Experimental subsolidus phase relations in the system CaCO3-CaMg(CO3)2 up to 6.5 GPa and implications for subducted marbles

NASA Astrophysics Data System (ADS)

Hermann, Jörg; Troitzsch, Ulrike; Scott, Dean

2016-10-01

The dissociation of dolomite to aragonite + magnesite and the reaction of dolomite + aragonite to Mg-calcite have been experimentally determined by piston cylinder experiments in the range of 650-1000 °C and 2-6.5 GPa. Friction decay within the salt sleeves used as pressure medium was monitored by continuously logging the travel distance of the piston. Piston movement ceased after the first 24 h of the experiment, and all experiments were kept at the steady-state conditions for an additional 24-196 h. The reaction of dolomite to aragonite + magnesite has a positive slope and has been bracketed at 650 °C between 5.1 and 5.8 GPa and at 750 °C between 5.7 and 6.5 GPa. The reaction is sluggish with a 0.6-GPa interval where all three phases coexist. The reaction dolomite + aragonite to Mg-calcite has been determined in 0.5-GPa intervals from 660 °C at 2 GPa to 940 °C at 6.5 GPa. The composition of Mg-calcite at the reaction curve is buffered and changes systematically from X(Ca) of 0.90 at 2 GPa to 0.57 at 6.5 GPa. The solvus between dolomite and Mg-calcite shrinks slightly with increasing pressure, providing evidence for a small negative slope of the critical curve dolomite = Mg-calcite. The degree of disorder in dolomite has been determined in some of the retrieved samples by Rietveld refinement based on X-ray diffraction patterns. The order parameter S decreases gradually from 1 to 0.7 as a function of temperature as the critical curve is approached and then drops dramatically after crossing it. No ordering on quench has been observed. The experimental results permit the construction of a petrogenetic grid for the system dolomite, aragonite, Mg-calcite, and magnesite, which has an invariant point at ~7.5 GPa and 980 °C, representing the maximum pressure stability of dolomite. X(Ca) isopleths of Mg-calcite coexisting with dolomite serve mainly as a thermometer, whereas in the presence of aragonite they are a useful barometer. The experimental results have been

Impact ionisation mass spectrometry of platinum-coated olivine and magnesite-dominated cosmic dust analogues

NASA Astrophysics Data System (ADS)

Hillier, Jon K.; Sternovsky, Z.; Kempf, S.; Trieloff, M.; Guglielmino, M.; Postberg, F.; Price, M. C.

2018-07-01

Impact ionisation mass spectrometry enables the composition of cosmic dust grains to be determined in situ by spacecraft-based instrumentation. The proportion of molecular ions in the impact plasma is a function of the impact velocity, making laboratory calibration vital for the interpretation of the mass spectra, particularly at the low velocities typical of lunar or asteroid encounters. Here we present an analysis of laboratory impact ionisation mass spectra from primarily low (<15 km s-1) velocity impacts of both olivine and magnesite-dominated particles onto the SUrface Dust Mass Analyzer (SUDA) laboratory mass spectrometer. The cation mass spectra show characteristic peaks due to their constituent elements, with Mg, Al, Si, C, Ca, O and Fe frequently present. Contaminant species from the conductive coating process (B, Na, K, C, Pt) also occur, at varying frequencies. Possible saponite or talc inclusions in the magnesite particles are revealed by the presence of Si, Fe, Ca and Al in the magnesite mass spectra. Magnesium is clearly present at the lowest impact velocities (3 km s-1), at which alkali metals were presumed to dominate. Peaks attributed to very minor amounts of water or hydroxyl present in the grains are also seen at low velocities in both cation and anion mass spectra, demonstrating the feasibility of impact ionisation mass spectrometry in identifying hydrated or hydrous minerals, during very low velocity encounters or with very low abundances of water or hydroxy groups, in the impinging grains. Velocity thresholds for the reliable identification of the major elements within the magnesite and olivine cation spectra are presented. Additionally, relative sensitivity factors for Mg (5.1), Fe (1.5) and O (0.6) with respect to Si, in the olivine particles, at impact speeds >19 km s-1, were found to be very similar to those previously determined for orthopyroxene-dominated particles, despite different target and projectile materials. This confirms that

[Experimental study of Raman spectra of magnesite at 297 K and at the pressure of 0.13-1 GPa].

PubMed

Wang, Yu; Zheng, Hai-fei

2005-09-01

The experimental study of Raman spectra of magnesite has been conducted at the pressure of 967 MPa and at the temperatureof 297 K using a cubic zirconia-anvil cell. The result shows that neither phase transition nor organic substances were observed during compression, and the Raman peak of magnesite shifted to higher frequency with increasing pressure. The relation between the pressure and the Raman peak position of magnesite (1094 cm(-1)) was obtained as follows: v (cm(-1)) = 0.007 44 x P(MPa) + 1 093.3. The value of dv/dP of magnesite is greater than the previous data obtained by Gillet, which was mostly taken under the mantle pressure. And at the ambient temperature, magnesite can be used as a pressure gauge, and the relation between the pressure and Raman shift of 1 094 cm(-1) peak position is given as following: P(MPa) = 125.8 x (deltavp) 1094 + 124.7 (1094 cm(-1) < vp < 1101 cm(-1)).

Magnesite Step Growth Rates as a Function of the Aqueous Magnesium:Carbonate Ratio

DOE PAGES

Bracco, Jacquelyn N.; Stack, Andrew G.; Higgins, Steven R.

2014-10-01

Step velocities of monolayer-height steps on the (101 ⁻4) magnesite surface have been measured as functions of the aqueous magnesium-to-carbonate ratio and saturation index (SI) using a hydrothermal atomic force microscope (HAFM). At SI ≤ 1.9 and 80-90 °C, step velocities were found to be invariant with changes in the magnesium-to-carbonate ratio, an observation in contrast with standard models for growth and dissolution of ionically-bonded, multi-component crystals. However, at high saturation indices (SI = 2.15), step velocities displayed a ratio dependence, maximized at magnesium-to-carbonate ratios slightly greater than 1:1. Traditional affinity-based models were unable to describe growth rates at themore » higher saturation index. Step velocities also could not be modeled solely through nucleation of kink sites, in contrast to other minerals whose bonding between constituent ions is also dominantly ionic in nature, such as calcite and barite. Instead, they could be described only by a model that incorporates both kink nucleation and propagation. Based on observed step morphological changes at these higher saturation indices, the step velocity maximum at SI = 2.15 is likely due to the rate of attachment to propagating kink sites overcoming the rate of detachment from kink sites as the latter becomes less significant under far from equilibrium conditions.« less

Carbonate dissolution rates in high salinity brines: Implications for post-Noachian chemical weathering on Mars

NASA Astrophysics Data System (ADS)

Phillips-Lander, Charity M.; Parnell, S. R.; McGraw, L. E.; Elwood Madden, M. E.

2018-06-01

A diverse suite of carbonate minerals including calcite (CaCO3) and magnesite (MgCO3) have been observed on the martian surface and in meteorites. Terrestrial carbonates usually form via aqueous processes and often record information about the environment in which they formed, including chemical and textural biosignatures. In addition, terrestrial carbonates are often found in association with evaporite deposits on Earth. Similar high salinity environments and processes were likely active on Mars and some areas may contain active high salinity brines today. In this study, we directly compare calcite and magnesite dissolution in ultrapure water, dilute sulfate and chloride solutions, as well as near-saturated sulfate and chloride brines with known activity of water (aH2O) to determine how dissolution rates vary with mineralogy and aH2O, as well as aqueous cation and anion chemistry to better understand how high salinity fluids may have altered carbonate deposits on Mars. We measured both calcite and magnesite initial dissolution rates at 298 K and near neutral pH (6-8) in unbuffered solutions containing ultrapure water (18 MΩ cm-1 UPW; aH2O = 1), dilute (0.1 mol kg-1; aH2O = 1) and near-saturated Na2SO4 (2.5 mol kg-1, aH2O = 0.92), dilute (0.1 mol kg-1, aH2O = 1) and near-saturated NaCl (5.7 mol kg-1, aH2O = 0.75). Calcite dissolution rates were also measured in dilute and near-saturated MgSO4 (0.1 mol kg-1, aH2O = 1 and 2.7 mol kg-1, aH2O = 0.92, respectively) and MgCl2 (0.1 mol kg-1, aH2O = 1 and 3 mol kg-1, aH2O = 0.73, respectively), while magnesite dissolution rates were measured in dilute and near-saturated CaCl2 (0.1 mol kg-1, aH2O = 1 and 9 mol kg-1, aH2O = 0.35). Initial calcite dissolution rates were fastest in near-saturated MgCl2 brine, while magnesite dissolution rates were fastest in dilute (0.1 mol kg-1) NaCl and CaCl2 solutions. Calcite dissolution rates in near-saturated Na2SO4 were similar to those observed in the dilute solutions (-8.00 ± 0

Strontium Incorporation Into Calcite Generated by Bacterial Ureolysis

NASA Astrophysics Data System (ADS)

Fujita, Y.; Ingram, J. A.; Cortez, M. M.; Redden, G. D.; Smith, R. W.

2002-12-01

Strontium incorporation into calcite generated by bacterial ureolytic activity was investigated as part of a larger effort to evaluate the use of in situ urea hydrolysis for accelerating co-precipitation of trace metals and radionuclides in contaminated aquifers. 90Sr, a uranium fission product with a half-life of 29 years, is a significant subsurface contaminant at several Department of Energy facilities and could be immobilized using this remediation strategy. Experiments were conducted in a medium designed to simulate the groundwater of the Snake River Plain Aquifer in eastern Idaho, amended with strontium. Initially the solution was undersaturated with respect to calcite. As a model ureolytic organism, we used Bacillus pasteurii, a well-characterized bacterium known for high urease activity and previously shown to induce calcite precipitation in urea-amended medium. To gain information on the effect of the bacterial surfaces, we also looked at precipitation in the presence of a bacterial species that did not hydrolyze urea, as well as in the absence of bacteria. In the absence of bacterial ureolysis, carbonate precipitation was induced by addition of ammonium carbonate. All products were identified as calcite by X-ray diffraction. Strontium uptake was observed in all cases, but was greatest in the system including bacterial ureolysis. Sputter depth element profiling by time-of-flight secondary ion mass spectrometry (TOF-SIMS) confirmed this finding, showing highest Sr:Ca ratios in the bacterially generated calcite throughout the depth (~350 nm) investigated. Environmental Scanning Electron Microscopy (ESEM) of the solids revealed regular crystals containing the outlines of embedded or entombed bacterial cells, suggesting that calcite precipitated directly on the cell surfaces when present. Analysis by X-ray Absorption Near Edge Spectroscopy (XANES) indicated that in both the biotically and abiotically generated calcites the Sr was incorporated into the calcite

Review of aragonite and calcite crystal morphogenesis in thermal spring systems

NASA Astrophysics Data System (ADS)

Jones, Brian

2017-06-01

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.

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

NASA Astrophysics Data System (ADS)

Burisch, Mathias; Walter, Benjamin F.; Gerdes, Axel; Lanz, Maximilian; Markl, Gregor

2018-02-01

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

Utilization and recycling of industrial magnesite refractory waste material for removal of certain radionuclides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morcos, T.N.; Tadrous, N.A.; Borai, E.H.

2007-07-01

Increased industrialization over the last years in Egypt has resulted in an increased and uncontrolled generation of industrial hazardous waste. The current lack of management of the solid waste in Egypt has created a situation where large parts of the land (especially industrial areas) are covered by un-planned dumps of industrial wastes. Consequently, in the present work, industrial magnesite waste produced in large quantities after production process of magnesium sulfate in Zinc Misr factory, Egypt, was tried to be recycled. Firstly, this material has been characterized applying different analytical techniques such as infrared spectroscopy (IR), surface analyzer (BET), particle sizemore » distribution (PSD), elemental analysis by X-ray fluorescence (XRF) and X-ray diffraction (XRD). The magnesite material has been used as a source of producing aluminum, chromium, and magnesium oxides that has better chemical stability than conventional metal oxides. Secondly, utilization of magnesite material for removal of certain radionuclides was applied. Different factors affecting the removal capability such as pH, contacting time, metal concentration, particle size were systematically investigated. The overall objective was aimed at determining feasible and economic solution to the environmental problems related to re-use of the industrial solid waste for radioactive waste management. (authors)« less

Amplitude-dependent internal friction, hysteretic nonlinearity, and nonlinear oscillations in a magnesite resonator.

PubMed

Nazarov, V E; Kolpakov, A B; Radostin, A V

2012-07-01

The results of experimental and theoretical studies of low-frequency nonlinear acoustics phenomena (amplitude-dependent loss, resonance frequency shifts, and a generation of second and third harmonics) in a magnesite rod resonator are presented. Acceleration and velocity oscillograms of vibrations of the free boundary of the resonator caused by harmonic excitations were measured and analyzed. A theoretical description of the observed amplitude dependences was carried out within the framework of the phenomenological state equations that contain either of the two types of hysteretic nonlinearity (elastic and inelastic). The type of hysteresis and parameters of acoustic nonlinearity of magnesite were established from comparing the experimental measurements with the theoretical dependences. The values of the parameters were anomalously high even when compared to those of other strongly nonlinear polycrystalline materials such as granite, marble, limestone, sandstone, etc.

The kinetics of dolomite reaction rim growth under isostatic and non-isostatic pressure conditions

NASA Astrophysics Data System (ADS)

Helpa, V.; Rybacki, E.; Morales, L. G.; Abart, R.; Dresen, G. H.

2013-12-01

and a 7 μm thick palisade-shaped layer evolve. At similar conditions and a differential stress of 30 MPa, the rim thickness remains similar; consequently the effect of non-isostatic stress on dolomite rim growth is negligible. Platinum markers show that the initial calcite-magnesite interface is located between granular and palisade-forming dolomite, indicating that rim growth occurs by counter diffusion of MgO and CaO. Diffusion of MgO across the dolomite reaction rim into calcite forms additionally magnesio-calcite grains with diameters of ≈ 13 - 46 μm, depending on the experimental conditions and increasing with increasing distance to the dolomite boundary. At T = 750°C, t = 29 hours, the thickness of the magnesio-calcite layer is 32 μm (isostatic) - 35 μm (σ = 30 MPa). The experiments indicate that solid-state reaction rim growth of dolomite between calcite and magnesite is primarily controlled by diffusion of MgO and CaO, forming layers with different microstructures during growth into the educt phases. The kinetics of the reaction in the carbonate system are not significantly changed by differential stresses up to 40 MPa. We suggest that volume diffusion is the dominant transport mechanism, which is presumably less affected by non-isostatic stresses than grain boundary diffusion.

Reproducing early Martian atmospheric carbon dioxide partial pressure by modeling the formation of Mg-Fe-Ca carbonate identified in the Comanche rock outcrops on Mars

NASA Astrophysics Data System (ADS)

Berk, Wolfgang; Fu, Yunjiao; Ilger, Jan-Michael

2012-10-01

The well defined composition of the Comanche rock's carbonate (Magnesite0.62Siderite0.25Calcite0.11Rhodochrosite0.02) and its host rock's composition, dominated by Mg-rich olivine, enable us to reproduce the atmospheric CO2partial pressure that may have triggered the formation of these carbonates. Hydrogeochemical one-dimensional transport modeling reveals that similar aqueous rock alteration conditions (including CO2partial pressure) may have led to the formation of Mg-Fe-Ca carbonate identified in the Comanche rock outcrops (Gusev Crater) and also in the ultramafic rocks exposed in the Nili Fossae region. Hydrogeochemical conditions enabling the formation of Mg-rich solid solution carbonate result from equilibrium species distributions involving (1) ultramafic rocks (ca. 32 wt% olivine; Fo0.72Fa0.28), (2) pure water, and (3) CO2partial pressures of ca. 0.5 to 2.0 bar at water-to-rock ratios of ca. 500 molH2O mol-1rock and ca. 5°C (278 K). Our modeled carbonate composition (Magnesite0.64Siderite0.28Calcite0.08) matches the measured composition of carbonates preserved in the Comanche rocks. Considerably different carbonate compositions are achieved at (1) higher temperature (85°C), (2) water-to-rock ratios considerably higher and lower than 500 mol mol-1 and (3) CO2partial pressures differing from 1.0 bar in the model set up. The Comanche rocks, hosting the carbonate, may have been subjected to long-lasting (>104 to 105 years) aqueous alteration processes triggered by atmospheric CO2partial pressures of ca. 1.0 bar at low temperature. Their outcrop may represent a fragment of the upper layers of an altered olivine-rich rock column, which is characterized by newly formed Mg-Fe-Ca solid solution carbonate, and phyllosilicate-rich alteration assemblages within deeper (unexposed) units.

High surface area calcite

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

Defects in Calcite.

DTIC Science & Technology

1991-05-13

AD-A245 645 A TRIDENT SCHOLAR PROJECT REPORT NO. 181 "DEFECTS IN CALCITE " DTTC %N FEB 5-1912 UNITED STATES NAVAL ACADEMY ANNAPOLIS, MARYLAND 92-02841...report; no. 181 (1991) "DEFECTS IN CALCITE " A Trident Scholar Project Report by Midshipman Anthony J. Kotarski, Class of 1991 U. S. Naval Academy Annapolis...REPORT TYPE AND DATES COVERED 13 May 1991 Final 1990/91 . TITLE AND SUBTITLE s. FUNDING NUMBERS DEFECTS IN CALCITE 6. AUTHOR(S) Anthony J. Kotarski 7

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

NASA Astrophysics Data System (ADS)

Reddy, Michael M.

2012-08-01

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

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

USGS Publications Warehouse

Reddy, Michael M.

2012-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-01-01

The interactions of trivalent lanthanides and actinides with secondary mineral phases such as calcite is of high importance for the safety assessment of deep geological repositories for high level nuclear waste (HLW). Due to similar ionic radii, calcium-bearing mineral phases are suitable host minerals for Ln(III) and An(III) ions. Especially calcite has been proven to retain these metal ions effectively by both surface complexation and bulk incorporation. Since anionic ligands (e.g., nitrate) are omnipresent in the geological environment and due to their coordinating properties, their influence on retentive processes should not be underestimated. Nitrate is a common contaminant in most HLW forms as a result of using nitric acid in fuel reprocessing. It is also formed by microbial activity under aerobic conditions. In this study, atomic force microscopy investigations revealed a major influence of nitrate upon the surface of calcite crystals. NaNO3 causes serious modifications even in trace amounts (<10-7 M) and forms a soft surface layer of low crystallinity on top of the calcite crystal. Time-resolved laser fluorescence spectroscopy of Eu(III) showed that, within this layer, Eu(III) ions are incorporated, while losing most of their hydration shell. The results show that solid solution modelling for actinides in calcite must take into account the presence of nitrate in pore and ground waters.

CO(2) partial pressure and calcite saturation in springs - useful data for identifying infiltration areas in mountainous environments.

PubMed

Hilberg, Sylke; Brandstätter, Jennifer; Glück, Daniel

2013-04-01

Mountainous regions such as the Central European Alps host considerable karstified or fractured groundwater bodies, which meet many of the demands concerning drinking water supply, hydropower or agriculture. Alpine hydrogeologists are required to describe the dynamics in fractured aquifers in order to assess potential impacts of human activities on water budget and quality. Delineation of catchment areas by means of stable isotopes and hydrochemical data is a well established method in alpine hydrogeology. To achieve reliable results, time series of (at least) one year and spatial and temporal close-meshed data are necessary. In reality, test sites in mountainous regions are often inaccessible due to the danger of avalanches in winter. The aim of our work was to assess a method based on the processes within the carbonic acid system to delineate infiltration areas by means of single datasets consisting of the main hydrochemical parameters of each spring. In three geologically different mountainous environments we managed to classify the investigated springs into four groups. (1) High PCO2 combined with slight super-saturation in calcite, indicating relatively low infiltration areas. (2) Low PCO2 near atmospheric conditions in combination with calcite saturation, which is indicative of relatively high infiltration areas and a fractured aquifer which is not covered by topsoil layers. (3) High PCO2 in combination with sub-saturation in calcite, representing a shallow aquifer with a significant influence of the topsoil layer. (4) The fourth group of waters is characterized by low PCO2 and sub-saturation in calcite, which is interpreted as evidence for a shallow aquifer without significant influence of any hard rock aquifer or topsoil layer. This study shows that CO2-partial pressure can be an ideal natural tracer to estimate the elevation of infiltration areas, especially in non-karstified fractured groundwater bodies.

Production Engineering for Growth of Synthetic Calcite Polarizer Material

DTIC Science & Technology

1974-08-01

AD-A008 043 PRODUCTION ENGINEERING FOR GROWTH OF SYNTHETIC CALCITE POLARIZER MATERIAL Roger F. Belt, et al Litton Systems...Production Bngin««ring for Growth of Synthetic Calcit « Polarizer Material I. RCCIPItNT’tCATALOO NUMMN i. T.vpc or ncpoMT • rtmoo covtnto Final Report...VOKOt (CanlliMit en »xift •id« II ntffrt Kid Idtnlllr br block iwmbmr) Crystal Growth Hydrothermal Growth Calcite Polarizers 30. AtSTHACT

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

USGS Publications Warehouse

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

2004-01-01

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

Morphology Controls on Calcite Recrystallization.

PubMed

Heberling, Frank; Paulig, Leonie; Nie, Zhe; Schild, Dieter; Finck, Nicolas

2016-11-01

Environmental scientists and geoscientists working in different fields regard the reactivity of calcite and corresponding changes in its trace elemental- or isotopic composition from diametrically opposed points of view. As one extreme, calcite based environmental remediation strategies rely on the fast recrystallization of calcite and the concurrent uptake and immobilization of pollutants. Paleo-ecological investigations denote the other extreme, and rely on the invariability of calcite composition over geological periods of time. We use long-term radiotracer experiments to quantify recrystallization rates of seven types of calcite powder with diverse morphology and particle size distribution. On the one hand our results demonstrate the long-term metastability of calcite with equilibrated crystal surfaces even at isotopic dis-equilibrium. On the other hand, we document the extremely high reactivity and interfacial free energy of freshly ground, rough calcite. Our results indicate that bulk calcite recrystallization is an interfacial free energy driven Ostwald-ripening process, in which particle roughness effects dominate over the effect of crystal habitus and particle size. We confirm that the dynamic equilibrium exchange of crystal constituents between kink sites involves an activation barrier of about 25 kJ/mol. At room temperature the equilibrium exchange is limited to a near surface region and proceeds at a rate of (3.6 ± 1.4)·10 -13 mol/(m 2 ·s).

Experimental study of the mechanism and sequence of calcite-dolomite replacement

NASA Astrophysics Data System (ADS)

Moraila-Martinez, Teresita; Putnis, Christine V.; Putnis, Andrew

2015-04-01

For many years the formation, mechanism and environmental settings of dolomite formation have been under discussion, mainly because dolomite is commonly found in ancient rocks, whereas it is rarely present in modern sediments. The most favoured hypothesis is the 'dolomitization' of limestone by Mg-bearing aqueous solutions [1,2]. The existence of sharp limestone-dolomite contacts in natural rocks suggests that dolomitization involves a coupled dissolution-precipitation process. For a better understanding of the replacement mechanism of calcite by dolomite we performed hydrothermal experiments using Carrara marble cubes of 1.5 mm size, that reacted with 1M (Ca,Mg)Cl2 solutions with a Mg:Ca ratio of 3, at 200°C for different duration times (10, 20, 40, 50 and 58 days). After reaction, the product phases were characterized using Raman spectroscopy, electron microprobe analysis, and scanning electron microscopy. After reaction, the external morphology of the samples was preserved. Back-scattered images revealed two replacement end products: dolomite and magnesite. Grain boundaries of the samples were maintained. Shorter time duration experiments resulted in the replacement reaction occurring mainly along grain boundaries, whereas in longer duration time experiments more replacement was located in the core of the sample. In this type of reaction, grain boundaries are very important for the replacement to occur, acting as fluid pathways, allowing the infiltration of the solution further from the rock surface, enhancing fluid permeability within the sample and allowing further replacement reactions to occur. 1. Kaczmarek S.E., Sibley D.F. On the evolution of dolomite stoichiometry and cation order during high temperature synthesis experiments: An alternative model for geochemical evolution of natural dolomites. Sedimentary Geology. 240, 30-40 (2011). 2. Etschmann B., Brugger J., Pearce M.A., Ta C., Brautigan D., Jung M., Pring A. Grain boundaries as microreactors during

Strain rate dependent activation of slip systems in calcite marbles from Syros (Cyclades, Greece)

NASA Astrophysics Data System (ADS)

Rogowitz, Anna; Grasemann, Bernhard; Morales, Luiz F. G.; Huet, Benjamin; White, Joseph C.

2017-04-01

The activation of certain slip systems in calcite has been experimentally proven to be highly temperature dependent, but also the strain rate plays an important role on the activation of the dominant slip system. In this study, observations from a flanking structure (i.e. shear zone) that developed under lower greenschist-facies conditions, in an almost pure calcite marble (Syros Island, Greece) are presented. The shear zone is characterized by a strain gradient from the slightly deformed tips (γ ˜ 50) to the highly strained centre (γ up to 1000) while the host rock is moderately deformed (γ ˜ 3). During the shear zone development, the strain gradient coincided with a strain rate gradient with strain rate varying from 10-13 to 10-9 s-1. The studied outcrop thus represents the final state of a natural experiment and gives us a great opportunity to get natural constraints on strain rate dependent mechanical behaviour in a calcite marble. Detailed microstructural analyses have been performed via optical microscopy, electron microscopy, electron backscatter diffraction mapping and transmission electron microscopy, on samples from the highly strained shear zone and the host rock. The analyses show that the calcite microfabric varies depending on position within the shear zone, indicating activation of different deformation, recrystallization mechanisms and slip systems at different strain rates. Up to strain rates of ˜10-10 s-1 the marble deformed exclusively within the dislocation creep field, showing a change in recrystallization mechanism and dominant active slip system. While the marble preferentially recrystallized by grain boundary migration at relatively low strain rates (˜10-13 s-1), subgrain rotation recrystallization seems to be the dominant mechanism at higher strain rates (˜10-12 to 10-10 s-1). At higher strain rates (˜10-9 s-1), the recrystallization mechanism is bulging, resulting in the development of an extremely fine grained ultramylonite

Corrosion Protection by Calcite-Type Coatings

DTIC Science & Technology

1989-10-01

CORROSION PROTECTION BY CALCITE -TYPE COATINGS OCTOBER, 1989 Prepared by: OCEAN CITY RESEARCH CORPORATION Tennessee Avenue & Beach Thorofare Ocean...REPORT DATE OCT 1989 2. REPORT TYPE N/A 3. DATES COVERED - 4. TITLE AND SUBTITLE Corrosion Protection by Calcite -Type Coatings 5a. CONTRACT... calcite -type coatings to segregated seawater ballast tanks. If perfected, a calcite coating approach could substantially reduce the cost of corrosion

Arsenic uptake in bacterial calcite

NASA Astrophysics Data System (ADS)

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

2018-02-01

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.

Regulation of calcite crystal morphology by intracrystalline acidic proteins and glycoproteins.

PubMed

Albeck, S; Addadi, I; Weiner, S

1996-01-01

Many biologically formed calcite crystals contain intracrystalline macromolecules. The ways in which they interact with growing calcite crystals were evaluated by monitoring changes in the morphology of calcite crystals grown in vitro in their presence. Macromolecules were extracted from within isolated prisms from the prismatic layer of the shell of the mollusk Atrina rigida and from spines of the sea urchin Paracentrotus lividus. Two modes of interaction were identified; the interaction of highly acidic proteins with calcite planes perpendicular to the c crystallographic axis and the interaction of glycoproteins with planes roughly parallel to the c axis. By different preparative procedures we demonstrated that the polysaccharide moieties of the sea urchin spine glycoproteins are directly involved in the latter mode of interactions. We suggest that organisms utilize the abilities of these macromolecules to interact in different ways with calcite crystals, and in so doing fine-tune aspects of the control of crystal growth in vivo.

Magnesite Dissolution Rates Across Scales: Role of Spatial Heterogeneity, Equilibrium Lengths, and Reactive Time Scales

NASA Astrophysics Data System (ADS)

Wen, H.; Li, L.

2017-12-01

This work develops a general rate law for magnesite dissolution in heterogeneous media under variable flow and length conditions, expanding the previous work under one particular flow and length conditions (Wen and Li, 2017). We aim to answer: 1) How does spatial heterogeneity influence the time and length scales to reach equilibrium? 2) How do relative timescales of advection, diffusion/dispersion, and reactions influence dissolution rates under variable flow and length conditions? We carried out 640 Monte-Carlo numerical experiments of magnesite dissolution within quartz matrix with heterogeneity characterized by permeability variance and correlation length under a range of length and flow velocity. A rate law Rhete = kAT(1-exp(τeq,m/τa))(1-exp(- Lβ))^α was developed. The former part is rates in equivalent homogeneous media kAT(1-exp(τeq,m/τa)), depending on rate constant k, magnesite surface area AT, and relative timescales of reactions τeq,m and advection τa. The latter term (1-exp(- Lβ))^α is the heterogeneity factor χ that quantifies the deviation of heterogeneous media from its homogeneous counterpart. The term has a scaling factor, called reactive transport number β=τa/(τad,r+τeq,m), for domain length L, and the geostatistical characteristics of heterogeneity α. The β quantifies the relative timescales of advection at the domain scale τa versus the advective-diffusive-dispersive transport time out of reactive zones τad,r and reaction time τeq,m. The χ is close to 1 and is insignificant under long residence time conditions (low flow velocity and / or long length) where the residence time is longer than the time needed for Mg to dissolve and transport out of reactive zones (τad,r+τeq,m) so that equilibrium is reached and homogenization occurs. In contrast, χ deviates from 1 and is significant only when β is small, which occurs at short length or fast flow where timescales of reactive transport in reactive zones are much longer than

Arsenic uptake in bacterial calcite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Catelani, Tiziano; Perito, Brunella; Bellucci, Francesco

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 cmore » 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.« less

Chemical and microbial properties in contaminated soils around a magnesite mine in northeast China

Treesearch

D Yang; D-H Zeng; J Zhang; L-J Li; R. Mao

2012-01-01

We measured soil chemical and microbial properties at a depth of 0–20 cm among mine tailings, abandoned mined land, contaminated cropland, and uncontaminated cropland around a magnesite mine near Haicheng City, Liaoning Province, China. The objective was to clarify the impact of Mg on the soils. We found that soluble Mg2+ concentration and pH...

Nickel adsorption on chalk and calcite

NASA Astrophysics Data System (ADS)

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

2014-12-01

Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite and chalk and pH ranging from 7.7 to 8.8, explored the influence of initial concentration and the amount and type of sorbent on Ni uptake. Adsorption increases with increased surface area and pH. A surface complexation model describes the data well. Stability constants for the Ni surface complex are log KNi = - 1.12 on calcite and log KNi = - 0.43 and - 0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts of polysaccharides and clay nanoparticles on the chalk surface.

Studies on densification, mechanical, micro-structural and structure–properties relationship of magnesium aluminate spinel refractory aggregates prepared from Indian magnesite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Chandrima; Ghosh, Arup; Haldar, Manas Kamal, E-mail: manashaldar@cgcri.res.in

The present work intends to study the development of magnesium aluminate spinel aggregates from Indian magnesite in a single firing stage. The raw magnesite has been evaluated in terms of chemical analysis, differential thermal analysis, thermogravimetric analysis, infrared spectroscopy, and X-ray diffraction. The experimental batch containing Indian magnesite and calcined alumina has been sintered in the temperature range of 1550 °C–1700 °C. The sintered material has been characterized in terms of physico-chemical properties like bulk density, apparent porosity, true density, relative density and thermo-mechanical/mechanical properties like hot modulus of rupture, thermal shock resistance, cold modulus of rupture and structural propertiesmore » by X-ray diffraction in terms of phase identification and evaluation of crystal structure parameters of corresponding phases by Rietveld analysis. The microstructures developed at different temperatures have been analyzed by field emission scanning electron microscope study and compositional analysis of the developed phase has been carried out by energy dispersive X-ray study. - Highlights: • The studies have been done to characterize the developed magnesium aluminate spinel. • The studies reveal correlation between refractory behavior of spinel and developed microstructures. • The studies show the values of lattice parameters of developed phases.« less

A fossil venting system in the Feragen Ultramafic Body, Norway?

NASA Astrophysics Data System (ADS)

Dunkel, Kristina G.; Jamtveit, Bjørn; Austrheim, Håkon

2017-04-01

Carbonation of ultramafic rocks in ophiolites and on the seafloor has recently been the focus of extensive research, as this alteration reaction not only influences the carbon flux between hydro- and lithosphere, but also provides natural analogues for industrial CO2 sequestration. It is a significant part of the hydrothermal circulation in the oceanic crust, as demonstrated by carbonate precipitation at hydrothermal vents. We provide microstructural and geochemical data from a previously little known ophicarbonate occurrence in the Feragen Ultramafic Body, Sør-Trøndelag, Norway. Along the northern edge of the Feragen Ultramafic Body, strongly serpentinised peridotites are carbonated. In places, the carbonation took place pervasively, leading to the formation of soapstones consisting mainly of talc and magnesite. More common is the carbonation of serpentinite breccias. Within the clasts, some of the serpentine mesh centres are replaced by magnesite, and, subordinately, dolomite or calcium carbonate. Four types of matrix have been identified in different localities: fine-grained magnesite, coarse-grained calcium carbonate, brucite occurring in large fans (up to 1 mm in diameter), and dolomite. Inclusion trails in the coarse-grained calcium carbonates record botryoidal growth, indicating crystallisation from a fluid in open space, and a hexagonal precursor phase, suggesting that aragonite was replaced by calcite. Brucite-cemented serpentinite breccias occur very locally in two outcrops with a size less than 10 m2. Many of the brucite fans have a similar arrangement of inclusions, with an area rich in dolomite inclusions in the centre of the brucite crystals, and magnetite inclusions concentrated in the tips. Dolomite as a matrix phase often grows inwards from hexagonal, rectangular, rhomboidal, or irregular pores. Many dolomite grains are probably cast pseudomorphs after (calcitised) aragonite. Some carbonate crystals are crosscut or replaced by serpentine. The

Nickel adsorption on chalk and calcite.

PubMed

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

2014-12-01

Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite and chalk and pH ranging from 7.7 to 8.8, explored the influence of initial concentration and the amount and type of sorbent on Ni uptake. Adsorption increases with increased surface area and pH. A surface complexation model describes the data well. Stability constants for the Ni surface complex are log KNi=-1.12 on calcite and log KNi=-0.43 and -0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts of polysaccharides and clay nanoparticles on the chalk surface. Copyright © 2014 Elsevier B.V. All rights reserved.

Factor analysis of rock, soil and water geochemical data from Salem magnesite mines and surrounding area, Salem, southern India

NASA Astrophysics Data System (ADS)

Satyanarayanan, M.; Eswaramoorthi, S.; Subramanian, S.; Periakali, P.

2017-09-01

Geochemical analytical data of 15 representative rock samples, 34 soil samples and 55 groundwater samples collected from Salem magnesite mines and surrounding area in Salem, southern India, were subjected to R-mode factor analysis. A maximum of three factors account for 93.8 % variance in rock data, six factors for 84 % variance in soil data, five factors for 71.2 % in groundwater data during summer and six factors for 73.7 % during winter. Total dissolved solids are predominantly contributed by Mg, Na, Cl and SO4 ions in both seasons and are derived from the country rock and mining waste by dissolution of minerals like magnesite, gypsum, halite. The results also show that groundwater is enriched in considerable amount of minor and trace elements (Fe, Mn, Ni, Cr and Co). Nickel, chromium and cobalt in groundwater and soil are derived from leaching of huge mine dumps deposited by selective magnesite mining activity. The factor analysis on trivalent, hexavalent and total Cr in groundwater indicates that most of the Cr in summer is trivalent and in winter hexavalent. The gradational decrease in topographical elevation from northern mine area to the southern residential area, combined regional hydrogeological factors and distribution of ultramafic rocks in the northern part of the study area indicate that these toxic trace elements in water were derived from mine dumps.

A novel determination of calcite dissolution kinetics in seawater

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

ERIC Educational Resources Information Center

Wilkinson, Bruce H.

1982-01-01

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

Modeling Remineralization of Desalinated Water by Micronized Calcite Dissolution.

PubMed

Hasson, David; Fine, Larissa; Sagiv, Abraham; Semiat, Raphael; Shemer, Hilla

2017-11-07

A widely used process for remineralization of desalinated water consists of dissolution of calcite particles by flow of acidified desalinated water through a bed packed with millimeter-size calcite particles. An alternative process consists of calcite dissolution by slurry flow of micron-size calcite particles with acidified desalinated water. The objective of this investigation is to provide theoretical models enabling design of remineralization by calcite slurry dissolution with carbonic and sulfuric acids. Extensive experimental results are presented displaying the effects of acid concentration, slurry feed concentration, and dissolution contact time. The experimental data are shown to be in agreement within less than 10% with theoretical predictions based on the simplifying assumption that the slurry consists of uniform particles represented by the surface mean diameter of the powder. Agreement between theory and experiment is improved by 1-8% by taking into account the powder size distribution. Apart from the practical value of this work in providing a hitherto lacking design tool for a novel technology. The paper has the merit of being among the very few publications providing experimental confirmation to the theory describing reaction kinetics in a segregated flow system.

The high-pressure behavior of spherocobaltite (CoCO3): a single crystal Raman spectroscopy and XRD study

NASA Astrophysics Data System (ADS)

Chariton, Stella; Cerantola, Valerio; Ismailova, Leyla; Bykova, Elena; Bykov, Maxim; Kupenko, Ilya; McCammon, Catherine; Dubrovinsky, Leonid

2018-01-01

Magnesite (MgCO3), calcite (CaCO3), dolomite [(Ca, Mg)CO3], and siderite (FeCO3) are among the best-studied carbonate minerals at high pressures and temperatures. Although they all exhibit the calcite-type structure ({R}\\bar{3}{c}) at ambient conditions, they display very different behavior at mantle pressures. To broaden the knowledge of the high-pressure crystal chemistry of carbonates, we studied spherocobaltite (CoCO3), which contains Co2+ with cation radius in between those of Ca2+ and Mg2+ in calcite and magnesite, respectively. We synthesized single crystals of pure spherocobaltite and studied them using Raman spectroscopy and X-ray diffraction in diamond anvil cells at pressures to over 55 GPa. Based on single crystal diffraction data, we found that the bulk modulus of spherocobaltite is 128 (2) GPa and K' = 4.28 (17). CoCO3 is stable in the calcite-type structure up to at least 56 GPa and 1200 K. At 57 GPa and after laser heating above 2000 K, CoCO3 partially decomposes and forms CoO. In comparison to previously studied carbonates, our results suggest that at lower mantle conditions carbonates can be stable in the calcite-type structure if the radius of the incorporated cation(s) is equal or smaller than that of Co2+ (i.e., 0.745 Å).

Time and metamorphic petrology: Calcite to aragonite experiments

USGS Publications Warehouse

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

1992-01-01

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

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

PubMed

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

2016-09-13

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

Incorporation of Eu(III) into Calcite under Recrystallization conditions

PubMed Central

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

2016-01-01

The interaction of calcite with trivalent europium under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). We conducted batch studies with a reaction time from seven days up to three years with three calcite powders, which differed in their specific surface area, recrystallization rates and impurities content. With increase of the recrystallization rate incorporation of Eu3+ occurs faster and its speciation comes to be dominated by one species with its excitation maximum at 578.8 nm, so far not identified during previous investigations of this process under growth and phase transformation conditions. A long lifetime of 3750 μs demonstrates complete loss of hydration, consequently Eu must have been incorporated into the bulk crystal. The results show a strong dependence of the incorporation kinetics on the recrystallization rate of the different calcites. Furthermore the investigation of the effect of different background electrolytes (NaCl and KCl) demonstrate that the incorporation process under recrystallization conditions strongly depends on the availability of Na+. These findings emphasize the different retention potential of calcite as a primary and secondary mineral e.g. in a nuclear waste disposal site. PMID:27618958

Giant calcite concretions in aeolian dune sandstones; sedimentological and architectural controls on diagenetic heterogeneity, mid-Cretaceous Iberian Desert System, Spain

NASA Astrophysics Data System (ADS)

Arribas, Maria Eugenia; Rodríguez-López, Juan Pedro; Meléndez, Nieves; Soria, Ana Rosa; de Boer, Poppe L.

2012-01-01

Aeolian dune sandstones of the Iberian erg system (Cretaceous, Spain) host giant calcite concretions that constitute heterogeneities of diagenetic origin within a potential aeolian reservoir. The giant calcite concretions developed in large-scale aeolian dune foresets, at the transition between aeolian dune toeset and damp interdune elements, and in medium-scale superimposed aeolian dune sets. The chemical composition of the giant concretions is very homogeneous. They formed during early burial by low Mg-calcite precipitation from meteoric pore waters. Carbonate components with yellow/orange luminescence form the nuclei of the poikilotopic calcite cement. These cements postdate earlier diagenetic features, characterized by early mechanical compaction, Fe-oxide cements and clay rims around windblown quartz grains resulting from the redistribution of aeolian dust over the grain surfaces. The intergranular volume (IGV) in friable aeolian sandstone ranges from 7.3 to 15.3%, whereas in cemented aeolian sandstone it is 18.6 to 25.3%. The giant-calcite concretions developed during early diagenesis under the influence of meteoric waters associated with the groundwater flow of the desert basin, although local (e.g. activity of fluid flow through extensional faults) and/or other regional controls (e.g. variations of the phreatic level associated with a variable water influx to the erg system and varying sea level) could have favoured the local development of giant-calcite concretions. The spatial distribution pattern of carbonate grains and the main bounding surfaces determined the spatial distribution of the concretions. In particular, the geometry of the giant calcite concretions is closely associated with main bounding aeolian surfaces. Thus, interdune, superimposition and reactivation surfaces exerted a control on the concretion geometries ranging from flat and tabular ones (e.g. bounded by interdunes) to wedge-shaped concretions at the dune foresets (e.g. bounded by

Cretaceous joints in southeastern Canada: dating calcite-filled fractures

NASA Astrophysics Data System (ADS)

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

2017-04-01

together, yielding an age of 101 ± 6 Ma (MSWD: 2.3). These veins are 200 km to the west and slightly younger than the c. 140-120 Ma alkaline igneous rocks which mark the surface trace of the Great Meteor Hotspot. The period of 110-90 Ma has been identified as a time of major plate reorganization that involved tectonic and magmatic events, which may be reflected in our new calcite dates. Nonetheless, LA-ICP-MS U-Pb dating of vein calcite was successful, and coupled with other geochemical information, can yield primary information about the timing and source of fluid flow through joints and fractures, which has direct applications to reducing risk associated with characterizing hydrocarbon reservoirs and deep geological repositories for nuclear waste.

The Origin of Fibrous Calcite Veins: Aragonite?

NASA Astrophysics Data System (ADS)

Elburg, M. A.; Bons, P. D.

2005-12-01

Truly fibrous calcite veins occur mainly in carbonaceous shales and are characterised by high length:width ratios of their fibres (>10). Previous studies on their Sr isotopic geochemistry (Elburg et al., 2002: Geol. Soc. London Spec. Publ. 200, 103-118; Hilgers and Sindern, 2005: Geofluids, in press) have shown that some of the material could be derived from the local wall rock. These studies also showed that the veins were always enriched in Sr compared to the calcite in the host rocks. Aragonite can contain significantly more Sr than calcite, while it also tends to have a fibrous crystal habit. It is therefore possible that the fibrous habit of these veins, which now consist of calcite, are a reflection of their initial aragonitic mineralogy, rather than of any special tectonic regime during their formation. This idea was investigated by analysing the major and trace element geochemistry of selected fibrous and non-fibrous calcite veins from Arkaroola (northern Flinders Ranges, Australia). The fibrous vein analysed for major elements contains less than 1% MgCO3, whereas calcite in the host rock, with which it is in Sr isotopic equilibrium, contains 18% MgCO3. Calcite can contain significant Mg, whereas the aragonitic structure cannot accomodate this ion, so this result is consistent with the idea of an original aragonitic mineralogy of the veins. The fibrous veins show an enrichment in the middle rare earth elements (REE) compared to the calcite in the host rock and blocky veins. In a Post-Archean Average Shale normalised diagram, Eu is more strongly enriched compared to its neighbouring elements in the fibrous veins, but not in the host calcite, blocky veins, or in the silicate fraction of the host rock, suggesting more reducing conditions during fibrous vein formation. This data cannot be used as direct evidence for the fibrous veins' aragonitic mineralogy. It does, however, show that significant differences exist between calcite in host rocks, blocky and

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Microbially Induced Calcite Precipitation Employing Environmental Isolates

PubMed Central

Kim, Gunjo; Youn, Heejung

2016-01-01

In this study, five microbes were employed to precipitate calcite in cohesionless soils. Four microbes were selected from calcite-precipitating microbes isolated from calcareous sand and limestone cave soils, with Sporosarcina pasteurii ATCC 11859 (standard strain) used as a control. Urease activities of the four microbes were higher than that of S. pasteurii. The microbes and urea–CaCl2 medium were injected at least four times into cohesionless soils of two different relative densities (60% and 80%), and the amount of calcite precipitation was measured. It was found that the relative density of cohesionless soils significantly affects the amount of calcite precipitation and that there is a weak correlation between urease activity and calcite precipitation. PMID:28773600

Microbially Induced Calcite Precipitation Employing Environmental Isolates.

PubMed

Kim, Gunjo; Youn, Heejung

2016-06-15

In this study, five microbes were employed to precipitate calcite in cohesionless soils. Four microbes were selected from calcite-precipitating microbes isolated from calcareous sand and limestone cave soils, with Sporosarcina pasteurii ATCC 11859 (standard strain) used as a control. Urease activities of the four microbes were higher than that of S. pasteurii . The microbes and urea-CaCl₂ medium were injected at least four times into cohesionless soils of two different relative densities (60% and 80%), and the amount of calcite precipitation was measured. It was found that the relative density of cohesionless soils significantly affects the amount of calcite precipitation and that there is a weak correlation between urease activity and calcite precipitation.

An XRPD and EPR spectroscopy study of microcrystalline calcite bioprecipitated by Bacillus subtilis

NASA Astrophysics Data System (ADS)

Perito, B.; Romanelli, M.; Buccianti, A.; Passaponti, M.; Montegrossi, G.; Di Benedetto, F.

2018-05-01

We report in this study the first XRPD and EPR spectroscopy characterisation of a biogenic calcite, obtained from the activity of the bacterium Bacillus subtilis. Microcrystalline calcite powders obtained from bacterial culture in a suitable precipitation liquid medium were analysed without further manipulation. Both techniques reveal unusual parameters, closely related to the biological source of the mineral, i.e., to the bioprecipitation process and in particular to the organic matrix observed inside calcite. In detail, XRPD analysis revealed that bacterial calcite has slightly higher c/a lattice parameters ratio than abiotic calcite. This correlation was already noticed in microcrystalline calcite samples grown by bio-mineralisation processes, but it had never been previously verified for bacterial biocalcites. EPR spectroscopy evidenced an anomalously large value of W 6, a parameter that can be linked to occupation by different chemical species in the next nearest neighbouring sites. This parameter allows to clearly distinguish bacterial and abiotic calcite. This latter achievement was obtained after having reduced the parameters space into an unbiased Euclidean one, through an isometric log-ratio transformation. We conclude that this approach enables the coupled use of XRPD and EPR for identifying the traces of bacterial activity in fossil carbonate deposits.

Microstructures and rheology of a calcite-shale thrust fault

NASA Astrophysics Data System (ADS)

Wells, Rachel K.; Newman, Julie; Wojtal, Steven

2014-08-01

A thin (˜2 cm) layer of extensively sheared fault rock decorates the ˜15 km displacement Copper Creek thrust at an exposure near Knoxville, TN (USA). In these ultrafine-grained (<0.3 μm) fault rocks, interpenetrating calcite grains form an interconnected network around shale clasts. One cm below the fault rock layer, sedimentary laminations in non-penetratively deformed footwall shale are cut by calcite veins, small faults, and stylolites. A 350 μm thick calcite vein separates the fault rocks and footwall shale. The vein is composed of layers of (1) coarse calcite grains (>5 μm) that exhibit a lattice preferred orientation (LPO) with pores at twin-twin and twin-grain boundary intersections, and (2) ultrafine-grained (0.3 μm) calcite that exhibits interpenetrating grain boundaries, four-grain junctions and lacks a LPO. Coarse calcite layers crosscut ultrafine-grained layers indicating intermittent vein formation during shearing. Calcite in the fault rock layer is derived from vein calcite and grain-size reduction of calcite took place by plasticity-induced fracture. The ultrafine-grained calcite deformed primarily by diffusion-accommodated grain boundary sliding and formed an interconnected network around shale clasts within the shear zone. The interconnected network of ultrafine-grained calcite indicates that calcite, not shale, was the weak phase in this fault zone.

Acidization of shales with calcite cemented fractures

NASA Astrophysics Data System (ADS)

Kwiatkowski, Kamil; Szymczak, Piotr; Jarosiński, Marek

2017-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Numerical Approaches about the Morphological Description Parameters for the Manganese Deposits on the Magnesite Ore Surface

NASA Astrophysics Data System (ADS)

Bayirli, Mehmet; Ozbey, Tuba

2013-07-01

Black deposits usually found at the surface of magnesite ore or limestone as well as red deposits in quartz veins are named as natural manganese dendrites. According to their geometrical structures, they may take variable fractal shapes. The characteristic origins of these morphologies have rarely been studied by means of numerical analyses. Hence, digital images of magnesite ore are taken from its surface with a scanner. These images are then converted to binary images in the form of 8 bits, bitmap format. As a next step, the morphological description parameters of manganese dendrites are computed by the way of scaling methods such as occupied fractions, fractal dimensions, divergent ratios, and critical exponents of scaling. The fractal dimension and the scaling range are made dependent on the fraction of the particles. Morphological description parameters can be determined according to the geometrical evaluation of the natural manganese dendrites which are formed independently from the process. The formation of manganese dendrites may also explain the stochastic selected process in the nature. These results therefore may be useful to understand the deposits in quartz vein parameters in geophysics.

Intensify dodecylamine adsorption on magnesite and dolomite surfaces by monohydric alcohols

NASA Astrophysics Data System (ADS)

Zhang, Hao; Liu, Wengang; Han, Cong; Wei, Dezhou

2018-06-01

The flotation of magnesite and dolomite were investigated with the presence of single dodecylamine (DDA) and combined mixtures of DDA and monohydric alcohols, respectively. The adsorption behavior of DDA, butanol, hexanol and octanol on the surface of the two minerals were shown by molecular dynamics simulation, and the results were corresponding with the analysis of zeta potential, measurements of the contact angle and adsorption. Flotation results indicated that part of DDA could be replaced by the three alcohols (butanol, hexanol, octanol) to get better flotation results. Molecular dynamics simulation and the results of zeta potential and contact angle measurements indicated that adsorption of DDA on mineral surfaces could be strengthened by monohydric alcohols.

Raman spectroscopic study of calcite III to aragonite transformation under high pressure and high temperature

NASA Astrophysics Data System (ADS)

Liu, Chuanjiang; Zheng, Haifei; Wang, Duojun

2017-10-01

In our study, a series of Raman experiments on the phase transition of calcite at high pressure and high temperature were investigated using a hydrothermal diamond anvil cell and Raman spectroscopy technique. It was found that calcite I transformed to calcite II and calcite III at pressures of 1.62 and 2.12 GPa and room temperature. With increasing temperature, the phase transition of calcite III to aragonite occurred. Aragonite was retained upon slowly cooling of the system, indicating that the transition of calcite III to aragonite was irreversible. Based on the available data, the phase boundary between calcite III and aragonite was determined by the following relation: P(GPa) = 0.013 × T(°C) + 1.22 (100°C ≤ T ≤ 170°C). It showed that the transition pressure linearly rose with increasing temperature. A better understanding of the stability of calcite III and aragonite is of great importance to further explore the thermodynamic behavior of carbonates and carbon cycling in the mantle.

The crystal structure of calcite III

NASA Astrophysics Data System (ADS)

Smyth, Joseph R.; Ahrens, Thomas J.

The crystal structure of calcite III has been deduced from existing high pressure powder X-ray diffraction patterns, based on the assumption that it is a displacive modification of the calcite I structure. The structure is monoclinic with space group C2 and a Z of 6. There are two Ca and two C positions, and five O positions, and atom coordinates have been refined by distance-least-squares methods to give reasonable octahedral coordination for Ca and parallel, planar CO3 groups. Unit cell parameters refined from a published powder diffraction pattern at 4.1 GPa are: a = 8.746(8)Å b = 4.685(5)Å c = 8.275(8)Å and β= 94.4°. The structure has a calculated density of 2.949 Mg/m³ at 4.1 GPa which is less than that of aragonite at this pressure and consistent with early piston cylinder studies. This implies that calcite III is indeed a metastable intermediary between calcite I and aragonite.

Influence of deformation on dolomite rim growth kinetics

NASA Astrophysics Data System (ADS)

Helpa, Vanessa; Rybacki, Erik; Grafulha Morales, Luiz Fernando; Dresen, Georg

2015-04-01

Using a gas-deformation apparatus stacks of oriented calcite (CaCO3) and magnesite (MgCO3) single crystals were deformed at T = 750° C and P = 400 MPa to examine the influence of stress and strain on magnesio-calcite and dolomite (CaMg[CO3]2) growth kinetics. Triaxial compression and torsion tests performed at constant stresses between 7 and 38 MPa and test durations between 4 and 171 hours resulted in bulk strains of 0.03-0.2 and maximum shear strains of 0.8-5.6, respectively. The reaction rims consist of fine-grained (2-7 μm) dolomite with palisade-shaped grains growing into magnesite reactants and equiaxed granular dolomite grains next to calcite. In between dolomite and pure calcite, magnesio-calcite grains evolved with an average grain size of 20-40 μm. Grain boundaries tend to be straighter at high bulk strains and equilibrium angles at grain triple junctions are common within the magnesio-calcite layer. Transmission electron microscopy shows almost dislocation free palisades and increasing dislocation density within granular dolomite towards the magnesio-calcite boundary. Within magnesio-calcite grains, dislocations are concentrated at grain boundaries. Variation of time at fixed stress (˜17 MPa) yields a parabolic time dependence of dolomite rim width, indicating diffusion-controlled growth, similar to isostatic rim growth behavior. In contrast, the magnesio-calcite layer growth is enhanced compared to isostatic conditions. Triaxial compression at given time shows no significant change of dolomite rim thickness (11±2 μm) and width of magnesio-calcite layers (33±5 μm) with increasing stress. In torsion experiments, reaction layer thickness and grain size decrease from the center (low stress/strain) to the edge (high strain/stress) of samples. Chemical analysis shows nearly stoichiometric composition of dolomite palisades, but enhanced Ca content within granular grains, indicating local disequilibrium with magnesio-calcite, in particular for twisted

Calcite saturation in the River Dee, NE Scotland.

PubMed

Wade, A J; Neal, C; Smart, R P; Edwards, A C

2002-01-23

The spatial and temporal variations in calcite (calcium carbonate) solubility within the Dee basin of NE Scotland were assessed using water chemistry data gathered from a network of 59 sites monitored for water quality from June 1996 to May 1997. Calcite solubility, expressed in terms of a saturation index (SIcalcite), was determined from measured streamwater pH, Gran alkalinity and calcium concentrations and water temperature. In general, the waters of the Dee system are undersaturated with respect to calcite, though the saturation index is higher during the summer months indicating a dependency on flow conditions and biological activity. Under low-flow conditions, the streamwaters are dominated by water derived from the lower soil horizons and deeper groundwater stores and therefore, ions such as Gran alkalinity and calcium are at their highest concentrations as they are derived mainly from bedrock weathering. The influence of biological activity on the carbonate system is also evident as the observed pH and estimated EpCO2 values indicate strong seasonal patterns, with the highest pH and lowest EpCO2 values occurring during the summer low-flow periods. Only at three sites in the lowland region of the catchment, during the summer low-flow period, are the waters oversaturated. As such, the Dee system represents an extreme 'end-member' case when compared to many UK rivers that span both under- and oversaturated conditions during the year. Regression analysis highlights a systematic change in the SIcalcite-pH relationship in a broad east-west direction across the Dee system. At sites draining the relatively impermeable upland areas, the regression of SIcalcite against pH gives a straight line with a gradient in the range 1.6-2.4. Correspondingly, under the most extreme alkaline conditions found at sites draining lowland agricultural areas, a straight-line relationship exists but with a gradient of unity. It is concluded that these changes in the SIcalcite

Dissolution of coccolithophorid calcite by microzooplankton and copepod grazing

NASA Astrophysics Data System (ADS)

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

2008-01-01

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

Molecular models of alginic acid: Interactions with calcium ions and calcite surfaces

NASA Astrophysics Data System (ADS)

Perry, Thomas D.; Cygan, Randall T.; Mitchell, Ralph

2006-07-01

Cation binding by polysaccharides is observed in many environments and is important for predictive environmental modeling, and numerous industrial and food technology applications. The complexities of these cation-organic interactions are well suited for predictive molecular modeling and the analysis of conformation and configuration of polysaccharides and their influence on cation binding. In this study, alginic acid was chosen as a model polymer system and representative disaccharide and polysaccharide subunits were developed. Molecular dynamics simulation of the torsion angles of the ether linkage between various monomeric subunits identified local and global energy minima for selected disaccharides. The simulations indicate stable disaccharide configurations and a common global energy minimum for all disaccharide models at Φ = 274 ± 7°, Ψ = 227 ± 5°, where Φ and Ψ are the torsion angles about the ether linkage. The ability of disaccharide subunits to bind calcium ions and to associate with the (101¯4) surface of calcite was also investigated. Molecular models of disaccharide interactions with calcite provide binding energy differences for conformations that are related to the proximity and residence densities of the electron-donating moieties with calcium ions on the calcite surface, which are controlled, in part, by the torsion of the ether linkage between monosaccharide units. Dynamically optimized configurations for polymer alginate models with calcium ions were also derived.

Sea urchin skeleton: Structure, composition, and application as a template for biomimetic materials

NASA Astrophysics Data System (ADS)

Shapkin, Nikolay P.; Khalchenko, Irina G.; Panasenko, Alexander E.; Drozdov, Anatoly L.

2017-07-01

SEM and optical microscopy, chemical and EDX analysis, XRD, and FT-IR spectroscopy of three sea urchins skeletons (tests) show that the test is a spongy stereom, consisting of calcite with high content of magnesium. The tests are composed of mineral-organic composite of calcite-magnesite crystals, coated with organic film, containing silicon in form of polyphenylsiloxane. In the test of sea urchin pore spaces are linked into united system of regular structure with structure motive period about 20 um. This developed three-dimensional structure was used as a template for polymer material based on polyferrofenilsiloxane [OSiC6H5OH]x[OSiC6H5O]y[OFeO]z, which is chemically similar to the native film, coating sea urchins skeleton.

Post-extension shortening strains preserved in calcites of the Keweenawan rift

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donnelly, K.; Craddock, J.; McGovern, M.

1993-02-01

The Keweenawan rift is part of failed triple junction system that underlies Lake Superior and the Michigan Basin. The rift experienced extensional stresses dating about 1.1 Ga, which were followed by compressional stresses from about 1,060 Ma to < 350 Ma. Associated with the rift are two thrust faults: the Douglas (dipping southeast) and the Keweenawan-Lake Owen (dipping northwest). To determine the direction of rifting, calcite twins were used to calculate strain ellipsoids (Groshong method) which are indicative of the intensity and direction of the stress applied to a rocks in a region at a given time. Rock samples whichmore » contain significant calcite within the zone of rifting were collected, slabbed, and made into thin sections. Calcite appears as amygdule, vein, and cement filings, as well as limestones. Analyses show that different calcite types show different stain orientations. Two principle directions of sub-horizontal shortening are present: one parallel to rift, and one normal to the rift, indicating that rifting motion varied out the time in which different calcite types were deposited. Shortening parallel to the rift is seen predominantly on the western margin while shortening normal to the rift is seen predominantly on the eastern margin.« less

Modelling the evolution of complex conductivity during calcite precipitation on glass beads

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Palaeoclimate determination from cave calcite deposits

NASA Astrophysics Data System (ADS)

Gascoyne, M.

Calcite deposits formed in limestone caves have been found to be an excellent repository of palaeoclimatic data for terrestrial environments. The very presence of a relict deposit indicates non-glacial conditions at the time of formation, and both 14C and uranium-series methods can be used to date the deposit and, hence, the age of these climatic conditions. Variations in 13C and 18O content of the calcite, in 2H and 18O content of fluid inclusions, in trace element concentrations and, more recently, in pollen assemblages trapped in the calcite, are all potentially available as synchronous palaeoclimatic indicators. Previous work has tended to concentrate mainly on abundance of deposits as a palaeoclimatic indicator for the last 300,000 years. This literature is briefly reviewed here, together with the theory and methods of analysis of the U-series and stable isotopic techniques. The combined use of U-series ages and 13C and 18O variations in cave calcites illustrates the potential for palaeoclimate determination. Previously unpublished results of stable isotopic variations in dated calcites from caves in northern England indicate the level of detail of stable isotopic variations and time resolution that can be obtained, and the complexity of interpretation that may arise. Tentative palaeoclimatic signals for the periods 90-125 ka and 170-300 ka are presented. More comprehensive studies are needed in future work, especially in view of the difficulty in obtaining suitable deposits and the ethics of cave deposits conservation.

Spectroscopic characterization of natural calcite minerals.

PubMed

Gunasekaran, S; Anbalagan, G

2007-11-01

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

Magnesium Contamination in Soil at a Magnesite Mining Area of Jelšava-Lubeník (Slovakia)

NASA Astrophysics Data System (ADS)

Fazekašová, D.; Fazekaš, J.; Hronec, O.; Horňak, M.

2017-10-01

Magnesium contamination in soil at a magnesite mining area of Jelšava-Lubeník (Slovakia) and their effect to the soil characteristics were determined. Soil samples were collected in the area Jelšava - Lubeník with specific alkaline pollutants, it is one of the most devastated regions of Slovakia and with the alarming degree of environmental damage. Magnesite air pollutants are a mixture of MgO and MgCO3 due to which a soil reaction can move above pH 8. Production of clink accompanies the enormous emissions of dust particles of MgO into the air and the leakage of gaseous compounds, mainly SO2 and NOx. The total content of heavy metals in soils (Pb, Zn, Cr, Mn, Mg) were determined by atomic absorption spectrometry and X-ray fluorescence spectrometry. Soil reaction was determined in solution of 0.01 M CaCl2. The research showed that the investigated sites are mostly strongly alkaline. Based on the obtained results, it can be stated that the contents of Pb, Zn is below the level of toxicity but for Cr, Mn and Mg, it does not apply. Their significant exceedance points contamination in which we can take into account the harmfulness and toxicity.

Experimental Constraints on the Stability of Clinopyroxene (+) Magnesite in Iron Bearing Planetary Mantles: Implications for Nakhlite Formation

NASA Technical Reports Server (NTRS)

Martin, Audrey M.; Righter, Kevin

2010-01-01

Carbon is present in various forms in the Earth s upper mantle (carbonate- or diamond-bearing mantle xenoliths, carbonatite magmas, CO2 emissions from volcanoes...). Moreover, there is enough carbon in chondritic material to stabilize carbonates into the mantles of Mars or Venus as well as in the Earth. However, the interactions with iron have to be constrained, because Fe is commonly thought to buffer oxygen fugacity into planetary mantles. [1] and [2] show evidences of the stability of clinopyroxene Ca(Mg,Fe)Si2O6 + magnesite (Mg,Fe)CO3 in the Earth s mantle around 6GPa (about 180km). The stability of oxidized forms of carbon (like magnesite) depends on the oxygen fugacity of the system. In the Earth s mantle, the maximum carbon content is 10000 ppm [3]. The fO2 parameter varies vertically as a function of pressure, but also laterally because of geodynamic processes like subduction. Thus, carbonates, graphite, diamond, C-rich gases and melts are all stable forms of carbon in the Earth s mantle. [4] show that the fO2 variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. [5] inferred from thermodynamic calculations that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond). After [6], a metasomatizing agent like a CO2-rich melt may infiltrate the mantle source of nakhlites. However, according to [7] and [8], the FeO wt% value in the Martian bulk mantle is more than twice that of the Earth s mantle (KLB-1 composition by [9]). As iron and carbon are two elements with various oxidation states, Fe/C interaction mechanisms must be considered.

Methanogenic calcite, 13C-depleted bivalve shells, and gas hydrate from a mud volcano offshore southern California

USGS Publications Warehouse

Hein, J.R.; Normark, W.R.; McIntyre, B.R.; Lorenson, T.D.; Powell, C.L.

2006-01-01

Methane and hydrogen sulfide vent from a cold seep above a shallowly buried methane hydrate in a mud volcano located 24 km offshore southern California in?? 800 m of water. Bivalves, authigenic calcite, and methane hydrate were recovered in a 2.1 m piston core. Aragonite shells of two bivalve species are unusually depleted in 13C (to -91??? ??13C), the most 13C-depleted shells of marine macrofauna yet discovered. Carbon isotopes for both living and dead specimens indicate that they used, in part, carbon derived from anaerobically oxidized methane to construct their shells. The ??13C values are highly variable, but most are within the range -12??? to -91???. This variability may be diagnostic for identifying cold-seep-hydrate systems in the geologic record. Authigenic calcite is abundant in the cores down to ???1.5 m subbottom, the top of the methane hydrate. The calcite is depleted in 13C (??13C = -46??? to -58???), indicating that carbon produced by anaerobically oxidized methane is the main source of the calcite. Methane sources include a geologic hydrocarbon reservoir from Miocene source rocks, and biogenic and thermogenic degradation of organic matter in basin sediments. Oxygen isotopes indicate that most calcite formed out of isotopic equilibrium with ambient bottom water, under the influence of gas hydrate dissociation and strong methane flux. High metal content in the mud volcano sediment indicates leaching of basement rocks by fluid circulating along an underlying fault, which also allows for a high flux of fossil methane. ?? 2006 Geological Society of America.

A Raman spectroscopic comparison of calcite and dolomite

NASA Astrophysics Data System (ADS)

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

2014-01-01

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

Study of reverse flotation of calcite from scheelite in acidic media

NASA Astrophysics Data System (ADS)

Deng, Rongdong; Huang, Yuqing; Hu, Yuan; Ku, Jiangang; Zuo, Weiran; Yin, Wanzhong

2018-05-01

A new coated-reactive reverse flotation method based on the generation of CO2 bubbles at a calcite surface in acidic solution was used to separate calcite from scheelite. The dissolution kinetics of coated and uncoated calcite were studied in sulfuric acid. The CO2 bubbles generated on the uncoated calcite particle surface are enough to float the particle. However, most of these bubbles left the surface quickly, preventing calcite from floating. Here, a mixture of polyvinyl alcohol polymer and sodium dodecyl sulfonate was used to coat the mineral particles and form a stable membrane, resulting in the formation of a stable foam layer on the calcite surface. After the calcite is coated, the generated bubbles could be successfully captured on the calcite surface, and calcite particles could float to the air-water interface and remain there for more than one hour. Flotation tests indicated that a high-quality tungsten concentrate with a grade of more than 75% and a recovery of more than 99% could be achieved when the particle size was between 0.3 and 1.5 mm. The present results provide theoretical support for the development of a highly efficient flotation separation for carbonate minerals.

Calcite crystal growth rate inhibition by polycarboxylic acids

USGS Publications Warehouse

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

2001-01-01

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

Experimental study of carbonate formation in oceanic peridotite

NASA Astrophysics Data System (ADS)

Grozeva, Niya G.; Klein, Frieder; Seewald, Jeffrey S.; Sylva, Sean P.

2017-02-01

Interactions of CO2-rich aqueous fluids with mantle peridotite have major implications for geochemical budgets and microbial life in the shallow oceanic lithosphere through the formation of carbonate minerals and reduced carbon species. However, the underlying mechanisms controlling the transformation of CO2 to carbonates in ultramafic-hosted hydrothermal systems remain incompletely understood. A long-term laboratory experiment was conducted at 300 °C and 35 MPa to investigate serpentinization and carbonate formation pathways during hydrothermal alteration of peridotite. Powdered harzburgite was initially reacted with a Ca-rich aqueous fluid for 14,592 h (608 days) and changes in fluid composition were monitored with time. Once the system reached a steady state, a CO2(aq)-rich fluid was injected and allowed to react with the system for 5907 h (246 days). Fluid speciation and mineral analyses suggest that serpentinization of harzburgite in the CO2-poor system led to the precipitation of serpentine, brucite, magnetite, and minor calcite, in addition to other minor phases including chlorite and sulfur-poor Ni sulfides. The addition of the CO2(aq)-rich fluid caused dolomite, Ca-rich dolomite, and high-Mg calcite to form at the expense of olivine, calcite, and brucite, while serpentine remained unreactive. Replacement textures and mineral assemblages mimic those documented in carbonate-altered seafloor serpentinites, particularly those from the Mid-Atlantic Ridge and the Iberia Margin. In contrast to thermodynamic predictions, magnesite did not form in the experiment because the dissolution of clinopyroxene, in combination with the lack of serpentine reactivity, maintained low Mg/Ca ratios in solution. Clinopyroxene dissolution and unreactive serpentine may similarly maintain low Mg/Ca ratios in submarine serpentinization systems and limit magnesite formation in subseafloor environments. Results of this study suggest that the formation of Ca-Mg carbonates by mineral

Experimental diagenesis: insights into aragonite to calcite transformation of Arctica islandica shells by hydrothermal treatment

NASA Astrophysics Data System (ADS)

Casella, Laura A.; Griesshaber, Erika; Yin, Xiaofei; Ziegler, Andreas; Mavromatis, Vasileios; Müller, Dirk; Ritter, Ann-Christine; Hippler, Dorothee; Harper, Elizabeth M.; Dietzel, Martin; Immenhauser, Adrian; Schöne, Bernd R.; Angiolini, Lucia; Schmahl, Wolfgang W.

2017-03-01

Biomineralised hard parts form the most important physical fossil record of past environmental conditions. However, living organisms are not in thermodynamic equilibrium with their environment and create local chemical compartments within their bodies where physiologic processes such as biomineralisation take place. In generating their mineralised hard parts, most marine invertebrates produce metastable aragonite rather than the stable polymorph of CaCO3, calcite. After death of the organism the physiological conditions, which were present during biomineralisation, are not sustained any further and the system moves toward inorganic equilibrium with the surrounding inorganic geological system. Thus, during diagenesis the original biogenic structure of aragonitic tissue disappears and is replaced by inorganic structural features. In order to understand the diagenetic replacement of biogenic aragonite to non-biogenic calcite, we subjected Arctica islandica mollusc shells to hydrothermal alteration experiments. Experimental conditions were between 100 and 175 °C, with the main focus on 100 and 175 °C, reaction durations between 1 and 84 days, and alteration fluids simulating meteoric and burial waters, respectively. Detailed microstructural and geochemical data were collected for samples altered at 100 °C (and at 0.1 MPa pressure) for 28 days and for samples altered at 175 °C (and at 0.9 MPa pressure) for 7 and 84 days. During hydrothermal alteration at 100 °C for 28 days most but not the entire biopolymer matrix was destroyed, while shell aragonite and its characteristic microstructure was largely preserved. In all experiments up to 174 °C, there are no signs of a replacement reaction of shell aragonite to calcite in X-ray diffraction bulk analysis. At 175 °C the replacement reaction started after a dormant time of 4 days, and the original shell microstructure was almost completely overprinted by the aragonite to calcite replacement reaction after 10 days

Major geochemical processes in the evolution of carbonate-Aquifer systems

USGS Publications Warehouse

Hanshaw, B.B.; Back, W.

1979-01-01

As a result of recent advances by carbonate petrologists and geochemists, hydrologists are provided with new insights into the origin and explanation of many aquifer characteristics and hydrologic phenomena. Some major advances include the recognition that: (1) most carbonate sediments are of biological origin; (2) they have a strong bimodal size-distribution; and (3) they originate in warm shallow seas. Although near-surface ocean water is oversaturated with respect to calcite, aragonite, dolomite and magnesite, the magnesium-hydration barrier effectively prevents either the organic or inorganic formation of dolomite and magnesite. Therefore, calcareous plants and animals produce only calcite and aragonite in hard parts of their bodies. Most carbonate aquifers that are composed of sand-size material have a high initial porosity; the sand grains that formed these aquifers originated primarily as small shells, broken shell fragments of larger invertebrates, or as chemically precipitated oolites. Carbonate rocks that originated as fine-grained muds were initially composed primarily of aragonite needles precipitated by algae and have extremely low permeability that requires fracturing and dissolution to develop into aquifers. Upon first emergence, most sand beds and reefs are good aquifers; on the other hand, the clay-sized carbonate material initially has high porosity but low permeability, a poor aquifer property. Without early fracture development in response to influences of tectonic activity these calcilutites would not begin to develop into aquifers. As a result of selective dissolution, inversion of the metastable aragonite to calcite, and recrystallization, the porosity is collected into larger void spaces, which may not change the overall porosity, but greatly increases permeability. Another major process which redistributes porosity and permeability in carbonates is dolomitization, which occurs in a variety of environments. These environments include back

Calcite precipitates in Slovenian bottled waters.

PubMed

Stanič, Tamara Ferjan; Miler, Miloš; Brenčič, Mihael; Gosar, Mateja

2017-06-01

Storage of bottled waters in varying ambient conditions affects its characteristics. Different storage conditions cause changes in the initial chemical composition of bottled water which lead to the occurrence of precipitates with various morphologies. In order to assess the relationship between water composition, storage conditions and precipitate morphology, a study of four brands of Slovenian bottled water stored in PET bottles was carried out. Chemical analyses of the main ions and measurements of the physical properties of water samples were performed before and after storage of water samples at different ambient conditions. SEM/EDS analysis of precipitates was performed after elapsed storage time. The results show that the presence of Mg 2+ , SO 4 2- , SiO 2 , Al, Mn and other impurities such as K + , Na + , Ba and Sr in the water controlled precipitate morphology by inhibiting crystal growth and leading to elongated rhombohedral calcite crystal forms which exhibit furrowed surfaces and calcite rosettes. Different storage conditions, however, affected the number of crystallization nuclei and size of calcite crystals. Hollow calcite spheres composed of cleavage rhombohedrons formed in the water with variable storage conditions by a combination of evaporation and precipitation of water droplets during high temperatures or by the bubble templating method.

Rheology and microstructure of synthetic halite/calcite porphyritic aggregates in torsion

NASA Astrophysics Data System (ADS)

Marques, F. O.; Burlini, L.; Burg, J.-P.

2010-03-01

Polymer jacketed porphyritic samples of 70% halite + 30% coarse calcite were subjected to torsion deformation to investigate the effects of a mixture of coarse calcite on the microstructure and mechanical properties of a two-phase aggregate. The experiments were run at 100 and 200 °C, a confining pressure of 250 MPa, and a constant shear strain rate of 3E-4 s -1. Ultimate strengths of single-phase halite synthetic aggregates at 100 and 200 °C were ca. 32 and 8 Nm, respectively, and of the two-phase aggregate 39 and 18 Nm, respectively; this shows that the two-phase aggregate was much stronger, especially at 200 °C. Stepping strain rate tests show that the two-phase aggregate behaved as power-law viscous, with stress exponents of ca. 19 and 13 at 100 °C at 200 °C, respectively. From these high exponents, we infer that the active deformation mechanisms were not efficient enough to rapidly relax the applied stress. Halite stress exponents at 100 and 200 °C are typically much lower, in the order of 4-6, which means that the calcite porphyroclasts were obstacles to halite plastic flow and hampered stress relaxation. The drop of the stress exponent with temperature indicates that the main deformation mechanism(s) was temperature sensitive. Matrix halite deformed plastically, while calcite rotated rigidly or deformed in a brittle fashion, with grain size reduction by fracturing (e.g. bookshelf and boudinage). We conclude that halite was softer than calcite in the investigated temperature range. Strain was homogeneous at the sample scale but not at the grain scale where the foliation delineated by plastically flattened halite contoured the rigid calcite clasts. The microstructures experimentally produced at 100 and 200 °C are very similar and find their counterparts in natural mylonites: rolling structures, σ and δ porphyroclast systems, bookshelf and boudinage in brittle calcite porphyroclasts, and ductile y and c' micro shear bands in the halite matrix.

Environmental controls for the precipitation of different fibrous calcite cement fabrics

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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

USGS Publications Warehouse

Komor, S.C.

1995-01-01

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

MicroRaman, PXRD, EDS and microscopic investigation of magnesium calcite biomineral phases. The case of sea urchin biominerals

NASA Astrophysics Data System (ADS)

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

2007-02-01

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

Surface Forces Apparatus Measurements of Interactions between Rough and Reactive Calcite Surfaces.

PubMed

Dziadkowiec, Joanna; Javadi, Shaghayegh; Bratvold, Jon E; Nilsen, Ola; Røyne, Anja

2018-06-26

nm-Range forces acting between calcite surfaces in water affect macroscopic properties of carbonate rocks and calcite-based granular materials and are significantly influenced by calcite surface recrystallization. We suggest that the repulsive mechanical effects related to nm-scale surface recrystallization of calcite in water could be partially responsible for the observed decrease of cohesion in calcitic rocks saturated with water. Using the surface forces apparatus, we simultaneously followed the calcite reactivity and measured the forces in water in two surface configurations: between two rough calcite surfaces (CC) and between rough calcite and a smooth mica surface (CM). We used nm-scale rough, polycrystalline calcite films prepared by atomic layer deposition. We measured only repulsive forces in CC in CaCO 3 -saturated water, which was related to roughness and possibly to repulsive hydration effects. Adhesive or repulsive forces were measured in CM in CaCO 3 -saturated water depending on calcite roughness, and the adhesion was likely enhanced by electrostatic effects. The pull-off adhesive force in CM became stronger with time, and this increase was correlated with a decrease of roughness at contacts, the parameter which could be estimated from the measured force-distance curves. That suggested a progressive increase of real contact areas between the surfaces, caused by gradual pressure-driven deformation of calcite surface asperities during repeated loading-unloading cycles. Reactivity of calcite was affected by mass transport across nm- to μm-thick gaps between the surfaces. Major roughening was observed only for the smoothest calcite films, where gaps between two opposing surfaces were nm-thick over μm-sized areas and led to force of crystallization that could overcome confining pressures of the order of MPa. Any substantial roughening of calcite caused a significant increase of the repulsive mechanical force contribution.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hargis, Craig W.; Telesca, Antonio; Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu

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

A Raman spectroscopic comparison of calcite and dolomite.

PubMed

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

2014-01-03

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

REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

DOE PAGES

Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

2017-10-26

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

X-ray driven reaction front dynamics at calcite-water interfaces

DOE PAGES

Laanait, Nouamane; Callagon, Erika Blanca R.; Zhang, Zhan; ...

2015-09-18

The interface of minerals with aqueous solutions is central to geochemical reactivity, hosting processes that span multiple spatiotemporal scales. Understanding such processes requires spatially and temporally resolved observations, and experimental controls that precisely manipulate the interfacial thermodynamic state. Using the intense radiation fields of a focused synchrotron X-ray beam, we drove dissolution at the calcite-aqueous interface and simultaneously probed the dynamics of the propagating reaction fronts using surface X-ray microscopy. Evolving surface structures are controlled by the time-dependent solution composition as characterized by a kinetic reaction model. At extreme disequilibria, the onset of reaction front instabilities was observed with velocitiesmore » of >30 nanometers per second. As a result, these instabilities are identified as a signature of transport-limited dissolution of calcite under extreme disequilibrium.« less

Replacement of Calcite (CaCO 3) by Cerussite (PbCO 3)

DOE PAGES

Yuan, Ke; Lee, Sang Soo; De Andrade, Vincent; ...

2016-10-21

The mobility of toxic elements, such as lead (Pb) can be attenuated by adsorption, incorporation, and precipitation on carbonate minerals in subsurface environments. Here in this paper, we report a study of the bulk transformation of single-crystal calcite (CaCO 3) into polycrystalline cerussite (PbCO 3) through reaction with acidic Pb-bearing solutions. This reaction began with the growth of a cerussite shell on top of calcite surfaces followed by the replacement of the remaining calcite core. The external shape of the original calcite was preserved by a balance between calcite dissolution and cerussite growth controlled by adjusting the Pb 2+ concentration and pH. The relation between the rounded calcite core and the surrounding lath-shaped cerussite aggregates was imaged by transmission X-ray microscopy, which revealed preferentially elongated cerussite crystals parallel to the surface and edge directions of calcite. The replacement reaction involved concurrent development ~100 nm wide pores parallel to calcite c-glide or (1more » $$\\overline{20}$$) planes, which may have provided permeability for chemical exchange during the reaction. X-ray reflectivity measurements showed no clear epitaxial relation of cerussite to the calcite (104) surface. These results demonstrate Pb sequestration through mineral replacement reactions and the critical role of nanoporosity (3% by volume) on the solid phase transformation through a dissolution-recrystallization mechanism.« less

Elastic constants of calcite

USGS Publications Warehouse

Peselnick, L.; Robie, R.A.

1962-01-01

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

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

PubMed

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

2017-03-08

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

Calcitic microlenses as part of the photoreceptor system in brittlestars

NASA Astrophysics Data System (ADS)

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

2001-08-01

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

Enhanced Reactant-Contaminant Contact through the Use of Persulfate In Situ Chemical Oxidation (ISCO)

DTIC Science & Technology

2011-02-01

cuprite [Cu2O], hematite [Fe2O3], ilmenite [FeTiO3], magnesite [MgCO3], malachite [Cu2(CO3)(OH)2], pyrite [FeS2], pyrolusite [MnO2], siderite [FeCO3...0.3 m2/g], malachite [3.65 ± 0.03 m2/g], pyrite [2.12 ± 0.01 m2/g], pyrolusite [1.39 ± 0.04 m2/g], siderite [6.8 ± 0.4 m2/g], willemite [1.8 ± 0.02 m2...0.4 0.6 0.8 1 0 10 20 30 40 50 60 Anatase Bauxite Calcite Cobaltite Control Cuprite Hematite Ilmenite Magnesite Malachite Pyrite Pyrolusite Siderite

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

The effect of sulfated polysaccharides on the crystallization of calcite superstructures

NASA Astrophysics Data System (ADS)

Fried, Ruth; Mastai, Yitzhak

2012-01-01

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

Sand-calcite crystals from Garfield County, Utah

USGS Publications Warehouse

Sargent, Kenneth A.; Zeller, H.D.

1984-01-01

Sand-calcite crystals are found in the Morrison Formation of Jurassic age in south-central Garfield County, Utah. The outcrop area is less than 1 acre, yet the locality contains many fine specimens of single, double, and complex crystals in good hexagonal form. This is the first known occurrence of sand-calcite crystals in rocks of Jurassic age and is the first reported occurrence in Utah.

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

USGS Publications Warehouse

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

2005-01-01

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

Seasonal variations in modern speleothem calcite growth in Central Texas, U.S.A

USGS Publications Warehouse

Banner, J.L.; Guilfoyle, A.; James, E.W.; Stern, L.A.; Musgrove, M.

2007-01-01

Variations in growth rates of speleothem calcite have been hypothesized to reflect changes in a range of paleoenvironmental variables, including atmospheric temperature and precipitation, drip-water composition, and the rate of soil CO2 delivery to the subsurface. To test these hypotheses, we quantified growth rates of modern speleothem calcite on artificial substrates and monitored concurrent environmental conditions in three caves across the Edwards Plateau in central Texas. Within each of two caves, different drip sites exhibit similar annual cycles in calcite growth rates, even though there are large differences between the mean growth rates at the sites. The growth-rate cycles inversely correlate to seasonal changes in regional air temperature outside the caves, with near-zero growth rates during the warmest summer months, and peak growth rates in fall through spring. Drip sites from caves 130 km apart exhibit similar temporal patterns in calcite growth rate, indicating a controlling mechanism on at least this distance. The seasonal variations in calcite growth rate can be accounted for by a primary control by regional temperature effects on ventilation of cave-air CO2 concentrations and/or drip-water CO2 contents. In contrast, site-to-site differences in the magnitude of calcite growth rates within an individual cave appear to be controlled principally by differences in drip rate. A secondary control by drip rate on the growth rate temporal variations is suggested by interannual variations. No calcite growth was observed in the third cave, which has relatively high values of and small seasonal changes in cave-air CO2. These results indicate that growth-rate variations in ancient speleothems may serve as a paleoenvironmental proxy with seasonal resolution. By applying this approach of monitoring the modern system, speleothem growth rate and geochemical proxies for paleoenviromnental change may be evaluated and calibrated. Copyright ?? 2007, SEPM (Society for

Sorption of the Rare Earth Elements and Yttrium (REE-Y) in calcite: the mechanism of a new effective tool in identifying paleoearthquakes on carbonate faults

NASA Astrophysics Data System (ADS)

Moraetis, Daniel; Mouslopoulou, Vasiliki; Pratikakis, Alexandros

2015-04-01

A new tool for identifying paleoearthquakes on carbonate faults has been successfully tested on two carbonate faults in southern Europe (the Magnola Fault in Italy and the Spili Fault in Greece): the Rare Earth Element and Yttrium (REE-Y) method (Manighetti et al., 2010; Mouslopoulou et al., 2011). The method is based on the property of the calcite in limestone scarps to absorb the REE and Y from the soil during its residence beneath the ground surface (e.g. before its exhumation due to earthquakes). Although the method is established, the details of the enrichment mechanism are poorly investigated. Here we use published data together with new information from pot-experiments to shed light on the sorption mechanism and the time effectiveness of the REE-Y method. Data from the Magnola and Spili faults show that the average chemical enrichment is ~45%, in REE-Y while the denudation rate of the enriched zones is ~1% higher every 400 years due to exposure of the fault scarp in weathering. They also show that the chemical enrichment is significant even for short periods of residence time (e.g., ~100 years). To better understand the enrichment mechanism, we performed a series of pot experiments, where carbonate tiles extracted from the Spili Fault were buried into soil collected from the hanging-wall of the same fault. We irrigated the pots with artificial rain that equals 5 years of rainfall in Crete and at temperatures of 15oC and 25oC. Following, we performed sorption isotherm, kinetic and pH-edge tests for the europium (Eu), the cerium (Ce) and the ytterbium (Yt) that occur in the calcite minerals. The processes of adsorption and precipitation in the batch experiments are simulated by the Mineql software. The pot experiments indicate incorporation of the REE and Y into the surface of the carbonate tile which is in contact with the soil. The pH of the leached solution during the rain application range from 7.6 to 8.3. Nutrient release like Ca is higher in the leached

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

PubMed

Andersson, M P; Hem, C P; Schultz, L N; Nielsen, J W; Pedersen, C S; Sand, K K; Okhrimenko, D V; Johnsson, A; Stipp, S L S

2014-11-13

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 asymmetric for the coccoliths and the synthetic calcite prepared using the carbonation method. It can be very well fitted by two peaks: a narrow Lorenzian at lower frequency and a broader Gaussian at higher frequency. These two samples both have a high specific surface area. Density functional theory for bulk calcite and several calcite surface systems allows for assignment of the infrared bands. The two peaks that make up the asymmetric carbonate stretch band come from the bulk (narrow Lorenzian) and from a combination of two effects (broad Gaussian): the surface or near surface of calcite and line broadening from macroscopic dielectric effects. We detect water adsorbed on the high surface area synthetic calcite, which permits observation of the chemistry of thin liquid films on calcite using transmission infrared spectroscopy. The combination of infrared spectroscopy and density functional theory also allowed us to quantify the amount of polysaccharides associated with the coccoliths. The amount of polysaccharides left in chalk, demonstrated to be present in other work, is below the IR detection limit, which is 0.5% by mass.

Effects of Pressure and Temperature on the Kinetics of Iron-magnesite Redox Reaction: Implication for the Genesis of Ultradeep Diamonds

NASA Astrophysics Data System (ADS)

Zhu, F.; Li, J.; Liu, J.; Lai, X.; Chen, B.; Meng, Y.

2016-12-01

Diamonds may be the products of redox reaction between carbonates in the subducted slabs and iron metal in the mantle [1]. Given the relatively low temperatures of the subducted slabs, however, it remains to be shown that such reaction can occur at sufficiently fast rate. To examine the influence of pressure and temperature (P-T) on the kinetics of iron-carbonate redox reaction, we performed in-situ synchrotron X-ray diffraction (XRD) experiments at the Advanced Photon Source, Argonne National Laboratory, using laser-heated diamond anvil cells. The starting material consists of an iron foil sandwiched between two magnesite pellets. Data were collected between 1050 and 1800 K at 50-100 K intervals, at seven pressures between 12 and 40 GPa, corresponding the depths where most ultradeep diamonds originated [2]. We obtained constraints on the Fe-MgCO3reaction boundary, which was located between the estimated temperatures on the surface of cold slabs near 1400 K and inside their interiors near 1000 K, and it had a similar slope as the slab geotherm [3]. Furthermore, the experiments revealed a significant effect of pressure on the extent and rate of the reaction. The XRD patterns showed that below 15 GPa the initial reaction products were iron carbides, which reacted with magnesite to form diamonds when the reaction completed in 60 minutes at 1300 to 1500 K. Above 18 GPa only iron carbides were observed in the XRD patterns even when all the iron was consumed, and iron carbides still coexisted with magnesite after 100 to 160 minutes at 1600 to 1800 K. Our results suggest that diamonds can be produced from iron-carbonate redox reaction at slab-mantle boundary conditions at the deeper part of the upper mantle, but diamond growth through this reaction is slow or kinetically hindered in the lower mantle. References[1] Palyanov, Y. N. et al. (2013). Proc. Nat. Aca. Sci., 110(51), 20408-20413. [2] Stachel, T. et al. (2005). Elements, 1(2), 73-78. [3] Eberle et al. (2002). Phys

Chemistry of the calcite/water interface: Influence of sulfate ions and consequences in terms of cohesion forces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pourchet, Sylvie, E-mail: sylvie.pourchet@u-bourgogne.fr; Pochard, Isabelle; Brunel, Fabrice

2013-10-15

Calcite suspensions are used to mimic the behavior of more complex cementitious systems. Therefore the characterization of calcite–water interface in strong alkaline conditions, through ionic adsorption, electrokinetic measurements, static rheology and atomic force microscopy is a prerequisite. Calcium, a potential determining ion for calcite, adsorbs specifically onto the weakly positively charged calcite surface in water. This leads to an increase of the repulsive electric double layer force and thus weakens the particle cohesion. Sulfate adsorption, made at constant calcium concentration and ionic strength, significantly increases the attractive interactions between the calcite particles despite its very low adsorption. This is attributedmore » to a lowering of the electrostatic repulsion in connection with the evolution of the zeta potential. The linear relationship found between the yield stress and ζ{sup 2} proves that the classical DLVO theory applies for these systems, contrary to what was previously observed with C–S–H particles under the same conditions.« less

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

PubMed

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

2014-08-22

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

Biotic Control of Skeletal Growth by Scleractinian Corals in Aragonite–Calcite Seas

PubMed Central

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

2014-01-01

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

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

USGS Publications Warehouse

Reddy, Michael M.; Plummer, Niel; Busenberg, E.

1981-01-01

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

Monoclinic deformation of calcite crystals at ambient conditions

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

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

PubMed

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

2016-04-15

Zeta potential is a physicochemical parameter of particular importance in describing the surface electrical properties of charged porous media. However, the zeta potential of calcite is still poorly known because of the difficulty to interpret streaming potential experiments. The Helmholtz-Smoluchowski (HS) equation is widely used to estimate the apparent zeta potential from these experiments. However, this equation neglects the influence of surface conductivity on streaming potential. We present streaming potential and electrical conductivity measurements on a calcite powder in contact with an aqueous NaCl electrolyte. Our streaming potential model corrects the apparent zeta potential of calcite by accounting for the influence of surface conductivity and flow regime. We show that the HS equation seriously underestimates the zeta potential of calcite, particularly when the electrolyte is diluted (ionic strength ⩽ 0.01 M) because of calcite surface conductivity. The basic Stern model successfully predicted the corrected zeta potential by assuming that the zeta potential is located at the outer Helmholtz plane, i.e. without considering a stagnant diffuse layer at the calcite-water interface. The surface conductivity of calcite crystals was inferred from electrical conductivity measurements and computed using our basic Stern model. Surface conductivity was also successfully predicted by our surface complexation model. Copyright © 2016 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Carbon and Oxygen Isotope Measurements of Ordinary Chondrite (OC) Meteorites from Antarctica Indicate Distinct Carbonate Species Using a Stepped Acid Extraction Procedure

NASA Technical Reports Server (NTRS)

Evans, Michael E.

2015-01-01

The purpose of this study is to characterize the stable isotope values of terrestrial, secondary carbonate minerals from five Ordinary Chondrite (OC) meteorites collected in Antarctica. These samples were identified and requested from NASA based upon their size, alteration history, and collection proximity to known Martian meteorites. They are also assumed to be carbonate-free before falling to Earth. This research addresses two questions involving Mars carbonates: 1) characterize terrestrial, secondary carbonate isotope values to apply to Martian meteorites for isolating in-situ carbonates, and 2) increase understanding of carbonates formed in cold and arid environments with Antarctica as an analog for Mars. Two samples from each meteorite, each approximately 0.5 grams, were crushed and dissolved in pure phosphoric acid for 3 sequential reactions: a) R times 0 for 1 hour at 30 degrees Centigrade (fine calcite extraction), b) R times 1 for 18 hours at 30 degrees Centigrade (course calcite extraction), and c) R times 2 for 3 hours at 150 degrees Centigrade (siderite and/or magnesite extraction). CO (sub 2) was distilled by freezing with liquid nitrogen from each sample tube, then separated from organics and sulfides with a TRACE GC using a Restek HayeSep Q 80/100 6 foot 2 millimeter stainless column, and then analyzed on a Thermo MAT 253 Isotope Ratio Mass Spectrometer (IRMS) in Dual Inlet mode. This system was built at NASA/JSC over the past 3 years and proof-tested with known carbonate standards to develop procedures, assess yield, and quantify expected error bands. Two distinct species of carbonates are found: 1) calcite, and 2) non-calcite carbonate (future testing will attempt to differentiate siderite from magnesite). Preliminary results indicate the terrestrial carbonates are formed at approximately sigma (sup 13) C equal to plus 5 per mille, which is consistent with atmospheric CO (sub 2) sigma (sup 13) C equal to minus 7 per mille and fractionation of plus

Catalysis and chemical mechanisms of calcite dissolution in seawater.

PubMed

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

2017-07-18

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.

High Resolution Mineral Mapping of the Oman Drilling Project Cores with Imaging Spectroscopy: Preliminary Results

NASA Astrophysics Data System (ADS)

Greenberger, R. N.; Ehlmann, B. L.; Kelemen, P. B.; Manning, C. E.; Teagle, D. A. H.; Harris, M.; Michibayashi, K.; Takazawa, E.

2017-12-01

The Oman Drilling Project provides an unprecedented opportunity to study the formation and alteration of oceanic crust and peridotite. Key to answering the main questions of the project are a characterization of the primary and secondary minerals present within the drill core and their spatial relationships. To that end, we used the Caltech imaging spectrometer system to scan the entire 1.5-km archive half of the core from all four gabbro and listvenite boreholes (GT1A, GT2A, GT3A, and BT1B) at 250 µm/pixel aboard the JAMSTEC Drilling Vessel Chikyu during the ChikyuOman core description campaign. The instrument measures the visible and shortwave infrared reflectance spectra of the rocks as a function of wavelength from 0.4 to 2.6 µm. This wavelength range is sensitive to many mineral groups, including hydrated minerals (phyllosilicates, zeolites, amorphous silica polytypes), carbonates, sulfates, and transition metals, most commonly iron-bearing mineralogies. To complete the measurements, the core was illuminated with a halogen light source and moved below the spectrometer at 1 cm/s by the Chikyu's Geotek track. Data are corrected and processed to reflectance using measurements of dark current and a spectralon calibration panel. The data provide a unique view of the mineralogy at high spatial resolution. Analysis of the images for complete downhole trends is ongoing. Thus far, a variety of minerals have been identified within their petrologic contexts, including but not limited to magnesite, dolomite, calcite, quartz (through an Si-OH absorption due to minor H2O), serpentine, chlorite, epidote, zeolites, mica (fuchsite), kaolinite, prehnite, gypsum, amphibole, and iron oxides. Further analysis will likely identify more minerals. Results include rapidly distinguishing the cations present within carbonate minerals and identifying minerals of volumetrically-low abundance within the matrix and veins of core samples. This technique, for example, accurately identifies

Microstructure of calcite deformed by high-pressure torsion: An X-ray line profile study

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Amino Acid-Assisted Incorporation of Dye Molecules within Calcite Crystals.

PubMed

Marzec, Bartosz; Green, David C; Holden, Mark A; Coté, Alexander S; Ihli, Johannes; Khalid, Saba; Kulak, Alexander; Walker, Daniel; Tang, Chiu; Duffy, Dorothy M; Kim, Yi-Yeoun; Meldrum, Fiona C

2018-05-23

Biomineralisation processes invariably occur in the presence of multiple organic additives, which act in combination to give exceptional control over structures and properties. However, few synthetic studies have investigated the cooperative effects of soluble additives. This work addresses this challenge and focuses on the combined effects of amino acids and coloured dye molecules. The experiments demonstrate that strongly coloured calcite crystals only form in the presence of Brilliant Blue R (BBR) and four of the seventeen soluble amino acids, as compared with almost colourless crystals using the dye alone. The active amino acids are identified as those which themselves effectively occlude in calcite, suggesting a mechanism where they can act as chaperones for individual molecules or even aggregates of dyes molecules. These results provide new insight into crystal-additive interactions and suggest a novel strategy for generating materials with target properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of calcite and dissolved calcium on uranium(VI) sorption to a hanford subsurface sediment.

PubMed

Dong, Wenming; Ball, William P; Liu, Chongxuan; Wang, Zheming; Stone, Alan T; Bai, Jing; Zachara, John M

2005-10-15

The influence of calcite and dissolved calcium on U(VI) adsorption was investigated using a calcite-containing sandy silt/clay sediment from the U. S. Department of Energy Hanford site. U(VI) adsorption to sediment, treated sediment, and sediment size fractions was studied in solutions that both had and had not been preequilibrated with calcite, at initial [U(VI)] = 10(-7)-10(-5) mol/L and final pH = 6.0-10.0. Kinetic and reversibility studies (pH 8.4) showed rapid sorption (30 min), with reasonable reversibility in the 3-day reaction time. Sorption from solutions equilibrated with calcite showed maximum U(VI) adsorption at pH 8.4 +/- 0.1. In contrast, calcium-free systems showed the greatest adsorption at pH 6.0-7.2. At pH > 8.4, U(VI) adsorption was identical from calcium-free and calcium-containing solutions. For calcite-presaturated systems, both speciation calculations and laser-induced fluorescence spectroscopic analyses indicated that aqueous U(VI) was increasingly dominated by Ca2UO2(CO3)3(0)(aq) at pH < 8.4 and thatformation of Ca2UO2(CO3)3(0)(aq) is what suppresses U(VI) adsorption. Above pH 8.4, aqueous U(VI) speciation was dominated by UO2(CO3)3(4-) in all solutions. Finally, results also showed that U(VI) adsorption was additive in regard to size fraction but not in regard to mineral mass: Carbonate minerals may have blocked U(VI) access to surfaces of higher sorption affinity.

Gallium isotope fractionation during Ga adsorption on calcite and goethite

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Catalysis and chemical mechanisms of calcite dissolution in seawater

PubMed Central

Adkins, Jess F.; Rollins, Nick E.; Naviaux, John; Erez, Jonathan; Berelson, William M.

2017-01-01

Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric CO2 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 13C-labeled calcites in natural seawater. We show that the time-evolving enrichment of 𝜹13C 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 13C-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 Ω= 0.7. 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 CO2 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 Ω= 0.7, which we interpret as the onset of homogeneous etch pit nucleation. PMID:28720698

Effect of molding pressure on fabrication of low-crystalline calcite block.

PubMed

Lin, Xin; Matsuya, Shigeki; Nakagawa, Masaharu; Terada, Yoshihiro; Ishikawa, Kunio

2008-02-01

We have reported that low-crystalline porous calcite block, which is useful as a bone substitute or a source material to prepare apatite-type bone fillers could be fabricated by exposing calcium hydroxide compact to carbon dioxide gas saturated with water vapor. In the present study, we investigated the effect of molding pressure on the transformation of calcium hydroxide into calcite and the mechanical strength of the carbonated compact. Transformation into calcite was almost completed within 72 h, however, a small amount of Ca(OH)(2) still remained unreacted at higher molding pressure because of incomplete penetration of CO(2) gas into the interparticle space due to dense packing of Ca(OH)(2) particles. On the other hand, high molding pressure resulted in an increase in diametral tensile strength (DTS) of the calcite compact formed. Critical porosity of the calcite block was calculated as approximately 68%.

Monitoring bacterially induced calcite precipitation in porous media using magnetic resonance imaging and flow measurements

NASA Astrophysics Data System (ADS)

Sham, E.; Mantle, M. D.; Mitchell, J.; Tobler, D. J.; Phoenix, V. R.; Johns, M. L.

2013-09-01

A range of nuclear magnetic resonance (NMR) techniques are employed to provide novel, non-invasive measurements of both the structure and transport properties of porous media following a biologically mediated calcite precipitation reaction. Both a model glass bead pack and a sandstone rock core were considered. Structure was probed using magnetic resonance imaging (MRI) via a combination of quantitative one-dimensional profiles and three-dimensional images, applied before and after the formation of calcite in order to characterise the spatial distribution of the precipitate. It was shown through modification and variations of the calcite precipitation treatment that differences in the calcite fill would occur but all methods were successful in partially blocking the different porous media. Precipitation was seen to occur predominantly at the inlet of the bead pack, whereas precipitation occurred almost uniformly along the sandstone core. Transport properties are quantified using pulse field gradient (PFG) NMR measurements which provide probability distributions of molecular displacement over a set observation time (propagators), supplementing conventional permeability measurements. Propagators quantify the local effect of calcite formation on system hydrodynamics and the extent of stagnant region formation. Collectively, the combination of NMR measurements utilised here provides a toolkit for determining the efficacy of a biological-precipitation reaction for partially blocking porous materials.

Microbial dissolution of calcite at T = 28 °C and ambient pCO 2

NASA Astrophysics Data System (ADS)

Jacobson, Andrew D.; Wu, Lingling

2009-04-01

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

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

NASA Astrophysics Data System (ADS)

Kowal-Linka, Monika

2010-03-01

Although bedding-parallel cone-in-cone structure calcite veins are present in the Middle Triassic Gogolin Formation in Opole Silesia, their occurrence is limited to the Emilówka Cellular Limestone Member. Marly limestones (dedolomites) consisting of calcite pseudospar are the host rocks. The veins, which are up to 3 mm high and 30 cm long, are built of densely packed cone columns, with individual cones up to 0.7 mm high and 0.6 mm wide at their bases, and with vertex angle values ranging from 30° to 50°. The cones are microfractured, and the adjacent cones are vertically shifted in oblique planes. The exceptionally small veins consist of calcite fibres up to 0.15 mm high. The veins are built of low-magnesium and non-ferroan calcite, characterized by low δ 18O values ranging from - 6.8‰ to - 7.4‰, and low δ 13C values ranging from - 2.9‰ to - 4.5‰ vs. PDB. These isotopic values are similar to those obtained from the host rocks (δ 18O from - 6.8‰ to - 7.4‰, and δ 13C from - 3.2‰ to - 3.6‰ vs. PDB) and they are strongly depleted in comparison with the isotopic values of other carbonate particles from the Gogolin Formation. The veins only formed in one lithostratigraphic member, suggesting that their origin is related to processes which acted only locally. There are two unique processes that the Emilówka Cellular Limestone Member alone in the Gogolin Formation underwent: early diagenetic evaporitic dolomitization of lime mud in the sabkha environment, and subsequent calcitization of dolomite. Dolomitization led to sediment cohesion loss, porosity increase and initial horizontal laminae separation as a result of the transformation of calcium carbonate to dolomite within anisotropic deposits. Similar values of geochemical parameters obtained from the vein calcite and the host rock calcite are evidence that vein-filling precipitation was contemporary with dedolomitization. Geochemical data combined with sedimentological research and burial history

Hydrochemical controls on aragonite versus calcite precipitation in cave dripwaters

NASA Astrophysics Data System (ADS)

Rossi, Carlos; Lozano, Rafael P.

2016-11-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

The quantitative determination of calcite associated with the carbonate-bearing apatites

USGS Publications Warehouse

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

1951-01-01

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

Nuclear anomalies in the buccal cells of calcite factory workers

PubMed Central

2010-01-01

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. PMID:21637497

Iodine Incorporation in Calcite: Insights from Computational and Experimental Study

NASA Astrophysics Data System (ADS)

Feng, X.; Redfern, S. A. T.

2016-12-01

The incorporation of iodine into calcite is important both in the context of radioactive waste disposal (carbonates seem to be the principal host for iodine at the Hnaford site) as well as in paleoproxy methods applied in paleo-oceanography, where iodine content has been proposed as a proxy for fO2. Here, we report on studies of iodine incorporation into calcite carried out by a combination of earlier X-Ray absorption spectroscopy, Raman spectroscopy, X-Ray diffraction and new ab initio DFT calculations (using VASP). Our results show that iodine is principally incorporated into the calcite lattice as IO3, replacing carbon in the carbonate group. The much larger size of iodine, and different outer shell electronic configuration, leads to a distortion of the calcite structure locally. Our DFT results show that the adjacent layers of CO3 groups are significantly distorted, over a length scale of around 0.5 nm, and that this distortion leads to a slight increase in enthalpy associated with the iodine point defect. The relationship to the distorted structure of calcite II is considered, and the role of iodine as an agent of "internal pressure" will be discussed.

The role of disseminated calcite in the chemical weathering of granitoid rocks

USGS Publications Warehouse

White, A.F.; Bullen, T.D.; Vivit, D.V.; Schulz, M.S.; Clow, D.W.

1999-01-01

Accessory calcite, present at concentrations between 300 and 3000 mg kg-1, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO2, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57-98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering. The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport

From synthetic to biogenic Mg-containing calcites: a comparative study using FTIR microspectroscopy.

PubMed

Long, Xia; Nasse, Michael J; Ma, Yurong; Qi, Limin

2012-02-21

The formation mechanism of the thermodynamically unstable calcite phase, very high Mg calcite, in biological organisms such as sea urchin or corallina algae has been an enigma for a very long time. In contrast to conventional methods such as KBr pellet Fourier Transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD), FTIR microspectroscopy (FTIRM) provides additional information about a local disorder such as an amorphous phase or the occlusion of Mg ions in the calcite lattice. In this work, we characterise for the first time systematically synthetic and biogenic Mg-containing calcium carbonate samples (especially sea urchin teeth--SUT) in detail by using two FTIRM instruments and compare these samples with KBr pellet FTIR measurements. Furthermore, we present spectra from geogenic calcite and dolomite minerals, recorded with both FTIRM systems, as well as KBr pellet FTIR spectra as references. We analyse the spectra by applying multi-peak curve fitting on the in-plane-bending (ν(4)) and out-of-plane (ν(2)) bands. Based on the obtained results we attribute the two singlet bands at ∼860-865 cm(-1) and ∼695-704 cm(-1) observed in the SUT FTIRM spectra to the existence of amorphous calcium carbonate (ACC), and report for the first time the existence of ACC at the mature end of SUT. In the other three studied biominerals, however, we did not find any ACC. Also, based on the FTIRM results, we observe that not only ν(4), but also ν(2) shifts to higher wavenumbers if more calcium ions are replaced by magnesium ions in the calcite lattices.

Incorporation of Metals into Calcite in a Deep Anoxic Granite Aquifer.

PubMed

Drake, Henrik; Mathurin, Frédéric A; Zack, Thomas; Schäfer, Thorsten; Roberts, Nick Mw; Whitehouse, Martin; Karlsson, Andreas; Broman, Curt; Åström, Mats E

2018-01-16

Understanding metal scavenging by calcite in deep aquifers in granite is of importance for deciphering and modeling hydrochemical fluctuations and water-rock interaction in the upper crust and for retention mechanisms associated with underground repositories for toxic wastes. Metal scavenging into calcite has generally been established in the laboratory or in natural environments that cannot be unreservedly applied to conditions in deep crystalline rocks, an environment of broad interest for nuclear waste repositories. Here, we report a microanalytical study of calcite precipitated over a period of 17 years from anoxic, low-temperature (14 °C), neutral (pH: 7.4-7.7), and brackish (Cl: 1700-7100 mg/L) groundwater flowing in fractures at >400 m depth in granite rock. This enabled assessment of the trace metal uptake by calcite under these deep-seated conditions. Aquatic speciation modeling was carried out to assess influence of metal complexation on the partitioning into calcite. The resulting environment-specific partition coefficients were for several divalent ions in line with values obtained in controlled laboratory experiments, whereas for several other ions they differed substantially. High absolute uptake of rare earth elements and U(IV) suggests that coprecipitation into calcite can be an important sink for these metals and analogousactinides in the vicinity of geological repositories.

Morphology and formation mechanism in precipitation of calcite induced by Curvibacter lanceolatus strain HJ-1

NASA Astrophysics Data System (ADS)

Zhang, Chonghong; Li, Fuchun; Lv, Jiejie

2017-11-01

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.

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

NASA Astrophysics Data System (ADS)

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

2013-07-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

Knowledge of He retention in crystalline calcite is mandatory to estimate the possibility of (U-Th)/He dating of calcite. To this aim, fault-filling calcite crystals from the Eocene/Oligocene Gondrecourt graben, Paris Basin, Eastern France, have been sampled, based on their relatively old, Eocene-Oligocene, precipitation age and cold thermal history (<40°C since precipitation). The samples were sorted into three main tectonic and morphological groups, including successively (1) micro-fracture calcites, (2) breccia and associated geodic calcites, and (3) vein and associated geodic calcites. (U-Th)/He dating of 63 calcite fragments yields ages dispersed from 0.2×0.02 to 35.8×2.7 Ma, as well as two older dates of 117×10 and 205×28 Ma (1s). These He ages correlate to grain chemistry, such as to Sr and ΣREE concentrations or (La/Yb)N ratios, and these correlations probably reflect the evolution of parent fluid. Only the oldest He ages are in agreement with the He-retentive character of calcite as determined by Copeland et al. (2007), and these ages were obtained for the most recently precipitated crystals. To better understand the large He-age scatter and why calcites precipitated earlier show younger ages, He diffusion experiments have been conducted on 10 Gondrecourt calcite fragments from 3 samples with He ages of 0.2 to 6 Ma. In addition, a crystallographic investigation by X-Ray Diffraction (XRD) performed on similar samples reveals that the crystal structure evolves with increasing temperature, showing with micro-cracks and cleavage opening. These XRD results indicate that, in fault-filling calcite, He retention is controlled by multiple diffusion domains (MDD, Lovera et al., 1991) with various sizes, and therefore, evolves through time with strong consequences on (U-Th)/He age. We thus interpret the Gondrecourt calcite (U-Th)/He age scatter of older samples as a consequence of cleavage opening due to a succession of calcite crystallization phases related to

Fluid mediated transformation of aragonitic cuttlebone to calcite

NASA Astrophysics Data System (ADS)

Perdikouri, C.; Kasioptas, A.; Putnis, A.

2009-04-01

The aragonite to calcite transition has been studied extensively over the years because of its wide spectra of applications and of its significant geochemical interest. While studies of kinetics (e.g. Topor et al., 1981), thermodynamics (e.g. Wolf et al., 1996) and behavior of ions such as Sr and Mg (e.g. Yoshioka et al., 1986) have been made there are still unanswered questions regarding this reaction especially in the cases where the effects of fluid composition are considered. It is well known that when heated in air, aragonite transforms by a solid state reaction to calcite. The aragonite cuttlebone of the sepia officinalis that was used for our experiments undergoes a phase transition at ~370-390˚ C, measured by in situ heating experiments in a Philips X'pert X-ray powder diffractometer equipped with a HTK 1200 High temperature oven. Successive X-ray scans were taken at isothermal temperatures at 200C intervals. A similar temperature range was found by Vongsavat et al. 2006, who studied this transition in Acropora corals. It is possible however to promote this transition at considerably lower temperatures by means of a fluid mediated reaction where the replacement takes place by a dissolution-precipitation mechanism (Putnis & Putnis, 2007). We have successfully carried out hydrothermal experiments where cuttlebone has been converted to calcite at 200˚ C. Using the PhreeqC program we calculated the required composition of a solution that would be undersaturated with respect to aragonite and saturated with respect to calcite leading to dissolution of the aragonite and to a consequent precipitation of the new calcite phase, similar to the experiments described in an earlier study (Perdikouri et al, 2008). This reaction is not pseudomorphic and results in the destruction of the morphology, presumably due to the molar volume increase. A total transformation of the cuttlebone produced a fine calcite powder. The cuttlebone exhibits a unique microstructure, made

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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.

Initial formation of calcite crystals in the thin prismatic layer with the periostracum of Pinctada fucata.

PubMed

Suzuki, Michio; Nakayama, Seiji; Nagasawa, Hiromichi; Kogure, Toshihiro

2013-02-01

Although the formation mechanism of calcite crystals in the prismatic layer has been studied well in many previous works, the initial state of calcite formation has not been observed in detail using electron microscopes. In this study, we report that the soft prismatic layer with transparent color (the thin prismatic layer) in the tip of the fresh shell of Pinctada fucata was picked up to observe the early calcification phase. A scanning electron microscope (SEM) image showed that the growth tip of the thin prismatic layer was covered by the periostracum, which was also where the initial formation of calcite crystals began. A cross-section containing the thin calcite crystals in the thin prismatic layer with the periostracum was made using a focused ion beam (FIB) system. In a transmission electron microscope (TEM) observation, the thin calcite crystal (thickness is about 1μm) on the periostracum was found to be a single crystal with the c-axis oriented perpendicular to the shell surface. On the other hand, many aggregated small particles consisting of bassanite crystals were observed in the periostracum suggesting the possibility that not only organic sulfate but also inorganic sulfates exist in the prismatic layer. These discoveries in the early calcification phase of the thin prismatic layer may help to clarify the mechanism of regulating the nucleation and orientation of the calcite crystal in the shell. Copyright © 2012 Elsevier Ltd. All rights reserved.

Mechanism of calcite co-orientation in the sea urchin tooth.

PubMed

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

2009-12-30

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(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 (muXRD). 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(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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitchell-Tapping, H.J.

1983-09-01

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

NMR spectroscopic study of organic phosphate esters coprecipitated with calcite

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Calcite Decarbonation and its Influence on the Mechanical Behaviour of Carbonate-bearing Faults

NASA Astrophysics Data System (ADS)

Carpenter, Brett; Collettini, Cristiano; Mollo, Silvio; Viti, Cecilia

2014-05-01

Calcite decarbonation has been identified as one of the important, thermally-activated physicochemical processes that are triggered by temperature rise during fast fault motion. This process has been observed in the laboratory during high-velocity friction experiments where the dynamic weakening that occurs for carbonate-rich gouges is strictly controlled by the thermal decomposition of calcite. Furthermore, this process has also been identified along ancient, exhumed faults and is an important indicator of seismic slip. The thermally-induced decarbonation (CaCO3 → CaO + CO2) and microcracking (due to thermal expansion) of calcite are likely to be primary mechanisms in controlling the mechanical and hydrologic properties of carbonate rocks. In addition, the process and products of decarbonation will likely exert significant influence on the behaviour of faults at both geologic and earthquake time scales by causing changes in (1) the effective normal stress on the fault and (2) the frictional behaviour of material within it. Due to the paucity of scientific information on the effects of decarbonation and thermal microcracking on the mechanical properties of carbonate fault rocks, we present results from experiments performed on portlandite (>90 wt.%), a hydrous mineral formed by the recombination of CaO and water, and stable product of the decarbonation reaction. We produced portlandite by thermally-treating powdered Carrara Marble (calcite >98 wt.%) in the laboratory at 1100 °C under air buffering conditions. We then sheared gouge layers of this water-reacted, decarbonation product under saturated conditions at room temperature. These tests were designed to evaluate the frictional strength, stability, and healing behaviour of portlandite-bearing rocks to better understand how its presence affects fault mechanics. Our data indicate that the conversion of calcite to portlandite, results in a distinct change in the mechanical behaviour of the fault gouge. The

A Synthetic Calcite Standard for Determination of Relative Mn/Cr Sensitivity Factor

NASA Astrophysics Data System (ADS)

Fujiya, W.; Ichimura, K.; Takahata, N.; Sugiura, N.; Sano, Y.

2009-12-01

Primitive chondrites which suffered from aqueous alteration often contain carbonates such as calcites, dolomites and breunnerites. 53Mn-53Cr decay system (half-life: 3.7 Myr) is applicable to dating their precipitation and many authors have measured their Mn-Cr ages using the SIMS. However, the relative Mn/Cr sensitivity factor: RSF (measured Mn+/Cr+ ratio divided by the true ratio) is not well established due to the absence of suitable standards, therefore the ages have systematic uncertainties. We prepared a synthetic Mn and Cr bearing calcite to evaluate the Mn/Cr RSF. Here we report the technical details of preparation for the standard and its Mn/Cr RSF. We also measured the Mn/Cr RSF of San Carlos olivine which is often assumed to be the same as that of a carbonate, and compared it with that of our synthetic calcite. The Cr-bearing calcite was produced in a N2 filled closed system by the reaction Ca2+ + CO32- = CaCO3 in an aqueous solution. The reaction proceeded by continuous addition of ammonium carbonate vapor to the solution. The crystal size of the calcite was ~300 μm. A small amount of hydrazine was added to the solution in order to keep chromous ion from oxidation. Mn and Cr concentrations in the calcite grains were determined by the SEM-EDS. A weak, defocused beam was used due to prevent electron beam damage. In a spherical grain, radial zoning of Mn and Cr concentrations occur and they decrease towards the periphery. At the center of the grains, Mn and Cr concentrations are ~0.5 atomic % and the values of the Mn/Cr ratios are relatively constant. The Mn/Cr RSF was determined with the CAMECA NanoSIMS 50 at Ocean Research Institute of Univ. of Tokyo. A primary O- beam of ~1 nA and 5 μm diameter was used. 43Ca+, 52Cr+, 53Cr+ and 55Mn+ ions were analyzed in a combined peak-jumping/multi-detection mode. The total measurement time was typically ~20 minutes. The measurements were started after presputtering of 15 minutes. The mass resolution power was

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

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

1989-01-01

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

Trace-element partition coefficients in the calcite-water system and their paleoclimatic significance in cave studies

NASA Astrophysics Data System (ADS)

Gascoyne, Melvyn

1983-02-01

Speleothems (stalactites, stalagmites) formed in limestone caves have been found to contain much information on the timing and intensity of past climates, from analysis of their U, Th, 13C and 18O contents. Because the incorporation of certain trace elements (e.g., Mg, Mn and Zn) in calcite is known to be temperature-dependent, it may be possible to use variations in trace-metal content of fossil speleothems as an alternative paleotem-perature indicator. Using specially developed ion-exchange sampling techniques, analysis of trace-metal content of seepage water and associated fresh calcite deposits in caves in Vancouver Island and Jamaica shows that Mg is distributed between phases in a consistent manner within the temperature regimes of the caves (7° and 23°C, respectively). Average values of the distribution coefficient for Mg are respectively 0.017 and 0.045 at these temperatures. These results indicate that the Mg content of calcite varies directly with temperature and in a sufficiently pronounced manner that a 1°C rise in depositional temperature of a speleothem containing 500 ppm Mg, at ˜10°C, would be seen as an increase of ˜35ppm Mg — a readily determinable shift. Other factors affecting Mg content of a speleothem are considered.

Sea urchin tooth mineralization: Calcite present early in the aboral plumula

PubMed Central

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

2012-01-01

In both vertebrate bone, containing carbonated hydroxyapatite as the mineral phase, and in invertebrate hard tissue comprised of calcium carbonate, a popular view is that the mineral phase develops from a long-lived amorphous precursor which later transforms into crystal form. Important questions linked to this popular view are: When and where is the crystallized material formed, and is amorphous solid added subsequently to the crystalline substrate? Sea urchin teeth, in which the earliest mineral forms within isolated compartments, in a time and position dependent manner, allow direct investigation of the timing of crystallization of the calcite primary plates. Living teeth of the sea urchin Lytechinus variegatus, in their native coelomic fluid, were examined by high-energy synchrotron x-ray diffraction. The diffraction data show that calcite is present in the most aboral portions of the plumula, representing the very earliest stages of mineralization, and that this calcite has the same crystal orientation as in the more mature adoral portions of the same tooth. Raman spectroscopy of the aboral plumula confirms the initial primary plate mineral material is calcite and does not detect amorphous calcium carbonate; in the more mature adoral incisal flange, it does detect a broader calcite peak, consistent with two or more magnesium compositions. We hypothesize that some portion of each syncytial membrane in the plumula provides the information for nucleation of identically oriented calcite crystals that subsequently develop to form the complex geometry of the single crystal sea urchin tooth. PMID:22940703

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

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Riggs, A.C.

2000-01-01

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

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

USGS Publications Warehouse

Plummer, Niel; Busenberg, Eurybiades; Riggs, Alan C.

2000-01-01

Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7 °C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34 °C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of PCO2, decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.

Friction behavior of Mg-Al-CO3 layered double hydroxide prepared by magnesite

NASA Astrophysics Data System (ADS)

Wang, Xiaobo; Bai, Zhimin; Zhao, Dong; Zhao, Fuyan

2013-07-01

In this paper, Mg-Al-CO3 LDH was prepared by magnesite under chemical precipitation and hydrothermal methods. In order to improve the dispersion of LDH in base oil, the as-prepared sample was modified with sodium laurate. The obtained material (GMAC-LDH) was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry and thermo gravimetric analyzer (DSC-TGA) and scanning electron microscope (SEM). The results show that the modified LDH has platelet morphology with a near hexagon shape. In addition, the tribological properties of GMAC-LDH were evaluated by four-ball friction tester and gear tester. As a lubricant, GMAC-LDH possesses an excellent property on reducing friction and wear of friction pair. The results of friction tests indicated that the friction coefficient, diameter of wear scar and power consumption of the oil with GMAC-LDH was reduced by 11.0%, 8.5% and 2.1% as compared with that of base oil.

Synthesis of sub-millimeter calcite from aqueous solution

NASA Astrophysics Data System (ADS)

Reimi, M. A.; Morrison, J. M.; Burns, P. C.

2011-12-01

A novel aqueous synthesis that leads to the formation of calcite (CaCO3) crystals, up to 500μm in diameter, will be used to facilitate the study of contaminant transport in aqueous environmental systems. Existing processes tend to be complicated and often yield nanometer-sized or amorphous CaCO3. The synthesis method presented here, which involves slow mixing of concentrated solutions of CaCl2 ¬and (NH4)2CO3, produces single crystals of rhombohedral calcite in 2 to 4 days. Variations on the experimental method, including changes in pH and solution concentration, were explored to optimize the synthesis. Scanning Electron Microscope images show the differences in size and purity observed when the crystals are grown at pH values ranging from 2 to 6. The crystals grown from solutions of pH 2 were large (up to 500 micrometers in diameter) with minimal polycrystalline calcium carbonate, while crystals grown from solutions with pH values beyond 4 were smaller (up to 100 micrometers in diameter) with significant polycrystalline calcium carbonate. The synthesis method, materials characterization, and use in future actinide contaminant studies will be discussed.

Dolomite-II: A new high pressure polymorph of CaMg(CO3)2

NASA Astrophysics Data System (ADS)

Santillan, J.; Williams, Q.; Knittle, E.

2002-12-01

We have measured the infrared spectra and x-ray diffraction of CaMg(CO3)2-dolomite to pressures of 50 GPa at 300 K. We observe both splittings and disappearances of x-ray diffraction peaks between 15 and 20 GPa, as well as new bands in the infrared spectrum of dolomite. The onset of the changes in both the x-ray and infrared data appears to be gradual, and thus kinetically impeded: this is consistent with previous shock results. The infrared and x-ray data are consistent with dolomite adopting a calcite-III-like structure. The net volume change associated with the transition based on a calcite-III monoclinic unit cell is ~4 percent. We calculate that the high pressure phase of dolomite has a volume virtually indistinguishable from that of magnesite plus aragonite. Similarly, an assemblage of the high pressure phase of dolomite and magnesium silicate perovskite has an essentially volume to a magnesite plus calcium silicate perovskite assemblage. Our results thus indicate that high-pressure polymorphism in dolomite could stabilize CaMg(CO3)2 in the deep mantle, and thus that high-pressure polymorphs of dolomite could represent the main reservoir for carbon storage within Earth's lower mantle.

Trace metal distribution and isotope variations in low-temperature calcite and groundwater in granitoid fractures down to 1 km depth

NASA Astrophysics Data System (ADS)

Drake, Henrik; Tullborg, Eva-Lena; Hogmalm, K. Johan; Åström, Mats E.

2012-05-01

Studies of low-temperature fracture calcite in Proterozoic or Archaean crystalline rocks are very limited, mainly because this calcite usually is, first, not very abundant and second, very fine-grained or forms rims on older (and much more abundant) hydrothermal calcite and is thus difficult to distinguish. Knowledge of chemical characteristics and the correlation with groundwater chemistry is thus scarce for low-temperature calcite in these settings, and consequently, knowledge of the recent palaeohydrogeological history is limited. Boreholes drilled with triple-tube technique in the upper 1 km of the Palaeoproterozoic crystalline crust at Laxemar, SE Sweden, have enabled preservation of fragile and potentially recently formed fracture minerals. Earlier investigations of these boreholes have resulted in an extensive set of groundwater chemistry data from various depths, and in detailed knowledge of the fracture mineral assemblages (ranging from 1.8 Ga to present). This has made it possible to identify and sample low-temperature, potentially recently formed, calcite from water-flowing fractures for which representative groundwater chemical data exists. This, in turn, provides an opportunity to detailed comparisons of fracture calcite (age span in the order of million years, with possibility of post-glacial contributes) and groundwater (age in the order of decades to more than a million year depending on depth) in terms of both isotopic and geochemical properties, giving input to the understanding of groundwater history, partition coefficients derived in laboratory experiment, and reliability of calcite geochemistry in terms of representing the actual source fluid composition. In this study, the focus is on trace elements (Fe, Mg, Mn and Sr), stable isotopes and Sr isotopes and, for the groundwater data set, also aquatic speciation with Visual MINTEQ. An optimised step-by-step sample specific analytical procedure was used for the collection of calcite coatings. The

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

PubMed

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

2012-11-01

In both vertebrate bone, containing carbonated hydroxyapatite as the mineral phase, and in invertebrate hard tissue comprised of calcium carbonate, a popular view is that the mineral phase develops from a long-lived amorphous precursor which later transforms into crystal form. Important questions linked to this popular view are: when and where is the crystallized material formed, and is amorphous solid added subsequently to the crystalline substrate? Sea urchin teeth, in which the earliest mineral forms within isolated compartments, in a time and position dependent manner, allow direct investigation of the timing of crystallization of the calcite primary plates. Living teeth of the sea urchin Lytechinus variegatus, in their native coelomic fluid, were examined by high-energy synchrotron X-ray diffraction. The diffraction data show that calcite is present in the most aboral portions of the plumula, representing the very earliest stages of mineralization, and that this calcite has the same crystal orientation as in the more mature adoral portions of the same tooth. Raman spectroscopy of the aboral plumula confirms the initial primary plate mineral material is calcite and does not detect amorphous calcium carbonate; in the more mature adoral incisal flange, it does detect a broader calcite peak, consistent with two or more magnesium compositions. We hypothesize that some portion of each syncytial membrane in the plumula provides the information for nucleation of identically oriented calcite crystals that subsequently develop to form the complex geometry of the single crystal sea urchin tooth. Copyright © 2012 Elsevier Inc. All rights reserved.

Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite

USGS Publications Warehouse

Tesoriero, A.J.; Pankow, J.F.

1996-01-01

Although solid solutions play important roles in controlling the concentrations of minor metal ions in natural waters, uncertainties regarding their compositions, thermodynamics, and kinetics usually prevent them from being considered. A range of precipitation rates was used here to study the nonequilibrium and equilibrium partitioning behaviors of Sr2+, Ba2+, and Cd2+ to calcite (CaCO3(s)). The distribution coefficient of a divalent metal ion Me2+ for partitioning from an aqueous solution into calcite is given by DMe = (XMeCO3(s)/[Me2+])/(XCaCO3(s)/[Ca 2+]). The X values are solid-phase mole fractions; the bracketed values are the aqueous molal concentrations. In agreement with prior work, at intermediate to high precipitation rates R (nmol/mg-min), DSr, DBa, and DCd were found to depend strongly on R. At low R, the values of DSr, DBa, and DCd became constant with R. At 25??C, the equilibrium values for DSr, DBa, and DCd for dilute solid solutions were estimated to be 0.021 ?? 0.003, 0.012 ?? 0.005, and 1240 ?? 300, respectively. Calculations using these values were made to illustrate the likely importance of partitioning of these ions to calcite in groundwater systems. Due to its large equilibrium DMe value, movement of Cd2+ will be strongly retarded in aquifers containing calcite; Sr2+ and Ba2+ will not be retarded nearly as much.

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

PubMed

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

2007-04-24

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

Site-specific incorporation of uranyl carbonate species at the calcite surface

NASA Astrophysics Data System (ADS)

Reeder, Richard J.; Elzinga, Evert J.; Tait, C. Drew; Rector, K. D.; Donohoe, Robert J.; Morris, David E.

2004-12-01

Spatially resolved luminescence spectra from U(VI) co-precipitated at the (101¯4) growth surface of synthetic calcite single crystals confirm heterogeneous incorporation corresponding to the distribution of structurally non-equivalent steps composing the vicinal surfaces of spiral growth hillocks. Spectral structure from U(VI) luminescence at the "-" vicinal regions and featureless, weak luminescence at the "+" vicinal regions are consistent with previously reported observations of enrichment at the former sites during calcite growth. Luminescence spectra differ between the non-equivalent regions of the crystal, with the spectral features from the "-" vicinal region corresponding to those observed in bulk calcite samples. Subtle spectral shifts are observed from U(VI) co-precipitated with microcrystalline calcite synthesized by a different method, and all of the U(VI)-calcite sample spectra differ significantly from that of U(VI) co-precipitated with aragonite. The step-selective incorporation of U(VI) can be explained by a proposed model in which the allowed orientation for adsorption of the dominant calcium uranyl triscarbonate species is controlled by the atomic arrangement at step edges. Differences in the tilt angles of carbonate groups between non-equivalent growth steps favor adsorption of the calcium uranyl triscarbonate species at "-" steps, as observed in experiments.

Calibration of carbonate composition using micro-Raman analysis: application to planetary surface exploration.

PubMed

Rividi, Nicolas; van Zuilen, Mark; Philippot, Pascal; Ménez, Bénédicte; Godard, Gaston; Poidatz, Emmanuel

2010-04-01

Stromatolite structures in Early Archean carbonate deposits form an important clue for the existence of life in the earliest part of Earth's history. Since Mars is thought to have had similar environmental conditions early in its history, the question arises as to whether such stromatolite structures also evolved there. Here, we explore the capability of Raman spectroscopy to make semiquantitative estimates of solid solutions in the Ca-Mg-Fe(+Mn) carbonate system, and we assess its use as a rover-based technique for stromatolite characterization during future Mars missions. Raman microspectroscopy analysis was performed on a set of carbonate standards (calcite, ankerite, dolomite, siderite, and magnesite) of known composition. We show that Raman band shifts of siderite-magnesite and ankerite-dolomite solid solutions display a well-defined positive correlation (r(2) > 0.9) with the Mg# = 100 x Mg/(Mg + Fe + Mn + Ca) of the carbonate analyzed. Raman shifts calibrated as a function of Mg# were used in turn to evaluate the chemical composition of carbonates. Raman analysis of a suite of carbonates (siderite, sidero-magnesite, ankerite, and dolomite) of hydrothermal and sedimentary origin from the ca. 3.2 Ga old Barite Syncline, Barberton greenstone belt, South Africa, and from the ca. 3.5 Ga old Dresser Formation, Pilbara Craton, Western Australia, show good compositional agreement with electron microprobe analyses. These results indicate that Raman spectroscopy can provide direct information on the composition and structure of carbonates on planetary surfaces.

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

USGS Publications Warehouse

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

1993-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2001-12-01

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

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

PubMed

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

2015-02-01

Although porous calcite has attracted attention as bone substitutes, limited studies have been made so far. In the present study, porous calcite block was fabricated by introducing chopped nylon fiber as porogen. Ca(OH)2 powder containing 10 wt% chopped nylon fiber was compacted at 150 MPa, and sintered to burn out the fiber and to carbonate the Ca(OH)2 under stream of 1:2 O2-CO2. Sintering of Ca(OH)2 at 750 °C or lower temperature resulted in incomplete burning out of the fiber whereas sintering at 800 °C or higher temperature resulted in the formation of CaO due to the thermal decomposition of Ca(OH)2. However, sintering at 770 °C resulted in complete burning out of the fiber and complete carbonation of Ca(OH)2 to calcite without forming CaO. Macro- and micro-porosities of the porous calcite were approximately 23 and 16%, respectively. Diameter of the macropores was approximately 100 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.

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

USGS Publications Warehouse

Busenberg, E.; Plummer, Niel

1985-01-01

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

Transient calcite fracture fillings in a welded tuff, Snowshoe Mountain, Colorado

USGS Publications Warehouse

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

2000-01-01

The core from two boreholes (13.1 and 19.2 m depth) drilled 500 m apart in the fractured, welded tuff near the summit of the Snowshoe Mountain, Colorado (47??30'N, 106??55'W) had unique petrographic and hydrodynamic properties. Borehole SM-4 had highly variable annual water levels, in contrast to SM-1a, whose water level remained near the land surface. Core samples from both boreholes (n = 10 and 11) were examined petrographically in thin sections impregnated with epoxy containing rhodamine to mark the pore system features, and were analyzed for matrix porosity and permeability. Core from the borehole sampling the vadose zone was characterized by open fractures with enhanced porosity around phenocrysts due to chemical weathering. Fractures within the borehole sampling the phreatic zone were mineralized with calcite and had porosity characteristics similar to Unweathered and unfractured rock. At the top of the phreatic zone petrography indicates that calcite is dissolving, thereby changing the hydrogeochemical character of the rock (i.e. permeability, porosity, reactive surface area, and mineralogy). Radiocarbon ages and C and O stable isotopes indicate that calcite mineralization occurred about 30 to 40 ka ago and that there was more than one mineralization event. Results of this study also provide some relationships between primary porosity development from 3 types of fracture in a welded tuff. (C) 2000 Elsevier Science Ltd.

The ubiquitous nature of accessory calcite in granitoid rocks: Implications for weathering, solute evolution, and petrogenesis

USGS Publications Warehouse

White, A.F.; Schulz, M.S.; Lowenstern, J. B.; Vivit, D.V.; Bullen, T.D.

2005-01-01

Calcite is frequently cited as a source of excess Ca, Sr and alkalinity in solutes discharging from silicate terrains yet, no previous effort has been made to assess systematically the overall abundance, composition and petrogenesis of accessory calcite in granitoid rocks. This study addresses this issue by analyzing a worldwide distribution of more than 100 granitoid rocks. Calcite is found to be universally present in a concentration range between 0.028 to 18.8 g kg-1 (mean = 2.52 g kg-1). Calcite occurrences include small to large isolated anhedral grains, fracture and cavity infillings, and sericitized cores of plagioclase. No correlation exists between the amount of calcite present and major rock oxide compositions, including CaO. Ion microprobe analyses of in situ calcite grains indicate relatively low Sr (120 to 660 ppm), negligible Rb and 87Sr/86Sr ratios equal to or higher than those of coexisting plagioclase. Solutes, including Ca and alkalinity produced by batch leaching of the granitoid rocks (5% CO2 in DI water for 75 d at 25??C), are dominated by the dissolution of calcite relative to silicate minerals. The correlation of these parameters with higher calcite concentrations decreases as leachates approach thermodynamic saturation. In longer term column experiments (1.5 yr), reactive calcite becomes exhausted, solute Ca and Sr become controlled by feldspar dissolution and 87Sr/ 86Sr by biotite oxidation. Some accessory calcite in granitoid rocks is related to intrusion into carbonate wall rock or produced by later hydrothermal alteration. However, the ubiquitous occurrence of calcite also suggests formation during late stage (subsolidus) magmatic processes. This conclusion is supported by petrographic observations and 87Sr/86Sr analyses. A review of thermodynamic data indicates that at moderate pressures and reasonable CO2 fugacities, calcite is a stable phase at temperatures of 400 to 700??C. Copyright ?? 2005 Elsevier Ltd.

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

PubMed Central

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

2011-01-01

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

Manganese-calcium intermixing facilitates heteroepitaxial growth at the (1014) calcite-water interface

DOE PAGES

Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.; ...

2017-09-05

For this research, in situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10more » $$\\bar{1}$$4) surface of calcite (CaCO 3) single crystals following reaction with Mn2 +-bearing aqueous solutions. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces. In situ time-sequenced measurements demonstrated that the 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 (MnCO 3) and calcite display a 10% lattice mismatch, based on the area of their (10$$\\bar{1}$$4) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO 3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals in calcite-equilibrated aqueous solutions with up to 250 μM MnCl 2. 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)CO 3 solid solution. The epitaxial solid solution had a spatially complex composition, 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 MnCO 3 for the thickest coatings. The effective lattice mismatch was therefore much smaller than the nominal mismatch thus explaining the measured growth rates. Lastly, these findings highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations

PubMed Central

2018-01-01

The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution. PMID:29614776

Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations.

PubMed

Wetzel, Maria; Kempka, Thomas; Kühn, Michael

2018-04-01

The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution.

SIMS analyses of minor and trace element distributions in fracture calcite from Yucca Mountain, Nevada, USA

NASA Astrophysics Data System (ADS)

Denniston, Rhawn F.; Shearer, Charles K.; Layne, Graham D.; Vaniman, David T.

1997-05-01

Fracture-lining calcite samples from Yucca Mountain, Nevada, obtained as part of the extensive vertical sampling in studies of this site as a potential high-level waste repository, have been characterized according to microbeam-scale (25-30 μm) trace and minor element chemistry, and cathodoluminescent zonation patterns. As bulk chemical analyses are limited in spatial resolution and are subject to contamination by intergrown phases, a technique for analysis by secondary ion mass spectrometry (SIMS) of minor (Mn, Fe, Sr) and trace (REE) elements in calcite was developed and applied to eighteen calcite samples from four boreholes and one trench. SIMS analyses of REE in calcite and dolomite have been shown to be quantitative to abundances < 1 × chondrite. Although the low secondary ion yields associated with carbonates forced higher counting times than is necessary in most silicates, Mn, Fe, Sr, and REE analyses were obtained with sub-ppm detection limits and 2-15% analytical precision. Bulk chemical signatures noted by Vaniman (1994) allowed correlation of minor and trace element signatures in Yucca Mountain calcite with location of calcite precipitation (saturated vs. unsaturated zone). For example, upper unsaturated zone calcite exhibits pronounced negative Ce and Eu anomalies not observed in calcite collected below in the deep unsaturated zone. These chemical distinctions served as fingerprints which were applied to growth zones in order to examine temporal changes in calcite crystallization histories; analyses of such fine-scale zonal variations are unattainable using bulk analytical techniques. In addition, LREE (particularly Ce) scavenging of calcite-precipitating solutions by manganese oxide phases is discussed as the mechanism for Ce-depletion in unsaturated zone calcite.

Fabrication of porous low crystalline calcite block by carbonation of calcium hydroxide compact.

PubMed

Matsuya, Shigeki; Lin, Xin; Udoh, Koh-ichi; Nakagawa, Masaharu; Shimogoryo, Ryoji; Terada, Yoshihiro; Ishikawa, Kunio

2007-07-01

Calcium carbonate (CaCO(3)) has been widely used as a bone substitute material because of its excellent tissue response and good resorbability. In this experimental study, we propose a new method obtaining porous CaCO(3) monolith for an artificial bone substitute. In the method, calcium hydroxide compacts were exposed to carbon dioxide saturated with water vapor at room temperature. Carbonation completed within 3 days and calcite was the only product. The mechanical strength of CaCO(3) monolith increased with carbonation period and molding pressure. Development of mechanical strength proceeded through two steps; the first rapid increase by bonding with calcite layer formed at the surface of calcium hydroxide particles and the latter increase by the full conversion of calcium hydroxide to calcite. The latter process was thought to be controlled by the diffusion of CO(2) through micropores in the surface calcite layer. Porosity of calcite blocks thus prepared had 36.8-48.1% depending on molding pressure between 1 MPa and 5 MPa. We concluded that the present method may be useful for the preparation of bone substitutes or the preparation of source material for bone substitutes since this method succeeded in fabricating a low-crystalline, and thus a highly reactive, porous calcite block.

An Investigation of Possible Ways to Enhance the Deposition of Calcite-Type Coatings

DTIC Science & Technology

1984-01-01

AN INVESTIGATION OF POSSIBLE WAYS TO ENHANCE THE DEPOSITION OF CALCITE -TYPE COATINGS JANUARY 1984 Prepared by: OCEAN CITY RESEARCH CORP. in...Enhance The Deposition of Calcite -Type Coatings 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e...City, New Jersey under the direction of Mr. The research study continued of applying calcite -type coatings George A. Gehring, Jr. an to investigation

Uranium in foraminiferal calcite as a recorder of seawater uranium concentrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Russell, A.D.; Emerson, S.; Nelson, B.K.

The authors present results of an investigation of uranium/calcium ratios in cleaned foraminiferal calcite as a recorder of seawater uranium concentrations. For accurate reconstruction of past seawater uranium content, shell calcite must incorporate uranium in proportion to seawater concentration and must preserve its original uranium composition over time. Laboratory culture experiments with live benthic (Amphistegina lobifera) and live planktonic (Globigerinell calida) foraminifera show that the U/Ca ratio of cleaned calcite tests is proportional to the concentration of uranium in solution. After correcting results for the presence of initial calcite, the apparent distribution coefficient D = (U/Ca[sub calcite])/(U/Ca)[sub solution] = 10.6more » [+-] 0.3 (x10[sup [minus]3]) for A. lobifera and D = 7.9 [+-] 0.1 (x10[sup [minus]3]) for G. calida. U/Ca ratios in planktonic foraminifera from core tops collected above 3900 m in the equatorial Atlantic and above 2100 m in the Pacific Ocean show no significant difference among the species analyzed. D estimated form core top samples ranges from 7.6 [+-] 0.4 (x10[sup [minus]3]) for O. universa to 8.4 [+-] 0.5 (x10[sup [minus]3]) for G. ruber. In benthic species C. wuellerstorfi, D = 7.0 [+-] 0.8 (x10[sup [minus]3]). U/Ca and Mg/Ca in G. tumida and G. sacculifer from core tops taken near and below the regional lysocline decrease with water depth. Smaller decreases in U/Ca and Mg/Ca with depth were observed in C. wuellerstorfi. In the planktonic species, the authors believe that U/CA and Mg/Ca are lower in the more dissolution-resistant fraction of calcite, leading to lower U/Ca in more highly dissolved samples.« less

Calcite phase determination of CaCO3 nanoparticles synthesized by one step drying method

NASA Astrophysics Data System (ADS)

Sulimai, N. H.; Rani, Rozina Abdul; Khusaimi, Z.; Abdullah, S.; Salifairus, M. J.; Alrokayan, Salman; Khan, Haseeb; Rusop, M.

2018-05-01

Calcium Carbonate (CaCO3) is a type of carbonic salt. It exist naturally as white odourless solid and may also be synthesized by chemical reactions. This work studies one-step precipitation of CaCO3 that was prepared by novel method of one-step precipitation method. The method was then proceeded by different types of drying. The first type is by normal drying in oven whereas the second type is with the presence of hydrothermal influence. From the results, precipitated CaCO3 dried by normal drying method produces CaCO3 with two polymorphs present; calcite and vaterite. Normal drying at 500°C has no vaterite phase left. Drying by hydrothermal precipitated CaCO3 has Nitrogen (N) left on the surfaces of the precipitated CaCO3. This work successfully identified calcite phase in the precipitated CaCO3.

Application of kinetic models to the design of a calcite permeable reactive barrier (PRB) for fluoride remediation.

PubMed

Cai, Qianqian; Turner, Brett D; Sheng, Daichao; Sloan, Scott

2018-03-01

The kinetics of fluoride sorption by calcite in the presence of metal ions (Co, Mn, Cd and Ba) have been investigated and modelled using the intra-particle diffusion (IPD), pseudo-second order (PSO), and the Hill 4 and Hill 5 kinetic models. Model comparison using the Akaike Information Criterion (AIC), the Schwarz Bayseian Information Criterion (BIC) and the Bayes Factor allows direct comparison of model results irrespective of the number of model parameters. Information Criterion results indicate "very strong" evidence that the Hill 5 model was the best fitting model for all observed data due to its ability to fit sigmoidal data, with confidence contour analysis showing the model parameters were well constrained by the data. Kinetic results were used to determine the thickness of a calcite permeable reactive barrier required to achieve up to 99.9% fluoride removal at a groundwater flow of 0.1 m.day -1 . Fluoride removal half-life (t 0.5 ) values were found to increase in the order Ba ≈ stonedust (a 99% pure natural calcite) < Cd < Co < Mn. A barrier width of 0.97 ± 0.02 m was found to be required for the fluoride/calcite (stonedust) only system when using no factor of safety, whilst in the presence of Mn and Co, the width increased to 2.76 ± 0.28 and 19.83 ± 0.37 m respectively. In comparison, the PSO model predicted a required barrier thickness of ∼46.0, 62.6 & 50.3 m respectively for the fluoride/calcite, Mn and Co systems under the same conditions. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

Experimental study of the replacement of calcite by calcium sulphates

NASA Astrophysics Data System (ADS)

Ruiz-Agudo, E.; Putnis, C. V.; Hövelmann, J.; Álvarez-Lloret, P.; Ibáñez-Velasco, A.; Putnis, A.

2015-05-01

Among the most relevant mineral replacement reactions are those involving sulphates and carbonates, which have important geological and technological implications. Here it is shown experimentally that during the interaction of calcite (CaCO3) cleavage surfaces with sulphate-bearing acidic solutions, calcite is ultimately replaced by gypsum (CaSO4 2H2O) and anhydrite (CaSO4), depending on the reaction temperature. Observations suggest that this occurs most likely via an interface-coupled dissolution-precipitation reaction, in which the substrate is replaced pseudomorphically by the product. At 120 and 200 °C gypsum and/or bassanite (CaSO4·0.5H2O) form as precursor phases for the thermodynamically stable anhydrite. Salinity promotes the formation of less hydrated precursor phases during the replacement of calcite by anhydrite. The reaction stops before equilibrium with respect to calcite is reached and during the course of the reaction most of the bulk solutions are undersaturated with respect to the precipitating phase(s). A mechanism consisting of the dissolution of small amounts of solid in a thin layer of fluid at the mineral-fluid interface and the subsequent precipitation of the product phase from this layer is in agreement with these observations. PHREEQC simulations performed in the framework of this mechanism highlight the relevance of transport and surface reaction kinetics on the volume change associated with the CaCO3-CaSO4 replacement. Under our experimental conditions, this reaction occurs with a positive volume change, which ultimately results in passivation of the unreacted substrate before calcite attains equilibrium with respect to the bulk solution.

Direct ink writing of silica-bonded calcite scaffolds from preceramic polymers and fillers.

PubMed

Fiocco, L; Elsayed, H; Badocco, D; Pastore, P; Bellucci, D; Cannillo, V; Detsch, R; Boccaccini, A R; Bernardo, E

2017-05-11

Silica-bonded calcite scaffolds have been successfully 3D-printed by direct ink writing, starting from a paste comprising a silicone polymer and calcite powders, calibrated in order to match a SiO 2 /CaCO 3 weight balance of 35/65. The scaffolds, fabricated with two slightly different geometries, were first cross-linked at 350 °C, then fired at 600 °C, in air. The low temperature adopted for the conversion of the polymer into amorphous silica, by thermo-oxidative decomposition, prevented the decomposition of calcite. The obtained silica-bonded calcite scaffolds featured open porosity of about 56%-64% and compressive strength of about 2.9-5.5 MPa, depending on the geometry. Dissolution studies in SBF and preliminary cell culture tests, with bone marrow stromal cells, confirmed the in vitro bioactivity of the scaffolds and their biocompatibility. The seeded cells were found to be alive, well anchored and spread on the samples surface. The new silica-calcite composites are expected to be suitable candidates as tissue-engineering 3D scaffolds for regeneration of cancellous bone defects.

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

USGS Publications Warehouse

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

2005-01-01

Experimental transformation of a rather pure natural calcite marble to aragonite marble did not proceed via the expected straightforward polymorphic replacement. Instead, the small amount of Mg in the starting material (0.36 wt %) was excluded from the growing aragonite and diffused preferentially into the remaining calcite grains, producing Mg-rich calcite rods that persisted as relicts. Nucleation of aragonite occurred exclusively on grain boundaries, with aragonite [001] oriented subparallel to calcite [0001]. The aragonite crystals preferentially consumed the calcite crystal on which they nucleated, and the reaction fronts developed preferentially along the {010} and {110} planes of aragonite. Each aragonite neoblast that grew was nearly free of Mg (typically <0.1 wt %). The excess Mg was taken up by the calcite grains in between, stabilizing them and causing a few volume percent rodlike relicts of Mg-enriched calcite (up to 10 wt % MgO) to be left behind by the advancing reaction front. The aragonite growth rates are approximately linear and range from ∼3 × 10−11 m s−1 at 600°C to ∼9 × 10−9 m s−1 at 850°C, with an apparent activation enthalpy of 166 ± 91 kJ mol−1. This reaction mechanism and the resultant texture are akin to cellular precipitation reactions in metals. Similar transformation textures have been reported from high-Mg marbles in Japan and China that disproportionated to low-Mg calcite and dolomite.

Resetting of Mg isotopes between calcite and dolomite during burial metamorphism: Outlook of Mg isotopes as geothermometer and seawater proxy

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Ikaite pseudomorphs in the Zaire deep-sea fan: An intermediate between calcite and porous calcite

NASA Astrophysics Data System (ADS)

Jansen, J. H. F.; Woensdregt, C. F.; Kooistra, M. J.; van der Gaast, S. J.

1987-03-01

Translucent brown aggregates of calcium-carbonate crystals have been found in cores from the Zaire deep-sea fan (west equatorial Africa). The aggregates are well preserved but very friable. Upon storage they become yellowish white and cloudy and release water. Chemical, mineralogical (XRD), petrographical, crystal-morphological, and stable-isotope data demonstrate that the crystals have passed through three phases: (1) an authigenic carbonate phase, probably calcium carbonate, which is represented by the external habit of the present crystals; (2) a translucent brown ikaite phase (CaCO3·6H2O), unstable at temperatures above 5 °C; and (3) a phase consisting of calcite microcrystals that are poorly cemented and form a porous mass within the crystal form of the morphologically unchanged first phase. The transformation from the first phase into ikaite was probably a kinetic replacement. The transformation from ikaite into the third phase occurred because of storage at room temperature. The presence of ikaite is indicative of a low-temperature, anaerobic, organic-carbon-rich marine environment. Ikaite is probably the precursor of a great number of porous calcite pseudomorphs, and possibly also of many marine authigenic microcrystalline carbonate nodules.

Microbially induced separation of quartz from calcite using Saccharomyces cerevisiae.

PubMed

Padukone, S Usha; Natarajan, K A

2011-11-01

Cells of Saccharomyces cerevisiae and their metabolites were successfully utilized to achieve selective separation of quartz and calcite through microbially induced flotation and flocculation. S. cerevisiae was adapted to calcite and quartz minerals. Adsorption studies and electrokinetic investigations were carried out to understand the changes in the surface chemistry of yeast cells and the minerals after mutual interaction. Possible mechanisms in microbially induced flotation and flocculation are outlined. Copyright © 2011 Elsevier B.V. All rights reserved.

Indications for the past redox environments in deep groundwaters from the isotopic composition of carbon and oxygen in fracture calcite, Olkiluoto, SW Finland.

PubMed

Sahlstedt, Elina; Karhu, Juha A; Pitkanen, Petteri

2010-09-01

In paleohydrogeological studies, the geochemical and isotope geochemical composition of fracture calcites can be utilised to gain information about the evolution of the composition of deep groundwaters in crystalline bedrock. The aim of our study was to investigate the latest hydrogeochemical evolution of groundwaters in the crystalline bedrock at Olkiluoto, which is the planned site for deep geological disposal of spent nuclear fuel. Samples were collected from drill cores intercepting water-conducting fractures at the upper ~500 m of the bedrock. The latest fracture calcite generations were identified using optical microscopy and electron microprobe. They occur as thin ~10-200 μm crusts or small euhedral crystals on open fracture surfaces. These latest calcite fillings were carefully sampled and analysed for the isotopic composition on carbon and oxygen. In addition, fluid inclusion homogenisation temperatures were determined on selected calcite samples. Fluid inclusion data indicated a low temperature of formation for the latest fracture calcite fillings. The δ(18)O values of calcite in these fracture fillings vary only slightly, from-7.3 to-11.5 ‰ (Vienna Pee Dee Belemnite, VPDB), whereas the δ(13)C values fluctuate widely, from-30 to+31 ‰ (VPDB). The δ(13)C values of latest calcite fillings show a systematic pattern with depth, with high and variable δ(13)C values below 50 m. The high δ(13)C values indicate active methanogenesis during the formation of the latest calcite fillings. In contrast, the present-day methanic redox environment is restricted to depths below 200-300 m. It is possible that the shift in the redox environment at Olkiluoto has occurred during infiltration of SO2-(4)-rich marine waters, the latest of such events being the infiltration of brackish waters of the Littorina Sea stage of the Baltic Sea at ~8000-3000 BP.

Experimental Study of Sr Partitioning into Calcite at Various Linear Growth Rates and Temperatures: Preliminary Results.

NASA Astrophysics Data System (ADS)

Gabitov, R. I.; Watson, B. E.

2004-05-01

The surface of a crystal in equilibrium with surrounding fluid can have a composition that differs from the bulk crystal. If growth rate of the crystal exceeds a minimum value at which partitioning-equilibrium can be maintained, then the crystal surface composition may be "captured" by the newly-formed lattice. The degree of this entrapment increases with increasing crystal growth rate. Non-equlibrium partitioning of Sr into calcite probably occurs by this entrapment mechanism. Sr and calcite are geochemically significant in understanding the thermal history of the ocean because the substitution of Sr for Ca in calcite is temperature dependent. To improve our understanding of the partitioning of Sr into calcite, we conducted two different types of experiment: 1) calcite growth from Sr-bearing solution with analysis of the crystal cross-section by electron microprobe (bulk crystal-liquid runs); and 2) treatment of calcite cleavage surfaces with Sr-bearing solutions and examination of the top few nm surface layer by X-ray photoelectron spectroscopy (surface-liquid runs). In the series of bulk-liquid experiments crystals were grown by three different procedures: 1) precipitation on glass slide (pre-coated with calcite), where a steady flow of CaCl2 - SrCl2 and Na2CO3 solutions were mixed just before passage through a tube and allowed to drip onto a slide ("cave"-type experiments, ionic strength I=0.01); 2) growth from a CaCl2 - NH4Cl - SrCl2 solution by diffusion of CO2 from an ammonium carbonate source ("drift" experiments, I=0.52); 3) coarsening of small calcite crystals in the CaCO3-SrCO3-NaCl-H2O system at 800-950° C and 0.5-1 kb in a cold seal apparatus. The growth rate of individual crystals was determined by periodic monitoring of crystal size with time or roughly by comparison of final size with duration of the experiment. Surface-liquid experiments were performed by treatment of cleavage surfaces of natural calcite fragments in a Sr(ClO4)2 solution for 1

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

NASA Technical Reports Server (NTRS)

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

2009-01-01

The Mars Phoenix Scout Mission with its diverse instrument suite successfully examined several soils on the Northern plains of Mars. The Thermal and Evolved Gas Analyzer (TEGA) was employed to detect organic and inorganic materials by coupling a differential scanning calorimeter (DSC) with a magnetic-sector mass spectrometer (MS). Martian soil was heated up to 1000 C in the DSC ovens and evolved gases from mineral decomposition products were examined with the MS. TEGA s DSC has the capability to detect endothermic and exothermic reactions during heating that are characteristic of minerals present in the Martian soil. Initial TEGA results indicated the presence of endothermic peaks with onset temperatures that ranged from 675 C to 750 C with corresponding CO2 release. This result suggests the presence of calcite (CaCO3. CaO + CO2). Organic combustion to CO2 is not likely since this mostly occurs at temperatures below 550 C. Fe-carbonate and Mg-carbonate are not likely because their decomposition temperatures are less than 600 C. TEGA enthalpy determinations suggest that calcite, may occur in the Martian soil in concentrations of approx.1 to 5 wt. %. The detection of calcite could be questioned based on previous results that suggest Mars soils are mostly acidic. However, the Phoenix landing site soil pH was measured at pH 8.3 0.5, which is typical of terrestrial soils where pH is controlled by calcite solubility. The range of onset temperatures and calcite concentration as calculated by TEGA is poorly con-strained in part because of limited thermal data of cal-cite at reduced pressures. TEGA operates at <30 mbar while most calcite literature thermal data was obtained at 1000 mbar or higher pressures.

Selective adsorption of benzhydroxamic acid on fluorite rendering selective separation of fluorite/calcite

NASA Astrophysics Data System (ADS)

Jiang, Wei; Gao, Zhiyong; Khoso, Sultan Ahmed; Gao, Jiande; Sun, Wei; Pu, Wei; Hu, Yuehua

2018-03-01

Fluorite, a chief source of fluorine in the nature, usually coexists with calcite mineral in ore deposits. Worldwide, flotation techniques with a selective collector and/or a selective depressant are commonly preferred for the separation of fluorite from calcite. In the present study, an attempt was made to use benzhydroxamic acid (BHA) as a collector for the selective separation of fluorite from calcite without using any depressant. Results obtained from the flotation experiments for single mineral and mixed binary minerals revealed that the BHA has a good selective collecting ability for the fluorite when 50 mg/L of BHA was used at pH of 9. The results from the zeta potential and X-ray photoelectron spectroscopy (XPS) indicated that the BHA easily chemisorbs onto the fluorite as compared to calcite. Crystal chemistry calculations showed the larger Ca density and the higher Ca activity on fluorite surface mainly account for the selective adsorption of BHA on fluorite, leading to the selective separation of fluorite from calcite. Moreover, a stronger hydrogen bonding with BHA and the weaker electrostatic repulsion with BHA- also contribute to the stronger interaction of BHA species with fluorite surface.

Altervalent substitution of sodium for calcium in biogenic calcite and aragonite

NASA Astrophysics Data System (ADS)

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

2017-04-01

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.

Catalytic Biomineralization of Fluorescent Calcite by the Thermophilic Bacterium Geobacillus thermoglucosidasius▿

PubMed Central

Yoshida, Naoto; Higashimura, Eiji; Saeki, Yuichi

2010-01-01

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

Sturgeon and paddlefish (Acipenseridae) saggital otoliths are composed of the calcium carbonate polymorphs vaterite and calcite: acipenseridae otoliths are vaterite and calcite

DOE PAGES

Pracheil, Brenda M.; Chakoumakos, Bryan C.; Feygenson, Mikhail; ...

2016-07-27

The otoliths of modern fishes are most commonly comprised of the metastable aragonite polymorph of calcium carbonate (CaCO3); however, sturgeons have otoliths reportedly comprised of the least stable of the three most-common polymorphs, vaterite. In this study, we used neutron diffraction to characterize CaCO3 polymorph composition of lake sturgeon and paddlefish otoliths. Based on previous summaries of CaCO3 composition over fish evolutionary history, we hypothesized that sturgeon and paddlefish otoliths would have similar polymorph composition. We found that despite previous reports of sturgeon otoliths being comprised entirely of vaterite, that all otoliths we examined in this study also had amore » calcite fraction that ranged from 17.9+ 6.0 wt. % to 35.9 + 2.9 wt. %. We also conducted a grinding experiment that demonstrated that calcite fractions were due to biological variation and not an artifact of polymorph transformation during preparation. Our study provides the initial characterization of the polymorph composition of the otoliths of lake sturgeon, and paddlefish and also provides the first-ever report of otoliths of Acipenserids as having a calcite fraction.« less

Sturgeon and paddlefish (Acipenseridae) saggital otoliths are composed of the calcium carbonate polymorphs vaterite and calcite: acipenseridae otoliths are vaterite and calcite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pracheil, Brenda M.; Chakoumakos, Bryan C.; Feygenson, Mikhail

The otoliths of modern fishes are most commonly comprised of the metastable aragonite polymorph of calcium carbonate (CaCO3); however, sturgeons have otoliths reportedly comprised of the least stable of the three most-common polymorphs, vaterite. In this study, we used neutron diffraction to characterize CaCO3 polymorph composition of lake sturgeon and paddlefish otoliths. Based on previous summaries of CaCO3 composition over fish evolutionary history, we hypothesized that sturgeon and paddlefish otoliths would have similar polymorph composition. We found that despite previous reports of sturgeon otoliths being comprised entirely of vaterite, that all otoliths we examined in this study also had amore » calcite fraction that ranged from 17.9+ 6.0 wt. % to 35.9 + 2.9 wt. %. We also conducted a grinding experiment that demonstrated that calcite fractions were due to biological variation and not an artifact of polymorph transformation during preparation. Our study provides the initial characterization of the polymorph composition of the otoliths of lake sturgeon, and paddlefish and also provides the first-ever report of otoliths of Acipenserids as having a calcite fraction.« less

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

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

Heterogeneous distribution of dye-labelled biomineralizaiton proteins in calcite crystals

NASA Astrophysics Data System (ADS)

Liu, Chuang; Xie, Liping; Zhang, Rongqing

2015-12-01

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

Experimental postseismic recovery of fractured rocks assisted by calcite sealing

NASA Astrophysics Data System (ADS)

Aben, F. M.; Doan, M.-L.; Gratier, J.-P.; Renard, F.

2017-07-01

Postseismic recovery within fault damage zones involves slow healing of coseismic fractures leading to permeability reduction and strength increase with time. To better understand this process, experiments were performed by long-term fluid percolation with calcite precipitation through predamaged quartz-monzonite samples subjected to upper crustal conditions of stress and temperature. This resulted in a P wave velocity recovery of 50% of its initial drop after 64 days. In contrast, the permeability remained more or less constant for the duration of the experiment. Microstructures, fluid chemistry, and X-ray microtomography demonstrate that incipient calcite sealing and asperity dissolution are responsible for the P wave velocity recovery. The permeability is unaffected because calcite precipitates outside of the main flow channels. The highly nonparallel evolution of strength recovery and permeability suggests that fluid conduits within fault damage zones can remain open fluid conduits after an earthquake for much longer durations than suggested by the seismic monitoring of fault healing.

Adsorption of a novel reagent scheme on scheelite and calcite causing an effective flotation separation.

PubMed

Gao, Yuesheng; Gao, Zhiyong; Sun, Wei; Yin, Zhigang; Wang, Jianjun; Hu, Yuehua

2018-02-15

The efficient separation of scheelite from calcium-bearing minerals, especially calcite, remains a challenge in practice. In this work, a novel reagent scheme incorporating a depressant of sodium hexametaphosphate (SHMP) and a collector mixture of octyl hydroxamic acid (HXMA-8) and sodium oleate (NaOl) was employed in both single and mixed binary mineral flotation, and it proved to be highly effective for the separation. Furthermore, the role of the pH value in the separation was evaluated. Additionally, the mechanism of the selective separation was investigated systemically via zeta potential measurements, fourier transform infrared (FTIR) spectroscopy analysis, X-ray photoelectron (XPS) spectroscopy analysis and crystal chemistry calculations. It turns out that the selective chemisorption of SHMP on calcite (in the form of complexation between H 2 PO 4 - /HPO 4 2- and Ca 2+ ) over scheelite is ascribed to the stronger reactivity and higher density of Ca ions on the commonly exposed surfaces of calcite minerals. The intense adsorption of HXMA-8 on scheelite over calcite due to the match of the OO distances in WO 4 2- of scheelite and CONHOH of HXMA-8 holds the key to the successful separation. We were also interested in warranting the previous claim that NaOl is readily adsorbed on both minerals via chemisorption. Our results provided valuable insights into the application of mixed collectors and an effective depressant for flotation separation. Copyright © 2017 Elsevier Inc. All rights reserved.

A Laboratory Study Investigating the Feasibility of Applying Calcite-Type Coatings to Segregated Ballast Tanks

DTIC Science & Technology

1981-08-01

A LABORATORY STUDY INVESTIGATIING THE FEASIBILITY OF APPLYING CALCITE -TYPE COATINGS TO SEGREGATED BALLAST TANKS AUGUST, 1981 Prepared by: Ocean City...Laboratory Study Investigating The Feasibility of Applying Calcite -Type Coatings to Segregated Ballast Tanks 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c...Executive Summary List of Figures I. Conclusions II. Introduction III. Background-The Development and Use of Calcite -Type Coatings IV. Experimental

Quantitative single molecule measurements on the interaction forces of poly(L-glutamic acid) with calcite crystals.

PubMed

Sonnenberg, Lars; Luo, Yufei; Schlaad, Helmut; Seitz, Markus; Cölfen, Helmut; Gaub, Hermann E

2007-12-12

The interaction between poly(L-glutamic acid) (PLE) and calcite crystals was studied with AFM-based single molecule force spectroscopy. Block copolymers of poly(ethylene oxide) (PEO) and PLE were synthesized and covalently attached to the tip of an AFM cantilever. In desorption measurements the molecules were allowed to adsorb on the calcite crystal faces and afterward successively desorbed. The corresponding desorption forces were detected with high precision, showing for example a force transition between the two blocks. Because of its importance in the crystallization process in biominerals, the PLE-calcite interaction was investigated as a function of the pH as well as the calcium concentration of the aqueous solution. The sensitivity of the technique was underlined by resolving different interaction forces for calcite (104) and calcite (100).

A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock.

PubMed

Xu, Tianfu; Sonnenthal, Eric; Bodvarsson, Gudmundur

2003-06-01

The percolation flux in the unsaturated zone (UZ) is an important parameter addressed in site characterization and flow and transport modeling of the potential nuclear-waste repository at Yucca Mountain, NV, USA. The US Geological Survey (USGS) has documented hydrogenic calcite abundances in fractures and lithophysal cavities at Yucca Mountain to provide constraints on percolation fluxes in the UZ. The purpose of this study was to investigate the relationship between percolation flux and measured calcite abundances using reactive transport modeling. Our model considers the following essential factors affecting calcite precipitation: (1) infiltration, (2) the ambient geothermal gradient, (3) gaseous CO(2) diffusive transport and partitioning in liquid and gas phases, (4) fracture-matrix interaction for water flow and chemical constituents, and (5) water-rock interaction. Over a bounding range of 2-20 mm/year infiltration rate, the simulated calcite distributions capture the trend in calcite abundances measured in a deep borehole (WT-24) by the USGS. The calcite is found predominantly in fractures in the welded tuffs, which is also captured by the model simulations. Simulations showed that from about 2 to 6 mm/year, the amount of calcite precipitated in the welded Topopah Spring tuff is sensitive to the infiltration rate. This dependence decreases at higher infiltration rates owing to a modification of the geothermal gradient from the increased percolation flux. The model also confirms the conceptual model for higher percolation fluxes in the fractures compared to the matrix in the welded units, and the significant contribution of Ca from water-rock interaction. This study indicates that reactive transport modeling of calcite deposition can yield important constraints on the unsaturated zone infiltration-percolation flux and provide useful insight into processes such as fracture-matrix interaction as well as conditions and parameters controlling calcite deposition.

Formation of complex fibrous calcite veins in Upper Triassic strata of Wrangellia Terrain, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Al-Aasm, I. S.; Coniglio, M.; Desrochers, A.

1995-12-01

Fibrous calcite veins are ubiquitous throughout the thinly bedded, organic-rich Upper Triassic marine mdrocks of the Queen Charlotte Islands and their lateral equivalents on Vancouver Island. These veins show variable and complex morphologies and can be grouped into several types: (a) simple; (b) anastomosing or composite; (c) boxwork; and (4) polygonal network oriented normal to bedding. Field, petrographic, and geochemical evidence suggest that vein opening, resulting from hydraulic fracturing due to elevated pore-fluid pressures, was an early phenomenon and occurred prior to significant compaction of the host sediments. Calcite fibers in the veins are up to 30 mm long and commonly oriented perpendicular to the wall but locally display conical structures. Fibrous calcites, with the exception of those in boxwork veins, are generally non-ferroan and dull to very weakly orange luminescent. The boxwork calcites are ferroan, zoned and show dull luminescence with some bright rims. δ18O values range from -8.2 to -21.6‰ (PDB) and δ13C values range from 2.0 to -4.4‰ (PDB). Although some variations are present among the different morphological types of calcite veins, oxygen and carbon isotopic values display important variations when compared geographically. The most depleted oxygen and carbon isotopic values are those of boxwork calcite and they are associated with areas where the effects of early Mesozoic plutonism were most severe. Precipitation of boxwork fibrous calcites is interpreted to have been related to hydrothermal discharge into unconsolidated host sediment, rather than to later burial. Although the hydrothermal influence on the formation of vein calcite is related to geological events specific to the Wrangellia Terrain, this study provides an alternative mechanism for the generation of fibrous calcite veins and demonstrates the local importance of hydrothermal input in the evolution of pore-water chemistry.

Estimation of past seepage volumes from calcite distribution in the Topopah Spring Tuff, Yucca Mountain, Nevada

USGS Publications Warehouse

Marshall, B.D.; Neymark, L.A.; Peterman, Z.E.

2003-01-01

Low-temperature calcite and opal record the past seepage of water into open fractures and lithophysal cavities in the unsaturated zone at Yucca Mountain, Nevada, site of a proposed high-level radioactive waste repository. Systematic measurements of calcite and opal coatings in the Exploratory Studies Facility (ESF) tunnel at the proposed repository horizon are used to estimate the volume of calcite at each site of calcite and/or opal deposition. By estimating the volume of water required to precipitate the measured volumes of calcite in the unsaturated zone, seepage rates of 0.005 to 5 liters/year (l/year) are calculated at the median and 95th percentile of the measured volumes, respectively. These seepage rates are at the low end of the range of seepage rates from recent performance assessment (PA) calculations, confirming the conservative nature of the performance assessment. However, the distribution of the calcite and opal coatings indicate that a much larger fraction of the potential waste packages would be contacted by this seepage than is calculated in the performance assessment.

Fabrication of microporous calcite block from calcium hydroxide compact under carbon dioxide atmosphere at high temperature.

PubMed

Otsu, Akihiro; Tsuru, Kanji; Maruta, Michito; Munar, Melvin L; Matsuya, Shigeki; Ishikawa, Kunio

2012-01-01

Effects of carbonation temperature and compacting pressure on basic properties of calcite block were studied using Ca(OH)2 compact made with 0.2-2.0 MPa and their carbonation at 200-800ºC for 1 h. Microporous calcite was obtained only when carbonated at 600ºC using Ca(OH)2 compact made with 0.2 MPa even though thermogravimetry analysis showed that calcite powder was stable up to 920ºC under CO2 atmosphere. CaO formed by carbonation at 700ºC and 800ºC is thought to be caused by the limited CO2 diffusion interior to the Ca(OH)2 compact. Also, unreacted Ca(OH)2 was found for Ca(OH)2 compact prepared with 0.5 MPa or higher pressure even when carbonated at 600ºC. As a result of high temperature carbonation, crystallite size of the calcite, 58.0 nm, was significantly larger when compared to that of calcite prepared at room temperature, 35.5 nm. Porosity and diametral tensile strength of the microporous calcite were 39.5% and 6.4 MPa.

Manganese-calcium intermixing facilitates heteroepitaxial growth at the 10 1 ¯ 4 calcite-water interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.

2017-10-01

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 amore » 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.« less

Collisional Histories of Comets and Trojan Asteroids: Diopside, Magnesite, and Fayalite Impact Studies

NASA Technical Reports Server (NTRS)

Lederer, S. M.; Jensen, E. A.; Wooden, D. H.; Lindsay, S. S.; Nakamura-Messenger, K.; Smith, D. C.; Keller, L. P.; Cintala, M. J.; Zolensky, M. E.

2012-01-01

Comets and asteroids have weathered dynamic histories, as evidenced by their rough surfaces. The Nice model describes a violent reshuffling of small bodies during the Late Heavy Bombardment, with collisions acting to grind these planetesimals away. This creates an additional source of impact material that can re-work the surfaces of the larger bodies over the lifetime of the solar system. Here, we investigate the possibility that signatures due to impacts (e.g. from micrometeoroids or meteoroids) could be detected in their spectra, and how that can be explained by the physical manifestation of shock in the crystalline structure of minerals. All impact experiments were conducted in the Johnson Space Center Experimental Impact Laboratory using the vertical gun. Impact speeds ranged from approx.2.0 km/s to approx.2.8 km/s. All experiments were conducted at room temperature. Minerals found in comets and asteroids were chosen as targets, including diopside (MgCaSi2O6, monoclinic pyroxene), magnesite (MgCO3, carbonate), and fayalite (FeSiO4, olivine). Impacted samples were analyzed using a Fourier Transform Infrared Spectrometer (FTIR) and a Transmission Electron Microscope (TEM). Absorbance features in the 8-13 m spectral region demonstrate relative amplitude changes as well as wavelength shifts. Corresponding TEM images exhibit planar shock dislocations in the crystalline structure, attributed to deformation at high strain and low temperatures. Elongating or shortening the axes of the crystalline structure of forsterite (Mg2SiO4, olivine) using a discrete dipole approximation model (Lindsay et al., submitted) yields changes in spectral features similar to those observed in our impacted laboratory minerals.

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

NASA Astrophysics Data System (ADS)

Neuweiler, Fritz; D'Orazio, Valeria; Immenhauser, Adrian; Geipel, Gerhard; Heise, Karl-Heinz; Cocozza, Claudio; Miano, Teodoro M.

2003-08-01

Intracrystalline organic compounds, enclosed within in situ precipitated 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) the degree of condensation, (3) the redox conditions involved, and (4) the catalytic role of natural organic matter for the precipitation of automicrite. Fluorescence spectrometry of the intracrystalline organic fraction extracted from these carbonates identifies a marine fulvic acid like organic compound with a low degree of polycondensation. This finding points to a temporal correlation of the initial stage of geopolymer formation with the precipitation of automicrite. Furthermore, the rare earth element (REE) distribution patterns in the mineral show a consistent positive Ce anomaly, suggesting an episode of reductive dissolution of iron-manganese oxyhydroxides during automicrite formation. In general, a relative enrichment of middle-weight REEs is observed, resulting in a convex distribution pattern typical for, e.g., phosphate concretions or humic acid material. By merging the results of spectrometry and REE geochemistry we thus conclude that the marine calcite precipitation was catalyzed by marine fulvic acid like compounds during the early stages of humification under suboxic conditions. This indicates that humification, driven by the presence of a benthic biomass, is more important for calcite authigenesis than any site-specific microbial metabolism. The Neoproterozoic rise of carbonate mounds supports this hypothesis; there is molecular evidence for early metazoan divergence then, but not for a major evolutionary episode of microorganisms.

On-line Raman spectroscopy of calcite and malachite during irradiation with swift heavy ions

NASA Astrophysics Data System (ADS)

Dedera, Sebastian; Burchard, Michael; Glasmacher, Ulrich A.; Schöppner, Nicole; Trautmann, Christina; Severin, Daniel; Romanenko, Anton; Hubert, Christian

2015-12-01

A new on-line Raman System, which was installed at the M3-beamline at the UNILAC, GSI Helmholtzzentrum für Schwerionenforschung Darmstadt was used for first "in situ" spectroscopic measurements. Calcite and malachite samples were irradiated in steps between 1 × 109 and 1 × 1012 ions/cm2 with Au ions (calcite) and Xe ions (malachite) at an energy of 4.8 MeV/u. After irradiation, calcite revealed a new Raman band at 437 cm-1 and change of the full width at half maximum for the 1087 cm-1 Raman band. The Raman bands of malachite change significantly with increasing fluence. Up to a fluence of 7 × 1010 ions/cm2, all existing bands decrease in intensity. Between 8 × 1010 and 1 × 1011 ions/cm2 a broad Cu2O band between 110 and 220 cm-1 occurs, which superimposes the pre-existing Raman bands. Additionally, a new broad band between 1000 and 1750 cm-1 is formed, which is interpreted as a carbon coating. In contrast to the Cu2O band, the carbon band vanished when further irradiating the sample. The installations as well as first in situ measurements at room temperature are presented.

Effect of acidified water glass on the flotation separation of scheelite from calcite using mixed cationic/anionic collectors

NASA Astrophysics Data System (ADS)

Dong, Liuyang; Jiao, Fen; Qin, Wenqing; Zhu, Hailing; Jia, Wenhao

2018-06-01

In this paper, the effect of acidified water glass (AWG) on the flotation separation of scheelite from calcite using mixed collector of dodecylamine (DDA) and sodium oleate (NaOL) was investigated. The flotation results show that AWG could selectively depress the flotation of calcite at pH 7. A series of mechanism experiments confirm that the chemisorption of AWG on calcite surface is more intense than scheelite. Although the chemisorption of NaOL on calcite surface is almost unaffected by the presence of AWG, the chemisorption of AWG hinders the adsorption of DDA on calcite surface.

Influence of water on clumped-isotope bond reordering kinetics in calcite

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Sorption-desorption of cadmium in aqueous palygorskite, sepiolite, and calcite suspensions: isotherm hysteresis.

PubMed

Shirvani, Mehran; Kalbasi, Mahmoud; Shariatmadari, Hosein; Nourbakhsh, Farshid; Najafi, Bijan

2006-12-01

Sorption isotherms have been widely used to assess the heavy metal retention characteristics of soil particles. Desorption behavior of the retained metals, however, usually differ from that of sorption, leading to a lack of coincidence in the experimentally obtained sorption and desorption isotherms. In this study, we examine the nonsingularity of cadmium (Cd) sorption-desorption isotherms, to check the possible hysteresis and reversibility phenomena, in aqueous palygorskite, sepiolite and calcite systems. Sorption of Cd was carried out using a 24-h batch equilibration experiment with eight different Cd solution concentrations, equivalent to 20-100% of maximum sorption capacity of each mineral. Immediately after sorption, desorption took place using successive dilution method with five consecutive desorption steps. Both Cd sorption and desorption data were adequately described by Freundlich equation (0.81Calcite showed much smaller hysteresis compared to the other two silicate clays at low Cd surface load, but its hysteresis indices significantly increased, and exceeded that of palygorskite, as the amount of Cd in the systems increased. The average amount of Cd released after five desorption steps, was 13.8%, 2.2% and 3.6% for the palygorskite, sepiolite and calcite, respectively, indicating that a large portion of Cd was irreversibly retained by the minerals.

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

PubMed

Naidu, Sonia; Scherer, George W

2014-12-01

Marble, a stone composed of the mineral calcite, is subject to chemically induced weathering in nature due to its relatively high dissolution rate in acid rain. To protect monuments and sculpture from corrosion, we are investigating the application of thin layers of hydroxyapatite (HAP) onto marble. The motivation for using HAP is its low dissolution rate and crystal and lattice compatibility with calcite. A mild, wet chemical synthesis route, in which diammonium hydrogen phosphate salt was reacted with marble, alone and with cationic and anionic precursors under different reaction conditions, was used to produce inorganic HAP layers on marble. Nucleation and growth on the calcite substrate was studied, as well as metastable phase evolution, using scanning electron microscopy, grazing incidence X-ray diffraction, and atomic force microscopy. Film nucleation was enhanced by surface roughness. The rate of nucleation and the growth rate of the film increased with cationic (calcium) and anionic (carbonate) precursor additions. Calcium additions also influenced phase formation, introducing a metastable phase (octacalcium phosphate) and a different phase evolution sequence. Copyright © 2014 Elsevier Inc. All rights reserved.

Cryogenic Origin for Mars Analog Carbonates in the Bockfjord Volcanic Complex Svalbard (Norway)

NASA Technical Reports Server (NTRS)

Amundsen, H. E. F.; Benning, L.; Blake, D. F.; Fogel, M.; Ming, D.; Skidmore, M.; Steele, A.

2011-01-01

The Sverrefjell and Sigurdfjell eruptive centers in the Bockfjord Volcanic Complex (BVC) on Svalbard (Norway) formed by subglacial eruptions ca. 1 Ma ago. These eruptive centers carry ubiquitous magnesian carbonate deposits including dolomitemagnesite globules similar to those in the Martian meteorite ALH84001. Carbonates in mantle xenoliths are dominated by ALH84001 type carbonate globules that formed during quenching of CO2-rich mantle fluids. Lava hosted carbonates include ALH84001 type carbonate globules occurring throughout lava vesicles and microfractures and massive carbonate deposits associated with vertical volcanic vents. Massive carbonates include < or equal 5 cm thick magnesite deposits protruding downwards into clear blue ice within volcanic vents and carbonate cemented lava breccias associated with volcanic vents. Carbonate cements comprise layered deposits of calcite, dolomite, huntite, magnesite and aragonite associated with ALH84001 type carbonate globules lining lava vesicles. Combined Mossbauer, XRD and VNIR data show that breccia carbonate cements at Sverrefjell are analog to Comanche carbonates at Gusev crater.

Direct observation of the transition from calcite to aragonite growth as induced by abalone shell proteins.

PubMed Central

Thompson, J B; Paloczi, G T; Kindt, J H; Michenfelder, M; Smith, B L; Stucky, G; Morse, D E; Hansma, P K

2000-01-01

The mixture of EDTA-soluble proteins found in abalone nacre are known to cause the nucleation and growth of aragonite on calcite seed crystals in supersaturated solutions of calcium carbonate. Past atomic force microscope studies of the interaction of these proteins with calcite crystals did not observe this transition because no information about the crystal polymorph on the surface was obtained. Here we have used the atomic force microscope to directly observe changes in the atomic lattice on a calcite seed crystal after the introduction of abalone shell proteins. The observed changes are consistent with a transition to (001) aragonite growth on a (1014) calcite surface. PMID:11106633

Stepped Acid Extractions of CO2 from Ancient Carbonates in Martian Nakhlites (MIL 03346, 090030, 090032, 090036) Show Distinct δ18O and δ13C Isotopic Values Compared to Secondary Terrestrial Carbonates Formed on Ordinary Chondrites (OC) Collected from Antarctica

NASA Astrophysics Data System (ADS)

Evans, M. E.; Niles, P. B.

2016-12-01

This study finds that 1) Martian Nakhlite meteorites contain insitu carbonates with distinctive δ13C from terrestrial carbonates formed on Antarctic Ordinary Chondrites (OCs), and 2) Martian carbonate formation δ18O values for atmospheric CO2 and meteoric water can be predicted with a mixing model created from Antarctic OC carbonate data. Nakhlite and OC meteorites collected in Antarctica contain both calcites and non-calcite carbonates. Rock samples were crushed, dissolved in pure phosphoric acid, and allowed to react at the following conditions: 1 hr@30°C (Rx0, fine calcite), 18 hr@30°C (Rx1, course calcite), and 3 hr@150°C (Rx2, siderite and/or magnesite). The collected CO2 was purified with a Thermo Trace GC and analyzed on a Thermo MAT 253 IRMS in dual inlet mode. Ten OC meteorite samples collected from three different Antarctic regions (RBT, ALH, MIL) were analyzed. These samples had no pre-terrestrial aqueous alterations, yet evaporite minerals were visible on the fusion crust. It is deduced these OC carbonates were completely terrestrial. These calcites have δ13C=+6‰ and are consistent with equilibrium formation to Earth atmospheric CO2 δ13C=-7‰ at 0°C to 10°C. Siderite or magnesite fractionation may create slightly heavier δ13C as seen in the Rx2 results. The range of δ18O from +3‰ to +30‰ is heavier than expected if carbonate forms in equilibrium with only meteoric water. A δ18O mixing model is created with Earth atmospheric CO2 and meteoric water as end members. This model predicts the OC calcites form with 60%-90% contribution from atmospheric CO2 at 0°C, and the non-calcites form with 40-60% contribution from atmospheric CO2. Four martian Nakhlites collected from the Antarctic Miller Range were analyzed. These samples contain low carbonate concentrations (avg. 0.007% by weight) with distinctly heavier δ13C = +7‰ to +59‰. In general, these carbonates are lighter than expected if formed in equilibrium with the modern martian

Tracing high-pressure metamorphism in marbles: Phase relations in high-grade aluminous calcite-dolomite marbles from the Greek Rhodope massif in the system CaO-MgO-Al 2O 3-SiO 2-CO 2 and indications of prior aragonite

NASA Astrophysics Data System (ADS)

Proyer, A.; Mposkos, E.; Baziotis, I.; Hoinkes, G.

2008-08-01

Four different types of parageneses of the minerals calcite, dolomite, diopside, forsterite, spinel, amphibole (pargasite), (Ti-)clinohumite and phlogopite were observed in calcite-dolomite marbles collected in the Kimi-Complex of the Rhodope Metamorphic Province (RMP). The presence of former aragonite can be inferred from carbonate inclusions, which, in combination with an analysis of phase relations in the simplified system CaO-MgO-Al 2O 3-SiO 2-CO 2 (CMAS-CO 2) show that the mineral assemblages preserved in these marbles most likely equilibrated at the aragonite-calcite transition, slightly below the coesite stability field, at ca. 720 °C, 25 kbar and aCO 2 ~ 0.01. The thermodynamic model predicts that no matter what activity of CO 2, garnet has to be present in aluminous calcite-dolomite-marble at UHP conditions.

A model for microbially induced precipitation of vadose-zone calcites in fractures at LOS Alamos, New Mexico, USA

NASA Astrophysics Data System (ADS)

Newman, Brent D.; Campbell, Andrew R.; Norman, David I.; Ringelberg, David B.

1997-05-01

Fractures are unique environments that can concentrate the flow of water, nutrients, and contaminants. As such, fractures play an important role in controlling the flux of various substances into and through the vadose zone. Calcite fracture fillings are present in the near surface in the Bandelier Tuff Formation at Los Alamos, New Mexico, and provide a record of the geochemical and hydrologic processes that have occurred in fractures. The objective of this study was to examine calcite fracture fills in order to improve understanding of processes within fractures, and in particular those that lead to precipitation of calcite. Samples of calcite fillings were collected from vertical and horizontal fractures exposed in a shallow waste-burial pit. Scanning electron microscopy show morphologies which suggest that plants, fungi, and bacteria were important in the precipitation process. Quadrupole mass spectrometric analyses of fluid inclusion gases show predominantly methane (17-99%) and little to no oxygen (0-8%), suggesting the development of anaerobic conditions in the fractures. Ester-linked phospholipid biomarkers are evidence for a diverse microbial community in the fractures, and the presence of di-ether lipids indicate that the methane was generated by anaerobic bacteria. The calcite fillings apparently resulted from multiple biological and chemical processes in which plant roots in the fractures were converted to calcite. Roots grew into the fractures, eventually died, and were decomposed by bacteria and fungi. Anaerobic gases were generated from encapsulated organic material within the calcite via microbial decomposition, or were generated by microbes simultaneously with calcite precipitation. It is likely that the biological controls on calcite formation that occurred in the Los Alamos fractures also occurs in soils, and may explain the occurrence of other types of pedogenic calcites.

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

PubMed Central

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

2002-01-01

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

Geochemical study of calcite veins in the Silurian and Devonian of the Barrandian Basin (Czech Republic): evidence for widespread post-Variscan fluid flow in the central part of the Bohemian Massif

NASA Astrophysics Data System (ADS)

Suchy, V.; Heijlen, W.; Sykorova, I.; Muchez, Ph; Dobes, P.; Hladikova, J.; Jackova, I.; Safanda, J.; Zeman, A.

2000-03-01

Carbonate fracture cements in limestones have been investigated by fluid inclusion and stable isotope analysis to provide insight into fluid evolution and deformation conditions of the Barrandian Basin (Silurian-Devonian) of the Czech Republic. The fractures strike generally north-south and appear to postdate major Variscan deformation. The most common fracture cement is calcite that is locally accompanied by quartz, natural bitumen, dolomite, Mn-oxides and fluorite. Three successive generations of fracture-filling calcite cements are distinguished based on their petrographical and geochemical characteristics. The oldest calcite cements (Stage 1) are moderate to dull brown cathodoluminescent, Fe-rich and exhibit intense cleavage, subgrain development and other features characteristic of tectonic deformation. Less tectonically deformed, variable luminescent Fe-poor calcite corresponds to a paragenetically younger Stage 2 cement. First melting temperatures, Te, of two-phase aqueous inclusions in Stages 1 and 2 calcites are often around -20°C, suggesting that precipitation of the cements occurred from H 2O-NaCl fluids. The melting temperature, Tm, has values between 0 and -5.8°C, corresponding to a low salinity between 0 and 8.9 eq. wt% NaCl. Homogenization temperatures, Th, from calcite cements are interpreted to indicate precipitation at about 70°C or less. No distinction could be made between the calcite of Stages 1 and 2 based on their fluid inclusion characteristics. In some Stage 2 cements, inclusions of highly saline (up to 23 eq. wt% NaCl) brines appear to coexist with low-salinity inclusions. The low salinity fluid possibly contains Na-, K-, Mg- and Ca-chlorides. The high salinity fluid has a H 2O-NaCl-CaCl 2 composition. Blue-to-yellow-green fluorescing hydrocarbon inclusions composed of medium to higher API gravity oils are also identified in some Stages 1 and 2 calcite cements. Stage 1 and 2 calcites have δ18O values between -13.2‰ and -7.2‰ PDB

Subsolidus and melting phase relations in the system CaCO3-MgCO3-FeCO3 at 35 kbar: from experiments to predictions based on a thermodynamic model

NASA Astrophysics Data System (ADS)

Franzolin, E.; Schmidt, M. W.; Poli, S.

2009-12-01

At convergent margins volatile components, most notably CO2 and H2O, stored in oceanic sediments and MORB are recycled into the mantle. Mafic protoliths become enriched in CO2 and H2O, stored in carbonates and hydrous phases, by hydrothermal alteration. As carbonates are more refractory than hydrous phases, CO2 is more likely to survive in the oceanic lithosphere beyond sub-arc depths [1,2]. Despite the main role of carbonates on cycling crustal and atmospheric CO2 into the mantle, experimental data within the system CaCO3-MgCO3-FeCO3 are scarce. To bridge this gap, piston-cylinder experiments have been performed at 35 kbar, 900-1100 °C to determine subsolidus relations, and up to 1300 °C to constrain melting relations. Pure synthetic calcite, natural magnesite and synthetic siderite have been mixed in different proportions in double Pt-C capsules, to avoid major siderite oxidation. Subsolidus experiments reveal the presence of two miscibility gaps at 900 °C: the solvus dolomite-calcite, which closes at XMgCO3 ~ 0.7, and the solvus dolomite-magnesite, which ranges to the Fe-side of the ternary. Increasing the temperature, the two miscibility gaps became narrower until complete solid solutions between CaCO3-Ca0.5Mg0.5CO3 at 1100 °C, and between CaCO3-FeCO3 at 1000 °C, are observed. The system is characterized by strong compositional asymmetry, thermodynamically described with a van Laar macroscopic formalism [3], and by R-3<=>R-3c phase transitions due to cation disordering, treated by redefining the compositional space with an independent set of end-members that describe both composition and states of ordering. The result is a solid solution model able to reproduce both the phase relations experimentally observed at 35 kbar and those experimentally determined and naturally observed at lower pressure [4-5]. Our model can be reliable extended to pressures of the breakdown of dolomite, e.g. 5-6 GPa, 600-1000 °C. Melting experiments carried out at 1250 °C along

Gallium(III) adsorption on carbonates and oxides: X-ray absorption fine structure spectroscopy study and surface complexation modeling.

PubMed

Pokrovsky, O S; Pokrovski, G S; Schott, J

2004-11-15

Adsorption of Ga on calcite, magnesite, amorphous silica, and manganese oxide as a function of pH and gallium concentration in solution was studied using a batch adsorption technique. Adsorbed complexes of Ga on calcite, magnesite, and delta-MnO2 were further characterized using XAFS spectroscopy. At high surface loadings from supersaturated solutions, Ga is likely to form a polymeric network at the surface (edge- and corner-sharing octahedra). At low surface loadings, Ga presents as isolated octahedra, probably attached to the Me-O sites on the surface, and coordinated by water molecules and hydroxide groups at 1.90-1.94 A. At pH>6, Ga therefore changes its coordination from 4 to 6 when adsorbing from solution (Ga(OH)(-)4(aq)) onto metal surface sites (MeOGa(OH)n(H2O)2-n(5-n), Me = Ca, Mg, or Mn, and n=1 and 2 for carbonate minerals and MnO2, respectively). Because the EXAFS is not capable of seeing hydrogen atoms, the protonation of surface complexes was determined by fitting the experimental pH-dependent Ga adsorption edge. A surface complexation model which assumes the constant capacitance of the electric double layer (CCM) and postulates the formation of positively charged, neutral and negatively charged surface complexes for carbonates, manganese oxide and silica, respectively, was used to describe the dependence of adsorption equilibria on aqueous solution composition in a wide range of pH and Ga concentration.

Surface Complexation Modeling of Calcite Zeta Potential Measurement in Mixed Brines for Carbonate Wettability Characterization

NASA Astrophysics Data System (ADS)

Song, J.; Zeng, Y.; Biswal, S. L.; Hirasaki, G. J.

2017-12-01

We presents zeta potential measurements and surface complexation modeling (SCM) of synthetic calcite in various conditions. The systematic zeta potential measurement and the proposed SCM provide insight into the role of four potential determining cations (Mg2+, SO42- , Ca2+ and CO32-) and CO2 partial pressure in calcite surface charge formation and facilitate the revealing of calcite wettability alteration induced by brines with designed ionic composition ("smart water"). Brines with varying potential determining ions (PDI) concentration in two different CO2 partial pressure (PCO2) are investigated in experiments. Then, a double layer SCM is developed to model the zeta potential measurements. Moreover, we propose a definition for contribution of charged surface species and quantitatively analyze the variation of charged species contribution when changing brine composition. After showing our model can accurately predict calcite zeta potential in brines containing mixed PDIs, we apply it to predict zeta potential in ultra-low and pressurized CO2 environments for potential applications in carbonate enhanced oil recovery including miscible CO2 flooding and CO2 sequestration in carbonate reservoirs. Model prediction reveals that pure calcite surface will be positively charged in all investigated brines in pressurized CO2 environment (>1atm). Moreover, the sensitivity of calcite zeta potential to CO2 partial pressure in the various brine is found to be in the sequence of Na2CO3 > Na2SO4 > NaCl > MgCl2 > CaCl2 (Ionic strength=0.1M).

The sensitized luminescence of manganese-activated calcite

USGS Publications Warehouse

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

1947-01-01

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

Biomimetic synthesis of calcite films by a polymer-induced liquid-precursor (PILP) process. 1. Influence and incorporation of magnesium

NASA Astrophysics Data System (ADS)

Cheng, Xingguo; Varona, Philip L.; Olszta, Matthew J.; Gower, Laurie B.

2007-09-01

Magnesium-bearing calcium carbonate films have been synthesized via a polymer-induced liquid-precursor (PILP) mineralization process. A variety of morphological features of biominerals can be mimicked with this PILP process; therefore, our group has proposed that this crystallization system can be used as an effective in vitro model system for examining mechanistic issues related to biomineralization. Here, the effect of the Mg 2+/Ca 2+ ratio on the rate of transformation of the amorphous precursor films was investigated using polarized optical microscopy (POM), and the final crystalline structure and composition were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), inductively coupled plasma spectroscopy (ICP) and energy dispersive spectroscopy (EDS). The entrapment of high levels of magnesium in the deposited precursor films had a pronounced inhibitory effect on the amorphous to crystalline transformation, and furthermore, influenced the polycrystalline nature of the film. The magnesium content incorporated within the calcite lattice (8-26%) resembles the range found in biologically formed high magnesium-bearing calcite, while much lower levels were formed via the conventional solution crystallization process. The formation of non-equilibrium morphologies and similar compositions of magnesium-bearing calcite via the PILP process further supports our hypothesis that the PILP process may play a fundamental role in the formation of calcitic biominerals in nature. In the realm of biomimetic engineering, the PILP process may also establish itself as a new method to produce thin ceramic films with variable compositions under ambient conditions.

Carbon sequestration via reaction with basaltic rocks: geochemical modeling and experimental results

USGS Publications Warehouse

Rosenbauer, Robert J.; Thomas, Burt; Bischoff, James L.; Palandri, James

2012-01-01

Basaltic rocks are potential repositories for sequestering carbon dioxide (CO2) because of their capacity for trapping CO2 in carbonate minerals. We carried out a series of thermodynamic equilibrium models and high pressure experiments, reacting basalt with CO2-charged fluids over a range of conditions from 50 to 200 °C at 300 bar. Results indicate basalt has a high reactivity to CO2 acidified brine. Carbon dioxide is taken up from solution at all temperatures from 50 to 200 °C, 300 bar, but the maximum extent and rate of reaction occurs at 100 °C, 300 bar. Reaction path simulations utilizing the geochemical modeling program CHILLER predicted an equilibrium carbonate alteration assemblage of calcite, magnesite, and siderite, but the only secondary carbonate identified in the experiments was a ferroan magnesite. The amount of uptake at 100 °C, 300 bar ranged from 8% by weight for a typical tholeite to 26% for a picrite. The actual amount of CO2 uptake and extent of rock alteration coincides directly with the magnesium content of the rock suggesting that overall reaction extent is controlled by bulk basalt Mg content. In terms of sequestering CO2, an average basaltic MgO content of 8% is equivalent to 2.6 × 108 metric ton CO2/km3 basalt.

Effect of organic ligands on Mg partitioning and Mg isotope fractionation during low-temperature precipitation of calcite

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Immenhauser, Adrian; Buhl, Dieter; Purgstaller, Bettina; Baldermann, Andre; Dietzel, Martin

2016-04-01

Calcite growth experiments have been performed at 25 oC and 1 bar pCO2 in the presence of aqueous Mg and six organic ligands in the concentration range from 10-5 to 10-3 M. These experiments were performed in order to quantify the effect of distinct organic ligands on the Mg partitioning and Mg stable isotope fractionation during its incorporation in calcite at similar growth rates normalized to total surface area. The organic ligands used in this study comprise of (i) acetate acid, (ii) citrate, (iii) glutamate, (iv) salicylate, (v) glycine and (vi) ethylenediaminetetraacetic acid (EDTA), containing carboxyl- and amino-groups. These fuctional groups are required for bacterial activity and growth as well as related to biotic and abiotic mineralization processes occurring in sedimentary and earliest diagenetic aquatic environments (e.g. soil, cave, lacustrine, marine). The results obtained in this study indicate that the presence of organic ligands promotes an increase in the partition coefficient of Mg in calcite (DMg = (Mg/Ca)calcite (Mg/Ca)fluid). This behaviour can be explained by the temporal formation of aqueous Mg-ligand complexes that are subsequently adsorbed on the calcite surfaces and thereby reducing the active growth sites of calcite. The increase of DMg values as a function of the supersaturation degree of calcite in the fluid phase can be described by the linear equation LogDMg =0.3694 (±0.0329)×SIcalcite - 1.9066 (±0.0147); R2=0.92 In contrast, the presence of organic ligands, with exception of citrate, does not significantly affect the Mg isotope fractionation factor between calcite and reactive fluid (Δ26Mgcalcite-fluid = -2.5 ±0.1). Citrate likely exhibits larger fractionation between the Mg-ligand complexes and free aqueous Mg2+, compared to the other organic ligands studied in this work, as evidenced by the smaller Δ26Mgcalcite-fluid values. These results indicate that in Earth's surface calcite precipitating environments that are

Comparison of solidification/stabilization effects of calcite between Australian and South Korean cements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Dongjin; Waite, T. David; Swarbrick, Gareth

2005-11-15

The differences in the effect of calcite on the strength and stability of Pb-rich wastes solidified and stabilized using Australian and South Korean ordinary Portland cements are examined in this study. Pb-rich waste stabilized using Australian OPC has been shown to possess both substantially higher unconfined compressive strength and lead immobilization ability than South Korean OPC as a result of its higher C{sub 3}S content and the associated enhanced degree of precipitation of lead on the surfaces of silicate phases present. Calcite addition is observed to have an accelerating effect on the OPC-induced solidification/stabilization of Pb-rich wastes as gauged bymore » the unconfined compressive strength and leachability of the solids formed. This effect is observed to be far more dramatic for South Korean OPC than for Australian OPC. Using scanning electron microscopy, waste stabilized with cement and calcite was observed to develop significantly greater proportions of hydrated crystals than wastes stabilized with cement alone. The results of X-ray diffraction studies have shown that the presence of calcite in South Korean OPC results in greater acceleration in the formation of portlandite than is the case for Australian OPC.« less

Amorphous calcium carbonate transforms into calcite during sea urchin larval spicule growth

PubMed Central

Beniash, E.; Aizenberg, J.; Addadi, L.; Weiner, S.

1997-01-01

Sea urchin larvae form an endoskeleton composed of a pair of spicules. For more than a century it has been stated that each spicule comprises a single crystal of the CaCO3 mineral, calcite. We show that an additional mineral phase, amorphous calcium carbonate, is present in the sea urchin larval spicule, and that this inherently unstable mineral transforms into calcite with time. This observation significantly changes our concepts of mineral formation in this well-studied organism.

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

NASA Astrophysics Data System (ADS)

Immenhauser, A.; Buhl, D.; Richter, D.; Niedermayr, A.; Riechelmann, D.; Dietzel, M.; Schulte, U.

2010-08-01

The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ 26Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ 26Mg values of loess-derived soil above the cave (-1.0 ± 0.5‰), soil water (-1.2 ± 0.5‰), the carbonate hostrock (-3.8 ± 0.5‰), dripwater in the cave (-1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; -4.3 ± 0.6‰), cave loam (-0.6 ± 0.1‰) and runoff water (-1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000ln αMg-cc-Mg(aq) = -2.4‰. A similar Mg-isotope fractionation (1000ln αMg-cc-Mg(aq) ≈ -2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, 26Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg 2+ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Strain rate dependent calcite microfabric evolution at natural conditions

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Strain rate dependent calcite microfabric evolution - an experiment carried out by nature

NASA Astrophysics Data System (ADS)

Rogowitz, A.; Huet, B.; Grasemann, B.; Habler, G.

2013-12-01

The deformation behaviour of calcite has been studied extensively in a number of experiments. Different strain rates and pressure and temperature conditions have been used to investigate a wide range of deformation regimes. However, a direct comparison with natural fault rocks remains difficult because of extreme differences between experimental and natural strain rates. A secondary shear zone (flanking structure) developed in almost pure calcite marble on Syros (Greece). Due to rotation of an elliptical inclusion (crack) a heterogeneous strain field in the surrounding area occurred resulting in different strain domains and the formation of the flanking structure. Assuming that deformation was active continuously during the development of the flanking structure, the different strain domains correspond to different strain-rate domains. The outcrop thus represents the final state of a natural experiment and gives us a great opportunity to get natural constraints on strain rate dependent deformation behaviour of calcite. Comparing the microfabrics in the 1 to 2.5 cm thick shear zone and the surrounding host rocks, which formed under the same metamorphic conditions but with different strain rates, is the central focus of this study. Due to the extreme variation in strain and strain rate, different microstructures and textures can be observed corresponding to different deformation mechanisms. With increasing strain rate we observe a change in dominant deformation mechanism from dislocation glide to dislocation creep and finally diffusion creep. Additionally, a change from subgrain rotation (SGR) to bulging (BLG) recrystallization can be observed in the dislocation creep regime. Textures and the degree of intracrystalline deformation have been measured by electron back scatter diffraction (EBSD). At all strain rates clear CPOs developed leading to the assumption that calcite preferentially deforms within the dislocation creep field. However, we can also find clear

Coccolith calcite time capsules preserve a molecule-specific record of pCO2

NASA Astrophysics Data System (ADS)

McClelland, H. L. O.; Pearson, A.; Hermoso, M.; Wilkes, E.; Lee, R. B. Y.; Rickaby, R. E. M.

2017-12-01

Coccolithophores are single-celled phytoplankton that have contributed organic matter and calcite to marine sediments since the Late Triassic. The carbon isotopic compositions of both the calcite, and the organic matter, constitute valuable archives of information about the interaction between these organisms and the environments in which they lived. The isotopic composition of alkenone lipids, a recalcitrant component of coccolithophore organic carbon produced by a single family of coccolithophores, has been widely used to reconstruct pCO2 in the geological past. However, the robustness of this approach has remained controversial, due in part to the difficulties associated with reproducing pCO2 changes across periods of known pCO2 change, and uncertainties in relevant physiological variables such as growth rate and cell size. Meanwhile the calcite, produced in the form of plates called coccoliths, and which has had limited utility in paleoclimate reconstructions due to its large and variable departures from the isotopic composition of abiogenic calcite, has garnered increasing attention in recent years for the environmental and physiological information it contains. Here we show that polysaccharides preserved within the calcite crystal lattice of near monospecific fractions of fossil coccoliths constitute an ancient pristine source of organic carbon that unlike alkenones is unambiguously associated with the coccolith1. The isotopic composition of these polysaccharides, in tandem with that of the host coccolith calcite, and morphometrics from the same coccoliths2, can be used simultaneously constrain a recently published cellular carbon isotope flux model3, embedded in a more complex nutrient limitation model, in a powerful new approach to simultaneously predict cellular parameters and pCO2. We demonstrate the validity of this approach across a glacial / interglacial cycle. Lee, R. B. Y., et al,, Nat. Commun. 7, 13144 (2016). McClelland, H. L. O. et al. Sci. Rep. 6

A dissolution model that accounts for coverage of mineral surfaces by precipitation in core floods

NASA Astrophysics Data System (ADS)

Pedersen, Janne; Jettestuen, Espen; Madland, Merete V.; Hildebrand-Habel, Tania; Korsnes, Reidar I.; Vinningland, Jan Ludvig; Hiorth, Aksel

2016-01-01

In this paper, we propose a model for evolution of reactive surface area of minerals due to surface coverage by precipitating minerals. The model is used to interpret results from an experiment where a chalk core was flooded with MgCl2 for 1072 days, giving rise to calcite dissolution and magnesite precipitation. The model successfully describes both the long-term behavior of the measured effluent concentrations and the more or less homogeneous distribution of magnesite found in the core after 1072 days. The model also predicts that precipitating magnesite minerals form as larger crystals or aggregates of smaller size crystals, and not as thin flakes or as a monomolecular layer. Using rate constants obtained from literature gave numerical effluent concentrations that diverged from observed values only after a few days of flooding. To match the simulations to the experimental data after approximately 1 year of flooding, a rate constant that is four orders of magnitude lower than reported by powder experiments had to be used. We argue that a static rate constant is not sufficient to describe a chalk core flooding experiment lasting for nearly 3 years. The model is a necessary extension of standard rate equations in order to describe long term core flooding experiments where there is a large degree of textural alteration.

Fatty acids in sparry calcite fracture fills and microsparite cement of septarian diagenetic concretions

NASA Astrophysics Data System (ADS)

Pearson, M. J.; Hendry, J. P.; Taylor, C. W.; Russell, M. A.

2005-04-01

Sparry calcite fracture fills and concretion body cements in concretions from the Flodigarry Shale Member of the Staffin Shale Formation, Isle of Skye, Scotland, entrap and preserve mineral and organic materials of sedimentary and diagenetic origin. Fatty acids are a major component of the lipids recovered by decarbonation and comprise mainly n-alkanoic and α-ω dicarboxylic acids. Two generations of fracture-fill calcite (early brown and later yellow) and the concretion body microspar yield significantly different fatty acid profiles. Early brown calcites yield mainly medium-chain n-alkanoic acids with strong even predominance; later yellow calcites are dominated by α-ω dicarboxylic acids with no even predominance. Both fracture fills lack the long-chain n-alkanoic and α-ω dicarboxylic acids additionally recovered from the concretion bodies. The absence of longer chain acids in the calcite spar fracture fills is inferred to result from the transport of fatty acids by septarian mineralising fluids whereby low-aqueous solubility of longer chain acids or their salts accounts for their relative immobility. Comparative experiments have been carried out using conventional solvent extraction on the concretion body and associated shales, both decarbonated and untreated. Extracted lipid yields are higher, but the fatty acids probably derive from mixed locations in the rock including both kerogen- and carbonate-associated lipid pools. Only experiments involving decarbonation yielded α-ω dicarboxylic acids in molecular distributions probably controlled mainly by fluid transport. Alkane biomarker ratios indicate very low thermal maturity has been experienced by the concretions and their host sediments. Septarian cracks lined by brown calcite formed during early burial. Microbial CO 2 from sulphate-reducing bacteria was probably the main source of mineralising carbonate. Emplacement of the later septarian fills probably involved at least one episode of fluid invasion.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-01-01

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

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

PubMed Central

Wu, Di; Navrotsky, Alexandra

2015-01-01

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. Herein, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. These thermochemical observations directly support a structure where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. These differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces. PMID:25870281

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

DOE PAGES

Wu, Di; Navrotsky, Alexandra

2015-04-13

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. In this paper, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. Furthermore, these thermochemical observations directly support a structuremore » where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. Finally, these differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces.« less

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

USGS Publications Warehouse

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

2001-01-01

Deposits of calcite and opal are present as coatings on open fractures and lithophysal cavities in unsaturated-zone tuffs at Yucca Mountain, Nevada, site of a potential high-level radioactive waste repository. Outermost layers of calcite and opal have radiocarbon ages of 16,000 to 44,000 years before present and thorium-230/uranium ages of 28,000 to more than 500,000 years before present. These ages are young relative to the 13-million-year age of the host rocks. Multiple subsamples from the same outer layer typically show a range of ages with youngest ages from the thinnest subsamples. Initial uranium-234/uranium-238 activity ratios between 1 and 9.5 show a distinct negative correlation with thorium-230/uranium age and are greater than 4 for all but one sample younger than 100,000 years before present. These data, along with micrometer-scale layering and distinctive crystal morphologies, are interpreted to indicate that deposits formed very slowly from water films migrating through open cavities. Exchanges of carbon dioxide and water vapor probably took place between downward-migrating liquids and upward-migrating gases at low rates, resulting in oversaturation of mineral constituents at crystal extremities and more or less continuous deposition of very thin layers. Therefore, subsamples represent mixtures of older and younger layers on a scale finer than sampling techniques can resolve. Slow, long-term rates of deposition (less than about 5 millimeters of mineral per million years) are inferred from subsamples of outermost calcite and opal. These growth rates are similar to those calculated assuming that total coating thicknesses of 10 to 40 millimeters accumulated over 12 million years. Calcite has a wide range of delta carbon-13 values from about -8.2 to 8.5 per mil and delta oxygen-18 values from about 10 to 21 per mil. Systematic microsampling across individual mineral coatings indicates basal (older) calcite tends to have the largest delta carbon-13 values

Viruses Occur Incorporated in Biogenic High-Mg Calcite from Hypersaline Microbial Mats

PubMed Central

De Wit, Rutger; Gautret, Pascale; Bettarel, Yvan; Roques, Cécile; Marlière, Christian; Ramonda, Michel; Nguyen Thanh, Thuy; Tran Quang, Huy; Bouvier, Thierry

2015-01-01

Using three different microscopy techniques (epifluorescence, electronic and atomic force microscopy), we showed that high-Mg calcite grains in calcifying microbial mats from the hypersaline lake “La Salada de Chiprana”, Spain, contain viruses with a diameter of 50–80 nm. Energy-dispersive X-ray spectrometer analysis revealed that they contain nitrogen and phosphorus in a molar ratio of ~9, which is typical for viruses. Nucleic acid staining revealed that they contain DNA or RNA. As characteristic for hypersaline environments, the concentrations of free and attached viruses were high (>1010 viruses per g of mat). In addition, we showed that acid treatment (dissolution of calcite) resulted in release of viruses into suspension and estimated that there were ~15 × 109 viruses per g of calcite. We suggest that virus-mineral interactions are one of the possible ways for the formation of nano-sized structures often described as “nanobacteria” and that viruses may play a role in initiating calcification. PMID:26115121

Field Experiment to Stimulate Microbial Urease Activity in Groundwater for in situ Calcite Precipitation

NASA Astrophysics Data System (ADS)

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.

2003-12-01

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

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

PubMed

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

2016-01-01

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

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

DOE PAGES

Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; ...

2016-06-15

Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. In this study, we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO 3) 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 generatedmore » 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. In conclusion, 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.« less

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

PubMed Central

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

2016-01-01

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

Novel Determination of the Orientation of Calcite on Mineral Substrates

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Tuning hardness in calcite by incorporation of amino acids

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Tuning hardness in calcite by incorporation of amino acids.

PubMed

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

2016-08-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

U-Pb Dating of Calcite to Constrain Basinal Brine Flux Events: An Example from the Upper Midwest USA

NASA Astrophysics Data System (ADS)

Rasbury, T.; Luczaj, J.

2017-12-01

Calcite forms in a variety of settings and can be the product of surface to deep basinal fluids. As such, this mineral can uniquely record details of the fluids responsible for its formation. The forms of calcium carbonates and their stratigraphic relationships from the thin section to the regional scale give important insights on pulses of fluids. A fundamental question is the age of such fluid pulses. While calcite excludes uranium (U) from its crystal structure, some is incorporated and depending on the U/Pb ratio, this provides an opportunity for radiometric dating. Calcite crystals of various sizes and crystal habits are found in Paleozoic carbonate rocks throughout the region from the western Michigan basin to the upper Mississippi valley. These are typically associated with Mississippi Valley-type (MVT) mineralization, including galena, sphalerite, and iron sulfides, but typically post-date the main MVT event. We have analyzed a variety of these calcites and find multiple generations of calcite, separated by tens of millions of years. The initial Pb isotope ratios are similar to the isotope ratios of nearby galena, strongly suggesting a genetic relationship. Our oldest ages are 200 Ma, and we find ages ranging into the Cenozoic. Based on the Paleozoic-hosted galena Pb-isotope isoscapes from the region, the fluids may have been sourced from both the Michigan and Illinois basins. An important and unanswered question is what would cause significant fluid movement out of the basins substantially after Appalachian orogenesis. Noble gas data from brines in the Michigan Basin have a mantle component and have been suggested to be responsible for recognized elevated temperatures across the basin (Ma et al., 2009). Multiple thermal events during the Paleozoic and Mesozoic eras may have an internal heat source related to reactivation of faults of the Keweenawan Rift system below the Michigan Basin. Perhaps a mantle heat source from below episodically fluxes into the

Biomineralization processes of calcite induced by bacteria isolated from marine sediments

PubMed Central

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

2015-01-01

Biomineralization is a known natural phenomenon associated with a wide range of bacterial species. Bacterial-induced calcium carbonate precipitation by marine isolates was investigated in this study. Three genera of ureolytic bacteria, Sporosarcina sp., Bacillus sp. and Brevundimonas sp. were observed to precipitate calcium carbonate minerals. Of these species, Sporosarcina sp. dominated the cultured isolates. B. lentus CP28 generated higher urease activity and facilitated more efficient precipitation of calcium carbonate at 3.24 ± 0.25 × 10−4 mg/cell. X-ray diffraction indicated that the dominant calcium carbonate phase was calcite. Scanning electron microscopy showed that morphologies of the minerals were dominated by cubic, rhombic and polygonal plate-like crystals. The dynamic process of microbial calcium carbonate precipitation revealed that B. lentus CP28 precipitated calcite crystals through the enzymatic hydrolysis of urea, and that when ammonium ion concentrations reached 746 mM and the pH reached 9.6, that favored calcite precipitation at a higher level of 96 mg/L. The results of this research provide evidence that a variety of marine bacteria can induce calcium carbonate precipitation, and may influence the marine carbonate cycle in natural environments. PMID:26273260

Controls of ionic strength and macromolecule chemistry on calcite nucleation: Salinity and ion hydration as levers for regulating biomineralization

NASA Astrophysics Data System (ADS)

Dove, P. M.; Giuffre, A. J.; Mergelsberg, S. T.; Han, N.; De Yoreo, J. J.

2016-12-01

Organisms form shells and skeletons with remarkable fidelity by controlling the timing and placement of the minerals that nucleate and subsequently grow. An extensive effort has identified features of the organic matrix that regulate this process. Recent measurements from our group show the energy barrier to nucleation onto polysaccharide (PS) substrates is dependent upon hydrophilicity through functional group chemistry and suggest that free energy of the macromolecule-liquid interface influences where and when mineral nucleation occurs (Giuffre et al., 2013, PNAS). The importance of interfacial free energy in regulating nucleation raises the question of whether local changes in salinity or electrolyte composition can be tuned to further modulate the onset of calcite nucleation. Using alginate (negatively charged by carboxyl groups) and chitosan (small positive charge by amine groups), the rate of calcite nucleation was measured at controlled supersaturations and pH as a function of NaCl concentration (65-600 mM). Analyses of the data show the thermodynamic barrier to calcite nucleation onto both types of PS increases with ionic strength. The evidence suggests this effect arises from an increasing concentration of solvated ions at the PS-water interface while also increasing the hydrophilic character of that interface; thus decreasing the substrate-liquid interfacial free energy. To test this explanation, a second group of nucleation experiments used a suite of electrolytes (alkali chlorides for alginate and sodium halides for chitosan) while holding ionic strength constant. Indeed, the nucleation barriers for calcite formation are electrolyte-specific and correlated with the hydration free energy of the ion. This suggests solvated electrolyte ions indirectly regulate calcite nucleation onto substrates through their competition with the substrate for water thereby influencing net interfacial free energy. These effects are consistent with the long

Formation and mosaicity of coccolith segment calcite of the marine algae Emiliania huxleyi.

PubMed

Yin, Xiaofei; Ziegler, Andreas; Kelm, Klemens; Hoffmann, Ramona; Watermeyer, Philipp; Alexa, Patrick; Villinger, Clarissa; Rupp, Ulrich; Schlüter, Lothar; Reusch, Thorsten B H; Griesshaber, Erika; Walther, Paul; Schmahl, Wolfgang W

2018-02-01

Coccolithophores belong to the most abundant calcium carbonate mineralizing organisms. Coccolithophore biomineralization is a complex and highly regulated process, resulting in a product that strongly differs in its intricate morphology from the abiogenically produced mineral equivalent. Moreover, unlike extracellularly formed biological carbonate hard tissues, coccolith calcite is neither a hybrid composite, nor is it distinguished by a hierarchical microstructure. This is remarkable as the key to optimizing crystalline biomaterials for mechanical strength and toughness lies in the composite nature of the biological hard tissue and the utilization of specific microstructures. To obtain insight into the pathway of biomineralization of Emiliania huxleyi coccoliths, we examine intracrystalline nanostructural features of the coccolith calcite in combination with cell ultrastructural observations related to the formation of the calcite in the coccolith vesicle within the cell. With TEM diffraction and annular dark-field imaging, we prove the presence of planar imperfections in the calcite crystals such as planar mosaic block boundaries. As only minor misorientations occur, we attribute them to dislocation networks creating small-angle boundaries. Intracrystalline occluded biopolymers are not observed. Hence, in E. huxleyi calcite mosaicity is not caused by occluded biopolymers, as it is the case in extracellularly formed hard tissues of marine invertebrates, but by planar defects and dislocations which are typical for crystals formed by classical ion-by-ion growth mechanisms. Using cryo-preparation techniques for SEM and TEM, we found that the membrane of the coccolith vesicle and the outer membrane of the nuclear envelope are in tight proximity, with a well-controlled constant gap of ~4 nm between them. We describe this conspicuous connection as a not yet described interorganelle junction, the "nuclear envelope junction". The narrow gap of this junction likely

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

The radiogenic and stable Sr isotope geochemistry of basalt weathering in Iceland: Role of hydrothermal calcite and implications for long-term climate regulation

NASA Astrophysics Data System (ADS)

Andrews, M. Grace; Jacobson, Andrew D.

2017-10-01

volcanic C flux introduced to the atmosphere-ocean system as HCO3- after subsurface silicate weathering does not regulate long-term climate. Because hydrothermal calcite simply sequesters some of this HCO3- and delays its transmission to the atmosphere-ocean system until it dissolves at the surface later in time, it can be concluded the weathering of hydrothermal calcite bearing non-atmospheric C also has no effect on long-term climate regulation. Icelandic riverine HCO3- fluxes should be corrected for the hydrothermal calcite weathering contribution prior to quantifying atmospheric CO2 consumption rates by basalt weathering at the Earth's surface.

Genesis and microstratigraphy of calcite coralloids analysed by high resolution imaging and petrography

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

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

USGS Publications Warehouse

Reddy, Michael M.; Leenheer, Jerry

2011-01-01

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

The Labrador Sea during the Last Glacial Maximum: Calcite dissolution or low biogenic carbonate fluxes?

NASA Astrophysics Data System (ADS)

Marshall, Nicole; de Vernal, Anne; Mucci, Alfonso; Filippova, Alexandra; Kienast, Markus

2017-04-01

Low concentrations of biogenic carbonate characterize the sediments deposited in the Labrador Sea during the last glaciation. This may reflect poor calcite preservation and/or low biogenic carbonate productivity and fluxes. Regional bottom water ventilation was reduced during the Last Glacial Maximum (LGM), so the calcite lysocline might have been shallower than at present in the deep Labrador Sea making dissolution of calcite shells in the deep Labrador Sea possible. To address the issue, a multi-proxy approach based on micropaleontological counts (coccoliths, foraminifers, palynomorphs) and biogeochemical analyses (alkenones) was applied in the investigation of core HU2008-029-004-PC recovered in the northwestern Labrador Sea. Calcite dissolution indices based on the relative abundance benthic foraminifera shells to their organic linings as well as on fragmentation of planktonic foraminifera shells were used to evaluate changes in calcite dissolution/ preservation since the LGM. In addition, the ratio of the concentrations of coccoliths, specifically of the alkenone-producer Emiliania huxleyi, and alkenones (Emiliania huxleyi: alkenones) was explored as a potential new proxy of calcite dissolution. A sharp increase in coccoliths, foraminifers and organic linings from nearly none to substantial concentrations at 12 ka, reflect a jump to significantly greater biogenic fluxes at the glacial-interglacial transition. Furthermore, conventional dissolution indices (shells/linings of benthic foraminifera and fragmentation of planktic foraminifers) reveal that dissolution is not likely responsible for the lower glacial abundances of coccoliths and foraminifers. Only the low Emiliania huxleyi: alkenones ratios in glacial sediments could be interpreted as evidence of increased dissolution during the LGM. Given the evidence of allochthonous alkenone input into the glacial Labrador Sea, the latter observations must be treated with caution. Overall, the records indicate that

Using neutron diffraction to examine the onset of mechanical twinning in calcite rocks

NASA Astrophysics Data System (ADS)

Covey-Crump, S. J.; Schofield, P. F.; Oliver, E. C.

2017-07-01

Experimental calibration of the calcite twin piezometer is complicated by the difficulty of establishing the stresses at which the twins observed in the final deformation microstructures actually formed. In principle, this difficulty may be circumvented if the deformation experiments are performed in a polychromatic neutron beam-line because this allows the elastic strain (and hence stress) in differently oriented grains to be simultaneously monitored from diffraction patterns collected as the experiment is proceeding. To test this idea small strain (<0.3%), uniaxial compression experiments have been performed on Carrara marble (grain size 150 μm) and Solnhofen limestone (5 μm) at temperatures of 20°-600 °C using the ENGIN-X instrument at the ISIS neutron facility, UK. At the lowest temperatures (25 °C Carrara; 200 °C Solnhofen) the deformation response was purely elastic up to the greatest stresses applied (60 MPa Carrara; 175 MPa Solnhofen). The sign of the calcite elastic stiffness component c14 is confirmed to be positive when the obverse setting of the calcite rhombohedral lattice in hexagonal axes is used. In the Carrara marble samples deformed at higher temperatures, elastic twinning was initiated at small stresses (<15 MPa) in grains oriented such that the Schmid factor for twinning was positive on more than one e-twin system. At greater stresses (65 MPa at 200 °C decreasing to 41 MPa at 500 °C) there was an abrupt onset of permanent twinning in grains with large Schmid factors for twinning on any one e-twin system. No twinning was observed in the Solnhofen limestone samples deformed at 200° or 400 °C at applied stresses of <180 MPa. These results highlight the potential of this approach for detecting the onset of twinning and provide, through experiments on samples with different microstructures, a strategy for systematically investigating the effects of microstructural variables on crystallographically-controlled inelastic processes.

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

PubMed Central

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

2003-01-01

Nanobacteria-like objects evidenced at the surface of the orthopyroxenes of the Tataouine meteorite in South Tunisia have been studied by scanning and transmission electron microscopies. A method of micromanipulation has been developed to ensure that exactly the same objects were studied by both methods. We have shown that the nanobacteria-like objects are spatially correlated with filaments of microorganisms that colonized the surface of the meteoritic pyroxene during its 70 years of residence in the aridic Tataouine soil. Depressions of a few micrometers in depth are observed in the pyroxene below the carbonates, indicating preferential dissolution of the pyroxene and calcite precipitation at these locations. The nanobacteria-like small rods that constitute calcium carbonate rosettes are well crystallized calcite single crystals surrounded by a thin amorphous layer of carbonate composition that smoothes the crystal edges and induces rounded shapes. Those morphologies are unusual for calcite single crystals observed in natural samples. A survey of recent literature suggests that the intervention of organic compounds derived from biological activity is likely in their formation. PMID:12792020

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

PubMed

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

2003-06-24

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

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

ERIC Educational Resources Information Center

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

1979-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Relating Mechanical Behavior and Microstructural Observations in Calcite Fault Gouge

NASA Astrophysics Data System (ADS)

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

2013-12-01

Many important earthquakes, magnitude 5-7, nucleate and/or propagate through carbonate-dominated lithologies. Additionally, the presence of precipitated calcite in (cement) and near (vein fill) faults indicates that the mechanical behavior of carbonate-dominated material likely plays an important role in shallow- and mid-crustal faulting. We report on laboratory experiments designed to explore the mechanical behavior of calcite and relate that behavior to post experiment microstructural observations. We sheared powdered gouge of Carrara Marble, >98% CaCO3, at constant normal stresses between 1 and 50 MPa under saturated conditions at room temperature. We performed velocity-stepping tests, 0.1-1000 μm/s, to evaluate frictional stability, and slide-hold-slide tests, 1-10,000 seconds, to measure the amount of frictional healing. Small subsets of experiments were performed under different environmental conditions and shearing velocities to better elucidate physicochemical processes and their role in the mechanical behavior of calcite fault gouge. All experimental samples were collected for SEM analysis. We find that the frictional healing rate is 7X higher under saturated conditions than under nominally dry conditions. We also observe a divergence between the rates of creep relaxation (increasing) and frictional healing (decreasing) as shear velocity is increased from 1 to 3000 μm/s. Our highest healing rates are observed at our lowest normal stresses. We observe a frictional strength of μ = 0.64, consistent with previous data under similar conditions. Furthermore, although we observe velocity-weakening frictional behavior in both the saturated and dry cases, rate- and-state friction parameters are distinctly different for each case. Our combined observations of rapid healing and of velocity-weakening frictional behavior indicate that faults where calcite-dominated gouge is present are likely to be seismic and have the ability to regain their strength quickly

An efficient phosphorus scavenging from aqueous solution using magnesiothermally modified bio-calcite.

PubMed

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

2018-07-01

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.

Microstructural Damage During High-Strain Torsion Experiments on Calcite-Anhydrite Aggregates

NASA Astrophysics Data System (ADS)

Cross, A. J.; Skemer, P. A.

2016-12-01

Ductile shear zones play a critical role in localising deformation in the Earth's crust and mantle. Severe grain size reduction - a ubiquitous feature of natural mylonites - is commonly thought to cause strain weakening via a transition to grain size sensitive deformation mechanisms. Although grain size reduction is modulated by grain growth in single-phase aggregates, grain boundary pinning in well-mixed poly-phase composites can inhibit grain growth, leading to microstructural `damage' which is likely a critical element of strain localization in the lithosphere. While dynamic recrystallization has been widely explored in rock mechanics and materials science, the mechanisms behind phase-mixing remain poorly understood. In this contribution we present results from high-strain, deformation experiments on calcite-anhydrite composites. Experiments were conducted in torsion at T = 500-700°C and P 1.5 GPa, using the new Large Volume Torsion (LVT) solid-medium apparatus, to shear strains of 0.5-30. As shear strain increases, progressive thinning and necking of initially large (≤ 1 mm) calcite domains is observed, resulting in an increase in the proportion of interphase boundaries. Grain-size is negatively correlated with the fraction of interphase boundaries, such that calcite grains in well-mixed regions are significantly smaller than those in single-phase domains. Crucially, progressive deformation leads to a reduction in grain-size beyond the lower limit established by the grain size piezometer for mono-phase calcite, implying microstructural damage. These data therefore demonstrate continued microstructural evolution in two-phase composites that is not possible in single-phase aggregates. These observations mark a new `geometric' mechanism for phase mixing, complementing previous models for phase mixing involving chemical reactions, material diffusion, and/or grain boundary sliding.

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

PubMed

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

2008-03-01

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) < 2) since the Late Archaean. To evaluate the viability of microbial carbonates as 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

The analysis of thermoluminescent glow peaks of natural calcite after beta irradiation.

PubMed

Yildirim, R Güler; Kafadar, V Emir; Yazici, A Necmeddin; Gün, Esen

2012-09-01

In this study, the thermoluminescence properties of natural calcite samples were examined in detail. The glow curve of the sample irradiated with beta radiation shows two main peaks, P1 (at 115 °C) and P4 (at 254 °C). The additive dose, variable heating rate, computer glow curve deconvolution, peak shape and three point methods have been used to evaluate the trapping parameters, namely the order of kinetics (b), activation energy (E) and the frequency factor (s) associated with the dosimetric thermoluminescent glow peaks (P1 and P4) of natural calcite after different dose levels with beta irradiation.

Induction of calcite precipitation through heightened production of extracellular carbonic anhydrase by CO2 sequestering bacteria.

PubMed

Sundaram, Smita; Thakur, Indu Shekhar

2018-04-01

The thermo-alkalotolerant bacterium exhibiting heightened extracellular carbonic anhydrase (CA) activity, survived at 100 mM sodium bicarbonateand 5% gaseous CO 2 was identified as Bacillus sp. by 16S rRNA sequencing. Extracellular carbonic anhydrase was purified by ammonium sulfate precipitation, gel filtration chromatography and affinity chromatography with a yield of 46.61% and specific activity of 481.66 U/mg. The size of purified carbonic anhydrase was approximately 28 kDa in SDS-PAGE gel filtration and further their role in calcium carbonate production was correlated. The purified enzyme was stable with half-life of 25.36 min at 90 °C and pH 8. K M and Vmax values of the enzyme were 1.77 mg/mL and 385.69 U/mg respectively. The production of calcite was confirmed by Scanning Electron Microscopy (SEM) analysis, FTIR, and Energy-Dispersive X-ray (EDX) analysis. Carbonic anhydrase and calcite deposition coupled with CO 2 fixingbacteria is a significant approach for CO 2 sequestration. Copyright © 2018 Elsevier Ltd. All rights reserved.

Decadal changes in the aragonite and calcite saturation state of the Pacific Ocean

NASA Astrophysics Data System (ADS)

Feely, Richard A.; Sabine, Christopher L.; Byrne, Robert H.; Millero, Frank J.; Dickson, Andrew G.; Wanninkhof, Rik; Murata, Akihiko; Miller, Lisa A.; Greeley, Dana

2012-09-01

Based on measurements from the WOCE/JGOFS global CO2 survey, the CLIVAR/CO2 Repeat Hydrography Program and the Canadian Line P survey, we have observed an average decrease of 0.34% yr-1 in the saturation state of surface seawater in the Pacific Ocean with respect to aragonite and calcite. The upward migrations of the aragonite and calcite saturation horizons, averaging about 1 to 2 m yr-1, are the direct result of the uptake of anthropogenic CO2 by the oceans and regional changes in circulation and biogeochemical processes. The shoaling of the saturation horizon is regionally variable, with more rapid shoaling in the South Pacific where there is a larger uptake of anthropogenic CO2. In some locations, particularly in the North Pacific Subtropical Gyre and in the California Current, the decadal changes in circulation can be the dominant factor in controlling the migration of the saturation horizon. If CO2 emissions continue as projected over the rest of this century, the resulting changes in the marine carbonate system would mean that many coral reef systems in the Pacific would no longer be able to sustain a sufficiently high rate of calcification to maintain the viability of these ecosystems as a whole, and these changes perhaps could seriously impact the thousands of marine species that depend on them for survival.

Integrated Approach for Understanding Impurity Adsorption on Calcite: Mechanisms for Micro-scale Surface Phenomena

NASA Astrophysics Data System (ADS)

Vinson, M. D.; Arvidson, R. S.; Luttge, A.

2004-12-01

A longstanding goal within the field of environmental geochemistry has been the development of a fundamental understanding of the kinetics that governs the interactions of solution-borne impurities with the calcite mineral surface. Recent dissolution experiments using Mg2+, Mn2+, and Sr2+ have shown distinct differences in the interaction of these three impurity ions with the calcite crystal surface. Because the dissolution of carbonate minerals in soils and sediments influences the uptake and migration of groundwater contaminants, a rigorous understanding of the basic processes that occur at the mineral-fluid interface is necessary. We have used vertical scanning interferometry (VSI) coupled with scanning probe microscopy (SPM) to examine calcite crystal dissolution in the presence of Mg2+, Mn2+, and Sr2+, all known dissolution inhibitors and possible groundwater contaminants. We have studied the kinetics of impurity-crystal interactions at a pH 8.8, and in the presence or absence of dissolved inorganic carbon. Our data show that, when individually introduced into undersaturated solutions, Mg2+ and Mn2+ are shown to activate the calcite crystal surface, resulting in enhanced etch pit nucleation rates and step density. Conversely, Sr2+ is shown to cause passivation of the calcite surface. The effect is intensified when solutions are saturated with respect to atmospheric CO2. Results indicate that aqueous CO32- (or HCO3-) may influence how aqueous metal ionic complexes interact with the crystal surface. Furthermore, the influence is differently exhibited, and passivation or activation ultimately depends on the properties of the diffusing metal ion or metal-hydroxide complex. These properties include for example, differences in hydration enthalpy, the effective ionic radius, and electron shell configuration.

From Peptides to Proteins: Systematic Control of Net Molecular Charge and Hydrophilicity on the Kinetics of Calcite Growth

NASA Astrophysics Data System (ADS)

Elhadj, S.; de Yoreo, J. J.; Hoyer, J. J.; Dove, P. M.

2006-12-01

The compartment-specific compositions of biologic molecules isolated from biominerals suggest that control of mineral growth may be linked to biochemical features. Here we define a systematic relationship between the ability of biomolecules in solution to promote the growth of calcite (CaCO3) and their net negative molecular charge and hydrophilicity. The degree of enhancement is dependent on peptide composition, but not on peptide sequence. Data analysis shows that this rate enhancement arises from an increase in the kinetic coefficient. We interpret the mechanism of growth enhancement to be a catalytic process whereby biomolecules reduce the magnitude of the diffusive barrier, Ek, by perturbations that displace water molecules- a water shell destruction mechanism. The result is a decrease in the repulsive barrier for attachment of solutes to the solid phase. This previously unrecognized relationship also rationalizes recently reported data showing acceleration of calcite growth rates over rates measured in the pure system by nanomolar levels of abalone nacre proteins. These findings show that the growth-modifying properties of small model peptides may be scaled up to analyze mineralization processes that are mediated by more complex proteins. We suggest that enhancement of calcite growth may now be estimated a priori from the composition of peptide sequences and the calculated values of hydrophilicity and net molecular charge without need for detailed tests for each biomolecule. This insight may contribute to an improved understanding of mineralization in diverse systems of biomineralization.

Inhibiting Effect of Additives on Pressure Solution of Calcite

NASA Astrophysics Data System (ADS)

Traskine, V.; Skvortsova, Z.; Badun, G.; Chernysheva, M.; Simonov, Ya.; Gazizullin, I.

2018-05-01

The task of protection of cultural heritage requires a better understanding of combined effects of mechanical and chemical factors involved in environmental deterioration of monuments. The present paper deals with extending some known physicochemical methods proposed for inhibiting the decay of unstressed materials to their study during water-assisted deformation. The tests have been carried out on natural limestone samples and calcite powders in CaCO3 saturated aqueous solutions under static loads causing measurable pressure solution creep. In the solutions containing 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotriacetic acid, or ethylenediaminetetraacetic acid, the creep rate decreases considerably with increasing concentration of additives. The extent of creep deceleration has been found to be proportional to the independently estimated calcite surface area occupied by adsorbed species. This fact enables us to discriminate the adsorption-induced effect from other variables controlling the pressure solution rate and may be used in screening of compounds able to minimize the environmental impact on marble and limestone objects undergoing mechanical stresses.

Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

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

NASA Technical Reports Server (NTRS)

Bell, Mary S.

2009-01-01

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

Reaction kinetics of dolomite rim growth

NASA Astrophysics Data System (ADS)

Helpa, V.; Rybacki, E.; Abart, R.; Morales, L. F. G.; Rhede, D.; Jeřábek, P.; Dresen, G.

2014-04-01

Reaction rims of dolomite (CaMg[CO3]2) were produced by solid-state reactions at the contacts of oriented calcite (CaCO3) and magnesite (MgCO3) single crystals at 400 MPa pressure, 750-850 °C temperature, and 3-146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO3 interface with length ranging from about 6 to 41 µm. At the same time, a 5-71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO3. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12-80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E a (CaO) = 192 ± 54 kJ/mol and E a (MgO) = 198 ± 44 kJ/mol, respectively.

An Exercise on Calibration: DRIFTS Study of Binary Mixtures of Calcite and Dolomite with Partially Overlapping Spectral Features

ERIC Educational Resources Information Center

De Lorenzi Pezzolo, Alessandra

2013-01-01

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

Fluid-inclusion technique for determining maximum temperature in calcite and its comparison to the vitrinite reflectance geothermometer

USGS Publications Warehouse

Barker, C.E.; Goldstein, R.H.

1990-01-01

The hypothesis that aqueous fluid inclusions in calcite can be used to establish maximum temperature (Tpeak) is tested. Fluid inclusion Th, mean random vitrinite reflectance (Rm), and present-day Tpeak from 46 diverse geologic systems that have been at Tpeak from 104 to 106 yr have been compiled. Present Tpeak ranged from 65 to 345??C, Th modes and means ranged from 59 to 350??C, and Rm data ranged from 0.4% to 4.6%, spanning the temperature and thermal maturity range associated with burial diagenesis, hydrothermal alteration, and low-grade metamorphism. Plots of Th and Tpeak data for systems thought to be currently at maximum temperature demonstrate close agreement between Th and present Tpeak in sedimentary basins. The relation suggests that Th of aqueous fluid inclusions in calcite may be a useful measure of maximum temperature. This study also compared Th to mean random vitrinite reflectance (Rm). Th correlates well with Rm and results in a curve similar to Rm vs. Tpeak calibrations determined by other workers. Strong correlation between Tpeak and Rm in these systems suggests that maximum temperature is the major control on thermal maturation. -after Authors

Chemical Evidence for Episodic Growth of a Fibrous Antitaxial Calcite Vein From Externally Derived Fluid

NASA Astrophysics Data System (ADS)

Barker, S. L.; Cox, S. F.; Eggins, S. M.; Gagan, M. K.

2005-12-01

Fibrous, massive and crustiform textured quartz and calcite veins occur within a deformed limestone-shale sequence at Taemas, in the Lachlan Fold Belt, eastern New South Wales, Australia. Stable isotope analyses of veins and host rock indicate that these veins formed from upwardly migrating, externally derived fluids. High spatial resolution (100 μm) analyses reveal per mil scale variations of stable C and O isotope ratios, and radiogenic Sr isotope ratios in a 1.5 cm thick, fibrous, antitaxial-growth calcite vein. LA-ICP-MS analyses (30 μm resolution) demonstrate significant variations in Fe, Mn, Sr, REE and Eu/Eu* parallel to the long axes of fibres. Stable and radiogenic isotopic ratio variations, and trace and REE concentration changes correlate with different cathodoluminesence zones, and slight changes in fibre orientation and thickness. The covariance of calcite textures and chemistry indicate that this fibrous vein grew episodically. Moreover, calcite in this vein was precipitated from externally derived fluid, which underwent variable fluid-rock interaction, and had a fluctuating oxidation state. This fibrous, antitaxial growth vein likely formed from fluid that migrated along fracture-controlled flow pathways.

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

NASA Astrophysics Data System (ADS)

Spalding, Jennifer; Schneider, David

2016-04-01

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

Fabrication of low-crystalline carbonate apatite foam bone replacement based on phase transformation of calcite foam.

PubMed

Maruta, Michito; Matsuya, Shigeki; Nakamura, Seiji; Ishikawa, Kunio

2011-01-01

Carbonate apatite (CO(3)Ap) foam may be an ideal bone substitute as it is sidelined to cancellous bone with respect to its chemical composition and structure. However, CO(3)Ap foam fabricated using α-tricalcium phosphate foam showed limited mechanical strength. In the present study, feasibility of the fabrication of calcite which could be a precursor of CO(3)Ap was studied. Calcite foam was successfully fabricated by the so-called "ceramic foam" method using calcium hydroxide coated polyurethane foam under CO(2)+O(2) atmosphere. Then the calcite foam was immersed in Na(2)HPO(4) aqueous solution for phase transformation based on dissolution-precipitation reaction. When CaO-free calcite foam was immersed in Na(2)HPO(4) solution, low-crystalline CO(3)Ap foam with 93-96% porosity and fully interconnected porous structure was fabricated. The compressive strength of the foam was 25.6 ± 6 kPa. In light of these results, we concluded that the properties of the precursor foam were key factors for the fabrication of CO(3)Ap foams.

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

USGS Publications Warehouse

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

2002-01-01

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

Calcite-forming bacteria for compressive strength improvement in mortar.

PubMed

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

2010-04-01

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

Technetium and iodine aqueous species immobilization and transformations in the presence of strong reductants and calcite-forming solutions: Remedial action implications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawter, Amanda R.; Garcia, Whitney L.; Kukkadapu, Ravi K.

At the Hanford Site in southeastern Washington State, radionuclide (Tc-99/I-129) laden liquid wastes have been discharged to ground, resulting in vadose zone contamination, which provides a continuous source of these contaminants to groundwater. The presence of multiple contaminants increases the complexity of finding viable remediation technologies to sequester vadose zone contaminants in situ and protect groundwater. Although previous studies have shown the efficiency of zero valent iron (ZVI) and sulfur modified iron (SMI) in reducing mobile Tc(VII) to immobile Tc(IV) and iodate incorporation into calcite, the coupled effects from simultaneously using these remedial technologies have not been previously studied. Inmore » this first-of-a-kind laboratory study, we used two efficient reductants (i.e., ZVI and SMI) and calcite-forming solutions to simultaneously remove aqueous Tc(VII) and iodate via reduction and incorporation, respectively. The results confirmed that Tc(VII) was rapidly removed from the aqueous phase via reduction to Tc(IV). ZVI removed Tc(VII) faster than SMI, although both had removed the same amount by the end of the experiments. Most of the aqueous iodate was rapidly transformed to iodide, and therefore was not incorporated into calcite, but instead remained in the aqueous phase. The iodate reduction to iodide was much faster than iodate incorporation into calcite, suggesting that this remedial pathway is not efficient in removing aqueous iodate when strong reductants are present. Other experiments suggested that iodate removal via calcite precipitation should occur first and then reductants should be added for Tc(VII) removal. Although ZVI can negatively impact microbial populations and thereby inhibit natural attenuation mechanisms, only changes in the makeup of the microbial community were observed. However, these changes in the microbial community may have an impact on remediation efforts in the long term that could not be seen in a short

Calcite-accumulating large sulfur bacteria of the genus Achromatium in Sippewissett Salt Marsh

PubMed Central

Salman, Verena; Yang, Tingting; Berben, Tom; Klein, Frieder; Angert, Esther; Teske, Andreas

2015-01-01

Large sulfur bacteria of the genus Achromatium are exceptional among Bacteria and Archaea as they can accumulate high amounts of internal calcite. Although known for more than 100 years, they remain uncultured, and only freshwater populations have been studied so far. Here we investigate a marine population of calcite-accumulating bacteria that is primarily found at the sediment surface of tide pools in a salt marsh, where high sulfide concentrations meet oversaturated oxygen concentrations during the day. Dynamic sulfur cycling by phototrophic sulfide-oxidizing and heterotrophic sulfate-reducing bacteria co-occurring in these sediments creates a highly sulfidic environment that we propose induces behavioral differences in the Achromatium population compared with reported migration patterns in a low-sulfide environment. Fluctuating intracellular calcium/sulfur ratios at different depths and times of day indicate a biochemical reaction of the salt marsh Achromatium to diurnal changes in sedimentary redox conditions. We correlate this calcite dynamic with new evidence regarding its formation/mobilization and suggest general implications as well as a possible biological function of calcite accumulation in large bacteria in the sediment environment that is governed by gradients. Finally, we propose a new taxonomic classification of the salt marsh Achromatium based on their adaptation to a significantly different habitat than their freshwater relatives, as indicated by their differential behavior as well as phylogenetic distance on 16S ribosomal RNA gene level. In future studies, whole-genome characterization and additional ecophysiological factors could further support the distinctive position of salt marsh Achromatium. PMID:25909974

Calcite-accumulating large sulfur bacteria of the genus Achromatium in Sippewissett Salt Marsh.

PubMed

Salman, Verena; Yang, Tingting; Berben, Tom; Klein, Frieder; Angert, Esther; Teske, Andreas

2015-11-01

Large sulfur bacteria of the genus Achromatium are exceptional among Bacteria and Archaea as they can accumulate high amounts of internal calcite. Although known for more than 100 years, they remain uncultured, and only freshwater populations have been studied so far. Here we investigate a marine population of calcite-accumulating bacteria that is primarily found at the sediment surface of tide pools in a salt marsh, where high sulfide concentrations meet oversaturated oxygen concentrations during the day. Dynamic sulfur cycling by phototrophic sulfide-oxidizing and heterotrophic sulfate-reducing bacteria co-occurring in these sediments creates a highly sulfidic environment that we propose induces behavioral differences in the Achromatium population compared with reported migration patterns in a low-sulfide environment. Fluctuating intracellular calcium/sulfur ratios at different depths and times of day indicate a biochemical reaction of the salt marsh Achromatium to diurnal changes in sedimentary redox conditions. We correlate this calcite dynamic with new evidence regarding its formation/mobilization and suggest general implications as well as a possible biological function of calcite accumulation in large bacteria in the sediment environment that is governed by gradients. Finally, we propose a new taxonomic classification of the salt marsh Achromatium based on their adaptation to a significantly different habitat than their freshwater relatives, as indicated by their differential behavior as well as phylogenetic distance on 16S ribosomal RNA gene level. In future studies, whole-genome characterization and additional ecophysiological factors could further support the distinctive position of salt marsh Achromatium.

The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals

PubMed Central

Freeman, Colin L.; Gong, Xiuqing; Levenstein, Mark A.; Wang, Yunwei; Kulak, Alexander; Anduix‐Canto, Clara; Lee, Phillip A.; Li, Shunbo; Chen, Li; Christenson, Hugo K.

2017-01-01

Abstract As crystallization processes are often rapid, it can be difficult to monitor their growth mechanisms. In this study, we made use of the fact that crystallization proceeds more slowly in small volumes than in bulk solution to investigate the effects of the soluble additives Mg2+ and poly(styrene sulfonate) (PSS) on the early stages of growth of calcite crystals. Using a “Crystal Hotel” microfluidic device to provide well‐defined, nanoliter volumes, we observed that calcite crystals form via an amorphous precursor phase. Surprisingly, the first calcite crystals formed are perfect rhombohedra, and the soluble additives have no influence on the morphology until the crystals reach sizes of 0.1–0.5 μm for Mg2+ and 1–2 μm for PSS. The crystals then continue to grow to develop morphologies characteristic of these additives. These results can be rationalized by considering additive binding to kink sites, which is consistent with crystal growth by a classical mechanism. PMID:28767197

Controlling the size and morphology of precipitated calcite particles by the selection of solvent composition

NASA Astrophysics Data System (ADS)

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

2017-11-01

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.

Effect of airborne particle on SO 2-calcite reaction

NASA Astrophysics Data System (ADS)

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

1999-02-01

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

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Peptides Enhance Mg Content of Calcite: Toward a Process-Based Understanding of Proxy Models

NASA Astrophysics Data System (ADS)

Dove, P.; Stephenson, A.; Wu, L.; Wu, K.; de Yoreo, J.; Hoyer, J.

2008-12-01

Investigations of modern organisms relating magnesium content of calcified skeletons to temperature often exhibit unexplained deviations from the signature expected for inorganically precipitated calcite. These 'vital effects' are believed to have kinetic and taxonomic origins but the mechanistic basis for measured offsets remains unclear. A complicating factor is that mineralization is isolated from the external environment within an organic-rich matrix whose roles in mineralization are implicated but not well understood. Here we show that a simple hydrophilic peptide, sharing the same acidic character as macromolecules isolated from sites of calcification, increases the magnesium content of calcite up to 3 mol%. Using in situ AFM, we demonstrate that (Asp3Gly)6Asp3 also enhances growth rate and step edge energy of calcite compared to inorganic controls. Kinetic and thermodynamic measurements indicate that biomolecules interact with calcite surfaces to lower the energy barrier to desolvating the more strongly hydrated magnesium ion, thereby increasing the probability of its incorporation relative to calcium. Comparisons to previous studies that correlate Mg content of carbonate minerals with temperature show this peptide-induced Mg- enhancement is equivalent to offsets of several degrees Centigrade. The findings suggest local macromolecule chemistry influences Mg signatures- a plausible origin of vital effects. Further, studies of nonskeletal carbonates have long-asked whether the natural marine humic and protein substances found in sedimentary environments may influence mineralization. These insights provide a physical basis for anecdotal evidence that organic chemistry modulates the mineralization of inorganic carbonates.

Clumped isotope thermometry of calcite and dolomite in a contact metamorphic environment

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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

USGS Publications Warehouse

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

2000-01-01

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

3D calcite heterostructures for dynamic and deformable mineralized matrices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yi, Jaeseok; Wang, Yucai; Jiang, Yuanwen

Scales are rooted in soft tissues, and are regenerated by specialized cells. The realization of dynamic synthetic analogues with inorganic materials has been a significant challenge, because the abiological regeneration sites that could yield deterministic growth behavior are hard to form. Here we overcome this fundamental hurdle by constructing a mutable and deformable array of three-dimensional calcite heterostructures that are partially locked in silicone. Individual calcite crystals exhibit asymmetrical dumbbell shapes and are prepared by a parallel tectonic approach under ambient conditions. Furthermore, the silicone matrix immobilizes the epitaxial nucleation sites through self-templated cavities, which enables symmetry breaking in reactionmore » dynamics and scalable manipulation of the mineral ensembles. With this platform, we devise several mineral-enabled dynamic surfaces and interfaces. For example, we show that the induced growth of minerals yields localized inorganic adhesion for biological tissue and reversible focal encapsulation for sensitive components in flexible electronics.« less

3D calcite heterostructures for dynamic and deformable mineralized matrices

DOE PAGES

Yi, Jaeseok; Wang, Yucai; Jiang, Yuanwen; ...

2017-09-11

Scales are rooted in soft tissues, and are regenerated by specialized cells. The realization of dynamic synthetic analogues with inorganic materials has been a significant challenge, because the abiological regeneration sites that could yield deterministic growth behavior are hard to form. Here we overcome this fundamental hurdle by constructing a mutable and deformable array of three-dimensional calcite heterostructures that are partially locked in silicone. Individual calcite crystals exhibit asymmetrical dumbbell shapes and are prepared by a parallel tectonic approach under ambient conditions. Furthermore, the silicone matrix immobilizes the epitaxial nucleation sites through self-templated cavities, which enables symmetry breaking in reactionmore » dynamics and scalable manipulation of the mineral ensembles. With this platform, we devise several mineral-enabled dynamic surfaces and interfaces. For example, we show that the induced growth of minerals yields localized inorganic adhesion for biological tissue and reversible focal encapsulation for sensitive components in flexible electronics.« less

Flotation selectivity of novel alkyl dicarboxylate reagents for apatite-calcite separation.

PubMed

Karlkvist, Tommy; Patra, Anuttam; Rao, Kota Hanumantha; Bordes, Romain; Holmberg, Krister

2015-05-01

The investigation aims to demonstrate the conceptual thoughts behind developing mineral specific reagents for use in flotation of calcium containing ores. For this purpose, a series of dicarboxylate-based surfactants with varying distance between the carboxylate groups (one, two or three methylene groups) was synthesized. A surfactant with the same alkyl chain length but with only one carboxylate group was also synthesized and evaluated. The adsorption behavior of these new reagents on pure apatite and pure calcite surfaces was studied using Hallimond tube flotation, FTIR and ζ potential measurements. The relation between the adsorption behavior of a given surfactant at a specific mineral surface and its molecular structure over a range of concentrations and pH values, as well as the region of maximum recovery, was established. It was found that one of the reagents, with a specific distance between the carboxylate groups, was much more selective for a particular mineral surface than the other homologues. For example, out of the four compounds synthesized, only the one where the carboxylate groups were separated by a single methylene group floated apatite but not calcite, whereas calcite was efficiently floated with the monocarboxylic reagent, but not with the other reagents synthesized. This selective adsorption of a given surfactant to a particular mineral surface relative to other mineral surfaces as evidenced in the flotation studies was substantiated by ζ potential and infra-red spectroscopy data. Copyright © 2014 Elsevier Inc. All rights reserved.

Geochemical characteristics of the San Miguel aquifer, Baja California, Mexico.

NASA Astrophysics Data System (ADS)

Tostado-Plascencia, Miriam; Rosas-Elguera, Jose; Kretzschmar, Thomas

2010-05-01

The valley of San Miguel, located in the state of Baja California, Mexico, is an important region because of the wine industry. It is therefore important to know groundwater characteristics. Two aquifers can be recognized in the San Miguel basin, first one is in fractured granitic rocks (in the upper part of the basin, called UB) and other is free-type in detritc sediments (in the lower part of the basin, close to the sea, called LB). The water temperature ranges between 25°C y 11°C without significant variations along the year. The conductivity increases with the water temperature and decreases in February when the temperature is lower. The pH of the waters in UB is between 8.5 and 6.5 but in the LB is in the range of 6.8 to 7.3. Our data show that Na, Mg, and HCO3- concentrations decrease during the rainy season due to ion exchange. According to the Stiff diagrams the waters of the LB are classified as sodium chloride. In the UB the water classification includes calcium and magnesium bicarbonate, magnesium chloride, and few calcium chloride and sodium chloride. The saturation indexes of the waters suggest that the mineral phases which can be present are: K-feldspar, gibbsite, albite, quartz, calcite, aragonite, gypsum, and magnesite. Because of SI>0 then the first four phases can precipitate but the SI of magnesite and gypsum is negative thus the can be dissolved. Finally, calcite and aragonite are in equilibrium due to they are close to zero. Our results suggest that the aquifers of the San Miguel basin do not show evidence of saline intrusion.

Subglacial Calcites from Northern Victoria Land: archive of Antarctic volcanism in the Last Glacial Maximum

NASA Astrophysics Data System (ADS)

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

2017-04-01

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.

The effect of CO2-fluid-rock interactions on the porosity and permeability of calcite-bearing sandstone

NASA Astrophysics Data System (ADS)

Lamy-Chappuis, B.; Yardley, B.; Grattoni, C.

2013-12-01

Brine acidification following CO2 dissolution will initiate fluid-rock interactions that could significantly modify porosity, permeability and therefore the capacity and injectivity of a reservoir. We have investigated experimentally the dissolution of calcite in sandstone cores injected with CO2-saturated brine, and the effect this has on permeability. A series of CT (Computerized Tomography) - monitored experiments were conducted on a Jurassic sandstone (porosity = 30%, permeability = 10mD, calcite content = 5% in the form of dispersed shell fragments). Brine saturated with CO2 at pressures up to 1 MPa was injected into 5cm long, 3.75cm diameter cores at a flow rate of 1 ml/min and room temperature. The data showed quasi-instantaneous dissolution of the calcite even at low CO2 concentrations (0.15 Molar) and high fluid interstitial velocities (1mm/s), with the migration of a calcite dissolution front through the core recorded by successive CT scans. The resulting permeability increase was 60 - 80% whereas the predicted permeability change for the observed increase in porosity is only 10 - 20% using the Kozeny-Carman relationship. This result is particularly significant because the effect of porosity increase on permeability is usually modelled with this relationship, irrespective of the mechanism of porosity increase. Micro-CT scans (pixel resolution: 2.5 microns) of unreacted cores were used to generate 3D porosity models with calcite either treated as solid (pre-reaction model) or converted to pores (post-reaction model). FLUENT simulations performed using these models predicted the observed large relative changes in permeability with calcite dissolution but overestimated absolute permeability by an order of magnitude. This was probably due to the scan resolution being too coarse to correctly model pore throats. The observed large change in permeability for a small change in porosity may have resulted from increase in connectivity, focused dissolution at the

Relative Abundances of Calcite and Silica in Fracture Coatings as a Possible Indicator of Evaporation in a Thick Unsaturated Zone, Yucca Mountain, Nevada

NASA Astrophysics Data System (ADS)

Marshall, B. D.; Moscati, R. J.

2005-12-01

Yucca Mountain, a ridge of shallowly dipping, Miocene-age volcanic rocks in southwest Nevada, is the proposed site for a nuclear waste repository to be constructed in the 500- to 700-m-thick unsaturated zone (UZ). At the proposed repository, the 300-m-thick Topopah Spring Tuff welded unit (TSw) is overlain by approximately 30 m of nonwelded tuffs (PTn); the Tiva Canyon Tuff welded unit (TCw) overlies the PTn with a range in thickness from 0 to approximately 130 m at the site. The amount of water percolation through the UZ is low and difficult to measure directly, but local seepage into mined tunnels has been observed in the TCw. Past water seepage in the welded tuffs is recorded by widespread, thin (0.3 cm) coatings of calcite and silica on fracture surfaces and within cavities. Abundances of calcite and silica in the coatings were determined by X-ray microfluorescence mapping and subsequent multispectral image analysis of over 200 samples. The images were classified into constituent phases including opal-chalcedony-quartz (secondary silica) and calcite. In the TCw samples, the median calcite/silica ratio is 8; in the TSw samples within 35 m below the PTn, median calcite/silica falls to 2, perhaps reflecting an increase in soluble silica from the presence of glass in the nonwelded tuffs. In the deeper parts of the TSw, median calcite/silica reaches 100 and many samples contain no detectable secondary silica phase. Evaporation and changing pCO2 control precipitation of calcite from water percolating downward in the UZ, but precipitation of opal requires only evaporation. Calcite/silica ratios, therefore, can constrain the relative importance of evaporation in the UZ. Although calcite/silica values scatter widely within the TSw, reflecting the spatial variability of gas and water flow, average calcite/silica ratios increase with stratigraphic depth, indicating less evaporation at the deeper levels of the UZ. Coupled with the much smaller calcite/silica ratios

Mineral contents and their solubility on calcium carbonat calcite nanocrystals from cockle shell powder (Anadara granosa Linn)

NASA Astrophysics Data System (ADS)

Widyastuti, S.; Pramushinta, I. A.

2018-03-01

Prepared and characterized calcium carbonat calcite nanocrystals improves solubility. Calcium carbonat calcite nanocrystals were synthesized using precipitation method from the waste of blood clam cockle shells (Anadara granosa Linn). This study was conducted to analyze mineral composition of nanocrystals calcium carbonat calcite cockle (Anadara granosa) shell for calcium fortification of food applications and to evaluate the solubilities of Calsium and Phospor. The sample of nanocrystals from cockle shells was evaluated to determine the content of 11 macro-and micro-elements. These elements are Calcium (Ca), Magnesium (Mg), Sodium (Na), Phosphorus (P), Potassium (K), Ferrum (Fe), Copper (Cu), Nickel (Ni), Zink (Zn), Boron (B) and Silica (Si)). Cockleshell powders were found to contain toxic elements below detectable levels. The solubilities of Calcium and Phospor were p<0.05.

Technetium and iodine aqueous species immobilization and transformations in the presence of strong reductants and calcite-forming solutions: Remedial action implications.

PubMed

Lawter, Amanda R; Garcia, Whitney L; Kukkadapu, Ravi K; Qafoku, Odeta; Bowden, Mark E; Saslow, Sarah A; Qafoku, Nikolla P

2018-04-30

At the Hanford Site in southeastern Washington, discharge of radionuclide laden liquid wastes resulted in vadose zone contamination, providing a continuous source of these contaminants to groundwater. The presence of multiple contaminants (i.e., 99 Tc and 129 I) increases the complexity of finding viable remediation technologies to sequester contaminants in situ and protect groundwater. Although previous studies have shown the efficiency of zero valent iron (ZVI) and sulfur modified iron (SMI) in reducing mobile Tc(VII) to immobile Tc(IV) and iodate incorporation into calcite, the coupled effects from simultaneously using these remedial technologies have not been previously studied. In this first-of-a-kind laboratory study, we used reductants (ZVI or SMI) and calcite-forming solutions to simultaneously remove aqueous Tc(VII) and iodate via reduction and incorporation, respectively. The results confirmed that Tc(VII) was rapidly removed from the aqueous phase via reduction to Tc(IV). Most of the aqueous iodate was transformed to iodide faster than incorporation into calcite occurred, and therefore the I remained in the aqueous phase. These results suggested that this remedial pathway is not efficient in immobilizing iodate when reductants are present. Other experiments suggested that iodate removal via calcite precipitation should occur prior to adding reductants for Tc(VII) removal. When microbes were included in the tests, there was no negative impact on the microbial population but changes in the makeup of the microbial community were observed. These microbial community changes may have an impact on remediation efforts in the long-term that could not be seen in a short-term study. The results underscore the importance of identifying interactions between natural attenuation pathways and remediation technologies that only target individual contaminants. Copyright © 2018 Elsevier B.V. All rights reserved.

Common Ion Effects In Zeoponic Substrates: Dissolution And Cation Exchange Variations Due to Additions of Calcite, Dolomite and Wollastonite

NASA Technical Reports Server (NTRS)

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

2003-01-01

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

Constraints on Neogene deformation in the southern Terror Rift from calcite twinning analyses of veins within the ANDRILL MIS core, Victoria Land Basin, Antarctica

NASA Astrophysics Data System (ADS)

Paulsen, T. S.; Demosthenous, C.; Wilson, T. J.; Millan, C.

2009-12-01

The ANDRILL MIS (McMurdo Ice Shelf) Drilling Project obtained over 1200 meters of Neogene sedimentary and volcanic rocks in 2006/2007. Systematic fracture logging of the AND-1B core identified 1,475 natural fractures, i.e. pre-existing fractures in the rock intersected by coring. The most abundant natural fractures are normal faults and calcite veins; reverse faults, brecciated zones, and sedimentary intrusions are also present. In order to better understand Neogene deformation patterns within the southern Terror Rift, we have been conducting strain analyses on mechanically twinned calcite within healed fractures in the drill core. Twinning strains using all of the data from each sample studied to date range from 2% to 10%. The cleaned data (20% of the largest magnitude deviations removed) typically show ≤30% negative expected values, consistent with a single deformation episode or multiple ~coaxial deformation episodes. The majority of the samples record horizontal extension, similar to strain patterns expected in a normal fault regime and/or vertical sedimentary compaction in a continental rift system. The morphology, width, and intensity of twins in the samples suggest that twinning typically occurred at temperatures <170° C. Twinning intensities suggest differential stress magnitudes that caused the twinning ranged from 216 to 295 MPa.

Simple, simultaneous gravimetric determination of calcite and dolomite in calcareous soils

USDA-ARS?s Scientific Manuscript database

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...

Quantifying the impact of early calcite cementation on the reservoir quality of carbonate rocks: A 3D process-based model

NASA Astrophysics Data System (ADS)

Hosa, Aleksandra; Wood, Rachel

2017-06-01

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.

Effects of limestone petrography and calcite microstructure on OPC clinker raw meals burnability

NASA Astrophysics Data System (ADS)

Galimberti, Matteo; Marinoni, Nicoletta; Della Porta, Giovanna; Marchi, Maurizio; Dapiaggi, Monica

2017-10-01

Limestone represents the main raw material for ordinary Portland cement clinker production. In this study eight natural limestones from different geological environments were chosen to prepare raw meals for clinker manufacturing, aiming to define a parameter controlling the burnability. First, limestones were characterized by X-Ray Fluorescence, X-Ray Powder Diffraction and Optical Microscopy to assess their suitability for clinker production and their petrographic features. The average domains size and the microstrain of calcite were also determined by X-Ray Powder Diffraction line profile analysis. Then, each limestone was admixed with clay minerals to achieve the adequate chemical composition for clinker production. Raw meals were thermally threated at seven different temperatures, from 1000 to 1450 °C, to evaluate their behaviour on heating by ex situ X-Ray Powder Diffraction and to observe the final clinker morphology by Scanning Electron Microscopy. Results indicate the calcite microstrain is a reliable parameter to predict the burnability of the raw meals, in terms of calcium silicates growth and lime consumption. In particular, mixtures prepared starting from high-strained calcite exhibit a better burnability. Later, when the melt appears this correlation vanishes; however differences in the early burnability still reflect on the final clinker composition and texture.

Mineralogical, crystallographic, and isotopic constraints on the precipitation of aragonite and calcite at Shiqiang and other hot springs in Yunnan Province, China

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2016-11-01

Two active spring vent pools at Shiqiang (Yunnan Province, China) are characterized by a complex array of precipitates that coat the wall around the pool and the narrow ledges that surround the vent pool. These precipitates include arrays of aragonite crystals, calcite cone-dendrites, red spar calcite, unattached dodecahedral and rhombohedral calcite crystals, and late stage calcite that commonly coats and disguises the earlier formed precipitates. Some of the microbial mats that grow on the ledges around the pools have been partly mineralized by microspheres that are formed of Si and minor amounts of Fe. The calcite and aragonite that are interspersed with each other at all scales are both primary precipitates. Some laminae, for example, change laterally from aragonite to calcite over distances of only a few millimetres. The precipitates at Shiqiang are similar to precipitates found in and around the vent pools of other springs found in Yunnan Province, including those at Gongxiaoshe, Zhuyuan, Eryuan, and Jifei. In all cases, the δDwater and δ18Owater indicate that the spring water is of meteoric origin. These are thermogene springs with the carrier CO2 being derived largely from the mantle and reaction of the waters with bedrock. Variations in the δ13Ctravertine values indicate that the waters in these springs were mixed, to varying degrees, with cold groundwater and its soil-derived CO2. Calcite and aragonite precipitation took place once the spring waters had become supersaturated with respect to CaCO3, probably as a result of rapid CO2 degassing. These precipitates, which were not in isotopic equilibrium with the spring water, are characterized by their unusual crystal morphologies. The precipitation of calcite and aragonite, seemingly together, can probably be attributed to microscale variations in the saturation levels that are, in turn, attributable to microscale variations in the rate of CO2 degassing.

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

NASA Astrophysics Data System (ADS)

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

2005-12-01

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

Effect of organic ligands on Mg partitioning and Mg isotope fractionation during low-temperature precipitation of calcite in the absence of growth rate effects

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Immenhauser, Adrian; Buhl, Dieter; Purgstaller, Bettina; Baldermann, Andre; Dietzel, Martin

2017-06-01

Calcite growth rate has been previously shown to be the dominating parameter controlling both Mg partitioning and Mg isotope fractionation during calcite growth. In natural calcite precipitation environments - characterized by abundant organic material - the presence of dissolved organic molecules may affect these two parameters. In order to assess the role of organic molecules, steady state calcite growth experiments have been performed at 25 °C, 1 bar pCO2 and constant, within analytical uncertainty growth rate (rp = 10-7.4 mol m-2 s-1) in the presence of aqueous Mg and six organic ligands in the concentration range from 0.01 to 10 mM. The organic ligands used in this study are: (i) acetic acid, (ii) citric acid, (iii) glutamic acid, (iv) salycilic acid, (v) glycine, and (vi) ethylenediaminetetraacetic acid (EDTA). These contain one or more carboxyl- and amino-groups that are commonly present in natural organic substances found in lacustrine, fluvial, soil, cave, as well as in marine and earliest diagenetic porewater environments. Results shown here indicate that the presence of these carboxyl- and amino-groups promotes an increase in the partition coefficient of Mg in calcite (DMg = (Mg/Ca)calcite/(Mg/Ca)fluid) that can be attributed to their adsorption onto the calcite surfaces and the subsequent reduction of the active sites of growth. This increase of DMg values as a function of the supersaturation degree of calcite in the fluid phase can be described by the linear equation:

Heteroepitaxial growth of cadmium carbonate at dolomite and calcite surfaces: Mechanisms and rates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Callagon, Erika Blanca R.; Lee, Sang Soo; Eng, Peter J.

Here, the systematic variation of rates and the mechanism of cadmium uptake on the (104) surface of dolomite (CaMg(CO 3) 2) were investigated using in situ and ex situ atomic force microscopy (AFM), ex situ specular X-ray reflectivity (XR), and ex situ X-ray fluorescence (XRF). Selected experiments were performed on the calcite (CaCO 3) (104) surface for comparison. Aqueous solutions of CdCl 2, CaCl 2, and NaHCO 3, undersaturated with respect to calcite and supersaturated with respect to otavite (CdCO 3) and the (Cd xCa 1-x)CO 3 solid solution, were reacted with dolomite surfaces for minutes to days. Calcite substratesmore » were reacted with solutions containing 1-50 μM CdCl 2, and with no added Ca or CO 3. Thin carbonate films following the Stranski-Krastanov growth mode were observed on both substrates. Specular XR and XRF revealed the formation of nm-thick Cd-rich carbonate films that were structurally ordered with respect to the dolomite (104) plane. Epitaxial films adopted the calcite crystal structure with a d 104- spacing (3.00 Å) larger than those of pure dolomite (2.88 Å) and otavite (2.95 Å) indicating either a solid solution with x approximate to 0.5, or a strained Cd-rich carbonate with a composition near that of otavite. The growth rate r of this phase increases with the initial supersaturation of the solution with respect to the solid solution, beta max, and follows the empirical relationship, as determined from XRF measurements, given by: r = 10 -4.88 ± 0.42 (β 2.29 ± 0.24 max - 1), (in units of atoms of Cd/Å 2/h).The morphology of the overgrowth also varied with β max, as exemplified by AFM observations. Growth at step edges occurred over the entire β max range considered, and additional growth features including 3 Å high monolayer islands and ~ 25 Å high tall islands were observed when log β max > 1. On calcite, in situ XR indicated that this phase is similar to the Cd-rich overgrowth formed on dolomite and images obtained from X

Heteroepitaxial growth of cadmium carbonate at dolomite and calcite surfaces: Mechanisms and rates

DOE PAGES

Callagon, Erika Blanca R.; Lee, Sang Soo; Eng, Peter J.; ...

2016-12-10

Here, the systematic variation of rates and the mechanism of cadmium uptake on the (104) surface of dolomite (CaMg(CO 3) 2) were investigated using in situ and ex situ atomic force microscopy (AFM), ex situ specular X-ray reflectivity (XR), and ex situ X-ray fluorescence (XRF). Selected experiments were performed on the calcite (CaCO 3) (104) surface for comparison. Aqueous solutions of CdCl 2, CaCl 2, and NaHCO 3, undersaturated with respect to calcite and supersaturated with respect to otavite (CdCO 3) and the (Cd xCa 1-x)CO 3 solid solution, were reacted with dolomite surfaces for minutes to days. Calcite substratesmore » were reacted with solutions containing 1-50 μM CdCl 2, and with no added Ca or CO 3. Thin carbonate films following the Stranski-Krastanov growth mode were observed on both substrates. Specular XR and XRF revealed the formation of nm-thick Cd-rich carbonate films that were structurally ordered with respect to the dolomite (104) plane. Epitaxial films adopted the calcite crystal structure with a d 104- spacing (3.00 Å) larger than those of pure dolomite (2.88 Å) and otavite (2.95 Å) indicating either a solid solution with x approximate to 0.5, or a strained Cd-rich carbonate with a composition near that of otavite. The growth rate r of this phase increases with the initial supersaturation of the solution with respect to the solid solution, beta max, and follows the empirical relationship, as determined from XRF measurements, given by: r = 10 -4.88 ± 0.42 (β 2.29 ± 0.24 max - 1), (in units of atoms of Cd/Å 2/h).The morphology of the overgrowth also varied with β max, as exemplified by AFM observations. Growth at step edges occurred over the entire β max range considered, and additional growth features including 3 Å high monolayer islands and ~ 25 Å high tall islands were observed when log β max > 1. On calcite, in situ XR indicated that this phase is similar to the Cd-rich overgrowth formed on dolomite and images obtained from X

Mineralogical Evidence for the Palaeohydrogeological Stability of a Deep Groundwater System in Fractured Rock, in West Cumbria, Northwest England

NASA Astrophysics Data System (ADS)

Milodowski, A. E.; Gillespie, M. R.; Chenery, S. R. N.; Naden, J.; Shaw, R. P.

2014-12-01

An important requirement of the safety assessment for a geological disposal facility (GDF) for radioactive waste is to be able to demonstrate the long-term chemical stability of the groundwater system at repository depth over the long period of time during which the waste will be a hazard, typically up to one million years. Of particular concern in the UK is the potential for oxidising groundwater to penetrate to repository depth during periods of glaciation, thereby increasing the mobility of some transuranic radionuclides.Between 1990 and 1998, United Kingdom Nirex Limited carried out geological investigations into the suitability of a potential site in the Sellafield area of NW England, for a GDF for L/ILW. As part of these investigations, detailed petrological analysis of fracture mineralisation in 23 deep boreholes identified a complex sequence of mineralisation events referred to as ME1-ME9. The distribution of the ME9 calcite mineralisation correlates closely with present-day groundwater flows. The ME9 calcite has been studied in more detail to understand the evolution of the deep groundwater system. The morphology and growth zoning characteristics of the calcites reflects the groundwater chemistry. Freshwater calcites display c-axis flattened to equant crystals, and are non-ferroan and strongly zoned with Mn-rich and Mn-free bands. Deeper saline-zone calcites display c-axis elongated crystals, with high Mn:Fe and low Mn:Fe growth zones. Calcite in the transition zone between the saline and fresh groundwater display saline-type cores overgrown by freshwater-type calcite, indicating a small depression of the position of the transition zone during the growth of the calcites. Sr isotope ratios and fluid inclusion chemistry confirm a link between ME9 calcite and the present regional groundwater system. Modelling of the oxygen isotope data indicates that some growth zones in the ME9 calcite precipitated from groundwater potentially containing a significant

Effect of otoconial proteins fetuin A, osteopontin, and otoconin 90 on the nucleation and growth of calcite

DOE PAGES

Hong, Mina; Moreland, K. Trent; Chen, Jiajun; ...

2014-10-30

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

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

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

PubMed Central

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

2016-01-01

Concrete, used in the construction of nuclear power plants (NPPs), may be exposed to radiation emanating from the reactor core. Until recently, concrete has been assumed immune to radiation exposure. Direct evidence acquired on Ar+-ion irradiated calcite and quartz indicates, on the contrary, that, such minerals, which constitute aggregates in concrete, may be significantly altered by irradiation. More specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, calcite only experiences random rotations, and distortions of its carbonate groups. As a result, irradiated quartz shows a reduction in density of around 15%, and an increase in chemical reactivity, described by its dissolution rate, similar to a glassy silica. Calcite however, shows little change in dissolution rate - although its density noted to reduce by ≈9%. These differences are correlated with the nature of bonds in these minerals, i.e., being dominantly ionic or covalent, and the rigidity of the mineral’s atomic network that is characterized by the number of topological constraints (nc) that are imposed on the atoms in the network. The outcomes have major implications on the durability of concrete structural elements formed with calcite or quartz bearing aggregates in nuclear power plants. PMID:26822012

Iodine-129 and iodine-127 speciation in groundwater at the Hanford site, US: iodate incorporation into calcite.

PubMed

Zhang, Saijin; Xu, Chen; Creeley, Danielle; Ho, Yi-Fang; Li, Hsiu-Ping; Grandbois, Russell; Schwehr, Kathleen A; Kaplan, Daniel I; Yeager, Chris M; Wellman, Dawn; Santschi, Peter H

2013-09-03

The geochemical transport and fate of radioiodine depends largely on its chemical speciation that is greatly affected by environmental factors. This study reports, for the first time, the speciation of stable and radioactive iodine in the groundwater from the Hanford Site. Iodate was the dominant species and accounted for up to 84% of the total iodine present. The alkaline pH (pH ∼ 8) and predominantly oxidizing environment may have prevented reduction of the iodate. In addition, groundwater samples were found to have large amounts of calcite precipitate which were likely formed as a result of CO2 degassing during removal from the deep subsurface (>70m depth). Further analyses indicated that between 7 and 40% of the dissolved (127)I and (129)I that was originally in the groundwater had coprecipitated in the calcite. Iodate was the main species incorporated into calcite and this incorporation process could be impeded by elevating the pH and decreasing ionic strength in groundwater. This study provides critical information for predicting the long-term fate and transport of (129)I. Furthermore, the common sampling artifact resulting in the precipitation of calcite by degassing CO2, had the unintended consequence of providing insight into a potential solution for the in situ remediation of groundwater (129)I.

Direct experimental evidence for differing reactivity alterations of minerals following irradiation. The case of calcite and quartz

DOE PAGES

Pignatelli, Isabella; Kumar, Aditya; Field, Kevin G.; ...

2016-01-29

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

Greenschist-Facies Pseudotachylytes and Gouge: a Microstructural Study of the Deformation Propagation at the Boundary Between Hp-Metabasite and Calcite Bearing Metasediments

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Crystallographic orientation inhomogeneity and crystal splitting in biogenic calcite

PubMed Central

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

2013-01-01

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

Ages and stable-isotope compositions of secondary calcite and opal in drill cores from Tertiary volcanic rocks of the Yucca Mountain area, Nevada

USGS Publications Warehouse

Szabo, B. J.; Kyser, T.K.

1990-01-01

Stable-isotope compositions of fracture- and cavity-filling calcite from the unsaturated zone of three drill cores at Yucca Mountain Tertiary volcanic complex indicate that the water from which the minerals precipitated was probably meteoric in origin. A decrease in 18O in the calcite with depth is interpreted as being due to the increase in temperature in drill holes corresponding to an estimated average geothermal gradient of 34?? per kilometer. A few of the calcite samples and all of the opal samples yielded uranium-series ages older than 400 000 yr, although most of the calcite samples yielded ages between 26 000 and 310 000 yr. The stable-isotope and uranium-series dates from precipitated calcite and opal of this reconnaissance study suggest a complex history of fluid movement through the volcanic pile, and episodes of fracture filling predominantly from meteoric water during at least the past 400 000 yr. -Authors

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

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2012-04-01

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

Physicochemical Processes and the Evolution of Strength in Calcite Fault Gouge at Room Temperature

NASA Astrophysics Data System (ADS)

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

2015-12-01

The presence of calcite in and near faults, as the dominant material, cement, or vein fill, indicates that the mechanical behavior of carbonate-dominated material likely plays an important role in shallow- and mid-crustal faulting. Furthermore, a variety of physical and chemical processes control the evolution of strength and style of slip along seismogenic faults and thus play a critical role in the seismic cycle. Determining the role and contributions of these types of mechanisms is essential to furthering our understanding of the processes and timescales that lead to the strengthening of faults during interseismic periods and their behavior during the earthquake nucleation process. To further our understanding of these processes, we performed laboratory-shearing experiments on calcite gouge at normal stresses from 1 to 100 MPa, under conditions of saturation and at room temperature. We performed velocity stepping (0.1-1000μm/s) and slide-hold-slide (1-3000s) tests, to measure the velocity dependence of friction and the amount of frictional strengthening respectively, under saturated conditions with pore fluid that was in equilibrium with CaCO3. At 5 MPa normal stress, we also varied the environmental conditions by performing experiments under conditions of 5% RH and 50 % RH, and saturation with: silicone oil, demineralized water, and the equilibrated solution combined with 0.5M NaCl. Finally, we collected post experimental samples for microscopic analysis. Our combined analyses of rate-dependence, strengthening behavior, and microstructures show that calcite fault gouge transitions from brittle to semi-brittle behavior at high normal stress and low sliding velocities. Furthermore, our results also highlight how changes in pore water chemistry can have significant influence on the mechanical behavior of calcite gouge in both the laboratory and in natural faults. Our observations have important implications for earthquake nucleation and propagation on faults in

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

USGS Publications Warehouse

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

1987-01-01

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

Exploring strategies to remove contaminants from subsurface plumes: iron-bearing materials and calcite

NASA Astrophysics Data System (ADS)

Lawter, A.; Qafoku, N. P.; Garcia, W.; Lee, B.; Freedman, V. L.

2017-12-01

At the Hanford site in eastern Washington, depending on the particular waste site, radionuclide (Tc99/I129) laden liquid waste was not of a sufficient volume to carry the contamination through the vadose zone to the groundwater. Contaminants are therefore retained in the vadose zone, which represents a continuous source of these contaminants to groundwater through flux created by precipitation recharge. Deployment of treatment technologies in the vadose zone that will intercept flow from vadose zone recharge and sequester contaminants is needed for future groundwater protection. In this study, first we tested zero valent iron (ZVI) and sulfur modified iron (SMI) to determine the feasibility of using these materials to intercept Tc migrating from the vadose zone into the groundwater. Secondly, this study focused on testing the ZVI and SMI in conjunction with several potential amendments needed for capture of additional contaminants present (e.g., IO3) to immobilize contaminants both individually and combined. Previous testing has shown removal of IO3 by incorporation into calcite; these experiments test the effect of ZVI/SMI on the efficiency of the removal of IO3 by calcite and vice versa. Preliminary results have shown strong removal of high Tc concentrations (i.e., 22 ppm or 44 ppm) at solid to solution ratios of 1 g to 100 mL, but when the solid and the Tc concentration was scaled down to more field relevant conditions (i.e., 0.42 ppm), the Tc removal was slower and the amount of Tc removed (per gram of Fe solid) was decreased. In some tests, results indicated that there is no interference from IO3 on Tc removal, but presence of ZVI/SMI has a negative impact on the removal of IO3 by calcite incorporation, likely due to the fast reduction of iodate to iodide by the ZVI/SMI (iodide is usually not incorporated into calcite).

Decoupling of Mg-C and Sr-Nd-O isotopes traces the role of recycled carbon in magnesiocarbonatites from the Tarim Large Igneous Province

NASA Astrophysics Data System (ADS)

Cheng, Zhiguo; Zhang, Zhaochong; Hou, Tong; Santosh, M.; Chen, Lili; Ke, Shan; Xu, Lijuan

2017-04-01

The Tarim Large Igneous Province in NW China hosts numerous magmatic carbonatite dikes along its northern margin. The carbonatites are composed mainly of dolomite (90 vol.%) and minor calcite (5 vol.%), with apatite, barite, celestine, aegirine, monazite and bastnaesite as accessory minerals. The rocks correspond to magnesiocarbonatites with a compositional range of 13.73-19.59 wt.% MgO, and 20.03-30.11 wt.% CaO, along with 1.65-3.31 wt.% total Fe2O3, 0.02-2.39 wt.% SiO2 and other minor elements, such as P2O5, Na2O and K2O. These magnesiocarbonatites are characterized by extreme enrichment in incompatible elements with high total rare earth element (REE) contents of 372-36965 ppm. The strontium [(87Sr/86Sr)i = 0.70378-0.70386], neodymium [εNd(t) = +2.51 - +3.59] and oxygen (δ18OV-SMOW = 5.9‰-8.0‰) isotope values of these rocks are consistent with a mantle origin, whereas the magnesium (δ26Mg = -1.09‰ to -0.85‰) and carbon (δ13CV-PDB = -4.1‰ to -5.9‰) isotopes are decoupled from mantle values and reflect signature of recycled sedimentary carbonates. Global plate tectonic models predict that sedimentary carbonates in convergent margins are subducted to deep domains in the mantle, with phase transitions from calcite/dolomite to magnesite, and eventually to periclase/perovskite. The involvement of a mantle plume enhances the normal mantle geotherms and promotes decomposition reactions of magnesite. The decoupling of Mg-C and Sr-Nd-O isotopes in the mangesiocarbonatites provides insights on the origin of carbonatites, and also illustrates a case of interaction between mantle plume and subduction-related components.

Characteristics of biogenic calcite in the prismatic layer of a pearl oyster, Pinctada fucata.

PubMed

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

2010-10-01

The fine structure of the calcite prism in the outer layer of a pearl oyster, Pinctada fucata, has been investigated using various electron beam techniques, in order to understand its characteristics and growth mechanism including the role of intracrystalline organic substances. As the calcite prismatic layer grows thicker, sinuous boundaries develop to divide the prism into a number of domains. The crystal misorientation between the adjacent domains is several to more than ten degrees. The component of the misorientation is mainly the rotation about the c-axis. There is no continuous organic membrane at the boundaries. Furthermore, the crystal orientation inside the domains changes gradually, as indicated by the electron back-scattered diffraction (EBSD) in a scanning electron microscope (SEM). Transmission electron microscopy (TEM) examination revealed that the domain consists of sub-grains of a few hundred nanometers divided by small-angle grain boundaries, which are probably the origin of the gradual change of the crystal orientation inside the domains. Spherular Fresnel contrasts were often observed at the small-angle grain boundaries, in defocused TEM images. Electron energy-loss spectroscopy (EELS) indicated the spherules are organic macromolecules, suggesting that incorporation of organic macromolecules during the crystal growth forms the sub-grain structure of the calcite prism.

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

PubMed

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

2010-09-01

Otoconia are biomineral particles of microscopic size essential for perception of gravity and maintenance of balance. Millions of older Americans are affected in their mobility, quality of life and in their health by progressive demineralization of otoconia. Currently, no effective means to prevent or counteract this process are available. Because of prohibitive anatomical and biological constraints, otoconial research is lagging far behind other systems such as bone and teeth. We have overcome these obstacles by generating otoconial matrix proteins by recombinant techniques. In the present study, we evaluated the effects of recombinant Otoconin 90 (OC90), the principal soluble matrix protein upon calcite crystal growth patterns in vitro. Our findings highlight multiple effects, including facilitation of nucleation, and inhibition of crystal growth in a concentration-dependent manner. Moreover, OC90 induces morphologic changes characteristic of native otoconia. OC90 is considerably less acidic than the prototypical invertebrate CaCO(3) -associated protein, but is nevertheless an effective modulator of calcite crystal growth. Based on homology modeling of the sPLA2-like domains of OC90, we propose that the lower density of acidic residues of the primary sequence is compensated by formation of major anionic surface clusters upon folding into tertiary conformation. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Effect of coccolith polysaccharides isolated from the coccolithophorid, Emiliania huxleyi, on calcite crystal formation in in vitro CaCO3 crystallization.

PubMed

Kayano, Keisuke; Saruwatari, Kazuko; Kogure, Toshihiro; Shiraiwa, Yoshihiro

2011-02-01

Marine coccolithophorids (Haptophyceae) produce calcified scales "coccoliths" which are composed of CaCO(3) and coccolith polysaccharides (CP) in the coccolith vesicles. CP was previously reported to be composed of uronic acids and sulfated residues, etc. attached to the polymannose main chain. Although anionic polymers are generally known to play key roles in biomineralization process, there is no experimental data how CP contributes to calcite crystal formation in the coccolithophorids. CP used was isolated from the most abundant coccolithophorid, Emiliania huxleyi. CaCO(3) crystallization experiment was performed on agar template layered onto a plastic plate that was dipped in the CaCO(3) crystallization solution. The typical rhombohedral calcite crystals were formed in the absence of CP. CaCO(3) crystals formed on the naked plastic plate were obviously changed to stick-like shapes when CP was present in the solution. EBSD analysis proved that the crystal is calcite of which c-axis was elongated. CP in the solution stimulated the formation of tabular crystals with flat edge in the agarose gel. SEM and FIB-TEM observations showed that the calcite crystals were formed in the gel. The formation of crystals without flat edge was stimulated when CP was preliminarily added in the gel. These observations suggest that CP has two functions: namely, one is to elongate the calcite crystal along c-axis and another is to induce tabular calcite crystal formation in the agarose gel. Thus, CP may function for the formation of highly elaborate species-specific structures of coccoliths in coccolithophorids.

Stratigraphic implications of trace element and strontium-isotope analyses of Kimmeridgian shell calcite from the Lower Saxony Basin, Germany

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

The review of recent carbonate minerals processing technology

NASA Astrophysics Data System (ADS)

Solihin

2018-02-01

Carbonate is one of the groups of minerals that can be found in relatively large amount in the earth crust. The common carbonate minerals are calcium carbonate (calcite, aragonite, depending on its crystal structure), magnesium carbonate (magnesite), calcium-magnesium carbonate (dolomite), and barium carbonate (barite). A large amount of calcite can be found in many places in Indonesia such as Padalarang, Sukabumi, and Tasikmalaya (West Java Provence). Dolomite can be found in a large amount in Gresik, Lamongan, and Tuban (East Java Provence). Magnesite is quite rare in Indonesia, and up to the recent years it can only be found in Padamarang Island (South East Sulawesi Provence). The carbonate has been being exploited through open pit mining activity. Traditionally, calcite can be ground to produce material for brick production, be carved to produce craft product, or be roasted to produce lime for many applications such as raw materials for cement, flux for metal smelting, etc. Meanwhile, dolomite has traditionally been used as a raw material to make brick for local buildings and to make fertilizer for coconut oil plant. Carbonate minerals actually consist of important elements needed by modern application. Calcium is one of the elements needed in artificial bone formation, slow release fertilizer synthesis, dielectric material production, etc. Magnesium is an important material in automotive industry to produce the alloy for vehicle main parts. It is also used as alloying element in the production of special steel for special purpose. Magnesium oxide can be used to produce slow release fertilizer, catalyst and any other modern applications. The aim of this review article is to present in brief the recent technology in processing carbonate minerals. This review covers both the technology that has been industrially proven and the technology that is still in research and development stage. One of the industrially proven technologies to process carbonate mineral is

13C 12C exchange between calcite and graphite: A possible thermometer in Grenville marbles

USGS Publications Warehouse

Valley, J.W.; O'Neil, J.R.

1981-01-01

The fractionation of 13C between calcite and graphite, ??(Cc-Gr). is consistently small (2.6-4.8 permil) in 34 assemblages from upper amphibolite- and granulite-facies marbles of the Grenville Province. In 25 samples from the Adirondack Mountains, New York, it decreases regularly with increasing metamorphic temperature. The fractionations are independent of absolute ??13C values of calcite (-2.9 to +5.0). For T = 600-800??C, the Adirondack data are described by ??(Cc-Gr) = -0.00748T (??C) + 8.68. This good correlation between ?? and T suggests that carbon isotope equilibrium was attained in these high-grade marbles and that the theoretical calculations of this fractionation by Bottinga are approximately 2 permil too large in this temperature range. Because of the relatively high temperature sensitivity suggested by these results and by Bottinga's calculations, and the pressure independence of isotope fractionation, ??(Cc-Gr) may provide a very good thermometer for high-grade marbles. Comparison of this field calibration for ??(Cc-Gr) vs temperature with results from other terranes supports the utility of ??(Cc-Gr) for geothermometry and suggests that graphite is much more sluggish to exchange than calcite, that exchange between calcite and graphite occurs at temperatures as low as 300??C, and that equilibrium may normally be attained only when peak metamorphic temperatures are greater than 500-600??C. Because 13C exchange is an unavoidable metamorphic process at temperatures above 300??C, high values of ??13C(Gr) in moderate- to high-grade carbonate-bearing rocks do not provide a sufficient criterion to infer an abiogenic origin for the graphite. ?? 1981.

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

PubMed Central

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

2016-01-01

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

Co-Precipitation of Trace Metals in Groundwater & Vadose Zone Calcite: In Situ Containment & Stabilization of Strontium-90 & Other Divalent Metals & Radionuclid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferris, F. Grant

2003-06-01

A suite of experiments were performed to investigate the partitioning of Sr2+ (to mimic the radionuclide 90Sr) between calcite and artificial groundwater in response to the hydrolysis of urea by Bacillus pasteurii under conditions that simulate in-situ aquifer conditions. Experiments were performed at 10, 15 and 20 C over 7 days in microcosms inoculated with B. pasteurii ATCC 11859 and containing an artificial groundwater and urea (AGW), and an AGW including a Sr contaminant treatment. During the experiments ammonium concentration from bacterial urea hydrolysis increased asymptotically, and derived rate constants (kurea) that were between 13 and 10 times greater atmore » 20 C, than at 15 and 10 C. Calcite precipitation was initiated after similar amounts of urea had been hydrolysed ({approx} 4.0 mmoles L-1) and a similar critical saturation state (mean Scritical = 53, variation = 20%) had been reached, independent of temperature and Sr treatment. Because of the positive relationship between urea hydrolysis rate and temperature, precipitation began by the end of day 1 at 20 C, and between days 1 and 2 at 15 and 10 C. The rate of calcite precipitation increased with, and was fundamentally controlled by S, irrespective of temperature, which connects the dissimilar patterns of urea hydrolysis and dissolved concentrations which are exhibited at the different experiments. The presence of Sr slightly slowed calcite precipitation rates at equivalent values of S, which may reflect the screening of active nucleation and crystal growth sites by Sr. Instantaneous heterogeneous partitioning coefficients (DSr) exhibited a positive association with calcite precipitation rates, but were greater at higher experimental temperatures at equivalent precipitation rates (20 C mean = 0.46; 15 C mean = 0.24; 10 C mean = 0.29). This is likely to reflect the large ionic radius of the Sr ion, which cannot fully co-ordinate relative to ions smaller than Ca at equilibrium conditions, but i s

An explanation for the 18O excess in Noelaerhabdaceae coccolith calcite

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Pb 2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite

DOE PAGES

Yuan, Ke; De Andrade, Vincent; Feng, Zhange; ...

2018-01-04

The presence of impurity ions is known to significantly influence mineral surface morphology during crystal growth from aqueous solution, but knowledge on impurity ion-mineral interactions during dissolution under far-from equilibrium conditions remains limited. Here we show that calcite (CaCO 3) exhibits a rich array of dissolution features in the presence of Pb. During the initial stage, calcite exhibits non-classical surface features characterized as micro pyramids developed spontaneously in acidic Pb-bearing solutions. Subsequent pseudomorphic growth of cerussite (PbCO 3) was observed, where nucleation occurred entirely within a pore space created by dissolution at the calcite/substrate interface. Uneven growth rates yielded amore » cerussite shell made of lath- or dendritic-shaped crystals. The cerussite phase was separated from the calcite by pores of less than 200 nm under transmission X-ray microscopy, consistent with the interface-coupled dissolution-precipitation mechanism. These results show that impurity metal ions exert significant control over the microscale dissolution features found on mineral surfaces and provide new insights into interpreting and designing micro structures observed in naturally-occurring and synthetic carbonate minerals by dissolution. In addition, heterogeneous micro-environments created in transport limited reactions under pore spaces may lead to unusual growth forms during crystal nucleation and precipitation.« less

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

USGS Publications Warehouse

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

2000-01-01

The crystallization of calcium carbonate minerals plays an integral role in the water chemistry of terrestrial ecosystems. Humic substances, which are ubiquitous in natural waters, have been shown to reduce or inhibit calcite crystal growth in experiments. The purpose of this study is to quantify and understand the kinetic effects of hydrophobic organic acids isolated from the Florida Everglades and a fulvic acid from Lake Fryxell, Antarctica, on the crystal growth of calcite (CaCO3). Highly reproducible calcite growth experiments were performed in a sealed reactor at constant pH, temperature, supersaturation (?? = 4.5), P(CO2) (10-3.5atm), and ionic strength (0.1 M) with various concentrations of organic acids. Higher plant-derived aquatic hydrophobic acids from the Everglades were more effective growth inhibitors than microbially derived fulvic acid from Lake Fryxell. Organic acid aromaticity correlated strongly with growth inhibition. Molecular weight and heteroatom content correlated well with growth inhibition, whereas carboxyl content and aliphatic nature did not. Copyright (C) 1999 Elsevier Science Ltd.

Angle-dependent rotation of calcite in elliptically polarized light

NASA Astrophysics Data System (ADS)

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

2017-08-01

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.

Sulfur in foraminiferal calcite as a potential proxy for seawater carbonate ion concentration

NASA Astrophysics Data System (ADS)

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

2017-07-01

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.

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

PubMed Central

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

2008-01-01

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

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

PubMed

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

2008-11-11

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

Aragonite-Calcite Inversion During Biogenic Carbonate Sampling: Considerations for Interpreting Isotopic Measurements in Paleoclimate Studies

NASA Astrophysics Data System (ADS)

Waite, A. J.; Swart, P. K.

2011-12-01

As aragonite is the metastable polymorph of calcium carbonate, it lends itself to monotropic inversion to the more stable polymorph, calcite. This inversion is possible through an increase in the temperature and pressure conditions to which the sample is exposed and, although first noted nearly a century ago, has been primarily discussed in the context of sample roasting prior to analyses in paleoclimatological studies. Over the last several decades, however, researchers have found evidence to suggest that the friction associated with the sampling of biogenic carbonates via milling/drilling also induces inversion. Furthermore, this inversion may be associated with a shift in measured oxygen isotopic values and ultimately have significant implications for the interpretation of paleoclimatic reconstructions. Despite this, the isotopic heterogeneity of biogenic aragonite skeletons makes the effects of inversion challenging to test and the subject remains underrepresented in the literature. Here we present a first order study into the effects of milling on both the mineralogy and isotopic compositions measured in sclerosponges, corals, and molluscs. X-Ray diffraction analysis of samples hand ground with a mortar and pestle reveal 100% aragonitic skeletons. Conversely, samples milled with a computerized micromill show measurable inversion to calcite. On average, percent inversion of aragonite to calcite for individual specimens was 15% for sclerosponges, 16% for corals, and 9% for molluscs. Isotopic data from these specimens show that the higher the percentage of aragonite inverted to calcite, the more depleted the measured oxygen isotopic values. In the largest of the datasets (sclerosponges), it is evident that the range of oxygen isotope values from milled samples (-0.02 to +0.84%) exceeds the range in values for those samples which were hand ground and showed no inversion (+0.53 to +0.90%). This, coupled with the strong correlation between the two variables

Aragonite→calcite transformation studied by EPR of Mn 2+ ions

NASA Astrophysics Data System (ADS)

Lech, J.; Śl|zak, A.

1989-05-01

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.

A simple method to model the reduced environment of lake bottom sapropel formation

NASA Astrophysics Data System (ADS)

Gaskova, Olga L.; Strakhovenko, Vera D.; Ermolaeva, Nadezhda I.; Zarubina, Eugene Yu.; Ovdina, Ekaterina A.

2017-07-01

The Kambala and Barchin brackish lakes (Baraba steppe, southern West Siberia) contain an organic-rich sapropel layer that was formed in oxygen-depleted waters. We measured the bulk sediment elemental composition, the water chemistry and determined the mineralogical composition and predominant biota species (Diatoms and Cyanobacteria in phytoplankton community respectively) in the lakes. The result indicates that the first lake has a siliceous type of sapropel and the second a carbonaceous one. A computer thermodynamic model was developed for chemical interaction in water-bottom sediment systems of the Kambala and Barchin Lakes. The surface sodium bicarbonate waters are supersaturated with respect to calcite, magnesite (or low Mg-calcite), quartz and chlorite with minor strontianite, apatite and goethite (pH 8.9-9.3, Eh 0.3 V). Nevertheless, it is shown that during sapropel deposition, deep silt waters should be anoxic (Eh<0 V). The virtual component CH2O has been used to create an anoxic environment suitable for pyrite formation due to the biotic community impact and abiotic reduction. Thermodynamic calculation has shown that silt water is not necessarily euxinic (anoxic and sulfidic). Depending on Eh, sulfate sulfur can dominate in solution, causing the formation of gypsum together with pyrite. An attempt was made to find a reason for solution supersaturation with respect to Ca and Mg ions due to their complexation with humic acids.

Paleoclimatic Inferences from a 120,000-Yr Calcite Record of Water-Table Fluctuation in Browns Room of Devils Hole, Nevada

USGS Publications Warehouse

Szabo, B. J.; Kolesar, Peter T.; Riggs, A.C.; Winograd, I.J.; Ludwig, K. R.

1994-01-01

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.

Jet-Suspended, Calcite-Ballasted Cyanobacterial Waterwarts in a Desert Spring

NASA Technical Reports Server (NTRS)

Pichel-Garcia, Ferran; Wade, Bman D.; Farmer, Jack D.

2002-01-01

We describe a population of colonial cyanobacteria (waterwarts) that develops as the dominant primary producer in a bottom-fed, warm spring in the Cuatro Cienegas karstic region of the Mexican Chihuahuan Desert. The centimeter-sized waterwarts were suspended within a central, conically shaped, 6-m deep well by upwelling waters. Waterwarts were built by an unicellular cyanobacterium and supported a community of epiphytic filamentous cyanobacteria and diatoms but were free of heterotrophic bacteria inside. Sequence analysis of genes revealed that this cyanobacterium is only distantly related to several strains of other unicellular teria Cyanothece, Waterwarts contained orderly arrangements of mineral made up of microcrystalline low-magnesium calcite with high levels of strontium and sulfur. Waterwarts were 95.9% (v/v) glycan, 2.8% cells, and 1.3% mineral grains and had a buoyant density of 1.034 kg/L. An analysis of the hydrological properties of the spring well and the waterwarts demonstrated that both large colony size and the presence of controlled amounts of mineral ballast are required to prevent the population from being washed out of the well. The unique hydrological characteristics of the spring have likely selected for both traits. The mechanisms by which controlled nucleation of extracellular calcite is achieved remain to be explored.

Isotopic analysis for degradation diagnosis of calcite matrix in mortar.

PubMed

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

2009-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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

PubMed

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

2016-07-15

There is growing concern that freshwater ecosystems may be negatively affected by ever-increasing anthropogenic inputs of extremely hard, highly alkaline effluent containing large quantities of Ca(2+), Mg(2+), CO3(2-), and HCO3(-) ions. In this study, the toxicity of rapid and extreme shifts in water hardness (38-600mg/L as CaCO3) and alkalinity (30-420mg/L as CaCO3) to Daphnia magna was tested, both independently and in combination. Within these ranges, where no precipitation event occurred, shifts in water hardness and/or alkalinity were not toxic to D. magna. In contrast, 98-100% of D. magna died within 96h after exposure to 600mg/L as CaCO3 water hardness and 420mg/L as CaCO3 alkalinity (LT50 of 60h with a 95% CI of 54.2-66.0h). In this treatment, a CaCO3 (calcite) precipitate formed in the water column which was ingested by and thoroughly coated the D. magna. Calcite collected from a mining impacted stream contained embedded organisms, suggesting field streams may also experience similar conditions and possibly increased mortality as observed in the lab tests. Although further investigation is required to determine the exact fate of aquatic organisms exposed to rapid calcite precipitation in the field, we caution that negative effects may occur more quickly or at lower concentrations of water hardness and alkalinity in which we observed effects in D. magna, because some species, such as aquatic insects, are more sensitive than cladocerans to changes in ionic strength. Our results provide evidence that both calcite precipitation and the major ion balance of waters should be managed in industrially affected ecosystems and we support the development of a hardness+alkalinity guideline for the protection of aquatic life. Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.

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

NASA Technical Reports Server (NTRS)

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

2010-01-01

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

Arsenic uptake by gypsum and calcite: Modelling and probing by neutron and X-ray scattering

NASA Astrophysics Data System (ADS)

Fernández-Martínez, A.; Román-Ross, G.; Cuello, G. J.; Turrillas, X.; Charlet, L.; Johnson, M. R.; Bardelli, F.

2006-11-01

Uptaking of contaminants by solid phases is relevant to many issues in environmental science as this process can remove them from solutions and retard their transport into the hydrosphere. Here we report on two structural studies performed on As-doped gypsum (CaSO 4 2H 2O) and calcite (CaCO 3), using neutron (D20-ILL) and X-ray (ID11-ESRF) diffraction data and EXAFS (BM8-ESRF). The aim of this study is to determine whether As gets into the bulk of gypsum and calcite structures or is simply adsorbed on the surface. Different mechanisms of substitution are used as hypotheses. The combined Rietveld analysis of neutron and X-ray diffraction data shows an expansion of the unit cell volume proportional to the As concentration within the samples. DFT-based simulations confirm the increase of the unit cell volume proportional to the amount of carbonate or sulphate groups substituted. Interpolation of the experimental Rietveld data allows us to distinguish As substituted within the structure from that adsorbed on the surface of both minerals. Results obtained by EXAFS analysis from calcite samples show good agreement with the hypothesis of replacement of As into the C crystallographic site.

Hydrocarbon-water interactions during brine migration: Evidence from hydrocarbon inclusions in calcite cements from Danish North Sea oil fields

USGS Publications Warehouse

Jensenius, J.; Burruss, R.C.

1990-01-01

Crude oils in primary and secondary fluid inclusions in calcite from fractures in seven offshore oil fields associated with diapiric salt structures in the Danish sector of the North Sea were analyzed by capillary column gas chromatography and compared with crude oils produced from the same reservoirs. Oils from fluid inclusions in all fields show evidence of biodegradation (decreased n-C17/pristane and n-C18/phytane ratios and loss of n-C7, 2-methyl hexane, and 3-methyl hexane relative to methyl cyclohexane) and water washing (absence of benzene and depletion of toluene). Some oils in inclusions are extremely enriched in C6 and C7 cyclic alkanes suggesting that these samples contain hydrocarbons exsolved from ascending, hotter formation waters. Compared to inclusion oils the produced oils are less biodegraded, but are water washed, indicating that both types of oil interacted with large volumes of formation water. The carbon isotopic composition of the calcite host of the fluid inclusions in the Dagmar and Skjold fields is as light as -16.5%. PDB and the sulfur isotopic composition of pyrite in and adjacent to the calcite veins in the Skjold field is as light as -39.6%. CDT, indicating that biodegradation of the oils was a source of some of the carbon in the calcite and sulfate reduction was the source of sulfur for the pyrite. The evidence for microbial degradation of petroleum is consistent with present-day reservoir temperatures (65??-96??C) but is not consistent with previous estimates of the temperatures of calcite vein filling (95??-130??C) which are much higher than the temperatures of known occurrences of biodegraded oil. ?? 1990.

Hydrocarbon-water interactions during brine migration: Evidence from hydrocarbon inclusions in calcite cements from Danish North Sea oil fields

NASA Astrophysics Data System (ADS)

Jensenius, Jørgen; Burruss, Robert C.

1990-03-01

Crude oils in primary and secondary fluid inclusions in calcite from fractures in seven offshore oil fields associated with diapiric salt structures in the Danish sector of the North Sea were analyzed by capillary column gas chromatography and compared with crude oils produced from the same reservoirs. Oils from fluid inclusions in all fields show evidence of biodegradation (decreased n- C17/pristane and n- C18/phytane ratios and loss of n-C 7, 2-methyl hexane, and 3-methyl hexane relative to methyl cyclohexane) and water washing (absence of benzene and depletion of toluene). Some oils in inclusions are extremely enriched in C 6 and C 7 cyclic alkanes suggesting that these samples contain hydrocarbons exsolved from ascending, hotter formation waters. Compared to inclusion oils the produced oils are less biodegraded, but are water washed, indicating that both types of oil interacted with large volumes of formation water. The carbon isotopic composition of the calcite host of the fluid inclusions in the Dagmar and Skjold fields is as light as -16.5%. PDB and the sulfur isotopic composition of pyrite in and adjacent to the calcite veins in the Skjold field is as light as -39.6%. CDT, indicating that biodegradation of the oils was a source of some of the carbon in the calcite and sulfate reduction was the source of sulfur for the pyrite. The evidence for microbial degradation of petroleum is consistent with present-day reservoir temperatures (65°-96°C) but is not consistent with previous estimates of the temperatures of calcite vein filling (95°-130°C) which are much higher than the temperatures of known occurrences of biodegraded oil.

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

NASA Astrophysics Data System (ADS)

Nishio, Takashi; Naka, Kensuke

2015-06-01

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

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

PubMed Central

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

2014-01-01

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

Sulphate partitioning into calcite: Experimental verification of pH control and application to seasonality in speleothems

NASA Astrophysics Data System (ADS)

Wynn, Peter M.; Fairchild, Ian J.; Borsato, Andrea; Spötl, Christoph; Hartland, Adam; Baker, Andy; Frisia, Silvia; Baldini, James U. L.

2018-04-01

Carbonate-associated sulphate (CAS) is a useful carrier of palaeoenvironmental information throughout the geologic record, particularly through its stable isotope composition. However, a paucity of experimental data restricts quantitative understanding of sulphate incorporation into carbonates, and consequently CAS concentrations and their diagenetic modifications are rarely interpreted. However, in the case of calcite speleothems, the remarkably high-resolution CAS records which are obtainable via modern microanalytical techniques represent a potentially invaluable source of palaeoenvironmental information. Here, we describe the results of controlled experiments of sulphate co-precipitation with calcite in freshwater solutions where pH, saturation state, and sulphate concentration were varied independently of each other. Solution pH is confirmed as the principal control on sulphate incorporation into calcite. The relative efficiency of incorporation was calculated as a partition coefficient DSO4 = (mSO4/mCO3)solid/(mSO4/mCO3)solution. High crystal growth rates (driven by either pH or saturation state) encouraged higher values of DSO4 because of an increasing concentration of defect sites on crystal surfaces. At low growth rates, DSO4 was reduced due to an inferred competition between sulphate and bicarbonate at the calcite surface. These experimental results are applied to understand the incorporation of sulphate into speleothem calcite. The experimentally determined pH-dependence suggests that strong seasonal variations in cave air PCO2 could account for annual cycles in sulphate concentration observed in stalagmites. Our new experimentally determined values of DSO4 were compared with DSO4 values calculated from speleothem-drip water monitoring from two caves within the Austrian and Italian Alps. At Obir cave, Austria, DSO4 (×105) varies between 11.1 (winter) and 9.0 (summer) and the corresponding figures for Ernesto cave, Italy, are 15.4 (winter) and 14

Influence of solution chemistry on the boron content in inorganic calcite grown in artificial seawater

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Helium diffusion in carbonates

NASA Astrophysics Data System (ADS)

Amidon, W. H.; Cherniak, D. J.; Watson, E. B.; Hobbs, D.

2013-12-01

directions and the maximum interstitial apertures in each 'slice' in the structure are identified. Preliminary results show that observed differences in diffusivities are consistent with the size of the smallest maximum aperture along each diffusion direction. In calcite, the smallest maximum apertures are ~0.92 and ~0.66 angstroms for cleavage-normal and c-axis parallel directions respectively. In dolomite, the smallest maximum aperture is ~0.78 angstroms for the cleavage normal direction. Work is in progress on characterizing helium diffusion for other orientations in dolomite, and in other carbonates, including aragonite and magnesite, and in implementing these diffusion findings in the interpretation and modeling of bulk volume diffusion in heterogeneous calcite crystals common in many geologic applications. Copeland et al. (2007) GCA 71, 4488-4511 Cherniak and Watson, (2011) Chem. Geo. 288, 149-161

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

PubMed

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

2015-05-01

In arthropods the cuticle forms an exoskeleton with its physical and chemical properties adapted to functions of distinct skeletal elements. The cuticle of the partes incisivae (PI) in mandibles of terrestrial isopods is a composite of chitin-protein fibrils/fibres and minerals. It consists of an unmineralized tip, a middle region with organic fibrils reinforced mainly with amorphous calcium phosphate and a base region mineralized with amorphous calcium carbonate and calcite. In this study we extend our work on the structure and material properties of the incisive cuticle employing electron backscatter diffraction (EBSD), and investigate calcite orientation patterns in the PI of two terrestrial isopod species from different habitats. We trace small-scale differences in texture sharpness and calcite microstructure, and compare calcite organization and orientation patterns in the PI with those in the tergites of the same isopod species. We observe that in the PI calcite orientation, the degree of crystal alignment, and mode of crystalline domain assemblage is highly varied within short length scales. This contrasts to calcite organization in the tergite cuticle, where calcite has only one specific texture pattern. Such a large range in the variation of calcite organization has not been observed in other carbonate biological hard tissues, such as shells and teeth, where one specific texture and microstructure prevails. Thus, the investigated isopod species are able to control crystallization of the amorphous carbonate precursor in a differential way, most probably related to the function of the individual skeletal element and the animals' behavior. Copyright © 2015 Elsevier Inc. All rights reserved.

Investigating the Basis of Biogenic Calcium Carbonate Formation from an Amorphous Precursor: Nature of the Transformation to Calcite on Hydroxyl Functionalized Surfaces

NASA Astrophysics Data System (ADS)

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

2006-12-01

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

{Carbon and oxygen isotope signals from marine ostracod calcite - results from present and past oceans}

NASA Astrophysics Data System (ADS)

Bornemann, A.; Speijer, R. P.

2009-04-01

Systematic stable isotope studies on ostracod calcite are generally rare, in particular for marine taxa only the work of DIDIÉ & BAUCH (2002) provides first clues towards an improved understanding of ostracod stable isotope data in paleoceanography. Here we present analyses from recent near surface sediments from the Gulf of Taranto, the Levantine Basin (15 ka, both Mediterranean Sea) and the Paleocene of Tunisia (southern Tethyan margin). Data are compared to those from selected benthic foraminiferal taxa from which the living habitat and the isotopic disequilibria from ambient sea-water are well known. In addition, size fractions of monospecific samples have been studied in order to test whether a size/mass dependent change exists with respect to the isotopic composition of the carapace calcite. Calcification of ostracod carapaces is a very rapid process, which often takes place within a few hours and the obtained signal provides only a snap-shot of the prevailing paleoceanographic conditions. Multiple mono-specific measurements show therefore a much higher variability than benthic foraminifera, but may give a more complete picture of the seasonal changes. Our study confirms the findings of DIDIÉ & BAUCH (2002) and others (for non-marine taxa) that ostracod calcite displays a positive species-specific deviation from the sea-water ^18O composition between 0.5 and 1.5 per mil with an intra-specific variability of less than 0.5 per mil. In contrast ^13C values cover a huge range with an off-set from sea-water of up to -5 per mil and show a high intra-specific variability of up to 2 per mil. Size-fraction data show no systematic change, although a statistically significant positive covariance between ^18O and ^13C has been observed. This covariance consists of a slope similar to a kinetic controlled fractionation as has been described from asymbiotic planktic foraminifera (Globigerina bulloides) and corals (MCCONNAUGHEY, 1989; SPERO & LEA, 1996). This suggests that

Hydrodynamic control of inorganic calcite precipitation in Huanglong Ravine, China: Field measurements and theoretical prediction of deposition rates

NASA Astrophysics Data System (ADS)

Zaihua, Liu; Svensson, U.; Dreybrodt, W.; Daoxian, Yuan; Buhmann, D.

1995-08-01

Hydrochemical and hydrodynamical investigations are presented to explain tufa deposition rates along the flow path of the Huanglong Ravine, located in northwestern Sichuan province, China, on an altitude of about 3400 m asl. Due to outgassing of CO 2 the mainly spring-fed stream exhibits, along a valley of 3.5 km, calcite precipitation rates up to a few mm/year. We have carried out in situ experiments to measure calcite deposition rates at rimstone dams, inside of pools and in the stream-bed. Simultaneously, the downstream evolution of water chemistry was investigated at nine locations with respect to Ca 2+, Mg 2+, Na +, Cl -, SO 42-, and alkalinity. Temperature, pH, and conductivity were measured in situ, while total hardness, Ca T, and alkalinity have been determined immediately after sampling, performing standard titration methods. The water turned out to be of an almost pure CaMgHCO 3 type. The degassing of CO 2 causes high supersaturation with respect to calcite and due to calcite precipitation the Ca 2+ concentration decreases from 6·10 -3 mole/1 upstream down to 2.5·10 -3 mole/1 at the lower course. Small rectangular shaped tablets of pure marble were mounted under different flow regimes, i.e., at the dam sites with fast water flow as well as inside pools with still water. After the substrate samples had stayed in the water for a period of a few days, the deposition rates were measured by weight increase, up to several tens of milligrams. Although there were no differences in hydrochemistry, deposition rates in fast flowing water were higher by as much as a factor of four compared to still water, indicating a strong influence of hydrodynamics. While upstream rates amounted up to 5 mm/year, lower rates of about 1 mm/year were observed downstream. Inspection of the marble substrate surfaces by EDAX and SEM (scanning electron microscope) revealed authigeneously grown calcite crystals of about 10 μm. Their shape and habit are indicative of a chemically

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

PubMed

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

2016-01-01

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

Potential for Ureolytically Driven Calcite Precipitation to Remediate Strontium-90 at the Hanford 100-N Area

NASA Astrophysics Data System (ADS)

Fujita, Y.; Taylor, J. L.; Wendt, L.; Reed, D.; Smith, R. W.

2009-12-01

A groundwater plume of Strontium-90 at the 100-N Springs Area of the U. S. Department of Energy’s Hanford Reservation in Washington is discharging into the Columbia River. Previous pump and treat activities to remove the 90Sr were ineffective and consequently discontinued; immobilization of the contaminant in situ is preferable, but no proven methods to accomplish this objective currently exist. This study was a preliminary assessment of the feasibility at the 100-N Area of a novel in situ remediation approach for 90Sr, where microbial urea hydrolysis is used to drive the precipitation of calcite and the co-precipitation of strontium in the calcite. Water quality data from the 100-N site indicated that geochemical conditions at the site were conducive to stable calcite precipitation, and groundwater and sediment samples from the site were examined to assess the urea hydrolyzing capabilities of the native microbial populations. Estimated average numbers of ureolytic organisms in the groundwater, determined using cultivation-based tests (Most Probable Number) for urease activity, ranged from 72 to 1,100 cells mL-1. Estimated numbers of ureC gene targets in the water samples, as determined by quantitative polymerase chain reaction (qPCR) assays, ranged from 850 to 17,600 copies mL-1; the ureC gene codes for the catalytic subunit of urease. In the sediment samples, ureC gene targets ranged from non-detectable to 925,000 copies g-1 of sediment. For both water and sediment, the number of ureolytic cells (estimated by qPCR) generally amounted to < 5% of the total microbial cell numbers. Nevertheless, estimates of in situ ureolysis rates using trace levels of 14C-labeled urea added to the groundwater and sediment samples in the laboratory indicate that significant urea hydrolyzing activity exists in the 100-N subsurface. Normalizing the measured urea hydrolysis rates to 1 L of in situ pore space resulted in hydrolysis rates on the order of 9.5 nmol L-1 hr-1 and 170 to 2

Modeling of Ureolytic Calcite Precipitation for the Remediation of Sr-90 Using a Variable Velocity Streamtube Ensemble

NASA Astrophysics Data System (ADS)

Weathers, T. S.; Ginn, T. R.; Spycher, N.; Barkouki, T. H.; Fujita, Y.; Smith, R. W.

2009-12-01

Subsurface contamination is often mitigated with an injection/extraction well system. An understanding of heterogeneities within this radial flowfield is critical for modeling, prediction, and remediation of the subsurface. We address this using a Lagrangian approach: instead of depicting spatial extents of solutes in the subsurface we focus on their arrival distribution at the control well(s). A well-to-well treatment system that incorporates in situ microbially-mediated ureolysis to induce calcite precipitation for the immobilization of strontium-90 has been explored at the Vadose Zone Research Park (VZRP) near Idaho Falls, Idaho. PHREEQC2 is utilized to model the kinetically-controlled ureolysis and consequent calcite precipitation. PHREEQC2 provides a one-dimensional advective-dispersive transport option that can be and has been used in streamtube ensemble models. Traditionally, each streamtube maintains uniform velocity; however in radial flow in homogeneous media, the velocity within any given streamtube is variable in space, 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 if kinetic reactions are present with multiple components, if kinetic reaction rates vary in space, if the reactions involve multiple phases (e.g. heterogeneous reactions), and/or if they impact physical characteristics (porosity/permeability), as does 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 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

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

NASA Astrophysics Data System (ADS)

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

2007-09-01

BIOSOPE cruise achieved an oceanographic transect from the Marquise Islands to the Peru-Chili upwelling (PCU) via the centre of the South Pacific Gyre (SPG). Water samples from 6 depths in the euphotic zone were collected at 20 stations. The concentrations of suspended calcite particles, coccolithophores cells and detached coccoliths were estimated together with size and weight using an automatic polarizing microscope, a digital camera, and a collection of softwares performing morphometry and pattern recognition. Some of these softwares are new and described here for the first time. The coccolithophores standing stocks are usually low and reach maxima west of the PCU. The coccoliths of Emiliania huxleyi, Gephyrocapsa spp. and Crenalithus spp. (Order Isochrysidales) represent 50% of all the suspended calcite particles detected in the size range 0.1-46 μm (21% of PIC in term of the calcite weight). The latter species are found to grow preferentially in the Chlorophyll maximum zone. In the SPG their maximum concentrations was found to occur between 150 and 200 m, which is very deep for these taxa. The weight and size of coccoliths and coccospheres are correlated. Large and heavy coccoliths and coccospheres are found in the regions with relative higher fertility in the Marquises Island and in the PCU. Small and light coccoliths and coccospheres are found west of the PCU. This distribution may correspond to that of the concentration of calcium and carbonate ions.

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

USGS Publications Warehouse

Faure, G.; Botoman, G.

1984-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2001-01-01

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

3D visualization of additive occlusion and tunable full-spectrum fluorescence in calcite

PubMed Central

Green, David C.; Ihli, Johannes; Thornton, Paul D.; Holden, Mark A.; Marzec, Bartosz; Kim, Yi-Yeoun; Kulak, Alex N.; Levenstein, Mark A.; Tang, Chiu; Lynch, Christophe; Webb, Stephen E. D.; Tynan, Christopher J.; Meldrum, Fiona C.

2016-01-01

From biomineralization to synthesis, organic additives provide an effective means of controlling crystallization processes. There is growing evidence that these additives are often occluded within the crystal lattice. This promises an elegant means of creating nanocomposites and tuning physical properties. Here we use the incorporation of sulfonated fluorescent dyes to gain new understanding of additive occlusion in calcite (CaCO3), and to link morphological changes to occlusion mechanisms. We demonstrate that these additives are incorporated within specific zones, as defined by the growth conditions, and show how occlusion can govern changes in crystal shape. Fluorescence spectroscopy and lifetime imaging microscopy also show that the dyes experience unique local environments within different zones. Our strategy is then extended to simultaneously incorporate mixtures of dyes, whose fluorescence cascade creates calcite nanoparticles that fluoresce white. This offers a simple strategy for generating biocompatible and stable fluorescent nanoparticles whose output can be tuned as required. PMID:27857076

Sulfate-dependent Anaerobic Oxidation of Methane as a Generation Mechanism for Calcite Cap Rock in Gulf Coast Salt Domes

NASA Astrophysics Data System (ADS)

Caesar, K. H.; Kyle, R.; Lyons, T. W.; Loyd, S. J.

2015-12-01

Gulf Coast salt domes, specifically their calcite cap rocks, have been widely recognized for their association with significant reserves of crude oil and natural gas. However, the specific microbial reactions that facilitate the precipitation of these cap rocks are still largely unknown. Insight into the mineralization mechanism(s) can be obtained from the specific geochemical signatures recorded in these structures. Gulf Coast cap rocks contain carbonate and sulfur minerals that exhibit variable carbon (d13C) and sulfur isotope (δ34S) signatures. Calcite d13C values are isotopically depleted and show a large range of values from -1 to -52‰, reflecting a mixture of various carbon sources including a substantial methane component. These depleted carbon isotope compositions combined with the presence of abundant sulfide minerals in cap rocks have led to interpretations that invoke microbial sulfate reduction as an important carbonate mineral-yielding process in salt dome environments. Sulfur isotope data from carbonate-associated sulfate (CAS: trace sulfate incorporated within the carbonate mineral crystal lattice) provide a more direct proxy for aqueous sulfate in salt dome systems and may provide a means to directly fingerprint ancient sulfate reduction. We find CAS sulfur isotope compositions (δ34SCAS) significantly greater than those of the precursor Jurassic sulfate-salt deposits (which exhibit δ34S values of ~ +15‰). This implies that cap rock carbonate generation occurred via microbial sulfate reduction under closed-system conditions. The co-occurrence of depleted carbonate d13C values (< ~30‰) and the enriched δ34SCAS values are evidence for sulfate-dependent anaerobic oxidation of methane (AOM). AOM, which has been shown to yield extensive seafloor carbonate authigenesis, is also potentially partly responsible for the carbonate minerals of the Gulf Coast calcite cap rocks through concomitant production of alkalinity. Collectively, these data shed

Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite

NASA Astrophysics Data System (ADS)

Tiraboschi, Carla; Tumiati, Simone; Sverjensky, Dimitri; Pettke, Thomas; Ulmer, Peter; Poli, Stefano

2018-01-01

We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 °C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni-NiO-H2O (ΔFMQ = - 0.21 to - 1.01), employing a double-capsule setting. Fluids, binary H2O-CO2 mixtures at the P, T, and fO2 conditions investigated, were generated from graphite, oxalic acid anhydrous (H2C2O4) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO2-bearing fluids. The experimental data show that forsterite + enstatite solubility in H2O-CO2 fluids is higher compared to pure water, both in terms of dissolved silica ( mSiO2 = 1.24 mol/kgH2O versus mSiO2 = 0.22 mol/kgH2O at P = 1 GPa, T = 800 °C) and magnesia ( mMgO = 1.08 mol/kgH2O versus mMgO = 0.28 mol/kgH2O) probably due to the formation of organic C-Mg-Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H2O-CO2 fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO2 ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO2 ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P- T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Imminent onset and abrupt increase in duration of low aragonite and calcite saturation state events in the Southern Ocean

NASA Astrophysics Data System (ADS)

Friedrich, T.; Hauri, C.; Timmermann, A.

2015-12-01

Rapid progression of ocean acidification is a threat to key organisms of the Southern Ocean ecosystem. While the severity of ocean acidification impacts is mainly determined by the duration, intensity, and spatial extent of low aragonite or calcite saturation state events, little is known about the nature of these events, their evolving attributes, and the timing of their onset. Using output of historical and RCP 8.5 simulations from ten Earth System Models from CMIP5, we found that aragonite undersaturation, which decreases the calcification rate of pteropods and causes dissolution of their aragonitic shell, will spread rapidly after 2035, covering 70 % of the Southern Ocean surface waters by 2095. Surface aragonite undersaturation events will last for about 5 months in areas south of 60°S by 2055, and for more than 8 months by the end of the century. Overall, the duration of these events increases from 1 month to more than 6 months within fewer than 20 years in >75 % of the affected area. This abrupt change in exposure duration to unfavorable conditions may be too fast for pteropods to adapt, as these chemical changes will occur within just a few generations. As a result of two month-long calcite undersaturation events projected for the end of this century, even organisms built of the more stable calcium carbonate mineral calcite will face prolonged chemical dissolution. The threat of ocean acidification to the Southern Ocean ecosystem may be more imminent than previously thought, and may spread quickly to the southern tips of New Zealand, South America, and South Africa, with potentially far-reaching consequences to fisheries, local economies, and livelihoods.

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

PubMed

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

2011-12-23

Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural analysis of the industrial grade calcite

NASA Astrophysics Data System (ADS)

Shah, Rajiv P.; Raval, Kamlesh G.

2017-05-01

The chemical, optical and structural characterization of the industrial grade Calcite by EDAX, FT-IR and XRD. EDAX is a widely used technique to analyze the chemical components in a material, FT-IR stands for Fourier Transform Infra-Red, the preferred method of infrared spectroscopy. The resultant spectrum represents the molecular absorption and transmission, creating a molecular fingerprint of the sample, The atomic planes of a crystal cause an incident beam of X-rays to interfere with one another as they leave the crystal. The phenomenon is called X ray diffraction.(XRD). Data analysis of EDAX, FT-IR and XRD has been carried out with help of various instruments and software and find out the results of the these industrial grade materials which are mostly used in ceramics industries

Fabrication of B-type carbonate apatite blocks by the phosphorization of free-molding gypsum-calcite composite.

PubMed

Zaman, Chowdury Tanira; Takeuchi, Akari; Matsuya, Shigeki; Zaman, Q H M Shawket; Ishikawa, Kunio

2008-09-01

B-type carbonate apatite (CO3Ap) block may be an ideal artificial bone substitute because it is closer in chemical composition to bone mineral. In the present study, the feasibility to fabricate CO3Ap blocks was investigated using compositional transformation, which was based on the dissolution-precipitation reaction of a gypsum-calcite composite with free-molding behavior. For the compositional change, or phosphorization, gypsum-calcite composites of varying CaCO3 contents were immersed in 1 mol/L (NH4)3PO4 aqueous solution at 100 degrees C for 24 hours. No macroscopic changes were found after the treatment, whereas microscopic change was observed at SEM level. X-ray diffraction, Fourier transform infrared spectroscopy and CHN analysis indicated that the composites were B-type CO3Ap containing approximately 6-7 wt% of CO3, a value similar to that of biological bone apatite. Diametral tensile strength of the CO3Ap block was approximately 1-3 MPa. Based on the results obtained, it was therefore concluded that gypsum-calcite was a good candidate for the fabrication of CO3Ap blocks, coupled with the advantage that the composite can be molded to any shape by virtue of the setting property of gypsum.

Strain localization in ultramylonitic calcite marbles by dislocation creep-accommodated grain boundary sliding

NASA Astrophysics Data System (ADS)

Rogowitz, Anna; Grasemann, Bernhard; Clancy White, Joseph

2015-04-01

Strain localization in monomineralic rocks is often associated with brittle precursors, resulting in stress and strain concentration, followed by grain size reduction and activation of grain-size-sensitive deformation mechanisms such as diffusion creep, grain boundary sliding and cataclastic flow. The aforementioned mechanisms typically tend to produce a random crystallographic orientation or a decrease in intensity of a pre-existing texture. However, reports of fine grained polycrystalline materials showing a preferred crystallographic orientation indicate a need for subsequent grain re-organization by either static annealing or the activation of additional deformation mechanisms in conjunction with grain boundary sliding. We present observations from an almost pure calcite marble layer from Syros Island (Cyclades, Greece) deformed in lower greenschist facies conditions. The presence of a crack (i.e. cross-cutting element) that rotated during shear resulted in the formation of a flanking structure. At the location of maximum displacement (120 cm) along the cross-cutting element, the marble is extremely fine grained (3 µm) leading to anticipation of deformation by grain-size-sensitive mechanisms. Detailed microstructural analysis of the highly strained (80 < gamma < 1000) calcite ultramylonite by optical microscopy, electron backscatter diffraction and scanning transmission electron microscopy show that recrystallization by bulging results in small, strain-free grains. The change in grain size appears to be concomitant with increased activity of independent grain boundary sliding as indicated by a random misorientation angle distribution. At the same time, dislocation multiplication through Frank-Read sources produces high mean dislocation density (~ 5x10^13 m^-2) as well as a weak primary CPO; the latter all argue that grain boundary sliding was accommodated by dislocation activity. Theoretical and experimental determined relationships (paleowattmeter

Melting relations in the system FeCO3-MgCO3 and thermodynamic modelling of Fe-Mg carbonate melts

NASA Astrophysics Data System (ADS)

Kang, Nathan; Schmidt, Max W.; Poli, Stefano; Connolly, James A. D.; Franzolin, Ettore

2016-09-01

To constrain the thermodynamics and melting relations of the siderite-magnesite (FeCO3-MgCO3) system, 27 piston cylinder experiments were conducted at 3.5 GPa and 1170-1575 °C. Fe-rich compositions were also investigated with 13 multi-anvil experiments at 10, 13.6 and 20 GPa, 1500-1890 °C. At 3.5 GPa, the solid solution siderite-magnesite coexists with melt over a compositional range of X Mg (=Mg/(Mg + Fetot)) = 0.38-1.0, while at ≥10 GPa solid solution appears to be complete. At 3.5 GPa, the system is pseudo-binary because of the limited stability of siderite or liquid FeCO3, Fe-rich carbonates decomposing at subsolidus conditions to magnetite-magnesioferrite solid solution, graphite and CO2. Similar reactions also occur with liquid FeCO3 resulting in melt species with ferric iron components, but the decomposition of the liquid decreases in importance with pressure. At 3.5 GPa, the metastable melting temperature of pure siderite is located at 1264 °C, whereas pure magnesite melts at 1629 °C. The melting loop is non-ideal on the Fe side where the dissociation reaction resulting in Fe3+ in the melt depresses melting temperatures and causes a minimum. Over the pressure range of 3.5-20 GPa, this minimum is 20-35 °C lower than the (metastable) siderite melting temperature. By merging all present and previous experimental data, standard state (298.15 K, 1 bar) thermodynamic properties of the magnesite melt (MgCO3L) end member are calculated and the properties of (Fe,Mg)CO3 melt fit by a regular solution model with an interaction parameter of -7600 J/mol. The solution model reproduces the asymmetric melting loop and predicts the thermal minimum at 1240 °C near the siderite side at X Mg = 0.2 (3.5 GPa). The solution model is applicable to pressures reaching to the bottom of the upper mantle and allows calculation of phase relations in the FeO-MgO-O2-C system.

Geochemical distinctions between igneous carbonate, calcite cements, and limestone xenoliths (Polino carbonatite, Italy): spatially resolved LAICPMS analyses

NASA Astrophysics Data System (ADS)

Rosatelli, G.; Wall, F.; Stoppa, F.; Brilli, M.

2010-11-01

Petrography-controlled laser ablation inductively coupled plasma mass spectrometry (LAICPMS) analyses of carbonate in fresh shallow level sub-volcanic Polino monticellite calcio-carbonatite tuffisite have been performed to assess the geochemical differences between fresh igneous, epigenetic carbonates and sedimentary accidental fragments. Igneous calcite has consistently high LREE/HREE ratios (La/Yb N , 15-130) due to high LREE (ΣLREE, 425-1,269 ppm). Secondary calcite cements are characterized by progressively lower and more variable trace element contents, with lower LREE/HREE ratios. A distinguishing geochemical feature is progressively increasing negative Ce anomalies observed through coarse secondary calcite that can be related to the surface environment processes. The limestone accidental fragments in the tuffisite have trace element contents almost two orders of magnitude lower than igneous carbonate and low LREE (ΣLREE < 9.5 ppm) with low LREE/HREE fractionation (La/Yb N ratios < 18). The stable isotope composition of different carbonate types is consistent with their formation in different environments. The tuffisitization processes during diatreme formation under high CO2-OH fugacity conditions may account for the differences noted in the igneous carbonates.

The dissolution of calcite in CO2-saturated solutions at 25°C and 1 atmosphere total pressure

USGS Publications Warehouse

Plummer, Niel; Wigley, T.M.L.

1976-01-01

The dissolution of Iceland spar in CO2-saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.

Metadynamics simulations of calcite crystallization on self-assembled monolayers

NASA Astrophysics Data System (ADS)

Quigley, D.; Rodger, P. M.; Freeman, C. L.; Harding, J. H.; Duffy, D. M.

2009-09-01

We show that recent developments in the application of metadynamics methods to direct simulations of crystallization make it possible to predict the orientation of crystals grown on self-assembled monolayers. In contrast to previous studies, the method allows for dynamic treatment of the organic component and the inclusion of explicit surface water without the need for computationally intensive interfacial energy calculations or prior knowledge of the interfacial structure. The method is applied to calcite crystallization on carboxylate terminated alkanethiols arrayed on Au (111). We demonstrate that a dynamic treatment of the monolayer is sufficient to reproduce the experimental results without the need to impose epitaxial constraints on the system. We also observe an odd-even effect in the variation of selectivity with organic chain length, reproducing experimentally observed orientations in both cases. Analysis of the ordering process in our simulations suggests a cycle of mutual control in which both the organic and mineral components induce complementary local order across the interface, leading to the formation of a critical crystalline region. The influence of pH, together with some factors that might affect the range of applicability of our method, is discussed.

A Sr-isotopic comparison between thermal waters, rocks, and hydrothermal calcites, Long Valley caldera, California

USGS Publications Warehouse

Goff, F.; Wollenberg, H.A.; Brookins, D.C.; Kistler, R.W.

1991-01-01

The 87Sr/86Sr values of thermal waters and hydrothermal calcites of the Long Valley caldera geothermal system are more radiogenic than those of young intracaldera volcanic rocks. Five thermal waters display 87Sr/86Sr of 0.7081-0.7078 but show systematically lighter values from west to east in the direction of lateral flow. We believe the decrease in ratio from west to east signifies increased interaction of deeply circulating thermal water with relatively fresh volcanic rocks filling the caldera depression. All types of pre-, syn-, and post-caldera volcanic rocks in the west and central caldera have (87Sr/86Sr)m between about 0.7060 and 0.7072 and values for Sierra Nevada granodiorites adjacent to the caldera are similar. Sierran pre-intrusive metavolcanic and metasedimentary rocks can have considerably higher Sr-isotope ratios (0.7061-0.7246 and 0.7090-0.7250, respectively). Hydrothermally altered volcanic rocks inside the caldera have (87Sr/86Sr)m slightly heavier than their fresh volcanic equivalents and hydrothermal calcites (0.7068-0.7105) occupy a midrange of values between the volcanic/plutonic rocks and the Sierran metamorphic rocks. These data indicate that the Long Valley geothermal reservoir is first equilibrated in a basement complex that contains at least some metasedimentary rocks. Reequilibration of Sr-isotope ratios to lower values occurs in thermal waters as convecting geothermal fluids flow through the isotopically lighter volcanic rocks of the caldera fill. ?? 1991.

The effect of fluids on the frictional behavior of calcite gouge

NASA Astrophysics Data System (ADS)

Rempe, M.; Di Toro, G.; Mitchell, T. M.; Hirose, T.; Smith, S. A. F.; Renner, J.

2016-12-01

The presence of fluids in fault zones affects the faults' strength and the nucleation and propagation of earthquakes due to mechanical or physico-chemical weakening effects. To better understand the effect of pore fluids on the frictional behavior of gouge-bearing faults, a series of intermediate- to high-velocity experiments was conducted using the Phv rotary-shear apparatus (Kochi Core Center, Japan) equipped with a servo-controlled pore-fluid pressure system. Calcite gouge was sheared up to several meters displacement at room-humidity (dry) and water-saturated conditions. The pore-fluid factor, λ=pf/σn, ranged from 0.15 to 0.7 and the effective normal stress, σn,eff=σn-pf, from 1 to 12 MPa. Sheared samples were analyzed using scanning electron microscopy and Raman spectroscopy. The steady-state shear stress is lower for saturated than for dry gouges sliding at V=1 mm/s, possibly due to higher intergranular lubrication and/or accelerated subcritical crack growth, as evidenced also by the observed higher degree of compaction. At V=1 m/s, dry gouges show a pronounced strengthening phase preceding the onset of dynamic weakening; saturated gouges weaken abruptly. The higher λ, the lower the peak and steady-state shear stress, but -counterintuitively- the less localized deformation. Degree of weakening and localization might be influenced by insufficient drainage at high λ. In undrained experiments, the shear stress is slightly decreased likely due to thermal pressurization of the pore fluid, but the onset of dynamic weakening is not accelerated, indicating that dynamic weakening is due to more efficient mechanisms. For example, amorphous carbon may lubricate the slip surfaces of dry and saturated calcite gouges and cause dynamic weakening, yet Raman spectra only show the presence of disordered carbon on the principal slip surface. Furthermore, the presence of small recrystallized grains suggests that strain accommodation during steady-state slip might occur by

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

NASA Technical Reports Server (NTRS)

Bell, M. S.

2016-01-01

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

Bacterial bio-mediated calcite precipitation for monumental stones conservation: methods of evaluation.

PubMed

Tiano, P; Biagiotti, L; Mastromei, G

1999-05-01

The weathering of monumental stones is a complex process inserted in the more general 'matter transformation cycle' operated by physical, chemical and biological factors. The consequence of these combined actions is a loss of cohesion with dwindling and scaling of stone material and the induction of a progressive mineral matrix dissolution. In the case of calcareous stones, calcite leaching increases the material porosity and decreases its mechanical features with a general weakening of the superficial structural strength. Attempts to stop, or at least to slow down, deterioration of monumental stones has been made by conservative treatments with both inorganic or organic products. More recent studies show a new approach to hinder these phenomena by inducing a bio-mediated precipitation of calcite directly inside the stone porosity. This can be achieved either through the application of organic matrix macromolecules extracted from sea shells or of living bacteria. The effectiveness of the treatment using calcinogenic bacteria has been evaluated with laboratory tests specifically developed to evaluate the parameters such as : porosity, superficial strength and chromatic changes, influenced by the treatment itself. The results obtained seem to indicate that this type of treatment might not be suitable for monumental stone conservation.

Calcite-graphite thermometry of the Franklin Marble, New Jersey Highlands

USGS Publications Warehouse

Peck, W.H.; Volkert, R.A.; Meredith, M.T.; Rader, E.L.

2006-01-01

We present new stable-isotope data for the Mesoproterozoic Franklin Marble from outcrops along an 80-km traverse parallel to and across strike of the structural grain of the western New Jersey Highlands. Calcite and dolomite from marble have an average ??13C of 0.35??? ?? 0.73??? PDB (n = 46) and a more limited range than other Mesoproterozoic marbles from the Adirondacks and the Canadian Grenville Province. The small range of ??13C values from the New Jersey samples is consistent with the preservation of a primary marine isotopic signature and limited postdepositional isotopic modification, except proximal to Zn or Fe ore deposits and fault zones. Fractionations between calcite and well-formed graphite (??13C[Cal-Gr]) for analyzed Franklin Marble samples average 3.31???. ?? 0.25??? (n = 34), and dolomite-graphite fractionations average 3.07??? ?? 0.30??? (n = 6). Taken together, these indicate an average temperature of 769?? ?? 43??C during metamorphism associated with the Ottawan Orogeny in the New Jersey Highlands. Thus, carbon isotope fractionations demonstrate that the Franklin Marble was metamorphosed at granulite facies conditions. Metamorphic temperatures are relatively constant for the area sampled and overprint the metamorphosed carbonatehosted Zn-Fe-Mn ore deposits. The results of this study support recent work proposing that pressure and temperature conditions during Ottawan orogenesis did not vary greatly across faults that partition the Highlands into structural blocks. ?? 2006 by The University of Chicago. All rights reserved.

Comparison of rates of ureolysis between Sporosarcina pasteurii and an indigenous groundwater community under conditions required to precipitate large volumes of calcite

NASA Astrophysics Data System (ADS)

Tobler, Dominique J.; Cuthbert, Mark O.; Greswell, Richard B.; Riley, Michael S.; Renshaw, Joanna C.; Handley-Sidhu, Stephanie; Phoenix, Vernon R.

2011-06-01

Ureolysis-driven calcite precipitation has potential to seal porosity and fracture networks in rocks thus preventing groundwater flow and contaminant transport. In this study urea hydrolysis and calcite precipitation rates for the model bacterium Sporosarcina pasteurii were compared with those of indigenous groundwater communities under conditions required to precipitate large volumes of calcite (up to 50 g L -1). We conducted microcosm experiments in oxic artificial and anoxic natural groundwaters (collected from the Permo-Triassic sandstone aquifer at Birmingham, UK) that were inoculated with aerobically grown S. pasteurii. The rate constants for urea hydrolysis, kurea, ranged between 0.06 and 3.29 d -1 and were only affected by inoculum density. Higher Ca 2+ concentration (50-500 mM Ca 2+) as well as differences in fO 2 did not inhibit the ureolytic activity of S. pasteurii and did not significantly impact kurea. These results demonstrate that S. pasteurii has potential to improve calcite precipitation in both oxic and anoxic groundwaters, especially if indigenous communities lack ureolytic activity. Urea hydrolysis by indigenous groundwater communities was investigated in anoxic, natural groundwaters amended with urea and CaCl 2. A notable increase in ureolysis rates was measured only when these communities were stimulated with dilute nutrients (with best results from blackstrap molasses). Furthermore, there was a considerable lag time (12-20 days) before ureolysis and calcite precipitation began. Calculated ureolysis rate constants, kurea, ranged between 0.03 and 0.05 d -1 and were similar to kurea values produced by S. pasteurii at low inoculum densities. Overall, this comparative study revealed that the growth of ureolytic microorganisms present within groundwaters can easily be stimulated to enhance rates of urea hydrolysis in the subsurface, and thus can be used to induce calcite precipitation in these environments. The time required for urea hydrolysis to

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Inhibition of phosphorus sorption on calcite by dairy manure-sourced DOC.

PubMed

Weyers, Eva; Strawn, Daniel G; Peak, Derek; Baker, Leslie L

2017-10-01

In confined animal feeding operations, such as dairies, manure is amended to soils at high rates leading to increases in P and organic matter in the soils. Phosphorus reacts with soil-Ca to form Ca-P minerals, which controls P availability for leaching and transport through the watershed. In this research, the effects of manure sourced dissolved organic matter (DOM) on P sorption on calcite were measured at different reaction times and concentrations. Reactions were monitored in 1% and 10% manure-to-water extract solutions spiked with P. When manure-DOM was present, a significant reduction in P sorption occurred (2-90% absolute decrease) compared to samples without manure-DOM. The greatest decrease occurred in the samples reacted in the 10% manure solution. XANES spectroscopic analysis showed that at 1% manure solution, a Ca-P phase similar to hydroxyapatite formed. In the calcite samples reacted in the 10% manure solution, K-edge XANES spectroscopy revealed that P occurred as a Ca-Mg-P phase instead of the less soluble hydroxyapatite-like phase. Results from this study suggest that in manure-amended calcareous soils, increased DOM from manure will decrease P sorption capacity and increase the overall P concentration in solution, which will increase the mobility of P and subsequently pose greater risks for impairment of surface water quality. Copyright © 2017 Elsevier Ltd. All rights reserved.

Temperature Dependence of the Structural Parameters in the Transformation of Aragonite to Calcite, as Determined from In Situ Synchrotron Powder X-ray-Diffratction Data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antao, Sytle M.; Hassan, Ishmael; West Indies)

The temperature dependency of the crystal structure and the polymorphic transition of CaCO{sub 3} from aragonite to calcite were studied using Rietveld structure refinement and high-temperature in situ synchrotron powder X-ray-diffraction data at ambient pressure, P. The orthorhombic metastable aragonite at room P, space group Pmcn, transforms to trigonal calcite, space group R{bar 3}c, at about T{sub c} = 468 C. This transformation occurs rapidly; it starts at about 420 C and is completed by 500 C, an 80 C interval that took about 10 minutes using a heating rate of 8 C/min. Structurally, from aragonite to calcite, the distributionmore » of the Ca atom changes from approximately hexagonal to cubic close-packing. A 5.76% discontinuous increase in volume accompanies the reconstructive first-order transition. Besides the change in coordination of the Ca atom from nine to six from aragonite to calcite, the CO{sub 3} groups change by a 30{sup o} rotation across the transition.« less

Stochastic control system parameter identifiability

NASA Technical Reports Server (NTRS)

Lee, C. H.; Herget, C. J.

1975-01-01

The parameter identification problem of general discrete time, nonlinear, multiple input/multiple output dynamic systems with Gaussian white distributed measurement errors is considered. The knowledge of the system parameterization was assumed to be known. Concepts of local parameter identifiability and local constrained maximum likelihood parameter identifiability were established. A set of sufficient conditions for the existence of a region of parameter identifiability was derived. A computation procedure employing interval arithmetic was provided for finding the regions of parameter identifiability. If the vector of the true parameters is locally constrained maximum likelihood (CML) identifiable, then with probability one, the vector of true parameters is a unique maximal point of the maximum likelihood function in the region of parameter identifiability and the constrained maximum likelihood estimation sequence will converge to the vector of true parameters.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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

PubMed

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

2016-10-01

Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ(18)Ocalc and δ(13)Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ(18)Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in (18)O relative to (16)O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ(18)Ocalc value of eggshell calcite to the δ(18)Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ(13)Ccalc and δ(18)Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ(13)Ccalc and high δ(18)Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions.

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Face-specific Replacement of Calcite by Amorphous Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Liesegang, M.; Milke, R.; Neusser, G.; Mizaikoff, B.

2016-12-01

Amorphous silica, composed of nanoscale spheres, is an important biomineral, alteration product of silicate rocks on the Earth's surface, and precursor material for stable silicate minerals. Despite constant progress in silica sphere synthesis, fundamental knowledge of natural silica particle interaction and ordering processes leading to colloidal crystals is absent so far. To understand the formation pathways of silica spheres in a geologic environment, we investigated silicified Cretaceous mollusk shell pseudomorphs from Coober Pedy (South Australia) using focused ion beam (FIB)-SEM tomography, petrographic microscopy, µ-XRD, and EMPA. The shells consist of replaced calcite crystals (<2 mm) composed of ordered arrays of uniform, close-packed silica spheres 300 ± 10 nm in size. Concentric layered spheres composed of 40 nm-sized subparticles provide evidence that, at least in the final stage, particle aggregation was the major sphere growth mechanism. Silica sphere arrays in periodically changing orientations perfectly replicate polysynthetic twinning planes of calcite. FIB-SEM tomography shows that cubic closed-packed sphere arrangements preserve the twin lamellae, while the twin plane consists of a submicrometer layer of randomly ordered spheres and vacancies. To transfer crystallographic information from parent to product, the advancement of synchronized dissolution and precipitation fronts along lattice planes is essential. We assume that the volume-preserving replacement process proceeds via a face-specific dissolution-precipitation mechanism with intermediate subparticle aggregation and subsequent layer-by-layer deposition of spheres along a planar surface. Porosity created during the replacement reaction allows permanent fluid access to the propagating reaction interface. Fluid pH and ionic strength remain constant throughout the replacement process, permitting continuous silica nanoparticle formation and diffusion-limited colloid aggregation. Our study

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

NASA Astrophysics Data System (ADS)

Raymond, Anne

2016-04-01

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

Specific effects of background electrolytes on the kinetics of step propagation during calcite growth

NASA Astrophysics Data System (ADS)

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

2011-07-01

The mechanisms by which background electrolytes modify the kinetics of non-equivalent step propagation during calcite growth were investigated using Atomic Force Microscopy (AFM), at constant driving force and solution stoichiometry. Our results suggest that the acute step spreading rate is controlled by kink-site nucleation and, ultimately, by the dehydration of surface sites, while the velocity of obtuse step advancement is mainly determined by hydration of calcium ions in solution. According to our results, kink nucleation at acute steps could be promoted by carbonate-assisted calcium attachment. The different sensitivity of obtuse and acute step propagation kinetics to cation and surface hydration could be the origin of the reversed geometries of calcite growth hillocks (i.e., rate of obtuse step spreading < rate of acute step spreading) observed in concentrated (ionic strength, IS = 0.1) KCl and CsCl solutions. At low IS (0.02), ion-specific effects seem to be mainly associated with changes in the solvation environment of calcium ions in solution. With increasing electrolyte concentration, the stabilization of surface water by weakly paired salts appears to become increasingly important in determining step spreading rate. At high ionic strength (IS = 0.1), overall calcite growth rates increased with increasing hydration of calcium in solution (i.e., decreasing ion pairing of background electrolytes for sodium-bearing salts) and with decreasing hydration of the carbonate surface site (i.e., increasing ion pairing for chloride-bearing salts). Changes in growth hillock morphology were observed in the presence of Li +, F - and SO42-, and can be interpreted as the result of the stabilization of polar surfaces due to increased ion hydration. These results increase our ability to predict crystal reactivity in natural fluids which contain significant amounts of solutes.

Calcite orientations and composition ranges within teeth across Echinoidea.

PubMed

Stock, Stuart R; Ignatiev, Konstantin; Lee, Peter L; Almer, Jonathan D

2014-08-01

Sea urchin's teeth from four families of order Echinoida and from orders Temnopleuroida, Arbacioida and Cidaroida were studied with synchrotron X-ray diffraction. The high and very high Mg calcite phases of the teeth, i.e. the first and second stage mineral constituents, respectively, have the same crystallographic orientations. The co-orientation of first and second stage mineral, which the authors attribute to epitaxy, extends across the phylogenic width of the extant regular sea urchins and demonstrates that this is a primitive character of this group. The range of compositions Δx for the two phases of Ca1-xMgxCO3 is about 0.20 or greater and is consistent with a common biomineralization process.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2004-06-15

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

Large-Scale Experiments in Microbially Induced Calcite Precipitation (MICP): Reactive Transport Model Development and Prediction

NASA Astrophysics Data System (ADS)

Nassar, Mohamed K.; Gurung, Deviyani; Bastani, Mehrdad; Ginn, Timothy R.; Shafei, Babak; Gomez, Michael G.; Graddy, Charles M. R.; Nelson, Doug C.; DeJong, Jason T.

2018-01-01

Design of in situ microbially induced calcite precipitation (MICP) strategies relies on a predictive capability. To date much of the mathematical modeling of MICP has focused on small-scale experiments and/or one-dimensional flow in porous media, and successful parameterizations of models in these settings may not pertain to larger scales or to nonuniform, transient flows. Our objective in this article is to report on modeling to test our ability to predict behavior of MICP under controlled conditions in a meter-scale tank experiment with transient nonuniform transport in a natural soil, using independently determined parameters. Flow in the tank was controlled by three wells, via a complex cycle of injection/withdrawals followed by no-flow intervals. Different injection solution recipes were used in sequence for transport characterization, biostimulation, cementation, and groundwater rinse phases of the 17 day experiment. Reaction kinetics were calibrated using separate column experiments designed with a similar sequence of phases. This allowed for a parsimonious modeling approach with zero fitting parameters for the tank experiment. These experiments and data were simulated using PHT3-D, involving transient nonuniform flow, alternating low and high Damköhler reactive transport, and combined equilibrium and kinetically controlled biogeochemical reactions. The assumption that microbes mediating the reaction were exclusively sessile, and with constant activity, in conjunction with the foregoing treatment of the reaction network, provided for efficient and accurate modeling of the entire process leading to nonuniform calcite precipitation. This analysis suggests that under the biostimulation conditions applied here the assumption of steady state sessile biocatalyst suffices to describe the microbially mediated calcite precipitation.

Parameter identifiability of linear dynamical systems

NASA Technical Reports Server (NTRS)

Glover, K.; Willems, J. C.

1974-01-01

It is assumed that the system matrices of a stationary linear dynamical system were parametrized by a set of unknown parameters. The question considered here is, when can such a set of unknown parameters be identified from the observed data? Conditions for the local identifiability of a parametrization are derived in three situations: (1) when input/output observations are made, (2) when there exists an unknown feedback matrix in the system and (3) when the system is assumed to be driven by white noise and only output observations are made. Also a sufficient condition for global identifiability is derived.

Origin and significance of postore dissolution collapse breccias cemented with calcite and barite at the Meikle gold deposit, Northern Carlin trend, Nevada

USGS Publications Warehouse

Emsbo, P.; Hofstra, A.H.

2003-01-01

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

Evaluation of the ability of calcite, bentonite and barite to enhance oil dispersion under arctic conditions.

PubMed

Jézéquel, Ronan; Receveur, Justine; Nedwed, Tim; Le Floch, Stéphane

2018-02-01

A test program was conducted at laboratory and pilot scale to assess the ability of clays used in drilling mud (calcite, bentonite and barite) to create oil-mineral aggregates and disperse crude oil under arctic conditions. Laboratory tests were performed in order to determine the most efficient conditions (type of clay, MOR (Mineral/Oil Ratio), mixing energy) for OMA (Oil Mineral Aggregate) formation. The dispersion rates of four crude oils were assessed at two salinities. Dispersion was characterized in terms of oil concentration in the water column and median OMA size. Calcite appeared to be the best candidate at a MOR of 2:5. High mixing energy was required to initiate OMA formation and low energy was then necessary to prevent the OMAs from resurfacing. Oil dispersion using Corexit 9500 was compared with oil dispersion using mineral fines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of the carbonate dissolution mechanism of Lactococcus sp.

NASA Astrophysics Data System (ADS)

Yanmiş, Derya; Orhan, Furkan; Güllüce, Medine; Şahin, Fikrettin

2017-04-01

Magnesite, the main source for magnesium and magnesium derivatives, are also commonly used in the production of caustic, dead-burned and fused magnesia. World magnesite resources are estimated to be at 12 billion tonnes mostly located in China, Russia, North Korea, Australia and Turkey. Turkey is the second producer of the magnesite. Magnesite deposits in Turkey are sedimentary magnesite which have been formed in specific conditions as high concentrations of MgSO4 and CO2 and presence of certain organic salts or created by hot or cold dissolution connected with carbonate rocks mainly with dolomites. According to the genesis of magnesite deposits, they have some impurities as calcium, quartz, iron, etc. Impurities of magnesite, especially CaCO3, reduce its economic value and industrial usability. In our previous study, we have performed biotechnologically enrichment of magnesite by Lactococcus sp., which gave significantly important results. However, we had no information about carbonate dissolution mechanism of bacteria. Therefore, it is aimed to reveal the metabolites of Lactococcus sp. and mechanism leading to the carbonate dissolution (MgCO3 and CaCO3).

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

F. Grant Ferris

2003-04-12

In situ remediation is an emerging technology that will play an important role in DOE's environmental restoration program, and is an area where enhancement in fundamental understanding will lead to significantly improved cleanup tools. In situ remediation technologies have inherent advantages because they do not require the costly removal, transport, and disposal of contamination. In addition, these technologies minimize worker exposure because contaminated materials are not brought to the surface. Finally, these technologies will minimize the generation of secondary waste streams with their associated treatment and disposal. A particularly promising in situ remediation technology is bioremediation. For inorganic contaminants suchmore » as radionuclides and metals, in situ bioremediation can be used to alter the mobility or reduce the toxicity of radionuclides and metals by changing the valence state of the radionuclides and metals, degrading or producing complexing ligands, or facilitating partitioning on to or off of solid phases. The purpose of the research presented here was to explore microbially facilitated partitioning of metal and radionuclides by their co-precipitation with calcium carbonate. Although this approach is a very attractive cleanup alternative, its practical implementation requires improved scientific understanding of the geochemical and biological mechanisms involved, particularly with respect to rates and mechanisms of microbially facilitated calcite precipitation. Of interest for this investigation is the in situ manipulation of calcite precipitation by the microbially catalyzed hydrolysis of urea. The production of ammonia during microbial decomposition of urea tends to drive pH upwards, and results in formation of alkaline conditions. When solution concentrations of Ca2+ and HCO3- are high enough, calcium carbonate precipitation may occur. A series of water samples collected from four wells tapping the aquifer underlying Eastern Snake

A laser GC-IRMS technique for in situ stable isotope analyses of carbonates and phosphates

NASA Astrophysics Data System (ADS)

Sharp, Z. D.; Cerling, T. E.

1996-08-01

A technique is described whereby in situ carbon and oxygen isotope analyses of carbonates and organic phosphates can be made with the use of a CO 2 laser. The CO 2 gas generated by thermal decarbonation from the laser is entrained in a helium carrier gas, passes through a chromatographic column (GC), and is admitted directly into the isotope ratio mass spectrometer (IRMS). No vacuum systems, pumps, or cryogenic traps are used. All carbonates and biogenic phosphates can be analyzed, no special sample preparation is required and analyses can be made every 3 minutes. The use of a helium carrier gas allows for extremely small samples to be analyzed and the GC column effectively separates CO 2 from any other potential contaminating gases (e.g., SO 2 which is a particular problem in organic apatite). The average reproducibility of calcite, dolomite, magnesite, rhodochrosite, siderite, and smithsonite (ZnCO 3) is 0.29‰ for oxygen and 0.1‰ for carbon (1σ); the most "homogeneous" samples are reproducible to better than 0.1‰ for carbon and 0.2‰ for oxygen. The difference between the laser and conventional values for carbon isotope ratios [Δ 13C (laser-conv)] is 0.05 ± 0.30‰ for all carbonates (excluding siderite). The Δ 18O(laser-conv) value varies from carbonate to carbonate and may be related to the electronegativities of the cations, grain size (or crystallinity), formation of CO and O 2, and reaction with included organic matter. For calcite and rhodochrosite, the Δ 18O(laser-conv) value is 0.3 ± 0.4‰; for siderite, magnesite, and dolomite, the Δ 18O(laser-conv) value is 1.7 ± 0.3‰. The δ 13C values of tooth enamel are the same as those obtained by conventional acid digestion. The laser δ 18O values are equal to the δ 18O values of the phosphate, and approx. 7‰ lighter than the "carbonate" oxygen. The carbonate group in the apatite (equiv. 7.6% oxygen) exchanges with the (PO 4=)-bound oxygen to produce CO 2 with a δ 18O equal to the phosphate

Cave air and hydrological controls on prior calcite precipitation and stalagmite growth rates: Implications for palaeoclimate reconstructions using speleothems

NASA Astrophysics Data System (ADS)

Sherwin, Catherine M.; Baldini, James U. L.

2011-07-01

Hourly resolved cave air P and cave drip water hydrochemical data illustrate that calcite deposition on stalagmites can be modulated by prior calcite precipitation (PCP) on extremely short timescales. A very clear second-order covariation between cave air P and drip water Ca 2+ concentrations during the winter months demonstrates the effects of degassing-induced PCP on drip water chemistry. Estimating the strength of the cave air P control on PCP is possible because the PCP signal is so clear; at our drip site a one ppm shift in Ca 2+ concentrations requires a P shift of between 333 and 667 ppm. This value will undoubtedly vary from site to site, depending on drip water flow rate, residence time, drip water-cave air P differential, and availability of low P void spaces in the vadose zone above the cave. High-resolution cave environmental measurements were used to model calcite deposition on one stalagmite in Crag Cave, SW Ireland, and modelled growth over the study period (222 μm over 171 days) is extremely similar to the amount of actual calcite growth (240 μm) over the same time interval, strongly suggesting that equations used to estimate stalagmite growth rates are valid. Although cave air P appears to control drip water hydrochemistry in the winter, drip water dilution caused by rain events may have played a larger role during the summer, as evidenced by a series of sudden drops in Ca 2+ concentrations (dilution) followed by much more gradual increases in drip water Ca 2+ concentrations (slow addition of diffuse water). This research demonstrates that PCP on stalactites, cave ceilings, and void spaces within the karst above the cave partially controls drip water chemistry, and that thorough characterisation of this process at individual caves is necessary to most accurately interpret climate records from those sites.

Calcite orientations and composition ranges within teeth across Echinoidea

PubMed Central

Stock, Stuart R.; Ignatiev, Konstantin; Lee, Peter L.; Almer, Jonathan D.

2016-01-01

Sea urchin’s teeth from four families of order Echinoida and from orders Temnopleuroida, Arbacioida and Cidaroida were studied with synchrotron x-ray diffraction. The high and very high Mg calcite phases of the teeth, i.e. the first and second stage mineral constituents, respectively, have the same crystallographic orientations. The co-orientation of first and second stage mineral, which the authors attribute to epitaxy, extends across the phylogenic width of the extant regular sea urchins and demonstrates that this is a primitive character of this group. The range of compositions Δx for the two phases of Ca1−xMgxCO3 is about 0.20 or greater and is consistent with a common biomineralization process. PMID:25158180

Evolution of a calcite marble shear zone complex on Thassos Island, Greece: microstructural and textural fabrics and their kinematic significance

NASA Astrophysics Data System (ADS)

Bestmann, Michel; Kunze, Karsten; Matthews, Alan

2000-11-01

The deformation history of a monophase calcite marble shear zone complex on Thassos Island, Northern Greece, is reconstructed by detailed geometric studies of the textural and microstructural patterns relative to a fixed reference system (shear zone boundary, SZB). Strain localization within the massive marble complex is linked to decreasing P- T conditions during the exhumation process of the metamorphic core complex. Solvus thermometry indicates that temperatures of 300-350°C prevailed during part of the shear zone deformation history. The coarse-grained marble protolith outside the shear zone is characterized by symmetrically oriented twin sets due to early coaxial deformation. A component of heterogeneous non-coaxial deformation is first recorded within the adjacent protomylonite. Enhanced strain weakening by dynamic recrystallization promoted strong localization of plastic deformation in the ultramylonite of the calcite shear zone, where high strain was accommodated by non-coaxial flow. This study demonstrates that both a pure shear and a simple shear strain path can result in similar crystallographic preferred orientations (single c-axis maximum perpendicular to the SZB) by different dominant deformation mechanisms. Separated a-axis pole figures (+ a- and - a-axis) show different density distributions with orthorhombic texture symmetry in the protolith marble and monoclinic symmetry in the ultramylonite marble consistently with the observed grain fabric symmetry.

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

USGS Publications Warehouse

Plummer, Niel; Sundquist, Eric T.

1982-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Chunlong; Qi, Jiahui; Tao, Jinhui

2014-09-05

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

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

PubMed Central

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

2014-01-01

In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic and hydrophobic interactions, with hydrophobic interactions playing the dominant role. While either strong electrostatic or hydrophobic interactions inhibit growth and reduces expression of the {104} faces, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate electrostatic interactions allow peptoids to weakly adsorb while moderate hydrophobic interactions cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of the {104} faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications. PMID:25189418

On the formation and functions of high and very high magnesium calcites in the continuously growing teeth of the echinoderm Lytechinus variegatus: development of crystallinity and protein involvement.

PubMed

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

2011-01-01

Sea urchin teeth grow continuously and develop a complex mineralized structure consisting of spatially separate but crystallographically aligned first stage calcitic elements of high Mg content (5-15 mol% mineral). These become cemented together by epitaxially oriented second stage very high Mg calcite (30-40 mol% mineral). In the tooth plumula, ingressing preodontoblasts create layered cellular syncytia. Mineral deposits develop within membrane-bound compartments between cellular syncytial layers. We seek to understand how this complex tooth architecture is developed, how individual crystalline calcitic elements become crystallographically aligned, and how their Mg composition is regulated. Synchrotron microbeam X-ray scattering was performed on live, freshly dissected teeth. We observed that the initial diffracting crystals lie within independent syncytial spaces in the plumula. These diffraction patterns match those of mature tooth calcite. Thus, the spatially separate crystallites grow with the same crystallographic orientation seen in the mature tooth. Mineral-related proteins from regions with differing Mg contents were isolated, sequenced, and characterized. A tooth cDNA library was constructed, and selected matrix-related proteins were cloned. Antibodies were prepared and used for immunolocaliztion. Matrix-related proteins are acidic, phosphorylated, and associated with the syncytial membranes. Time-of-flight secondary ion mass spectroscopy of various crystal elements shows unique amino acid, Mg, and Ca ion distributions. High and very high Mg calcites differ in Asp content. Matrix-related proteins are phosphorylated. Very high Mg calcite is associated with Asp-rich protein, and it is restricted to the second stage mineral. Thus, the composition at each part of the tooth is related to architecture and function. Copyright © 2011 S. Karger AG, Basel.

Calcite Phase Conversion Prediction Model for CaO-Al2O3-SiO2 Slag: An Aqueous Carbonation Process at Ambient Pressure

NASA Astrophysics Data System (ADS)

Zhang, Huining; Dong, Jianhong; Li, Hui; Xiong, Huihui; Xu, Anjun

2018-06-01

To evaluate the effect of the mineralogical phase on carbonation efficiency for CaO-Al2O3-SiO2 slag, a calcite phase conversion prediction model is proposed. This model combines carbon dioxide solubility with carbonation reaction kinetic analysis to improve the prediction capability. The effect of temperature and carbonation time on the carbonation degree is studied in detail. Results show that the reaction rate constant ranges from 0.0135 h-1 to 0.0458 h-1 and that the mineralogical phase contribution sequence for the carbonation degree is C2S, CaO, C3A and CS. The model accurately predicts the effect of temperature and carbonation time on the simulated calcite conversion, and the results agree with the experimental data. The optimal carbonation temperature and reaction time are 333 K and 90 min, respectively. The maximum carbonation efficiency is about 184.3 g/kg slag, and the simulation result of the calcite phase content in carbonated slag is about 20%.

Insights into Paleogene biogeochemistry from coupled carbon and sulfur isotopes in foraminiferal calcite.

NASA Astrophysics Data System (ADS)

Rennie, V.; Paris, G.; Abramovitch, S.; Sessions, A. L.; Adkins, J. F.; Turchyn, A. V.

2014-12-01

The Paleogene witnessed large-scale environmental changes, including the beginning of long-term Cenozoic cooling. The carbon isotope composition of foraminiferal calcite suggests a major reorganization of the carbon cycle over the Paleogene, with enhanced organic carbon burial in the Paleocene, and subsequent oxidation of this organic carbon or increased volcanism throughout the Eocene. The sulfur cycle is linked to the carbon cycle via the breakdown of organic carbon during bacterial sulfate reduction. Over geological time, carbon and sulfur isotopic shifts are often coupled due to enhanced pyrite burial being coupled to enhanced organic carbon burial, and enhanced pyrite weathering being coupled to enhanced organic carbon weathering. However, over the Paleogene, carbon and sulfur isotopes are fully decoupled, with the sulfur isotope record showing only one major shift in the early Eocene, after most of the carbon isotope variability is complete. One complication of interpreting the evolution of the sulfur cycle over the Cenozoic, is the fact that the mineral proxies used (typically barite) may not be temporally coincident with those used to reconstruct the carbon cycle (typically carbonate). Furthermore, these minerals are preserved in different locations, and therefore often must be extracted from different sediment cores in different ocean basins, leading to age-model uncertainty when the records are merged. To properly ascertain the phasing between early Cenozoic changes in the carbon cycle and the sulfur cycle, we would ideally measure all isotope records on the same mineral. A new sulfur isotope analytical technique [1] has been optimised for foraminiferal calcite as a proxy for seawater δ34SSO4. The δ34SSO4 in foraminiferal calcite can then be tied to records of carbon isotopes from stratigraphically identical samples, resolving previous age model uncertainties. We present coupled carbon and sulfur isotope records from the same core over the early

Soap-stone in architecture of North European cities. A nomination as a candidate for a Global Heritage Stones Resource

NASA Astrophysics Data System (ADS)

Bulakh, Andrey

2016-04-01

Soap stone represents soft Proterozoic rock type from the deposit Nunnalahti situated on the western shore of the big Lake Pielinen in Eastern Finland. It consists of talc (40 - 50 %), magnesite MgCO3 (40 - 50 %), chlorite (5 - 8 %), dolomite, calcite, etc. The colour of the stone is very spectacular and varies from yellow and brownish-yellow to grey, greenish grey. The soft stone is a highly workable material for a sculptor's chisel. It was one of the most popular ornamental rocks used architecture of the Modern style in St Petersburg, Helsinki, Turku, Tampere and other North European cities lately in the XIX-th centuries. Examples are given and discussed. References: Bulakh, A.G., Abakumova, N.B., and Romanovsky, J.V. St Petersburg: a History in Stone. 2010. Print House of St Petersburg State University. 173 p. (In English).

The effect of water on recrystallization behavior and grain boundary morphology in calcite observations of natural marble mylonites

NASA Astrophysics Data System (ADS)

Schenk, Oliver; Urai, Janos L.; Evans, Brian

2005-10-01

Fluids are inferred to play a major role in the deformation and recrystallization of many minerals (e.g. quartz, olivine, halite, feldspar). In this study, we sought to identify the effect of fluids on grain boundary morphology and recrystallization processes in marble mylonites during shear zone evolution. We compared the chemistry, microstructure and mesostructure of calcite marble mylonites from the Schneeberg Complex, Southern Tyrole, Italy, to that from the Naxos Metamorphic Core Complex, Greece. These two areas were selected for comparison because they have similar lithology and resemble each other in chemical composition. In addition, calcite-dolomite geothermometry indicates similar temperatures for shear zone formation: 279±25 °C (Schneeberg Complex) and 271±15 °C (Naxos high-grade core). However, the two settings are different in the nature of the fluids present during the shear zone evolution. In the Schneeberg mylonites, both the alteration of minerals during retrograde metamorphism in the neighboring micaschists and the existence of veins suggest that aqueous fluids were present during mylonitization. The absence of these features in the Naxos samples indicates that aqueous fluids were not as prevalent during deformation. This conclusion is also supported by the stable isotope signature. Observations of broken and planar surfaces using optical and scanning electron microscopes did not indicate major differences between the two mylonites: grain boundaries in both settings display pores with shapes controlled by crystallography, and have pore morphologies that are similar to observations from crack and grain-boundary healing experiments. Grain size reduction was predominantly the result of subgrain rotation recrystallization. However, the coarse grains inside the wet protomylonites (Schneeberg) are characterized by intracrystalline shear zones.

Sea urchin spine calcite forms via a transient amorphous calcium carbonate phase.

PubMed

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

2004-11-12

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

Incorporation of Mg, Sr, Ba, U, and B in High-Mg Calcite Benthic Foraminifers Cultured Under Controlled pCO2

NASA Astrophysics Data System (ADS)

Not, C.; Thibodeau, B.; Yokoyama, Y.

2018-01-01

Measurement of elemental ratios (E/Ca) has been performed in two symbiont-bearing species of high-Mg calcite benthic foraminifers (hyaline, Baculogypsina sphaerulata and porcelaneous, Amphisorus hemprichii), cultured under five pCO2 levels, representing preindustrial, modern, and three predicted future values. E/Ca ratios were analyzed by Laser Ablation coupled with Inductively Coupled Plasma Mass Spectrometer (LA-ICP-MS). We measured several E/Ca, such as Mg/Ca, Sr/Ca, Ba/Ca, U/Ca, and B/Ca simultaneously. We observed that high-Mg calcite benthic foraminifers possess higher E/Ca than low-Mg calcite foraminifers, irrespective of their calcification mode (hyaline or porcelaneous). In both modes of calcification, Mg, Sr, Ba, U, and B incorporation could be controlled by Rayleigh fractionation. However, more data are needed to validate and quantify the relative importance of this process and closely investigate the presence/absence of other mechanism. Therefore, it highlights the need for a multielemental approach when looking at trace element incorporation. Finally, no significant relationship was observed between the different ratios and the pCO2 of the water, suggesting that none of the Mg/Ca, Sr/Ca, Ba/Ca, U/Ca, and B/Ca is sensitive to bottom water pCO2 or pH for these species.

Distributed design approach in persistent identifiers systems

NASA Astrophysics Data System (ADS)

Golodoniuc, Pavel; Car, Nicholas; Klump, Jens

2017-04-01

The need to identify both digital and physical objects is ubiquitous in our society. Past and present persistent identifier (PID) systems, of which there is a great variety in terms of technical and social implementations, have evolved with the advent of the Internet, which has allowed for globally unique and globally resolvable identifiers. PID systems have catered for identifier uniqueness, integrity, persistence, and trustworthiness, regardless of the identifier's application domain, the scope of which has expanded significantly in the past two decades. Since many PID systems have been largely conceived and developed by small communities, or even a single organisation, they have faced challenges in gaining widespread adoption and, most importantly, the ability to survive change of technology. This has left a legacy of identifiers that still exist and are being used but which have lost their resolution service. We believe that one of the causes of once successful PID systems fading is their reliance on a centralised technical infrastructure or a governing authority. Golodoniuc et al. (2016) proposed an approach to the development of PID systems that combines the use of (a) the Handle system, as a distributed system for the registration and first-degree resolution of persistent identifiers, and (b) the PID Service (Golodoniuc et al., 2015), to enable fine-grained resolution to different information object representations. The proposed approach solved the problem of guaranteed first-degree resolution of identifiers, but left fine-grained resolution and information delivery under the control of a single authoritative source, posing risk to the long-term availability of information resources. Herein, we develop these approaches further and explore the potential of large-scale decentralisation at all levels: (i) persistent identifiers and information resources registration; (ii) identifier resolution; and (iii) data delivery. To achieve large-scale decentralisation

Uncovering the Atomistic Mechanism for Calcite Step Growth

DOE PAGES

De La Pierre, Marco; Raiteri, Paolo; Stack, Andrew G.; ...

2017-04-13

Determining a complete atomic-level picture of how minerals grow from aqueous solution remains a challenge as macroscopic rates can be a convolution of many reactions. For the case of calcite (CaCO 3) in water, computer simulations have been used in this paper to map the complex thermodynamic landscape leading to growth of the two distinct steps, acute and obtuse, on the basal surface. The carbonate ion is found to preferentially adsorb at the upper edge of acute steps while Ca 2+ only adsorbs after CO 3 2-. In contrast to the conventional picture, ion pairs prefer to bind at themore » upper edge of the step with only one ion, at most, coordinated to the step and lower terrace. Finally, migration of the first carbonate ion to a growth site is found to be rate-limiting for kink nucleation, with this process having a lower activation energy on the obtuse step.« less

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

PubMed

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

2017-10-15

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

Trustworthy persistent identifier systems of the future

NASA Astrophysics Data System (ADS)

Golodoniuc, Pavel; Klump, Jens; Car, Nicholas

2016-04-01

Over the last two decades, persistent identifier (PID) systems have seen some significant changes in their governance policies, system capabilities, and technology. The development of most systems was driven by two main application areas, namely archives and libraries. Guidelines and criteria for trustworthy PID systems have been clearly devised (Bütikofer, 2009) and many PID system implementations for the identification of static digital objects have been built (e.g., PURL). However systems delivering persistent identifiers for dynamic datasets are not yet mature. There has been a rapid proliferation of different PID systems caused by the specific technical or organisational requirements of various communities that could not be met by existing systems such as DOI, ISBN, and EAN. Many of these different systems were limited by their inability to provide native means of persistent identifier resolution. This has prompted a decoupling of PID-associated data from the resolution service and this is where the Handle system has played a significant role. The Handle allowed to build a distributed system of independently managed resolver services. A trustworthy PID system must be designed to outlive the objects it provides persistent identifiers for, which may cease to exist or otherwise be deprecated, and the technology used to implement it, which will certainly need to change with time. We propose that such a system should rest on four pillars of agreements - (i) definitions, (ii) policies, (iii) services, and (iv) data services, to ensure longevity. While we believe all four pillars are equally important, we intentionally leave regulating aspects of issuing of identifiers and their registration out of the scope of this paper and focus on the agreements that have to be established between PID resolver services and the data sources indicated by the persistent identifiers. We propose an approach to development of PID systems that combines the use of (a) the Handle system

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Robert W.; Fujita, Yoshiko; Hubbard, Susan S.

2013-11-15

Subsurface radionuclide and metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE's greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent ions, such as the short-lived radionuclide 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,more » 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 of the core

Calcite Dissolution Kinetics

NASA Astrophysics Data System (ADS)

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

2016-12-01

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 <=0.04 g/L) to enhance the dissolution 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

Acoustic emissions imaging and synchrotron X-ray diffraction analysis of calcite at high pressure and temperature

NASA Astrophysics Data System (ADS)

Gasc, J.; Brantut, N.; Schubnel, A.; Brunet, F.; Mueller, H.

2008-12-01

We have monitored from in-situ X-ray diffraction coupled to Acoustic Emission (AE) imaging, the behavior of a fine grained synthetic calcite aggregate, at 0.66 GPa and for temperatures ranging from ambient to 1200° C. The powder sample was placed in a boron-epoxy assembly with an 8 mm edge-length and loaded in the MAX80 cubic multi-anvil press installed on the German synchrotron (HASYLAB-DESY, Hamburg). AE were recorded using five piezoceramic transducers (5 MHz eigen frequency) glued on each of the five WC anvils (4 side anvils and upper one). Full waveforms were acquired using an eight channel digital oscilloscope and located using the software Insite (ASC Ltd). Beyond 600° C, calcite grains started growing as evidenced by huge changes in the relative intensity of the diffraction lines. This is correlated to a sudden burst of AE which all located within the sample volume. These AE may indicate that stress relaxation, going on as intra-crystalline plasticity mechanisms were activated, released enough acoustic energy to be recorded and located. Although the diffraction data showed that grain growth continued beyond 800° C, the acoustic activity progressively decreased to below the sensitivity of our recording device (i.e. the triggering level). However, at temperature higher than 1000° C, a large number of AE were recorded again ( 2000 events). AE location revealed that the AE front progressed inwards the sample. The complete loss of diffraction signal and the post-mortem recovery of small amounts of CaO suggest that the second AE burst may be related to calcite melting/decarbonation. Perspectives include thorough microstructural analysis of the samples using electron microscopies (SEM and TEM) as well as a statistical and mechanical analysis of the acoustic data.

Near Identifiability of Dynamical Systems

NASA Technical Reports Server (NTRS)

Hadaegh, F. Y.; Bekey, G. A.

1987-01-01

Concepts regarding approximate mathematical models treated rigorously. Paper presents new results in analysis of structural identifiability, equivalence, and near equivalence between mathematical models and physical processes they represent. Helps establish rigorous mathematical basis for concepts related to structural identifiability and equivalence revealing fundamental requirements, tacit assumptions, and sources of error. "Structural identifiability," as used by workers in this field, loosely translates as meaning ability to specify unique mathematical model and set of model parameters that accurately predict behavior of corresponding physical system.

Monitoring of a fast-growing speleothem site from the Han-sur-Lesse cave, Belgium, indicates equilibrium deposition of the seasonal δ18O and δ13C signals in the calcite

NASA Astrophysics Data System (ADS)

Van Rampelbergh, M.; Verheyden, S.; Allan, M.; Quinif, Y.; Keppens, E.; Claeys, P.

2014-10-01

Speleothems provide paleoclimate information on multimillennial to decadal scales in the Holocene. However, seasonal or even monthly resolved records remain scarce. Such records require fast-growing stalagmites and a good understanding of the proxy system on very short timescales. The Proserpine stalagmite from the Han-sur-Less cave (Belgium) displays well-defined/clearly visible darker and lighter seasonal layers of 0.5 to 2 mm thickness per single layer, which allows a measuring resolution at a monthly scale. Through a regular cave monitoring, we acquired a good understanding of how δ18O and δ13C signals in modern calcite reflect climate variations on the seasonal scale. From December to June, outside temperatures are cold, inducing low cave air and water temperature, and bio-productivity in the soil is limited, leading to lower pCO2 and higher δ13C values of the CO2 in the cave air. From June to December, the measured factors display an opposite behavior. The absence of epikarst water recharge between May and October increases prior calcite precipitation (PCP) in the vadose zone, causing drip water to display increasing pH and δ13C values over the summer months. Water recharge of the epikarst in winter diminishes the effect of PCP and as a result the pH and δ13C of the drip water gradually decrease. The δ18O and δ13C signals of fresh calcite precipitated on glass slabs also vary seasonally and are both reflecting equilibrium conditions. Lowest δ18O values occur during the summer, when the δ13C values are high. The δ18O values of the calcite display seasonal variations due to changes in the cave air and water temperature. The δ13C values reflect the seasonal variation of the δ13CDIC of the drip water, which is affected by the intensity of PCP. This same anticorrelation of the δ18O versus the δ13C signals is seen in the monthly resolved speleothem record that covers the period between 1976 and 1985 AD. Dark layers display lower δ18O and higher δ13C

Structural evolution of calcite at high temperatures: Phase V unveiled

PubMed Central

Ishizawa, Nobuo; Setoguchi, Hayato; Yanagisawa, Kazumichi

2013-01-01

The calcite form of calcium carbonate CaCO3 undergoes a reversible phase transition between Rc and Rm at ~1240 K under a CO2 atmosphere of ~0.4 MPa. The joint probability density function obtained from the single-crystal X-ray diffraction data revealed that the oxygen triangles of the CO3 group in the high temperature form (Phase V) do not sit still at specified positions in the space group Rm, but migrate along the undulated circular orbital about carbon. The present study also shows how the room temperature form (Phase I) develops into Phase V through an intermediate form (Phase IV) in the temperature range between ~985 K and ~1240 K. PMID:24084871

The Raman spectrum of Ca-Mg-Fe carbonates; Applications in geobiology

NASA Astrophysics Data System (ADS)

van Zuilen, M. A.; Rividi, N.; Ménez, B.; Philippot, P.

2012-04-01

Carbonates form a very important mineral group in geobiological studies. They are a common mineral matrix for putative carbonaceous microfossils in Archean greenstone belts, form an important chemical deposit in seafloor hydrothermal systems, and are a common product in biomineralization processes. In many geobiological studies there is a specific need for simple characterization of carbonate composition while avoiding complex sample preparation or sample destruction. Raman spectroscopy is a highly versatile non-destructive technique enabling in-situ characterization of minerals and carbonaceous materials. It can be combined with confocal microscopy enabling high-resolution Raman mapping of entire rock thin sections, or can be integrated in submersibles and potentially Mars-rovers for direct field-based mineral identification. It is thus important that well-established spectral databases exist which enable unambiguous identification of a wide variety of carbonate minerals. The most common carbonates in the Ca-Mg-Fe system include the CaCO3 polymorphs calcite, aragonite, and vaterite, as well as the solid solutions CaMg(CO3)2-CaFe(CO3)2 (dolomite-ankerite) and MgCO3-FeCO3 (magnesite-siderite). Although various carbonate end-members have been studied exhaustively by Raman spectroscopy, a simple protocol for rapid distinction of various carbonate solid solutions is still lacking. Here we present a detailed study of Raman shifts in various carbonate standards of known composition in the Ca-Mg-Fe system. Carbonates with rhombohedral symmetry display a Raman spectrum with six characteristic vibrational modes - four of these represent vibrations within the (CO3)2- unit and two represent external vibrations of the crystal lattice. We show that Raman band shifts of internal mode 2ν2 (range 1725-1765 cm-1), and external modes T (range 170-215 cm-1) and L (range 285-330 cm-1) for siderite-magnesite and ankerite-dolomite solid solutions display distinct and well defined

Zircon-quartz-calcite segregations in carbonate-alkaline metasomatic rocks of the western Baikal region and their petrogenetic implications

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

A paired apatite and calcite clumped isotope thermometry approach to estimating Cambro-Ordovician seawater temperatures and isotopic composition

NASA Astrophysics Data System (ADS)

Bergmann, Kristin D.; Finnegan, Seth; Creel, Roger; Eiler, John M.; Hughes, Nigel C.; Popov, Leonid E.; Fischer, Woodward W.

2018-03-01

The secular increase in δ18O values of both calcitic and phosphatic marine fossils through early Phanerozoic time suggests either that (1) early Paleozoic surface temperatures were high, in excess of 40 °C (tropical MAT), (2) the δ18O value of seawater has increased by 7-8‰ VSMOW through Paleozoic time, or (3) diagenesis has altered secular trends in early Paleozoic samples. Carbonate clumped isotope analysis, in combination with petrographic and elemental analysis, can deconvolve fluid composition from temperature effects and therefore determine which of these hypotheses best explain the secular δ18O increase. Clumped isotope measurements of a suite of calcitic and phosphatic marine fossils from late Cambrian- to Middle-late Ordovician-aged strata-the first paired fossil study of its kind-document tropical sea surface temperatures near modern temperatures (26-38 °C) and seawater oxygen isotope ratios similar to today's ratios.

Stress remagnetization in pyrrhotite-calcite synthetic aggregates

NASA Astrophysics Data System (ADS)

Robion, Philippe; Borradaile, Graham J.

2001-01-01

Stress-induced remagnetization has been applied to multidomain pyrrhotite-calcite synthetic aggregates in a triaxial rig. Experimental deformation used 150MPa confining pressure, a constant strain rate of 10-5 s-1 and applied differential stresses of up to 70MPa. New components of magnetization, parallel to the direction of the pressure vessel field, were added to the pre-deformational magnetization. The intensity of remagnetization (M'-M0) increases with the intensity of the applied differential stress and affects the coercivity fraction below 15mT. Bulk shortening is less than 8 per cent, thus grain rotation cannot explain selective remagnetization of the low-coercivity fraction. Remagnetization is thus attributed to deformational viscous remanent magnetization (DVRM). It is observed that high-coercivity (>15mT) grains do not remagnetize. There is, however, slight progressive rotation of pre-deformational magnetization with increasing strain up to 8 per cent of bulk shortening. The lack of piezoremanent magnetization in the high-coercivity range may be due to defects introduced in pyrrhotite during sample preparation. Experiments using synthetic pyrrhotite, expected to show low dislocation densities, would be necessary to test this effect.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2004-06-15

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

Role of fluids in experimental calcite-bearing faults at seismic deformation conditions.

NASA Astrophysics Data System (ADS)

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

2012-04-01

Fluids play a fundamental physical (fluid pressure, temperature buffering, etc.) and chemical (dissolution, hydrolytic weakening, etc.) role in controlling fault strength and earthquake nucleation, propagation and arrest. However, due to technical challenges, the influence of water at deformation conditions typical of earthquakes (i.e., slip rates of 1 m/s, displacements of 0.1-5 m, normal stress of tens of MPa) remains poorly constrained experimentally. Here we present results from high velocity friction experiments performed with a rotary shear apparatus (SHIVA: Slow to HIgh Velocity (friction) Apparatus) on Carrara marble. SHIVA is equipped with (1) an environmental/vacuum chamber to perform experiments in the absence of room-humidity, (2) a pressure vessel to perform experiments with fluids (up to 15 MPa confining pressure), including devices to determine fluid composition (Ca2+, Mg2+, HCO3-, etc). Experiments were conducted on hollow cylinders (50/30 mm ext/int diameter) of Carrara (98% calcite) marble at velocities of 1-6.5 m/s, displacements up to a few meters, normal stresses up to 40 MPa and fluid pressures between 0 (under vacuum) and 15 MPa (fluid-saturated conditions, with H2O in chemical equilibrium with the marble). Rock and fluid samples were recovered for post-run analysis to determine deformation mechanisms and changes in fluid composition. Under these deformation conditions: 1) the friction coefficient decays rapidly from a peak (= static) μp ~ 0.8 at the initiation of sliding towards a steady-state μss ~ 0.1. The absolute values of both peak and steady-state friction are not significantly influenced by the presence of fluids; 2) the decay from peak to steady-state friction is more abrupt in presence of fluids; 3) during deceleration of the friction apparatus, the friction coefficient recovers almost instantaneously to a value, μr, of 0.2-0.6 ( strength recovery) resulting in a small static stress drop. Strength recovery is smaller in the

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riechers, Shawn L.; Kerisit, Sebastien N.

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 significantmore » 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.« less

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

PubMed Central

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

2012-01-01

Karstic caves represent one of the most important subterranean carbon storages on Earth and provide windows into the subsurface. The recent discovery of the Herrenberg Cave, Germany, gave us the opportunity to investigate the diversity and potential role of bacteria in carbonate mineral formation. Calcite was the only mineral observed by Raman spectroscopy to precipitate as stalactites from seepage water. Bacterial cells were found on the surface and interior of stalactites by confocal laser scanning microscopy. Proteobacteria dominated the microbial communities inhabiting stalactites, representing more than 70% of total 16S rRNA gene clones. Proteobacteria formed 22 to 34% of the detected communities in fluvial sediments, and a large fraction of these bacteria were also metabolically active. A total of 9 isolates, belonging to the genera Arthrobacter, Flavobacterium, Pseudomonas, Rhodococcus, Serratia, and Stenotrophomonas, grew on alkaline carbonate-precipitating medium. Two cultures with the most intense precipitate formation, Arthrobacter sulfonivorans and Rhodococcus globerulus, grew as aggregates, produced extracellular polymeric substances (EPS), and formed mixtures of calcite, vaterite, and monohydrocalcite. R. globerulus formed idiomorphous crystals with rhombohedral morphology, whereas A. sulfonivorans formed xenomorphous globular crystals, evidence for taxon-specific crystal morphologies. The results of this study highlighted the importance of combining various techniques in order to understand the geomicrobiology of karstic caves, but further studies are needed to determine whether the mineralogical biosignatures found in nutrient-rich media can also be found in oligotrophic caves. PMID:22179248

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

PubMed

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

2012-02-01

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

Interrogator system for identifying electrical circuits

DOEpatents

Jatko, W.B.; McNeilly, D.R.

1988-04-12

A system for interrogating electrical leads to correctly ascertain the identity of equipment attached to remote ends of the leads is disclosed. The system includes a source of a carrier signal generated in a controller/receiver to be sent over the leads and an identifier unit at the equipment. The identifier is activated by command of the carrier and uses a portion of the carrier to produce a supply voltage. Each identifier is uniquely programmed for a specific piece of equipment, and causes the impedance of the circuit to be modified whereby the carrier signal is modulated according to that program. The modulation can be amplitude, frequency or phase modulation. A demodulator in the controller/receiver analyzes the modulated carrier signal, and if a verified signal is recognized displays and/or records the information. This information can be utilized in a computer system to prepare a wiring diagram of the electrical equipment attached to specific leads. Specific circuit values are given for amplitude modulation, and the system is particularly described for use with thermocouples. 6 figs.

Interrogator system for identifying electrical circuits

DOEpatents

Jatko, William B.; McNeilly, David R.

1988-01-01

A system for interrogating electrical leads to correctly ascertain the identity of equipment attached to remote ends of the leads. The system includes a source of a carrier signal generated in a controller/receiver to be sent over the leads and an identifier unit at the equipment. The identifier is activated by command of the carrier and uses a portion of the carrier to produce a supply voltage. Each identifier is uniquely programmed for a specific piece of equipment, and causes the impedance of the circuit to be modified whereby the carrier signal is modulated according to that program. The modulation can be amplitude, frequency or phase modulation. A demodulator in the controller/receiver analyzes the modulated carrier signal, and if a verified signal is recognized displays and/or records the information. This information can be utilized in a computer system to prepare a wiring diagram of the electrical equipment attached to specific leads. Specific circuit values are given for amplitude modulation, and the system is particularly described for use with thermocouples.

Calcite raft geochemistry as a hydrological proxy for Holocene aquifer conditions in Hoyo Negro and Ich Balam (Sac Actun Cave System), Quintana Roo, Mexico

NASA Astrophysics Data System (ADS)

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

2017-11-01

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.

On the origin of fiber calcite crystals in moonmilk deposits.

PubMed

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

2006-01-01

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

Low-threshold collinear parametric Raman comb generation in calcite under 532 and 1064 nm picosecond laser pumping

NASA Astrophysics Data System (ADS)

Smetanin, S. N.; Jelínek, M., Jr.; Kubeček, V.; Jelínková, H.

2015-09-01

Optimal conditions of low-threshold collinear parametric Raman comb generation in calcite (CaCO3) are experimentally investigated under 20 ps laser pulse excitation, in agreement with the theoretical study. The collinear parametric Raman generation of the highest number of Raman components in the short calcite crystals corresponding to the optimal condition of Stokes-anti-Stokes coupling was achieved. At the excitation wavelength of 1064 nm, using the optimum-length crystal resulted in the effective multi-octave frequency Raman comb generation containing up to five anti-Stokes and more than four Stokes components (from 674 nm to 1978 nm). The 532 nm pumping resulted in the frequency Raman comb generation from the 477 nm 2nd anti-Stokes up to the 692 nm 4th Stokes component. Using the crystal with a non-optimal length leads to the Stokes components generation only with higher thresholds because of the cascade-like stimulated Raman scattering with suppressed parametric coupling.

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

NASA Astrophysics Data System (ADS)

Milliere, Laure; Verrecchia, Eric; Gussone, Nikolaus

2014-05-01

Calcium (Ca), carbon (C) and oxygen (O) are important elements in terrestrial environment, as their biogeochemical cycles are directly related to the storage of atmospheric carbon. Nevertheless, contrarily to C and O, Ca isotope composition has been only poorly studied in the terrestrial carbonates. Needle Fibre Calcite (NFC) is one of the most common pedogenic carbonates, unless its origin is still under debate. Recent studies explain its formation by precipitation inside fungal hyphae. Due to this possible biogenic origin, NFC can be considered as a potential bridge between the biochemistry (precipitation inside organic structure) and geochemistry (pedogenic carbonate related to soil conditions) of the Ca. Thus, the study of the Ca isotope composition of NFC seem to be of first interest in order to shed light on the behaviour of Ca in terrestrial environment, especially when precipitation of secondary carbonates is involved. The sampling site is situated in the Swiss Jura Mountains and has been chosen due to a previous complete study of the C and O isotope composition of NFC in relation to the ecosystem, which represent a good precondition for the understanding of the NFC Ca isotope signatures in this context. In this study, the implication of the fungi in the origin of NFC is investigated, by comparing the Ca isotope composition of NFC and a purely physicochemical calcite cement (LCC), both precipitated in the same environment. The 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

Isotopic studies of authigenic sulfides, silicates and carbonates, and calcite and pyrite veinlets in the Creede Formation, San Juan Mountains, Southwest Colorado

USGS Publications Warehouse

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

2000-01-01

formed very late from unexchanged meteoric water. Concretions and possibly some cements at CCM-1 appear to have exchanged with the 17.6 Ma oxygen-shifted hydrothermal fluids. Such exchange is consistent with evidence that lacustrine carbonates at CCM-1 exchanged with low 18O waters, whereas those at CCM-2 underwent little, if any, exchange. The δ13C-δ18O values for calcite veinlets in the Creede Formation are similar to those for authegenic calcites. Fluid-inclusion temperatures and δ18O indicate that some were deposited during the 17.6 Ma hydrothermal event and others from unexchanged meteoric water at a later date. The isotope studies confirm that part of the model of Rye et al., proposing that the barites in the southern end of the Creede Mining District were formed by mixing of the Creede hydrotermal system with Lake Creede pore of lake waters. The silicate and carbonate isotope data indicate that the pores of the Creede Formation were occupied by at least three isotopically distinct water since the time of deposition. The original pore fluids were probably shifted to lower δ18O values during burial diagensis as a result of the hydrolysis of the volcanic glass to for smectites and other hydrous silicates. During or prior to a 17.6 Ma hydrothermal event in the vicinity of CCM-1, the Creede Formation was flushed with oxygen-shifted meteoric water, possibly related to the breaching of the east side of the caldera wall sometime between 20 and 22 Ma. Later, the Creede Formation was again flushed, this time with unexchanged meteoric water with δD-δ18O values of present-day waters, possibly during the incision of the Rio Grande drainage during uplifting of the southern Rocky Mountains beginning about 5 Ma.

Dislocation creep accommodated Grain Boundary Sliding: A high strain rate/low temperature deformation mechanism in calcite ultramylonites

NASA Astrophysics Data System (ADS)

Rogowitz, Anna; Grasemann, Bernhard

2014-05-01

Grain boundary sliding (GBS) is an important grain size sensitive deformation mechanism that is often associated with extreme strain localization and superplasticity. Another mechanism has to operate simultaneously to GBS in order to prevent overlaps and voids between sliding grains. One of the most common accommodating mechanisms is diffusional creep but, recently, dislocation creep has been reported to operate simultaneous to GBS. Due to the formation of a flanking structure in nearly pure calcite marble on Syros (Cyclades, Greece) at lower greenschist facies conditions, an extremely fine grained ultramylonite developed. The microstructure of the layer is characterized by (1) calcite grains with an average grain size of 3.6 µm (developed by low temperature/high strain rate grain boundary migration recrystallization, BLG), (2) grain boundary triple junctions with nearly 120° angles and (3) small cavities preferentially located at triple junctions and at grain boundaries in extension. These features suggest that the dominant deformation mechanism was GBS. In order to get more information on the accommodation mechanism detailed microstructural and textural analyses have been performed on a FEI Quanta 3D FEG instrument equipped with an EDAX Digiview IV EBSD camera. The misorientation distribution curves for correlated and uncorrelated grains follow almost perfect the calculated theoretical curve for a random distribution, which is typical for polycrystalline material deformed by GBS. However, the crystallographic preferred orientation indicates that dislocation creep might have operated simultaneously. We also report Zener-Stroh cracks resulting from dislocation pile up, indicating that dislocation movement was active. We, therefore, conclude that the dominant deformation mechanism was dislocation creep accommodated grain boundary sliding. This is consistent with the observed grain size range that plots at the field boundary between grain size insensitive and grain

Review of calcium carbonate polymorph precipitation in spring systems

NASA Astrophysics Data System (ADS)

Jones, Brian

2017-05-01

Many spring deposits throughout the world are characterized by spectacular deposits of calcium carbonate that are formed of various combinations of aragonite and calcite, and in very rare cases vaterite. The factors that control the precipitation of the aragonite and calcite have been the subject of considerable debate that has been based on natural precipitates and information gained from numerous laboratory experiments. Synthesis of this information indicates that there is probably no single universal factor that controls calcite and aragonite precipitation in all springs. Instead, the reason for aragonite as opposed to calcite precipitation should be ascertained by considering the following ordered series of possibilities for each system. First, aragonite, commonly with calcite as a co-precipitate, will form from spring water that has a high CO2 content and rapid CO2 degassing, irrespective of the Mg:Ca ratio and scale of precipitation. Second, aragonite can be precipitated from waters that have low levels of CO2 degassing provided that the Mg:Ca ratio is high enough to inhibit calcite precipitation. Third, the presence of biofilms may lead to the simultaneous precipitation of aragonite and calcite (irrespective of CO2 degassing or Mg:Ca ratio) either within the different microdomains that develop in the biofilm or because of diurnal changes in various geochemical parameters associated with the biofilm. Although the precipitation of calcite and aragonite has commonly been linked directly to water temperature, there is no clear evidence for this proposition. It is possible, however, that temperature may be influencing another parameter that plays a more direct role in the precipitation of these CaCO3 polymorphs. Despite the advances that have been made, the factors that ultimately control calcite and aragonite are still open to debate because this long-standing problem has still not been fully resolved.

Kinetics of carbonate mineral dissolution in CO2-acidified brines at storage reservoir conditions.

PubMed

Peng, Cheng; Anabaraonye, Benaiah U; Crawshaw, John P; Maitland, Geoffrey C; Trusler, J P Martin

2016-10-20

We report experimental measurements of the dissolution rate of several carbonate minerals in CO 2 -saturated water or brine at temperatures between 323 K and 373 K and at pressures up to 15 MPa. The dissolution kinetics of pure calcite were studied in CO 2 -saturated NaCl brines with molalities of up to 5 mol kg -1 . The results of these experiments were found to depend only weakly on the brine molality and to conform reasonably well with a kinetic model involving two parallel first-order reactions: one involving reactions with protons and the other involving reaction with carbonic acid. The dissolution rates of dolomite and magnesite were studied in both aqueous HCl solution and in CO 2 -saturated water. For these minerals, the dissolution rates could be explained by a simpler kinetic model involving only direct reaction between protons and the mineral surface. Finally, the rates of dissolution of two carbonate-reservoir analogue minerals (Ketton limestone and North-Sea chalk) in CO 2 -saturated water were found to follow the same kinetics as found for pure calcite. Vertical scanning interferometry was used to study the surface morphology of unreacted and reacted samples. The results of the present study may find application in reactive-flow simulations of CO 2 -injection into carbonate-mineral saline aquifers.

Ba, B, and U element partitioning in magnesian calcite skeletons of Octocorallia corals

NASA Astrophysics Data System (ADS)

Yoshimura, T.; Suzuki, A.; Iwasaki, N.

2015-01-01

Barium, boron and uranium element partitioning and oxygen and carbon isotope fractionation of high-Mg calcite skeletons of Octocorallia corals were investigated. The dissolved Ba concentration in seawater and the coral Ba/Ca ratio showed a clear positive correlation. The empirically derived barium partition coefficient is comparable to previous data for not only calcitic corals but also intermediate- to deep-water-dwelling scleractinian corals whose skeletons are composed of aragonite. Octocorallia corals are geologically important producers of biominerals, and they provide long-term records (up to hundreds of years) of environmental conditions in the deep ocean. Our data suggest that Ba/Ca ratios in Octocorallia corals may be a useful proxy for nutrients in intermediate and deep waters. The Ba/Ca ratio, a possible proxy for pH or carbonate ion concentration in seawater, showed the largest correlation with δ13C among the examined parameters. This result implies that the pH of the extracytoplasmic calcifying fluid (ECF) simultaneously influences δ18O, δ13C, and Ba/Ca by influencing the relative contributions of dissolved carbon sources in the ECF. Positive correlations of Ba/Ca with δ18 and δ13C suggest that δ18 and δ13C are enriched in light isotopes when conditions are less alkaline, suggesting a potential role of biological alkalinity pumping becomes more favorable with decreasing calcifying fluid pH. Substantial inter- and intra-specimen variations in Ba/Ca suggest that physicochemical factors do not exert a dominant systematic control on U incorporation.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cygan, Randall Timothy; Mitchell, Ralph; Perry, Thomas D.

2005-12-01

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

Kinetics of carbonate dissolution in CO2-saturated aqueous system at reservoir conditions

NASA Astrophysics Data System (ADS)

Peng, Cheng; Crawshaw, John P.; Maitland, Geoffrey; Trusler, J. P. Martin

2014-05-01

In recent years, carbon capture and storage (CCS) has emerged as a key technology for limiting anthropogenic CO2 emissions while allowing the continued utilisation of fossil fuels. The most promising geological storage sites are deep saline aquifers because the capacity, integrity and injection economics are most favourable, and the environmental impact can be minimal. Many rock-fluid chemical reactions are known to occur both during and after CO2 injection in saline aquifers. The importance of rock-fluid reactions in the (CO2 + H2O) system can be understood in terms of their impact on the integrity and stability of both the formation rocks and cap rocks. The chemical interactions between CO2-acidified brines and the reservoir minerals can influence the porosity and permeability of the formations, resulting in changes in the transport processes occurring during CO2 storage. Since carbonate minerals are abundant in sedimentary rocks, one of the requirements to safely implement CO2 storage in saline aquifers is to characterise the reactivity of carbonate minerals in aqueous solutions at reservoir conditions. In this work, we reported measurements of the intrinsic rate of carbonate dissolution in CO2-saturated water under high-temperature high-pressure reservoir conditions extending up to 373 K and 14 MPa. The rate of carbonate dissolution in CO2-free HCl(aq) was also measured at ambient pressure at temperatures up to 353 K. Various pure minerals and reservoir rocks were investigated in this study, including single-crystals of calcite and magnesite, and samples of dolomite, chalks and sandstones. A specially-designed batch reactor system, implementing the rotating disc technique, was used to obtain the intrinsic reaction rate at the solid/liquid interface, free of mass transfer effects. The effective area and mineralogy of the exposed surface was determined by a combination of surface characterisation techniques including XRD, SEM, EDX and optical microscopy. The

Fluids along the North Anatolian Fault, Niksar basin, north central Turkey: Insight from stable isotopic and geochemical analysis of calcite veins

NASA Astrophysics Data System (ADS)

Sturrock, Colin P.; Catlos, Elizabeth J.; Miller, Nathan R.; Akgun, Aykut; Fall, András; Gabitov, Rinat I.; Yilmaz, Ismail Omer; Larson, Toti; Black, Karen N.

2017-08-01

Six limestone assemblages along the North Anatolian Fault (NAF) Niksar pull-apart basin in northern Turkey were analyzed for δ18OPDB and δ13CPDB using bulk isotope ratio mass spectrometry (IRMS). Matrix-vein differences in δ18OPDB (-2.1 to 6.3‰) and δ13CPDB (-0.9 to 4.6‰) suggest a closed fluid system and rock buffering. Veins in one travertine and two limestone assemblages were further subjected to cathodoluminescence, trace element (Laser Ablation Inductively Coupled Plasma Mass Spectrometry) and δ18OPDB (Secondary Ion Mass Spectrometry, SIMS) analyses. Fluid inclusions in one limestone sample yield Th of 83.8 ± 7.3 °C (±1σ, mean average). SIMS δ18OPDB values across veins show fine-scale variations interpreted as evolving thermal conditions during growth and limited rock buffering seen at a higher-resolution than IRMS. Rare earth element data suggest calcite veins precipitated from seawater, whereas the travertine has a hydrothermal source. The δ18OSMOW-fluid for the mineralizing fluid that reproduces Th is +2‰, in range of Cretaceous brines, as opposed to negative δ18OSMOW-fluid from meteoric, groundwater, and geothermal sites in the region and highly positive δ18OSMOW-fluid expected for mantle-derived fluids. Calcite veins at this location do not record evidence for deeply-sourced metamorphic and magmatic fluids, an observation that differs from what is reported for the NAF elsewhere along strike.

Strontium Co-precipitation During Biomineralization of Calcite in Porous Media Using Differing Treatment Strategies

NASA Astrophysics Data System (ADS)

Lauchnor, E. G.; Schultz, L.; Mitchell, A.; Cunningham, A. B.; Gerlach, R.

2013-12-01

The process of ureolytically-induced calcium carbonate mineralization has been shown in laboratory studies to be effective in co-precipitation of heavy metals and radionuclides. During this process, the microbially catalyzed hydrolysis of urea increases alkalinity and pH, thus promoting CaCO3 precipitation in the presence of dissolved calcium. One proposed application of biomineralization includes the remediation of radionuclides such as strontium, which can be co-precipitated in situ within calcite. Strontium is of concern at several US DOE sites where it is a radioactive product of uranium fission and groundwater contaminant. Our research focuses on promoting attached bacteria, or biofilms, in subsurface environments where they serve as immobilized catalysts in biomineralization and can aide in co-precipitation of some contaminants. In this work, flat plate reactors with 1 mm etched flow channels designed to mimic a porous medium environment were used. Reactors were inoculated with the model ureolytic bacterium Sporosarcina pasteurii and addition of urea, calcium and strontium containing fluid was performed to induce biomineralization. Continuous flow and stopped-flow injection strategies were investigated to evaluate differences in strontium co-precipitation efficiency. During stopped-flow experiments, injection of cementation fluid containing urea, Ca2+ and Sr2+ was alternated with growth nutrients for stimulation of microbial activity. Control parameters such as urea and calcium concentration and injection flow rate are currently being varied to optimize rate and efficiency of strontium co-precipitation. Ureolytically induced calcite precipitation and strontium incorporation in the calcite was verified by chemical and mineralogical analyses, including X-ray diffraction and ICP-MS. Strontium co-precipitation efficiency was similar under different injection strategies. Alternating calcium-containing fluid with growth nutrients allowed for continued viability of

The Interpretation of Mg/Ca in Ostracode Valves: Biokinetic vs. Thermodynamic Controls

NASA Astrophysics Data System (ADS)

Dettman, D. L.; Palacios-Fest, M. R.; Cohen, A. S.

2004-12-01

The geochemistry of the calcite valves of ostracodes (a group of micro-crustacean) is often used to reconstruct the history of aqueous environments in both marine and fresh-water settings. These benthic animals can be very abundant in lakes and ponds and their low-Mg calcite valves are easily recovered from sediment cores. Many studies have used minor-element ratios (Mg/Ca and Sr/Ca) as indicators of temperature and/or salinity change through time and numerous calibration studies have been undertaken. There is considerable disagreement on the interpretation of both historical data and calibration studies because of differing views on what controls elemental ratios in ostracode valves. Here we focus on Mg/Ca ratios and critique the dominant assumption that Mg/Ca ratios in ostracode calcite are interpretable as a temperature-dependant distribution (or partition) coefficient. The use of a distribution coefficient, usually defined as a ratio of shell-to-water Mg/Ca ratios, assumes that the ratio in the water plays a significant role in the resultant ratio in the shell. Ostracode biomineralization is most commonly viewed as equivalent to inorganic precipitation of low-Mg calcite from solution, a system in which distribution coefficients are probably valid models. However, a re-examination of published studies shows that in many cases Mg/Ca(water) has no statistically demonstrable affect on the Mg/Ca ratio of ostracode valve calcite. The valve Mg/Ca ratio is most often a function of ambient temperature. In a number of studies the importance of the water's Mg/Ca ratio cannot be determined due to auto-correlation with other environmental factors. This implies that there is considerable biological control on the minor element chemistry of the ostracode valve. This is supported by a number of observations: valve calcification is rapid and initiated by the animal; Mg/Ca ratios within the valve vary greatly on a microscopic scale; the earliest carbonate formed during

Experimental constraints on the destabilization of basalt + calcite + anhydrite at high pressure-high temperature and implications for meteoroid impact modeling

NASA Astrophysics Data System (ADS)

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