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

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.

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

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.

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.

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.

Ocean chemistry controls trends in foraminiferal mineralogy

NASA Astrophysics Data System (ADS)

de Nooijer, Lennart; van Dijk, Inge; Reichart, Gert-Jan

2014-05-01

Foraminifera are unicellular marine protists of which many produce a calcium carbonate shell of either aragonite or calcite. Since they are responsible for a large part of open ocean calcium carbonate precipitation, it is necessary to understand their response to changes in ocean chemistry. On geological time scales, the ratio of Mg over Ca in seawater played an important role in controlling marine aragonite versus calcite mineralogy. Here we reconstructed occurrences of aragonite and low- and high-Mg calcite producing foraminifera through the Phanerozoic. We discovered a two-step impact of seawater chemistry and mass extinction events on the evolution of foraminifera. Seawater Mg to Ca ratios favor production of either calcite, or of high magnesium carbonate and aragonite shells. However, mass extinction events controlled the timing of shifts in dominance from one mineralogy to the other. This observation suggests that ongoing ocean acidification may have important consequences for foraminiferal calcification. Although reduced carbonate saturation state increases dissolution rates of high-Mg calcite and aragonite compared to low-Mg calcite, the current high Mg/Ca of the ocean kinetically favors precipitation of high-Mg calcite and aragonite. Contrary to the differential effects of dissolution, we argue that ongoing ocean acidification is likely to particularly impact calcite producers (e.g. planktonic foraminifera, coccolithophores) compared to those precipitating high-Mg calcite and aragonite (e.g. corals).

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).

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.

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.

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.

Post-deformational relocation of mica grains in calcite-dolomite marbles identified by cathodoluminescence microscopy

NASA Astrophysics Data System (ADS)

Kuehn, Rebecca; Duschl, Florian; Leiss, Bernd

2017-04-01

Hot-cathodoluminescence-microscopy (CL) reveals micas which are rotated or shifted within a calcite fabric from a foliation parallel to a random orientation. This feature has been recognized in calcite-dolomite marble samples from the locations Hammerunterwiesenthal, Erzgebirge, Germany and the Alpi Apuane, Italy. As obtained from petrographic thin section analysis, the micas either moved totally within a single calcite grain or from a grain boundary position, and then the calcite grain growth was dragged with the movement of the mica grain. In the moved-through grain, features like fluid-inclusions, twins or cleavage faces are erased and a new, clear calcite phase developed. This indicates dissolution-precipitation as process which led to the new calcite phase. As former deformation features are erased it can be assumed that the mica relocation is a fluid-driven, post-deformational equilibration process. In CL the new calcite mineral phase shows a zonation indicating a polycyclic process. Calcite CL gradually changes from a very dark purple, exactly as the surrounding grains, to a bright orange CL and supports the idea of fluid-induced deformation relocation. We suppose a specific lattice relationship between mica and calcite as initial driving factor for mica relocation. This recrystallization mechanism is probably supported by fluids - either from an external source or developed during retrograde metamorphosis fluid inclusion studies shall identify formation temperatures and origin of involved fluids and thereby clarify the timing of the post-deformational mica rotation. EBSD analysis of involved calcite and mica grains shall reveal a possible systematic relationship between the orientation of the hosting grains, the orientation of the mica and the final position of the mica. It will be interesting to learn in the future, if this kind of calcite-mica microstructure is a general phenomenon and how it can contribute to the understanding of fabric development.

Cyclic Stable-Unstable Slip Preserved along an Appalachian Fault

NASA Astrophysics Data System (ADS)

Wells, R. K.; Newman, J.; Holyoke, C. W., III; Wojtal, S. F.

2017-12-01

The inactive Copper Creek thrust, southern Appalachians, TN, preserves evidence suggesting cyclic aseismic and unstable slip. The Copper Creek thrust is a low-temperature (4-6 km burial depth) foreland thrust with an estimated net slip of 15-20 km. Immediately below the 2 cm thick calcite-shale fault zone, the footwall is composed of shale with cross-cutting calcite veins and is separated from the fault zone by a 300 µm thick layered calcite vein. Optical and electron microscopy indicates that this complex vein layer experienced grain size reduction by plasticity-induced fracturing followed by aseismic diffusion creep. The fault zone calcite exhibits interpenetrating grain boundaries and four-grain junctions suggesting diffusion creep, but also contains nanoscale grains (7 nm), vesicular calcite, and partially-coated clasts indicating unstable, possibly seismic, slip. Well-preserved clasts of deformed calcite vein layer material within the fault zone indicate repeated cycle(s) of aseismic diffusion creep. In addition, nanoscale calcite grains, 30 nm, with straight grain boundaries that form triple junctions, may represent earlier nanoscale grains formed during unstable slip that have experienced grain growth during periods of aseismic creep. Based on the spatial and temporal relations of these preserved microstructures, we propose a sequence of deformation processes consistent with cyclic episodes of unstable slip separated by intervals of aseismic creep. Formation of calcite-filled veins is followed by grain size reduction in vein calcite by plasticity-induced fracturing and aseismic grain-size sensitive diffusion creep deformation in fine-grained calcite. During aseismic creep, the combination of grain growth, resulting in fault strengthening, and an increase in pore fluid pressure, reducing the effective fault strength, leads to new fractures and/or an unstable slip event. During unstable slip, nanograins and vesicular calcite form as a result of thermal decomposition and coated clasts form as a result of fluidization of the fault zone, and are then incorporated within ductilely deforming calcite during a new interval of aseismic creep.

Heterogeneous alternation of fractured rock driven by preferential carbonate dissolution

NASA Astrophysics Data System (ADS)

Wen, H.; Zhi, W.; Li, L.

2016-12-01

Understanding the alternation of fractured rock induced by geochemical reactions is critical for predicting the flow, solute transport and energy production in geosystems. Most existing studies on fracture alterations focus on rocks with single minerals where reactions occur at the fracture wall resulting in fracture aperture alteration while ignoring rock matrix properties (e.g. the formation and development of altered zones). In this work, we aimed to mechanistically understand the role of preferential calcite dissolution in the long-term evolution of fracture and rock matrix. We use direct simulation of physics-based reactive transport processes in an image of fractured rock at the resolution of tens of micrometers. Three numerical experiments were carried out with the same initial physical properties however different calcite content. Simulation results show that the formation and development of altered zones in the rock matrix is highly related to the abundance of fast-dissolving calcite. Abundant calcite (50% (v/v), calcite50) leads to a localized, thick zone of large porosity increase while low calcite content (10% (v/v), calcite10) creates an extended and narrow zone of small porosity increase resulting in surprisingly larger change in effective transport property. After 300 days of dissolution, although with relatively similar dissolved calcite mass and matrix porosity increase, effective matrix diffusion coefficients increase by 9.9 and 19.6 times in calcite50 and calcite10, respectively. In turn, calcite dissolution rates are directly limited by diffusive transport in the altered matrix and the shape of the altered zone. This work sheds light on the unique characteristics of reactive transport in fractured, mineralogically complex rocks that are different from those with single minerals (Wen et al., 2016). Reference: Wen, H., Li, L., Crandall, D. and Hakala, J.A. (2016) Where Lower Calcite Abundance Creates More Alteration: Enhanced Rock Matrix Diffusivity Induced by Preferential Carbonate Dissolution. Energy & Fuels.

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-preserved microbial carbonates may be an archive of calcite-aragonite seas throughout Precambrian time. These results invite a systematic evaluation of microbial carbonate primary mineralogy to empirically constrain Precambrian seawater Mg/Ca.

Influence of lysozyme on the precipitation of calcium carbonate: a kinetic and morphologic study

NASA Astrophysics Data System (ADS)

Jimenez-Lopez, Concepcion; Rodriguez-Navarro, Alejandro; Dominguez-Vera, Jose M.; Garcia-Ruiz, Juan M.

2003-05-01

Several mechanisms have been proposed to explain the interactions between proteins and mineral surfaces, among them a combination of electrostatic, stereochemical interactions and molecular recognition between the protein and the crystal surface. To identify the mechanisms of interaction in the lysozyme-calcium carbonate model system, the effect of this protein on the precipitation kinetics and morphology of calcite crystals was examined. The solution chemistry and morphology of the solid were monitored over time in a set of time-series free-drift experiments in which CaCO 3 was precipitated from solution in a closed system at 25°C and 1 atm total pressure, in the presence and absence of lysozyme. The precipitation of calcite was preceded by the precipitation of a metastable phase that later dissolved and gave rise to calcite as the sole phase. With increasing lysozyme concentration, the nucleation of both the metastable phase and calcite occurred at lower Ω calcite, indicating that lysozyme favored the nucleation of both phases. Calcite growth rate was not affected by the presence of lysozyme, at least at protein concentrations ranging from 0 mg/mL to 10 mg/mL. Lysozyme modified the habit of calcite crystals. The degree of habit modification changed with protein concentration. At lower concentrations of lysozyme, the typical rhombohedral habit of calcite crystals was modified by the expression of {110} faces, which resulted from the preferential adsorption of protein on these faces. With increasing lysozyme concentration, the growth of {110}, {100}, and finally {001} faces was sequentially inhibited. This adsorption sequence may be explained by an electrostatic interaction between lysozyme and calcite, in which the inhibition of the growth of {110}, {100}, and {001} faces could be explained by a combined effect of the density of carbonate groups in the calcite face and the specific orientation (perpendicular) of these carbonate groups with respect to the calcite surface. Overgrowth of calcite in the presence of lysozyme demonstrated that the protein favored and controlled the nucleation on the calcite substrate. Overgrowth crystals nucleated epitaxially in lines which run diagonal to rhombohedral {104} faces.

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.

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.

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 methods used depended on the crystal homogeneity (one or several calcite generations), discerned by detailed SEM-investigations (back-scatter and cathodo-luminescence). 87Sr/86Sr ratios as well as δ18O signatures in calcite are in the range expected for the precipitates from present-day groundwater, or older groundwater with similar composition (except in sections with a considerable portion of glacial water, where calcite definitely is older than the latest glaciation). Stable carbon isotopes in calcite generally show values typically associated with HCO3- originating from soil organic matter but at intermediate depth frequently with HCO3- originating from in situ microbial anaerobic oxidation of methane (highly depleted δ13C). For one of the studied metals - manganese - there was a strong correlation between the sampled calcite coatings and hypothetical calcite predicted by applying laboratory-based partition coefficients (literature data) on groundwater chemistry for sections corresponding to those where the calcites were sampled. This points to temporal and spatial stability in groundwater Mn/Ca ratios over millions of years, or even more, and show that it is possible to assess, based on laboratory-derived data on Mn partitioning, past groundwater Mn-composition from fracture calcites. For other metals - Fe, Sr, and Mg - which are expected to interact with co-precipitating minerals to a higher degree than Mn, the correlations between measured and predicted calcite were weaker for various reasons.

(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 the deformation history. Finally, we propose that the crystallization age of a calcite crystal with a known thermal history can nevertheless be retrieved by the (U-Th)/He method provided the He diffusion pattern can be measured by careful step-heating degassing analysis. Copeland, P., Watson, E.B., Urizar, S.C., Patterson, D., Lapen, T.J., 2007. Alpha thermochronology of carbonates. Geochim. Cosmochim. Acta, 71: 4488-4511. Cros, A. Gautheron, C., Pagel, M., Berthet, P., Tassan-Got, L., Douville, E., Pinna-Jamme, R., Sarda, P., submitted GCA, He behavior in calcite filling viewed by (U-Th)/He dating, He diffusion and crystallographic studies. Lovera, O.M., Richter, F.M., Harrison, T.M., 1991. Diffusion domains determined by 39Ar released during step heating. Journal of Geophysical Research, 96: 2057-2069.

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).

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 Sr concentrations in the late calcite may record lower deposition rates and decreased percolation fluxes due to the drier climate. 1 Wilson, N.S.F., Cline, J.S., and Lundberg, S.A.W., 2000, Paragenesis and chemical composition of secondary mineralization at Yucca Mountain, Nevada, Geol. Soc. Am. Abs. Prog., v. 32, p. A260.

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 fibrous calcite veins, and this data should be incorporated in any model explaining the origin of fibrous veins.

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

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.

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).

Trace metal (Mg/Ca and Sr/Ca) analyses of single coccoliths by Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Prentice, Katy; Jones, Tom Dunkley; Lees, Jackie; Young, Jeremy; Bown, Paul; Langer, Gerald; Fearn, Sarah; EIMF

2014-12-01

Here we present the first multi-species comparison of modern and fossil coccolith trace metal data obtained from single liths. We present both trace metal analyses (Sr, Ca, Mg and Al) and distribution maps of individual Paleogene fossil coccoliths obtained by Secondary Ion Mass Spectrometry (SIMS). We use this data to determine the effects of variable coccolith preservation and diagenetic calcite overgrowths on the recorded concentrations of strontium and magnesium in coccolith calcite. The analysis of coccoliths from deep-ocean sediments spanning the Eocene/Oligocene transition demonstrates that primary coccolith calcite is resistant to the neomorphism that is common in planktonic foraminifera from similar depositional environments. Instead, where present, diagenetic calcite forms distinct overgrowths over primary coccolith calcite rather than replacing this calcite. Diagenetic overgrowths on coccoliths are easily distinguished in SIMS analyses on the basis of relatively higher Mg and lower Sr concentrations than co-occurring primary coccolith calcite. This interpretation is confirmed by the comparable SIMS analyses of modern cultured coccoliths of Coccolithus braarudii. Further, with diagenetic calcite overgrowth being the principle source of bias in coccolith-based geochemical records, we infer that lithologies with lower carbonate content, deposited below the palaeo-lysocline, are more likely to produce geochemical records dominated by primary coccolith calcite than carbonate-rich sediments where overgrowth is ubiquitous. The preservation of primary coccolith carbonate in low-carbonate lithologies thus provides a reliable geochemical archive where planktonic foraminifera are absent or have undergone neomorphism.

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.

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.

Technical note: An empirical method for absolute calibration of coccolith thickness

NASA Astrophysics Data System (ADS)

González-Lemos, Saúl; Guitián, José; Fuertes, Miguel-Ángel; Flores, José-Abel; Stoll, Heather M.

2018-02-01

As major calcifiers in the open ocean, coccolithophores play a key role in the marine carbon cycle. Because they may be sensitive to changing CO2 and ocean acidification, there is significant interest in quantifying past and present variations in their cellular calcification by quantifying the thickness of the coccoliths or calcite plates that cover their cells. Polarized light microscopy has emerged as a key tool for quantifying the thickness of these calcite plates, but the reproducibility and accuracy of such determinations has been limited by the absence of suitable calibration materials in the thickness range of coccoliths (0-4 µm). Here, we describe the fabrication of a calcite wedge with a constant slope over this thickness range, and the independent determination of calcite thickness along the wedge profile. We show how the calcite wedge provides more robust calibrations in the 0 to 1.55 µm range than previous approaches using rhabdoliths. We show the particular advantages of the calcite wedge approach for developing equations to relate thickness to the interference colors that arise in calcite in the thickness range between 1.55 and 4 µm. The calcite wedge approach can be applied to develop equations relevant to the particular light spectra and intensity of any polarized light microscope system and could significantly improve inter-laboratory data comparability.

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.

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

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%.

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.

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:

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 observed in coatings from the TCw, these data indicate that evaporation decreases with depth in the UZ. Evaporation at the repository horizon and in the overlying units is an important process that reduces the amount of seepage at the repository horizon.

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

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

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

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

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.

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.

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 studies of carbonate rocks with thermal history. By contrast, Mg isotopes of dolomite are less prone to post-depositional resetting due to a number of properties including high Mg abundance and high thermodynamic stability, and Mg isotopes in dolomite may be a more robust recorder for original carbonate precipitates.

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 characterized by low dissolved organic carbon levels, the presence of organic ligands is rather unlikely to significantly affect the Mg isotope composition of precipitated calcite.

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-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.

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.

Kinematics of Cone-In-Cone Growth, with Implications for Timing and Formation Mechanism

NASA Astrophysics Data System (ADS)

Hooker, J. N.; Cartwright, J. A.

2015-12-01

Cone-in-cone is an enigmatic structure. Similar to many fibrous calcite veins, cone-in-cone is generally formed of calcite and present in bedding-parallel vein-like accumulations within fine-grained rocks. Unlike most fibrous veins, cone-in-cone contains conical inclusions of host-rock material, creating nested, parallel cones throughout. A long-debated aspect of cone-in-cone structures is whether the calcite precipitated with its conical form (primary cone-in-cone), or whether the cones formed afterwards (secondary cone-in-cone). Trace dolomite within a calcite cone-in-cone structure from the Cretaceous of Jordan supports the primary hypothesis. The host sediment is a siliceous mud containing abundant rhombohedral dolomite grains. Dolomite rhombohedra are also distributed throughout the cone-in-cone. The rhombohedra within the cones are randomly oriented yet locally have dolomite overgrowths having boundaries that are aligned with calcite fibers. Evidence that dolomite co-precipitated with calcite, and did not replace calcite, includes (i) preferential downward extension of dolomite overgrowths, in the presumed growth-direction of the cone-in-cone, and (ii) planar, vertical borders between dolomite crystals and calcite fibers. Because dolomite overgrows host-sediment rhombohedra and forms fibers within the cones, it follows that the host-sediment was included within the growing cone-in-cone as the calcite precipitated, and not afterward. The host-sediment was not injected into the cone-in-cone along fractures, as the secondary-origin hypothesis suggests. This finding implies that cone-in-cone in general does not form over multiple stages, and thus has greater potential to preserve the chemical signature of its original precipitation. Because cone-in-cone likely forms before complete lithification of the host, and because the calcite displaces the host material against gravity, this chemical signature can preserve information about early overpressures in fine-grained sediments.

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

Petrography of Mayan mortar, Isla Mujeres, Quintana Roo, Mexico

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

Bain, R.J.

1985-01-01

Along coastal regions of the Yucatan Peninsula Mayan builders used a mixture of beach sand, shell fragments, and clasts of rock as mortar for construction. With exposure to subaerial conditions, the aragonitic sand was converted into a semi-lithified mortar. Petrographic analysis of mortar samples collected from Mayan ruins on the south end of Isla Mujeres indicates that the mortar is cemented by blocky, meniscus style, low Mg calcite. In addition to the cement, low Mg calcite also occurs as blocky equant crystals either replacing grains or filling grain-moldic porosity. X-ray analysis of both modern beach sand and mortar shows themore » sand is composed of aragonite and high Mg calcite but lacks low Mg calcite. Mortar, on the other hand, consists of low Mg calcite, high Mg calcite, and aragonite however aragonite is much less abundant than in the sand. Aragonitic ooids, pellets and bioclasts of beach sand used in mortar were dissolved producing moldic porosity. At the same time, CaCO/sub 3/ derived from this process was precipitated as low Mg calcite which formed meniscus cement and filled moldic porosity within the walls of Mayan structures producing a remarkably hard mortar.« less

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

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.

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.

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

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.

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

Evidence for Seismic and Aseismic Slip along a Foreland Thrust Fault, Southern Appalachians

NASA Astrophysics Data System (ADS)

Newman, J.; Wells, R. K.; Holyoke, C. W.; Wojtal, S. F.

2013-12-01

Studies of deformation along ancient thrust faults form the basis for much of our fundamental understanding of fault and shear zone processes. These classic studies interpreted meso- and microstructures as formed during aseismic creep. Recent experimental studies, and studies of naturally deformed rocks in seismically active regions, reveal similar microstructures to those observed locally in a carbonate foreland thrust from the southern Appalachians, suggesting that this thrust fault preserves evidence of both seismic and aseismic deformation. The Copper Creek thrust, TN, accommodated 15-20 km displacement, at depths of 4-6 km, as estimated from balanced cross-sections. At the Diggs Gap exposure of the Copper Creek thrust, an approximately 2 cm thick, vein-like shear zone separates shale layers in the hanging wall and footwall. The shear zone is composed of anastomosing layers of ultrafine-grained calcite and/or shale as well as aggregate clasts of ultrafine-grained calcite or shale. The boundary between the shear zone and the hanging wall is sharp, with slickensides along the boundary, parallel to the shear zone movement direction. A 350 μm-thick layer of ultrafine-grained calcite separates the shear zone and the footwall. Fault parallel and perpendicular calcite veins are common in the footwall and increase in density towards the shear zone. Microstructures within the vein-like shear zone that are similar to those observed in experimental studies of unstable slip include: ultrafine-grained calcite (~0.34 μm), nano-aggregate clasts (100-300 nm), injection structures, and vein-wrapped and matrix-wrapped clasts. Not all structures within the shear zone and ultrafine-grained calcite layer suggest seismic slip. Within the footwall veins and calcite aggregate clasts within the shear zone, pores at twin-twin intersections suggest plasticity-induced fracturing as the main mechanism for grain size reduction. Interpenetrating grain boundaries in ultrafine-grained calcite and a lack of a lattice preferred orientation suggest ultrafine-grained calcite deformed by diffusion creep accommodated grain boundary sliding. These structures suggest a strain-rate between 10-15 - 10-11 s-1, using calcite flow laws at temperatures 150-250 °C. Microstructures suggest both seismic and aseismic slip along this ancient fault zone. During periods of aseismic slip, deformation is accommodated by plasticity-induced fracturing and diffusion creep. Calcite veins suggest an increase in pore-fluid pressure, contributing to fluidized and unstable flow, but also providing the calcite that deformed by diffusion creep during aseismic creep.

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.

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.

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.

Ikaite precipitation in a lacustrine environment - implications for palaeoclimatic studies using carbonates from Laguna Potrok Aike (Patagonia, Argentina)

NASA Astrophysics Data System (ADS)

Oehlerich, Markus; Mayr, Christoph; Griesshaber, Erika; Lücke, Andreas; Oeckler, Oliver M.; Ohlendorf, Christian; Schmahl, Wolfgang W.; Zolitschka, Bernd

2013-07-01

The monoclinic mineral ikaite (CaCO3 · 6H2O) and its pseudomorphs are potentially important archives for palaeoenvironmental reconstructions. Natural ikaite occurs in a small temperature range near freezing point and is reported mainly from marine and only rarely from continental aquatic environments. Ikaite transforms to more stable anhydrous forms of CaCO3 after an increase in temperature or when exposed to atmospheric conditions. The knowledge about conditions for natural ikaite formation, its stable isotope fractionation factors and isotopic changes during transformation to calcite is very restricted. Here, for the first time, primary precipitation of idiomorphic ikaite and its calcite pseudomorphs are reported from a subsaline lake, Laguna Potrok Aike, in southern Argentina. The calculated stable oxygen isotope fractionation factor between lake water and ikaite-derived calcite (αPAI = 1.0324 at a temperature of 4.1 °C) is close to but differs from that of primarily inorganically precipitated calcite. Pseudomorphs after ikaite rapidly disintegrate into calcite powder that is indistinguishable from μm-sized calcite crystals in the sediment record of Laguna Potrok Aike suggesting an ikaite origin of sedimentary calcites. Therefore, the Holocene carbonates of Laguna Potrok Aike have the potential to serve as a recorder of past hydrological variation.

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.

Templating Growth of a Pseudomorphic Lepidocrocite Microshell at the Calcite–Water Interface

DOE PAGES

Yuan, Ke; Lee, Sang Soo; Wang, Jun; ...

2018-01-05

The growth of lepidocrocite (gamma-FeOOH) has been observed through oxidation of Fe(II) on calcite (CaCO 3). Here, we seek to understand the structural relation between lepidocrocite and the calcite substrate and its growth mechanism. The formation of iron oxyhydroxide layers having distinct morphologies was observed during the dissolution of calcite in acidic Fe(II)-rich solutions. A pseudomorphic lepidocrocite shell together with multiple iron oxyhydroxide layers encapsulated within the shell was imaged by optical and transmission X-ray microscopies. The presence of a several-nanometer-thick ordered lepidocrocite film was observed by X-ray reflectivity, with the lepidocrocite (100) plane oriented parallel to the calcite (104)more » surface. Lath-shaped lepidocrocite aggregates formed during the initial precipitation, which eventually grew into clusters of parallel platy crystals. The formation of a nanometer-thick well-ordered lepidocrocite film on a pristine calcite surface appears critical for the subsequent pseudomorphic overgrowth. Detachment of the lepidocrocite film from the dissolving calcite surface yielded a free-standing pseudomorphic iron oxyhydroxide shell, suggesting weak interactions between the shell and the calcite substrate. This growth mechanism yields the potential of using carbonate minerals as templates for pseudomorphic synthesis of iron oxyhydroxides having well-defined size and morphology.« less

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 proportion of glacially-recharged water, and that this may have reached depths of up to 1000 m. However, the chemical (REE,Fe and Mn) compositions of the ME9 calcite show that despite the potential contribution of glacially-recharged water to the deep groundwater system, conditions at repository depth (< 500 m) have continually remained reducing.

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 samples. The shift from local equilibrium is ˜3 mol% in triaxial compression and ˜7 mol% in torsion. Electron backscatter diffraction analysis reveals a crystallographic preferred orientation (CPO) within the reaction layers with [0001] axes parallel to the compression/rotation axis and poles of {2-1-10} and {10-10} prismatic planes parallel to the reaction interface. Compared to isostatic annealing, the CPO is more pronounced and the amount of low-angle grain boundaries is increased. At the imposed experimental conditions, most of the bulk deformation is accommodated by calcite single, which is stronger than magnesite. Application of flow laws for magnesio-calcite and dolomite suggest that the fine-grained reaction products should deform by grain boundary diffusion creep, resulting in lower flow strength than the single crystal reactants. However, microstructural observations indicate that deformation of granular dolomite and magnesio-calcite is at least partially assisted by dislocation creep, which would result in an almost similar strength to calcite. Therefore, flattening of the reaction layers during triaxial compression may be counterbalanced by enhanced reaction rates, resulting in almost constant layer thickness, independent of the applied stress. For simple shear, the reduced reaction kinetics in the high stress/strain region of twisted samples may be related to increased nucleation rates, resulting in a lower grain size and rim thickness.

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 grains of the wall rock. Some veins show minor displacement, including the mm-scale with fractured and displaced fossil fragments, and cm-scale offsets at the outcrop. The calcite veins show evidence of low temperature deformation (~200°C) through undulous extinction, bulging grain boundaries, tension gashes structures, and extensive lamellar twinning. The width and density of twinning (twin planes/mm) provides information regarding the temperature of deformation. The calcite crystals show two populations of twinning: type I (>10 μm), and type II (tabular twinning) with an average thickness of 35 μm, and a maximum thickness of 81 μm. Twinning can only accommodate a limited amount of strain such that the calcite lamellar twinning is often kinked, broken and offset, suggesting reactivation of the calcite-filled fractures. U-Pb calcite ages from calcitic veins in the Ordovician units within the Ottawa graben are c. 400 Ma and within Devonian units at the edge of the Michigan Basin in Canada are c. 110 Ma. Additional geochronology on the calcite from southern Ontario will help resolve the timing of fracture reactivation and is an important factor in consideration of the location of a deep geological repository for Canada's nuclear waste.

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 show meteoric-derived waters saturated with respect to calcite as a source of the vein calcite. Dedolomitization and vein precipitation may have taken place from the Norian/Early Jurassic to the Late Jurassic when the study area became eroded land, and the Emilówka Cellular Limestone Member may have acted as a local paleoaquifer conducting the meteoric-derived waters. Solid inclusions in the veins, detached from the host rock and the calcitized nodules, show that the force of calcite crystallization was the main factor responsible for vein widening. Vertical shifts of adjacent cones, remnants of primary fibrous calcite crystals, as well as the burial history justify the application of Tarr's theory in interpreting the origin of the secondary cone-in-cone structure within the fibrous structure veins. The timing and the particular conditions required for the cones to develop are uncertain.

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. The lower range of the calculated δ18O values of the ambient fluids (-3.5‰ to +2.7‰ SMOW) indicate precipitation of these cements from deeply circulating meteoric waters. The presence of petroleum hydrocarbon inclusions in some samples is interpreted to reflect partial mixing with deeper basinal fluids. The paragenetically youngest Stage 3 calcite cement has only been encountered in a few veins. These calcites are characterised by an intensely zoned luminescence pattern, with bright yellow and non-luminescent zones. Inclusions of Mn-oxides and siliceous sinters are commonly associated with Stage 3 calcite, which is interpreted to have precipitated from shallower meteoric waters. Regional structural analysis revealed that the calcite veins of the Barrandian basin belong to a large-scale system of north-south-trending lineaments that run through the territory of the Czech Republic. The veins probably reflect episodes of fluid migration that occurred along these lineaments during late stages of the Variscan orogeny.

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.

Optical properties of selected components of mineral dust aerosol processed with organic acids and humic material

NASA Astrophysics Data System (ADS)

Alexander, Jennifer M.; Grassian, V. H.; Young, M. A.; Kleiber, P. D.

2015-03-01

Visible light scattering phase function and linear polarization profiles of mineral dust components processed with organic acids and humic material are measured, and results are compared to T-matrix simulations of the scattering properties. Processed samples include quartz mixed with humic material, and calcite reacted with acetic and oxalic acids. Clear differences in light scattering properties are observed for all three processed samples when compared to the unprocessed dust or organic salt products. Results for quartz processed with humic acid sodium salt (NaHA) indicate the presence of both internally mixed quartz-NaHA particles and externally mixed NaHA aerosol. Simulations of light scattering suggest that the processed quartz particles become more moderate in shape due to the formation of a coating of humic material over the mineral core. Experimental results for calcite reacted with acetic acid are consistent with an external mixture of calcite and the reaction product, calcium acetate. Modeling of the light scattering properties does not require any significant change to the calcite particle shape distribution although morphology changes cannot be ruled out by our data. It is expected that calcite reacted with oxalic acid will produce internally mixed particles of calcite and calcium oxalate due to the low solubility of the product salt. However, simulations of the scattering for the calcite-oxalic acid system result in rather poor fits to the data when compared to the other samples. The poor fit provides a less accurate picture of the impact of processing in the calcite-oxalic acid system.

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

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

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.

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.

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.

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.

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.

A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

NASA Astrophysics Data System (ADS)

Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

2018-04-01

Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

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

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.

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.

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.

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

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

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 lattice structure, rather than forming strontium carbonate. These findings are encouraging with respect to long term containment and stabilization of strontium by the proposed remediation strategy.

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.

Mg/Ca, Sr/Ca and Ca isotope ratios in benthonic foraminifers related to test structure, mineralogy and environmental controls

NASA Astrophysics Data System (ADS)

Gussone, Nikolaus; Filipsson, Helena L.; Kuhnert, Henning

2016-01-01

We analysed Mg/Ca, Sr/Ca and Ca isotope ratios of benthonic foraminifers from sediment core tops retrieved during several research cruises in the Atlantic Ocean, in order to improve the understanding of isotope fractionation and element partitioning resulting from biomineralisation processes and changes in ambient conditions. Species include foraminifers secreting tests composed of hyaline low magnesium calcite, porcelaneous high magnesium calcite as well as aragonite. Our results demonstrate systematic isotope fractionation and element partitioning patterns specific for these foraminiferal groups. Calcium isotope fractionation is similar in porcelaneous and hyaline calcite tests and both groups demonstrate the previously described anomaly with enrichment of heavy isotopes around 3-4 °C (Gussone and Filipsson, 2010). Calcium isotope ratios of the aragonitic species Hoeglundina elegans, on the other hand, are about 0.4‰ lighter compared to the calcitic species, which is in general agreement with stronger fractionation in inorganic aragonite compared to calcite. However, the low and strongly variable Sr content suggests additional processes during test formation, and we propose that transmembrane ion transport or a precursor phase to aragonite may be involved. Porcelaneous tests, composed of high Mg calcite, incorporate higher amounts of Sr compared to hyaline low Mg calcite, in agreement with inorganic calcite systematics, but also porcelaneous tests with reduced Mg/Ca show high Sr/Ca. While calcium isotopes, Sr/Ca and Mg/Ca in benthonic foraminifers primarily appear to fractionate and partition with a dominant inorganic control, δ44/40Ca temperature and growth rate dependencies of benthonic foraminifer tests favour a dominant contribution of light Ca by transmembrane transport relative to unfractionated seawater Ca to the calcifying fluid, thus controlling the formation of foraminiferal δ44/40Ca and Sr/Ca proxy signals.

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

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.

The chemical evolution of a travertine-depositing stream: Geochemical processes and mass transfer reactions

USGS Publications Warehouse

Lorah, Michelle M.; Herman, Janet S.

1988-01-01

This field study focuses on quantitatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virginia. The processes of CO2outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. The observed chemical composition of the water was used with the computerized geochemical model WATEQF to calculate aqueous speciation, saturation indices, and CO2 partial pressure values. Mass balance calculations were performed to obtain mass transfers of CO2 and calcite. Reaction times, estimated from stream discharge, were used with the mass transfer results to calculate rates of CO2, outgassing and calcite precipitation between consecutive sampling points. The stream, which is fed by a carbonate spring, is supersaturated with respect to CO2 along the entire 5.2-km flow path. Outgassing of CO2 drives the solution to high degrees of supersaturation with respect to calcite. Metabolic uptake of CO2 by photosynthetic plants is insignificant, because the high supply rate of dissolved carbon dioxide and the extreme agitation of the stream at waterfalls and rapids causes a much greater amount of inorganic CO2 outgassing to occur. Calcite precipitation is kinetically inhibited until near the crest of a 20-m vertical waterfall. Calcite precipitation rates then reach a maximum at the waterfall where greater water turbulence allows the most rapid escape of CO2. Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall.

Occurrence and genesis of Quaternary microbialitic tufa at Hammam Al Ali, Oman

NASA Astrophysics Data System (ADS)

Khalaf, Fikry I.

2017-05-01

Remnants of late Quaternary microbialitic tufa occurs within a shallow depression in the Hammam Al Ali hot spring area, which is located approximately 14.5 km to the southwest of Muscat, Oman. The tufa precipitated from hot spring water supersaturated with respect to calcium carbonate and is mostly of a porous phytogenic type, with occasional detrital and stromatolitic types. Microscopic and nanoscopic examination revealed that the tufa deposits developed through two successive processes of calcite precipitation, biotic and abiotic, preceded by limited precipitation of unstable aragonite. It is suggested that biologically mediated precipitation results in the construction of incomplete skeletal calcite crystals. The latter provide a base for classical physiochemical precipitation and, eventually, the development of complete sparry calcite crystals. The initiation of dendritic calcite crystals in the stromatolitic tufa as incomplete biogenic skeletal crystals and their characteristic growth pattern indicates that the tufa represents a clear example of hot spring calcitic microbialite.

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. Newly formed calcite nucleated at locations which were in contact with the fluid, at the shell surface, in the open pore system, and along growth lines. In the experiments with fluids simulating meteoric water, calcite crystals reached sizes up to 200 µm, while in the experiments with Mg-containing fluids the calcite crystals reached sizes up to 1 mm after 7 days of alteration. Aragonite is metastable at all applied conditions. Only a small bulk thermodynamic driving force exists for the transition to calcite. We attribute the sluggish replacement reaction to the inhibition of calcite nucleation in the temperature window from ca. 50 to ca. 170 °C or, additionally, to the presence of magnesium. Correspondingly, in Mg2+-bearing solutions the newly formed calcite crystals are larger than in Mg2+-free solutions. Overall, the aragonite-calcite transition occurs via an interface-coupled dissolution-reprecipitation mechanism, which preserves morphologies down to the sub-micrometre scale and induces porosity in the newly formed phase. The absence of aragonite replacement by calcite at temperatures lower than 175 °C contributes to explaining why aragonitic or bimineralic shells and skeletons have a good potential of preservation and a complete fossil record.

Computer-Controlled Microwave Drying of Potentially Difficult Organic and Inorganic Soils

DTIC Science & Technology

1990-12-01

materials, fly ash, gypsum rich soils, calcite rich soils, organic clay,, peat, and halloysite rich soils. Because specimen sizes too large to be...measurement Field monitoring equipment User’s manual 19. A3STRACT (Continued). materials, organic clay, fly ash, and calcite rich soils are demonstrated...39 Factors Influencing Dehydration ..................................... 42 PART X: STUDIES OF CALCITE

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

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.

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.

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

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.

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.

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

USGS Publications Warehouse

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

2002-01-01

Calcite and silica form coatings on fracture footwalls and cavity floors in the welded tuffs at Yucca Mountain, the potential site of a high-level radioactive waste repository. These secondary mineral deposits are heterogeneously distributed in the unsaturated zone (UZ) with fewer than 10% of possible depositional sites mineralized. The paragenetic sequence, compiled from deposits throughout the UZ, consists of an early-stage assemblage of calcite??fluorite??zeolites that is frequently capped by chalcedony??quartz. Intermediate- and late-stage deposits consist largely of calcite, commonly with opal on buried growth layers or outermost crystal faces of the calcite. Coatings on steep-dipping fractures usually are thin (??? 3 mm) with low-relief outer surfaces whereas shallow-dipping fractures and lithophysal cavities typically contain thicker, more coarsely crystalline deposits characterized by unusual thin, tabular calcite blades up to several cms in length. These blades may be capped with knobby or corniced overgrowths of late-stage calcite intergrown with opal. The observed textures in the fracture and cavity deposits are consistent with deposition from films of water fingering down fracture footwalls or drawn up faces of growing crystals by surface tension and evaporated at the crystal tips. Fluid inclusion studies have shown that most early-stage and some intermediate-stage calcite formed at temperatures of 35 to 85??C. Calcite deposition during the past several million years appears to have been at temperatures < 30??C. The elevated temperatures indicated by the fluid inclusions are consistent with temperatures estimated from calcite ??18O values. Although others have interpreted the elevated temperatures as evidence of hydrothermal activity and flooding of the tuffs of the potential repository, the authors conclude that the temperatures and fluid-inclusion assemblages are consistent with deposition in a UZ environment that experienced prolonged heat input from gradual cooling of nearby plutons. The physical restriction of the deposits (and, therefore, fluid flow) to fracture footwalls and cavity floors and the heterogeneous and limited distribution of the deposits provides compelling evidence that they do not reflect flooding of the thick UZ at Yucca Mountain. The textures and isotopic and chemical compositions of these mineral deposits are consistent with deposition in a UZ setting from meteoric waters percolating downward along fracture flow paths.

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

USGS Publications Warehouse

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

2001-01-01

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

The influence of kinetics on the oxygen isotope composition of calcium carbonate

NASA Astrophysics Data System (ADS)

Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

2013-08-01

Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

Control and distribution of uranium in coral reefs during diagenesis

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

Gvirtzman, G.; Friedman, G.M.; Miller, D.S.

1973-12-01

The concentration of about 2 ppM of uranium in the aragonitic skeletons of modern scleractinian corals which we studied is a constant value, regardless of occurrence, anatomy, or taxonomy. The presence of cement of aragonite or high- magnesian calcite usually raises the concentration of bulk samples to about 3 ppM. Modern corals may contain up to 50% of cementing minerals. Organisms, such as corals and coralline algae, while secreting their skeleton, discriminate against the uptake of uranium, whereas the uptake of uranium by mineral cements is less restrained. Aragonite cement contains about 3.6 ppM and highmagnesian calcite cement 2.6 ppMmore » uranium. During leaching by freshwater, the aragonite of the skeletons of corals dissolves out. This creates hollow molds which fill with drusy low-magnesian calcite. In emergent reefs from the shores of the Red Sea which display the ellects of progressive diagenesis this calcite is enriched in uranium (3.9 ppM) beyond that found in marine cements. Second-generation calcite, which fills original voids in the corals from the emergent reefs, contains a lower level of uranium concent ration (1.3 ppM). The level of concentration of uranium in low-magnesian calcite of diagenetically altered corals is a function of the availability of uranium in meteoric waters. In aragonite as well as in high- and low-magnesian calcite uranium replaces calcium or occupies lattice vacancies in the crystal lattice. (auth)« less

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).

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.

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.

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

Dolomitic marbles from the ultrahigh-pressure metamorphic Kimi complex in Rhodope, N.E. Greece

NASA Astrophysics Data System (ADS)

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

2006-09-01

Dolomitic marbles from the Organi and Pandrosos areas of the ultrahigh-pressure (UHP) metamorphic Kimi complex in East Rhodope, N.E. Greece have the mineral assemblage: Cal + Dol + Ol + Phl ± Di ± Hbl ± Spl ± Ti Chu + retrograde Srp and Chl. Several generations of calcite and dolomite with variable composition and texture represent different stages of the P T evolution: The first stage is represented by matrix dolomite (X_MgCO_3 = 0.48) and relic domains of homogenous composition in matrix calcite (X_MgCO_3 = 0.11 0.13); the second stage is evident from precipitation of lath-shaped and vermicular dolomite in matrix calcite. The third stage is represented by veinlets of almost pure CaCO3 and domainal replacement of prior calcite by nearly pure CaCO3 + Ca-rich dolomite (X_MgCO_3 = 0.34 0.43). Matrix dolomite adjacent to CaCO3 veinlets also becomes Ca-rich (X_MgCO_3 = 0.42). In fact, Ca-rich dolomites with X_MgCO_3 in the range of 0.40 0.34 are reported for the first time from metamorphic marbles. Coexisting Ca-rich dolomite and Mg-poor calcite cannot be explained by the calcite-dolomite miscibility gap. This assemblage rather suggests that Mg-poor calcite was aragonite originally, which formed together with Ca-rich dolomite according to the reaction Mg Cal → Arg + Dol (1) at ultrahigh pressures and temperatures above at least 850 °C, when dolomite becomes disordered and incorporates more Ca than coexisting aragonite does in terms of Mg. The simplest explanation of these observations probably is to suggest two metamorphic events: The first one represented by relic matrix carbonates at relatively low to moderate pressures and temperatures of ca. 750 °C, and the second one limited by the minimum temperatures for dolomite disorder (ca. 850 °C) and in the aragonite + dolomite stability field, i.e. at a minimum pressure of 3 GPa and, if the presence of diamond-bearing metapelites nearby is considered, at conditions of at least 850 °C and 4.3 GPa in the diamond stability field. As there is hardly any back-reaction of Ca-rich dolomite + Mg-poor calcite to Mg-rich calcite, peak temperatures remained below the reaction (1) and the exhumation path probably crossed the aragonite-calcite transition at much lower than peak temperature. Cooling and decompression must have both occurred extremely fast in order for the µm-sized Ca-rich dolomite textures to be preserved. An alternative explanation of the formation of “UHP”-textures and compositions is by a fluid influx that not only caused serpentinisation and chloritisation of silicates but also Mg-leaching from carbonates, particularly from Mg-rich calcite and its fine grained dolomite-precipitates, thus transforming them into Mg-poor calcite + Ca-rich dolomite.

Occurrences of ikaite and pseudomorphs after ikaite in Patagonian lakes - crystal morphologies and stable isotope composition

NASA Astrophysics Data System (ADS)

Oehlerich, Markus; Mayr, Christoph; Griesshaber, Erika; Ohlendorf, Christian; Zolitschka, Bernd; Sánchez-Pastor, Nuria; Kremer, Barbara; Lücke, Andreas; Oeckler, Oliver; Schmahl, Wolfgang

2010-05-01

Ikaite (CaCO3•6H2O), a hydrated calcium carbonate mineral occasionally found in marine sediments, has so far rarely been reported from non-marine sites. Modern ikaite and calcitic pseudomorphs after ikaite were recently discovered in Patagonian Argentina at the polymictic lakes of Laguna Potrok Aike (51°57´S, 70°23´W) and Laguna Cháltel (49°57´S, 71°07´W), respectively. Both lakes are of volcanic origin and have phosphorous-rich, alkaline waters, but differ in altitude (790 m asl and 110 m asl for Laguna Cháltel and Laguna Potrok Aike, respectively) and water temperature. The aim of this study is (1) to investigate conditions for the formation of ikaite and its transformation to more stable, water-free carbonate pseudomorphs after ikaite and (2) to assess the potential of ikaite and calcite pseudomorphs after ikaite as a paleoenvironmental tool in freshwater lakes. Crystallographic, morphological and isotopic characteristics of the pseudomorphs were investigated. Ikaite crystals were found (in September 2008) primarily on aquatic macrophytes and cyanobacteria colonies at Laguna Potrok Aike. Ikaite crystals transformed quickly to calcite pseudomorphs after ikaite after recovery from the cool lake water (4°C). The crystal structure of ikaite was investigated with single crystal X-ray diffraction on samples that were permanently kept cold (in the lake water). At Laguna Cháltel calcite pseudomorphs after ikaite were discovered in littoral sediment cores from 25 m water depth. The mm-sized, porous, polycrystalline calcium carbonate aggregates from the 104 cm long sediment core of Laguna Cháltel are morphologically pseudomorphs after ikaite. SEM and XRD analyses highlight that these pseudomorphs consist of several µm-small calcite crystals in a calcitic matrix. The shape of these micro-crystals changes from rounded to fibrous with increasing sediment depth. Some specimens show casts of cyanobacteria trichomes. The oxygen isotopic composition of calcite pseudomorphs after ikaite from both lakes was analyzed. Calculating water temperatures during the ikaite precipitation assuming isotopic equilibrium for calcite and including modern water isotope ranges do not result in realistic estimates. Thus, either the calcite isotope fractionation factors are not applicable to these pseudomorphs, because e.g. the transformation to calcite pseudomorphs after ikaite caused isotope exchange or the carbonate precipitation occurred in disequilibrium. Nevertheless, the offset between oxygen isotope values of the sedimentary calcitic pseudomorphs from Laguna Cháltel and the modern ones from Laguna Potrok Aike corresponds to the differences present in lake water isotopic composition. Thus, calcite pseudomorphs after ikaite may serve as a proxy for paleo-lake water isotope variations. The crystallisation of ikaite in these lacustrine environments is presently simulated by different methods: (1) Evaporation from the lake water and (2) with modified diffusion silica gel experiments using the lake water and synthetic solutions.

Silicate versus carbonate weathering in Iceland: New insights from Ca isotopes

NASA Astrophysics Data System (ADS)

Jacobson, Andrew D.; Grace Andrews, M.; Lehn, Gregory O.; Holmden, Chris

2015-04-01

Several studies have measured riverine fluxes of Ca and carbonate alkalinity in Iceland with the aim of quantifying the role of basalt weathering in the long-term carbon cycle. A major assumption is that all of the Ca and alkalinity originates from the dissolution of Ca-bearing silicate minerals, such as plagioclase and clinopyroxene. However, hydrothermal calcite occurs throughout Iceland, and even trace levels are expected to impact river geochemistry owing to the mineral's high solubility and fast dissolution rate. To test this hypothesis, we used a new, high-precision Ca isotope MC-TIMS method (δ44/40Ca; 2σSD = ± 0.04 ‰) to trace sources of Ca in Icelandic rivers. We report elemental and Ca isotope data for rivers, high- and low-temperature groundwater, basalt, hydrothermal calcite (including Iceland Spar), and stilbite and heulandite, which are two types of zeolites commonly formed during low-grade metamorphism of basalt. In agreement with previous research, we find that rivers have higher δ44/40Ca values than basalt, with a maximum difference of ∼0.40‰. This difference may reflect isotope fractionation in the weathering zone, i.e., preferential uptake of 40Ca during clay mineral formation, adsorption, and other geochemical processes that cycle Ca. However, calcite δ44/40Ca values are also up to ∼0.40‰ higher than bedrock values, and on a diagram of δ44/40Ca versus Sr/Ca, nearly all waters plot within a plausible mixing domain bounded by the measured compositions of basalt and calcite, with glacial rivers plotting closer to calcite than non-glacial rivers. Calcite and heulandite form during hydrothermal alteration of basalt in the deep lava pile and often occur together in metabasalts now exposed at the surface. Because heulandite δ44/40Ca values are ∼1-2‰ lower than basalt, we suggest that 40Ca uptake by heudlandite explains the relatively high δ44/40Ca values of calcite and that calcite weathering in turn elevates riverine δ44/40Ca values. High mechanical erosion rates are known to facilitate the exposure and weathering of calcite, which explains the isotopic contrast between glacial and non-glacial watersheds. Using a mixing model, we find that calcite weathering provides ∼0-65% of the Ca in non-glacial rivers and ∼25-90% of the Ca in glacial rivers, with silicate weathering providing the remainder. Icelandic hydrothermal calcite contains mantle carbon. Noting that zeolite facies metamorphism and hydrothermal fluid circulation are ubiquitous characteristics of basaltic eruptions and assuming that hydrothermal calcite in other basaltic settings also contains mantle carbon, we suggest that the contribution of basalt weathering to long-term CO2 drawdown and climate regulation may be less significant than previously realized.

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

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

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

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.

Coupled phase and aqueous species equilibrium of the H 2O-CO 2-NaCl-CaCO 3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite

NASA Astrophysics Data System (ADS)

Duan, Zhenhao; Li, Dedong

2008-10-01

A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H 2O-CO 2-NaCl-CaCO 3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H +, Na +, Ca 2+, CaHCO3+, Ca(OH) +, OH -, Cl -, HCO3-, CO32-, CO 2(aq) and CaCO 3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO 2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T- P- m range, hence calcite solubility, CO 2 gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data. One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO 2 can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility. The functionality of pH value, alkalinity, CO 2 gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl (aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.

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]).

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.

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.

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

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

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

Ukita, Masaya, E-mail: uktia.masaya@f.mbox.nagoya-u.ac.jp; Toyoura, Kazuaki; Nakamura, Atsutomo

The thermodynamic phase stabilities of calcite and aragonite have been investigated from lattice vibrational analyses based on first-principles calculations. Different pressure dependences in phonon feature were found between the two polymorphs, suggesting different physical origins of the pressure-induced phase transitions. In the most stable phase in calcite (calcite I), an imaginary phonon mode consisting of rotation of CO{sub 3} ions with slight displacement of Ca ions appears at the F point in the Brillouin zone above 0.8 GPa. Such a soft mode means that external pressure induces the lattice-dynamical instability of calcite I leading to the phase transition to calcite II.more » On the other hand, the origin of the phase transition in aragonite is not due to such a lattice-dynamical instability. The estimated thermodynamical properties indicate that a first-order phase transition occurs between aragonite and post-aragonite at 34.7 GPa, coinciding with the reported experimental value at room temperature (35 GPa).« less

The long-term impact of magnesium in seawater on foraminiferal mineralogy: Mechanism and consequences

NASA Astrophysics Data System (ADS)

Dijk, I.; Nooijer, L. J.; Hart, M. B.; Reichart, G.-J.

2016-03-01

Foraminifera are unicellular protists, primarily known for their calcium carbonate shells that provide an extensive fossil record. This record, ranging from Cambrian to present shows both major shifts and gradual changes in the relative occurrence of taxa producing different polymorphs of carbonate. Here we present evidence for coupling between shifts in calcite- versus aragonite-producing species and periods with, respectively, low and high seawater Mg/Ca throughout the Phanerozoic. During periods when seawater Mg/Ca is <2 mol/mol, low-Mg calcite-producing species dominate the foraminiferal community. Vice versa, high-Mg calcite- and aragonite-producing species are more abundant during periods with relatively high seawater Mg/Ca. This alteration in dominance of the phase precipitated is due to selective recovery of groups producing the favorable polymorph after shifts from calcite to aragonite seas. In addition, relatively high extinction rates of species producing the mineral phase not favored by the seawater Mg/Ca of that time may be responsible for this alteration. These results imply that the current high seawater Mg/Ca will, in the long term, favor prevalence of high-Mg and aragonite-producing foraminifera over calcite-producing taxa, possibly shifting the balance toward a community in which calcite production is less dominant.

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.

Carbonate Minerals with Magnesium in Triassic Terebratula Limestone in the Term of Limestone with Magnesium Application as a Sorbent in Desulfurization of Flue Gases

NASA Astrophysics Data System (ADS)

Stanienda-Pilecki, Katarzyna

2017-09-01

This article presents the results of studies of Triassic (Muschelkalk) carbonate rock samples of the Terebratula Beds taken from the area of the Polish part of the Germanic Basin. It is the area of Opole Silesia. The rocks were studied in the term of possibility of limestone with magnesium application in desulfurization of flue gases executed in power plants. Characteristic features of especially carbonate phases including magnesium-low-Mg calcite, high-Mg calcite, dolomite and huntite were presented in the article. They were studied to show that the presence of carbonate phases with magnesium, especially high-Mg calcite makes the desulfurization process more effective. Selected rock samples were examined using a microscope with polarized, transmitted light, X-ray diffraction, microprobe measurements and FTIR spectroscopy. The results of studies show a domination of low magnesium calcite in the limestones of the Terebratula Beds. In some samples dolomite and lower amounts of high-Mg calcite occurred. Moreover, huntite was identified. The studies were very important, because carbonate phases like high-Mg calcite and huntite which occurred in rocks of the Triassic Terebratula Beds were not investigated in details by other scientists but they presence in limestone sorbent could influence the effectiveness of desulfurization process.

Analytical electron microscopy of biogenic and inorganic carbonates

NASA Technical Reports Server (NTRS)

Blake, David F.

1989-01-01

In the terrestrial sedimentary environment, the mineralogically predominant carbonates are calcite-type minerals (rhombohedral carbonates) and aragonite-type minerals (orthorhombic carbonates). Most common minerals precipitating either inorganically or biogenically are high magnesium calcite and aragonite. High magnesium calcite (with magnesium carbonate substituting for more than 7 mole percent of the calcium carbonate) is stable only at temperatures greater than 700 C or thereabouts, and aragonite is stable only at pressures exceeding several kilobars of confining pressure. Therefore, these carbonates are expected to undergo chemical stabilization in the diagenetic environment to ultimately form stable calcite and dolomite. Because of the strong organic control of carbonate deposition in organisms during biomineralization, the microchemistry and microstructure of invertebrate skeletal material is much different than that present in inorganic carbonate cements. The style of preservation of microstructural features in skeletal material is therefore often quite distinctive when compared to that of inorganic carbonate even though wholesale recrystallization of the sediment has taken place. Microstructural and microchemical comparisons are made between high magnesium calcite echinoderm skeletal material and modern inorganic high magnesium calcite inorganic cements, using analytical electron microscopy and related techniques. Similar comparisons are made between analogous materials which have undergone stabilization in the diagenetic environment. Similar analysis schemes may prove useful in distinguishing between biogenic and inorganic carbonates in returned Martian carbonate samples.

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.

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.

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

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

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.

NARROW LINE ABSORPTION IN CACO3.

DTIC Science & Technology

CARBONATES), (*CALCIUM COMPOUNDS, (*ABSORPTION SPECTRA, CALCITE), (*CALCITE, RADIATION EFFECTS), ELECTRON PARAMAGNETIC RESONANCE, SINGLE CRYSTALS , NEUTRONS, X RAYS, GAMMA RAYS, IONS, CRYSTAL DEFECTS, PARAMAGNETIC RESONANCE.

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.

Reconstruction of seasonal temperature variability in the tropical Pacific Ocean from the shell of the scallop, Comptopallium radula

NASA Astrophysics Data System (ADS)

Thébault, Julien; Chauvaud, Laurent; Clavier, Jacques; Guarini, Jennifer; Dunbar, Robert B.; Fichez, Renaud; Mucciarone, David A.; Morize, Eric

2007-02-01

We investigated the oxygen isotope composition (δ 18O) of shell striae from juvenile Comptopallium radula (Mollusca; Pectinidae) specimens collected live in New Caledonia. Bottom-water temperature and salinity were monitored in-situ throughout the study period. External shell striae form with a 2-day periodicity in this scallop, making it possible to estimate the date of precipitation for each calcite sample collected along a growth transect. The oxygen isotope composition of shell calcite (δ 18O shell calcite) measured at almost weekly resolution on calcite accreted between August 2002 and July 2003 accurately tracks bottom-water temperatures. A new empirical paleotemperature equation for this scallop species relates temperature and δ 18O shell calcite: t(°C)=20.00(±0.61)-3.66(±0.39)×(δ18O-δ18O) The mean absolute accuracy of temperature estimated using this equation is 1.0 °C at temperatures between 20 and 30 °C. Uncertainties regarding the precise timing of CaCO 3 deposition and the actual variations in δ 18O water at our study sites probably contribute to this error. Comparison with a previously published empirical paleotemperature equation indicates that C. radula calcite is enriched in 18O by ˜0.7‰ relative to equilibrium. Given the direction of this offset and the lack of correlation between shell growth rate and δ 18O shell calcite, this disequilibrium is unlikely to be related to kinetic isotope effects. We suggest that this enrichment reflects (1) a relatively low pH in the scallop's marginal extrapallial fluid (EPF), (2) an isotopic signature of the EPF different from that of seawater, or (3) Rayleigh fractionation during the biocalcification process. Relative changes in δ 18O shell calcite reflect seawater temperature variability at this location and we suggest that the shell of C. radula may be useful as an archive of past seawater temperatures.

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.

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 superimposition and reactivation surfaces) determining the spatial distribution of the heterogeneities of diagenetic origin in the aeolian reservoir.

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 Sedimentary Geology).

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

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2012-04-01

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

Barnacles - recorders of environmental conditions with unique geochemical signatures

NASA Astrophysics Data System (ADS)

Vinzenz Ullmann, Clemens; Gale, Andy; Korte, Christoph; Frei, Robert; Huggett, Jenny; Wray, Dave

2017-04-01

Barnacles are calcite-forming arthropods that occur in a wide range of habitats in modern times and are found in sedimentary successions reaching back to the Paleozoic. Despite potential use of their mostly low-Mg calcite hard parts for palaeoenvironmental reconstructions, their geochemical composition has been little studied. Here, we present the first comprehensive overview of barnacle geochemistry, with C and O isotope, as well as Mg/Ca, Sr/Ca, Mn/Ca and Fe/Ca data for multiple samples of 42 species covering the orders Sessilia, Scalpelliformes, and Lepadiformes. XRD analyses confirm calcite as the only significant carbonate mineral of the studied barnacle shell material. Apart from one species, median Mg/Ca ratios fall below 50 mmol/mol, the approximate limit for low-Mg-calcite. In the order Sessilia, the scuta and terga are on average enriched in Mg by 36 % over the unmoveable plates. Amongst the calcite-forming marine animals, barnacles have very high Sr/Ca ratios of 2.6 to 5.9 mmol/mol, amongst the highest known for calcite secreting animals. Mn/Ca and Fe/Ca ratios are commonly low and compatible with other modern shell calcite, but can be strongly enriched to > 1 mmol/mol in proximal habitats, particularly close to areas strongly affected by human activity. Carbon and oxygen isotope data indicate formation of the calcite in or near isotopic equilibrium with ambient water conditions. Apart from species showing δ18O values below 0 ‰ V-PDB, a negative correlation of oxygen isotope ratios with Sr/Ca ratios is observed, which may be related to metabolic activity. Compositional patterns in barnacle shell material, particularly high Sr concentrations and Mg distribution in shell plates of the Sessilia, point to a great potential of barnacles for high fidelity reconstruction of past seawater chemistry and environmental conditions complementary to other archives.

Carbonatite tuffs in the Laetolil Beds of Tanzania and the Kaiserstuhl in Germany

USGS Publications Warehouse

Hay, R.L.; O'Neil, J.R.

1983-01-01

Carbonatite lava and tephra are now well known. The only modern eruptive carbonatites, from Oldoinyo Lengai, Tanzania, are of alkali carbonatite, whereas all of the pre-modern examples are of calcite or dolomite. Chemical and stable isotope analyses were made of separate phases of Pliocene carbonatite tuffs of the Laetolil Beds in Tanzania and of Miocene carbonatite tuffs of the Kaiserstuhl in Germany in order to understand the reasons for this major difference. The Laetolil Beds contain numerous carbonatite and melilitite-carbonatite tuffs. It is proposed that the carbonatite ash was originally of alkali carbonate composition and that the alkali component was dissolved, leaving a residuum of calcium carbonate. The least recrystallized melilitite-carbonatite tuff contains early-deposited calcite cement and calcite pseudomorphs after nyerereite (?) that have contents of strontium and barium and ??18O and ??13C values suggestive of incomplete chemical and isotopic exchange during alteration and replacement of alkali carbonatite ash. Carbonatite tuffs of the Kaiserstuhl contain globules composed of calcite phenocrysts and microphenocrysts in a groundmass of calcite with a small amount of clay, apatite, and magnetite. The SrO contents of phenocrysts, microphenocrysts, and groundmass calcite average 0.90, 1.42, and 0.59 percent, respectively. The average ??18O and ??13C values of globules (+14.3 and -9.0, respectively) fall between those of coarse-grained intrusive Kaiserstuhl carbonatite (avg. +6.6, -5.8) and those of low-temperature calcite cement in the carbonatite tuffs (+21.8, -14.9). The phenocrysts and microphenocrysts are primary magmatic calcite, but several features indicate that the groundmass has been recrystallized and altered in contact with meteoric water, resulting in weathering of silicate to clay, leaching of strontium, and isotopic exchange. The weight of evidence favors an original high content of alkali carbonatite in the groundmass, with recrystallization following leaching of the alkalies. ?? 1983 Springer-Verlag.

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

PubMed Central

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

2016-01-01

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

Growth and development of spring towers at Shiqiang, Yunnan Province, China

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2017-01-01

Throughout the world, high artesian pressures in hydrothermal areas have led to the growth of tall spring towers that have their vents at their summits. The factors that control their development and formative precipitates are poorly understood because these springs, irrespective of location, are mostly inactive. Spring towers found at Shiqiang (Yunnan Province, China), which are up to 4 m high and 3 m in diameter, are formed largely of calcite and aragonite crystal bushes, euhedral calcite crystals and coated grains with alternating Fe-poor and Fe-rich zones, calcite rafts, and cements formed of various combinations of calcite, aragonite, strontianite, Mg-Si reticulate, needle fiber calcite, calcified and non-calcified microbes, diatoms, and insects. Collectively, the limestones that form the towers can be divided into (1) Group A that are friable, porous and form the cores of the towers and have δ18OSMOW values of + 15.7 to + 19.7‰ (average 17.8‰) and δ13CPDB values of + 5.1 to + 6.9‰ (average 5.9‰), and (2) Group B that are hard and well lithified and found largely around the vents and the tower sides, and have δ18OSMOW values of + 13.0 to + 22.0‰ (average 17.6‰) and δ13CPDB values of + 1.4 to + 3.6‰ (average 2.6‰). The precipitates and the isotopic values indicate that these were thermogene springs. Growth of the Shiqiang spring towers involved (1) Phase IA when precipitation of calcite and aragonite bushes formed the core of the tower and Phase IB when calcite, commonly Fe-rich, was precipitated locally, (2) Phase II that involved the precipitation of white cements, formed of calcite, aragonite, strontianite, and Mg-Si reticulate coatings in cavities amid the Phase I precipitates, and (3) Phase III, which formed probably after spring activity ceased, when needle-fiber calcite was precipitated and the mounds were invaded by microbes (some now calcified), diatoms, and insects. At various times during this complex history, pore waters mediated dissolution of the calcite and aragonite and sometimes partial alteration of the aragonite. The diverse array of precipitates, depositional fabrics and diagenetic changes clearly indicate that the composition of the spring water changed frequently. Growth of the spring towers at Shiqiang continued until there was insufficient artesian pressure to lift the water above the top of the tower vent.

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 the solubility and dissolution rate of calcite inversely correlate with pH, heterotrophic microbial growth in the presence of nonionic organic matter and NH 4+ appears to have the greatest potential for enhancing calcite weathering relative to abiotic conditions.

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 favored from a solubility viewpoint. We also show that unaccounted CaCO3 precipitation in intermediate sampling containers and splash effects may in cases result in underestimating dripwater Ca concentration and alkalinity, potentially leading to incorrect conclusions regarding the role of fluid Mg/Ca ratio and supersaturation on CaCO3 mineralogy. A simple way to elude the first effect is by taking water samples directly from stalactites and by titrating alkalinity in the same containers used to collect dripwaters.

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 minute. After treatment the remaining solution was blown out by a stream of nitrogen to preclude the precipitation of Sr phase. We observed that the precipitated calcite crystals can be very different in size even if the runs have the same input rate of calcite components. The cave-type and cold-seal runs yielded 15-40 μ m calcites, but in the drift experiments crystal size varied between 60 μ m and 1 mm. Electron microprobe analysis across the large crystals show that the concentration of Sr is higher in the center and decreases toward the edge. This is probably due to the cube-root dependence of radial growth on the volume change of the growing crystals. Like previous workers who measured bulk uptake of Sr as a function of precipitation rate, we observed that increased growth rate (V, nm/s) enhances Sr uptake into the crystal, raising Kdbulk/liquid=(Sr/Ca)bulk/(Sr/Ca)liquid. Kdbulk/liquid = 0.03 to 0.06 when log(V)=-1.1 to -0.6 at 25° C in the cave-type runs (I=0.01). At higher ionic strength (I=0.52) and T=55° C, Kdbulk/liquid=0.11 to 0.15 when log(V)=-0.6 to 0.4 in the drift experiments. XPS analysis of surface-liquid experiments yielded higher Kdsurface/liquid=(Sr/Ca)surface/(Sr/Ca)liquid values compared with Kdbulk/liquid. This combined evidence supports the idea that Sr is enriched at the calcite surface relative to the bulk crystal during crystal growth.

Amino Acid Hydrolysis and Analysis System for Investigation of Site Directed Nucleation and Growth of Ceramic Films on Metallic Surfaces

DTIC Science & Technology

2008-09-30

that composed the proteinaceous polymers found at the interface between calcite crystals deposited by oyster cells and the various n1etal substrates...proteinaceous polymers found at the interface between calcite crystals deposited by oyster cells and the various metal substrates. A recently...required for the mechanism of biomineralization and site-specific deposition of ceramic crystals on aluminum alloy substrates. These calcite crystals

An assessment of latest Cretaceous Pycnodonte vesicularis (Lamarck, 1806) shells as records for palaeoseasonality: a multi-proxy investigation

NASA Astrophysics Data System (ADS)

de Winter, Niels J.; Vellekoop, Johan; Vorsselmans, Robin; Golreihan, Asefeh; Soete, Jeroen; Petersen, Sierra V.; Meyer, Kyle W.; Casadio, Silvio; Speijer, Robert P.; Claeys, Philippe

2018-06-01

In order to assess the potential of the honeycomb oyster Pycnodonte vesicularis for the reconstruction of palaeoseasonality, several specimens recovered from late Maastrichtian strata in the Neuquén Basin (Argentina) were subject to a multi-proxy investigation, involving scanning techniques and trace element and isotopic analysis. Combined CT scanning and light microscopy reveals two calcite microstructures in P. vesicularis shells (vesicular and foliated calcite). Micro-XRF analysis and cathodoluminescence microscopy show that reducing pore fluids were able to migrate through the vesicular portions of the shells (aided by bore holes) and cause recrystallization of the vesicular calcite. This renders the vesicular portions not suitable for palaeoenvironmental reconstruction. In contrast, stable isotope and trace element compositions show that the original chemical composition of the foliated calcite is well-preserved and can be used for the reconstruction of palaeoenvironmental conditions. Stable oxygen and clumped isotope thermometry on carbonate from the dense hinge of the shell yield sea water temperatures of 11°C, while previous TEX86H palaeothermometry yielded much higher temperatures. The difference is ascribed to seasonal bias in the growth of P. vesicularis, causing warm seasons to be underrepresented from the record, while TEX86H palaeothermometry seems to be biased towards warmer surface water temperatures. The multi-proxy approach employed here enables us to differentiate between well-preserved and diagenetically altered portions of the shells and provides an improved methodology for reconstructing palaeoenvironmental conditions in deep time. While establishing a chronology for these shells was complicated by growth cessations and diagenesis, cyclicity in trace elements and stable isotopes allowed for a tentative interpretation of the seasonal cycle in late Maastrichtian palaeoenvironment of the Neuquén Basin. Attempts to independently verify the seasonality in sea water temperature by Mg / Ca ratios of shell calcite are hampered by significant uncertainty due to the lack of proper transfer functions for pycnodontein oysters. Future studies of fossil ostreid bivalves should target dense, foliated calcite rather than sampling bulk or vesicular calcite. Successful application of clumped isotope thermometry on fossil bivalve calcite in this study indicates that temperature seasonality in fossil ostreid bivalves may be constrained by the sequential analysis of well-preserved foliated calcite samples using this method.

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

PubMed

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

2016-01-01

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

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

NASA Technical Reports Server (NTRS)

Bell, Mary S.

2009-01-01

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

Chlorophyll and carotenoid pigments in solar saltern microbial mats

NASA Astrophysics Data System (ADS)

Villanueva, Joan; Grimalt, Joan O.; de Wit, Rutger; Keely, Brendan J.; Maxwell, James R.

1994-11-01

The distributions of carotenoids, chlorophylls, and their degradation products have been studied in two microbial mat systems developed in the calcite and calcite/gypsum evaporite domains of a solar saltern system. Phormidium valderianum and Microcoleus chthonoplastes are the dominant cyanobacterial species, respectively, and large amounts of Chloroflexus-like bacteria occur in the carbonate/gypsum mat. In both systems, the major pigments are chlorophyll a, zeaxanthin, β-carotene and myxoxanthophyll, which originate from these mat-building cyanobacteria. This common feature contrasts with differences in other pigments that are specific for each mat community. Thus, chlorophyll c and fucoxanthin, reflecting diatom inputs, are only found in the calcite mat, whereas the calcite/gypsum mat contains high concentrations of bacteriochlorophylls c produced by the multicellular green filamentous bacteria. In both cases, the depth concentration profiles (0-30 and 0-40 mm) show a relatively good preservation of the cyanobacterial carotenoids, zeaxanthin, β-carotene, myxoxanthophyll, and echinenone. This contrasts with the extensive biodegradation of cyanobacterial remains observed microscopically. Fucoxanthin in the calcite mat is also transformed at a faster rate than the cyanobacterial carotenoids. Chlorophyll a, the major pigment in both mats, exhibits different transformation pathways. In the calcite/gypsum mat, it is transformed via C-13 2 carbomethoxy defunctionalization prior to loss of the phytyl chain, leading to the formation of pyrophaeophytin a and, subsequently, pyrophaeophorbide a. On the other hand, the occurrence of the enzyme chlorophyllase, attributed to diatoms in the calcite mat, gives rise to extensive phytyl hydrolysis, with the formation of chlorophyllide a, pyrophaeophorbide a and, in minor proportion, phaeophorbide a. Studies of the sources of the photosynthetic pigments and of their transformation pathways in such simplified ecosystems provide a basis for the understanding of the distribution patterns of these compounds in more complex aquatic environments.

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.

Permeability generation and resetting of tracers during metamorphic fluid flow: implications for advection-dispersion models

NASA Astrophysics Data System (ADS)

Cartwright, Ian

Advection-dispersion fluid flow models implicitly assume that the infiltrating fluid flows through an already fluid-saturated medium. However, whether rocks contain a fluid depends on their reaction history, and whether any initial fluid escapes. The behaviour of different rocks may be illustrated using hypothetical marble compositions. Marbles with diverse chemistries (e.g. calcite + dolomite + quartz) are relatively reactive, and will generally produce a fluid during heating. By contrast, marbles with more restricted chemistries (e.g. calcite + quartz or calcite-only) may not. If the rock is not fluid bearing when fluid infiltration commences, mineralogical reactions may produce a reaction-enhanced permeability in calcite + dolomite + quartz or calcite + quartz, but not in calcite-only marbles. The permeability production controls the pattern of mineralogical, isotopic, and geochemical resetting during fluid flow. Tracers retarded behind the mineralogical fronts will probably be reset as predicted by the advection-dispersion models; however, tracers that are expected to be reset ahead of the mineralogical fronts cannot progress beyond the permeability generating reaction. In the case of very unreactive lithologies (e.g. pure calcite marbles, cherts, and quartzites), the first reaction to affect the rocks may be a metasomatic one ahead of which there is little pervasive resetting of any tracer. Centimetre-scale layering may lead to the formation of self-perpetuating fluid channels in rocks that are not fluid saturated due to the juxtaposition of reactants. Such layered rocks may show patterns of mineralogical resetting that are not predicted by advection-dispersion models. Patterns of mineralogical and isotopic resetting in marbles from a number of terrains, for example: Chillagoe, Marulan South, Reynolds Range (Australia); Adirondack Mountains, Old Woman Mountains, Notch Peak (USA); and Stephen Cross Quarry (Canada) vary as predicted by these models.

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

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.

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.

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).

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.

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.

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

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.

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.

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.

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

Microbial control of mineral–groundwater equilibria:Macroscale to microscale

USGS Publications Warehouse

Bennett, Philip C.; Hiebert, Franz K.; Roger, Jennifer Roberts

2000-01-01

macroscaleprocesses that perturb general groundwater chemistry and therefore mineral–water equilibria; and microscale interactions, where attached organisms locally perturb mineral–water equilibria, potentially releasing limiting trace nutrients from the dissolving mineral.In the contaminated unconfined glacio-fluvial aquifer near Bemidji, Minnesota, USA, carbonate chemistry is influenced primarily at the macroscale. Under oxic conditions, respiration by native aerobic heterotrophs produces excess carbon dioxide that promotes calcite and dolomite dissolution. Aerobic microorganisms do not colonize dolomite surfaces and few occur on calcite. Within the anoxic groundwater, calcite overgrowths form on uncolonized calcite cleavage surfaces, possibly due to the consumption of acidity by dissimilatory iron-reducing bacteria. As molecular oxygen concentration increases downgradient of the oil pool, aerobes again dominate and residual hydrocarbons and ferrous iron are oxidized, resulting in macroscale carbonate-mineral dissolution and iron precipitation.

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.

Direct Measurement of Initial 230TH/ 232TH Ratios in Central Texas Speleothems for More Accurate Age Determination

NASA Astrophysics Data System (ADS)

Wortham, B. E.; Banner, J. L.; James, E.; Loewy, S. L.

2013-12-01

Speleothems, calcite deposits in caves, preserve a record of climate in their growth rate, isotope ratios and trace element concentrations. These variables must be tied to precise ages to produce pre-instrumental records of climate. The 238U-234U- 230Th disequilibrium method of dating can yield precise ages if the amount of 230Th from the decay of radiogenic 238U can be constrained. 230Th in a speleothem calcite growth layer has two potential sources - 1) decay of radioactive 238U since the time of growth of the calcite layer; and 2) initial detrital 230Th, incorporated along with detrital 232Th, into the calcite layer at the time it grew. Although the calcite lattice does not typically incorporate Th, samples can contain impurities with relatively high Th contents. Initial 230Th/232Th is commonly estimated by assuming a source with bulk-Earth U/Th values in a state of secular equilibrium in the 238U-decay chain. The uncertainty in this 230Th/232Th estimate is also assumed, typically at +/-100%. Both assumptions contribute to uncertainty in ages determined for young speleothems. If the amount of initial detrital 230Th can be better quantified for samples or sites, then U-series ages will have smaller uncertainties and more precisely define the time series of climate proxies. This study determined the initial 230Th/232Th of modern calcite to provide more precise dates for central Texas speleothems. Calcite was grown on glass-plate substrates placed under active drips in central Texas caves. The 230Th/232Th of this modern calcite was determined using thermal ionization mass spectrometry. Results show that: 1) initial 230Th/232Th ratios can be accurately determined in these young samples and 2) measuring 230Th/232Th reduces the uncertainties in previously-determined ages on stalagmites from under the same drips. For example, measured initial 230Th/232Th in calcite collected on substrates from different locations in the cave at Westcave Preserve are 15.3 × 0.67 ppm, 14.6 × 0.83 ppm, 5.8 × 0.56 ppm, and 5.9 × 0.60 ppm, which are higher and more precise than the value commonly assumed for initial 230Th/232Th, 4.4 × 4.4 ppm. Soil sampled above Westcave, a potential source of detrital Th incorporated into speleothems, also has a high calculated 230Th/232Th. We calculate soil 230Th/232Th from measured U and Th concentrations of soil leachates (using DI water and ammonium acetate). Calculated 230Th/232Th for Westcave soils range from 0.39 to 28.4 ppm, which encompasses the range of initial 230Th/232Th values found in the modern calcite. Soil leachates from Natural Bridge Caverns and Inner Space Cavern were analyzed by the same method, yielding calculated 230Th/232Th ranging from 1.5 to 12.6 ppm (Natural Bridge), and from 1.43 to 272 ppm (Inner Space). Soil and calcite data indicate that the commonly assumed initial 230Th/232Th is not always applicable and that initial 230Th/232Th can be estimated more accurately by measuring Th isotope ratios in modern calcite and soils to determine speleothem U-series ages.

Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada

USGS Publications Warehouse

Neymark, L.A.; Amelin, Y.V.

2008-01-01

Extreme U and Pb isotope variations produced by disequilibrium in decay chains of 238U and 232Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my-1) contain excess 206Pb and 208Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable 206Pb/238U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect 207Pb/235U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages. Opal and calcite from outer (younger) portions of coatings have 230Th/U ages from 94.6 ?? 3.7 to 361.3 ?? 9.8 ka and initial 234U/238U activity ratios (AR) from 4.351 ?? 0.070 to 7.02 ?? 0.12, which indicate 234U enrichment from percolating water. Present-day 234U/238U AR is ???1 in opal/chalcedony from older portions of the coatings. The 207Pb/235U ages of opal/chalcedony samples range from 0.1329 ?? 0.0080 to 9.10 ?? 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my-1, in good agreement with previous results. Measured 234U/238U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ?? 0.006 to 2.091 ?? 0.006 and are >1 in most samples. The range of 87Sr/86Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool. In the U-poor calcite samples, measured 206Pb/207Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both 206Pb and 207Pb derived from Rn diffusion and from direct ??-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains 206Pb and 208Pb excesses, but no appreciable 207Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect 206Pb-238U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.

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.

Textural and isotopic evidence for Ca-Mg carbonate pedogenesis

NASA Astrophysics Data System (ADS)

Diaz-Hernandez, J. L.; Sánchez-Navas, A.; Delgado, A.; Yepes, J.; Garcia-Casco, A.

2018-02-01

Models for evaluating the terrestrial carbon cycle must take into account not only soil organic carbon, represented by a mixture of plant and animal remains, but also soil inorganic carbon, contained in minerals, mainly in calcite and dolomite. Thick soil caliches derived from weathering of mafic and ultramafic rocks must be considered as sinks for carbon storage in soils. The formation of calcite and dolomite from pedogenic alteration of volcanic tephras under an aridic moisture regime is studied in an unusually thick 3-m soil profile on Gran Canaria island (Canary Islands, Spain). The biological activity of the pedogenic environment (soil respiration) releases CO2 incorporated as dissolved inorganic carbon (DIC) in waters. It drives the formation of low-magnesian calcite and calcian dolomite over basaltic substrates, with a δ13C negative signature (-8 to -6‰ vs. V-PDB). Precipitation of authigenic carbonates in the soil is accompanied by the formation of Mg-rich clay minerals and quartz after the weathering of basalts. Mineralogical, textural, compositional, and isotopic variations throughout the soil profile studied indicate that dolomite formed at greater depths and earlier than the calcite. The isotopic signatures of the surficial calcite and deeper dolomite crusts are primary and resulted from the dissolution-precipitation cycles that led to the formation of both types of caliches under different physicochemical conditions. Dolomite formed within a clay-rich matrix through diffusive transport of reactants. It is precipitated from water with more negative δ18O values (-1.5 to -3.5‰ vs. V-SMOW) in the subsoil compared to those of water in equilibrium with surficial calcite. Thus, calcite precipitated after dolomite, and directly from percolating solutions in equilibrium with vadose water enriched in δ18O (-0.5 to +1.5‰) due to the evaporation processes. The accumulation of inorganic carbon reaches 586.1 kg m-2 in the soil studied, which means that the carbon sequestration capacity of mafic rocks must be taken into account for certain terrestrial settings. Dolomite together with calcite should be assessed when quantifying carbon stored in arid-semiarid soils as a result of the natural weathering processes.

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 signals occur with characteristics consistent with phosphate monoesters. The results of this study indicate that trace- to minor concentrations of dissolved organic molecules can be effectively taken up during calcite precipitation and incorporated in the structure, leaving a resilient record of materials present during crystallization.

An observational and thermodynamic investigation of carbonate partial melting

NASA Astrophysics Data System (ADS)

Floess, David; Baumgartner, Lukas P.; Vonlanthen, Pierre

2015-01-01

Melting experiments available in the literature show that carbonates and pelites melt at similar conditions in the crust. While partial melting of pelitic rocks is common and well-documented, reports of partial melting in carbonates are rare and ambiguous, mainly because of intensive recrystallization and the resulting lack of criteria for unequivocal identification of melting. Here we present microstructural, textural, and geochemical evidence for partial melting of calcareous dolomite marbles in the contact aureole of the Tertiary Adamello Batholith. Petrographic observations and X-ray micro-computed tomography (X-ray μCT) show that calcite crystallized either in cm- to dm-scale melt pockets, or as an interstitial phase forming an interconnected network between dolomite grains. Calcite-dolomite thermometry yields a temperature of at least 670 °C, which is well above the minimum melting temperature of ∼600 °C reported for the CaO-MgO-CO2-H2O system. Rare-earth element (REE) partition coefficients (KDcc/do) range between 9-35 for adjacent calcite-dolomite pairs. These KD values are 3-10 times higher than equilibrium values between dolomite and calcite reported in the literature. They suggest partitioning of incompatible elements into a melt phase. The δ18O and δ13C isotopic values of calcite and dolomite support this interpretation. Crystallographic orientations measured by electron backscattered diffraction (EBSD) show a clustering of c-axes for dolomite and interstitial calcite normal to the foliation plane, a typical feature for compressional deformation, whereas calcite crystallized in pockets shows a strong clustering of c-axes parallel to the pocket walls, suggesting that it crystallized after deformation had stopped. All this together suggests the formation of partial melts in these carbonates. A Schreinemaker analysis of the experimental data for a CO2-H2O fluid-saturated system indeed predicts formation of calcite-rich melt between 650-880 °C, in agreement with our observations of partial melting. The presence of partial melts in crustal carbonates has important physical and chemical implications, including a drastic drop in rock viscosity and significant change in the dynamics and distribution of fluids within both the contact aureole and the intrusive body.

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 importance of calcite as a proxy for chemical attack and quality of the ancient inorganic binder.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

Carbonate concretions from two distinct settings have been studied for their petrography, stable carbon and oxygen isotopes, and lipid biomarker content. Carbonate concretions are in large part products of microbial degradation of organic matter, as for example by sulfate-reducing bacteria, iron-reducing bacteria, and methanogenic archaea. For these prokaryotes certain lipid biomarkers such as hopanoids, terminally-branched fatty acids (bacteria) and isoprenoids (archaea) are characteristic. Two different types of concretions were studied: a) Upper Miocene septarian calcite concretions of the southern Vienna Basin embedded in brackish sediments represented by partly bituminous calcareous sands, silts and clays; b) Paleocene-Eocene siderite concretions enclosed in marine, sandy to silty turbidites with varying carbonate contents and marl layers from the Upper Gosau Subgroup in northern Styria. Calcite concretions consist of abundant calcite microspar (80-90 vol.%), as well as detrital minerals and iron oxyhydroxides. The septarian cracks show beginning cementation with dog-tooth calcite to varying degrees. Framboidal pyrite occurs in some of the calcite concretions, pointing to bacterial sulfate reduction. Siderite concretions consist of even finer carbonate crystals, mainly siderite (40-70 vol.%) but also abundant ferroan calcite, accompanied by iron oxyhydroxides and detrital minerals. The δ13C values of the calcite concretions (-6.8 to -4.1o ) most likely reflect a combination of bacterial organic matter oxidation and input of marine biodetrital carbonate. The δ18O values range from -8.9 to -7.8o agreeing with a formation within a meteoric environment. The surrounding host sediment shows about 1-2o higher δ13C and δ18O values. The siderite δ13C values (-11.1 to -7.5o ) point to microbial respiration of organic carbon and the δ18O values (-3.5 to +2.2o ) agree with a marine depositional environment. In contrast to the calcite concretions, the stable isotope composition of the host sediment differs significantly from the siderite concretions. The δ13C values of the Gosau host sediment reflect marine conditions, whereas the oxygen isotope values are best explained by meteoric overprint. Lipid biomarkers have been extracted before and after dissolution of the concretions in order to assess their authenticity and to exclude recent surface contamination. In the following, only the biomarkers extracted after dissolution are discussed, since they are thought to be related to concretion formation. The calcite concretions comprise abundant plant wax derived long-chain n-alkanes, reflecting high terrestrial input. Bacterial, terminally-branched fatty acids were found, but in overall low abundance. The siderite concretions did not yield biomarkers due to their high maturity. No archaeal biomarkers were found in any of the concretions. Considering the presence of framboidal pyrite, the moderately low δ13C values, and the biomarker inventory, bacterial sulfate reduction apparently contributed to the formation of the calcite concretions in a brackish environment. In contrast, ongoing sulfate reduction and resultant hydrogen sulfide production inhibit siderite precipitation. Therefore, the low δ13C values of the siderite concretions are best explained by bacterial iron reduction.

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.

On the densification and hydration of CaCO3 particles by Q-switched laser pulses in water

NASA Astrophysics Data System (ADS)

Lin, Peng-Wen; Wu, Chao-Hsien; Zheng, Yuyuan; Chen, Shuei-Yuan; Shen, Pouyan

2013-09-01

Calcite powders subjected to Q-switched laser pulses in water were characterized by X-ray/electron diffraction and optical spectroscopy to have a significant internal compressive stress (up to ca. 1.5 GPa) with accompanied transformation into defective calcite II and hydrates. The defective calcite II particles were (0 1 0), (0 0 1), (0 1¯ 1), (0 1 3) and (0 1¯ 3) faceted with 2×(0 2 0)II commensurate superstructure and tended to hydrate epitaxially as monohydrocalcite co-existing with ikaite (CaCO3·6H2O) with extensive cleavages and amorphous calcium carbonate with porous structure. The colloidal suspension containing the densified calcite polymorphs and hydrates showed two UV-visible absorptions corresponding to a minimum band gap of ca. 5 and 3 eV, respectively.

The inhibition of calcium carbonate crystal growth by the cysteine-rich Mdm2 peptide.

PubMed

Dalas, E; Chalias, A; Gatos, D; Barlos, K

2006-08-15

The crystal growth of calcite, the most stable calcium carbonate polymorph, in the presence of the cysteine-rich Mdm2 peptide (containing 48 amino acids in the ring finger configuration), has been investigated by the constant composition technique. Crystallization took place exclusively on well-characterized calcite crystals in solutions supersaturated only with respect to this calcium carbonate salt. The kinetic results indicated a surface diffusion spiral growth mechanism. The presence of the Mdm2 peptide inhibited the crystal growth of calcite by 22-58% in the concentration range tested, through adsorption onto the active growth sites of the calcite crystal surface. The kinetic results favored a Langmuir-type adsorption model, and the value of the calculated affinity constant was k(aff)=147x10(4) dm(3)mol(-1), a(ads)=0.29.

Hydrothermal karst and associated breccias in Neoproterozoic limestone from the Barker-Villa Cacique area (Tandilia belt), Argentina

NASA Astrophysics Data System (ADS)

Dristas, Jorge A.; Martínez, Juan C.; van den Kerkhof, Alfons M.; Massonne, Hans-Joachim; Theye, Thomas; Frisicale, María C.; Gregori, Daniel A.

2017-07-01

In the Barker-Villa Cacique area (Tandilia belt), remarkable megabreccias, limestone breccias and phosphate-bearing breccias hosted in black limestone and along the contact with the upper section of the sedimentary succession are exposed. These rocks are the result of extensive hydrothermal alteration of the original micritic limestone and other fine-grained clastic sediments. Typical alteration minerals are sericite, chlorite, interstratified chlorite/K-white mica, kaolinite, dickite, pyrite, chalcopyrite, goethite, quartz, calcite, Fe-calcite, dolomite, ankerite, fluor-apatite, barite and aluminium-phosphate-sulfate (APS) minerals. Quartz and calcite cements from hydraulic breccias in the limestone contain low-salinity aqueous fluid inclusions. Corresponding homogenization temperatures display 200-220 °C and 110-140 °C in hydrothermal quartz, and 130-150 °C in late calcite cement. Carbon and oxygen stable isotope analyses of carbonates from the Loma Negra quarry (LNQ) support the major role of hydrothermal activity. A significant difference was found between δ18Ocar values from unaltered micritic limestone (ca. 23.8‰ SMOW) and secondary calcite (ca. 18.5‰ SMOW). The lower δ18Ocar values are interpreted as a result of calcite precipitation from hot hydrothermal fluids. At a late stage, the hydrothermal fluid containing H2S mixed with descending and oxidizing meteoric waters. Circulation of the ensuing acid fluids resulted in the partly dissolution and collapse brecciation of the Loma Negra Formation. The hydrothermal stage can be tentatively dated ca. 590-620 Ma corresponding to the Brasiliano orogeny.

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.

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.

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. Results from the field experiment indicated that following the molasses addition, total cell counts and ureolytic cell numbers increased by one to two orders of magnitude. Ureolysis rates increased from <100 pmol L-1hr-1 to >25,000 pmol L-1hr-1. DNA extracted from groundwater was analyzed for 16S rRNA and urease gene diversity, and indicated that distinct changes in the microbial community resulted from our substrate additions. Following urea injection, calcite precipitation in the formation occurred. These results are promising with respect to the potential of this approach for remediation of radionuclides and metals in groundwater.

Aragonite pseudomorphs in high-pressure marbles of Syros, Greece

NASA Astrophysics Data System (ADS)

Brady, John B.; Markley, Michelle J.; Schumacher, John C.; Cheney, John T.; Bianciardi, Grace A.

2004-01-01

Numerous rod-shaped calcite crystals occur in the blueschist to eclogite facies marbles of Syros, Greece. The rods show a shape-preferred orientation, and the long axes of the rods are oriented at a large angle to foliation. The crystals also have a crystallographic-preferred orientation: calcite c-axes are oriented parallel to the long axes of the rods. Based on their chemical composition, shape, and occurrence in high-pressure marbles, these calcite crystals are interpreted as topotactic pseudomorphs after aragonite that developed a crystallographic-preferred orientation during peak metamorphism. This interpretation is consistent with deformation of aragonite by dislocation creep, which has been observed in laboratory experiments but has not been previously reported on the basis of field evidence. Subsequent to the high-pressure deformation of the aragonite marbles, the aragonite recrystallized statically into coarse rod-shaped crystals, maintaining the crystallographic orientation developed during deformation. During later exhumation, aragonite reverted to calcite, and the marbles experienced little further deformation, at least in the pseudomorph-rich layers. Some shearing of pseudomorph-bearing marble layers did occur and is indicated by twinning of calcite and by a variable inclination of the pseudomorphs relative to foliation.

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

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.

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.

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.

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

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.

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

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

Speleothems from Mawsmai and Krem Phyllut caves, Meghalaya, India: some evidences on biogenic activities

NASA Astrophysics Data System (ADS)

Baskar, Sushmitha; Baskar, R.; Lee, Natuschka; Theophilus, P. K.

2009-05-01

The Mawsmai cave and Krem Phyllut caves, East Khasi hills, Meghalaya, India has so far not yet attracted the attention of geomicrobiologists. Observations and hypotheses on the possible influence of identified microorganisms for speleothem formations in Meghalaya are reported for the first time. XRD studies identified calcite in speleothems and gypsum in cave wall deposits as the dominant minerals. SEM-EDAX showed interesting microfabric features showing strong resemblance with fossilised bacteria, calcified filaments, needle calcite and numerous nano scale calcite crystals, highly weathered and disintegrated crystals of calcite, that point towards a significant microbial influence in its genesis. Thin section petrography showed laminated stromatolitic features. The microorganisms identified by conventional isolation and further evaluation of isolates by molecular techniques include Bacillus cereus, Bacillus mycoides, Bacillus licheniformis, Micrococcus luteus, and Actinomycetes. Microscopic observations also showed unidentifiable cocci and four unidentifiable strains of CaSO4 (gypsum) precipitating bacteria. Experimental studies confirmed that these bacteria are able to precipitate calcium minerals (calcite, gypsum, minor amounts of dolomite) in the laboratory. These results allow us to postulate that species like these may contribute to active biogenic influence in the cave formations at Meghalaya.

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)

Thermal history of the unsaturated zone at Yucca Mountain, Nevada, USA

USGS Publications Warehouse

Whelan, J.F.; Neymark, L.A.; Moscati, R.J.; Marshall, B.D.; Roedder, E.

2008-01-01

Secondary calcite, silica and minor amounts of fluorite deposited in fractures and cavities record the chemistry, temperatures, and timing of past fluid movement in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a high-level radioactive waste repository. The distribution and geochemistry of these deposits are consistent with low-temperature precipitation from meteoric waters that infiltrated at the surface and percolated down through the unsaturated zone. However, the discovery of fluid inclusions in calcite with homogenization temperatures (Th) up to ???80 ??C was construed by some scientists as strong evidence for hydrothermal deposition. This paper reports the results of investigations to test the hypothesis of hydrothermal deposition and to determine the temperature and timing of secondary mineral deposition. Mineral precipitation temperatures in the unsaturated zone are estimated from calcite- and fluorite-hosted fluid inclusions and calcite ??18O values, and depositional timing is constrained by the 207Pb/235U ages of chalcedony or opal in the deposits. Fluid inclusion Th from 50 samples of calcite and four samples of fluorite range from ???35 to ???90 ??C. Calcite ??18O values range from ???0 to ???22??? (SMOW) but most fall between 12 and 20???. The highest Th and the lowest ??18O values are found in the older calcite. Calcite Th and ??18O values indicate that most calcite precipitated from water with ??18O values between -13 and -7???, similar to modern meteoric waters. Twenty-two 207Pb/235U ages of chalcedony or opal that generally postdate elevated depositional temperatures range from ???9.5 to 1.9 Ma. New and published 207Pb/235U and 230Th/Uages coupled with the Th values and estimates of temperature from calcite ??18O values indicate that maximum unsaturated zone temperatures probably predate ???10 Ma and that the unsaturated zone had cooled to near-present-day temperatures (24-26 ??C at a depth of 250 m) by 2-4 Ma. The evidence of elevated temperatures persisting in ash flow tuffs adjacent to parent calderas for as much as ???8 Ma is a new finding, but consistent with thermal modeling. Simulations using the HEAT code demonstrate that prolonged cooling of the unsaturated zone is consistent with magmatic heat inputs and deep-seated (sub-water table) hydrothermal activity generated by the large magma body ???8 km to the north that produced the 15-11 Ma ash flows and ash falls that make up Yucca Mountain. The evidence discussed in this and preceding papers strongly supports unsaturated zone deposition of the secondary minerals from descending meteoric waters. Although depositional temperatures reflect conductive (and possibly vapor-phase convective) heating of the unsaturated zone related to regional magmatic sources until perhaps 6 Ma, depositional conditions similar to the present-day unsaturated zone have prevailed for at least the past 2-4 Ma.

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 pore throats or reduction in tortuosity. SEM (Scanning Electron Microscope) imaging demonstrates dissolution of relatively large isolated shell fragments but this had little effect on the overall connectivity. No calcite cement was observed at the pore throats in the unreacted specimens. The micro-CT scans indicate a modest tortuosity decrease from 2.00 to 1.85 when calcite is dissolved, but this change in tortuosity results from the opening of new flow paths as the dissolution of discrete grains opened new flow paths and created shortcuts, not from changes to the sinuosity of existing pathways. We suggest that the marked discrepancy in the effect of calcite dissolution on permeability between our experimental data and standard models arises because of the very different way in which the porosity is increased (new pathways rather than inflation). While our results cast doubt on the general applicability of standard models for porosity-permeability relationships for situations in which porosity changes by grain-specific reactions, it is encouraging that pore scale modelling is able to reproduce the experimental relationships.

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, 34263 (2016). McClelland, H. L. O. et al., Nat. Commun. 8, 1-16 (2017)

Core-top calibration of B/Ca in Pacific Ocean Neogloboquadrina incompta and Globigerina bulloides as a surface water carbonate system proxy

NASA Astrophysics Data System (ADS)

Quintana Krupinski, Nadine B.; Russell, Ann D.; Pak, Dorothy K.; Paytan, Adina

2017-05-01

Practical methods for reconstructing past ocean carbonate chemistry are needed to study past periods of ocean acidification and improve understanding of the marine carbonate system's role in the global climate cycles. Planktic foraminiferal B/Ca may fill this role, but requires better understanding and improved proxy calibrations. We used Pacific Ocean core-top sediments to generate new calibrations of the B/Ca proxy for past carbonate system parameters in two upwelling/subpolar species of asymbiotic planktic foraminifera (Globigerina bulloides and Neogloboquadrina incompta). Both species show significant positive correlation of B/Ca with calcite saturation (Ωcalcite) and carbonate ion concentration ([3 2-CO]) across a broad range of environmental conditions. This suggests a calcification rate control on B/Ca incorporation (as Ωcalcite regulates calcification rate), in agreement with recent inorganic calcite studies. This is also consistent with a surface entrapment model of trace element incorporation into CaCO3. In neither species is B/Ca significantly correlated with pH, suggesting that pH does not directly regulate boron incorporation, and that calculation of pH directly from foraminiferal B/Ca is not suitable. Correlations between B/Ca and [B(OH)4-], [B(OH)4-/HCO3-], and [B(OH)4-]/DIC) are weaker than with Ωcalcite. Boron partition coefficients (KD =[ B / Ca ] solid /[ B4 -(OH) /HCO-3 ] seawater) show little or no correlation with [CO32-] or temperature and vary widely, providing no support for application of KD to calculate carbonate system parameters from B/Ca. We also discuss potential effects of depth-related dissolution, temperature, and salinity on B/Ca. These empirical calibrations linking foraminiferal calcite B/Ca with Ωcalcite provide a strong tool for reconstructing the past ocean carbonate system and improve our understanding of the proxy's geochemical basis.

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.

Research-derived insights into surface geochemical hydrocarbon exploration

USGS Publications Warehouse

Price, L.C.

1996-01-01

Research studies based on foreland basins (mainly in eastern Colorado) examined three surface geochemical exploration (SGE) methods as possible hydrocarbon (HC) exploration techniques. The first method, microbial soil surveying, has high potential as an exploration tool, especially hi development and enhanced recovery operations. Integrative adsorption, the second technique, is not effective as a quantitative SGE method because water, carbon dioxide, nitrous oxide, unsaturated hydrocarbons, and organic compounds are collected by the adsorbent (activated charcoal) much more strongly than covalently bonded microseeping Q-Cs thermogenic HCs. Qualitative comparisons (pattern recognition) of C8+ mass spectra cannot gauge HC gas microseepage that involves only the Q-Cs HCs. The third method, soil cakite surveying, also has no potential as an exploration tool. Soil calcite concentrations had patterns with pronounced areal contrasts, but these patterns had no geometric relationship to surface traces of established or potential production, that is, the patterns were random. Microscopic examination of thousands of soils revealed that soil calcite was an uncrystallized caliche coating soil particles. During its precipitation, caliche captures or occludes any gases, elements, or compounds in its immediate vicinity. Thus, increased signal intensity of some SGE methods should depend on increasing soil calcite concentrations. Analyses substantiate this hypothesis. Because soil calcite has no utility as a surface exploration tool, any surface method that depends on soil calcite has a diminished utility as an SGE tool. Isotopic analyses of soil calcites revealed carbonate carbon ??13C values of -4.0 to +2.07co (indicating a strong influence of atmospheric CO2) as opposed to expected values of-45 to -30%c if the carbonate carbon had originated from microbial oxidation of microseeping HC gases. These analyses confirm a surface origin for this soil calcite (caliche), which is not necessarily related to HC gas microseepage. This previously unappreciated pivotal role of caliche is hypothesized to contribute significantly to the poor and inconsistent results of some SGE methods.

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 low biogenic fluxes during the LGM were the most likely cause of the decreased biogenic carbonate concentrations.

Light rare earth element systematics as a tool for investigating the petrogenesis of phoscorite-carbonatite associations, as exemplified by the Phalaborwa Complex, South Africa

NASA Astrophysics Data System (ADS)

Milani, Lorenzo; Bolhar, Robert; Frei, Dirk; Harlov, Daniel E.; Samuel, Vinod O.

2017-12-01

In-situ trace element analyses of fluorapatite, calcite, dolomite, olivine, and phlogopite have been undertaken on representative phoscorite and carbonatite rocks of the Palaeoproterozoic Phalaborwa Complex. Textural and compositional characterization reveals uniformity of fluorapatite and calcite among most of the intrusions, and seems to favor a common genetic origin for the phoscorite-carbonatite association. Representing major repositories for rare earth elements (REE), fluorapatite and calcite exhibit tightly correlated light REE (LREE) abundances, suggesting that partitioning of LREE into these rock forming minerals was principally controlled by simple igneous differentiation. However, light rare earth element distribution in apatite and calcite cannot be adequately explained by equilibrium and fractional crystallization and instead favors a complex crystallization history involving mixing of compositionally distinct magma batches, in agreement with previously reported mineral isotope variability that requires open-system behaviour.

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.

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 River Plain (ESRP) in the vicinity of the Idaho National Engineering and Environmental Laboratory (INEEL) all tested positively for the presence of urea degrading bacteria. Calcite precipitation experiments were conducted with isolated ESRP urea degrading bacteria and B. pasteurii (ATCC 11859), a known urea hydrolyzer. In all of the experiments, visible white precipitates developed within the first thirty minutes after inoculation. The identity of the precipitates as calcite was confirmed by X-ray diffraction. Scanning electron micrographs of the solids revealed both spherical and amorphous precipitates, with microbes in close association with the minerals. The kinetics of calcite precipitation at 10 to 20 C was subsequently investigated using an artificial groundwater (AGW) medium based on the aqueous chemistry of the ESRP aquifer. Experimental data was fit using unconstrained nonlinear regression and optimization to determine rate constants and points of critical supersaturation (Scritical i.e., calcite nucleation). The highest rates of calcite precipitation (ca. 0.8 mmole L-1 day-1) occurred near Scritical. While unique time course trajectories of dissolved Ca2+ concentrations were observed at the different experimental temperatures, the calcite precipitation rates all followed the same asymptotic profile decreasing progressively with saturation state regardless of temperature. This emphasizes the fundamental kinetic dependence of calcite precipitation on saturation state, which connects the otherwise dissimilar temporal patterns of calcite precipitation that evolved under the different temperature and biogeochemical regimes of the experiments.« less

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.

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.

Influence of substrate mineralogy on bacterial mineralization of calcium carbonate: implications for stone conservation.

PubMed

Rodriguez-Navarro, Carlos; Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

2012-06-01

The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed.

Amorphous calcium carbonate controls avian eggshell mineralization: A new paradigm for understanding rapid eggshell calcification.

PubMed

Rodríguez-Navarro, Alejandro B; Marie, Pauline; Nys, Yves; Hincke, Maxwell T; Gautron, Joel

2015-06-01

Avian eggshell mineralization is the fastest biogenic calcification process known in nature. How this is achieved while producing a highly crystalline material composed of large calcite columnar single crystals remains largely unknown. Here we report that eggshell mineral originates from the accumulation of flat disk-shaped amorphous calcium carbonate (ACC) particles on specific organic sites on the eggshell membrane, which are rich in proteins and sulfated proteoglycans. These structures known as mammillary cores promote the nucleation and stabilization of a amorphous calcium carbonate with calcitic short range order which predetermine the calcite composition of the mature eggshell. The amorphous nature of the precursor phase was confirmed by the diffuse scattering of X-rays and electrons. The nascent calcitic short-range order of this transient mineral phase was revealed by infrared spectroscopy and HRTEM. The ACC mineral deposited around the mammillary core sites progressively transforms directly into calcite crystals without the occurrence of any intermediate phase. Ionic speciation data suggest that the uterine fluid is equilibrated with amorphous calcium carbonate, throughout the duration of eggshell mineralization process, supporting that this mineral phase is constantly forming at the shell mineralization front. On the other hand, the transient amorphous calcium carbonate mineral deposits, as well as the calcite crystals into which they are converted, form by the ordered aggregation of nanoparticles that support the rapid mineralization of the eggshell. The results of this study alter our current understanding of avian eggshell calcification and provide new insights into the genesis and formation of calcium carbonate biominerals in vertebrates. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

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.

Synthesis of calcium carbonate in alkali solution based on graphene oxide and reduced graphene oxide

NASA Astrophysics Data System (ADS)

Yaseen, Sarah Abduljabbar; Yiseen, Ghadah Abdaljabar; Li, Zongjin

2018-06-01

This paper reports a new approach of producing CaCO3 particles in alkali solution. CaCO3 particles with pure calcite structure were obtained from the reaction of water-dispersed graphene oxide (GO) or reduced graphene oxide (rGO) with either Ca(OH)2 or CaO. In Fourier Transform Infrared (FTIR) spectra, the pure calcite structure was demonstrated by fundamental bands at 1425 (ν3), 873 (ν2), and 712 cm-1 (ν4). The Raman spectra showed the characteristic peak of calcite structure at 1085 cm-1 (ν1). X-ray diffraction pattern (XRD) and X-ray photoelectron spectroscopy (XPS) analyses further confirmed that only the pure calcite phase of CaCO3 was formed in both synthesis approaches. Scanning electron microscopy (SEM), Energy dispersive X-ray analyzer (EDX), and High-resolution transmission electron microscopy (HRTEM) also confirmed that distorted cubic and rhombic calcite particles were obtained with GO, while the pine flower-like and flower-like particles were obtained with rGO, and the average crystallite sizes varied from 26 to 44 nm. The mechanism of the reaction was investigated and it was found that the decomposition of oxygen functional groups on the surface of GO or rGO in certain alkaline media to release CO, CO2, and water was a key process as the released CO2 further reacted with OH- and Ca2+ to form CaCO3. This demonstrated that both GO and rGO could be used as main reactants for the synthesis of calcite.

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.

Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

PubMed Central

Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

2012-01-01

The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed. PMID:22447589

Less-expensive Rochon prisms

NASA Technical Reports Server (NTRS)

Ammann, E. O.; Massey, G. A.

1970-01-01

Inexpensive Rochon prisms can be produced by substituting easily polished glass for one-half of the calcite. Reciprocal polarizing properties of a conventional Rochon prism are retained, and angular separation between ordinary and extraordinary rays is the same as in all-calcite prism.

Microstructures and composition of brittle faults in claystones: Constraints on the barrier behavior

NASA Astrophysics Data System (ADS)

Kneuker, Tilo; Hammer, Jörg; Jahn, Steffen; Zulauf, Gernold

2017-04-01

Investigations of fault rocks are crucial to evaluate the barrier properties of clay rich formations used for the storage of hydrocarbons, carbon dioxide gas or for the storage of heat generating radioactive waste. Claystones are considered as a geological barrier. However, their barrier capability can be reduced if the claystones are cut by brittle faults. Our study is focusing on the microfabrics and element mobility of artificially and naturally fractured claystones using a multi-method approach. Particular attention was paid to small scale lithological heterogeneities occurring in the clayey sequence. The microfabrics were investigated using SEM and optical microscopy. Geochemical and phase analyses were carried out using XRD, XRF and ICP-MS. In addition, organic (TOC) and inorganic carbon (TIC), total sulphur (TS) as well as the cation exchange capacity (CEC) were determined. Macroscopic observations of fault zones on outcrops and drill cores indicate closely spaced planar and undulating discontinuities, including slickenside striations. The investigated fault zones are often accompanied by calcite veins and calcite enriched zones. The fault core is formed by a mm to cm thick clayey, fine grained, cohesionless fault gouge including reworked calcite fragments. Duplex-like domains are separated by discrete microshears, along which the rocks disintegrate. Calcareous fossils, common in undeformed claystones, appear in these zones fragmented and rotated. In contrast to calcite, quartz is more resistant to solution-precipitation processes. Rarely intracrystalline fracturing was observed. The calcite mineralization in veins, and solution-precipitation processes of calcite, documented by stylolites, reflect enhanced palaeo-permeability and activity of Ca2+- and CO2-rich fluids inside some of the fault zones, mainly along fault parallel shear planes. Elevated Sr and Ba concentrations are bound to the tectonic, secondary calcite veins within and outside the investigated fault zone. The geochemical data presented in form of isocon diagrams suggest volume gain related to the opening of veins and pores, which are now filled with calcite. Our results do not provide evidence for presently open pores or fractures, which might be related to non-artificial tectonic deformation. However, (micro)fractures as well as mineralized veins represent inherited damage in the rock, and are prone to brittle reactivation during fluid pressure increase or during the excavation of underground galleries. A complex, polyphase deformation history including a possible reactivation of older structures is supported by our observations.

Salt-enhanced chemical weathering of building materials and bacterial mineralization of calcium carbonate as a treatment

NASA Astrophysics Data System (ADS)

Schiro, M.; Ruiz-Agudo, E.; Jroundi, F.; Gonzalez-Muñoz, M. T.; Rodriguez-Navarro, C.

2012-04-01

Salt weathering is an important mechanism contributing to the degradation and loss of stone building materials. In addition to the physical weathering resulting from crystallization pressure, the presence of salts in solution greatly enhances the chemical weathering potential of pore waters. Flow through experiments quantify the dissolution rates of calcite and quartz grains (63-125 micrometer diameter) when subjected to 1.0 ionic strength solutions of MgSO4, MgCl, Na2SO4 or NaCl. Results indicate that the identity of the cation is the primary control over the dissolution rate of both calcite and quartz substrates, with salt-enhanced dissolution occurring most rapidly in Mg2+ bearing solutions. It has been observed that weathering rates of rocks in nature, as well as building stones, are slowed down by naturally occurring or artificially produced patinas. These tend to be bacterially produced, durable mineralized coatings that lend some degree of protection to the underlying stone surface [1]. Our research shows that bacterially produced carbonate coatings can be quite effective at reducing chemical weathering of stone by soluble salts. The calcite-producing-bacteria used in this study were isolated from stone monuments in Granada, Spain [2] and cultivated in an organic-rich culture medium on a variety of artificial and natural substrates (including limestone, marble, sandstone, quartz, calcite single crystals, glass cover-slips, and sintered porous glass). Scanning electron microscopy (FESEM) was used to image bacterial calcite growth and biofilm formation. In-situ atomic force microscopy (AFM) enabled calculation of dissolution rates of untreated and bacterially treated surfaces. 2D-XRD showed the mineralogy and crystallographic orientation of bacterial calcium carbonate. Results indicate that bacterially produced calcite crystals form a coherent, mechanically resistant surface layer in perfect crystallographic continuity with the calcite substrate (self-epitaxy). These calcite biominerals are more resistant to chemical weathering by salt-enhanced dissolution, apparently due to the incorporation of organics (bacterial exopolymeric substances, EPS). Conversely, on silicate substrates, non-oriented vaterite forms, leading to limited protection. These preliminary results indicate that bacterial treatments have a significant potential to protect the stone built cultural heritage. [1] De Muynck et al. (2010) Ecol. Eng. 36, 118-136. [2] Jimenez-Lopez et al. (2007) Chemosphere 68, 1929-1936.

[Study on Archaeological Lime Powders from Taosi and Yinxu Sites by FTIR].

PubMed

Wei, Guo-feng; Zhang, Chen; Chen, Guo-liang; He, Yu-ling; Gao, Jiang-tao; Zhang, Bing-jian

2015-03-01

Archaeological lime powders samples from Taosi and Yinxu sites, natural limestone and experimentally prepared lime mortar were investigated by means of Fourier transform infrared spectrometry (FTIR) to identify the raw material of lime powders from Taosi and Yinxu sites. Results show that ν2/ν4 ratio of calcite resulted from carbonation reaction of man-made lime is around 6.31, which is higher than that of calcite in natural limestone and reflects the difference in the disorder of calcite crystal structure among the natural limestone and prepared lime mortar. With additional grinding, the values of v2 and ν4 in natural limestone and prepared lime mortar decrease. Meanwhile, the trend lines of ν2 versus ν4 for calcite in experimentally prepared lime mortar have a steeper slope when compared to calcite in natural limestone. These imply that ν2/ν4 ratio and the slope of the trend lines of ν2 versus ν4 can be used to determine the archaeological man-made lime. Based on the experiment results, it is possible that the archaeological lime powder from Taosi and Yinxu sites was prepared using man-made lime and the ancient Chinese have mastered the calcining technology of man-made lime in the late Neolithic period about 4 300 years ago.

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

Vertically oriented structure and its fracture behavior of the Indonesia white-pearl oyster.

PubMed

Chen, Guowei; Luo, Hongyun; Luo, Shunfei; Lin, Zhenying; Ma, Yue

2017-02-01

Structural calcites, aragonites, and the bonding organic network decide the growth, structure and mechanical properties of the mollusk bivalvia shell. Here, it was found out that the calcite prisms together with the coated organics construct another kind of 'brick and mortar' structure similar to the aragonite tablets. The calcite layer can be divided into three sublayers and direct evidences show that the calcite prisms are produced by two methods: nucleation and growing in the first sublayer; or fusing from the aragonites, which is quite different from some previous reports. The crystallographic orientation, micro hardness and crack propagations were tested and observed by XRD, micro harness tester, SEM and TEM. Submicron twin crystals were observed in the immature aragonite tablets. The fracture processes and the micro deformation of the aragonite tablets are detected by acoustic emission (AE) in the tensile tests, which gave the interpretation of the dynamical fracture processes: plastic deformation and fracture of the organics, and friction of the minerals at the first two stages; wear and fracture of the minerals at the third stage. Calcites and aragonites are combined and working together, like two layers of vertical 'brick and mortar's, ensuring the stable mechanical properties of the whole shell. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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.

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

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

Killian, Christopher; Metzler, Rebecca; Gong, Y. U. T.

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

Contrasting diagenetic histories of concretions vs. host rocks, Lion Mountain Member, Riley formation (upper Cambrian), Texas

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

McBride, E.F.

1988-02-01

White, elliptical, calcite-cemented concretion nuclei up to 1 m long contrast markedly in color, composition, and diagenetic history from more glauconite-rich concretion rinds and from dark-green glaucarenite host rocks. Concretion nuclei are loosely packed deposits of trilobite carapaces and minor quartz and glauconite that have intergranular volumes of 58%. The nuclei are shell-lag deposits that were cemented by calcite at the sea floor or after burial of a few meters. Concretion rinds, composed of subequal amounts of quartz and compactionally deformed glauconite, have an intergranular volume of only 32% and minor quartz overgrowths that preceded pore-occluding calcite cement. The rindsmore » underwent burial for several million years to tens of millions of years to depths of several hundred meters before they were cemented. The host rock is predominately glauconite with very minor quartz and calcite cement. Strontium isotopic ratios of host-rock calcite cement are variable (0.7084 to 0.7093), but the lowest value suggests precipitation during the Middle Ordovician. In the absence of significant amounts of carbonate cement, the host rock underwent complete dissolution of trilobite carapaces and maximum compaction with total loss of porosity through squashing of glauconite grains. Maximum burial during this stage was completed by the end of Ordovician time.« less

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

Circular economy in drinking water treatment: reuse of ground pellets as seeding material in the pellet softening process.

PubMed

Schetters, M J A; van der Hoek, J P; Kramer, O J I; Kors, L J; Palmen, L J; Hofs, B; Koppers, H

2015-01-01

Calcium carbonate pellets are produced as a by-product in the pellet softening process. In the Netherlands, these pellets are applied as a raw material in several industrial and agricultural processes. The sand grain inside the pellet hinders the application in some high-potential market segments such as paper and glass. Substitution of the sand grain with a calcite grain (100% calcium carbonate) is in principle possible, and could significantly improve the pellet quality. In this study, the grinding and sieving of pellets, and the subsequent reuse as seeding material in pellet softening were tested with two pilot reactors in parallel. In one reactor, garnet sand was used as seeding material, in the other ground calcite. Garnet sand and ground calcite performed equally well. An economic comparison and a life-cycle assessment were made as well. The results show that the reuse of ground calcite as seeding material in pellet softening is technologically possible, reduces the operational costs by €38,000 (1%) and reduces the environmental impact by 5%. Therefore, at the drinking water facility, Weesperkarspel of Waternet, the transition from garnet sand to ground calcite will be made at full scale, based on this pilot plant research.

Ultrasonic Monitoring of CO2 Uptake and Release from Sand Packs*

NASA Astrophysics Data System (ADS)

Toffelmier, D. A.; Dufrane, W. L.; Bonner, B. P.; Viani, B. E.; Berge, P. A.

2002-12-01

Sequestration of atmospheric CO2 occurs naturally during the formation of calcite cement in sedimentary rock. Acceleration of this process has been proposed as a means of reducing the atmospheric concentration of CO2, which is a major cause of global warming. Calcite may also be precipitated when highly alkaline waste fluid is introduced into the vadose zone from leaking storage tanks. Seismic methods have potential for monitoring these processes. We devised an experiment, guided by geochemical modeling, to determine how the formation of calcite cement in unsaturated sand affects wave propagation. We used the ultrasonic pulse transmission method to measure compressional (P) and shear (S) wave velocities at ultrasonic frequencies (100-500 kHz) through packs of Ottawa sand containing chemically active pore fluids. The samples were saturated with water containing 0.1mol/L of Ca(OH)2 and 0.1mol/L of NaCl and then drained by flowing water saturated, CO2 free N2 gas, to a residual saturation of ~5%, so that the remaining pore fluid resides mainly in pendular spaces between the sand grains. Ambient air saturated with water and containing atmospheric concentration of CO2 was then passed through the sample to effect the precipitation of calcite. Finally, pure water saturated CO2, was flushed through the sample to dissolve most of the precipitated calcite. Over a three day period, measurable changes in Vp and Vs were observed following water saturation, desaturation, calcite precipitation, and calcite dissolution treatments. Changes in the contents of the pore space require waveforms to be recorded before and after each stage of the experiment so both the short and long range effects can be seen. Wave velocities were slow, as is typical for unconsolidated materials, for the dry sand, with values of 365m/s for Vp and 163m/s for Vs. Compressional velocities increased upon desaturation (443m/s), and again following calcite precipitation (460m/s). The compressional velocity measured following the CO2 flush to dissolve the calcite decreased (451m/s). The shear velocities varied similarly to the compressional velocities except that the dry sand shear velocity was faster than the other shear velocities. These preliminary results suggest that ultrasonics could provide a tool to locate the path of certain types of waste fluid in the vadose zone. *This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under contract number W-7405-ENG-48 and was supported specifically by the Environmental Management Science Program of the Office of Environmental Management and the Office of Energy Research.

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

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

Helium diffusion in carbonates

NASA Astrophysics Data System (ADS)

Amidon, W. H.; Cherniak, D. J.; Watson, E. B.; Hobbs, D.

2013-12-01

The abundance and large grain size of carbonate minerals make them a potentially attractive target for 4He thermochronology and 3He cosmogenic dating, although the diffusive properties of helium in carbonates remain poorly understood. This work characterizes helium diffusion in calcite and dolomite to better understand the crystal-chemical factors controlling He transport and retentivity. Slabs of cleaved natural calcite and dolomite, and polished sections of calcite cut parallel or normal to c, were implanted with 3He at 3 MeV with a dose of 5x1015/cm2. Implanted carbonates were heated in 1-atm furnaces, and 3He distributions following diffusion anneals were profiled with Nuclear Reaction Analysis using the reaction 3He(d,p)4He. For 3He transport normal to cleavage surfaces in calcite, we obtain the following Arrhenius relation over the temperature range 78-300°C: Dcalcite = 9.0x10-9exp(-55 × 6 kJ mol-1/RT) m2sec-1. Diffusion in calcite exhibits marked anisotropy, with diffusion parallel to c about two orders of magnitude slower than diffusion normal to cleavage faces. He diffusivities for transport normal to the c-axis are similar in value to those normal to cleavage surfaces. Our findings are broadly consistent with helium diffusivities from step-heating measurements of calcite by Copeland et al. (2007); these bulk degassing data may reflect varying effects of diffusional anisotropy. Helium diffusion normal to cleavage surfaces in dolomite is significantly slower than diffusion in calcite, and has a much higher activation energy for diffusion. For dolomite, we obtain the following Arrhenius relation for He diffusion over the temperature range 150-400°C: Ddolomite = 9.0x10-8exp(-92 × 9 kJ mol-1/RT) m2sec-1. The role of crystallographic structure in influencing these differences among diffusivities was evaluated using the maximum aperture approach of Cherniak and Watson (2011), in which crystallographic structures are sectioned along possible diffusion 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

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 wormholes is the strongest when coating thickness is a few times larger than the initial aperture of the fracture. This leads to formation of favorable complex networks of wormholes which provide adequate transport of reactive fluids to fracture surfaces and - at the same time - are capable of supporting fracture surfaces. As a conclusion, acidization of the reactivated fractures with hydrochloric acid seems to be an attractive treatment to apply at fracking stage or later on as EGR. The results contribute to the discussion on the use of acidization to enhance the gas production in the shale reservoirs. This communication stresses the importance of the dissolution of calcite cement in natural fractures in shale formations, which are initially sealed and become reactivated during fracking. While this research is based on the analysis of fractures in the Pomeranian shale basin its results are general enough to be applicable to different formations worldwide.

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.

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

Jensenius, J.; Munksgaard, N.C.

Fracture filling calcite from the piercement fields of East Rosa, Skjold, Rolf, North Arne, Nils and Vagn and the dome field Dan have been studied by fluorescence and cathodoluminescence microscopy, fluid inclusion microthermometry and carbon and oxygen isotopes. The carbon and oxygen isotope compositions of the reservoir matrix chalk have also been measured. The temperature estimates obtained from fluid inclusion data suggest that the fracture filling calcite of the piercement fields precipitated during hot water flushing of the reservoirs. The flushing system only existed around the salt diapirs and was probably related to expulsion of overpressured fluid from the surroundingmore » sediments. The thermal anomaly and the faults associated with the diapirs probably were important factors in focusing the ascending water. Lower {delta}{sup 18}O values with shallower depth of burial suggest that the porosity of chalk in the shallower fields was more severely reduced by calcite cementation during the flushing event than in the deeper fields. In the case of North Arne, Nils, Vagn and Dan, {delta}{sup 13}C values of the fracture filling calcites are similar to those of normal chalk (0.5 to 3.5 {per thousand}). However, calcites from Rolf, Skjold and East Rosa are depleted by {minus}1.8, {minus}6.2 and {minus}16.7 {per thousand}, respectively. Only in East Rosa is the matrix chalk itself depleted in {sup 13}C. The low {delta}{sup 13}C values are interpreted as the result of biodegradation. Sulfate originating from the underlying diapirs was flushed into the reservoir and used by bacteria to degrade present hydrocarbons. This process produced {sup 13}c depleted bicarbonate which was incorporated into the fracture-filling calcites.« less

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

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.

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.

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.

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.

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.

In Situ Carbon Isotope Analysis by Laser Ablation MC-ICP-MS.

PubMed

Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Zhao, Kui-Dong; Duan, Deng-Fei

2017-12-19

Carbon isotopes have been widely used in tracing a wide variety of geological and environmental processes. The carbon isotope composition of bulk rocks and minerals was conventionally analyzed by isotope ratio mass spectrometry (IRMS), and, more recently, secondary ionization mass spectrometry (SIMS) has been widely used to determine carbon isotope composition of carbon-bearing solid materials with good spatial resolution. Here, we present a new method that couples a RESOlution S155 193 nm laser ablation system with a Nu Plasma II MC-ICP-MS, with the aim of measuring carbon isotopes in situ in carbonate minerals (i.e., calcite and aragonite). Under routine operating conditions for δ 13 C analysis, instrumental bias generally drifts by 0.8‰-2.0‰ in a typical analytical session of 2-3 h. Using a magmatic calcite as the standard, the carbon isotopic composition was determined for a suite of calcite samples with δ 13 C values in the range of -6.94‰ to 1.48‰. The obtained δ 13 C data are comparable to IRMS values. The combined standard uncertainty for magmatic calcite is <0.3‰ (1s). No significant matrix effects have been identified in calcite with the amplitude of chemical composition variation (i.e., MnO, SrO, MgO, or FeO) up to 2.5 wt %. Two modern corals were investigated using magmatic calcite as the calibration standard, and the average δ 13 C values for both corals are similar to the bulk IRMS values. Moreover, coral exhibits significant heterogeneity in carbon isotope compositions, with differences up to 4.85‰ within an individual coral. This study indicates that LA-MC-ICP-MS can serve as an appropriate method to analyze carbon isotopes of carbonate minerals in situ.

Diagenesis of the Machar Field (British North Sea) chalk: Evidence for decoupling of diagenesis in fractures and the host rock

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

Maliva, R.G.; Dickson, J.A.D.; Smalley, P.C.

1995-01-02

The Chalk Group (Cretaceous/Tertiary) in the Machar Field (British North Sea) contains both fracture-filling and microcrystalline calcite cements. Modeling of fluid-rock interaction using data on light stable isotopes obtained by whole rock analyses and laser ablation analyses of calcite cements reveal that the fracture and matrix diagenetic systems were largely decoupled. The calcium and carbonate of the fracture-filling calcite cements were derived largely from the adjacent chalk matrix. The fracture diagenetic system had a high water-rock ratio, which maintained a relatively stable water {delta}{sup 18}O ratio during calcite dissolution and precipitation. The chalk matrix, on the contrary, had a lowmore » molar water-rock ratio during recrystallization, which resulted in increases in the pore-water {delta}{sup 18}O value during recrystallization at elevated temperatures. This evolution of the pore-water {delta}{sup 18}O value is manifested by highly variable cement {delta}{sup 18}O values. The present-day formation waters of the Machar Field have {sup 87}Sr/{sup 86}Sr ratios significantly higher than the whole rock and fracture-filling cement calcite values, evidence that the chemical composition of the formation waters is not representative of that of the pore waters during chalk recrystallization. Little diagenesis is therefore now occurring in the Machar Field. The diagenetic systems of the chalk matrix and fractures both had a high degree of openness with respect to carbon, because of the introduction of organically derived bicarbonate rather than advection of water through the chalk. The bulk of calcite cementation in fractures and the recrystallization and cementation of the chalk matrix occurred at temperatures in the 80--100 C range, at or just below the present-day reservoir temperature of 97 C.« less

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.

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 ± 0.12 log mol m-2 s-1), while dissolution slowed in both NaCl solutions (0.1 mol kg-1; -8.23 ± 0.10 log mol m-2 s-1 and (5.7 mol kg-1; -8.44 ± 0.11 log mol m-2 s-1), as well as near-saturated MgSO4 brine (2.7 mol kg-1; -8.35 ± 0.05 log mol m-2 s-1). The slowest calcite dissolution rates observed in the near-saturated NaCl brine. Magnesite dissolution rates were ∼5 times faster in the dilute salt solutions relative to UPW, but similar to UPW (-8.47 ± 0.06 log mol m-2 s-1) in near-saturated Na2SO4 brines (-8.41 ± 0.18 log mol m-2 s-1). Magnesite dissolution slowed significantly in near-saturated CaCl2 brine (-9.78 ± 0.10 log mol m-2 s-1), likely due to the significantly lower water activity in these experiments. Overall, magnesite dissolution rates are slower than calcite dissolution rates and follow the trend: All dilute salt solutions >2.5 mol kg-1 Na2SO4 ≈ UPW > 5.7 mol kg-1 NaCl >> 9 mol kg-1 CaCl2. Calcite rates follow the trend 3 mol kg-1 MgCl2 > 2.5 mol kg-1 Na2SO4 ≈ UPW ≈ all dilute salt solutions >2.7 mol kg-1 MgSO4 ≈ 5.7 mol kg-1 NaCl. Magnesite dissolution rates in salt solutions generally decrease with decreasing aH2O in both chloride and sulfate brines, which indicates water molecules act as ligands and participate in the rate-limiting magnesite dissolution step. However, there is no general trend associated with water activity observed in the calcite dissolution rates. Calcite dissolution accelerates in near-saturated MgCl2, but slows in near-saturated NaCl brine despite both brines having similar water activities (aH2O = 0.73 and 0.75, respectively). High Mg calcite was observed as a reaction product in the near-saturated MgCl2, indicating Mg2+ from solution likely substituted for Ca2+ in the initial calcite, releasing additional Ca2+ into solution and increasing the observed calcite dissolution rate. Calcite dissolution rates also increase slightly as Na2SO4 concentration increases, while calcite dissolution rates slow slightly with increasing concentration of MgSO4 and NaCl. However, all of the carbonate rates vary by less than 0.5 log units and are within or near the standard deviation observed for each set of replicate experiments. Carbonate mineral lifetimes in high salinity brines indicate magnesite may be preferentially preserved compared to calcite on Mars. Therefore, Mg-carbonates that have experienced post-depositional aqueous alteration are more likely to preserve paleoenvironmental indicators and potential biosignatures. Rapid weathering of carbonates in circum-neutral pH sulfate brines may provide a potential source of cations for abundant sulfate minerals observed on Mars, Ceres, and other planetary bodies.

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…

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...

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.

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

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

Calcium carbonates: induced biomineralization with controlled macromorphology

NASA Astrophysics Data System (ADS)

Meier, Aileen; Kastner, Anne; Harries, Dennis; Wierzbicka-Wieczorek, Maria; Majzlan, Juraj; Büchel, Georg; Kothe, Erika

2017-11-01

Biomineralization of (magnesium) calcite and vaterite by bacterial isolates has been known for quite some time. However, the extracellular precipitation has hardly ever been linked to different morphologies of the minerals that are observed. Here, isolates from limestone-associated groundwater, rock and soil were shown to form calcite, magnesium calcite or vaterite. More than 92 % of isolates were indeed able to form carbonates, while abiotic controls failed to form minerals. The crystal morphologies varied, including rhombohedra, prisms and pyramid-like macromorphologies. Different conditions like varying temperature, pH or media components, but also cocultivation to test for collaborative effects of sympatric bacteria, were used to differentiate between mechanisms of calcium carbonate formation. Single crystallites were cemented with bacterial cells; these may have served as nucleation sites by providing a basic pH at short distance from the cells. A calculation of potential calcite formation of up to 2 g L-1 of solution made it possible to link the microbial activity to geological processes.

Castiglione (Oletta, Corsica): relationships between phenomena of calcification and tectonic fossiliferous fracture dating

NASA Astrophysics Data System (ADS)

Pereira, Elisabeth; Rouzaud, François; Salotti, Michelle; Dubois, Jean-Noël; Ferrandini, Jean; Ottaviani-Spella, Marie-Madeleine; Quinif, Yves

Six cavities have been discovered in the Oletta massif. The massif, today constitued of Schistes lustrés with several metres of calcareous layers above them, has undergone intense fracturing. The networks of cavities are organised along north-south and subequatorial directions, and form a narrow bayonnet-network. All the elements in the galleries appear to be karstic: stalagmites, stalactites and calcitic deposits along the walls; but no trace of dissolution or excavation was found. Thus, the origin of the galleries is only tectonic, while the calcitic deposits result from the dissolution of the old, thick calcareous layers above, which are no longer present. The thickness and the volume of the calcitic deposits, which is variable depending on the galleries, indicates the chronology of the different tectonic periods which have fractured the massif. Five tectonic and successsive events have been detected. Calcitic datings confirm the timing of successional fracturing, indicating also the variable age of the fossiliferous Middle Pleistocene deposits found in these cavities.

Molecular dynamics study of oil adsorption on the rock surface in presence of silica nanoparticles

NASA Astrophysics Data System (ADS)

Salehzadeh, Jamal; Tohidi, Zahra; Jafari, Arezou

2018-01-01

Despite the increasing applications of nanoparticles in enhanced oil recovery (EOR), there is not enough information about the mechanisms and microscopic aspects of nanoparticles' effects. Therefore, in this research, molecular dynamics simulation is used to provide the molecular-scale insight for investigation of the silica nanoparticles effects on the oil adsorption on calcite surface for the first time. The surface interacts with the mixture of heptane and decane as the oil phase with mole ratio of 1/2 and silica nanoparticles are dispersed in distilled water with concentration of 7000 ppm. Based on the simulation results, by using nanoparticles surface adsorption behavior have been changed to hydrophilic and the oil molecules departed from the calcite. This result is based on the oil-calcite binding energy calculation which is decreased from 5224 kcal/mol to 3278 kcal/mol by using silica nanoparticles. In addition, calculation of radial distribution functions showed that after adding silica nanoparticles, the picks fall which means increasing in average distance between oil and calcite surface.

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 level fluctuations facilitated the recrystallization of the GOA reef corals to calcite.

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 fluids. We explore the mechanism(s) by which clumped isotope reordering rates may be modestly increased under wet, high-pressure conditions, including changes in defect concentrations in the near surface environment due to reactions at the water-mineral interface, and lattice deformation resulting from pressurization of samples.

Do biofilms and clays alter the chemistry and fabric of a hyper-alklaine, saline, non-marine carbonate precipitate?

NASA Astrophysics Data System (ADS)

Rogerson, Michael; Saunders, Paul; Mercedes-Martin, Ramon; Brasier, Alex; Pedley, Martyn

2015-04-01

Non-marine carbonates comprise a hugely diverse family of deposits, which reflect a constellation of forcing factors from local hydraulics to regional climatology. However, the two dominant controls on precipitation are solution chemistry and benthic microbial biogeochemistry. Here, we present a unifying concept for understanding how these controls influence deposit characteristics, and re-emphasise the importance of biofilms. It is generally accepted that biofilms play an important part in the precipitation of authigenic minerals in a wide variety of settings. In carbonate settings, biofilms are recognised to increase the amount of calcite precipitation and alter the geometry and coarse scale petrography of the precipitate. They determine at what water marginal water chemistries calcite starts to precipitate and microbialites give way to chemical limestones. Biofilms also interact with ambient water, controlling chemical accumulation transport. New evidence, drawn from unique experimental approaches, is demonstrating that biofilm influence extends to control of calcite trace element composition, and crystal scale fabric. Under tightly controlled temperature and chemical conditions, fully replicated experiments show that Mg incorporation into tufa carbonate defies the expected thermodynamic control. However, there is a pronounced influence on (Mg/Ca)calcite from precipitation rate, so that rapidly forming precipitates develop with very low magnesium content indicating kinetic control on fractionation. Calcite precipitation rate in these experiments is controlled by biofilm growth rate and reflects kinetic fractionation arises from the electrochemical activity of extracellular organic acids. These effects are therefore likely to occur wherever these molecules occur, including stromatolites, soil and lake carbonates and (via colloidal organic acids) speleothems. The presence of Extracellular polymeric substances (EPS), even without the presence of cells, also alters precipitation style. Spherular and shrubby calcite growths are well known from the geological record, but their environmental significance is not clear. Sterile, microcosm experiments have shown that these forms occur in saline, hyperalkaline settings ' but only in the presence of organic acid molecules in solution. The presence of inorganic materials (hydrated magnesium clays) does not impact on precipitate morphology, and reduces the precipitation rate of calcite.

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 cements: a characterization usig electron backscattered diffraction (EBSD). International Journal of Speleology, 44, 91-98 Ritter, A.-C., et al., 2015. Application of redox sensitive proxies and carbonate clumped isotopes to Mesozoic and Palaeozoic radiaxial fibrous calcite cements. Chemical Geology, 417, 306-321

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 the transition from the calcite to the CaCO3-II stability field, if aragonite does not form.

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 begin is almost instantaneous if an inoculum of S. pasteurii is included, while it may take several weeks for ureolytic groundwater communities to grow and become ureolytically active.

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.

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.

Temperature reconstruction from dripwater hydrochemistry, speleothem fabric and speleothem δ13C: towards an integrated approach in temperate climate caves

NASA Astrophysics Data System (ADS)

Borsato, Andrea; Frisia, Silvia; Johnston, Vanessa; Spötl, Christoph

2017-04-01

Accurate reconstruction of past climate records from speleothem minerals requires a thorough understanding of both environmental and hydrologic conditions underpinning their formation. These conditions likely influenced how speleothems incorporate chemical signals that are used as climate proxies. Thus, a thorough investigation of environmental and hydrologic parameters is a pre-requisite to gain robust palaeoclimate reconstructions from stalagmites. Here, we present a systematic study of soil, dripwater and speleothems in temperate climate caves at different altitudes, which allowed the assessment of how mean annual air temperature in the infiltration area (MATinf) influences vegetation cover, soil pCO2 and, eventually, pCO2 of karst water and cave air. Our study demonstrates that for caves developed in pure carbonate rocks, the soil and aquifer pCO2 are directly related to the MATinf (Borsato et al., 2015). It is well known that soil and aquifer pCO2 control carbonate dissolution and the carbonate-carbonic acid system. By establishing a relationship between dripwater pCO2 and MATinf, we show that dripwater Ca content and calcite saturation state SIcc) are correlated with MATinf when unaffected by Prior Calcite Precipitation. In particular, dripwater saturation (SIcc = 0) is reached at a MATinf of 4.4°C in our study area. This MATinf delineates a ''speleothem limit", above which speleothems composed of sparitic calcite should not form (Borsato et al., 2016). In fact, sparitic calcite speleothems do not form, today, in caves with a MATinf < 4.4°C. This relationship offers the opportunity to estimate past MATinf from fossil sparitic calcite speleothems found in high-altitude caves by comparing the required SIcc for their formation to the present-day dripwater SIcc. Furthermore, soil and aquifer pCO2 control dripwater DIC δ13C as well as calcite δ13C in speleothems that were not significantly influenced by kinetic fractionation. A linear correlation between calcite δ13C and MATinf was obtained for modern sparitic speleothems that formed at isotopic equilibrium (Johnston et al., 2013). The combination of these two approaches (present-day dripwater SIcc and calcite δ13C in sparitic speleothems) can be used to reconstruct the past MATinf for high-altitude caves. References: Borsato et al., (2015). Earth Surf. Proc. Land. 40, 1158-1170. Borsato et al., (2016). Geochim. Cosmochim. Ac. 177, 275-297. Johnston et al., (2013). Clim. Past 9, 99-118.

Origin of minerals in joint and cleat systems of the Pottsville Formation, Black Warrior basin, Alabama: Implications for coalbed methane generation and production

USGS Publications Warehouse

Pitman, Janet K.; Pashin, J.C.; Hatch, J.R.; Goldhaber, M.B.

2003-01-01

Coalbed methane is produced from naturally fractured strata in the lower Pennsylvanian Pottsville Formation in the eastern part of the Black Warrior basin, Alabama. Major fracture systems include orthogonal fractures, which consist of systematic joints in siliciclastic strata and face cleats in coal that strike northeast throughout the basin. Calcite and minor amounts of pyrite commonly fill joints in sandstone and shale and, less commonly, cleats in coal. Joint-fill calcite postdates most pyrite and is a weakly ferroan, coarse-crystalline variety that formed during a period of uplift and erosion late in the burial history. Pyrite forms fine to coarse euhedral crystals that line jointwalls or are complexly intergrown with calcite. Stable-isotope data reveal large variations in the carbon isotope composition of joint- and cleat-fill calcite (-10.3 to +24.3 per mil Peedee belemnite [PDB]) but only a relatively narrow range in the oxygen-isotope composition of this calcite (-16.2 to -4.1 per mil PDB). Negative carbon values can be attributed to (super 13) C-depleted CO (sub 2) derived from the oxidation of organic matter, and moderately to highly positive carbon values can be attributed to bacterial methanogenesis. Assuming crystallization temperatures of 20-50 degrees C, most joint- and cleat-fill calcite precipitated from fluids with delta (super 18) O ratios ranging from about -11 to +2 per mil standard mean ocean water (SMOW). Uplift and unroofing since the Mesozoic led to meteoric recharge of Pottsville strata and development of freshwater plumes that were fed by meteoric recharge along the structurally upturned, southeastern margin of the basin. Influxes of fresh water into the basin via faults and coalbeds facilitated late-stage bacterial methanogenesis, which accounts for the high gas content in coal and the carbonate cementation of joints and cleats. Diagenetic and epigenetic minerals can affect the transmissivity and storage capacity of joints and cleats, and they appear to contribute significantly to interwell heterogeneity in the Pottsville Formation. In highly productive coalbed methane fields, joint- and cleat-fill calcite have strongly positive delta (super 13) C values, whereas calcite fill has lower delta (super 13) C values in fields that are shut in or abandoned. Petrographic analysis and stable-isotope geochemistry of joint- and cleat-fill cements provide insight into coalbed methane reservoir quality and the nature and extent of reservoir compartmentalization, which are important factors governing methane production.

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 applied to diamond-bearing marbles of the Kokchetav Massif, where Mg-calcite inclusions in garnet and zircon with X(Ca) of 0.76 most likely formed during prograde metamorphism close to the graphite-diamond transition.

Influence of CO2 on the long-term chemomechanical behavior of an oolitic limestone

NASA Astrophysics Data System (ADS)

Grgic, D.

2011-07-01

In order to study the long-term mechanical and petrographical evolutions of a carbonate rock (oolitic limestone) during storage of CO2, CO2 injection tests were performed in triaxial cells at temperature and mechanical stresses (isotropic and deviatoric) corresponding to the depth of the Dogger carbonate reservoirs of the Paris basin (˜800 m). We used a specific "flow-through" triaxial cell which allowed us to measure very low strain rates in both axial and lateral directions, while ensuring the sealing of the samples during the injection of CO2. Under isotropic loading, neither the dynamic percolation (i.e., flow-through tests) of dry supercritical/gaseous CO2, nor the diffusion of CO2, into initially saturated samples was shown to produce significant axial compaction and calcite dissolution. Indeed, even though the interstitial aqueous fluid becomes acidic, the progressive increase in dissolved species induces the H2O-CO2-calcite re-equilibrium. The dynamic injection of CO2-saturated solution induced significant axial compaction due to the dissolution of calcite at the sample/piston interface only under open flow conditions (i.e., the injected acidic solution is continuously renewed). Under closed flow conditions (i.e., acidic solution recirculation or no-flow conditions) which reproduce the physicochemical conditions of CO2 storage at the field scale better, the rapid H2O-CO2-calcite re-equilibrium inhibits calcite dissolution. Under deviatoric loading and closed conditions, the diffusion of CO2 induced a very small increase in the PSC (pressure solution creep) process which was stopped by the H2O-CO2-calcite re-equilibrium inside the sample. Therefore, a significant compaction of limestone samples was obtained only under open conditions and is mainly due to a purely chemical mechanism (calcite dissolution), while the contribution of the chemo-mechanical mechanism (PSC) was found to not be of any great importance. In the context of massive injection of CO2 at the field scale, if the reservoir can be considered as a closed system from a hydrodynamic point of view (i.e., the brine circulates in the aquifer but is not renewed by any groundwater), CO2 will not play a significant role in the chemistry of carbonate reservoirs due to the H2O-CO2-calcite re-equilibrium and will not induce reservoir compaction and affect its long-term storage capacity, whatever the stress state (isotropic or deviatoric).

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.

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).

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 at ca. 270-300°C, 8-10 km of the original glass. PT show plastic deformations overprinted by shear bands and fracturing. The matrix of cataclastic layers has the same mineral assemblage as PT and clasts of recrystallised PT, to indicate polyphase PSZ formation. In the metasedimentary footwall, the original foliation is deflected parallel to the PSZ and is cut by cm-spaced shear bands parallel to PSZ. Deformation propagates in the footwall through mm-thick injections veins, shear bans, P-shears and veins. Pockets of recrystallized PT occur along the pre-existing mylonitic foliation of metasediments. Worthnote is the presence of mm-thick deformation bands (CDB) that are post-mylonitic foliation and mainly composed of fine grained calcite bounded by dissolution seams or ribbon grains of deformed calcite. CDB are characterised by subrounded embayed and rebsorbed quartz grains rimmed by new Ca-Mg amphibole, K-feldspar (90-93%K), in a dinamic recrystallized calcite 2-10 micron in size and slightly elongated. The features of the CDB suggest that these structures can be considered as diagnostic of localised deformation during coesismic slip in metasedimentary rocks.

Fluid mediated transformation of aragonitic cuttlebone to calcite

NASA Astrophysics Data System (ADS)

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

2009-04-01

The aragonite to calcite transition has been studied extensively over the years because of its wide spectra of applications and of its significant geochemical interest. While studies of kinetics (e.g. Topor et al., 1981), thermodynamics (e.g. Wolf et al., 1996) and behavior of ions such as Sr and Mg (e.g. Yoshioka et al., 1986) have been made there are still unanswered questions regarding this reaction especially in the cases where the effects of fluid composition are considered. It is well known that when heated in air, aragonite transforms by a solid state reaction to calcite. The aragonite cuttlebone of the sepia officinalis that was used for our experiments undergoes a phase transition at ~370-390˚ C, measured by in situ heating experiments in a Philips X'pert X-ray powder diffractometer equipped with a HTK 1200 High temperature oven. Successive X-ray scans were taken at isothermal temperatures at 200C intervals. A similar temperature range was found by Vongsavat et al. 2006, who studied this transition in Acropora corals. It is possible however to promote this transition at considerably lower temperatures by means of a fluid mediated reaction where the replacement takes place by a dissolution-precipitation mechanism (Putnis & Putnis, 2007). We have successfully carried out hydrothermal experiments where cuttlebone has been converted to calcite at 200˚ C. Using the PhreeqC program we calculated the required composition of a solution that would be undersaturated with respect to aragonite and saturated with respect to calcite leading to dissolution of the aragonite and to a consequent precipitation of the new calcite phase, similar to the experiments described in an earlier study (Perdikouri et al, 2008). This reaction is not pseudomorphic and results in the destruction of the morphology, presumably due to the molar volume increase. A total transformation of the cuttlebone produced a fine calcite powder. The cuttlebone exhibits a unique microstructure, made up of interconnected chambers. The aragonite grown during biomineralization of the cuttlebone is interlaced with a β-chitin organic phase that provides the framework for the morphology that is observed. Experiments carried out with the same constant conditions but for different periods of time have revealed the evolution of the transformation to calcite. At shorter reaction times the product was made up of calcite powder and of well preserved aragonite septa, as was confirmed by powder X-ray diffraction. In other words, the vertical pillars appear to react at faster rates than the horizontal septa. It has been reported by Florek et al. 2008 that the septa contain higher quantities of β-chitin. The aim of this study is the investigation of these observations and the determination of the effect of the organic component on the kinetics of the aragonite to calcite transformation. Florek M., Fornal E., Gómez-Romero P., Zieba E., Paszkowicz W., Lekki J.,Nowak J., Kuczumow A. Materials Science and Engineering C, In Press (2008) Perdikouri C., Kasioptas A., Putnis C.V., Putnis A. Mineralogical Magazine 72, 111-114 (2008) Putnis A., Putnis C.V. Solid State Chemistry 180, 1783-1786 (2007) Topor N. D., Tolokonnikova L. I., Kadenatsi B. M. Journal of Thermal Analysis 20, 169-174 (1981) Vongsavat V., Winotai P., Meejoo S. Nuclear Instruments and Methods in Physics Research B 243, 167-173 (2006) Wolf G., Lerchner J., Schmidt H., Gamsjäger H., Königsberger E., Schmidt P. Journal of Thermal Analysis 46, 353-359 (1996) Yoshioka S., Ohde S., Kitano Y., Kanamori N. Marine Chemistry 18, 35-48 (1986)

The localization of occluded matrix proteins in calcareous spicules of sea urchin larvae.

PubMed

Seto, Jong; Zhang, Yang; Hamilton, Patricia; Wilt, Fred

2004-10-01

The sea urchin embryo forms calcareous endoskeletal spicules composed of calcite and an occluded protein matrix. Though the latter is approximately 0.1% of of the mass, the composite has substantially altered material properties, e.g., conchoidal fracture planes and increased hardness. Experiments were conducted to examine the localization of matrix proteins occluded in the mineral by use of immunocytochemistry coupled with scanning electron microscopy (SEM). The isolated, unfixed spicules were etched under relatively gentle conditions and exposed to affinity purified antibodies made against two different matrix proteins, as well as an antibody to the entire constellation of matrix proteins. Immunogold tagged secondary antibody was used to observe antibody localization in the back scatter mode of SEM. All proteins examined were very widely distributed throughout the calcite, supporting a model of the structure in which a multiprotein assemblage is woven with fine texture around microcrystalline domains of calcite. Gentle etching revealed a laminar arrangement of calcite solubility, consistent with a stepwise deposition of matrix and mineral to increase girth of the spicule.

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.

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.

Data set for the proteomic inventory and quantitative analysis of chicken eggshell matrix proteins during the primary events of eggshell mineralization and the active growth phase of calcification.

PubMed

Marie, Pauline; Labas, Valérie; Brionne, Aurélien; Harichaux, Grégoire; Hennequet-Antier, Christelle; Rodriguez-Navarro, Alejandro B; Nys, Yves; Gautron, Joël

2015-09-01

Chicken eggshell is a biomineral composed of 95% calcite calcium carbonate mineral and of 3.5% organic matrix proteins. The assembly of mineral and its structural organization is controlled by its organic matrix. In a recent study [1], we have used quantitative proteomic, bioinformatic and functional analyses to explore the distribution of 216 eggshell matrix proteins at four key stages of shell mineralization defined as: (1) widespread deposition of amorphous calcium carbonate (ACC), (2) ACC transformation into crystalline calcite aggregates, (3) formation of larger calcite crystal units and (4) rapid growth of calcite as columnar structure with preferential crystal orientation. The current article detailed the quantitative analysis performed at the four stages of shell mineralization to determine the proteins which are the most abundant. Additionally, we reported the enriched GO terms and described the presence of 35 antimicrobial proteins equally distributed at all stages to keep the egg free of bacteria and of 81 proteins, the function of which could not be ascribed.

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.

Biomineral nanoparticles are space-filling

NASA Astrophysics Data System (ADS)

Yang, Li; Killian, Christopher E.; Kunz, Martin; Tamura, Nobumichi; Gilbert, P. U. P. A.

2011-02-01

Sea urchin biominerals have been shown to form from aggregating nanoparticles of amorphous calcium carbonate (ACC), which then crystallize into macroscopic single crystals of calcite. Here we measure the surface areas of these biominerals and find them to be comparable to those of space-filling macroscopic geologic calcite crystals. These biominerals differ from synthetic mesocrystals, which are invariably porous. We propose that space-filling ACC is the structural precursor for echinoderm biominerals.Sea urchin biominerals have been shown to form from aggregating nanoparticles of amorphous calcium carbonate (ACC), which then crystallize into macroscopic single crystals of calcite. Here we measure the surface areas of these biominerals and find them to be comparable to those of space-filling macroscopic geologic calcite crystals. These biominerals differ from synthetic mesocrystals, which are invariably porous. We propose that space-filling ACC is the structural precursor for echinoderm biominerals. This article was submitted as part of a Themed Issue on Crystallization and Formation Mechanisms of Nanostructures. Other papers on this topic can be found in issue 11 of vol. 2 (2010). This issue can be found from the Nanoscale homepage [http://www.rsc.org/nanoscale

High-temperature molecular dynamics simulation of aragonite.

PubMed

Miyake, Akira; Kawano, Jun

2010-06-09

For molecular dynamics simulations using aragonite structure as the initial state, a new phase of space group P6₃22 (hexagonal aragonite) appeared at temperatures above 510 K at a pressure of 1 atm. It was a first-order phase transition which occurs metastably within the stable region of calcite and the dT/dP slope of the phase boundary between orthorhombic and hexagonal aragonite was about 1.25 × 10³ K GPa⁻¹. In the hexagonal aragonite structure, CO₃ groups were rotated by 30° around the c axis and move up and down along the c axis from their position in aragonite, and Ca ions were six-coordinated as they are in calcite. The CaO₆ octahedron of hexagonal aragonite was strongly distorted, whereas in the calcite structure it is an almost ideal octahedron. The transition between hexagonal and orthorhombic aragonite involves only small movements of CO₃ groups. Therefore, it is possible that hexagonal aragonite plays an important part in the metastable formation of aragonite within the stability field of calcite and in the development of sector trilling in aragonite.

Data set for the proteomic inventory and quantitative analysis of chicken eggshell matrix proteins during the primary events of eggshell mineralization and the active growth phase of calcification

PubMed Central

Marie, Pauline; Labas, Valérie; Brionne, Aurélien; Harichaux, Grégoire; Hennequet-Antier, Christelle; Rodriguez-Navarro, Alejandro B.; Nys, Yves; Gautron, Joël

2015-01-01

Chicken eggshell is a biomineral composed of 95% calcite calcium carbonate mineral and of 3.5% organic matrix proteins. The assembly of mineral and its structural organization is controlled by its organic matrix. In a recent study [1], we have used quantitative proteomic, bioinformatic and functional analyses to explore the distribution of 216 eggshell matrix proteins at four key stages of shell mineralization defined as: (1) widespread deposition of amorphous calcium carbonate (ACC), (2) ACC transformation into crystalline calcite aggregates, (3) formation of larger calcite crystal units and (4) rapid growth of calcite as columnar structure with preferential crystal orientation. The current article detailed the quantitative analysis performed at the four stages of shell mineralization to determine the proteins which are the most abundant. Additionally, we reported the enriched GO terms and described the presence of 35 antimicrobial proteins equally distributed at all stages to keep the egg free of bacteria and of 81 proteins, the function of which could not be ascribed. PMID:26306314

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.

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.

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%.

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

Preferential soft-tissue preservation in the Hot Creek carbonate spring deposit, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Rainey, Dustin K.; Jones, Brian

2010-05-01

The relict Holocene Hot Creek carbonate spring deposit in southeast British Columbia is characterized by excellent preservation of soft-tissue organisms (e.g. cyanobacteria), but poor preservation of organisms with hard-tissue (e.g. wood, diatoms). The deposit is formed mainly of calcified cyanobacteria, with fewer mineralized macrophytes (plants), bryophytes (mosses), wood, and diatoms. Cyanobacteria grew as solitary filaments ( Lyngbya) and as radiating hemispherical colonies ( Rivularia). Both were preserved by encrustation and encapsulation while alive, and as casts after filament death and decay. Sheath impregnation was rare to absent. Filament encrustation, whereby calcite crystals nucleated on, and grew away from the sheath exterior, produced moulds that replicated external filament morphology, but hastened filament decay. Filament encapsulation, whereby calcite nucleated in the vicinity of, and grew towards the encapsulated filament, promoted sheath preservation even after trichome decay. Subsequent calcite precipitation inside the hollow sheath generated sheath casts. The inability of mineralizing spring water to penetrate durable cell walls meant that bryophytes, macrophytes, and most wood was preserved by encrustation. Some wood resisted complete decay for several thousand years, and its lignified cell walls allowed rare permineralizations. Diatoms were not preserved in the relict deposit because the frustules were dissolved by the basic spring water. Amorphous calcium carbonate produced by photosynthetic CO 2 removal may have acted as nucleation sites for physicochemically precipitated calcite. Thus, metabolic activities of floral organisms probably initiated biotic mineralization, but continuous inorganic calcite precipitation on and in flora ensured that soft tissues were preserved.

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

New data on carbonatites of the Il'mensky-Vishnevogorsky alkaline complex, the southern Urals, Russia

NASA Astrophysics Data System (ADS)

Nedosekova, I. L.

2007-04-01

Carbonatites that are hosted in metamorphosed ultramafic massifs in the roof of miaskite intrusions of the Il’mensky-Vishnevogorsky alkaline complex are considered. Carbonatites have been revealed in the Buldym, Khaldikha, Spirikha, and Kagan massifs. The geological setting, structure of carbonatite bodies, distribution of accessory rare-metal mineralization, typomorphism of rock-forming minerals, geochemistry, and Sr and Nd isotopic compositions are discussed. Dolomite-calcite carbonatites hosted in ultramafic rocks contain tetraferriphlogopite, richterite, accessory zircon, apatite, magnetite, ilmenite, pyrrhotite, pyrite, and pyrochlore. According to geothermometric data and the composition of rock-forming minerals, the dolomite-calcite carbonatites were formed under K-feldspar-calcite, albite-calcite, and amphibole-dolomite-calcite facies conditions at 575-300°C. The Buldym pyrochlore deposit is related to carbonatites of these facies. In addition, dolomite carbonatites with accessory Nb and REE mineralization (monazite, aeschynite, allanite, REE-pyrochlore, and columbite) are hosted in ultramafic massifs. The dolomite carbonatites were formed under chlorite-sericite-ankerite facies conditions at 300-200°C. The Spirikha REE deposit is related to dolomite carbonatite and alkaline metasomatic rocks. It has been established that carbonatites hosted in ultramafic rocks are characterized by high Sr, Ba, and LREE contents and variable Nb, Zr, Ti, V, and Th contents similar to the geochemical attributes of calcio-and magnesiocarbonatites. The low initial 87Sr/86Sr = 0.7044-0.7045 and ɛNd ranging from 0.65 to -3.3 testify to their derivation from a deep mantle source of EM1 type.

High resolution cathodoluminescence spectroscopy of carbonate cementation in Khurmala Formation (Paleocene-L. Eocene) from Iraqi Kurdistan Region, Northern Iraq

NASA Astrophysics Data System (ADS)

Omer, Muhamed F.; Omer, Dilshad; Zebari, Bahroz Gh.

2014-12-01

A combination of high resolution cathodoluminsecnce-spectroscopy (HRS-CL) with spatial electron microprobe analysis and optical microscopy is used to determine paragenesis and history of cementation in the limestones and dolostones of Khurmala Formation which is exposed in many parts of Northern Iraq. Khurmala Formation was subjected to different diagenetic processes such as micritization, compaction, dissolution, neomorphism, pyritization and cementation that occurred during marine to shallow burial stages and culminated during intermediate to deep burial later stages. Five dolomite textures are recognized and classified according to crystal size distribution and crystal-boundary shape. Dolomitization is closely associated with the development of secondary porosity that pre-and postdates dissolution and corrosion; meanwhile such porosity was not noticed in the associated limestones. Microprobe analysis revealed three types of cement, calcite, dolomite and ankerite which range in their luminescence from dull to bright. Cathodoluminescence study indicated four main texture generations. These are (1) unzoned microdolomite of planar and subhedral shape, with syntaxial rim cement of echinoderm that show dull to red luminescence, (2) equant calcite cements filling interparticle pores which shows dull luminescence and weak zonal growth, (3.1) homogenous intrinsic blue stoichiometric calcite with dull luminescence and without activators, (3.2) coarse blocky calcite cement with strong oscillatory zoning and bright orange luminescence which postdates other calcite cements, (4) ankerite cement with red to orange, non-luminescence growth zonation which is the last formed cement.

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.

Limits on the UV Photodecomposition of Carbonates on Mars

NASA Technical Reports Server (NTRS)

Quinn, Richard; Zent, Aaron P.; McKay, Christopher P.; DeVincenzi, Donald L. (Technical Monitor)

2002-01-01

The effect of UV (ultraviolet) light on the stability of calcium carbonate in a simulated martian atmosphere was experimentally investigated. Sample cells containing C-13 labeled calcite were irradiated with a Xe arc lamp in 10 mbar of simulated martian atmosphere and a quadrupole mass spectrometer was used to monitor the headspace gases for the production of (13)CO2. We found no experimental evidence of the UV photodecomposition of calcium carbonate in a simulated martian atmosphere. Extrapolating the lower limit of detection of our experimental system to an upper limit of carbonate decomposition on Mars yields a quantum efficiency of 3.5 x 10(exp -8) molecules/photon over the wavelength interval of 190-390 nm and a maximum UV photodecomposition rate of 1.2 x 10(exp -13) kg m(exp -2) s(exp -1) from a calcite surface. The maximum loss of bulk calcite due to this process would be 2.5 nm yr(exp -1). However, calcite is expected to be thermodynamically stable on the surface of Mars and potential UV photodecomposition reaction mechanisms indicate that while calcium carbonate may decompose under vacuum, it would be stable in a CO2 atmosphere. Given the expected stability of carbonate on Mars and our inability to detect carbonate decomposition, we conclude that it is unlikely that the apparent absence of carbonate on the martian surface is due to UV photo decomposition of calcite in the current environment.

Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate.

PubMed

Radha, A V; Forbes, Tori Z; Killian, Christopher E; Gilbert, P U P A; Navrotsky, Alexandra

2010-09-21

Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC ⇒ anhydrous ACC ∼ biogenic anhydrous ACC ⇒ vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO(2) sequestration.

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.

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.

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.

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

Jones, B.; Renault, R.W.

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

Cyanobacterial diversity and related sedimentary facies as a function of water flow conditions: Example from the Monasterio de Piedra Natural Park (Spain)

NASA Astrophysics Data System (ADS)

Berrendero, Esther; Arenas, Concha; Mateo, Pilar; Jones, Brian

2016-05-01

The River Piedra in the Monasterio de Piedra Natural Park (NE Spain) is a modern tufa-depositing river that encompasses various depositional environments that are inhabited by different cyanobacterial populations. Molecular (16S rDNA) and morphological analyses of the cyanobacteria from different facies showed that Phormidium incrustatum dominates in the fast-flowing water areas where the mean depositional rate is 1.6 cm/year. Stromatolites in these areas are formed of palisades of hollow calcite tubes (inner diameter of 6.0-7.5 μm, walls 2-12 μm thick) that formed through calcite encrustation around the filaments followed by decay of the trichomes. In contrast, in slow-flowing water areas with lower depositional rates (mean depositional rate of 0.3 cm/year), Phormidium aerugineo-caeruleum is the dominant species. In these areas, randomly oriented calcite tubes (inner diameter of 5-6 μm, walls 3-8 μm thick) formed by calcite encrustation, are found in thin and uneven laminae and as scattered tubes in the loose lime mud and sand-sized carbonate sediment. Although this species did not build laminated deposits, it gave cohesiveness to the loose sediment. In the stepped and low waterfalls, with intermediate deposition rates (mean depositional rate of 0.9 cm/year), both species of Phormidium are found in association with spongy moss and algal boundstones, which is consistent with the variable flow conditions in this setting. The calcite encrustations on the cyanobacteria from different environments exhibit irregular patterns that may be linked to changes in the calcite saturation index. The physicochemical conditions associated with extracellular polymeric substances may be more significant to CaCO3 precipitation in microbial mats in slow-flowing water conditions than in fast-flowing water conditions. These results show that flow conditions may influence the distribution of different cyanobacteria that, in turn, leads to the development of different sedimentary facies and structures in fluvial carbonate systems.

Preservation of primary lake signatures in alkaline earth carbonates of the Eocene Green River Wilkins Peak-Laney Member transition zone

NASA Astrophysics Data System (ADS)

Murphy, John T.; Lowenstein, Tim K.; Pietras, Jeffrey T.

2014-12-01

Significant changes in carbonate mineralogy, texture, and stable isotope composition occur at the transition from the Wilkins Peak Member to the Laney Member in the Eocene Green River Formation, Bridger Basin, Wyoming, which reflect evolution of inflow waters, lake waters, and paleoenvironments. The top of the Wilkins Peak Member contains heterogeneous laminae of calcite and dolomite. Evaporites associated with these layers suggest deposition in hypersaline lakes. Diagenetic carbonate mineral textures include euhedral cement overgrowths and interlocking mosaics of calcite and dolomite crystals, 20-70 μm in size. Electron microprobe analyses indicate diagenetic overgrowth of Fe-rich dolomite on cloudy Fe-poor cores. δ18O values of carbonate laminae in the upper Wilkins Peak Member vary by ~ 6‰ with no depth dependent or mineralogic trends, which also suggests diagenetic overprinting. Alternating organic-rich and primary aragonite, calcite, and dolomite laminae were identified from the lower Laney Member. Primary lacustrine aragonite consists of well sorted, prismatic crystals 5-10 μm in length, with micro-lamination defined by crystal size variation. Primary precipitated calcite and dolomite laminae are monominerallic, with well sorted polyhedral crystals, ~ 10 μm in size. Primary mineralogy of the lower Laney Member changes from calcite to aragonite and dolomite stratigraphically upward. Along the same 15 m thick stratigraphic interval, δ18O values decrease upward by ~ 3‰, all of which suggests (1) lake waters underwent evaporative concentration, which together with calcite precipitation increased the lake water Mg/Ca ratios and led to formation of aragonite and dolomite, (2) source waters became lower in δ18O, possibly as inflow changed to higher altitude foreland rivers. The results from this study show that understanding the primary lacustrine versus diagenetic origin of Green River carbonate minerals is essential for paleoenvironmental and paleoclimate interpretations.

Diagenetic evidence for an epigenetic origin of the Courtbrown Zn-Pb deposit, Ireland

NASA Astrophysics Data System (ADS)

Reed, Christopher P.; Wallace, Malcolm W.

2001-08-01

Mineralisation at the Courtbrown deposit in south-western Ireland is concentrated in the basal section of the Chadian Waulsortian Limestone, immediately above the Courceyan Ballysteen Limestone. Two episodes of sulphide deposition have been identified: an early stage of minor pyrite precipitation, and a later base-metal-rich mineralisation event. Sphalerite, galena and pyrite of the later mineralisation event occur predominantly as replacement phases along stylolites, dissolution seams, and within the micritic matrix of the host limestone. These sulphide minerals also occur as cements within late stage fractures. The following diagenetic phases are present in the Waulsortian and Ballysteen Limestones in the Courtbrown area (from oldest to youngest): non-luminescent synsedimentary calcite cements, non-luminescent equant calcite cements, bright luminescent calcite cement, dull luminescent calcite cement, planar dolomite cement and replacement dolomite (regional dolomite), saddle dolomite cement, and fibrous dull luminescent calcite cement filling pressure-shadows around the sulphide minerals. Homogenisation temperatures for primary fluid inclusions within dull luminescent calcite cements (precipitated penecontemporaneously with base-metal mineralisation) range from 160 to 200 °C, with a mode at 170-180 °C. These values are unlikely to be representative of mineralisation temperatures as the fluid inclusions may have been significantly affected by heating and/or deformation during late burial (maximum paleotemperatures from Ro and CAI data around 310 °C). The observed paragenetic sequence indicates that mineralisation is completely epigenetic. As the earliest mineralisation is hosted by macro-stylolites, the sequence must have obtained a minimum burial depth of around 800 m prior to the onset of mineralisation. A burial depth of 800 m would correspond to an approximate early Chadian age for the Courtbrown area. Pressure-shadows around sphalerite further indicate that mineralisation preceded the major phase of Variscan deformation. Therefore, the base-metal mineralisation at Courtbrown is epigenetic, and the age of mineralisation is in the range of 350 to 307 Ma.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Effect of basin physical characteristics on solute fluxes in nine alpine/subalpine basins, Colorado, USA

USGS Publications Warehouse

Sueker, J.K.; Clow, D.W.; Ryan, J.N.; Jarrett, R.D.

2001-01-01

Alpine/subalpine basins may exhibit substantial variability in solute fluxes despite many apparent similarities in basin characteristics. An evaluation of controls on spatial patterns in solute fluxes may allow development of predictive tools for assessing basin sensitivity to outside perturbations such as climate change or deposition of atmospheric pollutants. Relationships between basin physical characteristics, determined from geographical information system (GIS) tools, and solute fluxes and mineral weathering rates were explored for nine alpine/subalpine basins in Rocky Mountain National Park, Colorado, using correlation analyses for 1993 and 1994 data. Stream-water nitrate fluxes were correlated positively with basin characteristics associated with the talus environment; i.e., the fractional amounts of steep slopes (??? 30??), unvegetated terrain and young debris (primarily Holocene till) in the basins, and were correlated negatively with fractional amounts of subalpine meadow terrain. Correlations with nitrate indicate the importance of the talus environment in promoting nitrate flux and the mitigating effect of areas with established vegetation, such as subalpine meadows. Total mineral weathering rates for the basins ranged from about 300 to 600 mol ha-1 year -1. Oligoclase weathering accounted for 30 to 73% of the total mineral weathering flux, and was positively correlated with the amount of old debris (primarily Pleistocene glacial till) in the basins. Although calcite is found in trace amounts in bedrock, calcite weathering accounted for up to 44% of the total mineral weathering flux. Calcite was strongly correlated with steep slope, unvegetated terrain, and young debris-probably because physical weathering in steep-gradient areas exposes fresh mineral surfaces that contain calcite for chemical weathering. Oligoclase and calcite weathering are the dominant sources of alkalinity in the basins. However, atmospherically deposited acids consume much of the alkalinity generated by weathering of calcite and other minerals in the talus environment. Published in 2001 by John Wiley and Sons, Ltd.

Effect of basin physical characteristics on solute fluxes in nine alpine/subalpine basins, Colorado, USA

NASA Astrophysics Data System (ADS)

Sueker, Julie K.; Clow, David W.; Ryan, Joseph N.; Jarrett, Robert D.

2001-10-01

Alpine/subalpine basins may exhibit substantial variability in solute fluxes despite many apparent similarities in basin characteristics. An evaluation of controls on spatial patterns in solute fluxes may allow development of predictive tools for assessing basin sensitivity to outside perturbations such as climate change or deposition of atmospheric pollutants. Relationships between basin physical characteristics, determined from geographical information system (GIS) tools, and solute fluxes and mineral weathering rates were explored for nine alpine/subalpine basins in Rocky Mountain National Park, Colorado, using correlation analyses for 1993 and 1994 data. Stream-water nitrate fluxes were correlated positively with basin characteristics associated with the talus environment; i.e., the fractional amounts of steep slopes ( 30°), unvegetated terrain and young debris (primarily Holocene till) in the basins, and were correlated negatively with fractional amounts of subalpine meadow terrain. Correlations with nitrate indicate the importance of the talus environment in promoting nitrate flux and the mitigating effect of areas with established vegetation, such as subalpine meadows. Total mineral weathering rates for the basins ranged from about 300 to 600 mol ha-1 year-1. Oligoclase weathering accounted for 30 to 73% of the total mineral weathering flux, and was positively correlated with the amount of old debris (primarily Pleistocene glacial till) in the basins. Although calcite is found in trace amounts in bedrock, calcite weathering accounted for up to 44% of the total mineral weathering flux. Calcite was strongly correlated with steep slope, unvegetated terrain, and young debris - probably because physical weathering in steep-gradient areas exposes fresh mineral surfaces that contain calcite for chemical weathering. Oligoclase and calcite weathering are the dominant sources of alkalinity in the basins. However, atmospherically deposited acids consume much of the alkalinity generated by weathering of calcite and other minerals in the talus environment. Published in 2001 by John Wiley & Sons, Ltd.

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.

Mineralogy and autoradiography of selected mineral-spring precipitates in the Western United States

USGS Publications Warehouse

Bove, Dana; Felmlee, J.K.

1982-01-01

X-ray diffaction analysis of 236 precipitate or sediment samples from 97 mineral-spring sites in nine Western States showed the presence of 25 minerals, some precipitated and some detrital. Calcite and (or) aragonite are the most common of all the precipitated minerals. Gypsum and (or) anhydrite, as well as barite and native sulfur, are less common but are also believed to be precipitated minerals. Precipitated manganese and iron oxides, including romanechite, manganite, pyrolusite, goethite, and hematite, were found in some of the samples. Various salts of sodium, including halite and thenardite, were also identified. Dolomite and an unknown type of siliceous material are present in some of the samples and were possibly precipitated at the spring sites. Quartz, feldspar, and mica are present in many of the samples and are believed to be detrital contaminants. An autoradiographic and thin section study of 11 samples from nine of the most radioactive spring sites showed the radioactivity, which is due primarily to radium, to be directly associated with mineral phases containing barium, manganese, iron, and (or) calcium as major constituents. Furthermore, the radioactivity has an exclusive affinity for the manganese-bearing minerals, which in these samples contain a substantial amount of barium, even if calcite or iron oxides are present. Where calcite predominates and manganese- and barium-bearing minerals are absent, the radioactivity shows a close association with the iron oxides present, especially hematite, but also shows a moderate association with the calcite and (or) aragonite cementing phases. In other samples composed predominantly of calcite but lacking iron oxides, the radioactivity is preferentially associated with an early stage of calcite development and is considerably lower in the later cementing stages. The radioactivity observed in all these samples is believed to be caused by radium substituting for barium in mineral lattices, filling irregularities in other crystal structures, or adsorbing on the surfaces of precipitated molecules.

Major factors controlling fracture development in the Middle Permian Lucaogou Formation tight oil reservoir, Junggar Basin, NW China

NASA Astrophysics Data System (ADS)

Zhang, Chen; Zhu, Deyu; Luo, Qun; Liu, Luofu; Liu, Dongdong; Yan, Lin; Zhang, Yunzhao

2017-09-01

Natural fractures in seven wells from the Middle Permian Lucaogou Formation in the Junggar Basin were evaluated in light of regional structural evolution, tight reservoir geochemistry (including TOC and mineral composition), carbon and oxygen isotopes of calcite-filled fractures, and acoustic emission (AE). Factors controlling the development of natural fractures were analyzed using qualitative and/or semi-quantitative techniques, with results showing that tectonic factors are the primary control on fracture development in the Middle Permian Lucaogou Formation of the Junggar Basin. Analyses of calcite, dolomite, and TOC show positive correlations with the number of fractures, while deltaic lithofacies appear to be the most favorable for fracture development. Mineral content was found to be a major control on tectonic fracture development, while TOC content and sedimentary facies mainly control bedding fractures. Carbon and oxygen isotopes vary greatly in calcite-filled fractures (δ13C ranges from 0.87‰ to 7.98‰, while δ18O ranges from -12.63‰ to -5.65‰), indicating that fracture development increases with intensified tectonic activity or enhanced diagenetic alteration. By analyzing the cross-cutting relationships of fractures in core, as well as four Kaiser Effect points in the acoustic emission curve, we observed four stages of tectonic fracture development. First-stage fractures are extensional, and were generated in the late Triassic, with calcite fracture fills formed between 36.51 °C and 56.89 °C. Second-stage fractures are shear fractures caused by extrusion stress from the southwest to the northeast, generated by the rapid uplift of the Tianshan in the Middle and Late Jurassic; calcite fracture fills formed between 62.91 °C and 69.88 °C. Third-stage fractures are NNW-trending shear fractures that resulted from north-south extrusion and thrusting in a foreland depression along the front of the Early Cretaceous Bogda Mountains. Calcite fracture fills formed between 81.74 °C and 85.43 °C. Fourth-stage fractures inherited the tectonic framework of the third stage, resulting in fractures with the same orientation, but without calcite filling. By differentiating the various stages of fracture development, we were able to better understand the origin of fractures in tight oil reservoirs and their significance for exploration and development.

Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Stronthium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

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

Smith, Robert W.; Fujita, Yoshiko

2007-11-07

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) energy research and weapons complex. In situ containment and stabilization of these contaminants represents a cost-effective treatment strategy that minimizes workers’ exposure to hazardous substances, does not require removal or transport of contaminants, and generally does not generate a secondary waste stream. We have investigated an in situ bioremediation approach that immobilizes radionuclides or contaminant metals (e.g., strontium-90) by their microbially facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Calcite, a common mineral in many aquifers and vadosemore » zones in the arid west, can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of a solid solution. Collaborative research undertaken by the Idaho National Laboratory (INL), University of Idaho, and University of Toronto as part of this Environmental Management Science Program project has focused on in situ microbially-catalyzed urea hydrolysis, which results in an increase in pH, carbonate alkalinity, ammonium, calcite precipitation, and co-precipitation of divalent cations. In calcite-saturated aquifers, microbially facilitated co-precipitation with calcium carbonate represents a potential long-term contaminant sequestration mechanism. Key results of the project include: **Demonstrating the linkage between urea hydrolysis and calcite precipitation in field and laboratory experiments **Observing strontium incorporation into calcite precipitate by urea hydrolyzers with higher distribution coefficient than in abiotic **Developing and applying molecular methods for characterizing microbial urease activity in groundwater including a quantitative PCR method for enumerating ureolytic bacteria **Applying the suite of developed molecular methods to assess the feasibility of the proposed bioremediation technique at a contaminated site located within the 100-N area of the Hanford, Washington site **Assessing the role of nitrification on the persistence of precipitated calcite by modifying primers for identification of the amoA gene region of various ammonia oxidizing bacteria (AOB) for characterizing AOB in the field« less

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 basins and displaces brines with important ore metals out of the basin. More work on the calcites will help to establish the geographic extent of the various fluid pulses in the region, which will lead to an improved understanding of the sources and paths of these fluids.

Downflow limestone beds for treatment of net-acidic, oxic, iron-laden drainage from a flooded anthracite mine, Pennsylvania, USA: 2. Laboratory evaluation

USGS Publications Warehouse

Cravotta, C.A.; Ward, S.J.; Hammarstrom, J.M.

2008-01-01

Acidic mine drainage (AMD) containing elevated concentrations of dissolved iron and other metals can be neutralized to varying degrees by reactions with limestone in passive treatment systems. We evaluated the chemical and mineralogical characteristics and the effectiveness of calcitic and dolomitic limestone for the neutralization of net-acidic, oxic, iron-laden AMD from a flooded anthracite mine. The calcitic limestone, with CaCO3 and MgCO3 contents of 99.8 and <0.1 wt%, respectively, and the dolomitic limestone, with CaCO3 and MgCO3 contents of 60.3 and 40.2 wt%, were used to construct a downflow treatment system in 2003 at the Bell Mine, a large source of AMD and baseflow to the Schuylkill River in the Southern Anthracite Coalfield, in east-central Pennsylvania. In the winter of 2002-2003, laboratory neutralization-rate experiments evaluated the evolution of effluent quality during 2 weeks of continuous contact between AMD from the Bell Mine and the crushed calcitic or dolomitic limestone in closed, collapsible containers (cubitainers). The cubitainer tests showed that: (1) net-alkaline effluent could be achieved with detention times greater than 3 h, (2) effluent alkalinities and associated dissolution rates were equivalent for uncoated and Fe(OH)3-coated calcitic limestone, and (3) effluent alkalinities and associated dissolution rates for dolomitic limestone were about half those for calcitic limestone. The dissolution rate data for the cubitainer tests were used with data on the volume of effuent and surface area of limestone in the treatment system at the Bell Mine to evaluate the water-quality data for the first 1.5 years of operation of the treatment system. These rate models supported the interpretation of field results and indicated that treatment benefits were derived mainly from the dissolution of calcitic limestone, despite a greater quantity of dolomitic limestone within the treatment system. The dissolution-rate models were extrapolated on a decadal scale to indicate the expected decreases in the mass of limestone and associated alkalinities resulting from the long-term reaction of AMD with the treatment substrate. The models indicated the calcitic limestone would need to be replenished approaching the 5-year anniversary of treatment operations to maintain net-alkaline effluent quality. ?? 2008 Springer-Verlag.

Sequence stratigraphic controls on synsedimentary cementation and preservation of dinosaur tracks: Example from the lower Cretaceous, (Upper Albian) Dakota Formation, Southeastern Nebraska, U.S.A.

USGS Publications Warehouse

Phillips, P.L.; Ludvigson, Greg A.; Matthew, Joeckel R.; Gonzalez, Luis A.; Brenner, Richard L.; Witzke, B.J.

2007-01-01

A thin cemented sandstone bed in the Upper Albian Dakota Formation of southeastern Nebraska contains the first dinosaur tracks to be described from the state. Of equal importance to the tracks are stable-isotope (C, O) analyses of cements in the track bed, especially in the context of data derived from generally correlative strata (sandstones and sphaerosiderite-bearing paleosols) in the region. These data provide the framework for interpretations of paleoenvironmental conditions, as well as a novel approach to understanding mechanisms of terrestrial vertebrate track preservation. High minus-cement-porosity (> 47%) and low grain-to-grain contacts (???2.5) in the track bed indicate early (pre-compaction) lithification. Although phreatic cements dominate, the history of cementation within this stratigraphic interval is complex. Cathodoluminescence petrography reveals two distinct calcite zones in the track-bearing horizon and four cement zones in stratigraphically equivalent strata from a nearby section. The earliest calcite cements from both localities are likely coeval because they exhibit identical positive covariant trends (??18O values of - 9.89 to - 6.32??? and ??13C values of - 28.01 to - 19.33??? VPDB) and record mixing of brackish and meteoric groundwaters. All other calcite cements define meteoric calcite lines with ??18O values clustering around - 9.42??? and - 8.21??? VPDB from the track-bearing horizon, and - 7.74???, - 5.81???, and - 3.95??? VPDB from the neighboring section. Distinct meteoric sphaerosiderite lines from roughly correlative paleosols serve as a proxy for locally recharged groundwaters. Back-calculated paleogroundwater ??18O estimates from paleosol sphaerosiderites range from - 7.4 to - 4.2??? SMOW; whereas, meteoric calcite lines from the track horizon are generally more depleted. Differences in cement ??18O values record changes in paleogroundwater recharge areas over time. Early calcite cements indicate mixing of fresh and brackish groundwaters during the syndepositional lithification of the track horizon. Later calcite cements, however, indicate recharge from a larger catchment basin that extended far inland. Therefore, the cements likely record a rise and subsequent fall in relative sea level. We conclude that scrutiny of the cement isotope geochemistry of genetically significant surfaces, especially track beds, can provide new data for interpreting sea level change. ?? 2006 Elsevier B.V. All rights reserved.

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 facilitates transport of Ca 2+ ions from the nuclear envelope to the coccolith vesicle. On the basis of our observations, we propose that formation of the coccolith utilizes the nuclear envelope-endoplasmic reticulum Ca 2+ -store of the cell for the transport of Ca 2+ ions from the external medium to the coccolith vesicle and that E. huxleyi calcite forms by ion-by-ion growth rather than by a nanoparticle accretion mechanism. © 2017 Phycological Society of America.

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

Diagenetic evolution and stable isotopes of Lower Permian platform marginal carbonates (Trogkofel Limestone, Carnic Alps, Austria)

NASA Astrophysics Data System (ADS)

Schaffhauser, Maria; Krainer, Karl; Sanders, Diethard Gerald; Spötl, Christoph

2010-05-01

The Trogkofel massif in the Carnic Alps, Austria/Italy, consists of a succession up to 400 m thick of limestones deposited along a platform margin (Trogkofel Limestone; Artinskian). The top of the Trogkofel Limestone is erosively overlain by the Tarvis Breccia. Up-section, the Trogkofel Limestone consists of well-bedded shallow-water bioclastic limestones with intercalated mud mounds, overlain by thick-bedded to unbedded limestones (bioclastic grainstones, packstones, rudstones) and cementstone mounds rich in phylloid algae, Tubiphytes, bryozoans and Archaeolithoporella. In the cementstone mounds, bioclasts are coated by thick fringes and botryoids of fibrous calcite, and of calcite spar that probably represents calcitized aragonite. Primary and intrinsic pores are filled by microbialite, and/or by mudstone to bioclastic wackestone. Shallow-water bioclastic grainstones are cemented by isopachous fringes of fibrous calcite, or by sparry calcite. Throughout the succession, evidence for meteoric-vadose dissolution is present. The Trogkofel Limestone is riddled by palaeokarstic dykes and caverns filled by (a) isopachous cement fringes up to a few decimetres thick, and/or (b) by red, geopetally-laminated lime mudstone to bio-lithoclastic wackestone; geopetal laminasets locally display convolute bedding. Small dissolution cavities are filled by grey internal sediment, or by crystal silt. Brecciated internal sediments overlain by unbrecciated, geopetally-laminated infillings record deformation during or after deposition of the Trogkofel Limestone. Polyphase fractures cemented by calcite may cross-cut both internal sediments and host rock. In the Trogkofel Limestone, local dolomitization is common. Replacement dolomites show a wide range of shapes and fabrics, including: (a) fine-crystalline anhedral xenotopic fabric, (b) coarse-crystalline subhedral to euhedral, hypidiotopic to idiotopic fabric of turbid or optically zoned crystals, and (c) saddle dolomite as replacement and filling of fractures. Closely below the erosional surface at the top of the Trogkofel Limestone, the dolomite is characterized by vuggy porosity. The Tarvis Breccia, which represents coarse alluvial fan deposits, in turn, is thick-bedded, poorly sorted, typically clast-supported, and consists of angular lithoclasts embedded in a matrix of former lime mudstone. Both, matrix as well as lithoclasts, are dolomitized. Various types of cement (isopachous, botryoidal, microbialite, calcite spar), karstic cavity fills (isopachous cements, internal sediments), and replacement dolomites of the Trogkofel section, as well as of the Tarvis Breccia were analysed for their stable isotopic composition. δ18O and δ13C data produced so far allow to differentiate between replacement dolomites and saddle dolomite of the Trogkofel Limestone and the Tarvis Breccia. Saddle dolomite shows the most depleted oxygen isotope values, suggesting formation during relatively high temperatures. Carbon isotope values are invariably positive in all dolomite types indicating lacking influence of organic diagenesis on the alkalinity of the deep-burial pore water. Matrix dolomite from the Tarvis Breccia shows slightly positive δ18O values. Calcite cements show a wide range in δ18O values (ca. -1 to -7 permil VPDB), which overlaps the composition of unaltered brachiopod shells (ca. -3 permil VPDB). Oxygen isotope values of calcite cements reveal a trend towards depleted δ18O values. This trend is reflecting most likely increasing temperature.

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 and experience significant evaporation. Paleotropical coals with coal balls are under- and overlain by siliciclastic sediments, and, if fresh, would have required ever-wet climatic conditions for peat to accumulate. Pervasive freshwater diagenesis, with low magnesium calcite enveloping individual grains of high-magnesium calcite, results in most coal-ball carbonates having a freshwater or mixed isotopic signature. In some coal balls, cell walls in the root cortex (a soft tissue) separate carbonate of differing magnesium content, resulting in cells filled with low-magnesium (freshwater) calcite adjacent to cells filled with high-magnesium (marine) calcite, suggesting that these cements formed in recently dead or dying roots. The juxtaposition of high-magnesium (marine) calcite and low-magnesium (freshwater) calcite in coal balls suggests that they formed at the marine/freshwater interface in mires that contained salt-tolerant plants. This model of coal-ball formation suggests that coals bearing coal balls accumulated early in marine transgression as glaciers melted and sea level rose. In modern coastal mires, tidal incursion of salt water can maintain high freshwater tables, enabling domed freshwater peat to form in climates that normally would be too dry for tropical freshwater peat accumulation. Peat accumulation in these mires may be due to marine transgression rather than the ever-wet paleoclimates.

Warm Tropical Sea Surface Temperatures During the Pliocene: a New Record from Mg/Ca and δ18O In Situ Techniques

NASA Astrophysics Data System (ADS)

Wycech, J.; Kelly, D.; Kozdon, R.; Fournelle, J.; Valley, J. W.

2013-12-01

The Pliocene Warm Period (PWP) was a global warming event that punctuated Earth's climate history ~3 Ma, and study of its geologic record is providing important constraints for models predicting future climate change. Many sea surface temperature (SST) reconstructions for the PWP indicate amplified polar warmth with minimal or absent warming in the tropics - a phenomenon termed the cool tropics paradox. Key pieces of evidence for the lack of tropical warmth are oxygen isotope (δ18O) and Mg/Ca ratios in planktic foraminiferal shells. However, the δ18O data used to reconstruct surface-ocean conditions are derived from whole foraminiferal shells with the assumption that their geochemical compositions are well preserved and homogeneous. To the contrary, most planktic foraminiferal shells found in deep-sea sediments are an aggregate mixture of three carbonate phases (18O-depleted pre-gametogenic calcite, 18O-rich gametogenic calcite added during reproduction, and very 18O-rich diagenetic calcite) that formed under different physiological and/or environmental conditions. Here we report preliminary results of an ongoing study that uses secondary ion mass spectrometry (SIMS) and electron probe microanalysis (EPMA) to acquire in situ δ18O and Mg/Ca data, respectively, from 3-10 μm domains within individual planktic foraminiferal shells (Globigerinoides sacculifer) preserved in a PWP record recovered at ODP Site 806 in the West Pacific Warm Pool. SIMS analyses show that the δ18O of gametogenic calcite is 1-2‰ higher than in the pre-gametogenic calcite of Gs. sacculifer. Mass-balance calculations using the mean δ18O of gametogenic and pre-gametogenic calcites predict a whole-shell δ18O that is ~1.9‰ lower than the published whole-shell δ18O for Gs. sacculifer in this same deep-sea section. Removal of 18O-depleted, pre-gametogenic calcite via dissolution cannot fully account for this isotopic offset since the mean δ18O of whole shells (-1.3‰) is higher than that of gametogenic calcite (-2.1‰); hence, we attribute the elevated whole-shell values to the addition of 18O-rich carbonate by post-depositional diagenesis. By contrast, in situ measurements indicate that the Mg/Ca ratios in the pre-gametogenic and gametogenic calcites are indistinguishable, and in situ Mg/Ca ratios are comparable to those of whole shells. Use of Mg/Ca calculated SSTs (~30°C) and published whole-shell δ18O to determine the δ18O of seawater (δ18Osw) yields unrealistically high values (2.1‰), while a similar computation using pre-gametogenic δ18O yields a more acceptable δ18Osw (-0.2‰) for this region during the PWP. This latter finding corroborates the view that the published whole-shell δ18O record has been compromised by diagenesis and demonstrates the potential of SIMS δ18O analysis to enhance our ability to reconstruct hydrographic conditions under differing climatic regimes.

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…

Preparation of Calcium Carbonate (from Shellfish)/Magnesium Oxide Composites as an Antibacterial Agent

NASA Astrophysics Data System (ADS)

Jannah, Z.; Mubarok, H.; Syamsiyah, F.; Putri, A. A. H.; Rohmawati, L.

2018-05-01

We have performed research on antibacterial substance from a natural substance, one of them is calcite from shellfish (Anadara granosa) in Kenjeran Beach Surabaya. This calcite is composed of magnesium oxide using PEG 4000 (Polyethylene glycol) as a solvent and then heated at 800 °C for 30 minutes. Weight variety of calcite used was 80% wt, 85% wt, and 90 wt%. Subsequently, that composites characterized using XRD, antibacterial activity test (Escherichia coli and Staphylococcus aureus), and SEM. The result of antibacterial assay shows that composite of CaCO3/MgO with 80% wt composition have the best activity inhibitory of 31,96 mm for Escherichia coli bacteria and 32.26 mm for Staphylococcus aureus bacteria.

Is organic matter alone sufficient to predict isoproturon sorption in calcareous soils?

PubMed

El Arfaoui, Achouak; Sayen, Stéphanie; Paris, Michaël; Keziou, Amor; Couderchet, Michel; Guillon, Emmanuel

2012-08-15

Eleven soils collected from Champagne-Ardenne area (France) were used to investigate isoproturon sorption in laboratory conditions. Our results identified the organic matter (OM) and the ratio of calcite content to OM content (Rt) as the main two parameters governing isoproturon retention in soils. While organic matter favored pesticide sorption, calcite had an antagonistic effect since it limited isoproturon retention. The Rt ratio of calcite content to organic matter content in soils appeared to be a parameter that should be considered in predictive models in addition to OM in regions presenting calcareous soils. Adsorption of isoproturon as a function of Rt and OM was successfully described through a simple empirical model. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

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.

Amorphous calcium carbonate associated with biofilms in hot spring deposits

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2012-08-01

Calcium carbonate nanoparticles are intimately associated with crystalline calcite and aragonite in the Eryuan, Gongxiaoshe, and Zhuyuan hot springs (water temperature > 75 °C), which are located in Yunnan Province, China. The nanoparticles, < 1 μm long, are spherical to disc-shaped and commonly fuse together into small clusters. Their general appearance and lack of crystal faces or edges indicate that they are noncrystalline. Morphologically, these nanoparticles are similar to calcified nannobacteria or the constituent grains in amorphous calcium carbonate (ACC), which can be formed by various biogenic and abiogenic processes. In the Chinese hot springs, the ACC is always found under, in, or on top of biofilms, commonly in close proximity to crystalline calcite and/or aragonite. Textural evidence indicates that the ACC probably developed in microdomains that develop in the complex biofilm hydrogels. Critically, there is no evidence to support the notion that the nanoparticles are calcified nannobacteria. In the Chinese springs, ACC appears to play a formative role in the development of wheat-sheaf arrays of aragonite crystals and some of the calcite crystals. Hollow cores in some of the aragonite bundles probably formed as ACC was dissolved and many of the aragonite crystals appear to have developed as ACC recrystallized. Similarly, layers of ACC that coat the surfaces of some calcite crystals could be diagenetically transformed into calcite. The development of ACC in hot spring systems may be widespread and may play a critical but transitory role in the development of crystalline CaCO3 in these high temperature environments.

Is the core top modern? Observations from the eastern equatorial Pacific

NASA Astrophysics Data System (ADS)

Mekik, Figen; Anderson, Robert

2018-04-01

A compilation of ages from 67 core tops in the eastern equatorial Pacific (EEP) does not display an easily discernible regional pattern. The ages range from 790 to over 15,000 years. The youngest core tops with the highest sediment focusing factors are located in the Panama Basin. There are weak but statistically significant inverse relationships between core top age and age-model based mass accumulation rates, bioturbation depth, linear sedimentation rate and sediment focusing factors. However, we found no statistically significant relationship between core top age and calcite dissolution in sediments or 230Th-normalized mass accumulation rates. We found evidence suggesting that greater amount of sediment focusing helps to preserve the carbonate fraction of the sediment where focusing is taking place. When focusing factors are plotted against percent calcite dissolved, we observe a strong inverse relationship, and core tops younger than 4500 years tend to occur where focusing factors are high and percent calcite dissolved values are low. Using labile organic carbon fluxes to estimate bioturbation depth in the sediments results in the observation that where bioturbation depth is shallow (<4 cm), the core top age has a strong, inverse relationship with sediment accumulation rate. We used the Globorotalia menardii Fragmentation Index (MFI) as an indicator of percent calcite dissolved in deep sea sediments. There is a distinct pattern to core top calcite dissolution in the EEP which delineates bands of high surface ocean productivity as well as the clear increase in dissolution downward on the flanks of the East Pacific Rise.

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

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.

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.

Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate

PubMed Central

Radha, A. V.; Forbes, Tori Z.; Killian, Christopher E.; Gilbert, P. U. P. A.; Navrotsky, Alexandra

2010-01-01

Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC⇒anhydrous ACC ∼ biogenic anhydrous ACC⇒vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO2 sequestration. PMID:20810918

Carbon-oxygen isotopes and rare earth elements as an exploration vector for Carlin-type gold deposits: A case study of the Shuiyindong gold deposit, Guizhou Province, SW China

NASA Astrophysics Data System (ADS)

Tan, Qin-Ping; Xia, Yong; Wang, Xueqiu; Xie, Zhuo-Jun; Wei, Dong-Tian

2017-10-01

The Shuiyindong gold deposit is a deeply concealed strata-bound Carlin-type deposit in southwestern Guizhou Province, China. The deposit lies on the eastern limb of the Huijiabao anticline with ores mainly along the anticline axis and hosted in bioclastic limestone, containing calcite veins, of the Permian Longtan Formation units. In this study, we measured carbon and oxygen isotopic ratios and rare earth element (REE) concentrations of the host rocks and calcite veins along a profile across the Shuiyindong deposit. Orebodies in the upper unit of the Longtan Formation have higher δ18O values (20.6-22.4‰) and lower δ13C values (-3.7 to -0.5‰) than the country rocks (δ18O: 18.8-21.4‰; δ13C: -0.7 to 0.8‰). However, there are no obvious trends of δ18O and δ13C values from the country rocks to the orebodies in the middle unit of the Longtan Formation. The spatial distribution of the calcite veins displays distinct halos of δ13C and δ18O values and REE concentrations. Calcite veins along the anticlinal axis and major reverse fault are enriched in Middle REE (Sm, Eu, Gd, and Tb) and 18O and depleted in 13C. Surficial veining calcite-filled fractures/faults that connect to deep concealed strata-bound gold mineralization systems can be vectors toward deep ores in southwestern Guizhou Province, China.

Ocean acidification reduces the crystallographic control in juvenile mussel shells.

PubMed

Fitzer, Susan C; Cusack, Maggie; Phoenix, Vernon R; Kamenos, Nicholas A

2014-10-01

Global climate change threatens the oceans as anthropogenic carbon dioxide causes ocean acidification and reduced carbonate saturation. Future projections indicate under saturation of aragonite, and potentially calcite, in the oceans by 2100. Calcifying organisms are those most at risk from such ocean acidification, as carbonate is vital in the biomineralisation of their calcium carbonate protective shells. This study highlights the importance of multi-generational studies to investigate how marine organisms can potentially adapt to future projected global climate change. Mytilus edulis is an economically important marine calcifier vulnerable to decreasing carbonate saturation as their shells comprise two calcium carbonate polymorphs: aragonite and calcite. M. edulis specimens were cultured under current and projected pCO2 (380, 550, 750 and 1000μatm), following 6months of experimental culture, adults produced second generation juvenile mussels. Juvenile mussel shells were examined for structural and crystallographic orientation of aragonite and calcite. At 1000μatm pCO2, juvenile mussels spawned and grown under this high pCO2 do not produce aragonite which is more vulnerable to carbonate under-saturation than calcite. Calcite and aragonite were produced at 380, 550 and 750μatm pCO2. Electron back scatter diffraction analyses reveal less constraint in crystallographic orientation with increased pCO2. Shell formation is maintained, although the nacre crystals appear corroded and crystals are not so closely layered together. The differences in ultrastructure and crystallography in shells formed by juveniles spawned from adults in high pCO2 conditions may prove instrumental in their ability to survive ocean acidification. Copyright © 2014 Elsevier Inc. All rights reserved.

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

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

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

Ultra-thin clay layers facilitate seismic slip in carbonate faults.

PubMed

Smeraglia, Luca; Billi, Andrea; Carminati, Eugenio; Cavallo, Andrea; Di Toro, Giulio; Spagnuolo, Elena; Zorzi, Federico

2017-04-06

Many earthquakes propagate up to the Earth's surface producing surface ruptures. Seismic slip propagation is facilitated by along-fault low dynamic frictional resistance, which is controlled by a number of physico-chemical lubrication mechanisms. In particular, rotary shear experiments conducted at seismic slip rates (1 ms -1 ) show that phyllosilicates can facilitate co-seismic slip along faults during earthquakes. This evidence is crucial for hazard assessment along oceanic subduction zones, where pelagic clays participate in seismic slip propagation. Conversely, the reason why, in continental domains, co-seismic slip along faults can propagate up to the Earth's surface is still poorly understood. We document the occurrence of micrometer-thick phyllosilicate-bearing layers along a carbonate-hosted seismogenic extensional fault in the central Apennines, Italy. Using friction experiments, we demonstrate that, at seismic slip rates (1 ms -1 ), similar calcite gouges with pre-existing phyllosilicate-bearing (clay content ≤3 wt.%) micro-layers weaken faster than calcite gouges or mixed calcite-phyllosilicate gouges. We thus propose that, within calcite gouge, ultra-low clay content (≤3 wt.%) localized along micrometer-thick layers can facilitate seismic slip propagation during earthquakes in continental domains, possibly enhancing surface displacement.

Porosity Development in a Coastal Setting: A Reactive Transport Model to Assess the Influence of Heterogeneity of Hydrological, Geochemical and Lithological Conditions

NASA Astrophysics Data System (ADS)

Maqueda, A.; Renard, P.; Cornaton, F. J.

2014-12-01

Coastal karst networks are formed by mineral dissolution, mainly calcite, in the freshwater-saltwater mixing zone. The problem has been approached first by studying the kinetics of calcite dissolution and then coupling ion-pairing software with flow and mass transport models. Porosity development models require high computational power. A workaround to reduce computational complexity is to assume the calcite dissolution reaction is relatively fast, thus equilibrium chemistry can be used to model it (Sanford & Konikow, 1989). Later developments allowed the full coupling of kinetics and transport in a model. However kinetics effects of calcite dissolution were found negligible under the single set of assumed hydrological and geochemical boundary conditions. A model is implemented with the coupling of FeFlow software as the flow & transport module and PHREEQC4FEFLOW (Wissmeier, 2013) ion-pairing module. The model is used to assess the influence of heterogeneities in hydrological, geochemical and lithological boundary conditions on porosity evolution. The hydrologic conditions present in the karst aquifer of Quintana Roo coast in Mexico are used as a guide for generating inputs for simulations.

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.

Monitoring biocalcification potential of Lysinibacillus sp. isolated from alluvial soils for improved compressive strength of concrete.

PubMed

Vashisht, Rajneesh; Attri, Sampan; Sharma, Deepak; Shukla, Abhilash; Goel, Gunjan

2018-03-01

The present study reports the potential of newly isolated calcite precipitating bacteria isolated from alluvial soil to improve the strength and durability of concrete. A total of sixteen samples of alluvial soil and sewage were collected from the different locations of province Solan (India). For isolation, enrichment culture technique was used to enrich calcite precipitating strains in Urea broth. After enrichment, fourteen distinct bacterial strains were obtained on Urea agar. Based on qualitative and quantitative screening for urease activity, five isolates were obtained possessing higher calcite formation and urease activities (38-77 μmhos/cm) as compared with standard strain of Bacillus megaterium MTCC 1684 (77 μmhos/cm). An isolate I13 identified as Lysinibacillus sp. was selected for self healing property in the concrete mix of M20. An improved compressive strength of 1.5 fold was observed in concrete samples amended with Lysinibacillus sp. over the concrete amended with B. megaterium MTCC 1684 after 28 days of curing. The higher calcite precipitation activity was indicated in Lysinibacillus sp. by FE-SEM micrographs and EDX analysis. Copyright © 2017 Elsevier GmbH. All rights reserved.

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

Yuan, Ke; De Andrade, Vincent; Feng, Zhange

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

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

PubMed

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

2013-04-01

We employ ab initio calculations and investigate the single-crystalline elastic properties of (Ca,Mg)CO3 crystals covering the whole range of concentrations from pure calcite CaCO3 to pure magnesite MgCO3. Studying different distributions of Ca and Mg atoms within 30-atom supercells, our theoretical results show that the energetically most favorable configurations are characterized by elastic constants that nearly monotonously increase with the Mg content. Based on the first principles-derived single-crystalline elastic anisotropy, the integral elastic response of (Ca,Mg)CO3 polycrystals is determined employing a mean-field self-consistent homogenization method. As in case of single-crystalline elastic properties, the computed polycrystalline elastic parameters sensitively depend on the chemical composition and show a significant stiffening impact of Mg atoms on calcite crystals in agreement with the experimental findings. Our analysis also shows that it is not advantageous to use a higher-scale two-phase mix of stoichiometric calcite and magnesite instead of substituting Ca atoms by Mg ones on the atomic scale. Such two-phase composites are not significantly thermodynamically favorable and do not provide any strong additional stiffening effect. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

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.

Early and late lithification of aragonitic bivalve beds in the Purbeck Formation (upper jurassic-lower cretaceous) of Southern England

NASA Astrophysics Data System (ADS)

El-Shahat, Adam; West, Ian

1983-05-01

Beds of euryhaline bivalves alternating with shales constitute much of the middle Purbeck Formation. They originated on "tidal" flats at the western margin of an extensive brackish lagoon. When these shell beds are thin and enclosed in shale they are often still preserved as aragonite and are associated with "beef", fibrous calcite formed during compaction. In most cases, however, the shell debris has been converted by diagenesis into calcitic biosparrudite limestones. A compacted type has been lithified at a late stage, after deep burial. In this, pyrite is abundant and most of the shell aragonite has been replaced neomorphically by ferroan pseudopleochroic calcite. A contrasting uncompacted type of biosparrudite is characterised by bivalve fragments with micrite envelopes. Shells and former pores are occupied by non-ferroan sparry calcite cement, and there is little pyrite. These limestones frequently contain dinosaur footprints and originated in "supratidal" environments where they were cemented early, mainly in meteoric water. Once lithified they were unaffected by compaction. This uncompacted type indicates phases of mild uplift or halts in subsidence. These shell-bed lithologies, and also intermediate types described here, will probably be recognised in other lagoonal formations.

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.

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

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.

Major, trace element and stable isotope geochemistry of synorogenic breccia bodies, Ellsworth Mountains, Antarctica

USGS Publications Warehouse

Craddock, J.P.; McGillion, M.S.; Webers, G.F.

2007-01-01

Cambrian carbonates in the Heritage Range of the Ellsworth Mountains, West Antarctica host a series of carbonate-rich breccia bodies that formed contemporaneously with the Permian Gondwanide orogen. The breccia bodies had a three-stage genesis, with the older breccias containing Cambrian limestone (and marble) clasts supported by calcite, whereas the younger breccias are nearly clast-free and composed entirely of matrix calcite. Breccia clasts, calcite matrix and detrital matrix samples were analyzed using x-ray fluorescence (major and trace elements), x-ray diffraction, and stable isotopes (C, O) and suggest that the breccias formed as part of a closed geochemical system, at considerable depth, within the Cambrian limestone host as the Ellsworth Mountains deformed into a fold-and-thrust belt along the margin of Gondwana

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

Micro-attenuated total reflection spectral imaging in archaeology: application to Maya paint and plaster wall decorations.

PubMed

Goodall, Rosemary A; Hall, Jay; Sharer, Robert J; Traxler, Loa; Rintoul, Llew; Fredericks, Peter M

2008-01-01

Fourier transform infrared (FT-IR) attenuated total reflection (ATR) imaging has been successfully used to identify individual mineral components of ancient Maya paint. The high spatial resolution of a micro FT-IR-ATR system in combination with a focal plane array detector has allowed individual particles in the paint to be resolved and identified from their spectra. This system has been used in combination with micro-Raman spectroscopy to characterize the paint, which was found to be a mixture of hematite and silicate particles with minor amounts of calcite, carbon, and magnetite particles in a sub-micrometer hematite and calcite matrix. The underlying stucco was also investigated and found to be a combination of calcite with fine carbon particles, making a dark sub-ground for the paint.

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.

Stability of Basalt plus Anhydrite plus Calcite at HP-HT: Implications for Venus, the Earth and Mars

NASA Technical Reports Server (NTRS)

Martin, A. M.; Righter, K.; Treiman, A. H.

2010-01-01

"Canali" observed at Venus surface by Magellan are evidence for very long melt flows, but their composition and origin remain uncertain. The hypothesis of water-rich flow is not reasonable regarding the temperature at Venus surface. The length of these channels could not be explained by a silicate melt composition but more likely, by a carbonate-sulfate melt which has a much lower viscosity (Kargel et al 1994). One hypothesis is that calcite CaCO3 and anhydrite CaSO4 which are alteration products of basalts melted during meteorite impacts. A famous example recorded on the Earth (Chicxulub) produced melt and gas rich in carbon and sulfur. Calcite and sulfate evaporites are also present on Mars surface, associated with basalts. An impact on these materials might release C- and S-rich melt or fluid. Another type of planetary phenomenon (affecting only the Earth) might provoke a high pressure destabilization of basalt+anhydrite+calcite. Very high contents of C and S are measured in some Earth s magmas, either dissolved or in the form of crystals (Luhr 2008). As shown by the high H content and high fO2 of primary igneous anhydrite-bearing lavas, the high S content in their source may be explained by subduction of an anhydrite-bearing oceanic crust, either directly (by melting followed by eruption) or indirectly (by release of S-rich melt or fluid that metasomatize the mantle) . Calcite is a major product of oceanic sedimentation and alteration of the crust. Therefore, sulfate- and calcite-rich material may be subducted to high pressures and high temperatures (HP-HT) and release S- and C-rich melts or fluids which could influence the composition of subduction zone lavas or gases. Both phenomena - meteorite impact and subduction - imply HP-HT conditions - although the P-T-time paths are different. Some HP experimental/theoretical studies have been performed on basalt/eclogite, calcite and anhydrite separately or on a combination of two. In this study we performed piston-cylinder experiments at 1 GPa between 950 and 1700 C using a mixture of 70wt% tholeiitic basalt + 15wt% anhydrite + 15wt% calcite. Up to 1440 C, an ultracalcic (CaO>13.5 wt%; CaO/Al2O3>1 wt%) picrobasaltic (SiO240-45 wt%; Na2O+K2O<2 wt%) melt containing up to 5 wt% SO3 and up to 5.3 wt% CO2+H2O (calculated by difference) is present in equilibrium with clinopyroxene, anhydrite, spinel-chromite, a CAS-phase and a gas composed mainly of CO and an aliphatic thiol (CH2)4SH. Hydrogen was incorporated either by contact between the starting material and air or by diffusion through the capsule during the experiments. The S content in the gas increases with temperature and run duration, implying that gases with various C/S ratios might be released during an impact or at subduction zones, depending on the P-T-t path and on the H content. Above approx.1440 C, a Ca-rich carbonate-sulfate melt forms (in equilibrium with the picrobasaltic melt) which contains a few percents of Na and K. Such melt is not expected to form at Earth s subduction temperatures. If it forms by meteorite impact, it might crystallize too fast to explain long flows like Venus canali. A different basalt/anhydrite/calcite ratio might, however, decrease its formation temperature.

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

During burial and exhumation, rocks are simultaneously exposed to metamorphic reactions and tectonic stresses. Therefore, the reaction rate of newly formed minerals may depend on chemical and mechanical driving forces. Here, we investigate the reaction kinetics of dolomite (CaMg[CO3]2) rim growth by solid-state reactions experiments on oriented calcite (CaCO3) and magnesite (MgCO3) single crystals under isostatic and non-isostatic pressure conditions. Cylindrical samples of 3-5 mm length and 7 mm diameter were drilled and polished perpendicular to the rhombohedral cleavage planes of natural clear crystals. The tests were performed using a Paterson-type deformation apparatus at P = 400 MPa confining pressure, temperatures, T, between 750 and 850°C, and reaction durations, t, of 2 - 146 h to calculate the kinetic parameters of dolomite rim growth under isostatic stress conditions. For non-isostatic reaction experiments we applied in addition differential stresses, σ, up to 40 MPa perpendicular to the contact interface at T = 750°C for 4 - 171 h duration, initiating minor inelastic deformation of calcite. The thickness of the resulting dolomite reaction rims increases linearly with the square root of time, indicating a diffusion-controlled reaction. The rims consist of two different textural domains. Granular dolomite grains (≈ 2 -5 μm grain size) form next to calcite and elongated palisade-shaped grains (1-6 μm diameter) grow perpendicular to the magnesite interface. Texture measurements with the electron backscatter diffraction technique indicate that the orientations of dolomite grains are mainly influenced by the orientation of the calcite educt crystal, in particular in the granular rim. To some extent, the texture of dolomite palisades is also influenced by the orientation of magnesite. The thickness of the two individual layers increases with temperature. At 400 MPa isostatic pressure, T = 750°C and t = 29 hours, a 5 μm thick granular dolomite layer 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.

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

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 ~3500, sufficient to resolve all relevant isobaric interferences. Several points near the center of calcite grains with constant Mn and Cr concentrations were measured. As for San Carlos olivine, a primary beam was rastered over 20 x 20 μm2 areas. Signals of all ions decreased with time during the measurements. The 55Mn/52Cr RSF also decreased with time. Initially it was ~0.7-0.8, and approached to a nearly constant value of ~0.5-0.6 after ~20 minutes. 53Cr+/52Cr+ isotopic ratio was 0.1105 ± 0.0002 (1σ), not dependent on time and space. This value corresponds to ~-26 permil fractionation from the reference value. On the other hand, the RSF of San Carlos olivine was found to be ~0.9, consistent with previous studies. The RSF of our calcite is significantly lower than the values used in previous studies and the RSF of San Carlos olivine measured in this study. This implies that Mn-Cr ages for carbonates obtained in previous studies may have systematic biases (~3 Myr).

Hydrothermal replacement of calcite by Mg-carbonates

NASA Astrophysics Data System (ADS)

Jonas, Laura; Mueller, Thomas; Dohmen, Ralf

2014-05-01

The transport of heat and mass through the Earth's crust is coupled to mineral reactions and the exchange of isotopes and elements between different phases. Carbonate minerals are a major constituent of the Earth's crust and play an important role in different physical, chemical and even biological processes. In this experimental study, the element exchange reaction between calcite (CaCO3) and a Mg-rich fluid phase is investigated under hydrothermal conditions. Single crystals of calcite (2x2x2 mm) react with 1 ml of a 1 M MgCl2 solution at 200° C in a Teflon-lined steel autoclave for different times between one day and four weeks. The reaction leads to the formation of a porous reaction front and the pseudomorphic replacement of calcite by dolomite [CaMg(CO3)2] and magnesite (MgCO3). Scanning electron microscopy revealed that the reaction rim consists of small Mg-carbonate rhombs closely attached to each other, suggesting that the replacement reaction takes place by a dissolution-precipitation mechanism. Typically, the observed reaction front can be divided into two different domains. The outer part of the reaction rim, i.e. from the mineral surface in contact to the fluid inwards, consists of magnesite, whereas the inner part of the rim surrounding the unreacted calcite core consists of Ca-rich dolomite. The formation of a porous microstructure that varies in different parts of the reaction rim is a direct result of the large molar volume change induced by the replacement of calcite by magnesite and dolomite. The developing porosity therefore creates fluid pathways that promote the progress of the reaction front towards the unreacted core of the single crystal. Compositional profiles measured perpendicular to the mineral surface across the reactions rims using electron microprobe (EMPA) further revealed a compositional gradient within the reaction rim with regard to the structure-forming elements Mg and Ca. Here, the amount of Mg incorporated in both product phases increases with increasing distance from the unreacted calcite core, countered by a decrease of Ca incorporated. Both the coexistence of two different product phases and the distinct compositional gradient within the forming reaction rim are unequivocal signs of a chemical zonation of Ca and Mg in the fluid phase which mediates the element exchange between the reaction interface and the bulk solution. Atomic adsorption spectroscopy revealed that the Ca/Mg ratio in the reacted fluid increases as a function of time, reflecting the progressive exchange of Mg and Ca between the fluid and the solid phase. The time-dependence of the evolving Ca/Mg ratio can be fitted with a square root of time relation that indicates a transport controlled reaction. We interpret the hydrothermal replacement of calcite to operate via a dissolution/re-precipitation mechanism, whereas the reaction progress is controlled by the transport of the structure forming elements through the developing reaction rim.

Reference Materials for Trace Element Microanalysis of Carbonates by SIMS and other Mass Spectrometric Techniques

NASA Astrophysics Data System (ADS)

Layne, G. D.

2009-12-01

Today, many areas of geochemical research utilize microanalytical determinations of trace elements in carbonate minerals. In particular, there has been an explosion in the application of Secondary Ion Mass Spectrometry (SIMS) to studies of marine biomineralization. SIMS provides highly precise determinations of Mg and Sr at the concentration levels normally encountered in corals, mollusks or fish otoliths. It is also a highly effective means for determining a wide range of other trace elements at ppm levels (e.g., Na, Fe, Mn, Ba, REE, Pb, Th, and U) in a variety of naturally occurring calcite and aragonite matrices - and so is potentially valuable in studies of diagenesis, hydrothermal fluids and carbonatitic magmas. For SIMS, modest time per spot (often <5 min), lateral spatial resolution (<10 μm), sample volume consumption (<10 ng) and overall reproducibility compare extremely favorably with other microanalytical techniques for these applications. However, accuracy and reproducibility are currently wholly limited by the homogeneity of available solid reference material - which is far inferior to the tenths of a percent levels of precision achieved by SIMS. Due to variation in the sputtered ion yields of most elements with the major element composition of the sample matrix, accuracy of SIMS depends intimately on matrix-matched solid reference materials. Despite its rapidly increasing use for trace element analyses of carbonates, there remains a dearth of certified reference materials suitable for calibrating SIMS. The pressed powders used by some analysts to calibrate LA-ICP-MS do not perform well for SIMS - they are not perfectly dense or homogeneous to the desired level at the micron scale of sampling. Further, they often prove incompatible with the sample high vacuum compatibility requirement for stable SIMS analysis (10-8 to 10-9 torr). Some naturally occurring calcite has apparent utility as a reference material. For example, equigranular calcite from some zones of carbonatite intrusions (sovites) and recrystallized calcites from highly metamorphosed metallic ore deposits. Most calcite marbles, though possibly appropriate as Sr standards, show substantial inhomogeneity in Mg, Mn and Ba. Some hydrothermal “Iceland Spar” calcite may prove useful as a reference for extremely low concentrations of Mg, Sr and Ba. The best carbonatitic calcites currently in use appear homogeneous to better than 2-3% for Sr (and somewhat less homogeneous for Mg). But these standards still require numerous replicate analyses during analytical sessions to reduce the overall uncertainty to <<1.0%.The availability of appropriate certified solid reference materials with a high degree of homogeneity would greatly benefit the utilization and inter-comparison of SIMS determinations in carbonates, while substantially reducing the time consumed in calibration. Some studies would also benefit from the extension of this effort to the characterization of appropriate standards of other rhombohedral carbonates (especially dolomite and Fe-rich calcite).

Origin of karst conduits in calcareous sandstone and carbonate-silicate rocks: Complex role of insoluble material

NASA Astrophysics Data System (ADS)

Bruthans, Jiri; Balak, Frantisek; Schweigstillova, Jana; Vojtisek, Jan

2017-04-01

Carbonate karst is best developed in high-grade limestones and majority of the studies is focused on these rocks. Features developed by dissolution of calcite cement in quartz sandstones and dissolution of various carbonate-silicate rocks are studied far less frequently. Unlike in common karst, the insoluble residuum has to be washed out after dissolution to create high-permeability conduits in these rocks. Aquifers in a Bohemian Cretaceous Basin (BCB), the most important hydrogeological basin in the Czech Republic, consist mainly of quartz and calcareous sandstones to siltstones. These rocks are intercalated by thin layers of calcite-cemented sandstone and low-grade limestone, the latter sometimes partly impregnated by a secondary silica. Results of tracer tests show a high flow velocity in some of the aquifers. Springs with flow rate up to 500 l/s and wells with yield up to 200 l/s occur in these rocks. Dissolution features in BCB were however not yet studied in detail. For identification and characterization of rocks prone to karstification, 350 cores were sampled mostly from boreholes but also from rock outcrops in several areas of BCB. Cores were taken from intervals where: (i) high carbonate content was expected, (ii) conduits and enlarged porosity was observed in rock outcrops or wells, (iii) inflows to boreholes were determined by well logging. Calcium carbonate content was determined by calcimetry in all cores. All cores were leached in hydrochloric acid to observe the degree of disintegration after removal of calcite, which was far dominating portion of total carbonate. Polished sections were prepared from selected cores and Ca, Si, Na, K, Al content was automatically mapped by microprobe to visualize the calcium, silica, feldspar and clay mineral distribution in cores. Conduits were photo documented in the field. Two types of sediments with distinct disintegration characteristics were observed: (i) In sandstone composed of quartz grains cemented by calcite the complete disintegration occurs when calcite content exceeds 30-50%. Such calcite-rich layers are mostly few tens of cms thick and are enclosed in quartz sandstone. Groundwater flow dissolves calcite cement and turns the rock into cohesion-less sand. Sand is consequently washed out by headward erosion in drainage areas forming high capacity conduits within the sandstone. (ii) In carbonates containing secondary silica which form reinforcing structure, even 70-80% calcite content may not be sufficient for rock disintegration during leaching. Disintegration occurs only on tectonically heavily fractured zones, where secondary silica structure is fragmented. It was found that inflows into wells are often associated with zones prone to karstification. Results clearly show that form of insoluble material is critical for karstification potential. Insoluble grain size defines minimum flow velocity needed to excavate the conduits in dissolved residuum. Impregnation by secondary silica needs to be tectonically fragmented prior conduits can occur. Research was funded by the Czech Science Foundation (GA CR No. 16-19459S) and Review of groundwater resources (Ident. No. 155996).

The nucleation of "fast" and "slow" stick slip instabilities in sheared granular aggregates

NASA Astrophysics Data System (ADS)

Korkolis, Evangelos; Ampuero, Jean-Paul; Niemeijer, André

2017-04-01

Seismological observations in the past few decades have revealed a diversity of slip behaviors of faults, involving interactions and transition between slow to fast slip phenomena. Field studies show that exhumed fault zones comprise mixtures of materials with variable frictional strength and stability. Emergent models of slip diversity emphasize the role of heterogeneities of fault zone properties and the potential interactions between seismic and aseismic deformation. Here, we develop analog laboratory experiments to study the mechanics of heterogeneous faults with the goal to identify factors controlling their slip stability and rupture style. We report on results from room temperature sliding experiments using a rotary shear apparatus. We simulated gouge heterogeneity by using materials with different frictional strength and stability. At room temperature conditions, dry glass beads typically stick slip, whereas dry granular calcite exhibits stable sliding. The peak strength of glass beads aggregates is typically lower than that of granular calcite aggregates. Our samples consisted of a layer of glass beads sandwiched between two layers of granular calcite. The initial particle size was between 100 and 200 μm for both materials and the initial thickness of each layer was about 1.5 mm. We tested our layered aggregates under 1 to 7 MPa normal stress and at sliding velocities between 1 and 100 μm/s. Within that range of conditions, high normal stress and slow sliding velocities promoted fast, regular stick slip. For normal stress values of less than about 4 MPa, the recurrence time and stress drop of stick slips became irregular, particularly at sliding rates above 20 μm/s. As the accumulated shear displacement increased, slip events became slower and the magnitudes of their stress drop, compaction and slip distance decreased. We recorded acoustic emissions (AEs) associated with each slip event (fast and slow) and estimated their source azimuth. AE activity was distributed in several clusters, some of which remained stationary, whereas others appeared to migrate with increasing shear displacement. We performed post-mortem microstructural analysis (tabletop SEM) of select AE nucleation sites and found significant mixing of glass beads with the calcite layer abutting the rotating piston ring. No mixing was observed between the glass beads and the calcite layer on the opposite side, nor any features that would indicate strain localization along the interface of the calcite and the adjacent stationary piston. These results show that the frictional behavior of our aggregates changed from fast to slow slip as the amount of glass beads mixed with granular calcite increased. Migrating AE clusters imply that nucleation occurred within the mixed calcite-glass beads layer, where most of the shear strain appears to have been accommodated, whereas stationary clusters probably originated within the adjacent, more slowly deforming layer of glass beads. This suggests that AEs belonging to migrating clusters were perhaps triggered by stress changes due to the gradual mixing of the two sample constituents. This process may explain migrating seismicity in natural fault zones.

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 controlled inorganic origin. By applying a mass transfer model for calcite precipitation taking into account the reaction rates at the surface given by Plummer et al. (1978), slow conversion of CO 2 into H + and HCO 3- , and diffusional mass transport across a diffusion boundary layer, we have calculated the deposition rates from the hydrochemistry of the corresponding locations. The calculated rates agree within a factor of two with the experimental results. Our findings confirm former conclusions with respect to fast flow conditions: reasonable rates of calcite precipitation can be estimated in reducing the PWP-rate calculated from the chemical composition of the water by a factor of about ten, thus correcting for the influence of the diffusion boundary layer.

Chemical and physical controls on the transformation of amorphous calcium carbonate into crystalline CaCO3 polymorphs

NASA Astrophysics Data System (ADS)

Blue, C. R.; Giuffre, A.; Mergelsberg, S.; Han, N.; De Yoreo, J. J.; Dove, P. M.

2017-01-01

Calcite and other crystalline polymorphs of CaCO3 can form by pathways involving amorphous calcium carbonate (ACC). Apparent inconsistencies in the literature indicate the relationships between ACC composition, local conditions, and the subsequent crystalline polymorphs are not yet established. This experimental study quantifies the control of solution composition on the transformation of ACC into crystalline polymorphs in the presence of magnesium. Using a mixed flow reactor to control solution chemistry, ACC was synthesized with variable Mg contents by tuning input pH, Mg/Ca, and total carbonate concentration. ACC products were allowed to transform within the output suspension under stirred or quiescent conditions while characterizing the evolving solutions and solids. As the ACC transforms into a crystalline phase, the solutions record a polymorph-specific evolution of pH and Mg/Ca. The data provide a quantitative framework for predicting the initial polymorph that forms from ACC based upon the solution aMg2+/aCa2+ and aCO32-/aCa2+ and stirring versus quiescent conditions. This model reconciles discrepancies among previous studies that report on the nature of the polymorphs produced from ACC and supports the previous claim that monohydrocalcite may be an important, but overlooked, transient phase on the way to forming some aragonite and calcite deposits. By this construct, organic additives and extreme pH are not required to tune the composition and nature of the polymorph that forms. Our measurements show that the Mg content of ACC is recorded in the resulting calcite with a ≈1:1 dependence. By correlating composition of these calcite products with the Mgtot/Catot of the initial solutions, we find a ≈3:1 dependence that is approximately linear and general to whether calcite is formed via an ACC pathway or by the classical step-propagation process. Comparisons to calcite grown in synthetic seawater show a ≈1:1 dependence. The relationships suggest that the local Mg2+/Ca2+ at the time of precipitation determines the calcite composition, independent of whether growth occurs via an amorphous intermediate or classical pathway for a range of supersaturations and pH conditions. The findings reiterate the need to revisit the traditional picture of chemical and physical controls on CaCO3 polymorph selection. Mineralization by pathways involving ACC can lead to the formation of crystalline phases whose polymorphs and compositions are out of equilibrium with local growth media. As such, classical thermodynamic equilibria may not provide a reliable predictor of observed compositions.

Lake Level Changes in the Mono Basin During the Last Deglacial Period

NASA Astrophysics Data System (ADS)

Wang, X.; Ali, G.; Hemming, S. R.; Zimmerman, S. R. H.; Stine, S. W.; Hemming, G.

2014-12-01

Mono Basin, located in the southwestern corner of the US Great Basin, has long been known to have experienced large lake level changes, particularly during the last deglaciation. But until recently it was not possible to establish a reliable lake level time series. We discovered many visually clean, white, shiny, dense calcite samples in the basin, associated with tufa deposits from high terraces. Their low thorium, but high uranium contents allow precise and reproducible U/Th age determinations. A highly resolved history of a minimum lake level through the last deglaciation can therefore be inferred based on sample locations and their ages. We found that the lake level reached ~2030 m asl at ~20.4 ka, evidenced by calcite coatings on a tufa mound at the upper Wilson Creek. The lake then rose to ~2075 m by ~19.1 ka, shown by calcite cements on conglomerates from the Hansen Cut terrace. The lake climbed to at least ~2140 m at ~15.9 ka, indicated by beach calcites from the east Sierra slope. Such timing of the highest lake stand, occurring within Heinrich Stadial 1, is reinforced by U/Th dates on calcite coatings from widespread locations in the basin, including the Bodie Hills and Cowtrack Mountains. The lake then dropped rapidly to ~2075 m at ~14.5 ka. It stood near this height over the next ~300 years, evidenced by a few-centimeter thick, laminated calcite rims on the Goat Ranch tufa mounds. It subsequently plunged to ~2007 m at ~13.8 ka, indicated by calcite coatings from cemetery road tufa mounds. The lake level came back to ~2030 m at ~12.9 ka, as seen in upper Wilson Creek tufa mounds. The lake level had a few fluctuations within the Younger Dryas, and even shot up to ~2075 m at ~12.0 ka. It then fell to levels in accord with Holocene climatic conditions. Relative to the present lake level of ~1950 m, Mono Lake broadly stood high during Heinrich Stadial 1 and Younger Dryas, when the climate was extremely cold over the North Atlantic, and the Asian monsoon was much weakened. When the climate shifted from cold to warm, the lake dropped significantly, during the transition between Heinrich Stadial 1 and the Bølling time interval, and then during the Allerød period. The U/Th ages on the tufa samples therefore not only establish a highly resolved chronology of hydroclimate history in the Mono Basin, but also put the lake level oscillations in a global context.

Geologic history of the Black Hills caves, South Dakota

USGS Publications Warehouse

Palmer, Arthur N.; Palmer, Margaret; Paces, James B.

2016-01-01

The caves reveal four phases of calcite deposition: eogenetic ferroan calcite (Mississippian replacement of sulfates); white scalenohedra in paleovoids deposited during deep post-Mississippian burial; palisade crusts formed during blockage of springs by Oligocene–Miocene continental sediments; and laminated crusts from late Pleistocene water-table fluctuations. The caves reveal more than 300 m.y. of geologic history and a close relationship to regional geologic events.

Surface area dependence of calcium isotopic reequilibration in carbonates: Implications for isotopic signatures in the weathering zone

NASA Astrophysics Data System (ADS)

Fernandez, N. M.; Druhan, J. L.; Potrel, A.; Jacobson, A. D.

2016-12-01

The concept of dynamic equilibrium carries the implicit assumption of continued isotopic exchange between a mineral and the surrounding fluid. While this effect has received much attention in the marine paleoproxy literature, it has been relatively overlooked in application to the terrestrial environment. In weathering systems, a potential consequence is that rapid reequilibration may alter or erase isotopic signatures generated during secondary mineral formation. The extent and timescale over which isotopic signatures are reset in these hydrologic systems is unknown. Using reactive transport modeling, we show isotopic reequilibration under conditions reflecting terrestrial hydrologic settings to be significant and dependent on the reactive surface area of the solid. In particular, we suggest that the non-traditional stable isotopes commonly used in application to carbonates (e.g., Ca, Mg, Sr) are sensitive to these effects due to their rapid reaction rates. We aim to characterize the dependence of Ca isotopic reequilibration on surface area during calcite precipitation via batch experiments conducted at ambient temperature over 48-hour time periods. Calcite precipitation was performed in a closed batch reactor utilizing a controlled free-drift method. The batch reactors contained mixed supersaturated solutions of CaCl2 and NaHCO3 at an initial pH of 8.54. Precipitation was initiated by seed inoculation of calcite crystals with two distinct, pre-constrained surface areas. All experiments achieved the same final state of chemical equilibrium, but as expected, the fastest approach to equilibrium occurred for experiments employing calcite seeds with the highest surface area. This implies that differences in equilibrated Ca isotope ratios (δ44/40Ca) should reflect differences in surface area. This prediction is upheld by models of the experiments, indicating a measureable difference in δ44Ca during calcite precipitation where the higher surface area corresponds to lower δ44Ca values and a faster approach to isotopic equilibrium. The dependence of δ44Ca resetting on calcite surface areas has broad ramifications for tracing carbonate weathering in the Critical Zone.

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-term study. The results underscore the importance of identifying interactions between natural attenuation pathways and remediation technologies that only target individual contaminants.« less

High resolution ion microprobe investigation of the δ18O of carbonate cements (Jurassic, Paris Basin, France): New insights and pending questions

NASA Astrophysics Data System (ADS)

Vincent, Benoit; Brigaud, Benjamin; Emmanuel, Laurent; Loreau, Jean-Paul

2017-04-01

The scope of this work is to investigate, at a high resolution, the oxygen isotope composition (δ18Ocarb) of diagenetic products (synsedimentary and burial calcite cements) in shallow-marine carbonates. SIMS (Secondary Ion Mass Spectrometry) microprobe analyses were performed on thin sections from Oxfordian and Kimmeridgian Formations of the eastern Paris Basin and compared to data obtained on the same diagenetic products by conventional mass spectrometry (acid digestion). Hereby obtained, δ18O are similar, but the SIMS dataset displays a larger range of values. The isotopic zonation obtained by SIMS transects through sequences of cements filling pores, reveals an (expected) isotopic depletion from older stage synsedimentary calcites to younger stage blocky calcites and that follows the CL (cathodoluminescence) zonation. SIMS analyses however show that synsedimentary cements precipitated in intra-skeletal pores, have heavier δ18O than their inter-particle counterparts, with an offset of + 4‰V-PDB, despite similar petrographical characteristics. This difference is maintained in the δ18O of the first stages of blocky calcite cements, intra-skeletal blocky calcites showing heavier δ18O than the time equivalent and petrographically identical inter-particle calcites, with an offset of + 5‰V-PDB. These offsets are tentatively explained by the precipitation of cements under non-equilibrium conditions in intra-skeletal pores, where organic matter decay may have played a key role, acting notably on the pH. The occurrence of isolated micro-diagenetic environments, co-existing at the thin section scale, is tentatively proposed as an explanation to these small scale and high amplitude δ18O heterogeneities. These results may question the sampling strategy for future works. Microdrilling may miss the observed range of variation, but averaging the values may not necessarily lead to real misinterpretations if a critical selection of samples is performed, targeting potentially similar micro-diagenetic environments and avoiding potentially specific ones, i.e. closed intra-skeletal pores. These results also definitely underscore the need for additional experiments to improve the reliability of SIMS, in order to develop the use of this very high resolution technique for carbonate diagenesis studies.

Colorado Yule Marble; building stone of the Lincoln Memorial

USGS Publications Warehouse

McGee, Elaine S.

1999-01-01

The Colorado Yule marble, quarried in Marble, Colo., is a very pure white marble, and it has been widely acclaimed for its quality and purity. This marble has been used for many prominent buildings; one of the most notable is the Lincoln Memorial in Washington, D.C., built nearly 80 years ago. Although most of the marble in the memorial appears to be in very good condition, some of the stones have developed pronounced surficial roughness and show a significant loss of carved details and rounded edges compared with adjacent stones. Because adjacent blocks of marble receive nearly identical exposure to weathering agents that cause deterioration of the marble, it seems very likely that this pronounced difference in durability of adjacent stones arises from some inherent characteristic of the marble. The Colorado Yule marble is a nearly pure calcite marble with minor inclusions of mica, quartz, and feldspar. Compositions of the calcite and the inclusion phases in the marble are typical for those phases. The calcite grains that compose the marble are irregularly shaped and range from 100 to 600 micrometers in diameter. The texture of the marble is even, with a slight preferred directional elongation that is visible when the marble is cut in certain directions. Physical tests of the marble show that its strength is comparable to that of other marbles typically used in buildings. Variations in the durability of the marble, like those seen at the Lincoln Memorial, are not related to variations in calcite composition or to the presence of inclusions in the marble. Most likely, the variations arise from differences in the calcite grain boundaries and the degree to which the grains interlock with one another. Weak grain boundaries that permit water or solutions to penetrate into the marble and dissolve the calcite grains at their edges cause the marble to disaggregate or ?sugar.? Subtle differences in texture that occur in the marble from various parts of the quarry probably cause some stones to be more susceptible to this form of deterioration. These differences may not be readily visible when the stone is freshly quarried.

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 inorganic precipitation experiments.

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-established salting-in phenomena of the Hofmeister series. The new insights from this experimental study reiterate the importance of electrolytes in reactions involving mineral-water interfaces and suggest a role for seemingly inert `spectator' ions in regulating the local timing and placement of minerals during biomineralization.

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 characterization suggest that urea hydrolysis occurred primarily within the upper portion of the inter-wellbore zone and that strontium was mobilized from cation exchange sites and subsequently co-precipitated with new calcium carbonate.« less

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 increasingly co-precipitated as all ions are indiscriminately incorporated at higher precipitation rates. The temperature dependence is likely to reflect the higher miscibility of ions in minerals, commonly observed in geochemical systems at higher temperatures.« less

Postorogenic carbonatites at Eden Lake, Trans-Hudson Orogen (northern Manitoba, Canada): Geological setting, mineralogy and geochemistry

NASA Astrophysics Data System (ADS)

Chakhmouradian, A. R.; Mumin, A. H.; Demény, A.; Elliott, B.

2008-07-01

The Eden Lake pluton in the Trans-Hudson Orogen is the first known occurrence of carbonatites in Manitoba. The pluton is largely made up of modally and geochemically diverse syenitic rocks derived from postorogenic magma(s) of shoshonitic affinity. Their diversity can be accounted for by a combination of crystal fractionation and fluid release in the final evolutionary stage (crystallization of quartz alkali-feldspar syenite). At Eden Lake, carbonatites, represented predominantly by coarse-grained massive to foliated sövite, occur as branching veins and lenticular bodies up to 4 m in thickness showing crosscutting relations with respect to all of the syenitic units. The host rocks are intensely fenitized at the contact, and there is also abundant mineralogical and textural evidence for assimilation of silicate material by carbonatitic magma through wallrock reaction and xenolith fragmentation and digestion. The bulk of the carbonatites are composed of (in order of crystallization): Sr-REE-rich fluorapatite, aegirine-augite, and coarse calcite crystals surrounded by fine-grained calcite (on average, ˜ 90 vol.% of the rock). Noteworthy accessory constituents are celestine, bastnäsite-(Ce) (both as primary inclusions in calcite), Nb-Zr-rich titanite, low-Hf zircon, allanite-(Ce) and andradite. The calcite is chemically uniform (Sr-rich, Mg-Mn-Fe-poor and low in 13C), but shows clear evidence of ductile deformation and syndeformational cataclasis. Geochemically, the carbonatites are enriched in Sr, Ba, light rare-earth elements, Th and U, but depleted in high-field-strength elements (particularly, Ti, Nb and Ta). The stable-isotope composition of coarse- and fine-grained calcite from the carbonatites and interstitial calcite from syenites is remarkably uniform: ca. - 8.16 ± 0.27‰ δ13C (PDB) and + 8.04 ± 0.19‰ δ18O (SMOW). The available textural and geochemical evidence indicates that the Eden Lake carbonatites are not consanguineous with the associated syenites and may have been derived from a Nb-Ti-retentive and 13C-depleted source such as the subducted crustal material underlying the Eden Lake deformation corridor.

Organic Combustion in the Presence of Ca-Carbonate and Mg-Perchlorate: A Possible Source for the Low Temperature CO2 Release Seen in Mars Phoenix Thermal and Evolved Gas Analyzer Data

NASA Technical Reports Server (NTRS)

Archer, Douglas; Ming, D.; Niles, P.; Sutter, B.; Lauer, H.

2012-01-01

Two of the most important discoveries of the Phoenix Lander were the detection of approx.0.6% perchlorate [1] and 3-5% carbonate [2] in landing site soils. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander could heat samples up to approx.1000 C and monitor evolved gases with a mass spectrometer. TEGA detected a low (approx.350 C) and high (approx.750 C) temperature CO2 release. The high temp release was attributed to the thermal decomposition of Ca-carbonate (calcite). The low temperature CO2 release could be due to desorption of CO2, decomposition of a different carbonate mineral, or the combustion of organic material. A new hypothesis has also been proposed that the low temperature CO2 release could be due to the early breakdown of calcite in the presence of the decomposition products of certain perchlorate salts [3]. We have investigated whether or not this new hypothesis is also compatible with organic combustion. Magnesium perchlorate is stable as Mg(ClO4)2-6H2O on the martian surface [4]. During thermal decomposition, this perchlorate salt releases H2O, Cl2, and O2 gases. The Cl2 can react with water to form HCl which then reacts with calcite, releasing CO2 below the standard thermal decomposition temperature of calcite. However, when using concentrations of perchlorate and calcite similar to what was detected by Phoenix, the ratio of high:low temperature CO2 evolved is much larger in the lab, indicating that although this process might contribute to the low temp CO2 release, it cannot account for all of it. While H2O and Cl2 cause calcite decomposition, the O2 evolved during perchlorate decomposition can lead to the combustion of any reduced carbon present in the sample [5]. We investigate the possible contribution of organic molecules to the low temperature CO2 release seen on Mars.

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.

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.

Speleothem chronology with sub-annual resolution in a near-entrance cave setting using oxygen isotope and trace element records

NASA Astrophysics Data System (ADS)

Carlson, P. E.; Miller, N. R.; Banner, J.; Breecker, D.

2016-12-01

Speleothems that grow in well-ventilated zones of caves are typically avoided when selecting specimens for paleoclimate reconstruction, due to concerns about evaporation and kinetic isotope effects. Near-entrance cave environments are characterized by near-ambient CO2 concentrations year-round and are influenced by surface temperature fluctuations. At Westcave Preserve (Westcave), a shallow, well-ventilated cave in central Texas, we have found seasonal temperature differences recorded in both the oxygen isotope and trace element compositions of speleothem calcite. The seasonal nature of these records has been confirmed by monitoring the chemical composition of drip water and substrate calcite since 2009 (Feng et al., 2014; Casteel and Banner, 2015). We present an ultrahigh-resolution (weekly to monthly) record of δ18O, Mg, Sr, and Ba in Westcave stalagmite WC-3, as well as monthly measurements of drip water geochemistry. We find drip water δ18O and [Mg] are essentially invariant, while seasonal variations in stalagmite calcite δ18O and Mg compositions are in good agreement with predicted temperature-dependent fractionation between water and calcite. Both drip water and speleothem calcite Sr and Ba vary seasonally, which we hypothesize is due to seasonal changes in moisture conditions in the epikarst. We use each of these annual geochemical cycles as independent chronological controls in order to develop a single age model for the stalagmite. These independent chronological counts are consistent with each other, and with 14C bomb-peak and U-series evidence. We argue that the potential for this kind of multi-proxy, seasonally-resolved dating in near-entrance stalagmites makes them especially valuable paleoclimate archives that should not be ignored in speleothem studies.

Trichomes of Tobacco Excrete Zinc as Zinc-Substituted Calcium Carbonate and Other Zinc-Containing Compounds1[W

PubMed Central

Sarret, Géraldine; Harada, Emiko; Choi, Yong-Eui; Isaure, Marie-Pierre; Geoffroy, Nicolas; Fakra, Sirine; Marcus, Matthew A.; Birschwilks, Mandy; Clemens, Stephan; Manceau, Alain

2006-01-01

Tobacco (Nicotiana tabacum L. cv Xanthi) plants were exposed to toxic levels of zinc (Zn). Zn exposure resulted in toxicity signs in plants, and these damages were partly reduced by a calcium (Ca) supplement. Confocal imaging of intracellular Zn using Zinquin showed that Zn was preferentially accumulated in trichomes. Exposure to Zn and Zn + Ca increased the trichome density and induced the production of Ca/Zn mineral grains on the head cells of trichomes. These grains were aggregates of submicrometer-sized crystals and poorly crystalline material and contained Ca as major element, along with subordinate amounts of Zn, manganese, potassium, chlorine, phosphorus, silicon, and magnesium. Micro x-ray diffraction revealed that the large majority of the grains were composed essentially of metal-substituted calcite (CaCO3). CaCO3 polymorphs (aragonite and vaterite) and CaC2O4 (Ca oxalate) mono- and dihydrate also were identified, either as an admixture to calcite or in separate grains. Some grains did not diffract, although they contained Ca, suggesting the presence of amorphous form of Ca. The presence of Zn-substituted calcite was confirmed by Zn K-edge micro-extended x-ray absorption fine structure spectroscopy. Zn bound to organic compounds and Zn-containing silica and phosphate were also identified by this technique. The proportion of Zn-substituted calcite relative to the other species increased with Ca exposure. The production of Zn-containing biogenic calcite and other Zn compounds through the trichomes is a novel mechanism involved in Zn detoxification. This study illustrates the potential of laterally resolved x-ray synchrotron radiation techniques to study biomineralization and metal homeostasis processes in plants. PMID:16731580

Parametric Raman anti-Stokes laser at 503 nm with phase-matched collinear beam interaction of orthogonally polarized Raman components in calcite under 532 nm 20 ps laser pumping

NASA Astrophysics Data System (ADS)

Smetanin, Sergei; Jelínek, Michal; Kubeček, Václav

2017-05-01

Lasers based on stimulated-Raman-scattering process can be used for the frequency-conversion to the wavelengths that are not readily available from solid-state lasers. Parametric Raman lasers allow generation of not only Stokes, but also anti-Stokes components. However, practically all the known crystalline parametric Raman anti-Stokes lasers have very low conversion efficiencies of about 1 % at theoretically predicted values of up to 40 % because of relatively narrow angular tolerance of phase matching in comparison with angular divergence of the interacting beams. In our investigation, to widen the angular tolerance of four-wave mixing and to obtain high conversion efficiency into the antiStokes wave we propose and study a new scheme of the parametric Raman anti-Stokes laser at 503 nm with phasematched collinear beam interaction of orthogonally polarized Raman components in calcite under 532 nm 20 ps laser pumping. We use only one 532-nm laser source to pump the Raman-active calcite crystal oriented at the phase matched angle for orthogonally polarized Raman components four-wave mixing. Additionally, we split the 532-nm laser radiation into the orthogonally polarized components entering to the Raman-active calcite crystal at the certain incidence angles to fulfill the tangential phase matching compensating walk-off of extraordinary waves for collinear beam interaction in the crystal with the widest angular tolerance of four-wave mixing. For the first time the highest 503-nm anti-Stokes conversion efficiency of 30 % close to the theoretical limit of about 40 % at overall optical efficiency of the parametric Raman anti-Stokes generation of up to 3.5 % in calcite is obtained due to realization of tangential phase matching insensitive to the angular mismatch.

Enzymatic, urease-mediated mineralization of gellan gum hydrogel with calcium carbonate, magnesium-enriched calcium carbonate and magnesium carbonate for bone regeneration applications.

PubMed

Douglas, Timothy E L; Łapa, Agata; Samal, Sangram Keshari; Declercq, Heidi A; Schaubroeck, David; Mendes, Ana C; der Voort, Pascal Van; Dokupil, Agnieszka; Plis, Agnieszka; De Schamphelaere, Karel; Chronakis, Ioannis S; Pamuła, Elżbieta; Skirtach, Andre G

2017-12-01

Mineralization of hydrogel biomaterials is considered desirable to improve their suitability as materials for bone regeneration. Calcium carbonate (CaCO 3 ) has been successfully applied as a bone regeneration material, but hydrogel-CaCO 3 composites have received less attention. Magnesium (Mg) has been used as a component of calcium phosphate biomaterials to stimulate bone-forming cell adhesion and proliferation and bone regeneration in vivo, but its effect as a component of carbonate-based biomaterials remains uninvestigated. In the present study, gellan gum (GG) hydrogels were mineralized enzymatically with CaCO 3 , Mg-enriched CaCO 3 and magnesium carbonate to generate composite biomaterials for bone regeneration. Hydrogels loaded with the enzyme urease were mineralized by incubation in mineralization media containing urea and different ratios of calcium and magnesium ions. Increasing the magnesium concentration decreased mineral crystallinity. At low magnesium concentrations calcite was formed, while at higher concentrations magnesian calcite was formed. Hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 .4H 2 O) formed at high magnesium concentration in the absence of calcium. The amount of mineral formed and compressive strength decreased with increasing magnesium concentration in the mineralization medium. The calcium:magnesium elemental ratio in the mineral formed was higher than in the respective mineralization media. Mineralization of hydrogels with calcite or magnesian calcite promoted adhesion and growth of osteoblast-like cells. Hydrogels mineralized with hydromagnesite displayed higher cytotoxicity. In conclusion, enzymatic mineralization of GG hydrogels with CaCO 3 in the form of calcite successfully reinforced hydrogels and promoted osteoblast-like cell adhesion and growth, but magnesium enrichment had no definitive positive effect. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Diagenetic evaluation of Pannonian lacustrine deposits in the Makó Trough, southeastern Hungary

NASA Astrophysics Data System (ADS)

Szőcs, Emese; Milovský, Rastislav; Gier, Susanne; Hips, Kinga; Sztanó, Orsolya

2017-04-01

The Makó Trough is the deepest sub-basin of the Pannonian Basin. As a possible shale gas and tight gas accumulation the area was explored by several hydrocarbon companies. In this study, we present the preliminary results on the diagenetic history and the porosity evolution of sandstones and shales. Petrographic (optical microscopy, CL, blue light microscopy) and geochemical methods (SEM-EDX, WDX, O and C stable isotopes) were applied on core samples of Makó-7 well (3408- 5479 m). Processes which influenced the porosity evolution of the sandstones were compaction, cementation, mineral replacement and dissolution. The most common diagenetic minerals are carbonates (non-ferroan and Fe-bearing calcite, dolomite and ankerite), clay minerals (kaolinite, mixed layer illite-smectite and chlorite) and other silicates (quartz and feldspar). Initial clay mineral and ductile grain content also influences reservoir quality. The volumetrically most significant diagenetic minerals are calcite and clay minerals. The petrography of calcite is variable (bright orange to dull red luminescence color, pore-filling cement, replacive phases which are occasionally scattered in the matrix). The δ13 C-PDB values of calcite range from 1.7 ‰ to -5.5 ‰, while δ18 O-PDB values range from 0.5 ‰ to -9.1 ‰, no depth related trend was observed. These data suggest that calcite occurs in more generations, i.e. eogenetic pre-compactional and mesogenetic post-compactional. Kaolinite is present in mottles in size similar to detrital grains, where remnants of feldspars can be seen. This indicates feldspar alteration via influx of water rich in organic derived carbon dioxide. Secondary porosity can be observed in carbonates and feldspars at some levels, causing the improvement of the reservoir quality.

Contrasting Impact of Future CO2 Emission Scenarios on the Extent of CaCO3 Mineral Undersaturation in the Humboldt Current System

NASA Astrophysics Data System (ADS)

Franco, A. C.; Gruber, N.; Frölicher, T. L.; Kropuenske Artman, L.

2018-03-01

The eastern boundary upwelling systems are among those regions that are most vulnerable to an ocean acidification-induced transition toward undersaturated conditions with respect to mineral CaCO3, but no assessment exists yet for the Humboldt Current System. Here we use a high-resolution (˜7.5 km) regional ocean model to investigate past and future changes in ocean pH and CaCO3 saturation state in this system. We find that within the next few decades, the nearshore waters off Peru are projected to become corrosive year round with regard to aragonite, the more soluble form of CaCO3. The volume of aragonite undersaturated water off Peru will continue to increase in the future irrespective of the amount of CO2 emitted to the atmosphere. In contrast, the development of the saturation state with regard to calcite, a less soluble form of carbonate, depends strongly on the scenario followed. By 2050, calcite undersaturation appears in the nearshore waters off Peru occasionally, but by 2090 in a high-emission scenario (RCP8.5), ˜60% of the water in the euphotic zone will become permanently calcite undersaturated. Most of this calcite undersaturation off Peru can likely be avoided if a low emission scenario (RCP2.6) consistent with the Paris Agreement is followed. The progression of ocean acidification off Chile follows a similar pattern, except that the saturation states are overall higher. But also here, calcite undersaturated waters will become common in the subsurface waters under the RCP8.5 scenario by the end of this century, while this can be avoided under the RCP2.6 scenario.

Glacial to Interglacial Climate and Sea Level Changes Recorded in Submerged Speleothems, Argentarola, Italy

NASA Astrophysics Data System (ADS)

Folz-Donahue, K.; Dutton, A.; Antonioli, F.; Richards, D. A.; Nita, D. C.; Lambeck, K.

2014-12-01

Direct records of Quaternary sea level change can provide insight on the timing and nature of ice sheet retreat during glacial terminations. Such records are generally rare, particularly prior to the last deglaciation, due in part to the difficulty of recovering material from sites that have been submerged by subsequent sea-level rise. A suite of stalagmites recovered from a submerged cave on Argentarola Island in the Tyrrhenian Sea contains hiatuses that were formed when the cave became submerged by seawater. These hiatuses are remarkable due to the presence of calcite tubes secreted by serpulid worms, providing direct evidence of marine inundation. As sea level drops during the following glacial inception, the cave is drained and dense spelean calcite encases the serpulid worm tubes, forming alternating layers of spelean and serpulid calcite. U-Th dates of spelean calcite directly above and below these serpulid layers has previously been used to constrain timing and amplitude of sea level highstands in the Mediterranean. Stable isotope records from the same cave have also been used to indicate increased precipitation across the Mediterranean during Sapropel 6 (175 ka). Here we present U-Th dates and stable isotope records for three Argentarola stalagmites. These specimens were recovered from -22, -18, and -14 m relative to present sea level (rpsl), and complement previously published data for Argentarola stalagmites at -21, -18.5, and -18 m rpsl. The timing and elevation of spelean calcite directly above and below serpulid tube layers provide rare insight on rates of sea-level change between -14 and -22 m during glacial terminations and inceptions prior to the last termination. Stable isotope records from the same stalagmites are used to investigate changes in western Mediterranean climate and potential relationships to Mediterranean sapropel events.

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.

Isotopic evidence for organic matter oxidation by manganese reduction in the formation of stratiform manganese carbonate ore

USGS Publications Warehouse

Okita, P.M.; Maynard, J.B.; Spiker, E. C.; Force, E.R.

1988-01-01

Unlike other marine-sedimentary manganese ore deposits, which are largely composed of manganese oxides, the primary ore at Molango (Hidalgo State, Mexico) is exclusively manganese carbonate (rhodochrosite, Mn-calcite, kutnahorite). Stable isotope studies of the carbonates from Molango provide critical new information relevant to the controversy over syngenetic and diagenetic models of stratiform manganese deposit formation. Negative ??13C values for carbonates from mineralized zones at Molango are strongly correlated with manganese content both on a whole rock scale and by mineral species. Whole rock ??13C data fall into three groups: high-grade ore = -16.4 to -11.5%.; manganese-rich, sub-ore-grade = -5.2 to 0%.; and unmineralized carbonates = 0 to +2.5%. (PDB). ??18O data show considerable overlap in values among the three groups: +4.8 to -2.8, -5.4 to -0.3%., and -7.4 to +6.2 (PDB), respectively. Isotopic data for individual co-existing minerals suggest a similar separation of ??13C values: ??13C values from calcite range from -1.1 to +0.7%. (PDB), whereas values from rhodochrosite are very negative, -12.9 to -5.5%., and values from kutnahorite or Mn-calcite are intermediate between calcite and rhodochrosite. 13C data are interpreted to indicate that calcite (i.e. unmineralized carbonate) formed from a normal marine carbon reservoir. However, 13C data for the manganese-bearing carbonates suggest a mixed seawater and organic source of carbon. The presence of only trace amounts of pyrite suggests sulfate reduction may have played a minor part in oxidizing organic matter. It is possible that manganese reduction was the predominant reaction that oxidized organic matter and that it released organic-derived CO2 to produce negative ??13C values and manganese carbonate mineralization. ?? 1988.

The chronology for the d18O record from Devils Hole, Nevada, extended into the Mid-Holocene

USGS Publications Warehouse

Landwehr, J.M.; Sharp, W.D.; Coplen, T.B.; Ludwig, K. R.; Winograd, I.J.

2011-01-01

This report presents the numeric values for the chronology of the paleoclimatically relevant mid-to-late Pleistocene record of the ratios of stable oxygen isotope (delta18O) in vein calcite from Devils Hole, Nev., which recently had been extended into the mid-Holocene. Dating was obtained using 230Th-234U-238U thermal ionization mass spectrometry. Devils Hole is a subaqueous cave of tectonic origin, which developed in the discharge zone of a regional aquifer in south-central Nevada. The primary groundwater recharge source area is the Spring Mountains, the highest mountain range in southern Nevada [altitude 3,630 meters (m)], approximately 80 kilometers to the east of the cavern. The walls of the open fault zone comprising the cave system are coated with dense vein calcite precipitated from the through-flowing groundwater. The calcite, up to 40 centimeters (cm) thick, contains a continuous record of the sequential variation of the composition of stable oxygen isotopes in the ground water over time. The vein calcite has also proven to be a suitable material for precise uranium-series dating via thermal ionization mass spectrometry utilizing the 230Th-234U-238U decay clock. Earlier work has presented data from the Devils Hole core DH-11, a 36-cm-long core of vein calcite recovered from a depth of about 30 m below the water table (about 45 m beneath the ground surface). The DH-11 core provided a continuous record of isotopic oxygen variation from 567,700 to 59,800 years before present. Recent work has extended this record up to 4,500 years before present, into the mid-Holocene epoch.

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.

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.

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.

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.

Growth and Mortality of Coccolithophores during spring in the Celtic Sea

NASA Astrophysics Data System (ADS)

Mayers, K.; Poulton, A. J.; Giering, S. L. C.; Daniels, C. J.; Wells, S. R.; Tarran, G.

2016-02-01

Coccolithophores are an important group of single celled protists which dominate pelagic calcite production, however little is currently known about the mortality rates within this group, or their importance in shelf seas regarding productivity and nutrient recycling. Measurements of coccolithophore calcification and cellular calcite quotas, as well as dilution experiments for microzooplankton grazing rates, were made during a spring cruise (April, 2015) in the Celtic Sea (NW European Shelf) and within an April bloom of Emiliania huxleyi. Calcite production and coccolithophore cell numbers showed a general positive trend throughout the progression of the spring bloom, ranging from 15 - 34µmol C m-3d-1 and 6 - 94 cells ml-1. Cell normalised calcification rates declined from 3 - 0.6 pmol C cell-1d-1 due to a shift from a mixed community to an E. huxleyi dominated one. Within the E. huxleyi bloom we recorded high daily calcite production (6049 µmol C m-3d-1) and cell normalised calcification of 3 pmol C cell-1d-1. This is significantly higher than E. huxleyi dominated sites in the Iceland Basin and more similar to a bloom on the Patagonian Shelf. Within the E. huxleyi bloom, mortality rates were 0.23 d-1 compared with growth rates of 0.29 d-1, meaning 80% of daily calcification was removed by grazers. In this study, coccolithophore mortality rates are presented from the central Celtic Sea throughout spring, and compared with an April E. huxleyi bloom in terms of species composition, trends in calcite production and composition of the phytoplankton community. These observations will potentially elucidate the role grazing plays in the fate of calcium carbonate, bloom formation and community composition.

A computational method for selecting short peptide sequences for inorganic material binding.

PubMed

Nayebi, Niloofar; Cetinel, Sibel; Omar, Sara Ibrahim; Tuszynski, Jack A; Montemagno, Carlo

2017-11-01

Discovering or designing biofunctionalized materials with improved quality highly depends on the ability to manipulate and control the peptide-inorganic interaction. Various peptides can be used as assemblers, synthesizers, and linkers in the material syntheses. In another context, specific and selective material-binding peptides can be used as recognition blocks in mining applications. In this study, we propose a new in silico method to select short 4-mer peptides with high affinity and selectivity for a given target material. This method is illustrated with the calcite (104) surface as an example, which has been experimentally validated. A calcite binding peptide can play an important role in our understanding of biomineralization. A practical aspect of calcite is a need for it to be selectively depressed in mining sites. © 2017 Wiley Periodicals, Inc.

Crystallization of calcium carbonate with the filtration of aqueous solutions through a microporous membrane

NASA Astrophysics Data System (ADS)

Ananeva, E. A.; Mesyats, E. A.; Sergievskii, V. V.

2017-11-01

It is established that the filtration of water through a microporous membrane does not change the hardness of the water; it does, however, reduce the amount of scale deposit, due to the crystallization of salts in water in the form of aragonite. The effect is consistently observed in water with a hardness of more than 7.0 H, a content of hydrocarbonate ions of more than 500 mg/L, and a pH ≥ 7.3. It is shown that introducing the seeds of calcite crystals into a filtrate results in the precipitation of calcite rather than aragonite. It is concluded that quasi-softening in the case of hard water microfiltration is caused by the removal of calcite micronuclei, and thus by conditions being created for the crystallization of aragonite as a thermodynamically less stable form.

A lacustrine carbonate record of Holocene seasonality and climate

USGS Publications Warehouse

Wittkop, Chad A.; Teranes, Jane L.; Dean, Walter E.; Guilderson, Thomas P.

2009-01-01

Annually laminated (varved) Holocene sediments from Derby Lake, Michigan, display variations in endogenic calcite abundance reflecting a long-(millennial-scale) decrease in burial punctuated with frequent short- (decadal-scale) oscillations due to carbonate dissolution. Since 6000 cal yr B.P., sediment carbonate abundance has followed a decreasing trend while organic-carbon abundance has increased. The correlation between organic-carbon abundance and the sum of March-April-October-November insolation has an r2 value of 0.58. We interpret these trends to represent a precession-driven lengthening of the Holocene growing season that has reduced calcite burial by enhancing net annual organic-matter production and associated calcite dissolution. Correlations with regional paleoclimate records suggest that changes in temperature and moisture balance have impacted the distribution of short- oscillations in carbonate and organic-matter abundance superimposed on the precession-driven trends.

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.

Comment on “Reconciliation of the Devils Hole climate record with orbital forcing”

USGS Publications Warehouse

Winograd, Isaac J.

2016-01-01

Moseley et al. (Reports, 8 January 2016, p. 165) postulate an increase in dissolved thorium isotope 230Th with depth below the water table as the explanation for the differing ages of Termination II. Flow of geothermal water through the Devils Hole caverns precludes this explanation. Deposition of younger secondary calcite into the initial porosity of the calcite comprising their cores is a plausible alternate explanation.

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.

Biomineral nanoparticles are space-filling.

PubMed

Yang, Li; Killian, Christopher E; Kunz, Martin; Tamura, Nobumichi; Gilbert, P U P A

2011-02-01

Sea urchin biominerals have been shown to form from aggregating nanoparticles of amorphous calcium carbonate (ACC), which then crystallize into macroscopic single crystals of calcite. Here we measure the surface areas of these biominerals and find them to be comparable to those of space-filling macroscopic geologic calcite crystals. These biominerals differ from synthetic mesocrystals, which are invariably porous. We propose that space-filling ACC is the structural precursor for echinoderm biominerals.

Comment on “Reconciliation of the Devils Hole climate record with orbital forcing”

NASA Astrophysics Data System (ADS)

Winograd, Isaac J.

2016-10-01

Moseley et al. (Reports, 8 January 2016, p. 165) postulate an increase in dissolved thorium isotope 230Th with depth below the water table as the explanation for the differing ages of Termination II. Flow of geothermal water through the Devils Hole caverns precludes this explanation. Deposition of younger secondary calcite into the initial porosity of the calcite comprising their cores is a plausible alternate explanation.

Neoproterozoic marine carbonates and their paleoceanographic significance

NASA Astrophysics Data System (ADS)

Hood, Ashleigh van Smeerdijk; Wallace, Malcolm William

2018-01-01

The primary mineralogy of marine carbonate precipitates has been a crucial factor in constraining the major element composition of ancient oceans. Secular changes in Phanerozoic marine chemistry, including Mg/Ca, have been well-documented using the original carbonate mineralogy of ooids, marine cements and biominerals. However, the history of Precambrian seawater chemistry is not as well constrained, partially due to the prevalence of dolomitisation in the Precambrian geological record. The Neoproterozoic ( 1000 Ma to 541 Ma) record of primary carbonate mineralogy is documented here using a combination of literature data and new analysis of marine carbonate precipitates from the Otavi Fold Belt, Namibia, the Death Valley succession, USA and the Adelaide Fold Belt, Australia. These data suggest that the last 460 million years of the Proterozoic were dominated by aragonite and high-Mg calcite precipitation in shallow marine settings. In contrast, low-Mg calcite has only been recognised in a small number of formations. In addition to aragonite and calcite precipitation, marine dolomite precipitation was widespread in Neoproterozoic oceans, including mimetic (syn-sedimentary) dolomitisation and primary dolomite marine cementation. The combination of marine aragonite, high Mg-calcite and dolomite precipitation during the Neoproterozoic suggests extremely high seawater Mg/Ca conditions relative to Phanerozoic oceans. Marine dolomite precipitation may also be linked to widespread marine anoxia during this time.

Amorphous and crystalline calcium carbonate distribution in the tergite cuticle of moulting Porcellio scaber (Isopoda, Crustacea).

PubMed

Neues, Frank; Hild, Sabine; Epple, Matthias; Marti, Othmar; Ziegler, Andreas

2011-07-01

The main mineral components of the isopod cuticle consists of crystalline magnesium calcite and amorphous calcium carbonate. During moulting isopods moult first the posterior and then the anterior half of the body. In terrestrial species calcium carbonate is subject to resorption, storage and recycling in order to retain significant fractions of the mineral during the moulting cycle. We used synchrotron X-ray powder diffraction, elemental analysis and Raman spectroscopy to quantify the ACC/calcite ratio, the mineral phase distribution and the composition within the anterior and posterior tergite cuticle during eight different stages of the moulting cycle of Porcellio scaber. The results show that most of the amorphous calcium carbonate (ACC) is resorbed from the cuticle, whereas calcite remains in the old cuticle and is shed during moulting. During premoult resorption of ACC from the posterior cuticle is accompanied by an increase within the anterior tergites, and mineralization of the new posterior cuticle by resorption of mineral from the anterior cuticle. This suggests that one reason for using ACC in cuticle mineralization is to facilitate resorption and recycling of cuticular calcium carbonate. Furthermore we show that ACC precedes the formation of calcite in distal layers of the tergite cuticle. Copyright © 2011 Elsevier Inc. All rights reserved.

ACBC to Balcite: Bioinspired Synthesis of a Highly Substituted High-Temperature Phase from an Amorphous Precursor

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

Whittaker, Michael L.; Joester, Derk

2017-04-28

Energy-efficient synthesis of materials locked in compositional and structural states far from equilibrium remains a challenging goal, yet biomineralizing organisms routinely assemble such materials with sophisticated designs and advanced functional properties, often using amorphous precursors. However, incorporation of organics limits the useful temperature range of these materials. Herein, the bioinspired synthesis of a highly supersaturated calcite (Ca0.5Ba0.5CO3) called balcite is reported, at mild conditions and using an amorphous calcium–barium carbonate (ACBC) (Ca1- x Ba x CO3·1.2H2O) precursor. Balcite not only contains 50 times more barium than the solubility limit in calcite but also displays the rotational disorder on carbonate sitesmore » that is typical for high-temperature calcite. It is significantly harder (30%) and less stiff than calcite, and retains these properties after heating to elevated temperatures. Analysis of balcite local order suggests that it may require the formation of the ACBC precursor and could therefore be an example of nonclassical nucleation. These findings demonstrate that amorphous precursor pathways are powerfully enabling and provide unprecedented access to materials far from equilibrium, including high-temperature modifications by room-temperature synthesis.« less

Batch sorption results for neptunium transport through Yucca Mountain tuffs. Yucca Mountain Site Characterization Program milestone 3349

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

Triay, I.R.; Cotter, C.R.; Huddleston, M.H.

1996-09-01

We studied the sorption of neptunium onto tuffs characteristic of the proposed nuclear waste repository at Yucca Mountain, Nevada. The neptunium was in the Np(V) oxidation state under oxidizing conditions in groundwaters from two wells located close to the repository site (J-13 and UE-25 p No.1). We used devitrified, vitric, zeolitic (with emphasis on clinoptilolite-rich samples), and calcite-rich tuffs characteristic of the geology of the site. Neptunium sorbed well onto calcite and calcite-rich tuffs, indicating that a significant amount of neptunium retardation can be expected under fractured-flow scenarios because of calcite coating of the fractures. Neptunium sorption onto clinoptilolite-rich zeoliticmore » tuffs in J-13 well water (pH from 7 to 8.5) was moderate, increased with decreasing pH, and correlated to surface area and amount of clinoptilolite. Neptunium sorbed poorly onto zeolitic tuffs from UE-25 p No.1 groundwater (pH from 7 to 9) and onto devitrified and vitric tuffs from J-13 and UE-25 p No.1 waters (pH from 7 to 9). Iron oxides appeared to be passivated in tuffs, not seeming to contribute to the observed neptunium sorption, even though neptunium sorption onto synthetic iron oxide is significant.« less

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.

Comparative thermometry on pelitic rocks and marbles of the Llano uplift, Texas

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

Letargo, C.M.R.; Lamb, W.M.

1992-01-01

The Llano Uplift in central Texas is a Grenville-aged metamorphic complex consisting of amphibolite facies assemblages whose development has been attributed to the emplacement of granite plutons between 1.0--1.1 Ga. Temperatures have been obtained from garnet-biotite, garnet-ilmenite, and calcite-dolomite pairs as well as from various silicate equilibria. Application of these geothermometers yield consistent results and are thus indicative of peak conditions attending the amphibolite facies metamorphism. Temperature determined using garnet-biotite and garnet-ilmenite thermometry compare favorably with calcite-dolomite temperatures obtained from marbles in contact with granite plutons in the southeastern part of the uplift. The highest calcite-dolomite temperatures of [approximately]600 Cmore » are obtained from marbles containing an isobarically invariant assemblage consisting of calcite + dolomite + diopside + tremolite + forsterite. At pressures of 2--3 kbar, this isobarically invariant assemblage will be stable at a temperature range of [approximately]600--650 C. Also in close proximity to granites in the southeast uplift is the assemblage muscovite + quartz + k-feldspar + sillimanite [approximately] andalusite which indicate T 650 C and P 2.5 kbar. Assemblages consisting of garnet + sillimanite + quartz + plagioclase (GASP) and garnet + rutile + ilmenite + plagioclase + quartz (GRIPS) are currently being studied to provide additional constraints on pressures of amphibolite facies metamorphism.« less

The sunstone and polarised skylight: ancient Viking navigational tools?

NASA Astrophysics Data System (ADS)

Ropars, Guy; Lakshminarayanan, Vasudevan; Le Floch, Albert

2014-10-01

Although the polarisation of the light was discovered at the beginning of the nineteenth century, the Vikings could have used the polarised light around the tenth century in their navigation to America, using a 'sunstone' evoked in the Icelandic Sagas. Indeed, the birefringence of the Iceland spar (calcite), a common crystal in Scandinavia, permits a simple observation of the axis of polarisation of the skylight at the zenith. From this, it is possible to guess the azimuth of a hidden Sun below the horizon, for instance. The high sensitivity of the differential method provided by the ordinary and extraordinary beams of calcite at its so-called isotropy point is about two orders higher than that of the best dichroic polariser and permits to reach an accuracy of ±1° for the Sun azimuth (at sunrise and sunset). Unfortunately, due to the relative fragility of calcite, only the so-called Alderney crystal was discovered on board a 16th ancient ship. Curiously, beyond its use as a sunstone by the Vikings, during these last millennia calcite has led to the discovery of the polarisation of the light itself by Malus and is currently being used to detect the atmospheres of exoplanets. Moreover, the differential method for the light polarisation detection is widely used in the animal world.

Bio-grout based on microbially induced sand solidification by means of asparaginase activity

PubMed Central

Li, Mengmeng; Fu, Qing-Long; Zhang, Qiuzhuo; Achal, Varenyam; Kawasaki, Satoru

2015-01-01

Bio-grout, a new ground improvement method, has been recently developed to improve the mechanical properties, decrease the permeability of porous materials, reinforce or repair cementitious materials and modify the properties of soil or sand. Bio-grout production depends on microbially induced calcite precipitation (MICP), which is driven mainly by an enzyme, urease. However, urease-based MICP process produces excessive ammonia, in addition to secondary pollution generated by urea that is used as substrate in it. In the present study, we reported asparaginase-based MICP process for sand bio-grout development using Bacillus megaterium, and results were also compared with urease-based bio-grouts. The asparaginase activity led to significantly less ammonia production compared to urease without compromising with desired properties of a novel grout. The UCS of bio-grout was obtained at 980 kPa, while the permeability was decreased substantially. The mineralogical composition of precipitated substance was identified as calcite using XRD and the crystal morphology was observed under SEM. The mass percentage of calcite in bio-grout was calculated by thermogravimetric analysis and XCT verified calcite precipitation in it. The results confirmed that biocalcification by means of bacterial asparaginase is a potential solution for geotechnical problems. The asparaginase-based MICP process could be of wider acceptance in future. PMID:26525435

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.

Laboratory study of fungal bioreceptivity of different fractions of composite flooring tiles showing efflorescence.

PubMed

Masaphy, Segula; Lavi, Ido; Sultz, Stephan; Zabari, Limor

2014-06-01

Fungi can grow in extreme habitats, such as natural stone and mineral building materials, sometimes causing deterioration. Efflorescence-concentrated salt deposits-results from water movement through building material; it can damage masonry materials and other bricks. Fungal isolate KUR1, capable of growth on, and dissolution of stone chips composing terrazzo-type floor tiles, was isolated from such tiles showing fiber-like crystalline efflorescence. The isolate's ribosomal DNA sequences were 100 % identical to those of Nigrospora sphaerica. The ability of KUR1 to colonize and degrade the different stone chips composing the tiles was studied in axenic culture experiments. When exposed to each of the different mineral chip types composed of dolomite, calcite, or calcite-apatite mineral in low-nutrition medium, the fungus showed selective nutrient consumption, and different growth and stone mineral dissolution rates. Micromorphological examination of the fungus-colonized chips by electron microscopy showed the production of a fungal biofilm with thin films around the hyphae on the surface of the examined chips and disintegration of the calcite-apatite fraction. More than 70 % dissolution of the introduced powdered (<1 mm particle size) mineral was obtained within 10 days of incubation for the soft calcite-apatite fraction.

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 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.

The effect of CO2 at low temperature and pressure on solutions supersaturated with silica in the presence of limestone and dolomite

USGS Publications Warehouse

Lovering, T.G.; Patten, L.E.

1962-01-01

The effect of 1 atm of CO2 over initially neutral solutions supersaturated with silica, at room temperature, as contrasted with 1 atm of air was determined over a period of 5 months, together with changes brought about by the introduction of calcite and dolomite to these solutions in the form of either chips or finely ground powder. In the absence of CO2 all solutions quickly reached equilibrium and no silica precipitated. In the presence of CO2 approximately two-thirds of the silica precipitated as silica gel within the first 2 months; the amount of silica precipitated was not affected by the presence of limestone or dolomite. Silica gel precipitated as a fine powder in the presence of finely ground calcite and dolomite, but as a cloudy gelatinous mass in the presence of coarse chips of dolomite and calcite, and in the absence of either calcite or dolomite. Preferential leaching of calcium from dolomite took place, both in the presence of air and in the presence of CO2, but was more pronounced in the presence of air. There was no evidence of physical replacement of either limestone or dolomite by precipitated silica. ?? 1962.

Formation of amorphous calcium carbonate in caves and its implications for speleothem research.

PubMed

Demény, Attila; Németh, Péter; Czuppon, György; Leél-Őssy, Szabolcs; Szabó, Máté; Judik, Katalin; Németh, Tibor; Stieber, József

2016-12-22

Speleothem deposits are among the most valuable continental formations in paleoclimate research, as they can be dated using absolute dating methods, and they also provide valuable climate proxies. However, alteration processes such as post-depositional mineralogical transformations can significantly influence the paleoclimatic application of their geochemical data. An innovative sampling and measurement protocol combined with scanning and transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy is presented, demonstrating that carbonate precipitating from drip water in caves at ~10 °C contains amorphous calcium carbonate (ACC) that later transforms to nanocrystalline calcite. Stable oxygen isotope fractionations among calcite, ACC and water were also determined, proving that ACC is 18 O-depleted (by >2.4 ± 0.8‰) relative to calcite. This, in turn, has serious consequences for speleothem-based fluid inclusion research as closed system transformation of ACC to calcite may induce a negative oxygen isotope shift in fluid inclusion water, resulting in deterioration of the original compositions. ACC formation increases the speleothems' sensitivity to alteration as its interaction with external solutions may result in the partial loss of original proxy signals. Mineralogical analysis of freshly precipitating carbonate at the studied speleothem site is suggested in order to determine the potential influence of ACC formation.

Copper and zinc removal from roof runoff: from research to full-scale adsorber systems.

PubMed

Steiner, M; Boller, M

2006-01-01

Large, uncoated copper and zinc roofs cause environmental problems if their runoff is infiltrated into the underground or discharged into receiving waters. Since source control is not always feasible, barrier systems for efficient copper and zinc removal are recommended in Switzerland. During the last few years, research carried out in order to test the performance of GIH-calcite adsorber filters as a barrier system. Adsorption and mass transport processes were assessed and described in a mathematical model. However, this model is not suitable for practical design, because it does not give explicit access to design parameters such as adsorber diameter and adsorber bed depth. Therefore, for e.g. engineers, an easy to use design guideline for GIH-calcite adsorber systems was developed, mainly based on the mathematical model. The core of this guideline is the design of the depth of the GIH-calcite adsorber layer. The depth is calculated by adding up the GIH depth for sorption equilibrium and the depth for the mass transfer zone (MTZ). Additionally, the arrangement of other adsorber system components such as particle separation and retention volume was considered in the guideline. Investigations of a full-scale adsorber confirm the successful application of this newly developed design guideline for the application of GIH-calcite adsorber systems in practice.

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.

Rehabilitating acid soils for increasing crop productivity through low-cost liming material.

PubMed

Bhat, Javid Ahmad; Kundu, Manik Chandra; Hazra, Gora Chand; Santra, Gour Hari; Mandal, Biswapati

2010-09-15

Productivity of red and lateritic soils is low because of their acidity and deficiencies in few essential nutrients viz., nitrogen, phosphorus, calcium, zinc, boron, molybdenum etc. We compared the effectiveness of basic slag, a low-cost liming material, with that of calcite as an ameliorant for these soils using mustard followed by rice as test crops. Experiments were conducted with three levels of each of basic slag and calcite along with a control on farmers' fields at 14 different locations. Influence of farmyard manure (FYM) and poultry manure (PM) on the effectiveness of the slag was also tested. On an average, basic slag performed better than calcite in increasing yields of both mustard and rice and left over higher amounts of available Ca, Si and Zn in residual soils. The slag also improved N, P, K and Ca nutrition of mustard and Si and Zn nutrition of rice with a favorable benefit:cost (B:C) ratio over the calcite (4.82 vs. 1.44). Effectiveness of the basic slag improved when it was applied in combination with FYM or PM (B:C, 5.83 and 6.27). Basic slag can, therefore, be advocated for use in the acidic red and lateritic soils for economically improving their productivity. Copyright 2010 Elsevier B.V. All rights reserved.

Carbon and oxygen isotope fractionation in non-marine ostracods: results from a 'natural culture' environment

NASA Astrophysics Data System (ADS)

Keatings, K. W.; Heaton, T. H. E.; Holmes, J. A.

2002-05-01

Carbon and oxygen isotope analysis of ostracods living in the near-constant conditions of spring-fed ponds in southern England allowed accurate determination of the ostracod's calcite-water 13C/12C and 18O/16O fractionations. The 13C/12C fractionations of two species, Candona candida and Pseudocandona rostrata, correspond to values expected for isotopic equilibrium with the pond's dissolved inorganic carbon at the measured temperature (11°C) and pH (6.9), whilst those of a third species, Herpetocypris reptans, would represent equilibrium at a slightly higher pH (7.1). The 18O/16O fractionations confirm two previous studies in being larger, by up to 3‰, than those 'traditionally' regarded as representing equilibrium. When the measured fractionations are considered in the context of more recent work, however, they can be explained in terms of equilibrium if the process of calcite formation at the ostracod lamella occurs at a relatively low pH (≤7) irrespective of the pH of the surrounding water. The pH of calcite formation, and therefore the calcite-water 18O/16O fractionation, may be species and stage (adult versus juvenile) specific, and related to the rate of calcification.

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.

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.

Effect of carbonate content on the mechanical behaviour of clay fault-gouges

NASA Astrophysics Data System (ADS)

Bakker, Elisenda; Niemeijer, André; Hangx, Suzanne; Spiers, Chris

2015-04-01

Carbon dioxide capture and storage (CCS) in depleted oil and gas reservoirs is considered to be the most promising technology to achieve large-scale reduction in anthropogenic emissions. In order to retain the stored CO2 from the atmosphere for the very long-term, i.e. on timescales of the order of 103-104 years, it is essential to maintain the integrity of the caprock, and more specifically of any faults penetrating the seal. When selecting suitable CO2-storage reservoirs, pre-exisiting faults within the caprock require close attention, as changes in the stress state resulting from CO2-injection may induce fault slip motion which might cause leakage. Little is known about the effect of fluid-rock interactions on the mineral composition, mechanical properties and the integrity and sealing capacity of the caprock. Previous studies on the effect of mineral composition on the frictional properties of fault gouges have shown that friction is controlled by the dominant phase unless there is a frictionally weak, through-going fabric. However, the effect on stability is less clear. Since long-term CO2-exposure might cause chemical reactions, potentially resulting in the dissolution or precipitation of carbonate minerals, a change in mineralogy could affect the mechanical stability of a caprock significantly. Calcite, for example, is known to be prone to micro-seismicity and shows a transition from velocity-strengthening to velocity-weakening behaviour around 100-150°C. Therefore, we investigated the effect of varying clay:carbonate ratios on fault friction behaviour, fault reactivation potential and slip stability, i.e. seismic vs. aseismic behaviour. Three types of simulated fault gouges were used: i) carbonate-free, natural clay-rich caprock samples, consisting of predominantly phyllosilicates (~80%) and quartz ~20%), ii) pure calcite, and iii) mixtures of carbonate-free clay-rich caprock and pure calcite, with predetermined clay:carbonate ratios. For the natural clay-rich caprock material we used Opalinus Claystone (Mont Terri, Switserland), which is considered to be an analogue for many shaly caprocks in Europe. We performed rotary shear experiments at in-situ reservoir conditions (T = 20-150˚C, σneff = 50 MPa, Pp = 25 MPa) at shear velocities of 0.22 -100 μm/s. Preliminary results show that the frictional strength of the carbonate-free, natural clay-rich caprock samples is 40-50% lower than for the pure calcite samples. Typical steady-state friction coefficient values obtained for the carbonate-free clay samples are ~0.3-0.4. These values are significantly smaller than the values of ~0.6-0.7 obtained for pure calcite. The friction coefficient values obtained for the mixture plot between the carbonate-free and pure calcite values. The samples show predominantly velocity-strengthening behaviour. However, the 90% pure calcite (and 10% clay-rich caprock) and 100% pure calcite samples show velocity-weakening behaviour at 100-150°C. This suggests that large amounts of carbonates, and thus significant carbonate precipitation as a result of CO2-exposure, are required to cause a transition from aseismic to seismic behaviour, at least under the experimental conditions investigated here.

Recent terebratulide brachiopods: Do they faithfully record oceanographic conditions throughout ontogeny?

NASA Astrophysics Data System (ADS)

Kercher, P.; Carlson, S. J.

2012-12-01

Brachiopods have commonly been used to infer secular changes in ocean chemistry over the Phanerozoic Eon since Lowenstam (1961) concluded that Recent brachiopod calcite was precipitated in equilibrium with seawater. In order to infer paleoenvironmental conditions with confidence, however, the impact of potential kinetic and metabolic fractionation effects on the final isotopic signature, as it varies among individuals, must be determined. In this study, we analyzed the oxygen and carbon isotopic composition of closely spaced (~2/mm) samples of calcite along growth transects from individuals of the rhynchonelliform brachiopod, Laqueus californianus. By combining local oceanographic information with knowledge of brachiopod shell structure and growth patterns through ontogeny, in individuals of different ages from the same locality that died simultaneously, we can address the fidelity of brachiopod shell calcite as both an environmental proxy and a recorder of biological activity among conspecific individuals, in real time. This is an essential, but largely ignored, component in the paleoenvironmental interpretation of brachiopod shell calcite. In May 2011, more than 75 live L. californianus specimens were collected by Dr. J. Barry at Monterey Bay Aquarium Research Institute (MBARI) from Monterey Bay at 160 m water depth (36.7322N, 121.9739W) and generously given to us for use in this study. The specimens range in length from 5.75 to 46.16 mm, representing a range of ontogenetic ages. Water temperatures at 160 m range annually from 8C in the spring/summer upwelling season to 10C during the winter, while salinity fluctuates from 33.76 ppt in the winter to 34.11 ppt in the summer. Daily temperature and salinity data collected by MBARI over three decades allow us to calculate approximate equilibrium calcite values. We use these values to evaluate the claim that brachiopods mineralize in isotopic equilibrium with seawater throughout their lifespan with minimal intraspecific variation. We also use the MBARI data to correlate annual temperature fluctuations with δ18O trends within the calcite to estimate ontogenetic ages and growth rates. Full-grown adults were 10-11 years old when collected live, and grow an average of about 4 mm/year over their lifespan, growing faster before sexual maturity and slowing down after. The early results of the ontogenetic sampling tracts indicate calcite δ18O and δ13C values are strongly positively correlated. This relationship suggests kinetic fractionation effects are likely influencing the isotopic composition of the shells. Cyclic isotopic fluctuations are also recorded, in accordance with seasonal temperature oscillations in Monterey Bay, apparent even at 160 m depth. In most of the specimens, the amplitudes of the isotopic fluctuations exceed those of the predicted equilibrium values. Furthermore, our data support the claim made by other researchers that the outer primary layer of the shell is significantly depleted in both oxygen and carbon isotopes, below the range of equilibrium calcite. Isotopic oscillations across individuals align reasonably well both with each other and with ambient water temperature patterns. These results suggest that intraspecific variability is low in L. californianus and that these organisms are recording their environment similarly.

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

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

Smith, Robert W; Fujita, Yoshiko; Ginn, Timothy R

2012-10-12

Subsurface radionuclide and metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE's greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent ions, such as the short-lived radionuclide 90Sr, is co-precipitation in calcite. We have previously found that that nutrient addition can stimulate microbial ureolytic activity that this activity accelerates calcite precipitation and co-precipitation of Sr, and that higher calcite precipitation rates can result in increased Sr partitioning. We have conducted integrated field, laboratory, and computational research to evaluate the relationships between ureolysis and calcite precipitation rates and trace metal partitioning under environmentally relevantmore » conditions, and investigated the coupling between flow/flux manipulations and precipitate distribution. A field experimental campaign conducted at the Integrated Field Research Challenge (IFRC) site located at Rifle, CO was based on a continuous recirculation design; water extracted from a down-gradient well was amended with urea and molasses (a carbon and electron donor) and re-injected into an up-gradient well. The goal of the recirculation design and simultaneous injection of urea and molasses was to uniformly accelerate the hydrolysis of urea and calcite precipitation over the entire inter-wellbore zone. The urea-molasses recirculation phase lasted, with brief interruptions for geophysical surveys, for 12 days followed by long-term monitoring which continued for 13 months. Following the recirculation phase we found persistent increases in urease activity (as determined from 14C labeled laboratory urea hydrolysis rates) in the upper portion of the inter-wellbore zone. We also observed an initial increase (approximately 2 weeks) in urea concentration associated with injection activities followed by decreasing urea concentration and associated increases in ammonium and dissolved inorganic carbon (DIC) following the termination of injection. Based on the loss of urea and the appearance of ammonium, a first order rate constant for urea hydrolysis of 0.18 day-1 rate with an associate Rf for ammonium of 11 were estimated. This rate constant is approximately 6 times higher than estimated for previous field experiments conducted in eastern Idaho. Additionally, DIC carbon isotope ratios were measured for the groundwater. Injected urea had a ´13C of 40.7±0.4 ° compared to background groundwater DIC of ´13C of -16.0±0.2°. Observed decreases in groundwater DIC ´13C of up to -19.8° followed temporal trends similar to those observed for ammonium and suggest that both the increase in ammonium and the sift in ´13C are the result of urea hydrolysis. Although direct observation of calcite precipitation was not possible because of the high pre-existing calcite content in the site sediments, an observed ´13C decrease for solid carbonates from sediment samples collect following urea injection (compared to pre-injection values) is likely the result of the incorporation of inorganic carbon derived from urea hydrolysis into newly formed solid carbonates.« less

Post-metamorphic fluid infiltration into granulites from the Adirondack Mountains, USA

NASA Technical Reports Server (NTRS)

Morrison, J.; Valley, John W.

1988-01-01

Post-metamorphic effects in the anorthosites of the Adirondacks, New York were described. Calcite-chlorite-sericite assemblages occur as veins, in disseminated form and as clots, and document retrograde fluid infiltration. These features are associated with late-state CO2-rich fluid inclusions. Stable isotope analyses of calcites indicates that the retrograde fluids interacted with meta-igneous and supracrustal lithologies, but the precise timing of the retrogression is as yet unknown.

Study of marbles from Middle Atlas (Morocco): elemental, mineralogical and structural analysis

NASA Astrophysics Data System (ADS)

Khrissi, S.; Bejjit, L.; Haddad, M.; Falguères, C.; Ait Lyazidi, S.; El Amraoui, M.

2018-05-01

A series of marbles sampled from the region of Middle Atlas (Morocco), are characterized by different complementary spectroscopic techniques. X-Ray fluorescence is used to determine elemental composition of rock while X-Ray diffraction and the Raman spectroscopy are used to determine major crystalline phases (calcite and dolomite) and minor ones (quartz).The samples display typical EPR spectra of Mn2+ in calcite and reveal the presence of Fe3+ ions.

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.

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

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.

Geology of the Devils Hole area, Nevada

USGS Publications Warehouse

Carr, W.J.

1988-01-01

Detailed and reconnaissance mapping of the Devils Hole, Nevada, area has improved definition of the local geologic structure within a regional carbonate aquifer near its primary discharge points -- the springs of Ash Meadows. Several formerly unmapped calcite veins, and other young calcite-lined paleo-spring feeder zones were found, as well as a number of previously unknown small collapse areas in the limestone. Although the predominant structural grain of the area is oriented northwest, the importance of the very subordinate northeast-striking faults and fractures is underscored by their association with Devils Hole itself, with most of the collapse depressions, and with many of the calcite veins in ' lake beds ' and alluvium. Probable channeling of groundwater flow may occur along one important northeast-striking fault zone. The persistent tendency for openings may have been facilitated by underlying low-angle faults that separate brittle carbonate rocks from underlying, less-competent clastic rocks. (Author 's abstract)

Fluidized bed combustion residue as an alternative liming material and Ca source. [Prunus persica

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

Edwards, J.H.; Horton, B.D.; White, A.W. Jr.

1985-01-01

Fluidized bed combustion residue (FBCR), a by-product of fossil fuel fired boilers, was evaluated as a liming material and a source of calcium for peaches (Prunus persica (L.) Batsch). Incubation studies involving a medium textured soil indicated that FBCR (calcite (FBCRC) or dolomitic (FBCRD) sources) was as effective a liming amendment as the respective agricultural limestone. Maximum soil pH occurred after 26 days incubation with FBCRC, but soil pH increased continuously throughout 137 days incubation with dolomitic limestone. Ammonium acetate extractable Ca was not affected by calcitic source, but Mg concentration increased with rates with the two dolomitic sources, andmore » was highest in the FBCRD source after 137 days incubation. In greenhouse studies with Elberta peach seedlings, FBCRC was more effective in neutralizing soil acidity and increasing extractable soil Ca than calcitic limestone.« less

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.

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

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.

Isotopic fractionation of oxygen and carbon in decomposed lower-mantle inclusions in diamond

DOE PAGES

Kaminsky, Felix; Matzel, Jennifer; Jacobsen, Ben; ...

2015-07-25

Two carbonatitic mineral assemblages, calcite + wollastonite and calcite + monticellite, which are encapsulated in two diamond grains from the Rio Soriso basin in the Juina area, Mato Grosso State, Brazil, were studied utilizing the NanoSIMS technique. The assemblages were formed as the result of the decomposition of the lower-mantle assemblage calcite + CaSi-perovskite + volatile during the course of the diamond ascent under pressure conditions from 15 to less than 0.8 GPa. The oxygen and carbon isotopic compositions of the studied minerals are inhomogeneous. They fractionated during the process of the decomposition of primary minerals to very varying values:more » δ 18O from –3.3 to +15.4 ‰ SMOW and δ 13C from –2.8 to +9.3 ‰ VPDB. As a result, these values significantly extend the mantle values for these elements in both isotopically-light and isotopically-heavy areas.« less

Planktic foraminifera form their shells by attachment of metastable carbonate particles

NASA Astrophysics Data System (ADS)

Wirth, R.; Jacob, D. E.; Eggins, S.

2016-12-01

Planktic foraminifera shells contribute up to half the inorganic carbon exported from the surface ocean to the seafloor. Their tiny calcium carbonate shells are preserved in sediments as calcite, and provide our most valuable geochemical archive of changes surface ocean conditions and climate spanning the last 100 million years. Here we show the shells of living planktic foraminifers Orbulina universa and Neogloboquadrina dutertrei consist of nano-particulate vaterite and amorphous calcium carbonate. This indicates formation via a non-classical crystallization pathway involving metastable carbonate intermediate phases before transforming to calcite, and requires a new perspective on how geochemical proxies are incorporated into planktic foraminifer shells. Our findings indicate planktic foraminifer shells could be far more susceptible to dissolution and ocean acidification than previously thought, and account for unexpected shell dissolution above the calcite saturation horizon in the ocean, which is a major uncertainty in modelling oceanic carbon fluxes.

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.

The origin of alteration "orangettes" in Dhofar 019: Implications for the age and aqueous history of the shergottites

NASA Astrophysics Data System (ADS)

Hallis, L. J.; Kemppinen, L.; Lee, M. R.; Taylor, L. A.

2017-12-01

The shergottites are the largest group of Martian meteorites, and the only group that has not been found to contain definitive evidence of Martian aqueous alteration. Given recent reports of current liquid water at the surface of Mars, this study aimed to investigate in detail the possibility of Martian phyllosilicate within shergottite Dhofar 019. Optical and scanning electron microscopy, followed by transmission electron microscopy, confirmed the presence of alteration orangettes, with a layered structure consisting of poorly ordered Mg-phyllosilicate and calcite. These investigations identified maskelynite dissolution, followed by Mg-phyllosilicate and calcite deposition within the dissolution pits, as the method of orangette production. The presence of celestine within the orangette layers, the absence of shock dislocation features within calcite, and the Mg-rich nature of the phyllosilicate, all indicate a terrestrial origin for these features on Dhofar 019.

A critical analysis of calcium carbonate mesocrystals

PubMed Central

Kim, Yi-Yeoun; Schenk, Anna S.; Ihli, Johannes; Kulak, Alex N.; Hetherington, Nicola B. J.; Tang, Chiu C.; Schmahl, Wolfgang W.; Griesshaber, Erika; Hyett, Geoffrey; Meldrum, Fiona C.

2014-01-01

The term mesocrystal has been widely used to describe crystals that form by oriented assembly, and that exhibit nanoparticle substructures. Using calcite crystals co-precipitated with polymers as a suitable test case, this article looks critically at the concept of mesocrystals. Here we demonstrate that the data commonly used to assign mesocrystal structure may be frequently misinterpreted, and that these calcite/polymer crystals do not have nanoparticle substructures. Although morphologies suggest the presence of nanoparticles, these are only present on the crystal surface. High surface areas are only recorded for crystals freshly removed from solution and are again attributed to a thin shell of nanoparticles on a solid calcite core. Line broadening in powder X-ray diffraction spectra is due to lattice strain only, precluding the existence of a nanoparticle sub-structure. Finally, study of the formation mechanism provides no evidence for crystalline precursor particles. A re-evaluation of existing literature on some mesocrystals may therefore be required. PMID:25014563

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.

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.

Microfacies and diagenesis of the Middle Jurassic Dhruma carbonates, southwest Riyadh, Saudi Arabia

NASA Astrophysics Data System (ADS)

El-Sorogy, Abdelbaset S.; Galmed, Mahmoud A.; Al-Kahtany, Khaled; Al-Zahrani, Ali

2017-06-01

In order to document the microfacies analysis and diagenetic alterations of the Middle Jurassic Dhruma Formation at southwest Riyadh City of central Saudi Arabia, a stratigraphic section was studied in detail at Khashm adh Dhi'bi area. Mudstones, wackstones, packstones, grainstones and boundstones are the main microfacies types in the studied area. These microfacies types with field investigations and fossil content indicated an environment ranging from deep shelf to organic buildup on platform margins for the studied carbonates. Cementation and recrystallization, dissolution, fragmentation and compaction, silicification, dolomitization, and bioerosion were the main diagenetic alterations affected the carbonate rocks of the Dhruma Formation. Cementation and recrystallization are represented by equant calcite crystals, Dog-tooth fringes of thin isopachous calcites and blocky low Mg-calcites. Gastrochaenolites, Trypanites and Meandropolydora spp. were the most bioeroders in coral heads and large bivalves and hardgrounds. These bioeroders indicated a long post-mortem period during the early diagenetic stage.

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

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 atmosphere (δ13Ccalcite ≈+60); however they may reflect formation values with an ancient (<1.3 Ga) martian atmosphere. If the martian carbonates formed with oxygen contribution ratios similar to the OC terrestrial carbonates, then the mixing model parametrically provides Mars δ18O for atmospheric CO2 and meteoric water that creates the measured values.

Fault and fluid systems in supra-subduction zones: The Troodos ophiolite

NASA Astrophysics Data System (ADS)

Quandt, Dennis; Micheuz, Peter; Kurz, Walter; Krenn, Kurt

2017-04-01

The Troodos massif on the island of Cyprus represents a well-preserved and complete supra-subduction zone (SSZ) ophiolite. It includes an extrusive sequence that is subdivided into Upper (UPL) and Lower Pillow Lavas (LPL). These volcanic rocks contain mineralized fractures (veins) and vesicles that record fluid availability probably related to slab dehydration and deformation subsequent to a period of subduction initiation in the framework of a SSZ setting. Here, we present electron microprobe element mappings and cathodoluminescence studies of vein minerals as well as analyses of fluid inclusions entrapped in zeolite, calcite and quartz from veins and vesicles of the Pillow Lavas of the Troodos ophiolite. Two different zeolite type assemblages, interpreted as alteration products of compositional varying volcanic glasses, occur: (1) Na-zeolites analcime and natrolite from the UPL that require lower formation temperatures, higher Na/Ca ratios and pH values than (2) Ca-zeolites heulandite and mordenite from the LPL which indicate temporal or spatial varying fluid compositions and conditions. Calcite represents a late stage phase in incompletely sealed blocky type (1) assemblage and in syntaxial quartz veins. Additionally, calcite occurs as major phase in syntaxial and blocky veins of UPL and LPL. These syntaxial quartz and calcite veins are assumed to be related to tectonic extension. Chalcedony is associated with quartz and occurs in typical veins and vesicles of the LPL. In addition, the presence of neptunian dykes in veins suggests that seawater penetrated fractures throughout the extrusive sequence. Thus, circulation in an open system via advective transport is favored while diffusion in a closed system is a subordinate, local and late stage phenomenon. Calcite veins and quartz vesicles contain primary, partly re-equilibrated two phase (liquid, vapor) fluid inclusions. The chemical system of all studied inclusions in both host minerals is restricted to aqueous chemistry with salinities below 5 mass% based on last melting of ice between -3 and -0.8° C. Homogenization around 100-200° C occurs always to the liquid phase indicative for a pressure dominated fluid origin. Well preserved zonation textures in blocky calcite veins consisting of partly decrepitated but also re-equilibrated large fluid inclusions are related to Mn-rich areas. This fluid inclusion generation shows also homogenization to the liquid phase and points to minimum temperature conditions for formation of Mn-enriched areas of about 220° C. Calcite microstructures within the veins are characterized by type I and II twins as well as undulatory extinction and subgrain boundaries indicative for deformation temperatures of approximately 200-250° C, with differential stresses of about 50 MPa. We acknowledge financial support by the Austrian Research Fund (P27982-N29) to W. Kurz

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 difference in frictional strength, between marble and portlandite, increases from 0µ to 0.4µ as the normal stress is increased from 1 to 50 MPa. Additionally, at the low shearing rates of 0.1 and 0.3 µm/s, portlandite fails through stick-slip motion whereas calcite slides stably. Furthermore, we observe power-law type healing in portlandite that results in a dramatic increase in static frictional strength of ~0.2 µ over a relatively short hold time of 3000s. We suggest that decarbonated fault patches are (1) frictionally weaker, (2) more frictionally unstable, and (3) likely to regain their frictional strength more quickly, than patches in pure carbonate rocks. Under water-saturated conditions, the occurrence of portlandite and other hydrous minerals is undoubtedly the key for interpreting changes in the mechanical behaviour, both transient and long-term, of decarbonated faults.

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 reflects the comparatively high value of correlation coefficient (R 2  = 0.94) for the Langmuir isotherm compared to those of the Freundlich isotherm (R 2  = 0.82) showed that the adsorption of diesel oil onto the hydrophobic CaCO 3 adsorbent was much better described by the Langmuir isotherm. The kinetics study of second-order rate expression (R 2  = 0.99) more fitted with the experimental data compare to first-order model (R 2  = 0.92). The synthesized calcite exhibited a significant dual oleophilic and hydrophobic nature that can be applicable for oil adsorption/or removal purpose in oil contaminated areas in environment and/or industrial oily wastewater for green, simple, and inexpensive environmental cleanup. Copyright © 2017 Elsevier Ltd. All rights reserved.

Multi-Wavelength, Multi-Beam, and Polarization-Sensitive Laser Transmitter for Surface Mapping

NASA Technical Reports Server (NTRS)

Yu, Anthony W.; Ramos-Izquierdo, Luis; Harding, David; Huss, Tim

2011-01-01

A multi-beam, multi-color, polarized laser transmitter has been developed for mapping applications. It uses commercial off-the-shelf components for a lowcost approach for a ruggedized laser suitable for field deployment. The laser transmitter design is capable of delivering dual wavelengths, multiple beams on each wavelength with equal (or variable) intensities per beam, and a welldefined state of polarization. This laser transmitter has been flown on several airborne campaigns for the Slope Imaging Multi-Polarization Photon Counting Lidar (SIMPL) instrument, and at the time of this reporting is at a technology readiness level of between 5 and 6. The laser is a 1,064-nm microchip high-repetition-rate laser emitting energy of about 8 microjoules per pulse. The beam was frequency-doubled to 532 nm using a KTP (KTiOPO4) nonlinear crystal [other nonlinear crystals such as LBO (LiB3O5) or periodically poled lithium niobiate can be used as well, depending on the conversion efficiency requirements], and the conversion efficiency was approximately 30 percent. The KTP was under temperature control using a thermoelectric cooler and a feedback monitoring thermistor. The dual-wavelength beams were then spectrally separated and each color went through its own optical path, which consisted of a beam-shaping lens, quarterwave plate (QWP), and a birefringent crystal (in this case, a calcite crystal, but others such as vanadate can be used). The QWP and calcite crystal set was used to convert the laser beams from a linearly polarized state to circularly polarized light, which when injected into a calcite crystal, will spatially separate the circularly polarized light into the two linear polarized components. The spatial separation of the two linearly polarized components is determined by the length of the crystal. A second set of QWP and calcite then further separated the two beams into four. Additional sets of QWP and calcite can be used to further split the beams into multiple orders of two. The spatially separated beams had alternating linearly polarization states; a half-wave plate (HWP) array was then made to rotate the alternating states of A multi-beam, multi-color, polarized laser transmitter has been developed for mapping applications. It uses commercial off-the-shelf components for a lowcost approach for a ruggedized laser suitable for field deployment. The laser transmitter design is capable of delivering dual wavelengths, multiple beams on each wavelength with equal (or variable) intensities per beam, and a welldefined state of polarization. This laser transmitter has been flown on several airborne campaigns for the Slope Imaging Multi-Polarization Photon Counting Lidar (SIMPL) instrument, and at the time of this reporting is at a technology readiness level of between 5 and 6. The laser is a 1,064-nm microchip high-repetition-rate laser emitting energy of about 8 microjoules per pulse. The beam was frequency-doubled to 532 nm using a KTP (KTiOPO4) nonlinear crystal [other nonlinear crystals such as LBO (LiB3O5) or periodically poled lithium niobiate can be used as well, depending on the conversion efficiency requirements], and the conversion efficiency was approximately 30 percent. The KTP was under temperature control using a thermoelectric cooler and a feedback monitoring thermistor. The dual-wavelength beams were then spectrally separated and each color went through its own optical path, which consisted of a beam-shaping lens, quarterwave plate (QWP), and a birefringent crystal (in this case, a calcite crystal, but others such as vanadate can be used). The QWP and calcite crystal set was used to convert the laser beams from a linearly polarized state to circularly polarized light, which when injected into a calcite crystal, will spatially separate the circularly polarized light into the two linear polarized components. The spatial separation of the two linearly polarized components is determined by the length of the crystal. A cond set of QWP and calcite then further separated the two beams into four. Additional sets of QWP and calcite can be used to further split the beams into multiple orders of two. The spatially separated beams had alternating linearly polarization states; a half-wave plate (HWP) array was then made to rotate the alternating states of

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-ray reflection interface microscopy (XRIM) reveal the existence of laterally variable Cd-rich domains.« less

Geochemical assessment of hydrocarbon migration phenomena: Case studies from the south-western margin of the Dead Sea Basin

NASA Astrophysics Data System (ADS)

Sokol, Ella; Kozmenko, Olga; Smirnov, Sergey; Sokol, Ivan; Novikova, Sofya; Tomilenko, Anatoliy; Kokh, Svetlana; Ryazanova, Tatyana; Reutsky, Vadim; Bul'bak, Taras; Vapnik, Yevgeny; Deyak, Michail

2014-10-01

Calcite veins with fluid and solid bitumen inclusions have been discovered in the south-western shoulder of the Dead Sea rift within the Masada-Zohar block, where hydrocarbons exist in small commercial gas fields and non-commercial fields of heavy and light oils. The gas-liquid inclusions in calcite are dominated either by methane or CO2, and aqueous inclusions sometimes bear minor dissolved hydrocarbons. The enclosed flake-like solid bitumen matter is a residue of degraded oil, which may be interpreted as “dead carbon”. About 2/3 of this matter is soot-like amorphous carbon and 1/3 consists of n-C8sbnd C18 carboxylic acids and traces of n-alkanes, light dicarboxylic acids, and higher molecular weight (>C20) branched and/or cyclic carboxylic acids. Both bitumen and the host calcites show genetic relationship with mature Maastrichtian chalky source rocks (MCSRs) evident in isotopic compositions (δ13C, δ34S, and δ18O) and in REE + Y patterns. The bitumen precursor may have been heavy sulfur-rich oil which was generated during the burial compaction of the MCSR strata within the subsided blocks of the Dead Sea graben. The δ18O and δ13C values and REE + Y signatures in calcites indicate mixing of deep buried fluids equilibrated with post-mature sediments and meteoric waters. The temperatures of fluid generation according to Mg-Li-geothermometer data range from 55 °С to 90 °С corresponding to the 2.5-4.0 km depths, and largely overlap with the oil window range (60-90 °С) in the Dead Sea rift (Hunt, 1996; Gvirtzman and Stanislavsky, 2000; Buryakovsky et al., 2005). The bitumen-rich vein calcites originated in the course of Late Cenozoic rifting and related deformation, when tectonic stress triggers damaged small hydrocarbon reservoirs in the area, produced pathways, and caused hydrocarbon-bearing fluids to rise to the subsurface; the fluids filled open fractures and crystallized to calcite with entrapped bitumen. The reported results are in good agreement with the existing views of maturation, migration, and accumulation of hydrocarbons, as well as basin fluid transport processes in the Dead Sea area.

Behaviour of calcium carbonate in sea water

USGS Publications Warehouse

Cloud, P.E.

1962-01-01

Anomalies in the behaviour of calcium carbonate in natural solutions diminish when considered in context. Best values found by traditional oceanographie methods for the apparent solubility product constant K'CaCO3 in sea water at atmospheric pressure are consistent mineralogically-at 36 parts per thousand salinity and T-25??C, K'aragonlte is estimated as 1.12 ?? 10-6 and K'calcite as 0.61 ?? 10-6. At 30??C the corresponding values are 0.98 ?? 10-6 for aragonite and 0.53 ?? 10-6 for calcite. Because the K' computations do not compensate for ionic activity, however, they cannot give thermodynamically satisfactory results. It is of interest, therefore, that approximate methods and information now available permit the estimation from the same basic data of an activity product constant KCaCO3 close to that found in solutions to which Debye-Hu??ckel theory applies. Such methods indicate approximate Karagonite 7.8 ?? 10-9 for surface sea water at 29??C; Kcalcite would be proportionately lower. Field data and experimental results indicate that the mineralogy of precipitated CaCO3 depends primarily on degree of supersaturation, thus also on kinetic or biologic factors that facilitate or inhibit a high degree of supersaturation. The shallow, generally hypersaline bank waters west of Andros Island yield aragonitic sediments with O18 O16 ratios that imply precipitation mainly during the warmer months, when the combination of a high rate of evaporation, increasing salinity (and ionic strength), maximal temperatures and photosynthetic removal of CO2 result in high apparent supersaturation. The usual precipitate from solutions of low ionic strength is calcite, except where the aragonite level of supersaturation is reached as a result of diffusion phenomena (e.g. dripstones), gradual and marked evaporation, or biologic intervention. Published data also suggest the possibility of distinct chemical milieus for crystallographic variations in skeletal calcium carbonate. It appears that in nature aragonite precipitates from solutions that are supersaturated with respect to both calcite and aragonite and calcite between saturation levels for the two species. Such a relation is consistent with Ostwald's rule of successive reactions. Aragonitc of marine origin persists in contact with supersaturated interstitial solutions at ordinary temperature and pressure. Conversion to calcite follows transfer to solutions undersaturated with respect to aragonite or upon exposure to the moist atmosphere. ?? 1962.

Using Strontium Isotopes in Arid Agricultural Soils to Determine a Sink or Source of CO2

NASA Astrophysics Data System (ADS)

Ortiz, A. C.; Jin, L.

2014-12-01

Arid and semi-arid regions of the world are predicted to continue to expand through land degradation and prolonged drought events. Agricultural practices in these drylands degrade soils through elevated salinity, sodicity and alkalinity. Indeed, flood irrigation loads salts onto the soils including carbonate minerals in the form of calcite. Alfalfa and Pecan are salt tolerant and commonly grown in the arid El Paso region, but need irrigation using Rio Grande water with little to no contribution from local ground waters. We hypothesize that the irrigation is loading extra Ca and bicarbonate to soils and anthropogenically enhancing the precipitation of carbonates. We intend to monitor soil CO2 efflux after irrigation, characterize soil minerals, and combine them to isotopic data of soil, irrigation, and drainage waters to link the sources of Ca and C, kinetics of calcite precipitation, to irrigation events. This will include strontium isotopic analysis to determine the source of calcium in the agricultural fields, U-disequilibrium isotopes to estimate the carbonate ages, and CO2 efflux to monitor atmosphere-soil exchange. Carbon dioxide emissions are expected to change during flood irrigation when soils are saturated. After irrigation events, evaporative effects increase Ca and dissolved inorganic carbon concentration in soil waters leading to precipitation of calcite and thus elevated CO2efflux. Preliminary measurements in the pecan field show a marginally significant difference in CO2 fluxes before and after irrigation (p=0.07, t-test). Carbon dioxide emissions are lower during moist conditions (0.6 g m-2hr-1 CO2) than those in dry conditions (1.0 g m-2hr-1 CO2). Future C isotope data are needed to identify the source of extra CO2, biogenic or calcite-precipitation related. A water leachable extraction of alfalfa soils shows 87Sr/86Sr ratios ranged from 0.7101 to 0.7103, indicating Rio Grande river as a dominant calcium source. Further Sr isotopic analysis of sequential extractions from both alfalfa soils (for calcite fraction), pore waters, irrigation waters, and drainage waters will allow us to quantitatively evaluate the source of calcium in calcite therefore, defining if anthropogenic sources of calcium lead to enhanced CO2 production in agricultural fields.

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 calcite on muscovite and feldspar to find out the main influence factor of the contact relationship.

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 14.9 (summer). These values approximate predicted DSO4 values based on our chamber experiments containing both low (2 ppm) and high (20 ppm) sulphate concentrations. Our experimental values of DSO4 obtained at crystal growth rates typical of stalagmites, closely match those observed in other cave sites from around the world. This validates the universality of the controls behind DSO4 and will enhance the use of speleothem CAS as a palaeoenvironmental proxy.

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-ray reflection interface microscopy (XRIM) reveal the existence of laterally variable Cd-rich domains.« less

Molecular-Scale Structural Controls on Nanoscale Growth Processes: Step-Specific Regulation of Biomineral Morphology

NASA Astrophysics Data System (ADS)

Dove, P. M.; Davis, K. J.; De Yoreo, J. J.; Orme, C. A.

2001-12-01

Deciphering the complex strategies by which organisms produce nanocrystalline materials with exquisite morphologies is central to understanding biomineralizing systems. One control on the morphology of biogenic nanoparticles is the specific interactions of their surfaces with the organic functional groups provided by the organism and the various inorganic species present in the ambient environment. It is now possible to directly probe the microscopic structural controls on crystal morphology by making quantitative measurements of the dynamic processes occurring at the mineral-water interface. These observations can provide crucial information concerning the actual mechanisms of growth that is otherwise unobtainable through macroscopic techniques. Here we use in situ molecular-scale observations of step dynamics and growth hillock morphology to directly resolve roles of principal impurities in regulating calcite surface morphologies. We show that the interactions of certain inorganic as well as organic impurities with the calcite surface are dependent upon the molecular-scale structures of step-edges. These interactions can assume a primary role in directing crystal morphology. In calcite growth experiments containing magnesium, we show that growth hillock structures become modified owing to the preferential inhibition of step motion along directions approximately parallel to the [010]. Compositional analyses have shown that Mg incorporates at different levels into the two types of nonequivalent steps, which meet at the hillock corner parallel to [010]. A simple calculation of the strain caused by this difference indicates that we should expect a significant retardation at this corner, in agreement with the observed development of [010] steps. If the low-energy step-risers produced by these [010] steps is perpendicular to the c-axis as seems likely from crystallographic considerations, this effect provides a plausible mechanism for the elongated calcite crystal habits found in natural environments that contain magnesium. In a separate study, step-specific interactions are also found between chiral aspartate molecules and the calcite surface. The L and D- aspartate enantiomers exhibit structure preferences for the different types of step-risers on the calcite surface. These site-specific interactions result in the transfer of asymmetry from the organic molecule to the crystal surface through the formation of chiral growth hillocks and surface morphologies. These studies yield direct experimental insight into the molecular-scale structural controls on nanocrystal morphology in biomineralizing systems.

Conservation of ornamental stone by Myxococcus xanthus-induced carbonate biomineralization.

PubMed

Rodriguez-Navarro, Carlos; Rodriguez-Gallego, Manuel; Ben Chekroun, Koutar; Gonzalez-Muñoz, Maria Teresa

2003-04-01

Increasing environmental pollution in urban areas has been endangering the survival of carbonate stones in monuments and statuary for many decades. Numerous conservation treatments have been applied for the protection and consolidation of these works of art. Most of them, however, either release dangerous gases during curing or show very little efficacy. Bacterially induced carbonate mineralization has been proposed as a novel and environmentally friendly strategy for the conservation of deteriorated ornamental stone. However, the method appeared to display insufficient consolidation and plugging of pores. Here we report that Myxococcus xanthus-induced calcium carbonate precipitation efficiently protects and consolidates porous ornamental limestone. The newly formed carbonate cements calcite grains by depositing on the walls of the pores without plugging them. Sonication tests demonstrate that these new carbonate crystals are strongly attached to the substratum, mostly due to epitaxial growth on preexisting calcite grains. The new crystals are more stress resistant than the calcite grains of the original stone because they are organic-inorganic composites. Variations in the phosphate concentrations of the culture medium lead to changes in local pH and bacterial productivity. These affect the structure of the new cement and the type of precipitated CaCO(3) polymorph (vaterite or calcite). The manipulation of culture medium composition creates new ways of controlling bacterial biomineralization that in the future could be applied to the conservation of ornamental stone.

Conservation of Ornamental Stone by Myxococcus xanthus-Induced Carbonate Biomineralization

PubMed Central

Rodriguez-Navarro, Carlos; Rodriguez-Gallego, Manuel; Ben Chekroun, Koutar; Gonzalez-Muñoz, Maria Teresa

2003-01-01

Increasing environmental pollution in urban areas has been endangering the survival of carbonate stones in monuments and statuary for many decades. Numerous conservation treatments have been applied for the protection and consolidation of these works of art. Most of them, however, either release dangerous gases during curing or show very little efficacy. Bacterially induced carbonate mineralization has been proposed as a novel and environmentally friendly strategy for the conservation of deteriorated ornamental stone. However, the method appeared to display insufficient consolidation and plugging of pores. Here we report that Myxococcus xanthus-induced calcium carbonate precipitation efficiently protects and consolidates porous ornamental limestone. The newly formed carbonate cements calcite grains by depositing on the walls of the pores without plugging them. Sonication tests demonstrate that these new carbonate crystals are strongly attached to the substratum, mostly due to epitaxial growth on preexisting calcite grains. The new crystals are more stress resistant than the calcite grains of the original stone because they are organic-inorganic composites. Variations in the phosphate concentrations of the culture medium lead to changes in local pH and bacterial productivity. These affect the structure of the new cement and the type of precipitated CaCO3 polymorph (vaterite or calcite). The manipulation of culture medium composition creates new ways of controlling bacterial biomineralization that in the future could be applied to the conservation of ornamental stone. PMID:12676699

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.

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.

Geochemical transformations and modeling of two deep-well injected hazardous wastes

USGS Publications Warehouse

Roy, W.R.; Seyler, B.; Steele, J.D.; Mravik, S.C.; Moore, D.M.; Krapac, I.G.; Peden, J.M.; Griffin, R.A.

1991-01-01

Two liquid hazardous wastes (an alkaline brine-like solution and a dilute acidic waste) were mixed with finely ground rock samples of three injection-related lithologies (sandstone, dolomite, and siltstone) for 155 to 230 days at 325??K-10.8 MPa. The pH and inorganic chemical composition of the alkaline waste were not significantly altered by any of the rock samples after 230 days of mixing. The acidic waste was neutralized as a consequence of carbonate dissolution, ion exchange, or clay-mineral dissolution, and hence was transformed into a nonhazardous waste. Mixing the alkaline waste with the solid phases yielded several reaction products: brucite, Mg(OH)2; calcite, CaCO3; and possibly a type of sodium metasilicate. Clay-like minerals formed in the sandstone, and hydrotalcite, Mg6Al2-CO3(OH)16??4H2O, may have formed in the siltstone at trace levels. Mixing the alkaline waste with a synthetic brine yielded brucite, calcite, and whewellite (CaC2O4??H2O). The thermodynamic model PHRQPITZ predicted that brucite and calcite would precipitate from solution in the dolomite and siltstone mixtures and in the alkaline waste-brine system. The dilute acidic waste did not significantly alter the mineralogical composition of the three rock types after 155 days of contact. The model PHREEQE indicated that the calcite was thermodynamically stable in the dolomite and siltstone mixtures.

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.

Skeletal aragonite dissolution from hypersaline seawater: a hypothesis

NASA Astrophysics Data System (ADS)

Qing Sun, S.

1992-05-01

Hypersaline seawater has often been invoked as a mechanism to explain the pervasive dolomitization of ancient platform carbonates, but its potential in causing skeletal aragonite dissolution of these carbonates has rarely been investigated. Previous experimental and theoretical studies have demonstrated that hypersaline seawater is undersaturated with respect to aragonite when evaporation reaches a certain degree. It is contended here that similar undersaturation could also have occurred in ancient evaporitic seas. Geological evidence from the Miocene carbonates of SE Spain, Gulf of Suez, Red Sea and Iraq suggests that this may have been the case. Despite differences in their geological settings, these carbonates have common diagenetic features including: (1) widespread dissolution of skeletal aragonite with little or no calcite cementation; and (2) pervasive dolomitization. Dolomite occurs as both a replacement of Mg calcite and mouldic pore-filling cement. The association of the dolomites with evaporites, their relatively heavy oxygen isotopic values and widespread distribution suggest a hypersaline seawater origin of these dolomites. Petrographic data indicate that skeletal aragonite was dissolved during dolomitization because the aragonite fossil moulds contain dolomite cements, but no pre-dolomitization calcite cements, implying that the dolomitizing fluids (hypersaline seawater) were probably undersaturated with respect to aragonite. The dissolved calcium may have been subsequently incorporated into the dolomite. This may help to explain the lack of calcite cementation despite the extensive skeletal aragonite dissolution.

Rietveld analysis of X-ray powder diffraction patterns as a potential tool for the identification of impact-deformed carbonate rocks

NASA Astrophysics Data System (ADS)

Huson, S. A.; Foit, F. F.; Watkinson, A. J.; Pope, M. C.

2009-12-01

Previous X-ray powder diffraction (XRD) studies revealed that shock deformed carbonates and quartz have broader XRD patterns than those of unshocked samples. Entire XRD patterns, single peak profiles and Rietveld refined parameters of carbonate samples from the Sierra Madera impact crater, west Texas, unshocked equivalent samples from 95 miles north of the crater and the Mission Canyon Formation of southwest Montana and western Wyoming were used to evaluate the use of X-ray powder diffraction as a potential tool for distinguishing impact deformed rocks from unshocked and tectonically deformed rocks. At Sierra Madera dolostone and limestone samples were collected from the crater rim (lower shock intensity) and the central uplift (higher shock intensity). Unshocked equivalent dolostone samples were collected from well cores drilled outside of the impact crater. Carbonate rocks of the Mission Canyon Formation were sampled along a transect across the tectonic front of the Sevier and Laramide orogenic belts. Whereas calcite subjected to significant shock intensities at the Sierra Madera impact crater can be differentiated from tectonically deformed calcite from the Mission Canyon Formation using Rietveld refined peak profiles, weakly shocked calcite from the crater rim appears to be indistinguishable from the tectonically deformed calcite. In contrast, Rietveld analysis readily distinguishes shocked Sierra Madera dolomite from unshocked equivalent dolostone samples from outside the crater and tectonically deformed Mission Canyon Formation dolomite.

The interfacial energetics of the oil molecules interactions with shale media using molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Zhang, Z.; Wang, J.

2017-12-01

Characterizing the behavior of oil molecules in nanopore is vital to the understanding of geochemistry of hydrocarbon-bearing fluid in ultra-tight source rocks, such as shale. The heterogeneous nature of hydrocarbon system of nanoscale complicates experimental studies of oil / shale interfacial interaction. Therefore, to gain mechanistic understanding of the interplay of oil molecules in rock nanopore, molecular dynamics simulations have been applied to study the interactions of polar and non-polar oil on both calcite and kerogen surfaces. The effect of surface wetting, oil polarity, and temperature on the Gibbs free energy of adsorption have been investigated. The free energy, entropy, and enthalpy profiles have been calculated using advanced molecular dynamics method: umbrella sampling. In agreement with experiment, 1) surface with adsorbed water layer significantly reduces the oil adsorption energy on kerogen and turns the calcite surface to highly oil-repellent; 2) polar oil has overall stronger adsorption free energy than that of non-polar oil on both non-wetted calcite and kerogen surface; 3) organic interface (e.g. kerogen) exhibits stronger adsorption of oil molecules compared to inorganic one (e.g. calcite). The finding of this study indicates that oil displacement in nanopores can be enhanced by promoting the water adsorption on surface and reducing the polarity of oil on both inorganic and organic interfaces.

Molecular insight into the nanoconfined calcite–solution interface

PubMed Central

Diao, Yijue; Espinosa-Marzal, Rosa M.

2016-01-01

Little is known about the influence of nanoconfinement on calcium carbonate mineralization. Here, colloidal probe atomic force microscopy is used to confine the calcite–solution interface with a silica microsphere and to measure Derjaguin–Landau–Verwey–Overbeek (DLVO) and non-DLVO forces as a function of the calcium concentration, also after charge reversal of both surfaces occurs. Through the statistical analysis of the oscillatory component of a strong hydration force, the subnanometer interfacial structure of the confined atomically flat calcite is resolved in aqueous solution. By applying a mechanical work, both water and hydrated counterions are squeezed out from the nanoconfined solution, leaving the calcite surface more negatively charged than the analogous unconfined surfaces. Layer size and applied work allow a distinction between the hydration states of the counterions in the Stern layer; we propose counterions to be inner- and outer-sphere calcium ions, with a population of inner-sphere calcium ions larger than on unconfined calcite surfaces. It is also shown that the composition of the nanoconfined solution can be tuned by varying calcium concentration. This is a fundamental study of DLVO and hydration forces, and of their connection, on atomically flat calcite. More broadly, our work scrutinizes the greatly unexplored relation between surface science and confined mineralization, with implications for diverse areas of inquiry, such as nanoconfined biomineralization, CO2 sequestration in porous aquifers, and pressure solution and crystallization in confined hydrosystems. PMID:27790988

Implications of Smectite Subduction at the Costa Rican Convergent Margin

NASA Astrophysics Data System (ADS)

Cardace, D.; Morris, J. D.; Underwood, M. B.; Spinelli, G.

2003-12-01

Legs 205/170 of the Ocean Drilling Program (ODP) drilled a reference section on the incoming plate and sites at the toe of the sedimentary prism at the Costa Rican convergent margin. Complete sediment subduction has been documented, with the prism described by Leg 205/170 shipboard scientists as a paleoslump prism. Despite sediment subduction, Costa Rican arc lava geochemistry shows little sediment signal. Though subduction erosion has been posited as a mechanism for damping the geochemical sediment signal, this abstract addresses whether the clay content and distribution in the subducting pile can (a) play a role in localizing the decollement and (b) impact subduction of sediment to depth. X-ray diffraction (XRD) analyses of bulk sediment, with biogenic silica determinations, have been carried out for samples from the prism, through the decollement, to the underthrust sediments. Clay fractions have been isolated and silica studied for a subset of these samples. XRD peak areas of bulk samples were transformed into relative abundances via matrix singular value decomposition (Fisher and Underwood, 1995, Proc. ODP, Init. Repts., 156: 29-37), and adjusted following silica determination; volcanic ash has been neglected as a sedimentary component. Average relative weight percents of dominant minerals and biogenic silica (bSiO2) for prism toe units (Site 1040) are: P1A (silty clay, 74.8 m thick) 82 wt% clay, 5 wt% quartz, 13 wt% plagioclase, 0 wt% calcite; P1B (silty clay, 296.4 m thick) 82.1 wt% clay, 6.0 wt% quartz, 10.4 wt% plagioclase, 0 wt% calcite, 1.4 wt% bSiO2. Below the decollement, underthrust abundances are: U1A (clayey diatomite, 13.2 m thick) 82.7 wt% clay, 5.2 wt% quartz, 8.9 wt% plagioclase, 0 wt% calcite, 3.2 wt% bSiO2; U1B (clayey diatomite, 38.2 m thick) 80.7 wt% clay, 4.4 wt% quartz, 6.6 wt% plagioclase, 0 wt% calcite, 8.2 wt% bSiO2; U2 (silty claystone, 57.1 m thick) 84.8 wt% clay, 4.5 wt% quartz, 6.8 wt% plagioclase, 0 wt% calcite, 3.9 wt% bSiO2; U3A (siliceous nannofossil chalk, 18.1 m thick) 44.1 wt% clay, 2.0 wt% quartz, 5.6 wt% plagioclase, 31.8 wt% calcite, 16.5 wt% bSiO2; U3B (siliceous nannofossil chalk, 75.55 m thick) 1.9 wt% clay, 0 wt% quartz, 1.1 wt% plagioclase, 92.4 wt% calcite, 4.7 wt% bSiO2; and U3C (siliceous nannofossil chalk, 80.18 m thick) 6.6 wt% clay, 6.1 wt% quartz, 4.6 wt% plagioclase, 74.1 wt% calcite, 8.7 wt% bSiO2. XRD peak areas for clay fractions of prism samples above and in the decollement (Site 1254 ˜Site 1040, 300-370 mbsf) were transformed into relative weight percent data with Biscaye weighting factors. Smectites ranged from 77-93 wt%, illites ranged from 0-4 wt%, and kaolinites/chlorites ranged from 5-20 wt%. The maximum smectite value was obtained in the lower decollement. Bulk mineralogy data for sediments subducting at Costa Rica show that the prism and uppermost underthrust sediments are 80-93 wt% clay sized minerals. Clay mineralogy suggests that the smectite maximum occurs in the lower decollement and decreases dramatically below. Low biogenic silica abundances persist down core, emphasizing the importance of clays to the subducting section at Costa Rica.

Geochemistry of the Birch Creek Drainage Basin, Idaho

USGS Publications Warehouse

Swanson, Shawn A.; Rosentreter, Jeffrey J.; Bartholomay, Roy C.; Knobel, LeRoy L.

2003-01-01

The U.S. Survey and Idaho State University, in cooperation with the U.S. Department of Energy, are conducting studies to describe the chemical character of ground water that moves as underflow from drainage basins into the eastern Snake River Plain aquifer (ESRPA) system at and near the Idaho National Engineering and Environmental Laboratory (INEEL) and the effects of these recharge waters on the geochemistry of the ESRPA system. Each of these recharge waters has a hydrochemical character related to geochemical processes, especially water-rock interactions, that occur during migration to the ESRPA. Results of these studies will benefit ongoing and planned geochemical modeling of the ESRPA at the INEEL by providing model input on the hydrochemical character of water from each drainage basin. During 2000, water samples were collected from five wells and one surface-water site in the Birch Creek drainage basin and analyzed for selected inorganic constituents, nutrients, dissolved organic carbon, tritium, measurements of gross alpha and beta radioactivity, and stable isotopes. Four duplicate samples also were collected for quality assurance. Results, which include analyses of samples previously collected from four other sites, in the basin, show that most water from the Birch Creek drainage basin has a calcium-magnesium bicarbonate character. The Birch Creek Valley can be divided roughly into three hydrologic areas. In the northern part, ground water is forced to the surface by a basalt barrier and the sampling sites were either surface water or shallow wells. Water chemistry in this area was characterized by simple evaporation models, simple calcite-carbon dioxide models, or complex models involving carbonate and silicate minerals. The central part of the valley is filled by sedimentary material and the sampling sites were wells that are deeper than those in the northern part. Water chemistry in this area was characterized by simple calcite-dolomite-carbon dioxide models. In the southern part, ground water enters the ESRPA. In this area, the sampling sites were wells with depths and water levels much deeper than those in the northern and central parts of the valley. The calcium and carbon water chemistry in this area was characterized by a simple calcite-carbon dioxide model, but complex calcite-silicate models more accurately accounted for mass transfer in these areas. Throughout the geochemical system, calcite precipitated if it was an active phase in the models. Carbon dioxide either precipitated (outgassed) or dissolved depending on the partial pressure of carbon dioxide in water from the modeled sites. Dolomite was an active phase only in models from the central part of the system. Generally the entire geochemical system could be modeled with either evaporative models, carbonate models, or carbonate-silicate models. In both of the latter types of models, a significant amount of calcite precipitated relative to the mass transfer to and from the other active phases. The amount of calcite precipitated in the more complex models was consistent with the amount of calcite precipitated in the simpler models. This consistency suggests that, although the simpler models can predict calcium and carbon concentrations in Birch Creek Valley ground and surface water, silicate-mineral-based models are required to account for the other constituents. The amount of mass transfer to and from the silicate mineral phases was generally small compared with that in the carbonate phases. It appears that the water chemistry of well USGS 126B represents the chemistry of water recharging the ESRPA by means of underflow from the Birch Creek Valley.

Laboratory batch experiments and geochemical modelling of water-rock-supercritical CO2 reactions in Southern San Joaquin Valley, California oil field sediments: Implications for future carbon capture and sequestration projects.

NASA Astrophysics Data System (ADS)

Mickler, P. J.; Rivas, C.; Freeman, S.; Tan, T. W.; Baron, D.; Horton, R. A.

2015-12-01

Storage of CO2 as supercritical liquid in oil reservoirs has been proposed for enhanced oil recovery and a way to lower atmospheric CO2 levels. The fate of CO2 after injection requires an understanding of mineral dissolution/precipitation reactions occurring between the formation minerals and the existing formation brines at formation temperatures and pressures in the presence of supercritical CO2. In this study, core samples from three potential storage formations, the Vedder Fm. (Rio Bravo oil field), Stevens Fm. (Elk Hills oil field) and Temblor Fm. (McKittrick oil field) were reacted with a synthetic brine and CO2(sc) at reservoir temperature (110°C) and pressure (245-250 bar). A combination of petrographic, SEM-EDS and XRD analyses, brine chemistry, and PHREEQ-C modelling were used to identify geochemical reactions altering aquifer mineralogy. XRD and petrographic analyses identified potentially reactive minerals including calcite and dolomite (~2%), pyrite (~1%), and feldspars (~25-60%). Despite the low abundance, calcite dissolution and pyrite oxidation were dominant geochemical reactions. Feldspar weathering produced release rates ~1-2 orders of magnitude slower than calcite dissolution. Calcite dissolution increased the aqueous concentrations of Ca, HCO3, Mg, Mn and Sr. Silicate weathering increased the aqueous concentrations of Si and K. Plagioclase weathering likely increased aqueous Ca concentrations. Pyrite oxidation, despite attempts to remove O2 from the experiment, increased the aqueous concentration of Fe and SO4. SEM-EDS analysis of post-reaction samples identified mixed-layered illite-smectites associated with feldspar grains suggesting clay mineral precipitation in addition to calcite, pyrite and feldspar dissolution. The Vedder Fm. sample underwent complete disaggregation during the reaction due to cement dissolution. This may adversely affect Vedder Formation CCS projects by impacting injection well integrity.

Hot spring deposits on a cliff face: A case study from Jifei, Yunnan Province, China

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2014-04-01

A cliff face in the Jifei karst area, southwest China, is covered by a spectacular succession of precipitates that formed from the hot spring water that once flowed down its surface. This layered succession is formed of aragonite layers that are formed largely of “fountain dendrites”, calcite layers that are formed mostly of “cone dendrites”, and microlaminated layers that contain numerous microbes and extracellular polymeric substances (EPS). Many of the aragonite crystals are hollow due to preferential dissolution of their cores. The calcite cone dendrites are commonly covered with biofilms, reticulate Si-Mg coatings, and other precipitates. The microbial layers include dodecahedral calcite crystals and accessory minerals that include opal-A, amorphous Si-Mg coatings, trona, barite, potassium sulfate crystals, mirabillite, and gaylussite. Interpretation of the δ18O(calcite) and δ18O(aragonite) indicates precipitation from water with a temperature of 54 to 66 °C. The active hot spring at the top of the cliff presently ejects water at a temperature of 65 °C. Layers, 1 mm to 6 cm thick, record temporal changes in the fluids from which the precipitates formed. This succession is not, however, formed of recurring cycles that can be linked to diurnal or seasonal changes in the local climate. Indeed, it appears that the climatic contrast between the wet season and the dry season had little impact on precipitation from the spring waters that flowed down the cliff face. Integration of currently available evidence suggests that the primary driving force was aperiodic changes in the CO2 content of the spring waters because that seems to be the prime control on the saturation levels that underpinned precipitation of the calcite and aragonite as well as the dissolution of the aragonite. Such variations in the CO2 content of the spring water were probably due to changes that took place in the subterranean plumbing system of the spring.

Mass-balance modeling of mineral weathering rates and CO2 consumption in the forested, metabasaltic Hauver Branch watershed, Catoctin Mountain, Maryland, USA

USGS Publications Warehouse

Rice, Karen; Price, Jason R.; Szymanski, David W.

2013-01-01

Mineral weathering rates and a forest macronutrient uptake stoichiometry were determined for the forested, metabasaltic Hauver Branch watershed in north-central Maryland, USA. Previous studies of Hauver Branch have had an insufficient number of analytes to permit determination of rates of all the minerals involved in chemical weathering, including biomass. More equations in the mass-balance matrix were added using existing mineralogic information. The stoichiometry of a deciduous biomass term was determined using multi-year weekly to biweekly stream-water chemistry for a nearby watershed, which drains relatively unreactive quartzite bedrock.At Hauver Branch, calcite hosts ~38 mol% of the calcium ion (Ca2+) contained in weathering minerals, but its weathering provides ~90% of the stream water Ca2+. This occurs in a landscape with a regolith residence time of more than several Ka (kiloannum). Previous studies indicate that such old regolith does not typically contain dissolving calcite that affects stream Ca2+/Na+ ratios. The relatively high calcite dissolution rate likely reflects dissolution of calcite in fractures of the deep critical zone.Of the carbon dioxide (CO2) consumed by mineral weathering, calcite is responsible for approximately 27%, with the silicate weathering consumption rate far exceeding that of the global average. The chemical weathering of mafic terrains in decaying orogens thus may be capable of influencing global geochemical cycles, and therefore, climate, on geological timescales. Based on carbon-balance calculations, atmospheric-derived sulfuric acid is responsible for approximately 22% of the mineral weathering occurring in the watershed. Our results suggest that rising air temperatures, driven by global warming and resulting in higher precipitation, will cause the rate of chemical weathering in the Hauver Branch watershed to increase until a threshold temperature is reached. Beyond the threshold temperature, increased recharge would produce a shallower groundwater table and reduced chemical weathering rates.

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).

Evaluation of the potential of indigenous calcareous shale for neutralization and removal of arsenic and heavy metals from acid mine drainage in the Taxco mining area, Mexico.

PubMed

Romero, F M; Núñez, L; Gutiérrez, M E; Armienta, M A; Ceniceros-Gómez, A E

2011-02-01

In the Taxco mining area, sulfide mineral oxidation from inactive tailings impoundments and abandoned underground mines has produced acid mine drainage (AMD; pH 2.2-2.9) enriched in dissolved concentrations (mg l⁻¹) sulfate, heavy metals, and arsenic (As): SO₄²⁻ (pH 1470-5454), zinc (Zn; 3.0-859), iron (Fe; pH 5.5-504), copper (Cu; pH 0.7-16.3), cadmium (Cd; pH 0.3-6.7), lead (Pb; pH < 0.05-1.8), and As (pH < 0.002-0.6). Passive-treatment systems using limestone have been widely used to remediate AMD in many parts of the world. In limestone-treatment systems, calcite simultaneously plays the role of neutralizing and precipitating agent. However, the acid-neutralizing potential of limestone decreases when surfaces of the calcite particles become less reactive as they are progressively coated by metal precipitates. This study constitutes first-stage development of passive-treatment systems for treating AMD in the Taxco mine area using indigenous calcareous shale. This geologic material consists of a mixture of calcite, quartz, muscovite, albite, and montmorillonite. Results of batch leaching test indicate that calcareous shale significantly increased the pH (to values of 6.6-7.4) and decreased heavy metal and As concentrations in treated mine leachates. Calcareous shale had maximum removal efficiency (100%) for As, Pb, Cu, and Fe. The most mobile metals ions were Cd and Zn, and their average percentage removal was 87% and 89%, respectively. In this natural system (calcareous shale), calcite provides a source of alkalinity, whereas the surfaces of quartz and aluminosilicate minerals possibly serve as a preferred locus of deposition for metals, resulting in the neutralizing agent (calcite) beings less rapidly coated with the precipitating metals and therefore able to continue its neutralizing function for a longer time.

Phylogenetic and Functional Substrate Specificity for Endolithic Microbial Communities in Hyper-Arid Environments

PubMed Central

Crits-Christoph, Alexander; Robinson, Courtney K.; Ma, Bing; Ravel, Jacques; Wierzchos, Jacek; Ascaso, Carmen; Artieda, Octavio; Souza-Egipsy, Virginia; Casero, M. Cristina; DiRuggiero, Jocelyne

2016-01-01

Under extreme water deficit, endolithic (inside rock) microbial ecosystems are considered environmental refuges for life in cold and hot deserts, yet their diversity and functional adaptations remain vastly unexplored. The metagenomic analyses of the communities from two rock substrates, calcite and ignimbrite, revealed that they were dominated by Cyanobacteria, Actinobacteria, and Chloroflexi. The relative distribution of major phyla was significantly different between the two substrates and biodiversity estimates, from 16S rRNA gene sequences and from the metagenomic data, all pointed to a higher taxonomic diversity in the calcite community. While both endolithic communities showed adaptations to extreme aridity and to the rock habitat, their functional capabilities revealed significant differences. ABC transporters and pathways for osmoregulation were more diverse in the calcite chasmoendolithic community. In contrast, the ignimbrite cryptoendolithic community was enriched in pathways for secondary metabolites, such as non-ribosomal peptides (NRP) and polyketides (PK). Assemblies of the metagenome data produced population genomes for the major phyla found in both communities and revealed a greater diversity of Cyanobacteria population genomes for the calcite substrate. Draft genomes of the dominant Cyanobacteria in each community were constructed with more than 93% estimated completeness. The two annotated proteomes shared 64% amino acid identity and a significantly higher number of genes involved in iron update, and NRPS gene clusters, were found in the draft genomes from the ignimbrite. Both the community-wide and genome-specific differences may be related to higher water availability and the colonization of large fissures and cracks in the calcite in contrast to a harsh competition for colonization space and nutrient resources in the narrow pores of the ignimbrite. Together, these results indicated that the habitable architecture of both lithic substrates- chasmoendolithic versus cryptoendolithic – might be an essential element in determining the colonization and the diversity of the microbial communities in endolithic substrates at the dry limit for life. PMID:27014224

Testing CO2 Sequestration in an Alkaline Soil Treated with Flue Gas Desulfurization Gypsum (FGDG)

NASA Astrophysics Data System (ADS)

Han, Y.; Tokunaga, T. K.

2012-12-01

Identifying effective and economical methods for increasing carbon storage in soils is of interest for reducing soil CO2 fluxes to the atmosphere in order to partially offset anthropogenic CO2 contributions to climate change This study investigates an alternative strategy for increasing carbon retention in soils by accelerating calcite (CaCO3) precipitation and promoting soil organic carbon (SOC) complexation on mineral surfaces. The addition of calcium ion to soils with pH > 8, often found in arid and semi-arid regions, may accelerate the slow process of calcite precipitation. Increased ionic strength from addition of a soluble Ca source also suppresses microbial activity which oxidizes SOC to gaseous CO2. Through obtaining C mass balances in soil profiles, this study is quantifying the efficiency of gypsum amendments for mitigating C losses to the atmosphere. The objective of this study is to identify conditions in which inorganic and organic C sequestration is practical in semi-arid and arid soils by gypsum treatment. As an inexpensive calcium source, we proposed to use flue gas desulfurization gypsum (FGDG), a byproduct of fossil fuel burning electric power plants. To test the hypothesis, laboratory column experiments have been conducted in calcite-buffered soil with addition of gypsum and FGDG. The results of several months of column monitoring are demonstrating that gypsum-treated soil have lowered amounts of soil organic carbon loss and increased inorganic carbon (calcite) production. The excess generation of FGDG relative to industrial and agricultural needs, FGDG, is currently regarded as waste. Thus application of FGDG application in some soils may be an effective and economical means for fixing CO2 in soil organic and inorganic carbon forms.Soil carbon cycle, with proposed increased C retention by calcite precipitation and by SOC binding onto soil mineral surfaces, with both processes driven by calcium released from gypsum dissolution.

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.

Monohydrocalcite: a promising remediation material for hazardous anions

PubMed Central

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-01-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3·H2O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite. PMID:27877452

Monohydrocalcite: a promising remediation material for hazardous anions.

PubMed

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-12-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO 3 ·H 2 O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO 4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO 4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO 4 than calcite and aragonite. The modes of PO 4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite.

Monohydrocalcite: a promising remediation material for hazardous anions

NASA Astrophysics Data System (ADS)

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-12-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3·H2O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite.

Uptake of CO2, SO2, HNO3 and HCl on calcite (CaCO3) at 300 K: mechanism and the role of adsorbed water.

PubMed

Santschi, Ch; Rossi, M J

2006-06-01

All experimental observations of the uptake of the four title compounds on calcite are consistent with the presence of a reactive bifunctional surface intermediate Ca(OH)(HCO3) that has been proposed in the literature. The uptake of CO2 and SO2 occurs on specific adsorption sites of crystalline CaCO3(s) rather than by dissolution in adsorbed water, H2O(ads). SO2 primarily interacts with the bicarbonate moiety whereas CO2, HNO3 and HCl all react first with the hydroxyl group of the surface intermediate. Subsequently, the latter two react with the bicarbonate group to presumably form Ca(NO3)2 and CaCl2.2H2O. The effective equilibrium constant of the interaction of CO2 with calcite in the presence of H2O(ads) is kappa = deltaCO2/(H2O(ads)[CO2]) = 1.62 x 10(3) bar(-1), where CO2 is the quantity of CO2 adsorbed on CaCO3. The reaction mechanism involves a weakly bound precursor species that is reversibly adsorbed and undergoes rate-controlling concurrent reactions with both functionalities of the surface intermediate. The initial uptake coefficients gamma0 on calcite powder depend on the abundance of H2O(ads) under the present experimental conditions and are on the order of 10(-4) for CO2 and 0.1 for SO2, HNO3 and HCl, with gamma(ss) being significantly smaller than gamma0 for HNO3 and HCl, thus indicating partial saturation of the uptake. At 33% relative humidity and 300 K there are 3.5 layers of H2O adsorbed on calcite that reduce to a fraction of a monolayer of weakly and strongly bound water upon pumping and/or heating.

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 carbonate-dominated lithologies.

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. Furthermore, our mechanical results highlight the important role of fluids in the evolution of frictional strength and thus fault behavior.

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.

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.

How reactive fluids alter fracture walls and affect shale-matrix accessibility

NASA Astrophysics Data System (ADS)

Fitts, J. P.; Deng, H.; Peters, C. A.

2014-12-01

Predictions of mass transfer across fracture boundaries and fluid flow in fracture networks provide fundamental inputs into risk and life cycle assessments of geologic energy technologies including oil and gas extraction, geothermal energy systems and geologic CO2 storage. However, major knowledge gaps exist due to the lack of experimental observations of how reactive fluids alter the pore structures and accessible surface area within fracture boundaries that control the mass transfer of organics, metals and salts, and influence fluid flow within the fracture. To investigate the fracture and rock matrix properties governing fracture boundary alteration, we developed a new flow-through cell that enables time-dependent 2D x-ray imaging of mineral dissolution and/or precipitation at a fracture surface. The parallel plate design provides an idealized fracture geometry to investigate the relationship between flow rate, reaction rate, and mineral spatial heterogeneity and variation. In the flow-cell, a carbonate-rich sample of Eagle Ford shale was reacted with acidified brine. The extent and rate of mineral dissolution were correlated with calcite abundance relative to less soluble silicate minerals. Three-dimensional x-ray tomography of the reacted fracture wall shows how calcite dissolution left behind a porous network of silicate minerals. And while this silicate network essentially preserved the location of the initial fracture wall, the pore network structures within the fracture boundary were dramatically altered, such that the accessible surface area of matrix components increased significantly. In a second set of experiments with a limestone specimen, however, the extent of dissolution and retreat of the fracture wall was not strictly correlated with the occurrence of calcite. Instead, the pattern and extent of dissolution suggested secondary causes such as calcite morphology, the presence of argillaceous minerals and other diagenetic features. Our experiments show that while calcite dissolution is the primary geochemical driver of fracture wall alterations, hydrodynamic properties and matrix accessibility within fracture boundaries evolve based on a complex relationship between mineral spatial heterogeneity and variation, fluid chemistry and flow rate.

Creep and Sliding in Clays Slopes: Mutual Effects of Interlayer Swelling and Ice Jacking.

DTIC Science & Technology

1984-01-11

chlorite 14% (6-21%) calcite 6,5% (1 - 15%) kaolinite 2% ( 1- 5%) dolomite 0,5% (0 - 4%) montmorillonite 23% (15-35%) Non clay phases 19% (15-30%) Clay...iconcretions, 200 mm coal lenses RE 3 4 Calcite N Quartz Feldspar Illite-muscovite Z Chlorite E Kaolinite montmori 1 loni te Fig. 10: Mineral content... montmorillonite , belong to a fluviatile fresh water cycle and are possibly influenced by volcanic ash falls. The series under investigation belongs to the upper

Desorption and Transformation of Nitroaromatic (TNT) and Nitramine (RDX and HMX) Explosive Residues on Detonated Pure Mineral Phases

DTIC Science & Technology

2011-11-01

surface area measurements were used to compare the pristine and detonated mineral surfaces and to determine if the extreme heat and/or pressures of...gas (N2) in a liquid nitrogen atmosphere (−194.8°C). Results from six relative pressure points were reduced to surface area values applying BET theory...include the minerals quartz, calcite, and dolomite . However, in some detonated Ottawa sand samples the highest intensity peak for calcite at 29° 2Θ

Transformation of the Surface Structure of Marble under the Action of a Shock Wave

NASA Astrophysics Data System (ADS)

Shcherbakov, I. P.; Vettegren, V. I.; Bashkarev, A. Ya.; Mamalimov, R. I.

2018-01-01

The structure of marble fracture fragments formed after the destruction under the action of a shock wave have been analyzed by Raman, infrared, and luminescence spectroscopic techniques. It has been found that calcite I in the surface layer of fragments with thicknesses of about 2 μm is transformed into high-pressure phase calcite III. At the same time, concentrations of Mn2+, Eu3+, and other ions decrease to about onefourth of their initial values.

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.

Spontaneous transition of replacive to displacive growth of dolomite in burial dolomitization, and of serpentine in serpentinization

NASA Astrophysics Data System (ADS)

Merino, E.; Canals, A.

2011-12-01

Burial dolostones consist of huge volumes of dolomite that has replaced limestone volume for volume, with patches < 10 meters across of thin, equidistant "zebra" veins that are displacive. Characteristically, the contact between the two dolomite types is, under the microscope, seamless. This has long puzzled carbonate petrologists, who have mistaken the displacive dolomite veins for "void-filling cements" and therefore expect a sharp contact between the two dolomite types. The replacive dolomite forms not by dissolution-precipitation as usually assumed, but by dolomite-growth-driven pressure solution of the host calcite -- if the host is sufficiently viscous, or rigid. The local stress induced by the dolomite growth self-adjusts automatically so as to force the rates of dolomite growth and calcite pressure-solution to be mutually equal at each moment of the replacement. That is why replacement is always isovolumetric. But the dolomite-for-calcite replacement is self-accelerating via Ca2+ (each replacement increment releases Ca2+, which increases the activity product for dolomite and thus the rate of the next replacement increment, and so on), and crystalline carbonates are non-newtonian solids of the softening kind (as shown experimentally, Heard & Raleigh 1972). Thus, when the dolomite-for-calcite replacement becomes fast enough to reduce the local rock viscosity sufficiently, and if aqueous Mg2+ has not run out by then, the replacive growth will inevitably, and seamlessly, transition to displacive growth. This is when incipient zebra veins start to form. Each vein interacts with its neighbors via the induced stress they exert on each other, which leads to a "weeding" feedback that pressure dissolves some veins (the ones that find themselves too close to their neighbors), leaving the surviving ones more equidistant than before. Dolomitic zebra veins, or "rhythmites", are a good example of syntaxial veins. The same process and feedbacks, via Mg2+ instead of via Ca2+, take place in the serpentinization of ultrabasic rocks, leading also to displacive zebra veins of serpentine in seamless contact with the host, replacive serpentine. The origin of the dolomite zebra veins above turns out to have a serendipitous proof. The same feedback that causes the dolomite-for-calcite replacement to self-accelerate exponentially, raises the pore-fluid Ca2+ concentration also exponentially. Consequently, when the rheological replacement-to-displacement transition takes place, the displacive dolomite is growing under such a huge Ca2+ concentration that some Ca2+, even as submicroscopic calcitic slivers, is forced to substitute for Mg2+ in the structure of the growing dolomite, deforming and curving it. This is why the displacive zebra veins always consist of dolomite crystals that are curved, called saddle dolomite. It also explains why some calcite forms right after the dolomite veins stop growing, as a cement and/or back-replacing dolomite.

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, suggests that the isotopic depletion is tied to the polymorphic inversion of aragonite to calcite, and not just random chance based on natural isotopic variability in the skeleton. There appears to be no relationship between the percent inversion and carbon isotopic composition. Elemental ratios also appear to remain stable during the heating and inversion process. The findings of this and published studies present, in many cases, conflicting views of the isotopic fractionation associated with inversion of aragonite to calcite. Discrepancies such as this likely result from subtle differences in sampling protocol related to instruments, drill bits, skeletal density, and possibly even laboratory conditions like temperature and humidity, further complicating our understanding and interpretation of such observations. Preliminary investigation suggests that altering milling conditions or wet milling may reduce the extent of alteration. Unfortunately, milling/drilling remains one of the only practical methods of sampling biogenic carbonates at a high resolution for paleoclimate work and, as such, caution should be taken in the interpretation of oxygen isotopic measurements from specimens of this nature.

{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 kinetic disequilibria control to a large extent isotope fractionation in ostracod calcite. While the ^13C values are probably also influenced by metabolic effects, previous studies suggest that the ^18O of ostracod calcite correlates well with the ^18O of the ambient water masses. However, this observation is not supported by our limited dataset from the Levantine Basin. The ostracod data do not trace the prominent shift in sea-water ^18O from 15 ka compared to today as it is apparent in the benthic foraminiferal data. High-resolution time series data since the Last Glacial Maximum are desirable to further explore the use of ^18O of marine ostracod calcite as a paleoenvironmental proxy. DIDIÉ, C. & BAUCH, H.A., 2002, Geophysical Monograph, v. 131, p. 279-299. MCCONNAUGHEY, T., 1989, Geochimica et Cosmochimica Acta, v. 53, p. 151-162. SPERO, H.J. & LEA, D.W., 1996, Marine Micropaleontology, v. 28, p. 231-246.

Calcium and Oxygen Isotopic Composition of Calcium Carbonates

NASA Astrophysics Data System (ADS)

Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

2016-04-01

Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40Ca. On the other hand, 40Ca may desorb more easily, especially if the bond strength is lower as in the case of aragonite. For kinetic oxygen isotopic fractionation, the faster deprotonation of HC16O3- and the faster incorporation of C16O32- at the surfaces causes a smaller enrichment of 18O in all three polymorphs, which will be preserved at higher precipitation rates. In consequence to the different behavior of calcium and oxygen isotopes, they can be useful for multiproxy applications. Thereby calcium isotopes can be used to identify kinetic effects, especially if both aragonite and calcite, can be analyzed in one sample. Oxygen isotopes are more strongly related to temperature. [1]A. Niedermayr, S.J. Köhler and M. Dietzel (2013), Chemical Geology, 340, 105-120.

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 2,500 nmol L-1 hr-1 for groundwater and sediments, respectively. The results suggest that the majority (99%) of the in situ urea hydrolyzing potential is associated with organisms attached to the sediments. A mixed kinetic-equilibrium model for ureolytically driven calcite precipitation was developed and parameterized using available characterization data for the 100-N site. The model was used to simulate the effects of urea treatment on the 100-N subsurface, and predict the quantities of calcite precipitated and Sr removed as a co-precipitate. Together, the microbial characterization data and geochemical modeling suggest that the Hanford 100-N area has the requisite microbial geochemical characteristics for application of the ureolytically driven calcite precipitation remediation approach for 90Sr.

Studies of biominerals relevant to the search for life on Mars.

PubMed

Blanco, Armando; D'Elia, Marcella; Licchelli, Domenico; Orofino, Vincenzo; Fonti, Sergio

2006-12-01

The evidence of the water erosion on Mars is particularly interesting since present climatic conditions are such that liquid water cannot exist at the surface. But, if water was present on the planet in the past, there may have been life, too. Since the discovery of carbonates on Mars also may have very important implications on the possibility that life developed there, we are studying minerals that can have biotic or abiotic origin: calcite (CaCO(3)) and aragonite, a metastable state of calcite.We have analysed biomineral aragonite, in the form of recent sea shells, as well as crystals of mineral aragonite. Infrared spectroscopy in the 2-25 mum wavelength range reveals that, after thermal processing, the biotic samples have a different spectral behaviour from the abiotic ones. As a result, it is possible to distinguish abiotic mineral aragonite from aragonite of recent biological origin.Obviously, if life existed in the past on the Red Planet, we could expect to find "ancient" biotic carbonates, which should therefore be investigated, in order to search for a way of discriminating them from abiotic minerals. For this reason, at the beginning we have considered samples of crushed fossil shells of aragonite composition. Afterwards, in order to take into account that fossilization processes almost always produce a transformation of metastable form (aragonite) into more stable form (calcite), we also studied samples of mineral calcite and different types of fossils completely transformed into calcite. All these biotic fossil samples show the same spectral behaviour as the fresh biotic material after thermal annealing at 485 degrees C. Instead, the calcite behaves like abiotic aragonite.Furthermore, it is known that seashells and other biominerals are formed through an intimate association of inorganic materials with organic macromolecules. The macromolecules control the nucleation, structure, morphology, crystal orientation and spatial confinement of the inorganic phase: this differentiates biominerals from minerals. Analysing the aragonite or calcite fossils with a Scanning Electron Microscope, we found that the fossilization process did not modify the structure of the biominerals which maintain their microscopic characteristics. Looking at the morphology of fossil biominerals, it is evident that the crystals are arranged in complex architectures compared with the compact structure of the mineral crystals. In conclusion, the properties and structure of the biominerals are different from those of the minerals. The rapid increase of the crystalline structure developed under biotic conditions makes these minerals less resistant to thermal treatments, compared with samples of abiotic origin. This result holds both for recent shells as well as all fossil samples. The spectroscopic behaviour of all analysed calcium carbonates of biotic origin is different from that of the abiotic one. Therefore, the infrared spectroscopy is a valid technique to discern the origin of the samples and a powerful tool for analysing in-situ and "sample-return" Mars missions specimens. Also Optical and Scanning Electron Microscopy can be useful to support this type of studies.

Polyphase vein mineralization in the Fennoscandian Shield at Åkerlandet, Järvsand, and Laisvall along the erosional front of the Caledonian orogen, Sweden

NASA Astrophysics Data System (ADS)

Saintilan, Nicolas J.; Stephens, Michael B.; Spikings, Richard; Schneider, Jens; Chiaradia, Massimo; Spangenberg, Jorge E.; Ulianov, Alexey; Fontboté, Lluís

2017-08-01

The Åkerlandet, Järvsand, and Laisvall deposits in Sweden are calcite-fluorite-sulfide vein deposits and occurrences located close to the current erosional front of the Caledonian orogen and hosted by crystalline basement rocks in the Fennoscandian Shield. At Laisvall, basement-hosted veinlets occur beneath Ediacaran to Cambrian sandstones that host a strata-bound Pb-Zn deposit. The mineralized fractures at Åkerlandet and Järvsand occur along fault systems oriented N-S to NNW-SSE. Veins or veinlets strike NNW-SSE and NW-SE at Åkerlandet, NNE-SSW at Järvsand, and NNW-SSE and NNE-SSW to NE-SW at Laisvall. At Åkerlandet and Järvsand, fractures acted as conduits for hydrothermal fluids of variable composition and formed during separate tectonic events. At Åkerlandet, the fault zone with NNW-SSE strike shows kinematic indicators consistent with NE-SW bulk horizontal extension. At Järvsand, the calcite-fluorite-galena veins formed along R-Riedel shears related to the host N-S to NNW-SSE fault system. The kinematic indicators are consistent with NW-SE bulk horizontal extension, similar to the extensional deformation during the later part of the Caledonian orogeny (Silurian to Devonian). At Åkerlandet, adularia-quartz deposition was followed by sphalerite ± galena and finally by precipitation of fluorite and calcite. 40Ar-39Ar thermochronology of a single adularia sample did not yield a well-defined plateau age but the gas released at higher temperatures suggests an early Tonian (980 to 950 Ma) crystallization age, i.e., during the later part of the Sveconorwegian orogeny, although the data do not exclude other less likely interpretations. Previous fluid inclusion microthermometry and geochronological studies and new petrographic and geochemical results suggest that sphalerite ± galena mineralization formed from saline, relatively oxidizing, moderate-temperature, and slightly acidic hydrothermal fluids, either during the Ediacaran or the Middle Ordovician. Metals and H2S were derived from local basement rocks. Based on petrographic evidence, rare earth element composition, and S, C, and O isotope data, fluorite and calcite precipitated under near neutral and relatively reducing conditions. Occurrence of solid bitumen in veins at Åkerlandet and C and O isotope data of calcite at Åkerlandet and in the Laisvall basement veinlets suggest that the precipitation of calcite and fluorite was triggered by interaction of hot and evolved hydrothermal fluids (87Sr/86Sr = 0.718-0.732) with organic matter. Structural, petrographic, and geochemical data at Laisvall suggest that the basement structures hosting calcite-fluorite ± pyrite veinlets were utilized in the Middle Ordovician as the plumbing system for the oxidizing, slightly acidic, metal-bearing brines that caused the economic Pb-Zn mineralization in the overlying sandstones.