice Research Experiment (SAFIRE): 3. Englacial and subglacial conditions revealed by seismic reflection data on Store Glacier, West Greenland. (United States)

    Hofstede, Coen; Eisen, Olaf; Young, Tun Jan; Doyle, Samuel; Hubbard, Bryn; Christoffersen, Poul; Hubbard, Alun


    Basal conditions have a profound influence on the dynamics of outlet glaciers. As part of the SAFIRE research programme, we carried out a seismic survey on Store Glacier, a tidewater glacier terminating in Uummanaq Fjord in West Greenland (see joint abstracts by Christoffersen et al. and Doyle et al. for details). At the survey site the ice moves 700m/a making the terrain crevassed and bumpy. Despite the rough terrain we collected two 1.5 km long survey lines parallel and perpendicular to the ice flow direction using a 300m snow streamer and explosives as a source. The seismic data reveal an ice thickness of about 620m and 20 to 30m of subglacial sediment on the upstream side of the area thinning in the downstream direction. From polarity reversals seen along the ice-bed contact we speculate that the sediments have varying degrees of water content. The ice itself has several englacial reflections parallel and close to the bed. At approximately 475m depth, a clear single englacial reflection is observed in the parallel survey line. Thermistor data installed at this location show a clear increase in ice temperature starting at this depth. We speculate that the observed englacial reflection is caused by a change in crystal orientation fabric allowing greater ice deformation below this depth causing increased strain heating.

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

    Directory of Open Access Journals (Sweden)

    Mansour Rezaei Azizi


    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

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

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


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

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

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


    The CO2 combined as calcite in carbonate-bearing apatites as been distinguished from that combined as carbonate-apatite, or present in some form other than calcite, by use of X-ray powder patterns, differential thermal analyses, and differential solubility tests. These methods were applied to several pure apatite minerals, to one fossil bone, and to a group of phosphorites from the Phosphoria formation of Permian age from Trail Canyon and the Conda mine, Idaho, and the Laketown district, Utah. With the exceptions of pure fluorapatite, pure carbonate-flueorapatite, and one phosphorite from Trail Canyon, these substances contain varying amounts of calcite, but in all the samples an appreciable part of the carbonite content is not present as calcite. The results of solubility tests, in which the particle size of sample and the length of solution time were varied, imply that the carbonate content is not due to shielded calcite entrapped along an internal network of surfaces.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  8. Subglacial processes revealed by the internal structure of drumlins, Stargard drumlin field, NW Poland (United States)

    Hermanowski, Piotr; Piotrowski, Jan A.; Szuman-Kalita, Izabela


    Numerous studies have provided insight into processes operating under contemporary and palaeo-ice sheets. Many of these studies concerned drumlins, landforms whose formation is essential to the understanding of subglacial soft-bedded systems. Despite the interdisciplinary efforts involving sophisticated analytical and interpretative tools the "drumlin problem" remains elusive and continues to generate much controversy. In this study the geological composition of two drumlins from the Stargard drumlin field (NW Poland) in the terminal area of a major last-glacial palaeo-ice stream was examined in three excavated trenches at macro- and microscales. In each trench, sediment description and fabric analyses were conducted, and samples collected for micromorphological, AMS (anisotropy of magnetic susceptibility) and grain size measurements. Both investigated drumlins are mainly composed of macroscopically homogeneous till with minor, max. 5 cm thick sand stringers and sparse silty inclusions. Distinct features are (1) a highly deformed, up to 18-cm thick till layer with clay- and pebble-sized clasts at the top, and (2) a continuous thin intra-till clay layer. Till macro-fabric measurements reveal a very high clustering strength and low isotropy index. AMS eigenvectors V1 vary significantly, but the dominant direction is consistent with the macrofabric measurements. Most of the observed microstructures indicate ductile deformation of the till. The overall observations suggest a shallow subglacial deformation not affecting the entire till thickness at any time intervening with ice/bed separation facilitating enhanced basal sliding. The intra-till clay layer of low hydraulic conductivity contributed to elevated pore-water pressure in the sediment causing its fluidization and deformation. Intervening thin-skinned sediment deformation and basal de-coupling resulted in fast ice flow that, coupled with material release from the ice sole and its accretion at the ice

  9. Melt-induced speed-up of Greenland ice sheet offset by efficient subglacial drainage. (United States)

    Sundal, Aud Venke; Shepherd, Andrew; Nienow, Peter; Hanna, Edward; Palmer, Steven; Huybrechts, Philippe


    Fluctuations in surface melting are known to affect the speed of glaciers and ice sheets, but their impact on the Greenland ice sheet in a warming climate remains uncertain. Although some studies suggest that greater melting produces greater ice-sheet acceleration, others have identified a long-term decrease in Greenland's flow despite increased melting. Here we use satellite observations of ice motion recorded in a land-terminating sector of southwest Greenland to investigate the manner in which ice flow develops during years of markedly different melting. Although peak rates of ice speed-up are positively correlated with the degree of melting, mean summer flow rates are not, because glacier slowdown occurs, on average, when a critical run-off threshold of about 1.4 centimetres a day is exceeded. In contrast to the first half of summer, when flow is similar in all years, speed-up during the latter half is 62 ± 16 per cent less in warmer years. Consequently, in warmer years, the period of fast ice flow is three times shorter and, overall, summer ice flow is slower. This behaviour is at odds with that expected from basal lubrication alone. Instead, it mirrors that of mountain glaciers, where melt-induced acceleration of flow ceases during years of high melting once subglacial drainage becomes efficient. A model of ice-sheet flow that captures switching between cavity and channel drainage modes is consistent with the run-off threshold, fast-flow periods, and later-summer speeds we have observed. Simulations of the Greenland ice-sheet flow under climate warming scenarios should account for the dynamic evolution of subglacial drainage; a simple model of basal lubrication alone misses key aspects of the ice sheet's response to climate warming.

  10. A Unified Constitutive Model for Subglacial Till, Part I: The Disturbed State Concept (United States)

    Jenson, J. W.; Desai, C. S.; Clark, P. U.; Contractor, D. N.; Sane, S. M.; Carlson, A. E.


    Classical plasticity models such as Mohr-Coulomb may not adequately represent the full range of possible motion and failure in tills underlying ice sheets. Such models assume that deformations are initially elastic, and that when a peak or failure stress level is reached the system experiences sudden failure, after which the stress remains constant and the deformations can tend to infinite magnitudes. However, theory suggests that the actual behavior of deforming materials, including granular materials such as glacial till, can involve plastic or irreversible strains almost from the beginning, in which localized zones of microcracking and "failure" can be distributed over the material element. As the loading increases, and with associated plastic and creep deformations, the distributed failure zones coalesce. When the extent of such coalesced zones reaches critical values of stresses and strains, the critical condition (failure) can occur in the till, which would cause associated movements of the ice sheet. Failure or collapse then may occur at much larger strain levels. Classical models (e.g., Mohr-Coulomb) may therefore not be able to fully and realistically characterize deformation behavior and the gradual developments of localized failures tending to the global failure and movements. We present and propose the application of the Disturbed State Concept (DSC), a unified model that incorporates the actual pre- and post-failure behavior, for characterizing the behavior of subglacial tills. In this presentation (Part I), we describe the DSC and propose its application to subglacial till. Part II (Desai et al.) describes our application of the DSC with laboratory testing, model calibration, and validations to evaluate the mechanical properties of two regionally significant Pleistocene tills.

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

    DEFF Research Database (Denmark)

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


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

  12. Unveiling subglacial geology and crustal architecture in the Recovery frontier of East Antarctica with recent aeromagnetic and airborne gravity imaging (United States)

    Ferraccioli, F.; Forsberg, R.; Jordan, T. A.; Matsuoka, K.; Olsen, A.; King, O.; Ghidella, M.


    East Antarctica is the least known continent, despite being a keystone in the Gondwana, Rodinia and Columbia supercontinents. Significant progress has been made in recent years in exploring East Antarctica using aeromagnetic and airborne gravity together with radar. Major aerogeophysical campaigns over the Wilkes Subglacial Basin (Ferraccioli et al., 2009 Tectonophysics), the Aurora Subglacial Basin (Aitken et al., 2014 GRL) and the Gamburtsev Subglacial Mountains (Ferraccioli et al., 2011, Nature) provide new glimpses into the crustal architecture of East Antarctica. However, a major sector of the continent that includes key piercing points for reconstructing linkages between East Antarctica and Laurentia within Rodinia, and also the inferred remnants of a major suture zone active during Gondwana amalgamation in Pan-African times (ca 500 Ma), has remained largely terra incognita. Here we present the results of a major aerogeophysical survey flown over this sector of East Antarctica, named the Recovery Frontier, from the major ice stream flowing in the region. The survey was flown during the IceGRAV 2012-13 field season, as part of a Danish-Norwegian-UK and Argentine collaboration and led to the collection of 29,000 line km of radar, laser altimetry, gravity and magnetic data. We present the new aeromagnetic anomaly, Bouguer and residual and enhanced anomaly maps for the region. Using these images we trace the extent of major subglacial faults and interpret these to delineate the tectonic boundaries separating the Coast block, the Shackleton Range and the Dronning Maud Land crustal provinces. Forward magnetic and gravity modelling enables us to examine the inferred Pan-African age suture zone in the Shackleton Range and address its tectonic relationships with older terranes of the Mawson Craton and Grenvillian-age terranes of Dronning Maud Land and interior East Antarctica. Finally, we present new models to test our hypothesis that Paleozoic to Mesozoic rift basins

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

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


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

  14. Effects of initial supersaturation on spontaneous precipitation of calcium carbonate in the presence of charged poly-L-amino acids. (United States)

    Njegić-Dzakula, Branka; Falini, Giuseppe; Brecević, Ljerka; Skoko, Zeljko; Kralj, Damir


    Spontaneous precipitation of calcium carbonate was investigated in two precipitation systems: (1) with initial supersaturation lower than that corresponding to the solubility of amorphous calcium carbonate (ACC), at which vaterite precipitated, and (2) with initial supersaturation higher than that of ACC solubility, at which a mixture of calcite and vaterite was formed. After the addition of an acidic polypeptide, poly-L-glutamic acid (pGlu) or poly-L-aspartic acid (pAsp), into (1) a significant inhibition of nucleation, expressed as an increase in induction time, and growth of vaterite, perceived as a dead zone, was observed. Extent of inhibition decreased in the order: Inh(pAps)>Inh(pGlu)>Inh(pLys). The addition of a polypeptide into (2) caused the inhibition of precipitation and changed the morphology and polymorphic composition of the precipitate; only vaterite appeared at approximately c(pAsp)=3 ppm, c(pGlu)=6 ppm, or c(pLys)=7 ppm. This finding is explained as a consequence of kinetic constraints through the inhibition of calcite nucleation and stronger binding of acidic polypeptide by the calcite surfaces than by the vaterite surfaces. Laboratory precipitation studies using conditions that resemble those in living organism should be run at an initial supersaturation corresponding to the solubility of ACC as a limiting condition. 2009 Elsevier Inc. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    J. C. Wit


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

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

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


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

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

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


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

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

    Raymond, Anne


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

  19. Palaeogeographical And Archaeological Records Of Natural Changes Of The Jordanowo-Niesulice Subglacial Channel Near Lubrza, The Lubusz Lakeland

    Directory of Open Access Journals (Sweden)

    Ratajczak-Szczerba Magdalena


    Full Text Available The region of the Lubusz Lakeland in western Poland where there are a lot of subglacial channels provides opportunity for multi-proxy palaeoenvironmental reconstructions. None of them has not been the object of a specific study. The developmental history of the palaeolakes and their vicinity in the subglacial trough Jordanowo-Niesulice, spanning the Late Glacial and beginning of the Holocene, was investigated using geological research, lithological and geomorphological analysis, geochemical composition, palynological and archaeological research, OSL and AMS-radiocarbon dating. Geological research shows varied morphology of subglacial channel where at least two different reservoirs functioned in the end of the Last Glacial period and at the beginning of the Holocene. Mostly during the Bølling-Allerød interval and at the beginning of the Younger Dryas there took place melting of buried ice-blocks which preserved the analysied course of the Jordanowo-Niesulice trough. The level of water, and especially depth of reservoirs underwent also changes. Palynological analysis shows very diversified course of the Allerød interval.

  20. Unrest at Bárdarbunga: Preparations for possible flooding due to subglacial volcanism (United States)

    Hardardottir, Jorunn; Roberts, Matthew; Pagneux, Emmanuel; Einarsson, Bergur; Thorarinsdottir, Tinna; Johannesson, Tomas; Sigurdsson, Oddur; Egilson, David; Sigurdsson, Gunnar; Imo hydrological-monitoring-team


    Located partly beneath northwest Vatnajökull, Iceland, the Bárdarbunga volcanic system comprises an ice-capped central volcano and a fissure swarm extending beyond the ice margin. During the last 1100 years the volcano has erupted on at least 26 occasions. Outburst floods (jökulhlaups) on a scale of >100,000 m3 s-1 are known to have occurred during major explosive eruptions. Repeated jökulhlaups from Bárdarbunga have inundated the Jökulsá á Fjöllum River, which drains over 200 km northwards from the Dyngjujökull outlet glacier to the north coast of Iceland. Depending on the location of the eruption within the 80 km2 caldera, jökulhlaups could also flow northwards along Skjálfandafljót River and towards west and southwest into present-day tributaries of the extensively hydropower-harnessed Thjórsá River. On 16 August 2014, an intense earthquake swarm began within the Bárdarbunga caldera. Seismicity propagated from the caldera, extending ~10 km northwards of the ice margin where a fissure eruption developed in late August and remains ongoing in early January 2015. In connection with the lateral migration of magma from the caldera, the ice surface of Bárdarbunga has lowered by over 60 m; also associated with increased geothermal heat on the caldera rim, as manifested by the development of ice-surface depressions. In preparation for a subglacial eruption in the Bárdarbunga volcanic system, the Icelandic Meteorological Office (IMO) has made several assessments of likely hydrological hazards. Assessments were undertaken on Jökulsá á Fjöllum and Skjálfandafljót at key locations where preliminary evacuation plans for populated areas were made in cooperation with the local police. Floodwater extent was estimated for key infrastructures, such as bridges, telecommunication and power lines for maximum discharge levels ranging from 3,000 to 20,000 m3 s-1. The estimations were made using either simple Manning's calculations or HEC-RAS modelling

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

    National Research Council Canada - National Science Library

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


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

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

    Nomeli, Mohammad


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

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

    DEFF Research Database (Denmark)

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


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

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

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


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

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

    Busenberg, Eurybiades; Niel Plummer, L.


    Significant amounts of SO 42-, Na +, and OH - are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO 42-. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na +, but very low concentrations of SO 42-. The SO 42- content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na + and SO 42- increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO 42- beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO 42- is the same as that of aragonite. Na + appears to have very little effect on the solubility product of calcites. The amounts of Na + and SO 42- incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient ( D) of SO 42- in calcite at 25.0°C and 0.50 molal NaCl is described by the equation D = k 0 + k 1R where k 0 and k 1 are constants equal to 6.16 × 10 -6 and 3.941 × 10 -6, respectively, and R is the rate of crystal growth of calcite in mg·min -1·g -1 of seed. The data on Na + are consistent with the hypothesis that a significant amount of Na + occupies interstitial positions in the calcite structure. The distribution of Na + follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na + distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na + contents of calcites are not very accurate indicators of environmental salinities.

  6. Modelled Precipitation Over Greenland (United States)

    National Aeronautics and Space Administration — This data set includes the annual total precipitation from 1985 to 1999 and monthly total precipitation from January 1985 to December 1999. The data is derived from...

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


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


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

  8. Fast flow of Jakobshavn Isbræ and its subglacial drainage system (United States)

    Werder, M. A.; Joughin, I. R.


    Jakobshavn Isbræ and many other outlet glaciers of present and past ice sheets lie in deep troughs which often have several overdeepened sections. The subglacial drainage system of such glaciers is heavily influenced by two effects caused by the pressure dependence of the melting point of water. The melting point decreases with increasing water pressure, this enhances wall-melt in downward sloping channels and diminishes wall-melt in upward sloping channels. Thus the first effect is the well known shutdown of channels on steep adverse bed slopes of overdeepenings and the associated high water pressure/low effective pressure. The second effect is a 2D effect and has not received much/any attention so far: the orientation of a channel will be deflected from the direction of the (negative) hydraulic potential gradient (which drives the water flow) towards the steepest slope of the bed. This leads to the enhanced formation of side channels dipping into the trough at about a 45° angle. This efficient connection between the margin and the trough equalizes the hydraulic potential, again leading to higher water pressure in the trough. We investigate these two effects with the 2D subglacial drainage system model GlaDS using Jakobshavn Isbræ as an example. We compare model runs with the pressure melt term disabled and enabled. With the term disabled the main channel situated in the trough is continuous and produces a large depression in the hydraulic potential and consequently high effective pressure in the trough (1-2MPa). Conversely, with the term enabled the main channel becomes discontinuous on steep adverse bed slopes and many side channels form on the margins of the trough. This leads to a hydraulic potential in the trough which is higher than in the surrounding area and consequently the effective pressure is low (0-1MPa). Low effective pressure leads to reduced basal drag and thus to more basal sliding. The modeled large decrease of effective pressure in the trough

  9. Inferring the tectonic setting of the Gamburtsev Subglacial Mts by ice cap surface lineaments (United States)

    Cianfarra, Paola; Salvini, Francesco


    Gamburtsev Subglacial Mts (GSM) are by far one of the most puzzling physiographic feature of the East Antactic craton. Located at the centre of the Antarctic continent and beneath the highest point of East Antarctic Ice Sheet (Dome A) they were discovered during the 1957-58 International Geophysical Year by a Soviet expedition using seismic instruments to measure the thickness of the ice sheet. This intracratonic mountain range is characterised by peaks with elevation exceeding 3500 m and covers an area bigger than the European Alps. The GSM were the target of a huge international geophysical expedition during the 2008-2009 summer season with the aim of revealing the geologic nature and origin of this mountain range, as well as to further understand the tectonic setting of two of the largest Antarctic subglacial lakes bounding to the East and to the West the GSM, namely the Vostok and Recovery lakes. Preliminary results of this international scientific campaign have been presented to the scientific community and showed that the GSM are characterised by a typical alpine landscape with a rectangular hydrographic network. These morphological features are commonly associated to recent/active tectonics. At present, four scenarios exists to explain the existence of such intracratonic mountain range: (i) a hot-spot beneath the Antarctic crust, in a Hoggar-like mantle plume scenario; (ii) a continental collision (of unknown age) similarly to the Alpine orogenic belt; (iii) a rifting process associated to flexural uplift or isostatic rebound of the rift shoulder, in a Transantarctic Mts like scenario or similarly to the mountains along the edges of the East African rift lakes; and (iv) a continental arching related to regional, continental-scale stress like the Black Hills in the North America continent or the russian platform arching located NE of Moscow. These geodynamic scenarios are characterised by different morpho-tectonic signatures that can be successfully

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

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


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

  11. Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Stronthium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Robert W.; Fujita, Yoshiko


    Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) energy research and weapons complex. In situ containment and stabilization of these contaminants represents a cost-effective treatment strategy that minimizes workers’ exposure to hazardous substances, does not require removal or transport of contaminants, and generally does not generate a secondary waste stream. We have investigated an in situ bioremediation approach that immobilizes radionuclides or contaminant metals (e.g., strontium-90) by their microbially facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Calcite, a common mineral in many aquifers and vadose zones in the arid west, can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of a solid solution. Collaborative research undertaken by the Idaho National Laboratory (INL), University of Idaho, and University of Toronto as part of this Environmental Management Science Program project has focused on in situ microbially-catalyzed urea hydrolysis, which results in an increase in pH, carbonate alkalinity, ammonium, calcite precipitation, and co-precipitation of divalent cations. In calcite-saturated aquifers, microbially facilitated co-precipitation with calcium carbonate represents a potential long-term contaminant sequestration mechanism. Key results of the project include: **Demonstrating the linkage between urea hydrolysis and calcite precipitation in field and laboratory experiments **Observing strontium incorporation into calcite precipitate by urea hydrolyzers with higher distribution coefficient than in abiotic **Developing and applying molecular methods for characterizing microbial urease activity in groundwater including a quantitative PCR method for enumerating ureolytic bacteria **Applying the suite of developed molecular methods to assess the feasibility of the

  12. Influence of eggshell matrix proteins on the precipitation of calcium carbonate (CaCO 3) (United States)

    Hernández-Hernández, A.; Vidal, M. L.; Gómez-Morales, J.; Rodríguez-Navarro, A. B.; Labas, V.; Gautron, J.; Nys, Y.; García Ruiz, J. M.


    To understand the role of eggshell organic matrix on the biomineralization process, we have tested the influence of different purified fractions of the eggshell organic matrix on calcium carbonate (CaCO 3) precipitation. Purification was carried out after successive anion-exchange chromatography, hydrophobic interaction chromatography and gel filtration chromatography of two different prepurified eggshell extracts (A) and (B); the purified fractions (named g, h, n and r) and ( c', g', i', k') respectively were diluted to 50 μg/ml before being tested in vitro and analysed by the sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) procedure and mass spectrometry. The precipitation experiments were carried out by the method of vapour diffusion on crystallization mushrooms. Each purified fraction showed a different effect on CaCO 3 precipitation. Some of them exhibited a strong inhibitory effect on nucleation, thus suppressing the precipitation of CaCO 3 almost totally while the others did not produce any notable effect. However, all fractions favoured the precipitation of calcite over the other CaCO 3 polymorphs. Additionally, all fractions modified in a different manner the size and morphology of the precipitated calcite crystals.

  13. Fluorite's precipitation in KOH solutions in view of removing fluorides from wastewaters


    Taraves, Raquel; Garcia, Daniel; Moutte, Jacques; Cameirão, Ana; Févotte, Gilles; Amaraggi, David; Morel, Bertrand


    International audience; The process under study aims at removing dissolved fluorides from effluent waters through the addition of calcium and the precipitation of fluorite in a fluidized bed. In the concept developed at COMURHEX, the effluent is a highly concentrated KOH solution and the calcium is provided as a suspension of portlandite with calcite as an impurity. COMURHEX's target is to achieve an efficient defluorination of KOH solutions prior to recycling and to control the growth of the...

  14. Geological controls on bedrock topography and ice sheet dynamics in the Wilkes Subglacial Basin sector of East Antarctica (United States)

    Ferraccioli, Fausto; Armadillo, Egidio; Young, Duncan; Blankenship, Donald; Jordan, Tom; Siegert, Martin


    The Wilkes Subglacial Basin extends for 1,400 km into the interior of East Antarctica and hosts several major glaciers that drain a large sector of the East Antarctic Ice Sheet. The deep northern Wilkes Subglacial Basin underlies the catchments of the Matusevich, Cook, Ninnis and Mertz Glaciers, which are largely marine-based and hence potentially particularly sensitive to past and also predicted future ocean and climate warming. Sediment provenance studies suggest that the glaciers flowing in this region may have retreated significantly compared to their modern configuration, as recently as the warm mid-Pliocene interval, potentially contributing several m to global sea level rise (Cook et al.,Nature Geosci., 2013). Here we combine airborne radar, aeromagnetic and airborne gravity observations collected during the international WISE-ISODYN and ICECAP aerogeophysical campaigns with vintage datasets to help unveil subglacial geology and deeper crustal architecture and to assess its influence on bedrock topography and ice sheet dynamics in the northern Wilkes Subglacial Basin. Aeromagnetic images reveal that the Matusevich Glacier is underlain by a ca 480 Ma thrust fault system (the Exiles Thrust), which has also been inferred to have been reactivated in response to intraplate Cenozoic strike-slip faulting. Further to the west, the linear Eastern Basins are controlled by the Prince Albert Fault System. The fault system continues to the south, where it provides structural controls for both the Priestley and Reeves Glaciers. The inland Central Basins continue in the coastal area underlying the fast flowing Cook ice streams, implying that potential ocean-induced changes could propagate further into the interior of the ice sheet. We propose based on an analogy with the Rennick Graben that these deep subglacial basins are controlled by the underlying horst and graben crustal architecture. Given the interpreted subglacial distribution of Beacon sediments and Ferrar

  15. Near-glacier surveying of a subglacial discharge plume: Implications for plume parameterizations (United States)

    Jackson, R. H.; Shroyer, E. L.; Nash, J. D.; Sutherland, D. A.; Carroll, D.; Fried, M. J.; Catania, G. A.; Bartholomaus, T. C.; Stearns, L. A.


    At tidewater glaciers, plume dynamics affect submarine melting, fjord circulation, and the mixing of meltwater. Models often rely on buoyant plume theory to parameterize plumes and submarine melting; however, these parameterizations are largely untested due to a dearth of near-glacier measurements. Here we present a high-resolution ocean survey by ship and remotely operated boat near the terminus of Kangerlussuup Sermia in west Greenland. These novel observations reveal the 3-D structure and transport of a near-surface plume, originating at a large undercut conduit in the glacier terminus, that is inconsistent with axisymmetric plume theory, the most common representation of plumes in ocean-glacier models. Instead, the observations suggest a wider upwelling plume—a "truncated" line plume of ˜200 m width—with higher entrainment and plume-driven melt compared to the typical axisymmetric representation. Our results highlight the importance of a subglacial outlet's geometry in controlling plume dynamics, with implications for parameterizing the exchange flow and submarine melt in glacial fjord models.

  16. Evaluating the hydrostatic equilibrium of the subglacial Lake Vostok, Antarctica, using a precise regional geoid model (United States)

    Schwabe, Joachim; Ewert, Heiko; Scheinert, Mirko; Dietrich, Reinhard


    We present a study on the determination and application of a precise geoid model for the region of the subglacial Lake Vostok, Antarctica. The geoid model is derived by combining a global satellite-only geopotential model mainly based on GOCE data with dense airborne gravity data and topographic information. Ice-thickness data and lake water depths are used for a residual terrain modelling (RTM) in a remove-restore approach. In that context, special focus is given to the correct treatment of the ice sheet when computing the residual terrain effects. The use of the refined regional geoid model for glaciological and geophysical applications is exemplarily demonstrated by means of the hydrostatic equilibrium surface (HE) of the lake. It was found that the mean quadratic residual geoid signal is about two times larger than the estimated deviations of the HE surface. Thus, the significance of the refined geoid solution is proven. In this context, a comparison with the strictly computed geopotential shows that the estimated apparent lake level may be expressed as a constant metric bias w.r.t. to the quasigeoid. Furthermore, the HE condition is used to derive an adjusted estimate of the lake water density. However, in this case the theoretical latitudinal trend of the equilibrium surface needs to be taken into account. Finally, the (hypothetical) deviations from the HE state at and around the shoreline of the lake indicate candidate outflow locations in case of a possible depletion event.

  17. Ecology of Subglacial Lake Vostok (Antarctica, Based on Metagenomic/Metatranscriptomic Analyses of Accretion Ice

    Directory of Open Access Journals (Sweden)

    Tom D'Elia


    Full Text Available Lake Vostok is the largest of the nearly 400 subglacial Antarctic lakes and has been continuously buried by glacial ice for 15 million years. Extreme cold, heat (from possible hydrothermal activity, pressure (from the overriding glacier and dissolved oxygen (delivered by melting meteoric ice, in addition to limited nutrients and complete darkness, combine to produce one of the most extreme environments on Earth. Metagenomic/metatranscriptomic analyses of ice that accreted over a shallow embayment and over the southern main lake basin indicate the presence of thousands of species of organisms (94% Bacteria, 6% Eukarya, and two Archaea. The predominant bacterial sequences were closest to those from species of Firmicutes, Proteobacteria and Actinobacteria, while the predominant eukaryotic sequences were most similar to those from species of ascomycetous and basidiomycetous Fungi. Based on the sequence data, the lake appears to contain a mixture of autotrophs and heterotrophs capable of performing nitrogen fixation, nitrogen cycling, carbon fixation and nutrient recycling. Sequences closest to those of psychrophiles and thermophiles indicate a cold lake with possible hydrothermal activity. Sequences most similar to those from marine and aquatic species suggest the presence of marine and freshwater regions.

  18. Glacial removal of late Cenozoic subglacially emplaced volcanic edifices by the West Antarctic ice sheet (United States)

    Behrendt, John C.; Blankenship, D.D.; Damaske, D.; Cooper, A. K.


    Local maxima of the horizontal gradient of pseudogravity from closely spaced aeromagnetic surveys over the Ross Sea, northwestern Ross Ice Shelf, and the West Antarctic ice sheet, reveal a linear magnetic rift fabric and numerous subcircular, high-amplitude anomalies. Geophysical data indicate two or three youthful volcanic edifices at widely separated areas beneath the sea and ice cover in the West Antarctic rift system. In contrast, we suggest glacial removal of edifices of volcanic sources of many more anomalies. Magnetic models, controlled by marine seismic reflection and radar ice-sounding data, allow us to infer that glacial removal of the associated late Cenozoic volcanic edifices (probably debris, comprising pillow breccias, and hyaloclastites) has occurred essentially concomitantly with their subglacial eruption. "Removal' of unconsolidated volcanic debris erupted beneath the ice is probably a more appropriate term than "erosion', given its fragmented, ice-contact origin. The exposed volcanoes may have been protected from erosion by the surrounding ice sheet because of more competent rock or high elevation above the ice sheet. -from Authors

  19. Subglacial hydrology of the lake district ice lobe during the Younger Dryas (ca. 12 500 - 11 600 years ago) in the Kylaeniemi area, SE Finland

    Energy Technology Data Exchange (ETDEWEB)

    Lunkka, J. P.; Moisio, K.; Vainio, A. [Univ. of Oulu (Finland)


    It is essential to gain knowledge on the subglacial hydrological conditions at the glacier bed / bedrock interface when assessing how bedrock fracture zones affect subglacial melt water flow and in which subglacial zones pressurized and oxygen-rich melt water penetrates into the bedrock fracture systems. In the warm-based glacier zones, a part of subglacial melt water will penetrate deep into the fracture systems although the major part of melt water is drained to and beyond the ice margin via subglacial tunnel networks especially in the areas where ice is flowing on the crystalline bedrock. During the last deglaciation phase of the former Scandinavian Ice Sheet, glaciofluvial accumulations were deposited and these sediment accumulations are highly important when picturing the subglacial hydrology of different ice streams during deglaciation in the crystalline bedrock area. The aim of the present work was to map the bedrock fracture zones in the Kylaeniemi area and to shed light on the subglacial hydrology of the Scandinavian Ice Sheet's Lake District Ice Stream that occupied the Kylaeniemi area during the Younger Dryas between ca. 12 500 - 11 600 years ago. The special emphasis within this general aim was to study the relationship between bedrock fracture zones and the routes of subglacial drainage paths. The methods used to map and study bedrock fracture zones and subglacial drainage paths included remotes sensing methods, field observations, ground penetrating radar (GPR) investigations and GIS-based reconstructions. Conventional geological field methods aided by the GPR-method were also used to map bedrock exposures and their structures and to define the type of glaciofluvial sediments and glaciofluvial landform associations. Two main fracture zone sets occur in the study area. The most prominent bedrock fracture zone set trends NW-SE while the other, less prominent fracture zone set is aligned in NE-SW direction. The majority of the minor joint sets in

  20. Regional reconstruction of subglacial hydrology and glaciodynamic behaviour along the southern margin of the Cordilleran Ice Sheet in British Columbia, Canada and northern Washington State, USA (United States)

    Lesemann, Jerome-Etienne; Brennand, Tracy A.


    Subglacial landsystems in and around Okanagan Valley, British Columbia, Canada are investigated in order to evaluate landscape development, subglacial hydrology and Cordilleran Ice Sheet dynamics along its southern margin. Major landscape elements include drumlin swarms and tunnel valleys. Drumlins are composed of bedrock, diamicton and glaciofluvial sediments; their form truncates the substrate. Tunnel valleys of various scales (km to 100s km length), incised into bedrock and sediment, exhibit convex longitudinal profiles, and truncate drumlin swarms. Okanagan Valley is the largest tunnel valley in the area and is eroded >300 m below sea level. Over 600 m of Late Wisconsin-age sediments, consisting of a fining-up sequence of cobble gravel, sand and silt fill Okanagan Valley. Landform-substrate relationships, landform associations, and sedimentary sequences are incompatible with prevailing explanations of landsystem development centred mainly on deforming beds. They are best explained by meltwater erosion and deposition during ice sheet underbursts. During the Late-Wisconsin glaciation, Okanagan Valley functioned as part of a subglacial lake spanning multiple connected valleys (few 100s km) of southern British Columbia. Subglacial lake development started either as glaciers advanced over a pre-existing sub-aerial lake (catch lake) or by incremental production and storage of basal meltwater. High geothermal heat flux, geothermal springs and/or subglacial volcanic eruptions contributed to ice melt, and may have triggered, along with priming from supraglacial lakes, subglacial lake drainage. During the underburst(s), sheetflows eroded drumlins in corridors and channelized flows eroded tunnel valleys. Progressive flow channelization focused flows toward major bedrock valleys. In Okanagan Valley, most of the pre-glacial and early-glacial sediment fill was removed. A fining-up sequence of boulder gravel and sand was deposited during waning stages of the underburst(s) and

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

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


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

  2. Modelling multiple mineral precipitation in anaerobic digester liquor. (United States)

    van Rensburg, P; Musvoto, E V; Wentzel, M C; Ekama, G A


    Mineral precipitation problems have been experienced with the conveyance and treatment of anaerobically digested primary and waste activated sludge blends. This paper describes an experimental investigation into mineral precipitation in anaerobic digester liquor (ADL) from the Cape Flats (CF) Wastewater Treatment Plant (WWTP) (Cape Town, South Africa), and application of the three-phase (aqueous/solid/gas) physical and chemical processes kinetic model developed by Musvoto et al. (Water Res. 34 (2000) 1857; Water Res. 34 (2000) 1868; Water SA 26(4) (2000) 417) to the experimental data. From the experimental investigation and theoretical modelling, it is concluded inter alia that: (i) there is a close correlation between experimental measured and theoretically predicted data, (ii) the dominating mineral that precipitates is struvite, with small amounts of amorphous calcium phosphate and negligible newberyite, calcite and magnesite, (iii) the precipitation of struvite is governed by the increase in pH when CO2 is lost from the ADL, (iv) the ADL is initially undersaturated with respect to struvite, but becomes supersaturated at pH > 7.3-7.7, (v) the rate and mass of struvite precipitation are controlled by the rate of pH increase and the initial Mg concentration and (vi) the three-phase kinetic model is able to simulate accurately the time dependent precipitation data for multiple minerals competing for the same species and allows determination of specific precipitation rates for a number of minerals simultaneously in an integrated manner from a single batch test. Some operational strategies to minimise struvite precipitation are proposed.

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

    Jacobson, Andrew D.; Wu, Lingling


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


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

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

    Directory of Open Access Journals (Sweden)

    Zijie Ren


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

  7. Tectonic and erosion-driven uplift in the Gamburtsev Subglacial Mountains of East Antarctica (United States)

    Ferraccioli, Fausto; Jordan, Tom; Watts, Tony; Bell, Robin; Jamieson, Stewart; Finn, Carol; Damaske, Detlef


    Understanding the mechanisms leading to intraplate mountain building remains a significant challenge in Earth Sciences compared to ranges formed along plate margins. The most enigmatic intraplate mountain range on Earth is the Gamburtsev Subglacial Mountains (GSM) located in the middle of the Precambrian East Antarctic Craton. During the International Polar Year, the AGAP project acquired 120,000 line km of new airborne geophysical data (Bell et al., 2011, Science) and seismological observations (Hansen et al., 2010, EPSL) across central East Antarctica. Models derived from these datasets provide new geophysical perspectives on crustal architecture and possible uplift mechanisms for the enigmatic GSM (Ferraccioli et al., 2011, Nature). The geophysical data define a 2,500-km-long Paleozoic to Mesozoic rift system in East Antarctica surrounding the GSM. A thick high-density lower crustal root is partially preserved beneath the range and has been interpreted as formed during the Proterozoic assembly of East Antarctica. Rifting could have triggered phase/density changes at deep crustal levels, perhaps restoring some of the latent root buoyancy, as well as causing rift-flank uplift. Permian rifting is well-established in the adjacent Lambert Rift, and was followed by Cretaceous strike-slip faulting and transtension associated with Gondwana break-up; this phase may have provided a more recent tectonic trigger for the initial uplift of the modern GSM. The Cretaceous rift-flank uplift model for the Gamburtsevs is appealing because it relates the initiation of intraplate mountain-building to large-scale geodynamic processes that led to the separation of Greater India from East Antarctica. It is also consistent with several geological and geophysical interpretations within the Lambert Rift. However, recent detrital thermochrology results from Oligocene-Quaternary sediments in Prydz Bay (Tochlin et al., 2012, G3) argue against the requirement for major Cretaceous rift

  8. Finding clouds, dunes, crevasses and subglacial valleys with surface-texture maps of Antarctica (United States)

    Smith, B. E.; Haran, T. M.; Morin, P. J.; Porter, C. C.; Scambos, T. A.


    An experienced glaciologist can often look at a satellite image of Antarctica and quickly identify glaciers, ice streams, ice shelves, and interstream ridges, and can easily distinguish cloudy from cloud-free images. These distinctions rely on the surface texture of the ice sheet, as revealed by the interaction of sunlight with small slope variations. We present a simple scheme for mapping quantities related to surface texture that are distinct between different ice-sheet terrains. We use the statistics of windowed Fourier transforms of images to map brightness variance in different ranges of scales, and to map the anisotropy of the variations at these scales. Based on the cloud cleared, resolution-enhanced MOA mosaic of Antarctica, we derive roughness and anisotropy estimates at scales between 0.25 and 16 km. While the major distinction between different terrains at these scales is in the variance spectrum, anisotropy is a strong marker of fast-flowing ice. Superimposed on these patterns are aeolean features generated by the interaction of snowfall, wind, and surface topography. In particular, Megadune fields have a distinct spectrum, with a strong spectral peak in the 1-4 km band. This signature is evident in known megadune fields, but can also be seen elsewhere, perhaps because aeolean features in the new areas lack spatial coherence. Based on this, the spatial patterns in accumulation associated with megadunes may be more prevalent that previously identified. MOA texture also shows unusually smooth areas over subglacial valley bottoms throughout Antarctica. This mapping may help in the design of future airborne-radar surveys in areas where the subglacial topography has not previously been measured. Applied to high-resolution imagery from Worldview satellites, at scales between one and 256 meters, our analysis allows easy mapping of crevasse fields, and reveals a widespread, consistent small-scale texture on inland ice associated with sastrugi and meter

  9. Paleoclimatic Inferences from a 120,000-Yr Calcite Record of Water-Table Fluctuation in Browns Room of Devils Hole, Nevada (United States)

    Szabo, B. J.; Kolesar, Peter T.; Riggs, A.C.; Winograd, I.J.; Ludwig, K. R.


    The petrographic and morphologic differences between calcite precipitated below, at, or above the present water table and uranium-series dating were used to reconstruct a chronology of water-table fluctuation for the past 120,000 yr in Browns Room, a subterranean air-filled chamber of Devils Hole fissure adjacent to the discharge area of the large Ash Meadows groundwater flow system in southern Nevada. The water table was more than 5 m above present level between about 116,000 and 53,000 yr ago, fluctuated between about +5 and +9 m during the period between about 44,000 and 20,000 yr ago, and declined rapidly from +9 to its present level during the past 20,000 yr. Because the Ash Meadows groundwater basin is greater than 12,000 km2 in extent, these documented water-table fluctuations are likely to be of regional significance. Although different in detail, water-level fluctuation recorded by Browns Room calcites generally correlate with other Great Basin proxy palcoclimatic data.

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

    Directory of Open Access Journals (Sweden)

    Jiaqing Liu


    Full Text Available Oil and gas have been found in the Upper Ordovician Lianglitag Formation carbonates in the Tahe Oilfield, Tarim Basin, NW China. This study documents the origin of diagenetic fluids by using a combination of petrology, SIMS, fluid inclusion, and radiogenic isotope analysis. Six stages of calcite cements were revealed. C1-C2 formed in marine to early burial environments. C3 has relatively low δ18OVPDB values (−8.45‰ to −6.50‰ and likely has a meteoric origin. Meteoric water probably fluxed into aquifers during the Early Paleozoic and Late Paleozoic uplift. C4 has δ18OVPDB values typically 3‰ higher than those of C3, and probably formed during shallow burial. C5 displays relatively negative δ18OVPDB values (−8.26‰ to −5.12‰, and the moderate-to-high fluid-inclusion temperatures imply that it precipitated in burial environments. C6 shows homogenization temperatures (up to 200°C higher than the maximum burial and much lower salinities (<10.61 wt% NaCl, which may suggest that the fluid was deeply recycled meteoric water. The average 87Sr/86Sr ratios of fracture- and vug-filling calcite cements are much higher, indicative of incorporation of radiogenic Sr. Caves and fractures constitute the dominant reservoir spaces. A corresponding diagenesis-related reservoir evolution model was established that favors exploration and prediction.

  11. Stable water isotopic composition of the Antarctic subglacial Lake Vostok: implications for understanding the lake's hydrology. (United States)

    Ekaykin, Alexey A; Lipenkov, Vladimir Y; Kozachek, Anna V; Vladimirova, Diana O


    We estimated the stable isotopic composition of water from the subglacial Lake Vostok using two different sets of samples: (1) water frozen on the drill bit immediately after the first lake unsealing and (2) water frozen in the borehole after the unsealing and re-drilled one year later. The most reliable values of the water isotopic composition are: -59.0 ± 0.3 ‰ for oxygen-18, -455 ± 1 ‰ for deuterium and 17 ± 1 ‰ for d-excess. This result is also confirmed by the modelling of isotopic transformations in the water which froze in the borehole, and by a laboratory experiment simulating this process. A comparison of the newly obtained water isotopic composition with that of the lake ice (-56.2 ‰ for oxygen-18, -442.4 ‰ for deuterium and 7.2 ‰ for d-excess) leads to the conclusion that the lake ice is very likely formed in isotopic equilibrium with water. In turn, this means that ice is formed by a slow freezing without formation of frazil ice crystals and/or water pockets. This conclusion agrees well with the observed physical and chemical properties of the lake's accreted ice. However, our estimate of the water's isotopic composition is only valid for the upper water layer and may not be representative for the deeper layers of the lake, so further investigations are required.

  12. Semi-automated extraction of longitudinal subglacial bedforms from digital terrain models - Two new methods (United States)

    Jorge, Marco G.; Brennand, Tracy A.


    Relict drumlin and mega-scale glacial lineation (positive relief, longitudinal subglacial bedforms - LSBs) morphometry has been used as a proxy for paleo ice-sheet dynamics. LSB morphometric inventories have relied on manual mapping, which is slow and subjective and thus potentially difficult to reproduce. Automated methods are faster and reproducible, but previous methods for LSB semi-automated mapping have not been highly successful. Here, two new object-based methods for the semi-automated extraction of LSBs (footprints) from digital terrain models are compared in a test area in the Puget Lowland, Washington, USA. As segmentation procedures to create LSB-candidate objects, the normalized closed contour method relies on the contouring of a normalized local relief model addressing LSBs on slopes, and the landform elements mask method relies on the classification of landform elements derived from the digital terrain model. For identifying which LSB-candidate objects correspond to LSBs, both methods use the same LSB operational definition: a ruleset encapsulating expert knowledge, published morphometric data, and the morphometric range of LSBs in the study area. The normalized closed contour method was separately applied to four different local relief models, two computed in moving windows and two hydrology-based. Overall, the normalized closed contour method outperformed the landform elements mask method. The normalized closed contour method performed on a hydrological relief model from a multiple direction flow routing algorithm performed best. For an assessment of its transferability, the normalized closed contour method was evaluated on a second area, the Chautauqua drumlin field, Pennsylvania and New York, USA where it performed better than in the Puget Lowland. A broad comparison to previous methods suggests that the normalized relief closed contour method may be the most capable method to date, but more development is required.

  13. Quasi-100 ky glacial-interglacial cycles triggered by subglacial burial carbon release

    Directory of Open Access Journals (Sweden)

    N. Zeng


    Full Text Available A mechanism is proposed in which climate, carbon cycle and icesheets interact with each other to produce a feedback that can lead to quasi-100 ky glacial-interglacial cycles. A central process is the burial and preservation of organic carbon by icesheets which contributes to the observed glacial-interglacial CO2 change (the glacial burial hypothesis, Zeng, 2003. Allowing carbon cycle to interact with physical climate, here I further hypothesize that deglaciation can be triggered by the ejection of glacial burial carbon when a major icesheet grows to sufficiently large size after a prolonged glaciation so that subglacial transport becomes significant. Glacial inception may be initiated by CO2 drawdown due to a relaxation from a high but transient interglacial CO2 value as the land-originated CO2 invades into deep ocean via thermohaline circulation and CaCO3 compensation. Also important for glacial inception may be the CO2 uptake by vegetation and soil regrowth in the previously ice-covered regions. When tested in a fully coupled Earth system model with comprehensive carbon cycle components and semi-empirical physical climate components, it produced under certain parameter regimes self-sustaining glacial-interglacial cycles with durations of 93 ky, CO2 changes of 90 ppmv, temperature changes of 6°C. Since the 100 ky cycles can not be easily explained by the Milankovitch astronomical forcing alone, this carbon-climate-icesheet mechanism provides a strong feedback that could interact with external forcings to produce the major observed Quaternary climatic variations. It is speculated that some glacial terminations may be triggered by this internal feedback while others by orbital forcing. Some observable consequences are highlighted that may support or falsify the theory.

  14. A subglacial meltwater channel system in Marguerite Bay: observations from sediment cores, an underwater ROV and ship-mounted instruments (United States)

    Hogan, Kelly; Dowdeswell, Julian; Bartholomew, Ian; Noormets, Riko; Evans, Jeffrey; Cofaigh, Colm Ó.


    On the western Antarctic Peninsula grounded ice is known to have advanced through Marguerite Bay to a position at the shelf edge during the last glacial. Multibeam bathymetry from Marguerite Trough have revealed streamlined subglacial bedforms along the length of the trough and meltwater features (subglacial basins and channels) in the bay and on the inner to middle continental shelf. The channels are inferred to be subglacial in origin based on the fact that they have sections with negative slope gradients and areas of overdeepening along their thalwegs. We investigate the subglacial channel systems on the continental shelf in several ways. First, we investigate channel origin by analysing a series of sediment cores acquired in the channels and in the flat areas immediately in front of them. Interestingly, the cores record a relatively "normal" Late Pleistocene glacial-postglacial stratigraphy of (glacial) diamicts overlain by (post-glacial) hemipelagic muds and do not sample any waterlain sediments (bedded sands, gravels). Physical parameters from the cores allow us to correlate these facies with sediment cores further out on the continental shelf (cf. Kilfeather et al., 2011) suggesting that ice was grounded in the channel system during the last glacial. Secondly, we investigate channel morphometry using high-resolution multibeam data (gridded surfaces have cell sizes c. 0.4 m) and the medium-resolution multibeam data (grid cell sizes of c. 40 m) from ship-mounted systems; the data are complimented by seafloor photographs taken by the Isis ROV. Integration of the these data reveals that the side slopes of the channels are much steeper than originally thought, with some even being undercut, which will affect estimates of potential meltwater flux through the channel system. Given the incredibly large meltwater fluxes that would be required for continuous flow through the channel system, and the evidence for grounded ice during the last glacial, we consider it

  15. A sedimentary record of middle Holocene precipitation and terrestrial vertebrates from Great Cistern Blue Hole (Abaco Island), The Bahamas (United States)

    Sullivan, R.; van Hengstum, P. J.; Winkler, T. S.; Donnelly, J. P.; Albury, N. A.; Steadman, D. W.


    Sinkholes and blueholes provide sheltered basins on carbonate landscapes for sediments and fossils to accumulate and remain protected from reworking by coastal processes. These sedimentary archives can span hundreds to thousands of years and may contain detailed records of environmental change and landscape evolution. Great Cistern Blue Hole on Great Abaco Island in the northern Bahamas provides such an archive. Today situated a few meters above sea level in the coastal zone, Great Cistern was likely located further inland prior to a geometric change to the local coastline and during lower sea-level. To explore the long-term record of environmental change in this region, sediment cores were collected between 2014 and 2015 that yielded an 8,000-year record of continuous sedimentation. Visual inspection of the core revealed multiple intervals dominated by coarse-grained sediment that subsequent microscopic examination identified as fragments of calcite rafts. Calcite rafts (common in caves) precipitate at an air-groundwater interface in quiescent environments from the offgassing of calcium carbonate saturated groundwater. The recurrent precipitation of calcite rafts in a sinkhole potentially reflects intervals of increased discharge of the local coastal aquifer in response to increased precipitation. The onset, peak, and decline of the calcite raft deposits are consistent with other precipitation proxy records from the Caribbean region, suggesting that the deposition is providing direct evidence for middle Holocene precipitation patterns in the northern Bahamas. In addition, numerous vertebrate bones have accumulated in Great Cistern including those of a Bahamian Boa (age: 7ka yBP), a species of crocodile no longer present on Abaco Island (age: 2ka yBP), and pre-European contact human remains (age: 600 yBP). As the project continues, other bones will be identified that may serve to enhance our knowledge of human and animal activity on the island.

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

    Energy Technology Data Exchange (ETDEWEB)



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

  17. Global Precipitation Measurement Poster (United States)

    Azarbarzin, Art


    This poster presents an overview of the Global Precipitation Measurement (GPM) constellation of satellites which are designed to measure the Earth's precipitation. It includes the schedule of launches for the various satellites in the constellation, and the coverage of the constellation, It also reviews the mission capabilities, and the mission science objectives.

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

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


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

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

    Miura, Y.


    Shocked minerals with simple chemical composition of silica, carbon or iron material reveal high-pressure phase during compression process [1]. As calcite mineral shows high-pressure phase of aragonite it should have the "shocked phase" formed from high-pressure phase mixed with quenched materials of gas-melt reaction [2,3,4]. The main purposes of this paper are (1) to discuss new shocked materials of calcite found in the Noerdlingen Ries impact crater. Germany and artificial impact phases. and (2) to show new findings of fine Fe-grains and anomalous plagioclase in suevite. Single grains of anomalous calcite for X-ray analysis were selected from limestone with wormy or bubble-included texture in Buschelberg Ries impact crater (sample R8) [3 4]. Powdered and single grain samples of anomalous calcites show low X-ray intensity and high Bragg angle shift. compared with standard calcite of Akiyoshi limestone as listed in Table 1 [2.3.4]. The unit-cell dimensions of the single grain measured with the four-axes X-ray diffractometer in Yamaguchi University were determined by the least square calculation from the "highest X-ray intensity peak" of each crystal plane which is the same data of the powdered X-ray diffraction sample as an average structure . Both powdered and single grain data reveal high density of 2.76 g/cm^3 (between aragonite of density: rho=2.8g/cm^3, and normal calcite: rho=2.71g/cm^3) of the calcite cell which is the same characters of shocked phases of quartz or graphite [1,2,3,4] (Table 1). Anomalous calcite contains minor amount of Si Fe Ti, though major cation is Ca of 99.4% in cation content. These foreign elements are mixed with during the formation in vapor plume [5]. Table 1, showing the x-ray density and unit-cell parameters of anomalous shocked calcite with high density from Ries and artificial impact craters, appears here in the hard copy. Two types of shocked calcites are found in artificial impact experiments of railgun of the ISAS. Japan. (a

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

    Directory of Open Access Journals (Sweden)

    Hristova E.


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

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

    DEFF Research Database (Denmark)

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


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

  2. Catalyzed precipitation in aluminum (United States)

    Mitlin, David

    The work reported in Chapter 1 concerned the influence of Si on the precipitation of theta' (metastable Al2Cu) during the isothermal aging of Al-2Cu-1Si (wt. %). The binary alloys Al-2Cu and Al-1Si were studied for comparison. Only two precipitate phases were detected: pure Si in Al-Si and Al-Cu-Si, and theta' (metastable Al 2Cu) in Al-Cu and Al-Cu-Si. On aging the ternary, Si precipitates first, and provides heterogeneous sites to nucleate theta'. As a consequence, the density of theta' precipitates in Al-Cu-Si is much higher than in the binary Al-Cu. Also, the theta ' precipitates in the ternary alloy have lower aspect ratio (at given particle size) and lose coherence on their broad faces at a slower rate. The principal focus of Chapter 2 is to explain precipitation in Al-lat.%Si-lat%Ge. The microstructure is characterized using conventional and high resolution transmission electron microscopy, as well as energy dispersive X-ray spectroscopy. The first precipitates to come out of solid solution have a cube-cube orientation relationship with the matrix. High resolution TEM demonstrated that all the precipitates start out, and remain multiply twinned throughout the aging treatment. There is a variation in the stoichiometry of the precipitates, with the mean composition being Si-44.5at%Ge. It is also shown that in Al-Si-Ge it is not possible to achieve satisfactory hardness through a conventional heat treatment. This result is explained in terms of sluggish precipitation of the diamond-cubic Si-Ge phase coupled with particle coarsening. The purpose of Chapters 3 and 4 is to explain these properties in terms of the role that the Si-Ge additions have on modifying the conventional Al-Cu aging sequence. In both AlCu and AlCuSiGe the room temperature microstructure consists of both GP zones and theta″ precipitates. Upon aging at 190°C Al-Cu displays the well known precipitation sequence; the slow dissolution of GP zones and theta″ and the gradual formation of theta

  3. Calcite raft geochemistry as a hydrological proxy for Holocene aquifer conditions in Hoyo Negro and Ich Balam (Sac Actun Cave System), Quintana Roo, Mexico (United States)

    Kovacs, Shawn E.; Reinhardt, Eduard G.; Chatters, James C.; Rissolo, Dominique; Schwarcz, Henry P.; Collins, Shawn V.; Kim, Sang-Tae; Nava Blank, Alberto; Luna Erreguerena, Pilar


    Two cores from calcite rafts deposits located in Cenote Ich Balam and Hoyo Negro were dated and analyzed for 87Sr/86Sr, δ18O, δ13C, Sr/Ca and Cl/Ca. The geochemical records show changing aquifer salinity spanning the last ∼ 8.5 cal kyrs BP and interrelationships with Holocene climate trends (wet and dry periods). During the wet mid-Holocene, the salinity of the meteoric Water Mass (WM; at 7.8-8.3 cal kyrs BP) was relatively high at 1.5-2.7 ppt and then became less saline (1.0-1.5 ppt) during the last ∼ 7000 yrs as climate became progressively drier. High salinity of the meteoric WM during the wet mid-Holocene is attributed to increased turbulent mixing between the meteoric and underlying marine WM. Increased precipitation, in terms of amount, frequency, and intensity (e.g. hurricanes) causes higher flow of meteoric water towards the coast and mixing at the halocline, a phenomenon recorded with recent instrumental monitoring of the aquifer. Conversely, during dry periods reduced precipitation and flow in the meteoric WM would result in lower salinity. Karst properties and Holocene sea-level rise also seem to have an effect on the aquifer. When the regionally extensive network of shallow cave passages (∼ 10-12 m water depth) are flooded at ∼ 8000 cal yrs BP, there is a rapid shift in salinity. This study demonstrates that calcite raft deposits can be used as paleo-environmental recorders documenting the effects of sea level and climate change on aquifer condition.

  4. δ13C signal of earthworm calcite granules: A new proxy for palaeoprecipitation reconstructions during the Last Glacial in western Europe (United States)

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


    Quantification of paleoprecipitation during the Last Glacial is a key element to reconstruct palaeoclimates. Recently, fossil calcite granules have been identified in loess sequences with high contents in specific horizons. In this study, we explored for the first time the potential of this new bio-indicator as a climatic proxy for precipitation in western Europe during the Last Glacial. We extracted 30 granules from eleven samples belonging to three tundra gleys and two brown soils from the Nussloch loess sequence previously dated between 50 and 20 ka. Stable carbon isotope measurements were performed on each granule and duplicated. Throughout the studied section, δ13C values range from -15.4 to -10.3‰ for tundra gleys and from -14.9 to -9.5‰ for brown soils. By taking into account the fractionation factor between the carbon ingested by the earthworm and the carbon output of the granules, the δ13C values of these granules reflect the composition of the C3 plant vegetation cover. Thus, we estimated the δ13C of the plants with a mean value of -24.3 ± 0.9‰ for tundra gleys and -24.1 ± 0.9‰ for brown soils, which are in agreement with values obtained from organic matter preserved in sediments. Palaeoprecipitation range over both tundra gley horizons and brown soils were estimated at about 333[159-574] mm/yr by using an empirical relationship determined between present-day plant leaf isotopic discrimination and the mean annual precipitation. This original preliminary study highlights the potential of earthworm calcite granule δ13C measurements as a new proxy for paleoprecipitation during the Last Glacial interstadials in continental environments.

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

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


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

  6. A Laboratory Investigation of the Effects of Subglacial Meltwater Plumes on Submarine Ablation at the Fronts of Tidewater Glaciers (United States)

    Kerr, R. C.; McConnochie, C. D.


    We investigate experimentally the effect of a basal freshwater source on the ablation of a vertical ice wall in salty water. We measure as a function of height the turbulent wall plume velocity, the ablation velocity of the ice, and the temperature at the ice wall. By systematically varying the volume flow rate of the freshwater source, we determine where the turbulent wall plume transitions from a free convection regime (controlled by the distributed buoyancy flux due to dissolution of the ice) to a forced convection regime (controlled by the buoyancy flux Bs of the basal freshwater source). In the forced convection regime, we find that the turbulent plume velocity is uniform with height and is proportional to Bs1/3, the interface temperature is independent of Bs, and the ablation velocity increases with Bs. In the two convection regimes, we find that there are fundamental differences in the wall turbulent plume, the turbulent entrainment coefficient, and the detrainment from the turbulent plume at the top of the wall. Lateral variations in subglacial discharge rates can enable these regimes to occur simultaneously along the front of a tidewater glacier, which will result in subglacial meltwater and submarine meltwater being seen at differing depths in the Greenland fjords.

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

    DEFF Research Database (Denmark)

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


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

  8. The Subglacial Access and Fast Ice Research Experiment - SAFIRE - on Store Glacier, West Greenland (United States)

    Christoffersen, P.; Hubbard, B. P.; Doyle, S. H.; Young, T. J.; Hofstede, C. M.; Bougamont, M. H.; Todd, J.; Toberg, N.; Nicholls, K. W.; Box, J.; Walter, J. I.; Hubbard, A.


    Marine-terminating outlet glaciers drain 90 percent of the Greenland Ice Sheet and are responsible for about half of the ice sheet's net annual mass loss, which currently raises global sea level by 1 mm per year. The basal controls on these fast-flowing glaciers are, however, poorly understood, with the implication that numerical ice sheet models needed to predict future dynamic ice loss from Greenland relies on uncertain and often untested basal parameterizations. The Subglacial Access and Fast Ice Research Experiment - SAFIRE - is addressing this paucity of observational constraints by drilling to the bed of Store Glacier, a fast-flowing outlet glacier terminating in Uummannaq Fjord, West Greenland. In 2014, we gained access to the bed in four boreholes drilled to depths of 603-616 m near the center of the glacier, 30 km inland from the calving terminus where ice flows at a rate of 700 m/year. A seismic survey showed the glacier bed to consist of water-saturated, soft sediment. The water level in all four boreholes nevertheless dropped rapidly to 80 m below the ice surface when the drill connected with a basal water system, indicating effective drainage over a sedimentary bed. We were able to install wired sensor strings at the bed (water pressure, temperature, electrical conductivity and turbidity) and within the glacier (temperature and tilt) in three boreholes. The sensors operated for up to 80+ days before cables stretched and ultimately snapped due to high internal strain. The data collected during this sensor deployment show ice as cold as -21 degrees Celcius; yet, temperature of water in the basal water system was persistently above the local freezing point. With diurnal variations detected in several sensor records, we hypothesise that surface water lubricates the ice flow while also warming basal ice. The fast basal motion of Store Glacier not only occurs by basal sliding, but from high rates of concentrated strain in the bottom third of the glacier

  9. Surface Features Parameterization and Equivalent Roughness Height Estimation of a Real Subglacial Conduit in the Arctic (United States)

    Chen, Y.; Liu, X.; Manko ff, K. D.; Gulley, J. D.


    The surfaces of subglacial conduits are very complex, coupling multi-scale roughness, large sinuosity, and cross-sectional variations together. Those features significantly affect the friction law and drainage efficiency inside the conduit by altering velocity and pressure distributions, thus posing considerable influences on the dynamic development of the conduit. Parameterizing the above surface features is a first step towards understanding their hydraulic influences. A Matlab package is developed to extract the roughness field, the conduit centerline, and associated area and curvature data from the conduit surface, acquired from 3D scanning. By using those data, the characteristic vertical and horizontal roughness scales are then estimated based on the structure functions. The centerline sinuosities, defined through three concepts, i.e., the traditional definition of a fluvial river, entropy-based sinuosity, and curvature-based sinuosity, are also calculated and compared. The cross-sectional area and equivalent circular diameter along the centerline are also calculated. Among those features, the roughness is especially important due to its pivotal role in determining the wall friction, and thus an estimation of the equivalent roughness height is of great importance. To achieve such a goal, the original conduit is firstly simplified into a straight smooth pipe with the same volume and centerline length, and the roughness field obtained above is then reconstructed into the simplified pipe. An OpenFOAM-based Large-eddy-simulation (LES) is then performed based on the reconstructed pipe. Considering that the Reynolds number is of the order 106, and the relative roughness is larger than 5% for 60% of the conduit, we test the validity of the resistance law for completely rough pipe. The friction factor is calculated based on the pressure drop and mean velocity in the simulation. Working together, the equivalent roughness height can be calculated. However, whether the

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

    DEFF Research Database (Denmark)

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


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

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

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

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

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


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


    Directory of Open Access Journals (Sweden)

    Jan Ondruska


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

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

    DEFF Research Database (Denmark)

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


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

  15. WPA Precipitation Tabulations (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Hourly precipitation data tabulated under the Work Projects Administration (WPA), a New Deal program created to reduce unemployment during the Great Depression....

  16. Is extreme precipitation changing? (United States)

    Papalexiou, Simon Michael


    For most of the scientists climate change is a fact. Climate change implies changes not only on the behavior of the temperature but also on other climatic variables like the precipitation. The question raised in this study is whether or not the annual daily maximum precipitation has changed. In order to evaluate if this question can be answered, several thousands of precipitation records are analyzed from all over the globe. Initially the annual daily maxima time series are carefully formed and sequentially all possible trends are estimated in a moving window framework and for several interannual periods, e.g., from 10 years to 100 years. The aim is to estimate the difference between the percentage of increasing and decreasing trends in the annual daily maximum precipitation and assess if this difference indicates any specific pattern.

  17. Storage Gage Precipitation Observations (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — A storage gage is a precipitation gage that requires reading and maintenance only monthly or seasonal intervals. This library includes reports from such gages,...

  18. Impact of a localized source of subglacial discharge on the heat flux and submarine melting of a tidewater glacier : A laboratory study

    NARCIS (Netherlands)

    Cenedese, Claudia; Gatto, V.M.


    Idealized laboratory experiments have been conducted in a two-layer stratified fluid to investigate the leading-order dynamics that control submarine melting and meltwater export near a vertical ice-ocean interface as a function of subglacial discharge. In summer, the discharge of surface runoff

  19. Evidence for Subglacial Deformation and Deposition during a Complete Advance-Stagnation Cycle of Kötlujökull, Iceland – A Case Study

    DEFF Research Database (Denmark)


    deformation and deposition from dynamically active ice, (4) subglacial deposition from stagnant ice and (5) supraglacial re-deposition in dead-ice environment during de-icing. This complete sedimentary sequence represents a single glacier advance-stagnation cycle. The melt-out till displays moderate...

  20. Diversity of culturable bacteria recovered from Pico Bolívar's glacial and subglacial environments, at 4950 m, in Venezuelan tropical Andes. (United States)

    Rondón, Johnma; Gómez, Wileidy; Ball, María M; Melfo, Alejandra; Rengifo, Marcos; Balcázar, Wilvis; Dávila-Vera, Delsy; Balza-Quintero, Alirio; Mendoza-Briceño, Rosa Virginia; Yarzábal, Luis Andrés


    Even though tropical glaciers are retreating rapidly and many will disappear in the next few years, their microbial diversity remains to be studied in depth. In this paper we report on the biodiversity of the culturable fraction of bacteria colonizing Pico Bolívar's glacier ice and subglacial meltwaters, at ∼4950 m in the Venezuelan Andean Mountains. Microbial cells of diverse morphologies and exhibiting uncompromised membranes were present at densities ranging from 1.5 × 10(4) to 4.7 × 10(4) cells/mL in glacier ice and from 4.1 × 10(5) to 9.6 × 10(5) cells/mL in subglacial meltwater. Of 89 pure isolates recovered from the samples, the majority were eurypsychrophilic or stenopsychrophilic, according to their temperature range of growth. Following analysis of their 16S rDNA nucleotidic sequence, 54 pure isolates were assigned to 23 phylotypes distributed within 4 different phyla or classes: Beta- and Gammaproteobacteria, Actinobacteria, and Bacteroidetes. Actinobacteria dominated the culturable fraction of glacier ice samples, whereas Proteobacteria were dominant in subglacial meltwater samples. Chloramphenicol and ampicillin resistance was exhibited by 73.07% and 65.38%, respectively, of the subglacial isolates, and nearly 35% of them were multiresistant. Considering the fast rate at which tropical glaciers are melting, this study confirms the urgent need to study the microbial communities immured in such environments.

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

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


    The role of dolomite on the strength and evolution of calcite-dolomite fold and thrust belts and nappes (as observed in the Canadian Rockies, the Swiss Alps, the Italian Apennines, and the Naukluft Nappe Complex) is largely unknown. Field investigations indicate that strain in natural systems is localized in calcite, resulting in a ductile response, while dolomite deforms in a dominantly brittle manner. To date, experimental studies on polymineralic carbonate systems are limited to homogeneous, fine-grained, calcite-dolomite composites of relatively low dolomite content. The effect of dolomite on limestone rheology, the onset of crystal-plastic deformation in dolomite in composites, and the potential for strain localization in composites have not yet been fully quantified. Constant displacement rate (3x10-4 s-1and 10-4 s-1), high confining pressure (300 MPa) and high temperature (750° C and 800° C) torsion experiments were conducted to address the role of dolomite on the strength of calcite-dolomite composites. Experiments were performed on samples produced by hot isostatic pressing (HIP) amalgams of a natural, pure dolomite and a reagent, pure calcite. We performed experiments on the following mixtures (given as dolomite%): 25%, 35%, 50%, and 75%. These synthetic HIP products eliminated concerns of mineralogical impurities and textural anomalies due to porosity, structural fabrics (e.g., foliation) and fossil content. The samples were deformed up to a maximum finite shear strain of 5.0 and the experimental set up was unvented to inhibit sample decarbonation. Mechanical data shows a considerable increase in sample yield strength with increasing dolomite content. Experimental products with low starting dolomite content (dol%: 25% and 35%) display macroscopic strain localization along compositionally defined foliation. Experimental products with high dolomite content (dol%: 50% and 75%) demonstrate no macroscopic foliation. Post-deformation microstructure analysis

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

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


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

  3. Dynamics of a vertical turbulent plume in a stratification typical of Greenland fjords: an idealized model of subglacial discharge (United States)

    Stenberg, Erik; Ezhova, Ekaterina; Cenedese, Claudia; Brandt, Luca


    We the report results of large eddy simulations of a turbulent buoyant plume in a configuration providing an idealized model of subglacial discharge from a submarine glacier in stratifications typical of Greenland Fjords. We neglect a horizontal momentum of the plume and assume that its influence on the plume dynamics is small and important only close to the source. Moreover, idealized models have considered the plume adjacent to the glacier as a half-conical plume (e.g., [1]). Thus, to compare the results for such plume with the classical plume theory, developed for free plumes entraining ambient fluid from all directions, it is convenient to add the second half-conical part and consider a free plume with double the total discharge as a model. Given the estimate of the total subglacial discharge for Helheim Glacier in Sermilik Fjord [2], we perform simulations with double the total discharge in order to investigate the dynamics of the flow in typical winter and summer stratifications in Greenland fjords [3]. The plume is discharged from a round source of various diameters. In winter, when the stratification is similar to an idealised two-layers case, turbulent entrainment and generation of internal waves by the plume top are in agreement with the theoretical and numerical results obtained for turbulent jets in a two-layer stratification. In summer, instead, the stratification is more complex and turbulent entrainment is significantly reduced. The subsurface layer in summer is characterized by a strong density gradient and the oscillating plume generates non-linear internal waves which are able to mix this layer even if the plume does not penetrate to the surface. The classical theory for the integral parameters of a turbulent plume in a homogeneous fluid gives accurate predictions of the plume parameters in the weakly stratified lower layer up to the pycnocline. [1] Mankoff, K. D., F. Straneo, C. Cenedese, S. B. Das, C. D. Richards, and H. Singh, 2016: Structure

  4. Examples of Models Fit to Magnetic Anomalies Observed Over Subaerial, Submarine, and Subglacial Volcanoes in the West Antarctic Rift System (United States)

    Behrendt, J. C.; Finn, C. A.; Blankenship, D. D.


    Aeromagnetic and marine magnetic surveys over the volcanically active West Antarctic rift system, constrained by seismic reflection profiles over the Ross Sea continual shelf, and radar ice sounding surveys over the West Antarctic Ice Sheet (WAIS) allowed calculation of models fit to very high-amplitude anomalies. We present several examples: exposed 2700-m high, subaerial erupted volcano Mt Melbourne; the 750-m high source of anomaly D (Hamilton submarine volcano) in the Ross sea; and the 600-m high edifice of Mt. CASERTZ beneath the WAIS. The character of these anomalies and their sources varies greatly, and is inferred to be the result of subaerial, submarine and subglacial emplacement respectively. Mt. Melbourne erupted through the WAIS at a time when it was grounded over the Ross Sea continental shelf. Highly magnetic volcanic flows inferred to have high remanent (normal) magnetization in the present field direction produce the 600-nT positive anomaly. The flows protected the edifice above the ice from erosion. Negligible amounts of probably subglacially erupted, apparently non-magnetic hyaloclastite exist in association with Mt. Melbourne. Mt. CASERTZ is nonmagnetic and the edifice is interpreted as consisting of a transient mound of unconsolidated hyaloclastite injected into the WAIS. However Mt. CASERTZ, about 8-km diameter, overlies a 200-m high, 40-km wide highly magnetic residual edifice modeled as the top of the source (an active subglacial volcano) of a 400-nT high positive anomaly. Any former edifices comprising hyaloclastite, pillow breccia or other volcanic debris injected into the moving WAIS apparently have been removed. About 400 other high- amplitude anomalies associated with low relief (80 percent less than 200 m) edifices at the base of the ice (the tops of the sources of these steep gradient anomalies) beneath the WAIS defined by radar ice sounding have been interpreted as having former hyaloclastite edifices, which were removed by the moving

  5. Impact of precipitation intermittency on NAO-temperature signals in proxy records

    Directory of Open Access Journals (Sweden)

    M. Casado


    Full Text Available In mid and high latitudes, the stable isotope ratio in precipitation is driven by changes in temperature, which control atmospheric distillation. This relationship forms the basis for many continental paleoclimatic reconstructions using direct (e.g. ice cores or indirect (e.g. tree ring cellulose, speleothem calcite archives of past precipitation. However, the archiving process is inherently biased by intermittency of precipitation. Here, we use two sets of atmospheric reanalyses (NCEP (National Centers for Environmental Prediction and ERA-interim to quantify this precipitation intermittency bias, by comparing seasonal (winter and summer temperatures estimated with and without precipitation weighting. We show that this bias reaches up to 10 °C and has large interannual variability. We then assess the impact of precipitation intermittency on the strength and stability of temporal correlations between seasonal temperatures and the North Atlantic Oscillation (NAO. Precipitation weighting reduces the correlation between winter NAO and temperature in some areas (e.g. Québec, South-East USA, East Greenland, East Siberia, Mediterranean sector but does not alter the main patterns of correlation. The correlations between NAO, δ18O in precipitation, temperature and precipitation weighted temperature are investigated using outputs of an atmospheric general circulation model enabled with stable isotopes and nudged using reanalyses (LMDZiso (Laboratoire de Météorologie Dynamique Zoom. In winter, LMDZiso shows similar correlation values between the NAO and both the precipitation weighted temperature and δ18O in precipitation, thus suggesting limited impacts of moisture origin. Correlations of comparable magnitude are obtained for the available observational evidence (GNIP (Global Network of Isotopes in Precipitation and Greenland ice core data. Our findings support the use of archives of past δ18O for NAO reconstructions.

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

    Directory of Open Access Journals (Sweden)

    Tamilselvi S.M


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

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

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


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

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

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


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

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

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


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

  10. 3D Mapping of calcite and a demonstration of its relevance to permeability evolution in reactive fractures (United States)

    Ellis, Brian R.; Peters, Catherine A.


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

  11. Heat sources for glacial ice melt in a West Greenland tidewater outlet glacier fjord: The role of subglacial freshwater discharge

    DEFF Research Database (Denmark)

    Bendtsen, Jørgen; Mortensen, John; Lennert, Kunuk


    The melting of tidewater outlet glaciers from the Greenland Ice Sheet contributes significantly to global sea level rise. Accelerated mass loss is related to melt-processes in front of calving glaciers, yet the role of ocean heat transports is poorly understood. Here we present the first direct...... measurements from a subglacial plume in front of a calving tidewater outlet glacier. Surface salinity in the plume corresponded to a meltwater content of 7 %, which is indicative of significant entrainment of warm bottom water and, according to plume model calculations, significant ice melt. Energy balance...... of the area near the glacier showed that ice melt was mainly due to ocean heat transport and that direct plume-associated melt was only important in periods with high meltwater discharge rates of ~100 m3 s−1. Ocean mixing outside of the plume area was thus the primary heat source for melting glacier ice....

  12. Final report for grant number DE-FG02-06ER64244 to the University of Idaho (RW Smith)-coupling between flow and precipitation in heterogeneous subsurface environments and effects on contaminant fate and transport

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Robert W. [Univ. of Idaho, Idaho Falls, ID (United States); Beig, Mikala S. [Univ. of Idaho, Idaho Falls, ID (United States); Gebrehiwet, Tsigabu [Univ. of Idaho, Idaho Falls, ID (United States); Corriveau, Catherine E. [Univ. of Idaho, Idaho Falls, ID (United States); Redden, George [Idaho National Lab. (INL), Idaho Falls, ID (United States); Fujita, Yoshiko [Idaho National Lab. (INL), Idaho Falls, ID (United States)


    Engineered remediation strategies for inducing mineral precipitation in the subsurface typically involve the introduction of at least one reactant either by direct injection or by in situ generation. The localization of reactant sources means a wide range of saturation states and ion ratios will be created as reactants are mixed: These conditions together can result in a wide range of precipitation rates, as well as impact which mineral phase precipitates. This is potentially important for the capacity of the precipitates to take up of trace metal contaminants, for their long term stability. Aragonite, for example, is able to sequester a larger amount of Sr than calcite. However, aragonite is less stable under typical groundwater conditions, and so may release sequestered Sr over time as the aragonite transforms to a more stable phase. In addition, previous experimental studies have indicated that other system constituents may influence calcium carbonate precipitation and consequently the Sr uptake potential of a system. For example, dissolved organic carbon (at levels typical of groundwaters) can suppress crystal growth. As a result, the continuous nucleation of small crystals, rather than growth of existing crystals, may be the dominant mode of precipitation. This has the potential for greater uptake of Sr because the smaller crystal sizes associated with nucleated calcite may more readily accommodate the distortion resulting from substitution of the larger Sr ion for Ca ions than can larger crystals. However, these smaller crystals may also be less stable and over the long term release Sr as a result of Ostwald ripening. To better understand the formation and composition of relevant calcium carbonate mineral phases two related series of mineral precipitation experiments were conducted. The first series of experiments, conducted using a Continuously Stirred Tank Reactor (CSTR) operated at steady state rates of precipitation was focused on understanding the

  13. 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


    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

  14. Origin and significance of postore dissolution collapse breccias cemented with calcite and barite at the Meikle gold deposit, Northern Carlin trend, Nevada (United States)

    Emsbo, P.; Hofstra, A.H.


    The final event in a complicated hydrothermal history at the Meikle gold deposit was gold deficient but caused extensive postore dissolution of carbonate, collapse brecciation, and precipitation of calcite and barite crystals in the resulting cavities. Although previously interpreted to be part of the Carlin-type hydrothermal system, crosscutting relationships and U-Th-Pb geochronology constrain this hydrothermal event to late Pliocene time (ca. 2 Ma), nearly 36 Ma after ore formation. Mineralogic, fluid inclusion, and stable isotope data indicate that postore hydrothermal fluids were reduced, H2S-rich, unevolved meteoric waters ((??18O = -17???) of low temperature (ca. 65??C). The ??18O values of barite and calcite indicate that these minerals were in isotopic equilibrium, requiring that barite SO4 was derived from the oxidation of reduced sulfur; however, preexisting sulfides in breccia cavities were not oxidized. The ??34S (15???) values of barite are higher than those of local bulk sulfide and supergene alunite indicating that SO4 was not derived from supergene oxidation of local sulfide minerals. The 15 per mil ??34S value suggests that the H2S in the fluids may have been leached from sulfur-rich organic matter in the local carbonaceous sedimentary rocks. A reduced H2S-rich fluid is also supported by the bright cathodoluminescence of calcite which indicates that it is Mn rich and Fe poor. Calcite has a narrow range of ??13C values (0.3-1.8???) that are indistinguishable from those of the host Bootstrap limestone, indicating that CO2 in the fluid was from dissolution of the local limestone. These data suggest that dissolution and brecciation of the Bootstrap limestone occurred where H2S-rich fluids encountered more oxidizing fluids and formed sulfuric acid (H2SO4). Intense fracturing in the mine area by previous structural and hydrothermal events probably provided conduits for the descent of oxidized surface water which mixed with the underlying H2S-rich waters

  15. Effect of some organic solvent-water mixtures composition on precipitated calcium carbonate in carbonation process (United States)

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


    Precipitated calcium carbonate particles were obtained during carbonation of calcium hydroxide slurry with carbon dioxide. Aqueous solutions of isopropyl alcohol, n-butanol and glycerol were used as solvents. Concentration of organic additives in the reactive mixture was from 0% to 20% (vol). Precipitation process were performed in a stirred tank reactor equipped with gas distributor. Multimodal courses of particles size distribution were determined for produced CaCO3 particles. Calcium carbonate as calcite was precipitated in all experiments. The mean Sauter diameter of CaCO3 particles decreased when the concentration of all used organic additives increased. The amount of small particle fraction in the product increased with the increasing concentration of organic solvents. Similar physical properties of used liquid phase resulted in the similar characteristics of obtained particles.

  16. Test of simultaneous synthetic DNA tracer injections for the estimation of the englacial and subglacial drainage system structure of Storglaciären, northern Sweden (United States)

    Dahlke, H. E.; Leung, S.; Lyon, S. W.; Sharma, A. N.; Walter, M. T.; Williamson, A.


    Storglaciären glacier, located in the sub-arctic Tarfala catchment, in northern Sweden is one of the world's longest continuously monitored glaciers which provides a unique research platform for the long-term assessment of glacier and ice sheet processes. For example, small mountain glacier hydrological knowledge of the subglacial water distribution at the ice-bed interface has been applied to ice sheets to predict basal sliding processes. Basal sliding promoted by hydraulic jacking is an important glacial-velocity control that is dependent on the subglacial flow pathways' morphology. Thus, understanding subglacial water distribution and drainage system structure and morphology is crucial for modeling ice masses' flow. In order to estimate subglacial drainage system structure and morphology dye tracing experiments are widely employed. Tracer experiments provide quantitative parameters for any input location including tracer transit velocity, dispersivity, recovery and storage. However, spatial data coverage is limited by the finite number of tracers available for simultaneous tracing. In the presented study we test the use of synthetic DNA tracers for the assessment of the englacial and subglacial drainage system structure of Storglaciären. The synthetic DNA tracer is composed of polylactic acid (PLA) microspheres into which short strands of synthetic DNA and paramagnetic iron oxide nanoparticles are incorporated (Sharma et al., 2012, Environmental Science & Technology). Because the DNA sequences can be randomly combined the synthetic DNA tracer provides an enormous number of unique tracers (approximately 1.61 x 1060). Thus, these synthetic tracers have the advantage that multiple (>10) experiments can be conducted simultaneously, allowing a greater information gain within a shorter measurement period. Quantities of a certain DNA strand can be detected using biotechnology tools such as polymerase chain reaction (PCR) and quantitative PCR (qPCR). During the 2013

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

    Busenberg, Eurybiades; Plummer, L. Niel


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

  18. The elemental composition of purple sea urchin (Strongylocentrotus purpuratus calcite and potential effects of pCO2 during early life stages

    Directory of Open Access Journals (Sweden)

    M. LaVigne


    Full Text Available Ocean acidification will likely have negative impacts on invertebrates producing skeletons composed of calcium carbonate. Skeletal solubility is partly controlled by the incorporation of "foreign" ions (e.g. magnesium into the crystal lattice of these skeletal structures, a process that is sensitive to a variety of biological and environmental factors. Here we explore effects of life stage, oceanographic region of origin, and changes in the partial pressure of carbon dioxide in seawater (pCO2 on trace elemental composition in the purple sea urchin (Strongylocentrotus purpuratus. We show that, similar to other urchin taxa, adult purple sea urchins have the ability to precipitate skeleton composed of a range of biominerals spanning low- to high-Mg calcites. Mg / Ca and Sr / Ca ratios were substantially lower in adult spines compared to adult tests. On the other hand, trace elemental composition was invariant among adults collected from four oceanographically distinct regions spanning a range of carbonate chemistry conditions (Oregon, Northern California, Central California, and Southern California. Skeletons of newly settled juvenile urchins that originated from adults from the four regions exhibited intermediate Mg / Ca and Sr / Ca between adult spine and test endmembers, indicating that skeleton precipitated during early life stages is more soluble than adult spines and less soluble than adult tests. Mean skeletal Mg / Ca or Sr / Ca of juvenile skeleton did not vary with source region when larvae were reared under present-day, global-average seawater carbonate conditions (400 μatm; pHT = 8.02 ± 0.03 1 SD; Ωcalcite = 3.3 ± 0.2 1 SD. However, when reared under elevated pCO2 (900 μatm; pHT = 7.73 ± 0.03; Ωcalcite = 1.8 ± 0.1, skeletal Sr / Ca in juveniles exhibited increased variance across the four regions. Although larvae from the northern populations (Oregon, Northern California, Central California did not exhibit differences in Mg or Sr

  19. The elemental composition of purple sea urchin (Strongylocentrotus purpuratus) calcite and potential effects of pCO2 during early life stages (United States)

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


    Ocean acidification will likely have negative impacts on invertebrates producing skeletons composed of calcium carbonate. Skeletal solubility is partly controlled by the incorporation of "foreign" ions (e.g. magnesium) into the crystal lattice of these skeletal structures, a process that is sensitive to a variety of biological and environmental factors. Here we explore effects of life stage, oceanographic region of origin, and changes in the partial pressure of carbon dioxide in seawater (pCO2) on trace elemental composition in the purple sea urchin (Strongylocentrotus purpuratus). We show that, similar to other urchin taxa, adult purple sea urchins have the ability to precipitate skeleton composed of a range of biominerals spanning low- to high-Mg calcites. Mg / Ca and Sr / Ca ratios were substantially lower in adult spines compared to adult tests. On the other hand, trace elemental composition was invariant among adults collected from four oceanographically distinct regions spanning a range of carbonate chemistry conditions (Oregon, Northern California, Central California, and Southern California). Skeletons of newly settled juvenile urchins that originated from adults from the four regions exhibited intermediate Mg / Ca and Sr / Ca between adult spine and test endmembers, indicating that skeleton precipitated during early life stages is more soluble than adult spines and less soluble than adult tests. Mean skeletal Mg / Ca or Sr / Ca of juvenile skeleton did not vary with source region when larvae were reared under present-day, global-average seawater carbonate conditions (400 μatm; pHT = 8.02 ± 0.03 1 SD; Ωcalcite = 3.3 ± 0.2 1 SD). However, when reared under elevated pCO2 (900 μatm; pHT = 7.73 ± 0.03; Ωcalcite = 1.8 ± 0.1), skeletal Sr / Ca in juveniles exhibited increased variance across the four regions. Although larvae from the northern populations (Oregon, Northern California, Central California) did not exhibit differences in Mg or Sr

  20. Effects of calcium source on biochemical properties of microbial CaCO3 precipitation

    Directory of Open Access Journals (Sweden)

    Jing eXu


    Full Text Available The biochemical properties of CaCO3 precipitation induced by Sporosarcina pasteurii, an ureolytic type microorganism, were investigated. Effects of calcium source on the precipitation process were examined, since calcium source plays a key role in microbiologically-induced mineralization. Regardless of the calcium source type, three distinct stages in the precipitation process were identified by Ca2+, NH4+, pH and cell density monitoring. Compared with stage 1 and 3, stage 2 was considered as the most critical part since biotic CaCO3 precipitation occurs during this stage. Kinetics studies showed that the microbial CaCO3 precipitation rate for calcium lactate was over twice of that for calcium nitrate, indicating that calcium lactate is more beneficial for the cell activity, which in turn determines urease production and CaCO3 precipitation. X-ray diffraction analysis confirmed the CaCO3 crystal as calcite, although scanning electron microscopy revealed a difference in crystal size and morphology if calcium source was different. The findings of this paper further suggest a promising application of microbiologically-induced CaCO3 precipitation in remediation of surface and cracks of porous media, e.g. cement-based composites, particularly by using organic source of calcium lactate.

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

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


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

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

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


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

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

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


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

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

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


    Eiler and Schauble (2004) showed that the isotopes of C and O are not randomly distributed within single phases such as CO2 gas and carbonates, and in particular, that heavy isotopes of C and O tend to bond preferentially (clump) at lower temperatures. Consequently, the measurement of the deviation from a random distribution of C and O isotope distributions in a single phase can be used as a thermometer. As with other geothermometers based on homogeneous or heterogeneous equilibria, the clumped-isotope thermometer is susceptible to resetting (e.g., if the phase is reheated or experiences slow cooling). Thus, clumped-isotope "temperatures" of phases that have experienced complex thermal histories may, in fact, be closure temperatures, the interpretation of which requires quantification of the kinetics of redistribution of C and O isotopes as a function of temperature. These kinetics have received increasing attention (Dennis and Schrag, 2010; Passey 2010), and are likely to be critical for understanding clumped-isotope temperatures of samples that have been buried for long periods of time. To better constrain these kinetics we performed experiments on natural optical calcite from Mexico and carbonate-bearing apatite from the Siilinjarvi carbonatite (Finland). For each experiment, multiple single crystal grains (~2 mm in diameter) of calcite or apatite were loaded in open Pt capsules, pressurized with Ar gas, and held at 400-700 °C, 550 bars using a rapid quench TZM apparatus for 5 min to 520 hrs. After quenching, 13C-18O clumping was measured in the samples; the change from the initial Δ47 with time for each phase at each temperature was fit to simple mechanistic models of isotope exchange between sites in these phases. One conclusion of the experimental study is that resetting the internal ordering of carbonate groups proceeds more rapidly in calcites than in apatites. For example, heating apatite at 400 °C results in no change in clumping over a 24 hr period

  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.


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

  6. Development and Antarctic Testing of a Maneuverable Probe for Clean In-Situ Analysis and Sampling of Subsurface Ice and Subglacial Aquatic Ecosystems (United States)

    Francke, G.; Dachwald, B.; Kowalski, J.; Digel, I.; Tulaczyk, S. M.; Mikucki, J.; Feldmann, M.; Espe, C.; Schöngarth, S.; Hiecker, S.; Blandfort, D.; Schüller, K.; Plescher, E.


    There is significant interest in sampling subglacial environments for geochemical and microbiological studies, but those environments are difficult to access. Such environments exist not only on Earth but are also expected beneath the icy crusts of some outer solar system bodies, like the Jovian moon Europa and the Saturnian moon Enceladus. Existing ice drilling technologies make it cumbersome to maintain microbiologically clean access for sample acquisition and environmental stewardship of potentially fragile subglacial aquatic ecosystems. The "IceMole" is a maneuverable subsurface ice probe for clean in-situ analysis and sampling of glacial ice and subglacial materials. The design is based on combining melting and mechanical propulsion, using an ice screw at the tip of the melting head to maintain firm contact between the melting head and the ice. It can change melting direction by differential heating of the melting head and optional side wall heaters. The first two prototypes were successfully tested between 2010 and 2012 on glaciers in Switzerland and Iceland, where they demonstrated downward, horizontal and upward melting, as well as curve driving and dirt layer penetration. Hence, the IceMole allows maneuvers which may be necessary for obstacle avoidance or target selection. Maneuverability, however, necessitates a sophisticated on-board navigation system capable of autonomous operations. Therefore, between 2012 and 2014, a more advanced probe was developed as part of the "Enceladus Explorer" (EnEx) project. The EnEx-IceMole offers systems for relative positioning based on in-ice attitude determination, acoustic positioning, ultrasonic obstacle and target detection, which is all integrated through a high-level sensor fusion. In December 2014, it was used for clean access into a unique subglacial aquatic environment at Blood Falls, Antarctica, where a subglacial brine sample was successfully obtained after about 17 meters of oblique melting. Particular

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

    KAUST Repository

    Li, Yan Vivian


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

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

    Lech, J.; Śl|zak, A.


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

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


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


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

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

    DEFF Research Database (Denmark)

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


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


    DEFF Research Database (Denmark)

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


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

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

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  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


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

  16. The Global Precipitation Mission (United States)

    Braun, Scott; Kummerow, Christian


    The Global Precipitation Mission (GPM), expected to begin around 2006, is a follow-up to the Tropical Rainfall Measuring Mission (TRMM). Unlike TRMM, which primarily samples the tropics, GPM will sample both the tropics and mid-latitudes. The primary, or core, satellite will be a single, enhanced TRMM satellite that can quantify the 3-D spatial distributions of precipitation and its associated latent heat release. The core satellite will be complemented by a constellation of very small and inexpensive drones with passive microwave instruments that will sample the rainfall with sufficient frequency to be not only of climate interest, but also have local, short-term impacts by providing global rainfall coverage at approx. 3 h intervals. The data is expected to have substantial impact upon quantitative precipitation estimation/forecasting and data assimilation into global and mesoscale numerical models. Based upon previous studies of rainfall data assimilation, GPM is expected to lead to significant improvements in forecasts of extratropical and tropical cyclones. For example, GPM rainfall data can provide improved initialization of frontal systems over the Pacific and Atlantic Oceans. The purpose of this talk is to provide information about GPM to the USWRP (U.S. Weather Research Program) community and to discuss impacts on quantitative precipitation estimation/forecasting and data assimilation.

  17. Precipitation Reconstruction (PREC) (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The PREC data set is an analysis of monthly precipitation constructed on a 2.5(o)lat/lon grid over the global for the period from 1948 to the present. The land...

  18. Glacial age precipitation and temperature estimates for the tropical Guatemalan highlands (United States)

    Roy, A. J.; Lachniet, M. S.


    The Sierra Cuchumatanes of Western Guatemala supported a large ice cap of approximately 44 square km area, and a group of 5-6 small valley glaciers during the local last glacial maximum (LLGM). We propose that a temperature reduction during the Guatemalan LLGM was between -4.5 degrees C and -6.0 degrees C from present accompanied by precipitation totals that fall between 80-100% of present day levels. Our new field work on moraine limits expands upon previous reconnaissance-level studies. Here we present a comprehensive reconstruction of the Guatemalan glacial geomorphology on a high limestone plateau; including delineations between morphologically different moraine sequences, boundaries of sub-glacial till deposits and locations of dry moraine dammed lakes. The glacial geologic map was produced via field mapping and GPS surveying, coupled with aerial photographic analysis. A 50m digital elevation model (DEM) created for the mapping portion was employed as input for a physically based GIS mass-balance model, developed by Plummer and Phillips (2003). The mass-balance model data was calculated for varying precipitation, temperature, environmental lapse rates, cloudiness, wind speed and humidity. A sensitivity analysis using variations in temperature and precipitation provided constraints on Guatemalan highland paleoclimate. Although the ages of the glaciations are unconstrained, a qualitative assessment of moraine morphology suggests correlation with the LLGM (20 - 17.5 ka) moraines of Mexico.

  19. Late-stage anhydrite-gypsum-siderite-dolomite-calcite assemblages record the transition from a deep to a shallow hydrothermal system in the Schwarzwald mining district, SW Germany (United States)

    Burisch, Mathias; Walter, Benjamin F.; Gerdes, Axel; Lanz, Maximilian; Markl, Gregor


    The majority of hydrothermal vein systems of economic interest occur at relatively shallow crustal levels, although many of them formed at significantly greater depths. Their present position is a consequence of uplift and erosion. Although, many aspects of their formation are well constrained, the temporal chemical evolution of such systems during uplift and erosion is still poorly understood. These vein minerals comprise calcite, dolomite-ankerite, siderite-magnesite, anhydrite and gypsum forming the last gangue assemblages in Jurassic and Tertiary sulphide-fluorite-quartz-barite veins of the Schwarzwald mining district, SW Germany. Mineral textures of samples from nine localities reveal that in these sequences, mineral precipitation follows a recurring pattern: early calcite is followed by anhydrite or gypsum, siderite and/or dolomite. This succession may repeat up to three times. In-situ (LA-ICP-MS) U-Pb age dating of 15 carbonates from three subsequent generations of the late-stage vein assemblage yield robust ages between 20 and 0.6 Ma. Each mineral sequence forms in a distinctive period of about 2-5 Ma. These ages clearly relate these late-stage mineral phases to the youngest geological episode of the Schwarzwald, which is associated with the Cenozoic Rhine Graben rifting and basement uplift. Based on thermodynamic modelling, the formation of the observed mineral assemblages required an deeply sourced Mg-, Fe- and SO4-rich fluid (b), which was episodically mixed with a shallow crustal HCO3-rich fluid (a). As a consequence of fluid mixing, concentrations of Mg, Fe and SO4 temporarily increased and initiated the formation of the observed sulphate-carbonate mineral sequences. This discontinuous large-scale vertical fluid mixing was presumably directly related to episodes of active tectonics associated with the Cenozoic strike-slip regime of the Upper Rhine Graben. Analogously, episodic fluid mixing is a major key in the formation of older (Jurassic to early

  20. Reconstruction of drip-water δ18O based on calcite oxygen and clumped isotopes of speleothems from Bunker Cave (Germany

    Directory of Open Access Journals (Sweden)

    T. Kluge


    Full Text Available The geochemical signature of many speleothems used for reconstruction of past continental climates is affected by kinetic isotope fractionation. This limits quantitative paleoclimate reconstruction and, in cases where the kinetic fractionation varies with time, also affects relative paleoclimate interpretations. In carbonate archive research, clumped isotope thermometry is typically used as proxy for absolute temperatures. In the case of speleothems, however, clumped isotopes provide a sensitive indicator for disequilibrium effects. The extent of kinetic fractionation co-varies in Δ47 and δ18O so that it can be used to account for disequilibrium in δ18O and to extract the past drip-water composition. Here we apply this approach to stalagmites from Bunker Cave (Germany and calculate drip-water δ18Ow values for the Eemian, MIS3, and the Holocene, relying on independent temperature estimates and accounting for disequilibrium. Applying the co-variation method to modern calcite precipitates yields drip-water δ18Ow values in agreement with modern cave drip-water δ18Ow of −7.9 ± 0.3‰, despite large and variable disequilibrium effects in both calcite δ18Oc and Δ47. Reconstructed paleo-drip-water δ18Ow values are lower during colder periods (e.g., MIS3: −8.6 ± 0.4‰ and the early Holocene at 11 ka: −9.7 ± 0.2‰ and show higher values during warmer climatic periods (e.g., the Eemian: −7.6 ± 0.2‰ and the Holocene Climatic Optimum: −7.2 ± 0.3‰. This new approach offers a unique possibility for quantitative climate reconstruction including the assessment of past hydrological conditions while accounting for disequilibrium effects.

  1. 16S rRNA gene-based characterization of bacteria potentially associated with phosphate and carbonate precipitation from a granular autotrophic nitrogen removal bioreactor. (United States)

    Gonzalez-Martinez, Alejandro; Rodriguez-Sanchez, Alejandro; Rivadeneyra, María Angustias; Rivadeneyra, Almudena; Martin-Ramos, Daniel; Vahala, Riku; Gonzalez-Lopez, Jesús


    A bench-scale granular autotrophic nitrogen removal bioreactor (completely autotrophic nitrogen removal over nitrite (CANON) system) used for the treatment of synthetic wastewater was analyzed for the identification of microbiota with potential capacity for carbonate and phosphate biomineral formation. 16S ribosomal RNA (rRNA) gene-based studies revealed that different bacterial species found in the granular biomass could trigger the formation of phosphate and calcite minerals in the CANON bioreactor. iTag analysis of the microbial community in the granular biomass with potential ability to precipitate calcium carbonate and hydroxyapatite constituted around 0.79-1.32 % of total bacteria. Specifically, the possible hydroxyapatite-producing Candidatus Accumulibacter had a relative abundance of 0.36-0.38 % and was the highest phosphate-precipitating bacteria in the granular CANON system. With respect to calcite precipitation, the major potential producer was thought to be Stenotrophomonas with a 0.38-0.50 % relative abundance. In conclusion, our study showed evidences that the formation of hydroxyapatite and calcite crystals inside of the granular biomass of a CANON system for the treatment wastewater with high ammonium concentration was a biological process. Therefore, it could be suggested that microorganisms play an important role as a precipitation core and also modified the environment due to their metabolic activities.

  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)


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

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

    Randich, E.; Acton, R.U.


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

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

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


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

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

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


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

  8. Magnetic Field Effects on CaCO3 Precipitation Process in Hard Water

    Directory of Open Access Journals (Sweden)

    Nelson Saksono


    Full Text Available Magnetic treatment is applied as physical water treatment for scale prevention especially CaCO3, from hard water in piping equipment by reducing its hardness.Na2CO3 and CaCl2 solution sample was used in to investigate the magnetic fields influence on the formation of particle of CaCO3. By changing the strength of magnetic fields, exposure time and concentration of samples solution, this study presents quantitative results of total scale deposit, total precipitated CaCO3 and morphology of the deposit. This research was run by comparing magnetically and non-magnetically treated  samples. The results showed an increase of deposits formation rate and total number of precipitated CaCO3 of magnetically treated samples. The increase of concentration solution sample will also raised the deposit under magnetic  field. Microscope images showed a greater number but smaller size of CaCO3 deposits form in magnetically treated samples, and aggregation during the processes. X-ray diffraction (XRD analysis showed that magnetically samples were dominated by calcite. But, there was a significant decrease of calcite’s peak intensities from magnetized  samples that indicated the decrease of the amount of calcite and an increase of total amorphous of deposits. This result  showed that magnetization of hard water leaded to the decreasing of ion Ca2+ due to the increasing of total CaCO3 precipitation process.

  9. Morphology and phase identification of synthesized precipitated calcium carbonate from acetylene gas industry waste (United States)

    Sabri, Siti Noorzidah Mohd; Othman, Rohaya; Othman, Anuar


    Precipitated calcium carbonate (PCC) is also known as synthetic calcium carbonate. In this paper, PCC was synthesized from carbide lime, which is the by-product from acetylene gas industry. The method used to produce PCC from carbide lime waste was ionic sucrose precipitation technique. The experiments were performed by varying the stirring rate. In this technique, carbide lime was first dissolved in ionic sucrose solution and then chilled at 10 °C for 24 hours before carbon dioxide gasses was introduced into the solution. The carbonation and precipitation process was took place and PCC was formed. The PCC was further filtered to obtain the solid PCC. The sample was then further characterised by using FESEM and XRD to determine the morphology and to identify the phase that exists in the synthesized compound respectively. The XRD and FESEM results clearly shown that the PCC obtained has mixed phases of calcite and vaterite, with mixtures of spherical and irregular shape morphologies formed. The irregular shapes corresponded to vaterite formation, meanwhile spherical shapes corresponded to calcite formation.

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

    National Research Council Canada - National Science Library

    Davidson, Paula M


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

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

    DEFF Research Database (Denmark)

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


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

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

    NARCIS (Netherlands)

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


    The origin of spherical-radial calcite bodies - spherulites - in sublacustrine, hyperalkaline and saline systems is unclear, and therefore their palaeoenvironmental significance as allochems is disputed. Here, we experimentally investigate two hypotheses concerning the origin of spherulites. The

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

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt

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

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

    DEFF Research Database (Denmark)

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


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

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

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


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

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

    KAUST Repository

    Yutkin, Maxim P.


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

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

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  19. Thin-layer effects in glaciological seismic amplitude-versus-angle (AVA analysis: implications for characterising a subglacial till unit, Russell Glacier, West Greenland

    Directory of Open Access Journals (Sweden)

    A. D. Booth


    Full Text Available Seismic amplitude-versus-angle (AVA methods are a powerful means of quantifying the physical properties of subglacial material, but serious interpretative errors can arise when AVA is measured over a thinly-layered substrate. A substrate layer with a thickness less than 1/4 of the seismic wavelength, λ, is considered "thin", and reflections from its bounding interfaces superpose and appear in seismic data as a single reflection event. AVA interpretation of subglacial till can be vulnerable to such thin-layer effects, since a lodged (non-deforming till can be overlain by a thin (metre-scale cap of dilatant (deforming till. We assess the potential for misinterpretation by simulating seismic data for a stratified subglacial till unit, with an upper dilatant layer between 0.1–5.0 m thick (λ / 120 to > λ / 4, with λ = 12 m. For dilatant layers less than λ / 6 thick, conventional AVA analysis yields acoustic impedance and Poisson's ratio that indicate contradictory water saturation. A thin-layer interpretation strategy is proposed, that accurately characterises the model properties of the till unit. The method is applied to example seismic AVA data from Russell Glacier, West Greenland, in which characteristics of thin-layer responses are evident. A subglacial till deposit is interpreted, having lodged till (acoustic impedance = 4.26±0.59 × 106 kg m−2 s−1 underlying a water-saturated dilatant till layer (thickness < 2 m, Poisson's ratio ~ 0.5. Since thin-layer considerations offer a greater degree of complexity in an AVA interpretation, and potentially avoid misinterpretations, they are a valuable aspect of quantitative seismic analysis, particularly for characterising till units.

  20. Testing the influence of subglacial erosion on the long-term evolution and stability of continental ice sheets using numerical modelling (United States)

    Swift, D. A.; Egholm, D. L.; Brædstrup, C. F.; Cook, S.; Livingstone, S. J.; Clark, C.; Patton, H.; Ely, J.


    Focussed erosion beneath continental ice sheets promotes efficient evacuation of ice along fast-flowing marine outlet glacier systems. Theory indicates that bed profiles should tend toward uniformly overdeepened geometries that will reduce ice sheet stability because (a) grounding lines situated on negative slopes are vulnerable to catastrophic retreat and (b) grounding-line stability is sensitive to ice velocity, meaning grounding lines should become unstable as overdeepening causes subglacial water pressures and basal sediment thickness and continuity to increase. This suggests a conceptual model of ice-bed evolution in which ice sheets are self-destructive, because bed erosion reduces equilibrium ice sheet volume and extent. However, many outlet glacier and ice stream systems possess complex bed topographies, raising questions about the nature of subglacial landscape evolution that have major implications for our understanding of ice sheet evolution and stability. For example, a contrasting model of ice-bed evolution in which strong ice-erosion feedbacks produce multiple overdeepenings might enhance ice sheet stability, because numerous bed undulations should resist fast ice flow and impede grounding line retreat. We therefore explore the possible glaciological significance of contrasting models of subglacial landscape evolution using a higher-order ice sheet model (iSOSIA) and assess the implications for the evolution and stability of continental ice sheets. The results will also aid understanding of contemporary ice sheet stability and identify weaknesses in process understanding that will aid further development of ice-erosion models.

  1. Hourly Precipitation Data (HPD) Publication (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Hourly Precipitation Data (HPD) Publication is archived and available from the National Climatic Data Center (NCDC). This publication contains hourly precipitation...

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

    Reddy, Michael M.; Leenheer, Jerry


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

  3. Precipitation Indices Low Countries (United States)

    van Engelen, A. F. V.; Ynsen, F.; Buisman, J.; van der Schrier, G.


    Since 1995, KNMI published a series of books(1), presenting an annual reconstruction of weather and climate in the Low Countries, covering the period AD 763-present, or roughly, the last millennium. The reconstructions are based on the interpretation of documentary sources predominantly and comparison with other proxies and instrumental observations. The series also comprises a number of classifications. Amongst them annual classifications for winter and summer temperature and for winter and summer dryness-wetness. The classification of temperature have been reworked into peer reviewed (2) series (AD 1000-present) of seasonal temperatures and temperature indices, the so called LCT (Low Countries Temperature) series, now incorporated in the Millennium databases. Recently we started a study to convert the dryness-wetness classifications into a series of precipitation; the so called LCP (Low Countries Precipitation) series. A brief outline is given here of the applied methodology and preliminary results. The WMO definition for meteorological drought has been followed being that a period is called wet respectively dry when the amount of precipitation is considerable more respectively less than usual (normal). To gain a more quantitative insight for four locations, geographically spread over the Low Countries area (De Bilt, Vlissingen, Maastricht and Uccle), we analysed the statistics of daily precipitation series, covering the period 1900-present. This brought us to the following definition, valid for the Low Countries: A period is considered as (very) dry respectively (very) wet if over a continuous period of at least 60 days (~two months) cq 90 days (~three months) on at least two out of the four locations 50% less resp. 50% more than the normal amount for the location (based on the 1961-1990 normal period) has been measured. This results into the following classification into five drought classes hat could be applied to non instrumental observations: Very wet period

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

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


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

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

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


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

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

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


    This study is part of the research program of the Yucca Mountain Project intended to provide the State of Nevada with a detailed assessment of the geology and geochemistry of Yucca Mountain and adjacent regions. The purpose of this paper is to consider all of the geological and geochemical data available for the calcite/