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

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Huifang Xu

2018-01-01

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

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

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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.

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

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Liu, Chuanjiang; Zheng, Haifei; Wang, Duojun

2017-10-01

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

Mg-lattice associations in red coralline algae

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Kamenos, N. A.; Cusack, M.; Huthwelker, T.; Lagarde, P.; Scheibling, R. E.

2009-04-01

Recent investigations have shown red coralline algae to record ambient temperature in their calcite skeletons. Temperature recorded by variation in Mg concentrations within algal growth bands has sub-annual resolution and high accuracy. The conversion of Mg concentration to temperature is based on the assumption of Ca replacement by Mg within the algal calcite skeleton at higher temperatures. While Mg-temperature relationships in coralline algae have been calibrated for some species, the location of Mg within the calcite lattice remains unknown. Critically, if Mg is not a lattice component but associated with organic components this could lead to erroneous temperature records. Before coralline algae are used in large scale climate reconstructions it is therefore important to determine the location of Mg. Synchrotron Mg-X-ray absorbance near edge structure (XANES) indicates that Mg is associated with the calcite lattice in Lithothamnion glaciale (contemporary free-living, contemporary encrusting and sub-fossil free-living) and Phymatolithon calcareum (contemporary free-living) coralline algae. Mg is deposited within the calcite lattice in all seasons ( L. glaciale & P. calcareum) and thallus areas ( P. calcareum). These results suggest L. glaciale and P. calcareum are robust Mg-palaeotemperature proxies. We suggest that similar confirmation be obtained for Mg associations in other species of red coralline algae aiding our understanding of their role in climate reconstruction at large spatial scales.

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

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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

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

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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.

Calcite precipitates in Slovenian bottled waters.

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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.

Surface tension alteration on calcite, induced by ion substitution

DEFF Research Database (Denmark)

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

2014-01-01

The interaction of water and organic molecules with mineral surfaces controls many processes in nature and industry. The thermodynamic property, surface tension, is usually determined from the contact angle between phases, but how does one understand the concept of surface tension at the nanoscale...... preferentially as ion pairs at solution-calcite interfaces. Mg2+ incorporation weakens organic molecule adhesion while strengthening water adsorption so Mg2+ substitution renders calcite more water wet. When Mg2+ replaces 10% of surface Ca2+, the contact angle changes dramatically, by 40 to 70, converting...

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

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

1997-01-01

and differences in the degree of early diagenesis. Cemented layers and hardgrounds are the result of differential early marine calcite cementation. In these limestones early calcite cementation cannot be explained by the supply of cementing materials from saturated seawater, An alternative model for early marine......The Campanian-Maastrichtian limestones in the south of the Netherlands are well-sorted fine-grained mudstones and silt- to fine sand-sized bioclastic grainstones. These limestones show a distinct lithological cyclicity manifested by fining-upward grain-size cycles with calcite-cemented layers...... calcite cementation is proposed, in which early calcite cementation occurred within the sediment at some distance below the seafloor as a result of organic matter degradation and internal redistribution of bioclastic carbonate. Bacterial organic matter degradation caused dissolution of relatively unstable...

Mechanism of Calcite Co-Orientation in the Sea Urchin Tooth

Energy Technology Data Exchange (ETDEWEB)

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

2009-12-01

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

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

OpenAIRE

Huifang Xu; Mo Zhou; Yihang Fang; H. Henry Teng

2018-01-01

The substrate effect of mica and hematite on the nucleation and crystallization of calcite was investigated using scanning electron microscope (SEM), X-ray diffraction (XRD), and electron backscatter diffraction (EBSD) methods. On mica, we found, in the absence of Mg2+, the substrates’ (001) surfaces with hexagonal and pseudo-hexagonal two-dimensional (2-D) structure can affect the orientation of calcite nucleation with calcite (001) ~// mica (001) and calcite (010) ~// mica (010) to be the m...

Mineralogical-Chemical Characteristics of Calcite from Zletovo, Sasa and Buchim Deposits

International Nuclear Information System (INIS)

Shijakova-lvanova, Tena; Paneva-Zajkova, Vesna; Donova, Ilinka

2006-01-01

The paper presents mineralogical-chemical characteristics, dependence between some elements and concentration of some calcite elements of Zletovo, Sasa and Buchim deposits. Calcite from Sasa, Zletovo and Buchim occurs in rhombohedral crystals of different size. The colour is white, but in Buchim it is white, pink, and yellow. Their twinning is very common. Chemical composition of calcite was determined by AES-ICP. Results show that in calcite from Buchim the concentration of Ba is much higher in pink calcite from than in white or yellow. The concentration of Zn and Ph is the lowest in white calcite. The calcite from Zletovo contains much higher concentrations of Pb, Zn, Sr, but calcite of Buchim which is pink contains higher amounts of Ba and Co. The concentrations of CaO, MgO, and MnO in all calcite simples are approximately equal. Concentration of all other elements in calcite of Sasa, Zletovo and Buchim is approximately equal. TG and DTA curves out on all simples were recorded.The decompositions of the samples of calcite starts at different temperature and it is not finish until 1000 o C. (Author)

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

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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)

Environmental controls for the precipitation of different fibrous calcite cement fabrics

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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

Model study of initial adsorption of SO2 on calcite and dolomite

International Nuclear Information System (INIS)

Malaga-Starzec, Katarina; Panas, Itai; Lindqvist, Oliver

2004-01-01

The rate of calcareous stone degradation is to a significant extent controlled by their surface chemistry with SO 2 . Initial surface sulphite is converted to a harmful gypsum upon, e.g. NO 2 catalysed oxidation. However, it has been observed by scanning electron microscopy that the lateral distributions of gypsum crystals differ between calcitic and dolomitic marbles. The first-principles density functional theory is employed to understand the origin of these fundamentally different morphologies. Here, the stability differences of surface sulphite at calcite CaCO 3 (s) and dolomite Ca x Mg 1-x CO 3 (s) are determined. A qualitative difference in surface sulphite stability, favouring the former, is reported. This is taken to imply that calcitic micro-crystals embedded in a dolomitic matrix act as sinks in the surface sulphation process, controlled by SO 2 diffusion. The subsequent formation of gypsum under such conditions will not require SO 4 2- (aq) ion transport. This explains the homogeneous distribution of gypsum observed on the calcitic micro-crystals in dolomite. In contrast, sulphation on purely calcitic marbles never reaches such high SO 2 coverage. Rather, upon oxidation, SO 4 2- (aq) transport to nucleation centres, such as grain boundaries, is required for the growth of gypsum crystals

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

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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.

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

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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

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

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Tomihiko Higuchi

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

Origin of calcite in the glacigenic Virttaankangas complex

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Nina M. Kortelainen

2007-01-01

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

CaCO3-III and CaCO3-VI, high-pressure polymorphs of calcite: Possible host structures for carbon in the Earth's mantle

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Merlini, M.; Hanfland, M.; Crichton, W. A.

2012-06-01

Calcite, CaCO3, undergoes several high pressure phase transitions. We report here the crystal structure determination of the CaCO3-III and CaCO3-VI high-pressure polymorphs obtained by single-crystal synchrotron X-ray diffraction. This new technical development at synchrotron beamlines currently affords the possibility of collecting single-crystal data suitable for structure determination in-situ at non-ambient conditions, even after multiphase transitions. CaCO3-III, observed in the pressure range 2.5-15 GPa, is triclinic, and it presents two closely related structural modifications, one, CaCO3-III, with 50 atoms in the unit cell [a=6.281(1) Å, b=7.507(2) Å, c=12.516(3) Å, α=93.76(2)°, β=98.95(2)°, γ=106.49(2)°, V=555.26(20) Å3 at 2.8 GPa], the second, CaCO3-IIIb, with 20 atoms [a=6.144(3) Å, b=6.3715(14) Å, c=6.3759(15) Å, α= 93.84(2)°, β=107.34(3)°, γ=107.16(3)°, V=224.33(13) Å3 at 3.1 GPa]. Different pressure-time experimental paths can stabilise one or the other polymorph. Both structures are characterised by the presence of non-coplanar CO3 groups. The densities of CaCO3-III (2.99 g/cm3 at 2.8 GPa) and CaCO3-IIIb (2.96 g/cm3 at 3.1 GPa) are lower than aragonite, in agreement with the currently accepted view of aragonite as the thermodynamically stable Ca-carbonate phase at these pressures. The presence of different cation sites, with variable volume and coordination number (7-9), suggests however that these structures have the potential to accommodate cations with different sizes without introducing major structural strain. Indeed, this structure can be adopted by natural Ca-rich carbonates, which often exhibit compositions deviating from pure calcite. Mg-calcites are found both in nature (Frezzotti et al., 2011) and in experimental syntheses at conditions corresponding to deep subduction environments (Poli et al., 2009). At these conditions, the low pressure rhombohedral calcite structure is most unlikely to be stable, and, at the same

The impact of Mg contents on Sr partitioning in benthic foraminifers

NARCIS (Netherlands)

Mewes, Antje; Langer, Gerald; Reichart, Gert Jan; de Nooijer, L.J.; Nehrke, Gernot; Bijma, Jelle

2015-01-01

Foraminiferal calcite Mg/Ca (Mg/CaCC) is used in paleoceanographic studies to reconstruct temperature. Furthermore, the Mg/CaCC is influenced by different seawater Mg/Ca (Mg/CaSW). Foraminiferal calcite Sr/Ca (Sr/CaCC) can potentially be used to reconstruct Sr/Ca ratios of seawater (Sr/CaSW). As

Relationships Between Temperature, pH, and Crusting on Mg/Ca Ratios in Laboratory-Grown Neogloboquadrina Foraminifera

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Davis, Catherine V.; Fehrenbacher, Jennifer S.; Hill, Tessa M.; Russell, Ann D.; Spero, Howard J.

2017-11-01

Mg/Ca ratio paleothermometry in foraminifera is an important tool for the reconstruction and interpretation of past environments. However, existing Mg/Ca:temperature relationships for planktic species inhabiting middle- and high-latitude environments are limited by a lack of information about the development and impact of low-Mg/Ca ratio "crusts" and the influence of the carbonate system on Mg/Ca ratios in these groups. To address this, we cultured individual specimens of Neogloboquadrina incompta and Neogloboquadrina pachyderma in seawater across a range of temperature (6°-12°C) and pH (7.4-8.2). We found by laser ablation inductively couple mass spectrometry analyses of shells that culture-grown crust calcite in N. incompta had a lower Mg/Ca ratio than ontogenetic calcite formed at the same temperature, suggesting that temperature is not responsible for the low-Mg/Ca ratio of neogloboquadrinid crusts. The Mg/Ca:temperature relationship for ontogenetic calcite in N. incompta was consistent with the previously published culture-based relationship, and no significant relationship was found between Mg/Ca ratios and pH in this species. However, the Mg/Ca ratio in laboratory-cultured N. pachyderma was much higher than that reported in previous core top and sediment trap samples, due to lack of crust formation in culture. Application of our ontogenetic calcite-specific Mg/Ca:temperature relationships to fossil N. pachyderma and N. incompta from five intervals in cores from the Santa Barbara Basin and the Bering Sea shows that excluding crust calcite in fossil specimens may improve Mg/Ca-based temperature estimates.

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

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Iris Heine

2017-01-01

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

Model study of initial adsorption of SO{sub 2} on calcite and dolomite

Energy Technology Data Exchange (ETDEWEB)

Malaga-Starzec, Katarina; Panas, Itai; Lindqvist, Oliver

2004-01-30

The rate of calcareous stone degradation is to a significant extent controlled by their surface chemistry with SO{sub 2}. Initial surface sulphite is converted to a harmful gypsum upon, e.g. NO{sub 2} catalysed oxidation. However, it has been observed by scanning electron microscopy that the lateral distributions of gypsum crystals differ between calcitic and dolomitic marbles. The first-principles density functional theory is employed to understand the origin of these fundamentally different morphologies. Here, the stability differences of surface sulphite at calcite CaCO{sub 3} (s) and dolomite Ca{sub x}Mg{sub 1-x}CO{sub 3} (s) are determined. A qualitative difference in surface sulphite stability, favouring the former, is reported. This is taken to imply that calcitic micro-crystals embedded in a dolomitic matrix act as sinks in the surface sulphation process, controlled by SO{sub 2} diffusion. The subsequent formation of gypsum under such conditions will not require SO{sub 4}{sup 2-} (aq) ion transport. This explains the homogeneous distribution of gypsum observed on the calcitic micro-crystals in dolomite. In contrast, sulphation on purely calcitic marbles never reaches such high SO{sub 2} coverage. Rather, upon oxidation, SO{sub 4}{sup 2-} (aq) transport to nucleation centres, such as grain boundaries, is required for the growth of gypsum crystals.

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

Science.gov (United States)

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.

Effect of different seawater Mg

NARCIS (Netherlands)

Mewes, A.; Langer, G.; de Nooijer, L.J.; Bijma, J.; Reichart, G.J.

2014-01-01

Magnesium, incorporated in foraminiferal calcite (Mg/CaCC), is used intensively to reconstruct past seawater temperatures but, in addition to temperature, the Mg/CaCC of foraminiferal tests also depends on the ratio of Mg and Ca in seawater (Mg/CaSW). The physiological mechanisms responsible for

Magnesian calcite and the problem of the origin of carbonates in the deep-sea Old Black Sea sediments

Energy Technology Data Exchange (ETDEWEB)

Georgiev, V M

1988-04-01

The Old Black Sea (Lower-Middle Holocene) deep-sea sediments in the Black Sea basin contain carbonate laminae with a fixed position in the section - in the base of the typical sapropelic muds. The areal distribution of these laminae covers the whole continental slope and rise. They are usually lacking in the sediments of the abyssal plain. XRD, SEM and EDS studies show that the laminae comprise mainly authigenic carbonates - aragonite and magnesian calcite. Aragonite occurs as elongated rice-shaped monocrystals or as diverse aggregates of elongated crystal platelets. The magnesian calcite (6-14 mol % MgCO/sub 3/) forms aggregates of isometric grains with submicritic dimensions between the aragonite grains or individual laminae consisting of idiomorphic rhombohedral and/or skeleton crystals. Low-magnesian calcite is also found sometimes. Usually it is related to Holocene coccoliths without traces of recrystallization. The laminae do not show traces of lithification. A hemogenic-synsedimentary genesis of the carbonate laminae is suggested; their mineral composition witnesses marine chemical composition of the initial solutions with a high Mg/Ca ratio.

Intracrystalline deformation of calcite

NARCIS (Netherlands)

Bresser, J.H.P. de

1991-01-01

It is well established from observations on natural calcite tectonites that intracrystalline plastic mechanisms are important during the deformation of calcite rocks in nature. In this thesis, new data are presented on fundamental aspects of deformation behaviour of calcite under conditions where

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

Science.gov (United States)

Reddy, Michael M.; Leenheer, Jerry

2011-01-01

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

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

Science.gov (United States)

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.

Biomineralization processes of calcite induced by bacteria isolated from marine sediments.

Science.gov (United States)

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

2015-06-01

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.

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

Science.gov (United States)

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).

Influence of the Mg-content on ESR-signals in synthetic calcium carbonate

International Nuclear Information System (INIS)

Barabas, M.; Bach, A.; Mudelsee, M.; Mangini, A.

1989-01-01

Carbonate crystals doped with various concentrations of Mg 2+ -ions have been grown by a gel-diffusion method. An increase of the Mg/Ca-ratio to more than about 1 caused a phase change in the crystal lattice from calcite to aragonite. The properties of the ESR-signals of the synthetic carbonates were studied and compared with natural marine carbonates. The following results were derived: (a) In the presence of Mg 2+ -ions the synthetic carbonates display the same ESR-signals as natural calcites of marine origin with similar properties (thermal stability, radiation sensitivity). (b) The saturation value of the signal at g=2.0006 in synthetic calcites was found to be strongly related with the Mg-content in the crystals. (c) The signal at g=2.0036 (axial symmetry) which is present in calcite was not influenced by the Mg-concentration. Its saturation value decreases when the crystal phase changed from calcite to aragonite and in complement the signal at g=2.0031 appeared. (d) The signals at g=2.0057 and g=2.0031 are most probably not of organic origin. (author)

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

Science.gov (United States)

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

2016-04-01

microreactors during reactive fluid flow: experimental dolomitization of a calcite marble. Contributions to Mineralogy and Petrology. 168:1045. 2. Jonas L., Müller T., Dohmen R., Baumgartner L., Putlitz B. (2015). Transport-controlled hydrothermal replacement of calcite by Mg-carbonates. Geology. doi:10.1130/G36934.1 3. Kaczmarek S.E., Sibley D.F., (2011). On the evolution of dolomite stoichiometry and cation order during high-temperature synthesis experiments: An alternative model for geochemical evolution of natural dolomites. Sedimentary Geology. 246, 30-40.

Study of reverse flotation of calcite from scheelite in acidic media

Science.gov (United States)

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

2018-05-01

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

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

Science.gov (United States)

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

. 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.

The coprecipitation of Sr2+ with calcite at 250C and 1 atm

International Nuclear Information System (INIS)

Pingitore, N.E. Jr.; Eastman, M.P.

1986-01-01

The incorporation of Sr 2+ into calcite at earth surface aqueous conditions is affected by the absolute concentration of Sr 2+ , the presence of Ba 2+ and NaCl in the solution and the rate of precipitation. At solution ratios (molar) of Sr 2+ to Ca 2+ in the low 10 -3 range, which yield calcites with several hundred ppm Sr 2+ , kappasub(calcite) sup(Sr) typically assumes a value between 0.10 and 0.20. Above these concentrations the value of kappasub(calcite) sup(Sr) drops to approximately 0.06. Furthermore, if minor amounts of Ba 2+ or large amounts of Na + (0.48 M) are added to a dilute Sr 2+ solution, a value around 0.06 for kappasub(calcite)sup(Sr) is found. This 'strontium concentration effect' and the associated 'competitive cation effect' suggest that small amounts of Sr 2+ may be incorporated into a limited number of nonlattice sites in calcite. Incorporation of Sr 2+ into these sites, presumably defects, noticeably affects kappasub(calcite)sup(Sr) only at low Sr 2+ concentrations and in the absence of competition from other large cations. An increase in kappasub(calcite)sup(Sr) with rate of precipitation, qualitatively similar to that found in other studies, was observed only when precipitation times were decreased from days to hours. For many geologic settings a partition coefficient for Sr 2+ into calcite of 0.06 appears appropriate, but there are situations - very low Sr 2+ concentrations, the presence of Mg 2+ , and fast precipitation rates - in which a larger value might better approximate natural partitioning. (author)

Two new solid solutions in calcite-magnesite system identified in a sample from coral reefs in the northern Perth basin

International Nuclear Information System (INIS)

Li, D.Y.; O'Connor, B.H.; Zhu, Z.R.; Collins, L.B.; Hunter, B.

1998-01-01

Full text: Dolomite, CaMg(CO 3 ) 2 , is an economically important mineral, being of particular significance in petroleum geology. Carbonate rocks have long been a focus of investigation because these rocks contain an estimated 60 percent of the world's recoverable petroleum, and include most of the world's largest reservoirs. Correct phase identification in carbonates has concerned sedimentologists and petroleum geologists for decades. A new type of solid solution in the calcite (CaCO 3 ) - magnesite (MgCO 3 ) system has been identified at Curtin University by Rietveld XRD and neutron diffraction data analysis in a sample from late Pleistocene reefs in the northern Perth Basin. It is known that the structure of calcite (space group R3C) will be transformed to dolomite (R3), which has an ordered distribution of Ca and Mg in the structure, if 50% of its Ca atoms are substituted by Mg in terms of the Ca-Mg atomic ratio. However, the upper limit of Mg substitution for Ca in calcite under sedimentary-geological conditions without there being a change in structure to dolomite is still unknown. Two carbonates examined at Curtin showed Mg substitution for Ca in calcite under coral reef sedimentary conditions of 18.1% and 37.7%, whereas Bragg peak shifts for a 'dolomite, line for these samples were interpreted by geologists as indicative of dolomite with a certain extent of order-disorder distribution between Ca and Mg atoms. The observations have provided an opportunity to re-examine the origins of dolomite and aspects of dolomitization in a coral reef environment in the Quaternary

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

KAUST Repository

Li, Yan Vivian

2016-03-02

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

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

Energy Technology Data Exchange (ETDEWEB)

Li, Yan Vivian, E-mail: yan.li@colostate.edu [Colorado State University, Department of Design and Merchandising (United States); Cathles, Lawrence M., E-mail: lmc19@cornell.edu [Cornell University, Earth and Atmospheric Sciences (United States)

2016-03-15

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

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

International Nuclear Information System (INIS)

Li, Yan Vivian; Cathles, Lawrence M.

2016-01-01

A new class of nearly charge-neutral carbon-cored nanoparticle tracers are remarkably non-interactive with solid surfaces and could provide a valuable baseline for diverse hydrological and environmental studies of subsurface flow and particle transport. We investigate the causes of inertness by studying the interactions with calcite of a nanoparticle of this class synthesized from malic acid and ethanolamine (M-dots) dispersed in brine (NaCl, CaCl_2, and MgCl_2) solutions. None of the M-dots are retained in calcite sand-packed columns when dispersed in DI water. Dispersed in the NaCl and mixed brine solutions, 5.6 % of and 7.3 % of the M-dots are initially retained, but 65 and 13 % of these retained particles are subsequently released when the column is flushed with DI water. When dispersed in the CaCl_2 and MgCl_2 solutions, 65 and 54 % of the M-dots are initially retained, and 28 and 26 % subsequently released in the DI water flush. The M-dots have a small negative zeta potential in all solutions, but the calcite zeta potential changes from strongly negative to strongly positive across the solution series, and the particle retention tracks this change. Derjaguin–Landau–Verwey–Overbeek (DLVO) modeling of the force between a calcite probe and an M-dot coated surface shows that hydration forces repel the particles in the DI water, NaCl, and mixed solutions, but not in the CaCl_2 and MgCl_2 solutions. These results show that near-zero charge and strongly hydrophilic decoration are the causes of the remarkable inertness of carbon-cored nanoparticles, and also suggest that nanoparticles could be useful in solute-surface interaction studies.Graphical Abstract

Evolution and the Calcite Eye Lens

OpenAIRE

Williams, Vernon L.

2013-01-01

Calcite is a uniaxial, birefringent crystal, which in its optically transparent form, has been used for animal eye lenses, the trilobite being one such animal. Because of the calcite birefringence there is a difficulty in using calcite as a lens. When the propagation direction of incoming light is not exactly on the c-axis, the mages blur. In this paper, calcite blurring is evaluated, and the non-blurring by a crystallin eye lens is compared to a calcite one.

Nickel adsorption on chalk and calcite

DEFF Research Database (Denmark)

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

2014-01-01

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

Shock-induced devolatilization of calcite

Science.gov (United States)

Boslough, M. B.; Ahrens, T. J.; Vizgirda, J.; Becker, R. H.; Epstein, S.

1982-01-01

Experimental measurements of the release adiabats by Vizgirda (1981) indicate that substantial vaporization takes place upon release from shock pressures of 37 GPa for calcite and 14 GPa for aragonite. The present investigation includes the first controlled partial vaporization experiments on calcite. The experiments were conducted to test the predictions of the release adiabat experiments. The quantities of the gaseous species produced from shocked calcite and their carbon and oxygen isotopic compositions were determined, and the shock-induced effect on the Mn(2+) electron spin resonance spectrum in the shock-recovered calcite was observed. On the basis of the obtained results, it is concluded that shock stresses at the 17-18 GPa level give rise to volatilization of 0.03-0.3 (mole) percent of calcite to CO2 and CO. The devolatilization of calcite occurs at low pressure at significantly lower entropy densities than predicted on the basis of thermodynamic continuum models.

Utilization of calcite produced in Turkey for paper coating

Directory of Open Access Journals (Sweden)

Hüdaverdi Eroğlu

2002-03-01

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

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

Science.gov (United States)

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.

Strontium Incorporation into Calcite Generated by Bacterial Ureolysis

International Nuclear Information System (INIS)

Yoshiko Fujita; George D. Redden; Jani C. Ingram; Marnie M. Cortez; Robert W. Smith

2004-01-01

Strontium incorporation into calcite generated by bacterial ureolysis was investigated as part of an assessment of a proposed remediation approach for 90Sr contamination in groundwater. Urea hydrolysis produces ammonium and carbonate and elevates pH, resulting in the promotion of calcium carbonate precipitation. Urea hydrolysis by the bacterium Bacillus pasteurii in a medium designed to mimic the chemistry of the Snake River Plain Aquifer in Idaho resulted in a pH rise from 7.5 to 9.1. Measured average distribution coefficients (DEX) for Sr in the calcite produced by ureolysis (0.5) were up to an order of magnitude higher than values reported in the literature for natural and synthetic calcites (0.02-0.4). They were also higher than values for calcite produced abiotically by ammonium carbonate addition (0.3). The precipitation of calcite in these experiments was verified by X-ray diffraction. Time-of-flight secondary ion mass spectrometry (ToF SIMS) depth profiling (up to 350 nm) suggested that the Sr was not merely sorbed on the surface, but was present at depth within the particles. X-ray absorption near edge spectra showed that Sr was present in the calcite samples as a solid solution. The extent of Sr incorporation appeared to be driven primarily by the overall rate of calcite precipitation, where faster precipitation was associated with greater Sr uptake into the solid. The presence of bacterial surfaces as potential nucleation sites in the ammonium carbonate precipitation treatment did not enhance overall precipitation or the Sr distribution coefficient. Because bacterial ureolysis can generate high rates of calcite precipitation, the application of this approach is promising for remediation of 90Sr contamination in environments where calcite is stable over the long term

Biocementation of Concrete Pavements Using Microbially Induced Calcite Precipitation.

Science.gov (United States)

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

2017-07-28

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

Molecular ordering of ethanol at the calcite surface

DEFF Research Database (Denmark)

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

2012-01-01

To produce biominerals, such as shells, bones, and teeth, living beings create organic compounds that control the growth of the solid phase. Investigating the atomic scale behavior of individual functional groups at the mineral-fluid interface provides fundamental information that is useful...... for constructing accurate predictive models for natural systems. Previous investigations of the activity of coccolith-associated polysaccharides (CAP) on calcite, using atomic force microscopy (AFM) [ Henriksen, K., Young, J. R., Bown, P. R., and Stipp, S. L. S.Palentology 2004, 43 (Part 3), 725...... dynamics (MD) simulations, the structuring on calcite of a layer of the simplest carbon chain molecule that contains an OH group, ethanol (CH 3-CH2-OH). We found evidence that EtOH forms a highly ordered structure at the calcite surface, where the first layer molecules bond with calcite. The ethanol...

Arsenic uptake in bacterial calcite

Science.gov (United States)

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.

Arsenic uptake in bacterial calcite

Energy Technology Data Exchange (ETDEWEB)

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

2018-02-01

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

Fracture calcites at Olkiluoto. Evidence from quaternary infills for palaeohydrogeology

International Nuclear Information System (INIS)

Gehoer, S.; Kaerki, A.; Taikina-aho, O.; Karhu, J.; Loefman, J.; Pitkaenen, P.; Ruotsalainen, P.

2002-02-01

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

Fracture calcites at Olkiluoto. Evidence from quaternary infills for palaeohydrogeology

Energy Technology Data Exchange (ETDEWEB)

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

2002-02-01

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

Coprecipitation of cadmium with calcite

International Nuclear Information System (INIS)

Fujino, Osamu; Kumagai, Tetsu; Shigematsu, Tsunenobu; Matsui, Masakazu

1976-01-01

The distribution of cadmium between precipitates of calcite and saturated aqueous solution was measured at 25 0 C to understand the distribution of cadmium in the bivalves. Calcite was precipitated from calcium bicarbonate solution by the gradual release of carbon dioxide. The cadmium ions were coprecipitated in calcite, obeying the logarithmic distribution law. The apparent distribution coefficient was decreased as α, α'-dipyridyl increased, but the true distribution coefficient was found to be an almost constant value, 560. This value is fairly close to the ratio of solubility product constants K sub(calcite)/K sub(CdCO 3 ), 890. This suggests that the deviation of the present solid solution from ideality is not very large. (auth.)

Sealing process with calcite in the Nojima active fault zone revealed from isotope analysis of calcite

International Nuclear Information System (INIS)

Arai, Takashi; Tsukahara, Hiroaki; Morikiyo, Toshiro

2003-01-01

The Nojima fault appeared on the surface in the northern part of Awaji Island, central Japan as a result of the Hyogo-ken Nanbu earthquake (1995, M=7.2). Active fault drilling was performed by the Disaster Prevention Research Institute (DPRI), Kyoto University, and core samples were retrieved from 1410 to 1710 m, which were composed of intact and fractured granodiorites. We obtained calcite samples and gas samples from the vein in marginal fracture and non-fracture zones. We analyzed the carbon and oxygen isotope ratios of calcite and carbon dioxide to investigate the characteristic isotope ratios of fluids in the active fault zone, to estimate the origins of fluids, and to determine the sealing process of fractures. The analyzed values of carbon and oxygen isotope ratios of calcite were -10.3 to -7.2 per mille, 18 to 23 per mille, respectively, and carbon isotope ratios of CO 2 were -21 to -17 per mille. If carbon isotope ratios of calcite were at equilibrium with those of CO 2 , the precipitation temperature of calcite is calculated to be 30 to 50 deg C. This temperature is consistent with the present temperature of the depth where drilling cores were retrieved. Oxygen isotope ratios of H 2 O that, precipitated calcite were calculated to be -1.8 to -5.5 per mille. These values indicate calcite were precipitated from mixed fluids of sea water and meteoric water. Therefore, the marginal fracture zone of the Nojima fault was sealed with calcite, which was generated from mixing of sea water and meteoric water in situ. (author)

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

Science.gov (United States)

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

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

Directory of Open Access Journals (Sweden)

Bernd ZOLITSCHKA

2009-08-01

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

Cretaceous joints in southeastern Canada: dating calcite-filled fractures

Science.gov (United States)

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

Diagenesis of echinoderm skeletons: Constraints on paleoseawater Mg/Ca reconstructions

Science.gov (United States)

Gorzelak, Przemysław; Krzykawski, Tomasz; Stolarski, Jarosław

2016-09-01

One of the most profound environmental changes thought to be reflected in chemical composition of numerous geological archives is Mg/Ca ratio of the seawater, which has varied dramatically throughout the Phanerozoic. Echinoderms that today typically form high magnesium calcite skeletons are increasingly being utilized as a proxy for interpreting secular changes in seawater chemistry. However, accurate characterization of the diagenetic changes of their metastable high magnesium calcite skeletons is a prerequisite for assessing their original, major-element geochemical composition. Here we expand the existing models of diagenesis of echinoderm skeleton by integration of various analytical methods that up to now rarely have been used to assess the diagenetic changes of fossil echinoderms. We validated the preservation of a suite of differently preserved echinoderm ossicles, mostly crinoids, ranging in age from the Cambrian through Recent. In 13 of 99 fossil echinoderm ossicles we found well-preserved porous microstructure (stereom), non-luminescent behaviour or blotchy dark color in cathodoluminescence, and distinct nanostructural features (layered and nanocomposite structure). Moreover, in representatives of such preserved samples, distribution of sulphates associated with organic matter is identical to those in Recent echinoderms. Only such ossicles, despite of local micrometer-scale diagenetic changes, were herein considered well-preserved, retaining their original major-element skeletal composition. By contrast, majority of samples show transformation to the stable low magnesium calcite that leads to obliteration of the primary geochemical and micro/nanostructural features and is accompanied with increase in cathodoluminescence emission intensity. Using only well-preserved fossil echinoderm samples, we found purely random variation in Mg/Ca in echinoderm skeletons through the observed time series; any periodicities in echinoderm skeletal Mg/Ca ratio which might

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

Science.gov (United States)

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 calcite literature thermal data was obtained at 1000 mbar or higher pressures.

Effect of different seawater Mg2 + concentrations on calcification in two benthic foraminifers

Science.gov (United States)

Mewes, Antje; Langer, Gerald; de Nooijer, Lennart Jan; Bijma, Jelle; Reichart, Gert-Jan

2014-01-01

Magnesium, incorporated in foraminiferal calcite (Mg/CaCC), is used intensively to reconstruct past seawater temperatures but, in addition to temperature, the Mg/CaCC of foraminiferal tests also depends on the ratio of Mg and Ca in seawater (Mg/CaSW). The physiological mechanisms responsible for these proxy relationships are still unknown. This culture study investigates the impact of different seawater [Mg2 +] on calcification in two benthic foraminiferal species precipitating contrasting Mg/CaCC: Ammonia aomoriensis, producing low-Mg calcite and Amphistegina lessonii, producing intermediate-Mg calcite. Foraminiferal growth and test thickness were determined and, Mg/Ca was analyzed using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). Results show that at present-day seawater Mg/CaSW of ~ 5, both species have highest growth rates, reflecting their adaptation to modern seawater element concentrations. Test thickness is not significantly affected by different Mg/CaSW. The relationship between Mg/CaSW and Mg/CaCC shows a distinct positive y-axis intercept, possibly reflecting at least two processes involved in foraminiferal biomineralization. The associated Mg partition (DMg) changes non-linearly with increasing Mg/CaSW, hence suggesting that the DMg is best described by an exponential function approaching an asymptote. PMID:26089590

Calcite encrustation in macro-algae Chara and its implication to the formation of carbonate-bound cadmium

International Nuclear Information System (INIS)

Siong, Kian; Asaeda, Takashi

2009-01-01

We studied the relationship between macro-algae Chara (Stoneworts) calcite (CaCO 3 ) encrustation and the speciation of cadmium (Cd) accumulated by the plant. Results showed that 17% of the total Cd (0.3 mg kg -1 ) accumulated by Chara fibrosa exposed to 1 μg Cd L -1 was carbonate-bound. The percentage of carbonate-bound Cd in the plant exposed to 10 μg Cd L -1 increased from 48% in young thalli (total Ca -1 , total Cd: 125 mg kg -1 ) to 63% in calcified mature thalli (total Ca: 190 mg g -1 ; total Cd: 134 mg kg -1 ). Based on mineral saturation calculation and reliability analysis of the sequential fractionation procedure, precipitation of otavite (CdCO 3 ) and co-precipitation of Cd with calcite, occurring in the alkaline regions of Chara cell wall, are probably the mechanisms of carbonate-bound Cd formation. Thick marl sediment frequently found beneath charophyte meadows suggests a long-term storage of Ca as well as the precipitated or co-precipitated Cd in the sediment after the plant senescence and decomposition.

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

Science.gov (United States)

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

2014-01-01

In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic and hydrophobic interactions, with hydrophobic interactions playing the dominant role. While either strong electrostatic or hydrophobic interactions inhibit growth and reduces expression of the {104} faces, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate electrostatic interactions allow peptoids to weakly adsorb while moderate hydrophobic interactions cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of the {104} faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications. PMID:25189418

Kinetics and Mechanisms of Calcite Reactions with Saline Waters

Energy Technology Data Exchange (ETDEWEB)

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

2015-09-02

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

Structural evolution of calcite at high temperatures: Phase V unveiled

Science.gov (United States)

Ishizawa, Nobuo; Setoguchi, Hayato; Yanagisawa, Kazumichi

2013-01-01

The calcite form of calcium carbonate CaCO3 undergoes a reversible phase transition between Rc and Rm at ~1240 K under a CO2 atmosphere of ~0.4 MPa. The joint probability density function obtained from the single-crystal X-ray diffraction data revealed that the oxygen triangles of the CO3 group in the high temperature form (Phase V) do not sit still at specified positions in the space group Rm, but migrate along the undulated circular orbital about carbon. The present study also shows how the room temperature form (Phase I) develops into Phase V through an intermediate form (Phase IV) in the temperature range between ~985 K and ~1240 K. PMID:24084871

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

Science.gov (United States)

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.

Acidization of shales with calcite cemented fractures

Science.gov (United States)

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

Paleohydrogeological implications from fracture calcites in fissures of low transmissivity. A report of investigations in 2011

International Nuclear Information System (INIS)

Sahlstedt, E.; Karhu, J.

2014-07-01

Samples of fracture fillings were collected from 26 bedrock fractures at Olkiluoto. Special attention was paid to fractures having low transmissivities of <1E-8 m 2 /s. The chemical composition and the C and O isotopic composition of the fracture filling calcite were analysed. In addition, fluid inclusions were studied and microthermometric measurements conducted on fracture filling calcite. The most common minor element in calcite fillings was Mn, having concentrations up to 3.4 wt-%. The δ13C values had a wide range, from -13.0 to 14.5 per mille, and the δ18O values a narrower range, from -13.4 to -7.3 per mille. The δ18O values of late-stage calcite appear to be independent of the transmissivity of the fractures, ranging from -11.2 to -7.3 per mille over a T range from 3E -6 to 1.6E -1 1 m 2 /s. The δ13C values of late-stage calcite appear to have more variation at high transmissivities of >1E-8 m 2 /s. Unusually low and high δ13C values in late-stage calcite fillings occur in the upper ∼ 400 m of the bedrock and are probably related to microbial reduction processes, at near surface (<60 m) conditions to oxidation of organic matter resulting in low δ13C values and at ∼ 55-400 m to methanogenesis, causing high δ 13C values. A relatively low spread in the δ 13C values of late-stage calcite precipitates in low transmissivity (<1E-8 m 2 /s) fractures is most likely caused by stable conditions in the areas of low conductivity in the bedrock, reflecting slow dissolution/reprecipitation of older carbonate fillings. Fluid inclusion data indicate variation in fracture water types from high temperature, ∼ 200 deg C, low salinity fluid with < 4 wt-% of NaCl eq to low temperature, <100 deg C, high salinity fluid with 17-29 wt-% of NaCl eq . The high temperature fluid is associated with Group 5 calcite fillings and the low temperature fluid with Group 3 calcite. The composition of fluids related to Group 4 calcite falls roughly between the compositions

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

Directory of Open Access Journals (Sweden)

C. Neal

2001-01-01

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

Mechanisms of metasomatism in the calcite-pitchblende system: 2. Replacement of pitchblende by calcite

International Nuclear Information System (INIS)

Dymkov, Yu.M.

1996-01-01

The principal mechanisms of the nasturan replacement by calcite -intrametasomatism, frontal metasomatism, dispersive metasomatism, and transformative metasomatism - are discussed in terms of G.L. Pospelov's (1973) concept. The main chemical condition required by the process is an oxidized environment, in which the tetravalent uranium of pitchblende or transitional reduced phases (coffinite) oxidizes to yield readily soluble uranyl compounds. The latter are replaced by calcite

The role of Mg in the crystallization of monohydrocalcite

Science.gov (United States)

Rodriguez-Blanco, Juan Diego; Shaw, Samuel; Bots, Pieter; Roncal-Herrero, Teresa; Benning, Liane G.

2014-02-01

Monohydrocalcite is a member of the carbonate family which forms in Mg-rich environments at a wide range of Mg/Ca ratios Mg2+aq/Ca2+aq≥0.17stock solutions. However, its crystallite and particle size are inversely proportional to these parameters. At high supersaturations (SIMHC = 3.89) nanometer-sized single crystals of monohydrocalcite form, while at low values (SIMHC = 2.43) the process leads to low-angle branching spherulites. Many carbonates produced during biomineralization form at similar conditions to most synthetic monohydrocalcites, and thus we hypothesize that some calcite or aragonite deposits found in the geologic record that have formed at high Mg/Ca ratios could be secondary in origin and may have originally formed via a metastable monohydrocalcite intermediate. High-Mg monohydrocalcite (χMgCO3 > 0.06) consists of individual nanometer-sized crystals (500 °C (Fig. 9b). Such high-Mg monohydrocalcites are uncommon in nature, but can be synthesized in the laboratory at high initial supersaturation levels (SI > 3.25). Low-Mg monohydrocalcite (χMgCO3 bonded to Mg, so it fully dehydrates at low temperatures (150-200 °C). They have the same composition as natural monohydrocalcites reported in the literature, and can be synthesized in the laboratory at lower supersaturation levels (SI relationships. Firstly, our on-line experiment shows an increase in nanocrystal sizes during the secondary crystallization of monohydrocalcite, which is coupled with a significant decrease in χMgCO3 (from ˜0.26 to ˜0.065). This corresponds to the transition from high- to low-Mg monohydrocalcite, suggesting that the former would be metastable and rapidly transforming to the latter, possibly triggered by the removal of Mg from aqueous solution. Secondly, Davis et al. (2000) determined that the solubility of Mg-calcite (Ca1-xMgxCO3; x = 0-0.20) varies by approximately half an order of magnitude depending on the Mg content of the solid (Ksp = 10-8.0-10-8.5). A similar

X-ray scattering of calcite thin films deposited by atomic layer deposition: Studies in air and in calcite saturated water solution

Energy Technology Data Exchange (ETDEWEB)

Wang, Peng [Lujan Neutron Scattering Center, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Hudak, Michael R.; Lerner, Allan [Earth and Environmental Sciences Division, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Grubbs, Robert K. [Sandia National Laboratories, P.O. Box 5800, Albuquerque, NM 87185 (United States); Wang, Shanmin [Lujan Neutron Scattering Center, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Zhang, Zhan; Karapetrova, Evguenia [Advance Photon Source, Argonne National Laboratory, 9700S Cass Ave, Argonne, IL 60439 (United States); Hickmott, Donald [Earth and Environmental Sciences Division, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Majewski, Jaroslaw, E-mail: jarek@lanl.gov [Lujan Neutron Scattering Center, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States)

2014-08-28

Carbonates are one of the most abundant groups of minerals in earth systems and are important in many geological settings and industrial processes. Calcite (CaCO{sub 3}) thin films produced by atomic layer deposition offer a method to evaluate the surficial properties of carbonates as well as interactions at the carbonate–fluid interface. Using synchrotron X-ray reflectivity and X-ray diffraction, these films are observed to be porous, polycrystalline, and have crystallites oriented with the major (104) calcite cleavage plane parallel to the surface of the z-cut single crystal quartz substrate. An Al{sub 2}O{sub 3} buffer layer, present between quartz and the calcite film, does not affect the as-deposited film, but does influence how the films reorganize in contact with fluid. Without a buffer layer, calcite reorients its crystallites to have populations of (006) and (030) parallel to the substrate, while those with an Al{sub 2}O{sub 3} buffer layer become more amorphous. Amorphous films may represent an analog to amorphous calcium carbonate and provide insights into that material's thermophysical behavior. Due to a higher percentage of pore spaces available for fluid infiltration, films deposited at higher temperature make the calcite thin films more susceptible to amorphization. These films are chemically similar, but structurally dissimilar to bulk natural calcite. Nevertheless, they can be a complementary system to traditional single crystal X-ray surface scattering studies on carbonates, particularly for important but less common minerals, to evaluate mineral–fluid interfacial interactions. - Highlights: • Atomic layer deposition (ALD) used to produce calcite films. • Calcite film orientation and crystallinity depend on ALD parameters. • ALD calcite films can be both crystalline and amorphous. • Interaction of water with films can re-orient or amorphize the films. • ALD calcite films may be useful to study carbonate–fluid interfacial

X-ray scattering of calcite thin films deposited by atomic layer deposition: Studies in air and in calcite saturated water solution

International Nuclear Information System (INIS)

Wang, Peng; Hudak, Michael R.; Lerner, Allan; Grubbs, Robert K.; Wang, Shanmin; Zhang, Zhan; Karapetrova, Evguenia; Hickmott, Donald; Majewski, Jaroslaw

2014-01-01

Carbonates are one of the most abundant groups of minerals in earth systems and are important in many geological settings and industrial processes. Calcite (CaCO 3 ) thin films produced by atomic layer deposition offer a method to evaluate the surficial properties of carbonates as well as interactions at the carbonate–fluid interface. Using synchrotron X-ray reflectivity and X-ray diffraction, these films are observed to be porous, polycrystalline, and have crystallites oriented with the major (104) calcite cleavage plane parallel to the surface of the z-cut single crystal quartz substrate. An Al 2 O 3 buffer layer, present between quartz and the calcite film, does not affect the as-deposited film, but does influence how the films reorganize in contact with fluid. Without a buffer layer, calcite reorients its crystallites to have populations of (006) and (030) parallel to the substrate, while those with an Al 2 O 3 buffer layer become more amorphous. Amorphous films may represent an analog to amorphous calcium carbonate and provide insights into that material's thermophysical behavior. Due to a higher percentage of pore spaces available for fluid infiltration, films deposited at higher temperature make the calcite thin films more susceptible to amorphization. These films are chemically similar, but structurally dissimilar to bulk natural calcite. Nevertheless, they can be a complementary system to traditional single crystal X-ray surface scattering studies on carbonates, particularly for important but less common minerals, to evaluate mineral–fluid interfacial interactions. - Highlights: • Atomic layer deposition (ALD) used to produce calcite films. • Calcite film orientation and crystallinity depend on ALD parameters. • ALD calcite films can be both crystalline and amorphous. • Interaction of water with films can re-orient or amorphize the films. • ALD calcite films may be useful to study carbonate–fluid interfacial interactions

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

NARCIS (Netherlands)

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

2016-01-01

The origin of spherical-radial calcite bodies - spherulites - in sublacustrine, hyperalkaline and saline systems is unclear, and therefore their palaeoenvironmental significance as allochems is disputed. Here, we experimentally investigate two hypotheses concerning the origin of spherulites. The

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

NARCIS (Netherlands)

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

2012-01-01

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

Molecular dynamics simulation of the rotational order-disorder phase transition in calcite

International Nuclear Information System (INIS)

Kawano, Jun; Miyake, Akira; Shimobayashi, Norimasa; Kitamura, Masao

2009-01-01

Molecular dynamics (MD) simulation of calcite was carried out with the interatomic potential model based on ab initio calculations to elucidate the phase relations for calcite polymorphs and the mechanism of the rotational order-disorder transition of calcite at high temperature at the atomic scale. From runs of MD calculations with increasing temperature within a pressure range of 1 atm and 2 GPa, the transition of calcite with R3-barc symmetry into a high-temperature phase with R3-barm symmetry was reproduced. In the high-temperature R3-barm phase, CO 3 groups vibrate with large amplitudes either around the original positions in the R3-barc structure or around other positions rotated ± 60 deg., and their positions change continuously with time. Moreover, contrary to the suggestion of previous investigators, the motion of CO 3 groups is not two-dimensional. At 1 atm, the transition between R3-barc and R3-barm is first order in character. Upon increasing temperature at high pressure, however, first a first-order isosymmetric phase transition between the R3-barc phases occurs, which corresponds to the start of ± 120 deg. flipping of CO 3 groups. Then, at higher temperatures, the transition of R3-barc to R3-barm phases happens, which can be considered second order. This set of two types of transitions at elevated pressure can be characterized by the appearance of an 'intermediate' R3-barc phase between the stable region of calcite and the high-temperature R3-barm phase, which may correspond to the CaCO 3 -IV phase.

Is bicarbonate stable in and on the calcite surface?

Science.gov (United States)

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

2016-03-01

We have used density functional theory with the COSMO-RS implicit solvent model to predict the pKa for the deprotonation of bicarbonate to carbonate, i.e. HCO3- CO32- + H+, when HCO3- is included in, and adsorbed on, a calcite surface. We have used cluster models (80-100 atoms) to represent the flat {10.4} surface, acute steps, obtuse steps, two types of kinks on the acute step and two types of kinks on the obtuse steps. Based on the predicted pKa values, which range from -6.0 to 2.4 depending on the surface site, we conclude that bicarbonate deprotonates to carbonate when it is in calcite even when pH in solution is very low. This is true for all surface sites, even for solutions where 2.4 < pH < 6.35, where H2CO30 is the dominant dissolved species. When bicarbonate is adsorbed on calcite, the predicted pKa for deprotonation is 7.5, which is ∼3 pH units lower than in aqueous solution, 10.35. This means that adsorbed carbonate is stable even when the concentration of dissolved CO32- is several orders of magnitude lower. This has a significant effect on surface charge and thus the behaviour of the calcite surface. Our results help explain the potential determining behaviour of the carbonate species in calcite-water systems, particularly in the pH range where the bicarbonate species dominates in water and where the carbonate species dominates at the surface, i.e. when 7.5 < pH < 10.35. Our atomic scale data for the various calcite surface sites provide the needed input to improve and constrain surface complexation modelling and are especially useful for predicting behaviour in systems where experiments are difficult or impossible, such as at high temperature and pressure.

An investigation of the heterogeneous nucleation of calcite

International Nuclear Information System (INIS)

House, W.A.; Tutton, J.A.

1982-01-01

The heterogeneous precipitation kinetics of calcite from dilute calcium bicarbonate solutions onto pyrex glass seeds is investigated by using a modified form of the Davies and Jones equation. The rate constant is evaluated from experiments using calcite seeds and it is demonstrated that the growth rate does not increase in proportion to the increase in surface area accompanying precipitation. The number of heteronucleated particles is estimated by assuming a constant density of growth sites on the different calcite surfaces. A comparison is made between the specific surface areas of calcite obtained by the calcium-45 isotopic exchange method and other values. (orig.)

Dissolution of coccolithophorid calcite by microzooplankton and copepod grazing

Science.gov (United States)

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

2008-01-01

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

Thermoluminescence from natural calcites

International Nuclear Information System (INIS)

Calderon, T.; Jaque, F.; Coy-yll, R.

1984-01-01

Thermoluminescence (TL) as well as absorption and EPR spectra of x-irradiated natural calcites have been obtained. Irradiation produces UV absorption bands and a decrease of the Mn 2+ EPR spectrum. A correlation of each TL peak with the bleaching steps of UV absorption bands and the recovering in intensity of the Mn 2+ EPR spectrum has been found. These experimental results support a new model for the radiation damage and thermoluminescence process in calcites. The main point in this model is that holes become trapped at impurities, and the electrons are trapped at dislocations in the form of CO 3 3- . (author)

The role of silicate surfaces on calcite precipitation kinetics

DEFF Research Database (Denmark)

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

2014-01-01

The aim of this study is to illuminate how calcite precipitation depends on the identity and structure of the growth substrate. Calcite was precipitated at 25°C from supersaturated aqueous solutions in the presence of seeds of either calcite or one of six silicate materials: augite, enstatite......, labradorite, olivine, basaltic glass and peridotite rock. Calcite saturation was achieved by mixing a CaCl2-rich aqueous solution with a NaHCO3-Na2CO3 aqueous buffer in mixed-flow reactors containing 0.5-2g of mineral, rock, or glass seeds. This led to an inlet fluid calcite saturation index of 0.6 and a p...

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

Science.gov (United States)

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

Biogenic processes in crystalline bedrock fractures indicated by carbon isotope signatures of secondary calcite

International Nuclear Information System (INIS)

Sahlstedt, Elina; Karhu, Juha A.; Pitkänen, Petteri; Whitehouse, Martin

2016-01-01

Variation in 13 C/ 12 C-isotope ratios of fracture filling calcite was analyzed in situ to investigate carbon sources and cycling in fractured bedrock. The study was conducted by separating sections of fracture fillings, and analyzing the 13 C/ 12 C-ratios with secondary ion mass spectrometry (SIMS). Specifically, the study was aimed at fillings where previously published sulfur isotope data indicated the occurrence of bacterial sulfate reduction. The results showed that the δ 13 C values of calcite were highly variable, ranging from −53.8‰ to +31.6‰ (VPDB). The analysis also showed high variations within single fillings of up to 39‰. The analyzed calcite fillings were mostly associated with two calcite groups, of which Group 3 represents possible Paleozoic fluid circulation, based on comparison with similar dated coatings within the Baltic Shield and the succeeding Group 1–2 fillings represent late-stage, low temperature mineralization and are possibly late Paleozoic to Quaternary in age. Both generations were associated with pyrite with δ 34 S values indicative of bacterial sulfate reduction. The δ 13 C values of calcite, however, were indicative of geochemical environments which were distinct for these generations. The δ 13 C values of Group 3 calcite varied from −22.1‰ to +11‰, with a distinct peak at −16‰ to −12‰. Furthermore, there were no observable depth dependent trends in the δ 13 C values of Group 3 calcite. The δ 13 C values of Group 3 calcite were indicative of organic matter degradation and methanogenesis. In contrast to the Group 3 fillings, the δ 13 C values of Group 1–2 calcite were highly variable, ranging from −53.8‰ to +31.6‰ and they showed systematic variation with depth. The near surface environment of <30 m (bsl) was characterized by δ 13 C values indicative of degradation of surface derived organic matter, with δ 13 C values ranging from −30.3‰ to −5.5‰. The intermediate depth of

New Environmentalconditions Responsible for the amount of mg Incorporated in Biogenic Carbonates

Science.gov (United States)

Zuddas, P.; Cherchi, A.; DeGiudici, G. B.; Buosi, C.

2012-12-01

The composition of carbonate minerals formed in past and present oceans is assumed to be significantly controlled by temperature and seawater composition. Several kinetic laboratory investigations have suggested that the temperature is kinetically responsible for the amount of Mg incorporated in both abiotic and biogenic calcites and that variation of kinetic reaction mechanism resulting from the temperature changes are correlated with the variable amount of Mg incorporated in calcites. These results explain why in present-day marine carbonates low-Mg calcite cements are mainly associated with cool water while high-Mg carbonates are dominantly found in warm-water environments. An apparent inverse relationship between the global average paleo-temperature and the Mg/Ca ratio is however observed in the past formed marine carbonate. This apparent contradiction has been interpreted as resulting from a possible changing in the relative seawater geochemical cycles of these cations. Recent monitoring of costal areas in presence of heavy metals and CO2 released from industrial polluted area reveals the presence of porcelanaceous miliolids infested by microscopic boring microflora (cyanobacteria, algae and fungi). Here, benthonic foraminifera have Mg/Ca molar ratio by one order of magnitude higher when compared to the average value of the same genus living under uncontaminated environments. A similar behaviour has been found for Zn, Cd and Pb. In these contaminated environments, temperature and average major seawater composition remain constant, while PCO2 partial pressure (estimated by pH and alkalinity using the ion pairing model) is 3-5 times higher than the average for the open sea nearby. Geochemical models predicts that CO2 increase is affecting carbonate saturation state of surface water in the twenty-first century indicating that calcareous organisms may have difficulty calcifying leading to production of weaker skeletons and greater vulnerability to erosion. The

Molecular ordering of ethanol at the calcite surface.

Science.gov (United States)

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

2012-02-07

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

Calcite growth kinetics: Modeling the effect of solution stoichiometry

NARCIS (Netherlands)

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

2012-01-01

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

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

Science.gov (United States)

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

2012-01-01

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

Phosphate adsorption and precipitation on calcite under calco-carbonic equilibrium condition.

Science.gov (United States)

Li, Zhenxuan; Sun, Xiaowen; Huang, Lidong; Liu, Dagang; Yu, Luji; Wu, Hongsheng; Wei, Dongyang

2017-09-01

Phosphate (PO 4 3- ) removal on calcite often entails two processes: adsorption and precipitation. Separating these two processes is of great importance for assessment of PO 4 3- stability after removal. Thus, this study was aimed at finding a critical range of conditions for separating these two processes in calco-carbonic equilibrium, by adjusting PO 4 3- concentration, reaction time and pH. PO 4 3- removal kinetic results showed that: (I) At pH7.7, PO 4 3- removal was mainly by adsorption at initial PO 4 3- concentration ≤2.2 mg L -1 and reaction time ≤24 h, with dominant precipitation occurring at initial PO 4 3- concentration ≥3 mg L -1 after 24 h reaction; (II) At pH8.3, adsorption was the key removal process at initial PO 4 3- concentration ≤7.5 mg L -1 and reaction time ≤24 h, whereas precipitation was observed at initial PO 4 3- concentration of 10 mg L -1 after 24 h reaction, (III) At pH 9.1 and 10.1, PO 4 3- removal mechanism was mainly by adsorption at initial PO 4 3- concentration ≤10 mg L -1 within 24 h reaction. Based on the kinetic results, it is suggested that PO 4 3- precipitation will occur after 24 h reaction when saturation index of amorphous calcium phosphate is between 1.97 and 2.19. Besides, increasing PO 4 3- concentration does not cause a continuous decline of PO 4 3- removal percentage. Moreover, experimental removal data deviated largely from the theoretical adsorption value by CD-MUSIC model. These indicate occurrence of precipitation which is in agreement with the kinetic result. Therefore our study will provide fundamental reference information for better understanding of phosphorous stabilization after removal by calcite. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mechanism of Enhancing Extraction of Vanadium from Stone Coal by Roasting with MgO

Directory of Open Access Journals (Sweden)

Fang Chen

2017-02-01

Full Text Available In this paper, the extraction of vanadium from stone coal by roasting with MgO and leaching with sulfuric acid has been investigated, and the mechanism analysis of stone coal roasting with MgO was studied. The results indicated that under the conditions that the mass fraction of the particles with grain size of 0–0.074 mm in raw ore was 75%, the roasting temperature was 500 °C, the roasting time was 1 h, MgO addition was 3 wt %, the sulfuric acid concentration was 20 vol %, the liquid-to-solid ratio was 1.5 mL/g, the leaching temperature was 95 °C, and leaching time was 2 h, resulting in a vanadium leaching efficiency of 86.63%, which increased by 7.73% compared with that of blank roasting. The mechanism analysis showed that the degree of calcite decomposition was low and, thus, magnesium vanadate was more easily formed than calcium vanadate below 500 °C. Moreover, magnesium vanadate was easier to dissolve than calcium vanadate during the sulfuric acid leaching process. Thus, the vanadium leaching efficiency was enhanced by using MgO as a roasting additive below 500 °C. Additionally, at high temperature the formation of tremolite would consume calcium oxide produced from the decomposition of calcite, thus, the formation of calcium vanadate was hindered, and V2O5 would react with MgO to form magnesium vanadate. Therefore, the vanadium leaching efficiency of roasting with MgO was higher than that of blank roasting at high temperature.

Atom-resolved AFM imaging of calcite nanoparticles in water

Energy Technology Data Exchange (ETDEWEB)

Imada, Hirotake; Kimura, Kenjiro [Department of Chemistry, School of Science, Kobe University, Rokko-dai, Nada, Kobe 657-8501 (Japan); Onishi, Hiroshi, E-mail: oni@kobe-u.ac.jp [Department of Chemistry, School of Science, Kobe University, Rokko-dai, Nada, Kobe 657-8501 (Japan)

2013-06-20

Highlights: ► An advanced frequency-modulation AFM (FM-AFM) was applied for imaging particles. ► Atom-resolved topography of nano-sized particles of calcite was observed in water. ► Locally ordered structures were found and assigned to a (104) facet of calcite. ► A promising ability of FM-AFM was demonstrated in imaging nano-sized particles. - Abstract: The atom-resolved topography of calcite nanoparticles was observed in water using a frequency-modulation atomic force microscope. Locally ordered structures were found and assigned to a (104) facet of crystalline calcite.

Atom-resolved AFM imaging of calcite nanoparticles in water

International Nuclear Information System (INIS)

Imada, Hirotake; Kimura, Kenjiro; Onishi, Hiroshi

2013-01-01

Highlights: ► An advanced frequency-modulation AFM (FM-AFM) was applied for imaging particles. ► Atom-resolved topography of nano-sized particles of calcite was observed in water. ► Locally ordered structures were found and assigned to a (104) facet of calcite. ► A promising ability of FM-AFM was demonstrated in imaging nano-sized particles. - Abstract: The atom-resolved topography of calcite nanoparticles was observed in water using a frequency-modulation atomic force microscope. Locally ordered structures were found and assigned to a (104) facet of crystalline calcite

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

Science.gov (United States)

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

2012-11-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Asperger, R.G.

1982-08-01

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

Calcite Fluid Inclusion, Paragenetic, and Oxygen Isotopic Records of Thermal Event(s) at Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Peterman, B.; Moscati, R.

2000-01-01

Yucca Mountain, Nevada, is under consideration as a potential high-level radioactive waste repository situated above the water table in 12.7 Ma tuffs. A wealth of textural and geochemical evidence from low-temperature deposits of calcite and silica, indicates that their genesis is related to unsaturated zone (UZ) percolation and that the level of the potential repository has never been saturated. Nonetheless, some scientists contend that thermal waters have periodically risen to the surface depositing calcite and opal in the tuffs and at the surface. This hypothesis received some support in 1996 when two-phase fluid inclusions (FIs) with homogenization temperatures (Th) between 35 and 75 C were reported from UZ calcite. Calcite deposition likely followed closely on the cooling of the tuffs and continues into the present. The paragenetic sequence of calcite and silica in the UZ is early stage calcite followed by chalcedony and quartz, then calcite with local opal during middle and late stages. Four types of FIs are found in calcite assemblages: (1) all-liquid (L); (2) all-vapor (V); (3) 2-phase with large and variable V:L ratios; and (4) a few 2-phase with small and consistent V:L ratios. Late calcite contains no FI assemblages indicating elevated depositional temperatures. In early calcite, the Th of type 4 FIs ranges from ∼ 40 to ∼ 85 C. Such temperatures (sub-boiling) and the assemblage of FIs are consistent with deposition in the UZ. Some delta 18O values < 10 permil in early calcite support such temperatures. Type 4 FIs, however, seem to be restricted to the early calcite stage, during which either cooling of the tuffs or regional volcanism were possible heat sources. Nonetheless, at present there is no compelling evidence of upwelling water as a source for the calcite/opal deposits

Controls of Ca/Mg/Fe activity ratios in pore water chemistry models of the Callovian-Oxfordian clay formation

International Nuclear Information System (INIS)

Lerouge, C.; Grangeon, S.; Wille, G.; Flehoc, C.; Gailhanou, H.; Gaucher, E.C.; Tournassat, C.; Vinsot, A.; Made, B.; Altmann, S.

2013-01-01

In the pore water chemistry model of the Callovian-Oxfordian clay formation, the divalent cations Ca, Mg, and Fe are controlled by equilibrium reactions with pure carbonates: calcite for Ca, dolomite for Mg, and siderite for Fe. Results of a petrological study and computing of the Ca/Mg and Ca/Fe activity ratios based on natural pore water chemistry provide evidence that equilibrium with pure calcite and pure dolomite is a reasonable assumption for undisturbed pore waters; on the other hand, siderite cannot be considered at equilibrium with pore waters at the formation scale. (authors)

Controls of Ca/Mg/Fe activity ratios in pore water chemistry models of the Callovian-Oxfordian clay formation

Energy Technology Data Exchange (ETDEWEB)

Lerouge, C.; Grangeon, S.; Wille, G.; Flehoc, C.; Gailhanou, H.; Gaucher, E.C.; Tournassat, C. [BRGM av. Claude Guillemin BP6009 45060 Orleans cedex 2 (France); Vinsot, A. [ANDRA Meuse/Haute-Marne Underground research Laboratory (URL), RD 960, 55290 Bure (France); Made, B.; Altmann, S. [ANDRA - Parc de la Croix Blanche, 1-7 rue Jean Monnet, 92298 Chatenay-Malabry Cedex (France)

2013-07-01

In the pore water chemistry model of the Callovian-Oxfordian clay formation, the divalent cations Ca, Mg, and Fe are controlled by equilibrium reactions with pure carbonates: calcite for Ca, dolomite for Mg, and siderite for Fe. Results of a petrological study and computing of the Ca/Mg and Ca/Fe activity ratios based on natural pore water chemistry provide evidence that equilibrium with pure calcite and pure dolomite is a reasonable assumption for undisturbed pore waters; on the other hand, siderite cannot be considered at equilibrium with pore waters at the formation scale. (authors)

The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite.

Science.gov (United States)

Rodriguez-Blanco, Juan Diego; Shaw, Samuel; Benning, Liane G

2011-01-01

The kinetics and mechanisms of nanoparticulate amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite, were studied at a range of environmentally relevant temperatures (7.5-25 °C) using synchrotron-based in situ time-resolved Energy Dispersive X-ray Diffraction (ED-XRD) in conjunction with high-resolution electron microscopy, ex situ X-ray diffraction and infrared spectroscopy. The crystallization process occurs in two stages; firstly, the particles of ACC rapidly dehydrate and crystallize to form individual particles of vaterite; secondly, the vaterite transforms to calcite via a dissolution and reprecipitation mechanism with the reaction rate controlled by the surface area of calcite. The second stage of the reaction is approximately 10 times slower than the first. Activation energies of calcite nucleation and crystallization are 73±10 and 66±2 kJ mol(-1), respectively. A model to calculate the degree of calcite crystallization from ACC at environmentally relevant temperatures (7.5-40 °C) is also presented.

On the complex conductivity signatures of calcite precipitation

Energy Technology Data Exchange (ETDEWEB)

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

2009-11-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-11-28

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

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

Directory of Open Access Journals (Sweden)

Vučinić Dušica R.

2012-01-01

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

Interactions of Ni and Ca at the calcite-solution interface

International Nuclear Information System (INIS)

Carlsson, T.; Aalto, H.

1996-10-01

The performance assessment of repositories for spent nuclear fuel need, among other things, data describing the solubilities of radionuclides in the near field and far field. The solubility limits are often used in order to estimate the maximum concentrations of radionuclides during their possible transport to the biosphere. The solubilities used are mostly the individual solubilities for pure solids of the actual radionuclides. This way of using solubility limits represents a conservative performance assessment where the estimated nuclide concentrations are unrealistically high. This is acceptable from a performance assessment point of view but very unsatisfactory for an optimal design of the repository. In order to make the assessment more realistic, coprecipitation and solid solution formation should be taken into account. Only solids which are, in geological terms, formed in fast reactions need to be considered, which in practice restricts the number of radionuclide scavengers to calcite and iron(III)oxihydroxide. This work focuses on the Ni coprecipitation with calcite. The systems were studied under anoxic conditions and consisted of calcite-saturated 0.05 M NaCl solutions in equilibrium with synthetic calcite. The solutions were initially spiked with 63 Ni and 45 Ca and the concentrations of these elements were determined using liquid scintillation counting. (18 refs.)

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

Science.gov (United States)

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

High-Resolution Mg/Ca Ratios in a Coralline Red Alga as a Proxy for Bering Sea Temperature Variations and Teleconnections

Science.gov (United States)

Halfar, J.; Steffen, H.; Kronz, A.; Steneck, R. S.; Adey, W.; Lebednik, P. A.

2009-05-01

We present the first continuous high-resolution record of Mg/Ca variations within an encrusting coralline red alga of the species Clathromorphum nereostratum from Amchitka Island, Aleutian Islands. Mg/Ca ratios of individual growth increments were analyzed by measuring a single point electron microprobe transect yielding a resolution of 15 samples/year on average, generating a continuous record from 1830 to 1967 of algal Mg/Ca variations. Results show that Mg/Ca ratios in the high-Mg calcite skeleton display pronounced annual cyclicity and archive late spring to late fall sea surface temperature (SST) corresponding to the main season of algal growth. Mg/Ca values correlate well to local SST (ERSSTJun-Nov, 1902-1967; r = 0.73 for 5-year mean), as well as to an air temperature record from the same region. Our data correlate well to a shorter Mg/Ca record from a second site, corroborating the ability of the alga to reliably record regional environmental signals. In addition, Mg/Ca ratios relate well to a 29-year stable oxygen isotope time series measured on the same sample, which provides additional support for the use of Mg as a paleotemperature proxy in coralline red algae, that is, unlike stable oxygen isotopes, not influenced by salinity fluctuations. High spatial correlation to large-scale SST variability in the North Pacific is observed, with patterns of strongest correlation following the direction of major oceanographic features (i.e., the signature of the Alaska Current and the Alaskan Stream), which play a key role in the exchange of water masses between the North Pacific and the Bering Sea through Aleutian Island passages. The time series further displays significant teleconnections with the signature of the Pacific Decadal Oscillation in the northeast Pacific and the Atlantic Multidecadal Oscillation.

Role of Fungi in the Biomineralization of Calcite

Directory of Open Access Journals (Sweden)

Saskia Bindschedler

2016-05-01

Full Text Available In the field of microbial biomineralization, much of the scientific attention is focused on processes carried out by prokaryotes, in particular bacteria, even though fungi are also known to be involved in biogeochemical cycles in numerous ways. They are traditionally recognized as key players in organic matter recycling, as nutrient suppliers via mineral weathering, as well as large producers of organic acids such as oxalic acid for instance, an activity leading to the genesis of various metal complexes such as metal-oxalate. Their implications in the transformation of various mineral and metallic compounds has been widely acknowledged during the last decade, however, currently, their contribution to the genesis of a common biomineral, calcite, needs to be more thoroughly documented. Calcite is observed in many ecosystems and plays an essential role in the biogeochemical cycles of both carbon (C and calcium (Ca. It may be physicochemical or biogenic in origin and numerous organisms have been recognized to control or induce its biomineralization. While fungi have often been suspected of being involved in this process in terrestrial environments, only scarce information supports this hypothesis in natural settings. As a result, calcite biomineralization by microbes is still largely attributed to bacteria at present. However, in some terrestrial environments there are particular calcitic habits that have been described as being fungal in origin. In addition to this, several studies dealing with axenic cultures of fungi have demonstrated the ability of fungi to produce calcite. Examples of fungal biomineralization range from induced to organomineralization processes. More examples of calcite biomineralization related to direct fungal activity, or at least to their presence, have been described within the last decade. However, the peculiar mechanisms leading to calcite biomineralization by fungi remain incompletely understood and more research is

Surface Forces Apparatus measurements of interactions between rough and reactive calcite surfaces.

Science.gov (United States)

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

2018-05-28

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

Rearrangement of porous CaO aggregates during calcite decomposition in vacuum

International Nuclear Information System (INIS)

Beruto, D.; Barco, L.; Searcy, A.W.

1983-01-01

High-resolution SEM photographs, N 2 adsorption isotherms, Hg porosimetry, and micrometer measurements were used to characterize CaO particle shapes and pore-size distributions that result when calcite crystals are decomposed in vacuum at 686 0 C. The surface area of the CaO produced from large calcite crystals is constant at 116 + or - 4 m 2 /g independent of the extent of reaction. The volume occupied by a CaO aggregate is approx. = 98 + or - 2% that of the original calcite crystal. The approx. = 54% total porosity is comprised of 42% pores of approx. = 5 nm cross section and 12% pores of approx. = 10 μm cross section. The duplex pore structure is formed by a diffusionless repacking of CaO particles that initially form with a more uniform distribution of particles and pores

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

Science.gov (United States)

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

2011-01-01

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

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

DEFF Research Database (Denmark)

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

2011-01-01

The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3h) and low concentrations of phosphate (⩽50μM). Sorption of phosphate on calcite was stud......The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3h) and low concentrations of phosphate (⩽50μM). Sorption of phosphate on calcite...... of a high degree of super-saturation with respect to hydroxyapatite (SIHAP⩽7.83). The amount of phosphate adsorbed varied with the solution composition, in particular, adsorption increases as the CO32- activity decreases (at constant pH) and as pH increases (at constant CO32- activity). The primary effect...... of ionic strength on phosphate sorption onto calcite is its influence on the activity of the different aqueous phosphate species. The experimental results were modeled satisfactorily using the constant capacitance model with >CaPO4Ca0 and either >CaHPO4Ca+ or >CaHPO4- as the adsorbed surface species...

Geobacillus thermoglucosidasius Endospores Function as Nuclei for the Formation of Single Calcite Crystals

Science.gov (United States)

Murai, Rie

2013-01-01

Geobacillus thermoglucosidasius colonies were placed on an agar hydrogel containing acetate, calcium ions, and magnesium ions, resulting in the formation of single calcite crystals (calcites) within and peripheral to the plating area or parent colony. Microscopic observation of purified calcites placed on the surface of soybean casein digest (SCD) nutrient medium revealed interior crevices from which bacterial colonies originated. Calcites formed on the gel contained [1-13C]- and [2-13C]acetate, demonstrating that G. thermoglucosidasius utilizes carbon derived from acetate for calcite formation. During calcite formation, vegetative cells swam away from the parent colony in the hydrogel. Hard-agar hydrogel inhibited the formation of calcites peripheral to the parent colony. The calcite dissolved completely in 1 M HCl, with production of bubbles, and the remaining endospore-like particles were easily stained with Brilliant green dye. The presence of DNA and protein in calcites was demonstrated by electrophoresis. We propose that endospores initiate the nucleation of calcites. Endospores of G. thermoglucosidasius remain alive and encapsulated in calcites. PMID:23455343

Uranyl incorporation into calcite and aragonite: XAFS and luminescence studies

International Nuclear Information System (INIS)

Reeder, R.J.; Nugent, M.; Lamble, G.M.; Tait, C.D.; Morris, D.E.

2000-01-01

X-ray absorption, luminescence, and Raman spectroscopic studies of U(VI)-containing calcite and aragonite show that the UO 2 2+ ion, the dominant and mobile form of dissolved uranium in near-surface waters, has a disordered and apparently less stable coordination environment when incorporated into calcite in comparison to aragonite, both common polymorphs of CaCO 3 . Their findings suggest that calcite, a widely distributed authigenic mineral in soils and near-surface sediments and a principal weathering product of concrete-based containment structures, is not likely to be a suitable host for the long-term sequestration of U(VI). The more stable coordination provided by aragonite suggests that its long-term retention should be favored in this phase, until it inverts to calcite. Consequently, future remobilization of U(VI) coprecipitated with calcium carbonate minerals should not be ruled out in assessments of contaminated sites. Their observation of a similar equatorial coordination of UO 2 2+ in aragonite and the dominant aqueous species [UO 2 (CO 3 ) 3 4- ] but a different coordination in calcite indicates that a change in UO 2 2+ coordination is required for its incorporation into calcite. This may explain the observed preferential uptake of U(VI) by aragonite relative to calcite

Structural incorporation of Neptunyl(V) into Calcite: Interfacial Reactions and Kinetics

OpenAIRE

Heberling, Frank

2010-01-01

In this experimental work the calcite-water interface is characterized by means of zetapotential and surface diffraction measurements. Based on the experimental results a new Basic Stern Surface Complexation model for calcite is developed. Neptunyl(V) adsorption at the calcite surface and incorporation into the calcite structure is studied by batch type adsorption- and mixed flow reactor experiments. Adsorption and incorporation species of Neptunyl are investigated by EXAFS spectroscopy.

Concentration effect on inter-mineral equilibrium isotope fractionation: insights from Mg and Ca isotopic systems

Science.gov (United States)

Huang, F.; Wang, W.; Zhou, C.; Kang, J.; Wu, Z.

2017-12-01

Many naturally occurring minerals, such as carbonate, garnet, pyroxene, and feldspar, are solid solutions with large variations in chemical compositions. Such variations may affect mineral structures and modify the chemical bonding environment around atoms, which further impacts the equilibrium isotope fractionation factors among minerals. Here we investigated the effects of Mg content on equilibrium Mg and Ca isotope fractionation among carbonates and Ca content on equilibrium Ca isotope fractionation between orthopyroxene (opx) and clinopyroxene (cpx) using first-principles calculations. Our results show that the average Mg-O bond length increases with decreasing Mg/(Mg+Ca) in calcite when it is greater than 1/48[1] and the average Ca-O bond length significantly decreases with decreasing Ca/(Ca+Mg+Fe) in opx when it ranges from 2/16 to 1/48[2]. Equilibrium isotope fractionation is mainly controlled by bond strengths, which could be measured by bond lengths. Thus, 103lnα26Mg/24Mg between dolomite and calcite dramatically increases with decreasing Mg/(Mg+Ca) in calcite [1] and it reaches a constant value when it is lower than 1/48. 103lnα44Ca/40Ca between opx and cpx significantly increases with decreasing Ca content in opx when Ca/(Ca+Mg+Fe) ranges from 2/16 to 1/48 [2]. If Ca/(Ca+Mg+Fe) is below 1/48, 103lnα44Ca/40Ca is not sensitive to Ca content. Based on our results, we conclude that the concentration effect on equilibrium isotope fractionation could be significant within a certain range of chemical composition of minerals, which should be a ubiquitous phenomenon in solid solution systems. [1] Wang, W., Qin, T., Zhou, C., Huang, S., Wu, Z., Huang, F., 2017. GCA 208, 185-197. [2] Feng, C., Qin, T., Huang, S., Wu, Z., Huang, F., 2014. GCA 143, 132-142.

Inter- and intra-specimen variability masks reliable temperature control on shell Mg/Ca ratios in laboratory- and field-cultured Mytilus edulis and Pecten maximus (bivalvia

Directory of Open Access Journals (Sweden)

H. A. Kennedy

2008-09-01

Full Text Available The Mg/Ca ratios of biogenic calcite is commonly seen as a valuable palaeo-proxy for reconstructing past ocean temperatures. The temperature dependence of Mg/Ca ratios in bivalve calcite has been the subject of contradictory observations. The palaeoceanographic use of a geochemical proxy is dependent on initial, rigorous calibration and validation of relationships between the proxy and the ambient environmental variable to be reconstructed. Shell Mg/Ca ratio data are reported for the calcite of two bivalve species, Mytilus edulis (common mussel and Pecten maximus (king scallop, which were grown in laboratory culturing experiments at controlled and constant aquarium seawater temperatures over a range from ~10 to ~20°C. Furthermore, Mg/Ca ratio data of laboratory- and field-grown M. edulis specimens were compared. Only a weak, albeit significant, shell Mg/Ca ratio–temperature relationship was observed in the two bivalve species: M. edulis (r2=0.37, p0.001 for laboratory-cultured specimens and r2=0.50, p0.001 for field-cultured specimens and P. maximus (r2=0.21, p0.001 for laboratory-cultured specimens only. In the two species, shell Mg/Ca ratios were not found to be controlled by shell growth rate or salinity. The Mg/Ca ratios in the shells exhibited a large degree of variability among and within species and individuals. The results suggest that the use of bivalve calcite Mg/Ca ratios as a temperature proxy is limited, at least in the species studied to date. Such limitations are most likely due to the presence of physiological effects on Mg incorporation in bivalve calcite. The utilization is further limited by the great variability both within and among shells of the same species that were precipitated under the same ambient conditions.

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

DEFF Research Database (Denmark)

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

2014-01-01

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...... 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...

Examination of TL and optical absorption in calcite's mineral

International Nuclear Information System (INIS)

Sabikoglu, I.; Can, N.

2009-01-01

Calcite which is a form of crystalline of the calcium carbonate composes parent material of chalk stone (limestone) and marble. Calcite which presents in various colors also in our country consists of yellow, blue, transparent and green colors. In this study, green calcite mineral which is taken from the region of Ayvalik, was examined of its thermoluminescence (TL) and optical absorption features in different doses. It has been obtained a large TL peak in 179 degree C and absorption peak in 550 mm.

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

Science.gov (United States)

Naidu, Sonia; Scherer, George W

2014-12-01

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

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

DEFF Research Database (Denmark)

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

2002-01-01

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

Paleohydrogeological implications from fracture calcites and sulfides in a major hydrogeological zone HZ19 at Olkiluoto

International Nuclear Information System (INIS)

Sahlstedt, E.; Karhu, J.; Rinne, K.

2009-08-01

30 samples of fracture mineral fillings in or near water conducting fractures at Olkiluoto were collected from 10 drill cores for fracture mineral studies. The aim of the study was to obtain information about past hydrogeochemical conditions at Olkiluoto using the calcite morphology, the chemical characteristics and the isotopic composition of carbon and oxygen in calcite. The chemical composition of fracture calcites at Olkiluoto is nearly stoichiometric CaCO 3 . Most variation in the composition of calcite is due to differences in the Mn content, which could indicate variations in groundwater redox conditions. Meaningful REE patterns were obtained for the calcites. REE patterns showed generally negative Eu anomalies, but one fracture calcite specimen had a distinct positive Eu anomaly. This positive anomaly could be related to ancient hydrothermal conditions, although derivation of the anomaly from the host rock cannot be excluded. Preliminary results for calcite U-Th dating of fracture calcites are reported. The isotopic composition of U and Th were analysed by a new multiple collector LA-ICPMS instrument. U and Th concentrations in fracture calcites are generally 18 O values of calcite range from -17 to -7 per mille. Most of the calcites may have been precipitated in the presence of waters with oxygen isotope ratios similar to those in the present-day groundwaters at Olkiluoto. Two samples with an oxygen isotopic composition highly depleted in 18 O were interpreted to have been precipitated at elevated temperatures. The δ 13 C values of calcite showed a wide range of values from -26 to +35 per mille. Multiple sources for carbon are implied. The highest δ 13 C values indicate methanic conditions in the fracture at the time of calcite precipitation. It appears that the methanic environment has earlier extended to shallower depths compared to the location of the methanic environment in the present-day fracture system (> 300 m). Ten pyrite samples were analysed

Mg and Ca isotope fractionation during CaCO3 biomineralisation

International Nuclear Information System (INIS)

Chang, Veronica T.-C.; Williams, R.J.P.; Makishima, Akio; Belshawl, Nick S.; O'Nions, R. Keith

2004-01-01

The natural variation of Mg and Ca stable isotopes of carbonates has been determined in carbonate skeletons of perforate foraminifera and reef coral together with Mg/Ca ratios to assess the influence of biomineralisation processes. The results for coral aragonite suggest its formation, in terms of stable isotope behaviour, approximates to inorganic precipitation from a seawater reservoir. In contrast, results for foraminifera calcite suggest a marked biological control on Mg isotope ratios presumably related to its low Mg content compared with seawater. The bearing of these observations on the use of Mg and Ca isotopes as proxies in paleoceanography is considered

Interaction mechanisms of europium and nickel with calcite

International Nuclear Information System (INIS)

Sabau, Andrea

2015-01-01

In the context of the safety assessment of an underground repository for nuclear waste, sorption reactions are one of the main processes to take into account to predict the migration of the radionuclides which might be transferred from the waste canisters to underground waters over geological time scales. Sorption of aqueous species on minerals can include adsorption processes, surface (co)-precipitation, and even incorporation in the bulk of the material, which can lead to the irreversibility of some sorption reactions. This work is focused on two elements: Eu(III) as an analogue of trivalent actinides and Ni(II) as activation product. Calcite was chosen as adsorbent due to its presence in Callovian-Oxfordian clay rocks. Our study combines batch experiments with spectroscopic techniques (TRLFS, RBS and SEM-EDXS) to elucidate the mechanisms occurring at Eu(III)/Ni(II) calcite interface. To obtain a better understanding on the systems, before starting sorption experiments, aqueous chemistry of Eu(III) and Ni(II) was carefully investigated. Macroscopic results showed a strong retention of Eu(III) on calcite, no matter the initial concentration, contact time and CO 2 partial pressure. Ni(II) was also readily sorbed by calcite, but the retention was influenced by contact time and concentration. Time-dependent sorption experiments showed a marked and slow increase of retention upon a long time range (up to 4 months).Desorption results indicated a partly reversible sorption for Ni(II). TRLFS highlighted the influence of initial concentration and contact time on the interaction of Eu(III) with calcite. With the help of RBS and SEM-EDXS, it enabled to discriminate between different mechanisms like surface precipitation, inner-sphere complexation and incorporation. RBS showed incorporation of Eu(III) into calcite up to 250 nm, contrary to Ni(II) which was located at the surface. (author) [fr

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

Science.gov (United States)

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).

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

Science.gov (United States)

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

2016-04-15

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

Sorption and desorption of arsenate and arsenite on calcite

DEFF Research Database (Denmark)

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

2008-01-01

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

Origin of calcite in the glacigenic Virttaankangas complex

OpenAIRE

Nina M. Kortelainen; Petri J. Korkeakoski; Juha A. Karhu

2007-01-01

Groundwaters of the glacigenic Virttaankangas complex in southern Finland are characterized by high pH values ranging up to 9.5. These values are significantly higher than those observed in silicate-rich shallow groundwater formations in crystalline bedrock areas. TheVirttaankangas sediments were discovered to contain small amounts of fine grained, dispersed calcite, which has a high tendency to increase the pH of local groundwaters. The primary goal of this study was to determine the mode of...

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

Science.gov (United States)

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

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

Directory of Open Access Journals (Sweden)

Ahmadreza Sheikhhosseini

2017-03-01

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

Depressing effect of phenoxyl acetic acids on flotation of minerals containing Ca2+/Mg2+ gangues

Institute of Scientific and Technical Information of China (English)

无

2007-01-01

Phenoxyl acetic acids were applied to determine their depressing effect on minerals containing Ca2+/Mg2+ gangues. Calcite,mixture of calcite and fluorite, and nickel ore were used in the flotation. And the depression mechanism was studied by the determination of contact angle, zeta potential, adsorptive capacity of collector, and IR analysis as well. It is found that 0.1 mmol/L of phenoxyl acetic acid derived from pyrogallol or gallic acid exhibits strong depressing ability on calcite in almost zero yields at pH value of 9.8, and calcite can be depressed in the flotation of calcite/fluorite mixture for approximate 87% yield of fluorite. The flotation result of practical nickel ore containing serpentine indicates that these two depressants may also show better depression performance to serpentine than traditional depressants such as sodium fluosilicate and carboxylmethyl cellulose. Analysis for the depression mechanism reveals that there exists strong chemical interaction between the depressants and minerals.

Control of temperature and aqueous Mg2+/Ca2+ ratio on the (trans-)formation of ikaite

Science.gov (United States)

Purgstaller, B.; Dietzel, M.; Baldermann, A.; Mavromatis, V.

2017-11-01

The calcium carbonate hexahydrate mineral ikaite (CaCO3 ṡ 6 H2O) has been documented in aquatic environments at near-freezing temperatures. An increase of the prevailing temperature in the depositional environment, results in the transformation of natural ikaite into less soluble calcium carbonate phases occasionally leaving calcite pseudomorphs in the sediments, which are considered as an indicator for primary cold water temperatures. Detailed understanding on the physicochemical parameters controlling ikaite (trans-)formation however, such as temperature and reactive solution chemical composition, are still under debate. In order to study the formation of ikaite, we conducted precipitation experiments under controlled physicochemical conditions (pH = 8.3 ± 0.1; T = 6, 12, and 18 ± 0.1 °C) at defined aqueous molar Mg/Ca ratios. The transformation of ikaite into anhydrous calcium carbonate polymorphs was investigated in solution and at air exposure. The obtained results reveal the formation of ikaite at temperatures up to 12 °C, whereas Mg-rich amorphous calcium carbonate precipitated at 18 °C. In contact with the reactive solution ikaite transformed into aragonite at aqueous molar Mg2+/Ca2+ ratios of ≥14. In contrast, ikaite separated from the Mg-rich solution and exposed to air transformed in all cases into calcite/vaterite. The herein obtained temperature limit of ≤12 for ikaite formation is significantly higher than formerly expected and most probably caused by (i) the high saturation degree of the solution with respect to ikaite and (ii) the slow dehydration of the aqueous Ca2+ ion at low temperatures. This result questions the suitability of calcite pseudomorphs (i.e. glendonites) as a proxy for near-freezing temperatures. Moreover, our findings show that the CaCO3 polymorph formed from ikaite is strongly controlled by the physicochemical conditions, such as aqueous molar Mg2+/Ca2+ ratio of the reactive fluid and H2O availability throughout the

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

International Nuclear Information System (INIS)

Ramakrishna, Chilakala; Thenepalli, Thriveni; Ahn, Ji Whan

2017-01-01

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

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

Science.gov (United States)

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

2012-12-01

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

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

Directory of Open Access Journals (Sweden)

P. S. Freitas

2009-07-01

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

Trace element partitioning in fluvial tufa reveals variable portions of biologically influenced calcite precipitation

Science.gov (United States)

Ritter, Simon M.; Isenbeck-Schröter, Margot; Schröder-Ritzrau, Andrea; Scholz, Christian; Rheinberger, Stefan; Höfle, Bernhard; Frank, Norbert

2018-03-01

The formation of tufa is essentially influenced by biological processes and, in order to infer environmental information from tufa deposits, it has to be determined how the geochemistry of biologically influenced tufa deviates from equilibrium conditions between water and calcite precipitate. We investigated the evolution of the water and tufa geochemistry of consecutive tufa barrages in a small tufa-depositing creek in Southern Germany. High incorporation of divalent cations into tufa is ubiquitous, which is probably promoted by an influence of biofilms in the tufa element partitioning. The distribution coefficients for the incorporation of Mg, Sr and Ba into tufa at the Kaisinger creek D(Mg), D(Sr) and D(Ba) are 0.020-0.031, 0.13-0.18 and 0.26-0.43, respectively. This agrees with previous research suggesting that biofilm influenced tufa will be enriched in divalent cations over equilibrium values in the order of Mg formation with likely higher distribution coefficients and inorganically-driven tufa formation with likely lower distribution coefficients. Additionally, the distribution coefficients of metals in tufa of the Kaisinger creek D(Cd), D(Zn), D(Co) and D(Mn) show values of 11-22, 2.2-12, 0.7-4.9 and 30-57, respectively. These metals are highly enriched in upstream tufa deposits and their contents in tufa strongly decrease downstream. Such highly compatible elements could therefore be used to distinguish easily between different lateral sections in fluvial barrage-dam tufa depositional systems and could serve as a useful geochemical tool in studying ancient barrage-dam tufa depositional systems.

Effect of dissolution kinetics on flotation response of calcite with oleate

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D. G. Horta

Full Text Available Abstract Phosphate flotation performance can be influenced by the dissolution kinetics of the minerals that compose the ore. The purpose of this work was to investigate the effect of dissolution kinetics on flotation response with oleate (collector of calcites from different origins and genesis. The calcite samples were first purified and characterized by x-ray Fluorescence (XRF and the Rietveld method applied to x-ray Diffractometry data (RXD. Experiments of calcite dissolution and microflotationwere performed at pH 8 and pH 10.The pH effect on the calcite dissolution and flotation indicates the possible influence of the carbonate/bicarbonate ions provided by the CO2 present in the air. In addition, the flotation response is greater as the dissolution increases, making more Ca2+ ions available to interact with collector molecules. This result corroborates the surface precipitation mechanism proposed foroleate adsorption on the calcite surface.

Interactions of U(VI), Nd, and Th(IV) at the Calcite-solution interface

International Nuclear Information System (INIS)

Carroll, S.A.; Dran, J.C.

1992-01-01

The interactions of U(VI), Nd, and Th(IV) at the calcite-solution interface at controlled pCO 2 (g) have been investigated by Rutherford backscattering (RBS), scanning electron microscopy (SEM) and energy dispersive (EDS) analyses of reacted calcite. Uranium precipitation at the calcite-solution interface was observed only for those experiments in which the initial [U(VI)] was greater than the solubility of rutherfordine, UO 2 CO 3 (s). At pH 8.0, flat radial uranium and calcium zoned precipitates form at the mineral-solution interface. At pH 4.3, uranium forms an anastomosing precipitate throughout the calcite surface. RBS analyses confirmed the SEM analyses showing that uranium forms a solid phase within the calcite surface, but formation of an uranium-calcium solid solution at depth is limited. In sharp contrast to U(VI), Nd is concentrated in the solid phase as individual neodymium-calcium carbonate crystals. Calcite and pure orthorhombic neodymium carbonate crystals dissolve at the expense of the formation of a more stable neodymium-calcium solid solution. In the presence of calcite, a thorium-calcium solid solution forms by exchanging Th for Ca in the calcite structure. Thorium precipitates in two linear trends which intersect each other at approximately 105deg C and 75deg C, parallel to calcite rhombohedral cleavage faces. (orig.)

High resolution electron backscatter diffraction (EBSD) data from calcite biominerals in recent gastropod shells.

Science.gov (United States)

Pérez-Huerta, Alberto; Dauphin, Yannicke; Cuif, Jean Pierre; Cusack, Maggie

2011-04-01

Electron backscatter diffraction (EBSD) is a microscopy technique that reveals in situ crystallographic information. Currently, it is widely used for the characterization of geological materials and in studies of biomineralization. Here, we analyze high resolution EBSD data from biogenic calcite in two mollusk taxa, Concholepas and Haliotis, previously used in the understanding of complex biomineralization and paleoenvironmental studies. Results indicate that Concholepas has less ordered prisms than in Haliotis, and that in Concholepas the level of order is not homogenous in different areas of the shell. Overall, the usefulness of data integration obtained from diffraction intensity and crystallographic orientation maps, and corresponding pole figures, is discussed as well as its application to similar studies. © 2010 Elsevier Ltd. All rights reserved.

Sorption and catalytic oxidation of Fe(II) at the surface of calcite

NARCIS (Netherlands)

Mettler, S.; Wolthers, M.; Charlet, L.; Von Gunten, U.

The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps:

Neutron-activation determination of the rare earths in natural calcites using a semiconductor detector

International Nuclear Information System (INIS)

Vaganov, N.A.; Bulnaev, A.I.; Mejer, V.A.; Ponomarev, V.S.

1976-01-01

The application of germanium semiconducting detector is described. The detector has an energy resolution about 1 KeV and makes it possible to determine the content of Ce, Nd, Eu, Gd, Tb, and Yb in natural calcites with high sensitivity. The region of soft γ-radiation of activated calcites is more favourable for measurements to be performed than the region of hard γ-rays. Semiconducting detectors of radiation type are relatively cheap; they can be stored at room temperature. The limit of determining rare earth elements in calcites is (g): Eu-1.5.10 -9 ; Tb-4.0.10 -9 ; Yb-7.0.10 -9 ; Ce-1.0.10 -7 ; Nd-5.0.10 -7 ; Gd-1.0.10 -6 . A relative error of concentration determination is 10-20%

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-06-15

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

Textural and isotopic evidence for Ca-Mg carbonate pedogenesis

Science.gov (United States)

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

Time scales for dissolution of calcite fracture fillings and implications for saturated zone radionuclide transport at Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Winterle, J.R.; Murphy, W.M.

1999-01-01

An analysis was performed to estimate time scales for dissolution of calcite fracture fillings in the fractured tuff aquifer that underlies Yucca Mountain (YM), Nevada, where groundwater is chemically undersaturated with respect to calcite. The impetus for this analysis originates from speculation that undissolved calcite in the saturated zone is evidence for limited diffusive exchange between fracture and matrix waters. Assuming that matrix diffusion is the rate-limiting process, the time scale for dissolution of calcite fracture fillings depends on the amount of calcite initially deposited, the distance between flowing fractures, the degree of chemical disequilibrium, and the rate of diffusion. Assuming geochemistry of J-13 well water in free-flowing fractures, estimated time scales for complete dissolution of matrix-entrapped calcite range from about 10 4 yr for a 2 mm-thick deposit located 1 m from a flowing fracture, to over 10 7 yr for a 2 cm-thick deposit located 100 m from a flowing fracture. The authors conclude that, given the geochemical and hydrologic characteristics observed at YM, the persistence of calcite minerals over geologic time scales in aquifers where flowing water is under-saturated with calcite does not necessarily preclude matrix diffusion as a dilution mechanism. However, the model suggests that the effective spacing between flowing fractures may be large enough to diminish the overall benefit of matrix diffusion to proposed high-level waste repository performance

Conditions of uranium-bearing calcite formation in ore-enclosing sediments of the Semizbaj deposit (Kazakhstan)

International Nuclear Information System (INIS)

Kondrat'eva, I.A.; Maksimova, I.G.; Dojnikova, O.I.

1995-01-01

Consideration is given to results of investigation into uranium-bearing calcite, forming the cement of gravelly-sandy rocks of the Semizbaj uranium deposit. Core sampling in prospecting boreholes were used to establish geological conditions, place and time of uranium-bearing calcite formation. Calcite was investigated by optical, electron-microscope and radiographic methods. It is shown that uranium in calcite doesn't form its own mineral phase and exists in scattered state. Uranium in calcite-bearing minerals is present in isomorphic form. Uranium content in calcite was equal to 0.009-0.15 %. It is proposed that mineralization, formed in sedimentary rocks by processes of ground-stratum oxidation, is the source of uranium, enriching calcite. refs., 5 figs., 2 tabs

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

Science.gov (United States)

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.

Skeletal mineralogy of coral recruits under high temperature and pCO2

Science.gov (United States)

Foster, T.; Clode, P. L.

2016-03-01

Aragonite, which is the polymorph of CaCO3 precipitated by modern corals during skeletal formation, has a higher solubility than the more stable polymorph calcite. This higher solubility may leave animals that produce aragonitic skeletons more vulnerable to anthropogenic ocean acidification. It is therefore important to determine whether scleractinian corals have the plasticity to adapt and produce calcite in their skeletons in response to changing environmental conditions. Both high pCO2 and lower Mg / Ca ratios in seawater are thought to have driven changes in the skeletal mineralogy of major marine calcifiers in the past ˜ 540 Ma. Experimentally reduced Mg / Ca ratios in ambient seawater have been shown to induce some calcite precipitation in both adult and newly settled modern corals; however, the impact of high pCO2 on the mineralogy of recruits is unknown. Here we determined the skeletal mineralogy of 1-month-old Acropora spicifera coral recruits grown under high temperature (+3 °C) and pCO2 (˜ 900 µatm) conditions, using X-ray diffraction and Raman spectroscopy. We found that newly settled coral recruits produced entirely aragonitic skeletons regardless of the treatment. Our results show that elevated pCO2 alone is unlikely to drive changes in the skeletal mineralogy of young corals. Not having an ability to switch from aragonite to calcite precipitation may leave corals and ultimately coral reef ecosystems more susceptible to predicted ocean acidification. An important area for prospective research would be the investigation of the combined impact of high pCO2 and reduced Mg / Ca ratio on coral skeletal mineralogy.

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

Energy Technology Data Exchange (ETDEWEB)

Bakke, N.E.

1996-12-31

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

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

Science.gov (United States)

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

On the origin of calcite-cemented sandstones in the clearwater formation oil-sands, Alberta

Energy Technology Data Exchange (ETDEWEB)

Colquhoun, I.M.

1999-01-01

This thesis examined the formation of calcite-cemented sandstones in the Clearwater Formation within the Cold Lake and southern Primrose areas of the Alberta oil sands. Three stages of diagenesis have been recognized, both in the calcite-cemented sandstones and reservoir sands. Diagenesis of the Clearwater Formation in the Cold Lake and southern Primrose areas ended once the reservoir filled with hydrocarbons, but in the Cold Lake area, diagenesis of water-saturated sands likely continued after hydrocarbon emplacement. The reservoir sands in the formation contain a diverse clay mineral assemblage. In general, 0.7 nm clays dominate the diagenetic clay mineralogy of the Clearwater sands. Reservoir sands that contain large amounts of detrital clays and early diagenetic, grain-coating chlorite/smectite have significantly reduced bitumen-saturation. The presence of detrital and diagenetic smectitic clays complicates the removal of bitumen from the Clearwater formation using cyclic steam stimulation techniques because they swell during steam stimulation and reduce porosity and permeability of reservoir sands. Reservoir sands that contain kaolinite, feldspar and calcite react to form smectitic clays, which swell upon cyclic steam stimulation and further reduce porosity and permeability of reservoir sands. However, in the Cold Lake and Primrose areas, the dominant clay mineral is berthierine, which is associated with high calcite, which help to preserve porosity, permeability and bitumen saturation. The porous nature of bitumen-saturated, calcite-cemented sandstones that are laterally extensive could possibly provide a preferential path for steam to initiate calcite dissolution and produce significant concentrations of dissolved carbon dioxide in injected fluids. It was noted that this may then precipitate as carbonate scale within the reservoir and could cause formation damage or affect production equipment. 207 refs., 9 tabs., 58 figs., 3 appendices.

Speciation of As in calcite by micro-XAFS: Implications for remediation of As contamination in groundwater

International Nuclear Information System (INIS)

Yokoyama, Y; Takahashi, Y; Iwatsuki, T; Terada, Y

2013-01-01

To evaluate the role of calcite as a host phase of arsenic (As) in As-contaminated groundwater, distribution behavior of Asbetween natural calcite and groundwater in deep underground was investigated based on As oxidation state. Speciation analyses of As in natural calcite by μ-XRF-XAFS analyses showed (i) preferentialarsenate uptake by calcite, and (ii) promptness of arsenate uptake by minor iron (Fe) carbonate minerals coprecipitated with calcite. These findings suggest that the effect of calcite on As remediation of the As-contamination systems stronglydepends on arsenite to arsenate ratio (i.e., redox condition) in groundwater, and maybe governed bythe amount of Fe coprecipitated with calcite.

Highly Resolved Mg/Ca Depth Profiles of Planktic Foraminifer test Walls Using Single shot Measurements of fs-LA-ICPMS

Science.gov (United States)

Jochum, K. P.; Schiebel, R.; Stoll, B.; Weis, U.; Haug, G. H.

2017-12-01

Foraminifers are sensitive archives of changes in climate and marine environment. It has been shown that the Mg/Ca signal is a suitable proxy of seawater temperature, because the incorporation of Mg depends on ambient water temperature. In contrast to most former studies, where this ratio is determined by solution-based bulk analysis of 20 - 30 specimens, we have investigated Mg/Ca in single specimens and single chambers at high resolution. A new fs-200 nm-LA-ICPMS technique was developed for the µm-sized layered calcite shells. To generate depth profiles with a resolution of about 50 nm/shot, we chose a low fluence of about 0.3 Jcm-2 and performed single shot measurements of the double charged 44Ca++ and the single charged 25Mg+ ions together. Precision (RSD) of the Mg/Ca data is about 5 %. Calibration was performed with the carbonate reference material MACS-3 from the USGS. Our results for different species from the Arabian Sea and Caribbean Sea demonstrate that Mg/Ca of different chambers vary and indicate that the foraminifer individuals built their chambers in different water depths and/or experienced seasonal changes in seawater temperature caused, for example, by upwelling (cold) versus stratified (warm) conditions. Typically, the Mg/Ca ratios of the final two chambers of the planktic foraminifer Globorotalia menardii from a sediment core of the Arabian Sea differ by about 5 mmol/mol from earlier chambers (2 mmol/mol) corresponding to seawater temperatures of 28 °C and 18 °C, respectively. In addition, mass fractions of other elements like Sr, Mn, Fe, Ba, and U have been determined with fs-LA-ICPMS using fast line scans, and thus provide further insights in the ecology of foraminifers.

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

Science.gov (United States)

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.

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

International Nuclear Information System (INIS)

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

2014-01-01

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. (paper)

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

Science.gov (United States)

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.

A study on the coprecipitation of arsenite and arsenate into calcite coupled with the determination of oxidation states of arsenic both in calcite and water

International Nuclear Information System (INIS)

Yokoyama, Yuka; Takahashi, Yoshio; Mitsunobu, Satoshi; Tanaka, Kazuya; Itai, Takaaki

2009-01-01

It was found that the amount of arsenite incorporated into calcite is much less than that of arsenate. The result suggests that the sequestration of arsenic by coprecipitation with calcite cannot be an important chemical process under reducing conditions such as in groundwater where arsenite is the dominant arsenic species. (author)

Organic geochemistry and stable isotope composition of New Zealand carbonate concretions and calcite fracture fills

International Nuclear Information System (INIS)

Pearson, M.J.; Nelson, C.S.

2005-01-01

Carbonate concretion bodies, representing a number of morphological types, and associated calcite fracture fills, mainly from New Zealand, have been studied both organically and inorganically. Extracted organic material is dominated by a complex polymeric dark brown highly polar fraction with a subordinate less polar and lighter coloured lipid fraction. The relative proportion of the two fractions is the principal control on the colour of fracture fill calcites. Concretions are classified mainly by reference to their carbonate stable carbon and oxygen isotope and cation composition. Typical subspherical calcitic septarian concretions, such as those in the Paleocene Moeraki and the Eocene Rotowaro Siltstones, contain carbon derived mainly by bacterial sulfate reduction in marine strata during early diagenesis. Other concretions, including a septarian calcitic type from the Northland Allochthon, have a later diagenetic origin. Siderite concretions, abundant in the nonmarine Waikato Coal Measures, are typically dominated by methanogenic carbon, whereas paramoudra-like structures from the Taranaki Miocene have the most extreme carbon isotope compositions, probably resulting from methane formation or oxidation in fluid escape conduits. Lipids from concretion bodies and most fracture fill calcites contain significant concentrations of fatty acids. Concretion bodies dominated by bimodally distributed n-fatty acids with strong even-over-odd preference, in which long chain n-acids are of terrestrial origin, have very low hydrocarbon biomarker maturities. Concretion bodies that lack long chain n-acids often have higher apparent biomarker maturity and prominent alpha-omega diacids. Such diacids are abundant in fracture fill calcites at Rotowaro, especially where calcite infills the septaria of a siderite concretion in the non-marine Waikato Coal Measures, and support the view that fluid transport resulted in carbonate entrapment of the fracture-hosted acids. Diacids also

Impact of seawater [Ca2+] on the calcification and calcite Mg / Ca of Amphistegina lessonii

NARCIS (Netherlands)

Mewes, A.; Langer, G.; Thoms, S.; Nehrke, G.; Reichart, G. J.; de Nooijer, L. J.; Bijma, J.

2015-01-01

Mg / Ca ratios in foraminiferal tests are routinely used as paleotemperature proxies, but on long timescales, they also hold the potential to reconstruct past seawater Mg / Ca. The impact of both temperature and seawater Mg / Ca on Mg incorporation in Foraminifera has been quantified by a number of

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

DEFF Research Database (Denmark)

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

2010-01-01

Molecular dynamics simulations have been used to model the interaction between ethanol, water, and the {1014} surface of calcite. Our results demonstrate that a single ethanol molecule is able to form two interactions with the mineral surface (both Ca-O and O-H), resulting in a highly ordered, st...

Early to Middle Jurassic palaeoenvironmental changes: High resolution δ13C and δ18O records from the UK

DEFF Research Database (Denmark)

Korte, Christoph; Hesselbo, Stephen; Ullmann, Clemens Vinzenz

Low-Mg-calcite fossils, such as bivalves, belemnites and brachiopods, and bulk rocks have been extensively utilized to reconstruct past seawater chemistry and paleoenviron¬mental changes. Recent work on major bioevents demonstrated that particularly higher resolution stable isotope records...... are necessary to reveal short-term paleoenviron¬mental fluctuations and, in addition, to discover its causes. Here we present a new high resolution carbon and oxygen isotope dataset generated from low-Mg-calcite fossils, fossil wood and bulk rocks collected from Early to Middle Jurassic marine successions...

FORMATION OF CALCITE AND SILICA FROM PERCOLATION IN A HYDROLOGICALLY UNSATURATED SETTING, YUCCA MOUNTAIN, NEVADA

International Nuclear Information System (INIS)

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

2000-01-01

Geological, mineralogical, chemical, and isotopic evidence from coatings of calcite and silica on open fractures and lithophysal cavities within welded tuffs at Yucca Mountain indicate an origin from meteoric water percolating through a thick (500 to 700 m) unsaturated zone (UZ) rather than from pulses of ascending ground water. Geologic evidence for a UZ setting includes the presence of coatings in only a small percentage of cavities, the restriction of coatings to fracture footwalls and cavity floors, and an absence of mineral high-water marks indicative of water ponding. Systematic mineral sequences (early calcite, followed by chalcedony with minor quartz and fluorite, and finally calcite with intercalated opal forming the bulk of the coatings) indicate progressive changes in UZ conditions through time, rather than repeated saturation by flooding. Percolation under the influence of gravity also results in mineral textures that vary between steeply dipping sites (thinner coatings of blocky calcite) and shallowly dipping sites (thicker coatings of coarse, commonly bladed calcite, with globules and sheets of opal). Micrometer-scale growth banding in both calcite and opal reflects slow average growth rates (scale of mm/m.y.) over millions of years rather than only a few rapidly deposited growth episodes. Isotopic compositions of C, O, Sr, and U from calcite and opal indicate a percolation-modified meteoric water source, and collectively refute a deeper ground-water source. Chemical and isotopic variations in coatings also indicate long-term evolution of water compositions. Although some compositional changes are related to shifts in climate, growth rates in the deeper UZ are buffered from large changes in meteoric input. Coatings most likely formed from films of water flowing down connected fracture pathways. Mineral precipitation is consistent with water vapor and carbon dioxide loss from films at very slow rates. Data collectively indicate that mineral coatings

Interactions between cadmium and calcite

NARCIS (Netherlands)

van der Weijden, R.D.

1995-01-01

The thesis is composed of five chapters, some of which have been published or have been accepted for publication. The contents in some of the chapters may therefore slightly overlap, also because the subjects are closely related. The first two chapters focus mostly on the sorption of Cd on calcite,

Morphological changes of calcite single crystals induced by graphene-biomolecule adducts

Science.gov (United States)

Calvaresi, Matteo; Di Giosia, Matteo; Ianiro, Alessandro; Valle, Francesco; Fermani, Simona; Polishchuk, Iryna; Pokroy, Boaz; Falini, Giuseppe

2017-01-01

Calcite has the capability to interact with a wide variety of molecules. This usually induces changes in shape and morphology of crystals. Here, this process was investigated using sheets of graphene-biomolecule adducts. They were prepared and made dispersible in water through the exfoliation of graphite by tip sonication in the presence tryptophan or N-acetyl-D-glucosamine. The crystallization of calcium carbonate in the presence of these additives was obtained by the vapor diffusion method and only calcite formed. The analysis of the microscopic observations showed that the graphene-biomolecule adducts affected shape and morphology of rhombohedral {10.4} faced calcite crystals, due to their stabilization of additional {hk.0} faces. The only presence of the biomolecule affected minimally shape and morphology of calcite crystals, highlighting the key role of the graphene sheets as 2D support for the adsorption of the biomolecules.

Mg and 18O Variations in the Shell of the Chilean Gastropod Concholepas concholepas Reflect SST and Growth Rate variations

Science.gov (United States)

Guzman, N.; Lazareth, C. E.; Poitrasson, F.; Cuif, J.; Ortlieb, L.

2004-12-01

To validate the use of fossil mollusc shells as recorders of environmental conditions, a primary calibration study was carried out on modern shells of the Chilean gastropod Concholepas concholepas, the so-called southern hemisphere abalone which is particularly abundant in Holocene archaeological sites. Organisms were maintained in culture tanks and feed with live mytilids. The sea water temperature in the tank was recorded every half-an-hour by an automatic device. The experiment lasted several months. Periodical marking with calcein provided a precise chronological control of the shell growth. Thus, well-dated high resolution chemical profiles could be directly compared with temperatures during shell formation. Geochemical analyses of the calcite layers include Mg, Sr and 16O/18O composition. Trace elements were analysed using Laser Ablation ICP-MS and Electron Microprobe while stable isotopes were measured on a Secondary Ion Mass spectrometry (SIMS). The shell growth rate during two months of formation varied between 30 and 140 µm/day which allows us to reach a temporal resolution for chemical profiles between a few hours and three days. The growth rate variations do not seem to be related to temperature fluctuations. Only Mg content was analytically reproducible and showed significant variations across the shells. The Mg high-resolution profiles display a grossly sinusoidal shape. Shells from different sites along the coasts of Chile showed mean Mg contents of 300 ppm and 500 ppm for mean temperatures of 17 and 20° C, respectively. This suggests a gross correlation between Mg and temperature. However, high resolution Mg results do not show an exact fitting neither with temperature nor with growth rates. Other parameters, like shell ageing as suggested by an amplitude increase observed near the edge of one of the shells, or other complex biological factors, may influence Mg incorporation into the shell. \\delta 18O values of the calcite vary between -1,5 and 2

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-01-01

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

Sequestration of Antimony on Calcite Observed by Time-Resolved Nanoscale Imaging.

Science.gov (United States)

Renard, François; Putnis, Christine V; Montes-Hernandez, German; King, Helen E; Breedveld, Gijs D; Okkenhaug, Gudny

2018-01-02

Antimony, which has damaging effects on the human body and the ecosystem, can be released into soils, ground-, and surface waters either from ore minerals that weather in near surface environments, or due to anthropogenic releases from waste rich in antimony, a component used in batteries, electronics, ammunitions, plastics, and many other industrial applications. Here, we show that dissolved Sb can interact with calcite, a widespread carbonate mineral, through a coupled dissolution-precipitation mechanism. The process is imaged in situ, at room temperature, at the nanometer scale by using an atomic force microscope equipped with a flow-through cell. Time-resolved imaging allowed following the coupled process of calcite dissolution, nucleation of precipitates at the calcite surface and growth of these precipitates. Sb(V) forms a precipitate, whereas Sb(III) needs to be oxidized to Sb(V) before being incorporated in the new phase. Scanning-electron microscopy and Raman spectroscopy allowed identification of the precipitates as two different calcium-antimony phases (Ca 2 Sb 2 O 7 ). This coupled dissolution-precipitation process that occurs in a boundary layer at the calcite surface can sequester Sb as a solid phase on calcite, which has environmental implications as it may reduce the mobility of this hazardous compound in soils and groundwaters.

Interaction of alcohols with the calcite surface

DEFF Research Database (Denmark)

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

2015-01-01

. Controlling their growth requires complex polysaccharides. Polysaccharide activity depends on the functionality of OH groups, so to simplify the system in order to get closer to a molecular level understanding, we investigated the interaction of OH from a suite of alcohols with clean, freshly cleaved calcite...... surfaces. X-ray photoelectron spectroscopy (XPS) provided binding energies and revealed the extent of surface coverage. Molecular dynamics (MD) simulations supplemented with information about molecule ordering, orientation and packing density. The results show that all alcohols studied bond...... with the calcite surface through the OH group, with their carbon chains sticking away in a standing-up orientation. Alcohol molecules are closely packed and form a well-ordered monolayer on the surface....

Fabrication of calcite blocks from gypsum blocks by compositional transformation based on dissolution-precipitation reactions in sodium carbonate solution.

Science.gov (United States)

Ishikawa, Kunio; Kawachi, Giichiro; Tsuru, Kanji; Yoshimoto, Ayami

2017-03-01

Calcium carbonate (CaCO 3 ) has been used as a bone substitute, and is a precursor for carbonate apatite, which is also a promising bone substitute. However, limited studies have been reported on the fabrication of artificial calcite blocks. In the present study, cylindrical calcite blocks (ϕ6×3mm) were fabricated by compositional transformation based on dissolution-precipitation reactions using different calcium sulfate blocks as a precursor. In the dissolution-precipitation reactions, both CaSO 4 ·2H 2 O and CaSO 4 transformed into calcite, a polymorph of CaCO 3 , while maintaining their macroscopic structure when immersed in 1mol/L Na 2 CO 3 solution at 80°C for 1week. The diametral tensile strengths of the calcite blocks formed using CaSO 4 ·2H 2 O and CaSO 4 were 1.0±0.3 and 2.3±0.7MPa, respectively. The fabrication of calcite blocks using CaSO 4 ·2H 2 O and CaSO 4 proposed in this investigation may be a useful method to produce calcite blocks because of the self-setting ability and high temperature stability of gypsum precursors. Copyright © 2016 Elsevier B.V. All rights reserved.

Speleothem Mg-isotope time-series data from different climate belts

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Riechelmann, S.; Buhl, D.; Richter, D. K.; Schröder-Ritzrau, A.; Riechelmann, D. F. C.; Niedermayr, A.; Vonhof, H. B.; Wassenburg, J.; Immenhauser, A.

2012-04-01

Speleothem Mg-isotope time-series data from different climate belts Sylvia Riechelmann (1), Dieter Buhl(1), Detlev K. Richter (1), Andrea Schröder-Ritzrau (2), Dana F.C. Riechelmann (3), Andrea Niedermayr (1), Hubert B. Vonhof (4) , Jasper Wassenburg (1), Adrian Immenhauser (1) (1) Ruhr-University Bochum, Institute for Geology, Mineralogy and Geophysics, Universitätsstraße 150, D-44801 Bochum, Germany (2) Heidelberg Academy of Sciences, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany (3) Johannes Gutenberg-University Mainz, Institute of Geography, Johann-Joachim-Becher-Weg 21, D-55128 Mainz, Germany (4) Faculty of Earth and Life Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1085, 1081 HV, Amsterdam, The Netherlands The Magnesium isotope proxy in Earth surface research is still underexplored. Recently, field and laboratory experiments have shed light on the complex suite of processes affecting Mg isotope fractionation in continental weathering systems. Magnesium-isotope fractionation in speleothems depends on a series of factors including biogenic activity and composition of soils, mineralogy of hostrock, changes in silicate versus carbonate weathering ratios, water residence time in the soil and hostrock and disequilibrium factors such as the precipitation rate of calcite in speleothems. Furthermore, the silicate (here mainly Mg-bearing clays) versus carbonate weathering ratio depends on air temperature and rainfall amount, also influencing the soil biogenic activity. It must be emphasized that carbonate weathering is generally dominant, but under increasingly warm and more arid climate conditions, silicate weathering rates increase and release 26Mg-enriched isotopes to the soil water. Furthermore, as shown in laboratory experiments, increasing calcite precipitation rates lead to elevated delta26Mg ratios and vice versa. Here, data from six stalagmite time-series Mg-isotope records (Thermo Fisher Scientific Neptune MC-ICP-MS) are shown. Stalagmites

Dissolution Processes at Step Edges of Calcite in Water Investigated by High-Speed Frequency Modulation Atomic Force Microscopy and Simulation.

Science.gov (United States)

Miyata, Kazuki; Tracey, John; Miyazawa, Keisuke; Haapasilta, Ville; Spijker, Peter; Kawagoe, Yuta; Foster, Adam S; Tsukamoto, Katsuo; Fukuma, Takeshi

2017-07-12

The microscopic understanding of the crystal growth and dissolution processes have been greatly advanced by the direct imaging of nanoscale step flows by atomic force microscopy (AFM), optical interferometry, and X-ray microscopy. However, one of the most fundamental events that govern their kinetics, namely, atomistic events at the step edges, have not been well understood. In this study, we have developed high-speed frequency modulation AFM (FM-AFM) and enabled true atomic-resolution imaging in liquid at ∼1 s/frame, which is ∼50 times faster than the conventional FM-AFM. With the developed AFM, we have directly imaged subnanometer-scale surface structures around the moving step edges of calcite during its dissolution in water. The obtained images reveal that the transition region with typical width of a few nanometers is formed along the step edges. Building upon insight in previous studies, our simulations suggest that the transition region is most likely to be a Ca(OH) 2 monolayer formed as an intermediate state in the dissolution process. On the basis of this finding, we improve our understanding of the atomistic dissolution model of calcite in water. These results open up a wide range of future applications of the high-speed FM-AFM to the studies on various dynamic processes at solid-liquid interfaces with true atomic resolution.

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

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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

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

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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

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

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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.

Is bicarbonate stable in and on the calcite surface?

DEFF Research Database (Denmark)

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

2016-01-01

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

Paleotransport of lanthanides and strontium recorded in calcite compositions from tuffs at Yucca Mountain, Nevada, USA

International Nuclear Information System (INIS)

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

1996-01-01

Secondary calcite occurs in both saturated and unsaturated hydrologic zones (SZ and UZ, respectively) in the tuffs at Yucca Mountain, Nevada, USA. In the upper UZ, the major constituents of the calcite crystal structure (C, O) have surface origins. At greater depth there is a open-quotes barren zone,close quotes straddling the water table, where calcite is rare and mixing of surface and subsurface sources may occur. Deep in the SZ, distinctive Mn calcites reflect deep sources, including Ca released as analcime or albite formed and carbonates derived from underlying Paleozoic rocks. In the UZ and in the barren zone, above the deep Mn calcites, variations in calcite lanthanide chemistry can be used to distinguish rhyolitic from quartz-latitic sources. Lanthanide ratios and Sr contents of calcites record the chemical evolution of waters flowing through the UZ and upper SZ. Variations in calcite chemistry in the UZ and in the barren zone show that (1) Sr, which is readily exchanged with clays or zeolites, is essentially removed from some flowpaths that are in contact with these minerals and (2) traces of Mn oxides found in the tuffs have a significant effect of groundwater chemistry in the UZ and in the barren zone by removing almost all Ce from solution (evidenced by characteristic Ce depletions in calcite throughout this zone). Extreme Ce removal may be a result of Ce oxidation (Ce 3+ → Ce 4+ ) at the surfaces of some Mn oxides, particularly rancieite. Higher Sr contents and lack of Ce depletions in the deeper Mn calcites reflect different ages, origins, and transport systems. The calcite record of lanthanide and Sr transport in the UZ shows that minor minerals (clays and zeolites) and even trace minerals (Mn oxides) will affect the compositions of groundwaters that flow over distances greater than a few tens of meters. 43 refs., 8 figs., 4 tabs

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

Science.gov (United States)

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

2007-11-01

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

Morphology of calcite crystals in clast coatings from four soils in the Mojave desert region

Science.gov (United States)

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

1989-01-01

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

Isolation and identification of Pseudomonas azotoformans for induced calcite precipitation.

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Heidari Nonakaran, Siamak; Pazhouhandeh, Maghsoud; Keyvani, Abdullah; Abdollahipour, Fatemeh Zahra; Shirzad, Akbar

2015-12-01

Biomineralization is a process by which living organisms produce minerals. The extracellular production of these biominerals by microbes has potential for various bioengineering applications. For example, crack remediation and improvement of durability of concrete is an important goal for engineers and biomineral-producing microbes could be a useful tool in achieving this goal. Here we report the isolation, biochemical characterization and molecular identification of Pseudomonas azotoformans, a microbe that produces calcite and which potentially be used to repair cracks in concrete structures. Initially, 38 bacterial isolates were isolated from soil and cements. As a first test, the isolates were screened using a urease assay followed by biochemical tests for the rate of urea hydrolysis, calcite production and the insolubility of calcite. Molecular amplification and sequencing of a 16S rRNA fragment of selected isolates permitted us to identify P. azotoformans as a good candidate for preparation of biotechnological concrete. This species was isolated from soil and the results show that among the tested isolates it had the highest rate of urea hydrolysis, produced the highest amount of calcite, which, furthermore was the most adhesive and insoluble. This species is thus of interest as an agent with the potential ability to repair cracks in concrete.

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

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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.

The elemental composition of purple sea urchin (Strongylocentrotus purpuratus) calcite and potential effects of pCO2 during early life stages

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

2013-06-01

Ocean acidification will likely have negative impacts on invertebrates producing skeletons composed of calcium carbonate. Skeletal solubility is partly controlled by the incorporation of "foreign" ions (e.g. magnesium) into the crystal lattice of these skeletal structures, a process that is sensitive to a variety of biological and environmental factors. Here we explore effects of life stage, oceanographic region of origin, and changes in the partial pressure of carbon dioxide in seawater (pCO2) on trace elemental composition in the purple sea urchin (Strongylocentrotus purpuratus). We show that, similar to other urchin taxa, adult purple sea urchins have the ability to precipitate skeleton composed of a range of biominerals spanning low- to high-Mg calcites. Mg / Ca and Sr / Ca ratios were substantially lower in adult spines compared to adult tests. On the other hand, trace elemental composition was invariant among adults collected from four oceanographically distinct regions spanning a range of carbonate chemistry conditions (Oregon, Northern California, Central California, and Southern California). Skeletons of newly settled juvenile urchins that originated from adults from the four regions exhibited intermediate Mg / Ca and Sr / Ca between adult spine and test endmembers, indicating that skeleton precipitated during early life stages is more soluble than adult spines and less soluble than adult tests. Mean skeletal Mg / Ca or Sr / Ca of juvenile skeleton did not vary with source region when larvae were reared under present-day, global-average seawater carbonate conditions (400 μatm; pHT = 8.02 ± 0.03 1 SD; Ωcalcite = 3.3 ± 0.2 1 SD). However, when reared under elevated pCO2 (900 μatm; pHT = 7.73 ± 0.03; Ωcalcite = 1.8 ± 0.1), skeletal Sr / Ca in juveniles exhibited increased variance across the four regions. Although larvae from the northern populations (Oregon, Northern California, Central California) did not exhibit differences in Mg or Sr

The elemental composition of purple sea urchin (Strongylocentrotus purpuratus calcite and potential effects of pCO2 during early life stages

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M. LaVigne

2013-06-01

Full Text Available Ocean acidification will likely have negative impacts on invertebrates producing skeletons composed of calcium carbonate. Skeletal solubility is partly controlled by the incorporation of "foreign" ions (e.g. magnesium into the crystal lattice of these skeletal structures, a process that is sensitive to a variety of biological and environmental factors. Here we explore effects of life stage, oceanographic region of origin, and changes in the partial pressure of carbon dioxide in seawater (pCO2 on trace elemental composition in the purple sea urchin (Strongylocentrotus purpuratus. We show that, similar to other urchin taxa, adult purple sea urchins have the ability to precipitate skeleton composed of a range of biominerals spanning low- to high-Mg calcites. Mg / Ca and Sr / Ca ratios were substantially lower in adult spines compared to adult tests. On the other hand, trace elemental composition was invariant among adults collected from four oceanographically distinct regions spanning a range of carbonate chemistry conditions (Oregon, Northern California, Central California, and Southern California. Skeletons of newly settled juvenile urchins that originated from adults from the four regions exhibited intermediate Mg / Ca and Sr / Ca between adult spine and test endmembers, indicating that skeleton precipitated during early life stages is more soluble than adult spines and less soluble than adult tests. Mean skeletal Mg / Ca or Sr / Ca of juvenile skeleton did not vary with source region when larvae were reared under present-day, global-average seawater carbonate conditions (400 μatm; pHT = 8.02 ± 0.03 1 SD; Ωcalcite = 3.3 ± 0.2 1 SD. However, when reared under elevated pCO2 (900 μatm; pHT = 7.73 ± 0.03; Ωcalcite = 1.8 ± 0.1, skeletal Sr / Ca in juveniles exhibited increased variance across the four regions. Although larvae from the northern populations (Oregon, Northern California, Central California did not exhibit differences in Mg or Sr

Index of refraction enhancement of calcite particles coated with zinc carbonate

Science.gov (United States)

Lattaud, Kathleen; Vilminot, Serge; Hirlimann, Charles; Parant, Hubert; Schoelkopf, Joachim; Gane, Patrick

2006-10-01

ZnCO 3 coating on calcite particles has been developed in order to enhance the index of refraction of this mineral that is used as a charge in paper, paint and polymer industries. Chemical reaction between calcite particles in an aqueous suspension with zinc chloride promotes the formation of a ZnCO 3 coating consisting of two layers with different interactions with the calcite particle. The refraction index of the resulting composite particles increases with the Zn/Ca ratio. A model allows to evaluate the coating thickness. The value of the scattering S and diffusion K coefficients of sheets coated with the ZnCO 3 coated particles reveal a dependence on the preparation conditions with a 15% increase for the best samples.

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

Science.gov (United States)

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.

Rate of radiocarbon retention onto calcite by isotope exchange

Energy Technology Data Exchange (ETDEWEB)

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

2016-11-01

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

Rate of radiocarbon retention onto calcite by isotope exchange

International Nuclear Information System (INIS)

Lempinen, Janne; Lehto, Jukka

2016-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Lecocq, D

2002-12-15

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

Microbially induced separation of quartz from calcite using Saccharomyces cerevisiae.

Science.gov (United States)

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.

Self-healing of drying shrinkage cracks in cement-based materials incorporating reactive MgO

Science.gov (United States)

Qureshi, T. S.; Al-Tabbaa, A.

2016-08-01

Excessive drying shrinkage is one of the major issues of concern for longevity and reduced strength performance of concrete structures. It can cause the formation of cracks in the concrete. This research aims to improve the autogenous self-healing capacity of traditional Portland cement (PC) systems, adding expansive minerals such as reactive magnesium oxide (MgO) in terms of drying shrinkage crack healing. Two different reactive grades (high ‘N50’and moderately high ‘92-200’) of MgO were added with PC. Cracks were induced in the samples with restraining end prisms through natural drying shrinkage over 28 days after casting. Samples were then cured under water for 28 and 56 days, and self-healing capacity was investigated in terms of mechanical strength recovery, crack sealing efficiency and improvement in durability. Finally, microstructures of the healing materials were investigated using FT-IR, XRD, and SEM-EDX. Overall N50 mixes show higher expansion and drying shrinkage compared to 92-200 mixes. Autogenous self-healing performance of the MgO containing samples were much higher compared to control (only PC) mixes. Cracks up to 500 μm were sealed in most MgO containing samples after 28 days. In the microstructural investigations, highly expansive Mg-rich hydro-carbonate bridges were found along with traditional calcium-based, self-healing compounds (calcite, portlandite, calcium silicate hydrates and ettringite).

Sulphate partitioning into calcite: Experimental verification of pH control and application to seasonality in speleothems

Science.gov (United States)

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

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

What concentration of actinides can be packed into calcite? Hints from rare earth element (REE) composition

International Nuclear Information System (INIS)

Christiansen, J.; Stipp, S.L.S.; Waight, T.; Baker, J.A.

2005-01-01

Full text of publication follows: For reliable modelling of actinide mobility in the event of spent fuel repository failure, we need data describing the uptake capacity of the minerals likely to find themselves in the transport path. Calcite (CaCO 3 ) is a common secondary mineral in fractures and pore fillings, especially downstream from degrading concrete facilities, so it is a likely candidate for incorporation. Investigations made under ACTAF, a 5. Framework EURATOM integrated project, as well as some other research studies, have shown that actinides are successfully incorporated as substituting ions within the calcite mineral structure. The question remaining, is how much can calcite take up. Geologists routinely use relative concentrations of rare Earth elements (REE's), the lanthanides, for interpreting rock genesis and history. One can also adopt them as analogues for the radioactive elements because their f-orbital electron configuration makes them behave very much like actinides. We collected and analysed a suite of 70 calcite samples from a great number of possible formation environments, geological ages and geographical locations, for the purpose of finding the range and maximum of total f-orbital substitution possible in calcite, under natural conditions. We analysed them using Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). The maximum concentration found was about 5 x 10 -3 mole/kg total REE in a sample that had a geological history of formation where REE fluids played a role. Over the whole suite, total REE ranged from less than 10 -4 moles/kg for limestone samples formed from biogenic calcite where REE-enriched fluids would have played a negligible role. Thus, in natural calcite, REE's are present and all evidence points to a structural incorporation within the mineral rather than as a separate REE-rich phase. These data compare favourably with mole fractions from calcite grown synthetically, where as much as 6 x 10 -3

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

Science.gov (United States)

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

Review of aragonite and calcite crystal morphogenesis in thermal spring systems

Science.gov (United States)

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.

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

Science.gov (United States)

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

2018-02-15

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

A time-resolved laser fluorescence spectroscopy (TRLFS) study of the interaction of trivalent actinides (curium(III)) with calcite

International Nuclear Information System (INIS)

Stumpf, Th.; Fanghaenel, Th.

2002-01-01

Cm(III) interaction with calcite was investigated in the trace concentration range. Two different Cm(III)/calcite sorption species were found. The first Cm(III) sorption species consists of a curium ion that is bonded onto the calcite surface. The second Cm(III) sorption species has lost its complete hydration sphere and is incorporated into the calcite bulk structure /1/. (orig.)

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

Institute of Scientific and Technical Information of China (English)

2008-01-01

interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.

Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

Science.gov (United States)

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…

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

International Nuclear Information System (INIS)

Hill, C.A.; Schluter, C.M.; Harmon, R.S.

1994-01-01

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

Calcite production by coccolithophores in the south east Pacific Ocean

Directory of Open Access Journals (Sweden)

L. Beaufort

2008-08-01

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

Biomimetic mineralization of CaCO3 on a phospholipid monolayer: from an amorphous calcium carbonate precursor to calcite via vaterite.

Science.gov (United States)

Xiao, Junwu; Wang, Zhining; Tang, Yecang; Yang, Shihe

2010-04-06

A phospholipid monolayer, approximately half the bilayer structure of a biological membrane, can be regarded as an ideal model for investigating biomineralization on biological membranes. In this work on the biomimetic mineralization of CaCO(3) under a phospholipid monolayer, we show the initial heterogeneous nucleation of amorphous calcium carbonate precursor (ACC) nanoparticles at the air-water interface, their subsequent transformation into the metastable vaterite phase instead of the most thermodynamically stable calcite phase, and the ultimate phase transformation to calcite. Furthermore, the spontaneity of the transformation from vaterite to calcite was found to be closely related to the surface tension; high surface pressure could inhibit the process, highlighting the determinant of surface energy. To understand better the mechanisms for ACC formation and the transformation from ACC to vaterite and to calcite, in situ Brewster angle microscopy (BAM), ex situ scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray diffraction analysis were employed. This work has clarified the crystallization process of calcium carbonate under phospholipid monolayers and therefore may further our understanding of the biomineralization processes induced by cellular membranes.

Sealing of rock joints by induced calcite precipitation. A case study from Bergeforsen hydro power plant

International Nuclear Information System (INIS)

Hakami, E.; Qvarfort, U.; Ekstav, A.

1991-01-01

The possibilities of sealing rock fractures by injecting water saturated with calcite solution, and hereby inducing a calcite precipitation inside the fracture, is investigated. The way of reaction and the amount of calcite precipitation will depend on the saturation of calcium carbonate in the water, the temperature, the pH and the CO 2 -pressure. There is experience of lime-saturated water injection in the rock foundation below the dam at Bergeforsens power plant (1955-1968). It was observed that the consumption of injected lime water decreased with time. A possible reason to the decrease in lime water consumption is that calcite has precipitated such that the permeability of the rock in general is lowered. Another explanation to this could be that calcite precipitation is concentrated to the fractures surrounding the injection holes, thus preventing the lime water from penetrating further into the rock. It is recommended that further studies of the fracture fillings in drill cores from Bergeforsen is performed. The aim of such study should be to determine the extent of induced calcite precipitation and to investigate its chemical and physical properties. (authors)

Preliminary study of the characteristics of a high Mg containing Al-Mg-Si alloy

International Nuclear Information System (INIS)

Yan, F; McKay, B J; Fan, Z; Chen, M F

2012-01-01

An Al-20Mg-4Si high Mg containing alloy has been produced and its characteristics investigated. The as-cast alloy revealed primary Mg 2 Si particles evenly distributed throughout an α-Al matrix with a β-Al 3 Mg 2 fully divorced eutectic phase observed in interdendritic regions. The Mg 2 Si particles displayed octahedral, truncated octahedral, and hopper morphologies. Additions of Sb, Ti and Zr had a refining influence reducing the size of the Mg 2 Si from 52 ± 4 μm to 25 ± 0.1 μm, 35 ± 1 μm and 34 ± 1 μm respectively. HPDC tensile test samples could be produced with a 0.6 wt.% Mn addition which prevented die soldering. Solution heating for 1 hr was found to dissolve the majority of the Al 3 Mg 2 eutectic phase with no evidence of any effect on the primary Mg 2 Si. Preliminary results indicate that the heat treatment has a beneficial effect on the elongation and the UTS.

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

International Nuclear Information System (INIS)

Stipp, S.L.S.; Christensen, J.T.; Waight, T.E.; Lakshtanov, L.Z.; Baker, J.A.

2006-01-01

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

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

KAUST Repository

Yutkin, Maxim P.

2017-08-25

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

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

Directory of Open Access Journals (Sweden)

Agus Haris Widayat

2015-09-01

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

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

DEFF Research Database (Denmark)

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

2012-01-01

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

Effect of coccolith polysaccharides isolated from the coccolithophorid, Emiliania huxleyi, on calcite crystal formation in in vitro CaCO3 crystallization.

Science.gov (United States)

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.

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

Directory of Open Access Journals (Sweden)

Zijie Ren

2017-02-01

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

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

Science.gov (United States)

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

Immobilization of nanoparticles by occlusion into microbial calcite

DEFF Research Database (Denmark)

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

2017-01-01

systems. In this study, the ureolytic bacteria Sporosarcina pasteurii was used to induce calcium carbonate precipitation in the presence of organo-metallic manufactured nanoparticles. As calcite crystals grew the nanoparticles in the solution became trapped inside these crystals. Capture of NPs within...

High production rate of IBAD-MgO buffered substrate

Energy Technology Data Exchange (ETDEWEB)

Yoshizumi, M., E-mail: myoshizumi@istec.or.j [Superconductivity Research Laboratory, ISTEC, Shinonome 1-10-13, Koto-ku, Tokyo 135-0062 (Japan); Miyata, S.; Ibi, A.; Fukushima, H.; Yamada, Y.; Izumi, T.; Shiohara, Y. [Superconductivity Research Laboratory, ISTEC, Shinonome 1-10-13, Koto-ku, Tokyo 135-0062 (Japan)

2009-10-15

The conventional IBAD (Ion Beam Assisted Deposition) process using fluorite materials yields low production rates, resulting in high production cost, which reduces the motivation for practical application in spite of its high quality. The IBAD process using rock salt materials, e.g. MgO, is well known as a strong candidate of practical application due to its potential of high production rate and high in-plane grain alignment. In this work, the IBAD-MgO process was investigated for a newly developed architecture of PLD (Pulsed Laser Deposition)-CeO{sub 2}/sputter-LMO (LaMnO{sub 3})/IBAD-MgO/sputter-GZO (Gd{sub 2}Zr{sub 2}O{sub 7})/Hastelloy{sup TM} to make long buffered metal tapes with high properties and a high production rate. The 50 m-long IBAD-MgO substrates with about 4 deg. of DELTAphiCeO{sub 2} in an XRD phi scan could be fabricated repeatedly. A GdBCO (GdBa{sub 2}Cu{sub 3}O{sub x}) layer deposited on the buffered substrate showed the minimum I{sub c} value of 325 A/cm-w in a 41 m-long tape. Almost of the tape showed 500-600 A/cm-w of I{sub c} value. The deposition time for the IBAD-MgO layer was 60 s which was about 2 orders of magnitude shorter than the conventional IBAD process. The production rate of 24 m/h was realized at the IBAD-MgO process to fabricate the GdBCO coated conductor with high J{sub c} and I{sub c} properties.

A high resolution atlas of Mg II profiles

Science.gov (United States)

Ewald, R.; Nichols-Bohlin, Joy Y.; Kondo, Yoji

1990-01-01

An atlas of high dispersion Mg II profiles for standard stars of spectral types B0 through G9 is presented. The atlas contains plots of the Mg II profiles for approximately 65 stars and associated equivalent width measurements for both absorption and emission components, and the subordinate lines. The atlas is used to investigate systematic behavior of the Mg II profiles and correlation of the behavior with spectral classification.

Jet-Suspended, Calcite-Ballasted Cyanobacterial Waterwarts in a Desert Spring

Science.gov (United States)

Pichel-Garcia, Ferran; Wade, Bman D.; Farmer, Jack D.

2002-01-01

We describe a population of colonial cyanobacteria (waterwarts) that develops as the dominant primary producer in a bottom-fed, warm spring in the Cuatro Cienegas karstic region of the Mexican Chihuahuan Desert. The centimeter-sized waterwarts were suspended within a central, conically shaped, 6-m deep well by upwelling waters. Waterwarts were built by an unicellular cyanobacterium and supported a community of epiphytic filamentous cyanobacteria and diatoms but were free of heterotrophic bacteria inside. Sequence analysis of genes revealed that this cyanobacterium is only distantly related to several strains of other unicellular teria Cyanothece, Waterwarts contained orderly arrangements of mineral made up of microcrystalline low-magnesium calcite with high levels of strontium and sulfur. Waterwarts were 95.9% (v/v) glycan, 2.8% cells, and 1.3% mineral grains and had a buoyant density of 1.034 kg/L. An analysis of the hydrological properties of the spring well and the waterwarts demonstrated that both large colony size and the presence of controlled amounts of mineral ballast are required to prevent the population from being washed out of the well. The unique hydrological characteristics of the spring have likely selected for both traits. The mechanisms by which controlled nucleation of extracellular calcite is achieved remain to be explored.

The inclusions of Mg-B (MgB12?) as potential pinning centres in high-pressure-high-temperature-synthesized or sintered magnesium diboride

International Nuclear Information System (INIS)

Prikhna, T A; Gawalek, W; Savchuk, Ya M; Habisreuther, T; Wendt, M; Sergienko, N V; Moshchil, V E; Nagorny, P; Schmidt, Ch; Dellith, J; Dittrich, U; Litzkendorf, D; Melnikov, V S; Sverdun, V B

2007-01-01

A systematic study of the structure and superconductive characteristics of high-pressure-high-temperature (2 GPa, 700-1000 deg. C )-synthesized and sintered MgB 2 without additions from different initial powders was performed. Among various secondary phases Mg-B inclusions with a stoichiometry close to MgB 12 were identified. With an increasing amount of these inclusions the critical current density increased. So these inclusions can be feasible pinning centres in MgB 2 . The highest j c values in zero field were 1300 kA cm -2 at 10 K, 780 kA cm -2 at 20 K and 62 kA cm -2 at 35 K and in 1 T field were 1200 kA cm -2 at 10 K, 515 kA cm -2 at 20 K and 0.1 kA cm -2 at 35 K for high-pressure-synthesized magnesium diboride and the field of irreversibility at 20 K reached 8 T. The average grain sizes calculated from x-ray examinations in materials having high j c were 15-37 nm

Tuning the wettability of calcite cubes by varying the sizes of the polystyrene nanoparticles attached to their surfaces

International Nuclear Information System (INIS)

He Yongjun; Li Tanliang; Yu Xiangyang; Zhao Shiyong; Lu Jianhua; He Jia

2007-01-01

The wettability of calcite cubes was tuned by varying the sizes of the polystyrene nanoparticles attached to their surfaces via a dispersion polymerization. The products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersion spectrum (EDS) and Fourier transformation infrared spectrum (FTIR). The results showed that the hydrophobicity of the calcite cubes was enhanced with the increase of the size of the polystyrene nanoparticles attached. Using polystyrene nanoparticle-attached calcite cubes (PNACC) as emulsifiers, stable water-in-tricaprylin Pickering emulsions were produced. By gelling the water droplets of the Pickering emulsions, the hierarchical structures of polystyrene nanoparticle-attached calcite cube-armored microspheres were obtained. The polystyrene nanoparticle-attached calcite cubes were expected to have novel surface properties similar neither to traditional Pickering particles, nor to macroscopically asymmetrical Janus particles

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

Science.gov (United States)

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

The effect of annealing atmosphere on the thermoluminescence of synthetic calcite

International Nuclear Information System (INIS)

Pagonis, Vasilis

1998-01-01

Samples of high purity calcite powder were annealed in air, nitrogen and carbon dioxide atmospheres in the temperature range 300-700 deg. C and in atmospheric pressure. The samples were subsequently irradiated and the effect of the annealing atmosphere and temperature on the thermoluminescence (TL) of the samples was studied. Our results show that both carbonate and oxygen ions play an important part in the TL of calcite annealed in this temperature range. The intensities of the TL signal in the nitrogen and carbon dioxide anneals rise continuously with the annealing temperature. For all annealing temperatures it was found that the carbon dioxide atmosphere caused an increase in the observed TL signal as compared with anneals in an inert nitrogen atmosphere, while the shape of the TL glow curves remained the same. This increase in the observed TL signal is explained via the surface adsorption of carbonate ions. The shape and location of the TL peaks suggest that samples annealed in air exhibit a different type of TL center than samples annealed in nitrogen and carbon dioxide atmospheres. A possible mechanism for the role of oxygen ions involves a surface adsorption process and a subsequent diffusion of oxygen ions in the bulk of the crystal. Annealing of the samples in air at temperatures T>600 deg. C causes a collapse of the TL signal, in agreement with previous studies of calcite powders. No such collapse of the TL signal is observed for the nitrogen and carbon dioxide anneals, suggesting that a different type of TL center and/or recombination center is involved in air anneals. Arrhenius plots for the air anneals yield an activation energy E=0.45±0.05 eV, while the carbon dioxide and nitrogen anneals yield a lower activation energy E=0.28±0.04 eV

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

Science.gov (United States)

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

Adsorption of polar aromatic hydrocarbons on synthetic calcite

DEFF Research Database (Denmark)

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

1996-01-01

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

The Effects of Temperature and Salinity on Mg Incorporation in Planktonic Foraminifera Globigerinoides ruber (white): Results from a Global Sediment Trap Mg/Ca Database

Science.gov (United States)

Gray, W. R.; Weldeab, S.; Lea, D. W.

2015-12-01

Mg/Ca in Globigerinoides ruber is arguably the most important proxy for sea surface temperature (SST) in tropical and sub tropical regions, and as such guides our understanding of past climatic change in these regions. However, the sensitivity of Mg/Ca to salinity is debated; while analysis of foraminifera grown in cultures generally indicates a sensitivity of 3 - 6% per salinity unit, core-top studies have suggested a much higher sensitivity of between 15 - 27% per salinity unit, bringing the utility of Mg/Ca as a SST proxy into dispute. Sediment traps circumvent the issues of dissolution and post-depositional calcite precipitation that hamper core-top calibration studies, whilst allowing the analysis of foraminifera that have calcified under natural conditions within a well constrained period of time. We collated previously published sediment trap/plankton tow G. ruber (white) Mg/Ca data, and generated new Mg/Ca data from a sediment trap located in the highly-saline tropical North Atlantic, close to West Africa. Calcification temperature and salinity were calculated for the time interval represented by each trap/tow sample using World Ocean Atlas 2013 data. The resulting dataset comprises >240 Mg/Ca measurements (in the size fraction 150 - 350 µm), that span a temperature range of 18 - 28 °C and 33.6 - 36.7 PSU. Multiple regression of the dataset reveals a temperature sensitivity of 7 ± 0.4% per °C (p < 2.2*10-16) and a salinity sensitivity of 4 ± 1% per salinity unit (p = 2*10-5). Application of this calibration has significant implications for both the magnitude and timing of glacial-interglacial temperature changes when variations in salinity are accounted for.

Intermediate-scale tests of sodium interactions with calcite and dolomite aggregate concretes

International Nuclear Information System (INIS)

Randich, E.; Acton, R.U.

1983-09-01

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

Distribution of vesicular-arbuscular mycorrhizal fungi in coal, lignite and calcite mine spoils of India

Energy Technology Data Exchange (ETDEWEB)

Ganesan, V.; Ragupathy, S.; Parthipan, B.; Rani, D.B.R.; Mahadevan, A.

1991-12-31

Vesicular-arbuscular mycorhizzal (VAM) status was assessed for coal, lignite and calcite mine spoils. The three study sites were: The Kothagudem coal field in the south central region where waste materials are piled 1 to 2 m high on the soil surface. Samples were collected from plants growing on the waste. Neyveli, on the southeastern coast, is a lignite coal mine where the spoil is piled 70 to 100 m high on the soil surface. Samples were collected from recently revegetated mine spoil and from 25 year old revegetated sites. The calcite mine at Thazhaiyuthu in the south where the spoil is piled up 2 to 3 m on the soil surface. Samples were collected from 4 to 7 year old reclaimed sites. The wastes generally supported different plant species. The level of VAM infection of plants was markedly different in each mine spoil, with the maximum infection in the coal and calcite spoils, and the least in the lignite spoil. There was more infection in the 25 year old lignite spoil than in the newly revegetated spoil. There were different VAM species in each spoil, and no one species was present in all of the samples. The authors conclude that one of the factors leading to the differences between spoils is the amount of topsoil contained in the spoil (least in the lignite spoils which are very deep). The other is age of the spoils. Unfortunately the authors concluded that the best approach is to enrich the spoils with VAM rather than salvaging and replacing topsoil

Oxidation characteristics of MgF2 in air at high temperature

Science.gov (United States)

Chen, H. K.; Jie, Y. Y.; Chang, L.

2017-02-01

High temperature oxidation properties of MgF2 in air were studied. The changes of phase composition, macro surface morphology, weight and elemental composition of MgF2 samples with temperature were investigated by using XRD, EDS and gravimetric analyses. The results show that the oxidation reaction of MgF2 converted to MgO occurred at high temperature, and the reaction was accelerated by the increase of temperature and the presence of impurities. This result clarifies the understanding of the high temperature oxidation behavior of MgF2 in air, and provides a theoretical basis for the reasonable application of MgF2 in optical coating materials, electronic ceramic materials and magnesium melt protection.

Neutralization of sulfuric acid solutions by calcite dissolution and the application to anoxic limestone drain design

International Nuclear Information System (INIS)

Huminicki, Danielle M.C.; Rimstidt, J. Donald

2008-01-01

Batch reactor (BR) experiments were conducted to measure the effect of hydrodynamics and gypsum coatings on calcite neutralization rates. A factorial array of BR experiments measured the H + concentration change by calcite dissolution over a pH range of 1.5-3.5 and Na 2 SO 4 concentrations of 0-1 M. The rate of H + concentration change with time was determined by numerical differentiation of H + concentration versus time. Regression modeling showed that for uncoated calcite, rates are only significantly affected by pH, r=-10 -2.32 a H + 0.76 . Whereas, for calcite coated with gypsum only time had a significant effect on calcite dissolution rates, r = -10 -1.96 t -0.53 . Because transport-limited dissolution rates for uncoated calcite are a function of the pH and Reynolds number, a model was developed to express the effects of these two variables on the rate of H + consumption for a solution with a Darcy velocity, q, through a porous medium with a particle radius, r p , such that r ' =1.08x10 -3 q 0.31 r p -0.69 m H + 0.87 . This equation was integrated via a numerical model to simulate the performance of an idealized anoxic limestone drain (ALD). This model predicts the pH and alkalinity change along the length of an ALD. The model shows that the efficiency of an ALD is greater when the Darcy velocity is low and the particle radius is small. In addition, the growth of gypsum coatings causes the rate of H + neutralization to decline as the square root of time as they form and block the H + transport to the calcite surface. Supersaturation with respect to gypsum, leading to coating formation, can be avoided by diluting the ALD feed solution or by replacing limestone with dolomite

Adsorption and migration of single metal atoms on the calcite (10.4) surface

International Nuclear Information System (INIS)

Pinto, H; Haapasilta, V; Lokhandwala, M; Foster, Adam S; Öberg, S

2017-01-01

Transition metal atoms are one of the key ingredients in the formation of functional 2D metal organic coordination networks. Additionally, the co-deposition of metal atoms can play an important role in anchoring the molecular structures to the surface at room temperature. To gain control of such processes requires the understanding of adsorption and diffusion properties of the different transition metals on the target surface. Here, we used density functional theory to investigate the adsorption of 3 d (Ti, Cr, Fe, Ni, Cu), 4 d (Zr, Nb, Mo, Pd, Ag) and 5 d (Hf, W, Ir, Pt, Au) transition metal adatoms on the insulating calcite (10.4) surface. We identified the most stable adsorption sites and calculated binding energies and corresponding ground state structures. We find that the preferential adsorption sites are the Ca–Ca bridge sites. Apart from the Cr, Mo, Cu, Ag and Au all the studied metals bind strongly to the calcite surface. The calculated migration barriers for the representative Ag and Fe atoms indicates that the metal adatoms are mobile on the calcite surface at room temperature. Bader analysis suggests that there is no significant charge transfer between the metal adatoms and the calcite surface. (paper)

Tuning hardness in calcite by incorporation of amino acids.

Science.gov (United States)

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

2016-08-01

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

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

Science.gov (United States)

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

2016-08-01

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

Isostructural exclusion of elements between aragonite and calcite layers in the shell of the Pacific oyster Crassostrea gigas

International Nuclear Information System (INIS)

Markwitz, A.; Gauldie, R.W.; Trompetter, W.J.; Pithie, J.; Jamieson, D.N.; Sharma, S.K.

1999-01-01

Sections of the shell of the farmed Pacific oyster 'Crassostrea gigas' that are available commercially in Wellington, New Zealand, showed a distinct alternating pattern in the shell mineral when observed by reflected light. The layers were identified by Raman scattering as alternating bands of the calcite and aragonite mineral forms of calcium carbonate using the micro-Raman facility at the Hawaii Institute of Geophysics and Planetology. The differences in the unit cell structure of calcite and aragonite favour different trace elements in the two minerals. Aragonite is isostructural with Strontianite SrCO 3 , and calcite is isostructural with Smithsonite ZnCO 3 . As a result, Sr deposition should be favoured in the aragonite layer and is excluded from the calcite layer; and, conversely, Zn deposition should be favoured in the calcite layer and is excluded from the aragonite layer. However, up to today, significant differences in the pattern of Sr and Zn in microprobe scans are not discovered. By ion microprobe analysis, it was shown that differences in the unit cell structure of calcite and aragonite favor different trace elements in the two minerals

Microstratigraphic logging of calcite fabrics in speleothems as tool for palaeoclimate studies

Directory of Open Access Journals (Sweden)

Silvia Frisia

2015-01-01

Full Text Available The systematic documentation of calcite fabrics in stalagmites and flowstones provides robustness to palaeoclimate interpretation based on geochemical proxies, but it has been neglected because it is difficult to transform crystal morphologies into numerical values, and construct fabric time series. Here, general criteria that allow for coding fabrics of calcite composing stalagmites and flowstones is provided. Being based on known models of fabric development, the coding ascribes sequential numbers to each fabric, which reflect climate-related parameters, such as changes in drip rate variability, bio-mediation or diagenetic modifications. Acronyms are proposed for Columnar types, Dendritic, Micrite, Microsparite and Mosaic fabrics, whose use could then render possible comparison of calcite fabrics in stalagmites and flowstones from diverse latitudinal and altitudinal settings. The climatic and environmental significance of similarities in the geochemical signals and trends analysed in coeval stalagmites and flowstones (or differences in the signals and trends will be more robust when compared with fabric time series. This is particularly true where, such as in the Holocene, changes in geochemical values may be subtle, yet fabrics may show changes related to variations in supersaturation, drip rate or input of detrital particles or organic compounds. The proposed microstratigraphic logging allows recognition of changes in stable isotope ratio or trace element values that can be ascribed to hydrology and diagenesis, with considerable improvement of reconstructions based on the chemical proxies of stalagmites and flowstones composed of calcite.

Investigating the hydrological significance of stalagmite geochemistry (Mg, Sr) using Sr isotope and particulate element records across the Late Glacial-to-Holocene transition

Science.gov (United States)

Belli, R.; Borsato, A.; Frisia, S.; Drysdale, R.; Maas, R.; Greig, A.

2017-02-01

The trace element and Sr isotope records in two coeval stalagmites characterized by different growth rates and flow regimes at Savi cave (Grotta Savi, NE Italy) reveal different sources and incorporation mechanisms for Mg and Sr. Mg is sourced primarily from dissolved cave host rock while particulate Mg derived from soil plays a subordinate role. The presence of particulate-borne Mg is inferred from the co-variation of Mg and particle-associated elements (Th, Al and Mn) which are preferentially concentrated in open columnar calcite layers. Variation in Mg concentrations corrected for particle-influenced components, the Mgc parameter, is controlled by water-rock interaction, with higher and lower Mgc during dry and wet phases, respectively. This is thought to reflect incongruent dissolution of Mg-rich phases. Correction of Sr concentrations for contributions from airborne exogenic Sr, based on 87Sr/86Sr ratios, yields the bedrock-only contribution (Src). Src variation in stalagmite calcite is influenced by speleothem growth rate and by variation of the calcite-water Sr partitioning in wet and dry phases, and only to a minor extent by incongruent dissolution of Mg-rich phases. Concentration profiles for Mgc and Srcg (corrected for growth rate effects) show inverse correlations and are inferred to show hydrological significance which is captured in a hydrological index, HI. We suggest HI provides robust information on water-rock interaction related to hydrological changes and can be utilized in both wet and semi-arid environments, provided the corrections for soil Mg and exogenic Sr can be applied with confidence. Application of the HI index allows correction of Grotta Savi oxygen isotope data, to yield a δ18Oc time series that shows when changes in moisture sources and atmospheric reorganization, or changes in moisture amount, were significant. This is especially evident during the Younger Dryas (YD). The Savi record supports the concept of a two-phase YD, marked by

The origin of the ore-bearing solution in the Pb-Zn veins of the western Harz, Germany, as deduced from rare-earth element and isotope distributions in calcites

International Nuclear Information System (INIS)

Moeller, P.; Parekh, P.P.; Morteani, G.; Hoefs, J.

1979-01-01

Rare-earth element (REE) and stable-isotope distribution patterns in calcites from the mining areas of St. Andreasberg, Clausthal and Bad Grund, western Harz, Germany, have been determined. Three types of REE distribution patterns were found: type I is characterized by high amounts of light REE without any Ce and Eu anomalies and relativity homogeneous C- and O-isotopic composition. Type II displays conspicuous Ce and Eu anomalies at lower levels of concentration of the light REE. Type III has very low amounts of REE. Type II and III exhibit a more variable C-isotopic composition than type I. The calcite with type I patterns is assumed to be derived mainly from magnetic waters. A possible source for the magnetic waters seems to be the Brocken-Oker granite. Type-II calcites and the sulfides are probably derived from upheated country rock whereas calcite with type-III pattern mineralized from relatively cold descending solutions. The calcite with type-I pattern turns out to be not in equilibrium with sulfides, although both are in intimate contact, e.g. in banded ores. This non-equilibrium indicates two independent sources for this calcite with type-I pattern and the sulfides. (Auth.)

High Temperature Properties and Recent Research Trend of Mg-RE Alloys

Energy Technology Data Exchange (ETDEWEB)

Nam, Soo Woo [Korea Institute of Science and Technology Information, Seoul (Korea, Republic of)

2017-04-15

For the applications in automotive, aircraft, aerospace, and electronic industries, the lightest structural Mg alloys have received much attention since 2000. There has been some progress for the improvement of the mechanical properties such as room temperature strength, formability and mechanical anisotropy. However, the high temperature strength of Mg alloys is very low to be used for the parts and structures of high temperature conditions. For the last decade, considerable efforts are concentrated for the development of Mg alloys to be used at high temperature. Newly developing Mg-RE alloys are the good examples for the high temperature use. In this regard, this review paper introduces the recent research trends for the development of Mg-RE alloys strengthened with some precipitates and the long period stacking ordered (LPSO) structures related RE elements.

High Temperature Properties and Recent Research Trend of Mg-RE Alloys

International Nuclear Information System (INIS)

Nam, Soo Woo

2017-01-01

For the applications in automotive, aircraft, aerospace, and electronic industries, the lightest structural Mg alloys have received much attention since 2000. There has been some progress for the improvement of the mechanical properties such as room temperature strength, formability and mechanical anisotropy. However, the high temperature strength of Mg alloys is very low to be used for the parts and structures of high temperature conditions. For the last decade, considerable efforts are concentrated for the development of Mg alloys to be used at high temperature. Newly developing Mg-RE alloys are the good examples for the high temperature use. In this regard, this review paper introduces the recent research trends for the development of Mg-RE alloys strengthened with some precipitates and the long period stacking ordered (LPSO) structures related RE elements.

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Energy Technology Data Exchange (ETDEWEB)

Soler, Josep M. [Institute of Earth Sciences ' Jaume Almera' (CSIC), Lluis Sole i Sabaris s/n, 08028 Barcelona, Catalonia (Spain); Institute of Environmental Assessment and Water Research (CSIC), Jordi Girona 18, 08034 Barcelona, Catalonia (Spain)], E-mail: jsoler@ija.csic.es; Boi, Marco [Institute of Earth Sciences ' Jaume Almera' (CSIC), Lluis Sole i Sabaris s/n, 08028 Barcelona, Catalonia (Spain); Institute of Environmental Assessment and Water Research (CSIC), Jordi Girona 18, 08034 Barcelona, Catalonia (Spain); Mogollon, Jose Luis [Institute of Earth Sciences ' Jaume Almera' (CSIC), Lluis Sole i Sabaris s/n, 08028 Barcelona, Catalonia (Spain); Instituto de Ciencias de la Tierra, Universidad Central de Venezuela, Caracas 1020-A (Venezuela, Bolivarian Republic of); Cama, Jordi; Ayora, Carlos [Institute of Earth Sciences ' Jaume Almera' (CSIC), Lluis Sole i Sabaris s/n, 08028 Barcelona, Catalonia (Spain); Institute of Environmental Assessment and Water Research (CSIC), Jordi Girona 18, 08034 Barcelona, Catalonia (Spain); Nico, Peter S.; Tamura, Nobumichi; Kunz, Martin [Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720 (United States)

2008-12-15

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H{sub 2}SO{sub 4}, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L{sup -1}, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe-oxyhydroxysulfates (Fe(III)-SO{sub 4}-H{sup +} solutions) or Fe-oxyhydroxychlorides (Fe(III)-Cl-H{sup +} solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to {approx}6-7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)-SO{sub 4}-H{sup +} solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)-Cl-H{sup +} solutions.

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

Science.gov (United States)

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

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

Science.gov (United States)

Zhang, Chonghong; Li, Fuchun; Lv, Jiejie

2017-11-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-07-01

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

High surface hole concentration p-type GaN using Mg implantation

International Nuclear Information System (INIS)

Long Tao; Yang Zhijian; Zhang Guoyi

2001-01-01

Mg ions were implanted on Mg-doped GaN grown by metalorganic chemical vapor deposition (MOCVD). The p-type GaN was achieved with high hole concentration (8.28 x 10 17 cm -3 ) conformed by Van derpauw Hall measurement after annealing at 800 degree C for 1 h. this is the first experimental report of Mg implantation on Mg-doped GaN and achieving p-type GaN with high surface hole concentration

Gallium isotope fractionation during Ga adsorption on calcite and goethite

Science.gov (United States)

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

2018-02-01

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

Radiation-induced paramagnetic species in natural calcite speleothems

International Nuclear Information System (INIS)

Rossi, A.M.; Poupeau, G.

1989-01-01

The ESR natural spectrum of humic-free speleothem calcite single crytals in the region of g = 2.0000 is a composite of lines from 4 radiogenic species, in addition to Mn ++ lines. Laboratory irradiation causes appearrance of three more species. Use of isotropic F species (g = 2.0003) for dating is possible if specific cautions are followed. (author) [pt

Pinning in high performance MgB{sub 2} thin films and bulks: Role of Mg-B-O nano-scale inhomogeneities

Energy Technology Data Exchange (ETDEWEB)

Prikhna, Tatiana, E-mail: prikhna@mail.ru [Institute for Superhard Materials of the National Academy of Sciences of Ukraine , 2, Avtozavodskaya Str. , Kiev 07074 (Ukraine); Shapovalov, Andrey [Institute for Superhard Materials of the National Academy of Sciences of Ukraine , 2, Avtozavodskaya Str. , Kiev 07074 (Ukraine); Eisterer, Michael [Atominstitut, Vienna University of Technology, Stadionallee 2, 1020 Vienna (Austria); Shaternik, Vladimir [G.V. Kurdyumov Institute for Metal Physics of the National Academy of Sciences of Ukraine, 36 Academician Vernadsky blvd., Kiev, 03680 (Ukraine); Goldacker, Wilfried [Karlsruhe Institute of Technology (KIT), 76344 Eggenstein (Germany); Weber, Harald W. [Atominstitut, Vienna University of Technology, Stadionallee 2, 1020 Vienna (Austria); Moshchil, Viktor; Kozyrev, Artem; Sverdun, Vladimir [Institute for Superhard Materials of the National Academy of Sciences of Ukraine , 2, Avtozavodskaya Str. , Kiev 07074 (Ukraine); Boutko, Viktor [Donetsk Institute for Physics and Engineering named after O.O. Galkin of the National Academy of Sciences of Ukraine, R. Luxemburg str.72, Donetsk-114, 83114 (Ukraine); Grechnev, Gennadiy [B. Verkin Institute for Low Temperature Physics of the National Academy of Sciences of Ukraine, 47, Prospekt Nauky, Kharkiv 61103 (Ukraine); Gusev, Alexandr [Donetsk Institute for Physics and Engineering named after O.O. Galkin of the National Academy of Sciences of Ukraine, R. Luxemburg str.72, Donetsk-114, 83114 (Ukraine); Kovylaev, Valeriy; Shaternik, Anton [Institute for Superhard Materials of the National Academy of Sciences of Ukraine , 2, Avtozavodskaya Str. , Kiev 07074 (Ukraine)

2017-02-15

Highlights: • Pinning in MgB{sub 2} depends on the Mg-B-O nano-scaled inhomogeneities. • Finer oxygen-enriched inhomogeneities is the reason of the higher J{sub c} in MgB{sub 2} thin films as compared to bulk. • The results of DOS calculations for MgB{sub 2-x}O{sub x} compounds demonstrate that they have metal-like behavior. • Ordered oxygen distribution in MgB{sub 2} (in pairs or zigzags) reduces binding energy. - Abstract: The comparison of nano-crystalline MgB{sub 2} oxygen-containing thin film (140 nm) and highly dense bulk materials showed that the critical current density, J{sub c}, depends on the distribution of Mg-B-O nano-scale inhomogeneities. It has been shown that MgB{sub 2} bulks with high J{sub c} in low (∼10{sup 6} A/cm{sup 2} in 0-1 T at 10 K) and medium magnetic fields contain MgB{sub 0.6-0.8}O{sub 0.8-0.9} nano-inclusions, where δT{sub c} or a combined δT{sub c} (dominant) / δ{sub l} pinning mechanism prevails, while in bulk MgB{sub 2} with high J{sub c} in high magnetic fields (B{sub irr}(18.5 K) = 15 T, B{sub c2}(0 K) = 42.1 T) MgB{sub 1.2-2.7}O{sub 1.8-2.5} nano-layers are present and δ{sub l} pinning prevails. The structure of oxygen-containing films with high J{sub c} in low and high magnetic fields (J{sub c} (0 T) = 1.8 × 10{sup 7} A/cm{sup 2} and J{sub c} (5 T) = 2 × 10{sup 6} A/cm{sup 2} at 10 K) contains very fine oxygen-enriched Mg-B-O inhomogeneities and δ{sub l} pinning is realized. The results of DOS calculations in MgB{sub 2-x}O{sub x} cells for x = 0, 0.125, 0.25, 0.5, 1 demonstrate that all compounds are conductors with metal-like behaviour. In the case of ordered oxygen substitution for boron the binding energy, E{sub b}, does not increase sufficiently as compared with that for MgB{sub 2}, while when oxygen atoms form zigzag chains the calculated E{sub b} is even lower (E{sub b} = −1.15712 Ry).

High surface hole concentration p-type GaN using Mg implantation

CERN Document Server

Long Tao; Zhang Guo Yi

2001-01-01

Mg ions were implanted on Mg-doped GaN grown by metalorganic chemical vapor deposition (MOCVD). The p-type GaN was achieved with high hole concentration (8.28 x 10 sup 1 sup 7 cm sup - sup 3) conformed by Van derpauw Hall measurement after annealing at 800 degree C for 1 h. this is the first experimental report of Mg implantation on Mg-doped GaN and achieving p-type GaN with high surface hole concentration

Aragonite-Calcite Inversion During Biogenic Carbonate Sampling: Considerations for Interpreting Isotopic Measurements in Paleoclimate Studies

Science.gov (United States)

Waite, A. J.; Swart, P. K.

2011-12-01

, 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.

MgB2 and Mg1-xAlxB2 single crystals: high pressure growth and physical properties

International Nuclear Information System (INIS)

Karpinski, J.; Kazakov, S.M.; Jun, J.; Zhigadlo, N.D.; Angst, M.; Puzniak, R.; Wisniewski, A.

2004-01-01

Single crystals of MgB 2 have been grown with a high pressure cubic anvil technique. They grow via the peritectic decomposition of the MgNB 9 ternary nitride. The crystals are of a size up to 2 x 1 x 0.1 mm 3 with a weight up to 230 μg. Typically they have transition temperatures between 38 and 38.6 K with a width of 0.3-0.5 K. Investigations of the P-T phase diagram prove that the MgB 2 phase is stable at least up to 2190 deg. C at high hydrostatic pressure in the presence of Mg vapor under high pressure. Substitution of aluminum for magnesium in single crystals leads to stepwise decrease of T c . This indicates a possible appearance of superstructures or phases with different T c 's. The upper critical field decreases with Al doping

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

International Nuclear Information System (INIS)

Roedder, E.; Whelan, J.F.; Vaniman, D.T.

1994-01-01

Calcite vein and vug fillings at fourth depths (130-314m), all above the present water table in USW G-1 bore hole at Yucca Mountain, Nevada, contain primary fluid inclusions with variable vapor/liquid ratios: most of these inclusions are either full of liquid or full of vapor. The liquid-filled inclusions show that most of the host calcite crystallized from fluids at 2 vapor phase at open-quotes 100 degrees Cclose quotes. Our new studies reveal the additional presence of major methane in the vapor-filled inclusion, indicating even lower temperatures of trapping, perhaps at near-surface temperatures. They also show that the host calcite crystals grew from a flowing film of water on the walls of fractures open to the atmosphere, the vapor-filled inclusions representing bubbles that exsolved from this film onto the crystal surface

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

International Nuclear Information System (INIS)

Roedder, E.; Whelan, J.F.; Vaniman, D.T.

1994-01-01

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

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

DEFF Research Database (Denmark)

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

2010-01-01

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

Inhibiting Effect of Additives on Pressure Solution of Calcite

Science.gov (United States)

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

2018-05-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-08-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-07-15

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

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

Science.gov (United States)

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

Calcite deposits in drill cores USW G-2 and USW GU-3/G-3 at Yucca Mountain, Nevada: Preliminary report

International Nuclear Information System (INIS)

Vaniman, D.T.

1994-04-01

Yucca Mountain is being studied as a potential site for deep geologic disposal of high-level radioactive waste. Should a repository be developed at Yucca Mountain, the preferred location is within the upper unsaturated tuffaceous volcanic rocks. In this location, one factor of concern is the amount and rate of aqueous transport through the unsaturated rocks toward the underlying saturated intervals. Calcite, one of the most recently-formed minerals at Yucca Mountain, is of minor abundance in the unsaturated rocks but is widely distributed. Studies of calcite ages, isotopic systematics, chemistry and petrography could lead to a better understanding of transport processes at Yucca Mountain

Inferences of paleoenvironment from petrographic, chemical and stable-isotope studies of calcretes and fracture calcites

International Nuclear Information System (INIS)

Vaniman, D.T.; Whelan, J.F.

1994-01-01

Past research has indicated a genetic connection between calcite formed in calcretes at the surface of Yucca Mountain, Nevada, and calcites deposited in underlying fractures of the unsaturated zone. This common genesis suggests that paleoenvironmental information, as well as the timing and pathways of past recharge episodes, might be obtained from studies of the deposits in both the calcretes and the unsaturated fractures. Chemical and isotopic modification of calcite-precipitating fluids appears to begin at the surface, largely under the influence of plant roots and their decay products. Chemical characteristics of the deeper calcites are either initiated or largely defined within the first few meters of fluid migration into the unsaturated tuffs beneath the calcretes. However, petrographic and isotopic data indicate a very unique low-δ 13 C microenvironment that is localized at the upper surfaces of the calcretes. These surfaces form an interface in the soil horizon where infiltration may pond above the underlying carbonate ''plug.'' In order to decipher the chemistry and petrology of past recharge events, it is important to first understand microenvironments such as this that contribute to mineral precipitation/dissolution events in the pedogenic environment

Influence of Calcite and Dissolved Calcium on Uranium(VI) Sorption to a Hanford Subsurface Sediment

International Nuclear Information System (INIS)

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

2005-01-01

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 that formation 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

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

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Hristova E.

2003-01-01

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

Synthesis of sub-millimeter calcite from aqueous solution

Science.gov (United States)

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

2011-12-01

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

Mechanical Properties and Fabrication of Nanostructured Mg_2SiO_4-MgAl_2O_4 Composites by High-Frequency Induction Heated Combustion

International Nuclear Information System (INIS)

Shon, In-Jin; Kang, Hyun-Su; Hong, Kyung-Tae; Doh, Jung-Mann; Yoon, Jin-Kook

2011-01-01

Nanopowders of MgO, Al_2O_3 and SiO_2 were made by high energy ball milling. The rapid sintering of nanostructured MgAl_2O_4-Mg_2SiO_4 composites was investigated by a high-frequency induction heating sintering process. The advantage of this process is that it allows very quick densification to near theoretical density and inhibition of grain growth. Nanocrystalline materials have received much attention as advanced engineering materials with improved physical and mechanical properties. As nanomaterials possess high strength, high hardness, excellent ductility and toughness, undoubtedly, more attention has been paid for the application of nanomaterials. Highly dense nanostructured MgAl_2O_4-Mg_2SiO_4 composites were produced with simultaneous application of 80 MPa pressure and induced output current of total power capacity (15 kW) within 2 min. The sintering behavior, gain size and mechanical properties of MgAl_2O_4-Mg_2SiO_4 composites were investigated.

Principles of calcite dissolution in human and artificial otoconia.

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Leif Erik Walther

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

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

Science.gov (United States)

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.

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

DEFF Research Database (Denmark)

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

2014-01-01

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

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

International Nuclear Information System (INIS)

Marshall, Brian D.; Futa, Kiyoto

2001-01-01

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

Formation of nanocrystalline MgB sub 2 under high pressure

CERN Document Server

Sun, L; Kikegawa, T; Cao, L; Zhan, Z; Wu, Q; Wu, X; Wang, W

2002-01-01

The microstructural features of MgB sub 2 at ambient pressure and high pressure have been investigated by means of in situ synchrotron radiation x-ray diffraction and transmission electron microscopy (TEM). The x-ray diffraction measurements indicated that nanocrystalline MgB sub 2 formed in the pressure range of 26.3-30.2 GPa. TEM investigations reveal complex structure domains with evident lattice distortion in the relevant samples. The superconductivity of nanocrystalline MgB sub 2 was measured and compared with that of the starting sample of MgB sub 2.

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

International Nuclear Information System (INIS)

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

2002-10-01

Calcite is an important component of Valanginian marl, a potential host rock for a low and intermediate level radioactive waste (L/ILW) repository in Switzerland. This mineral also forms an important component of the disturbed zone around a repository, as it remains largely unaffected by the hyperalkaline waters migrating out of the cementitious repository . The sorption behaviour of Eu(III) and Th(IV) on Merck calcite in an artificial cement pore water (ACW) at pH 13.3 has been studied in batch-type sorption experiments. In addition, the effect of α-isosaccharinic acid (ISA) and gluconic acid (GLU) on the sorption of these two cations has been investigated. In the absence of ISA and GLU, a strong interaction of Eu(III) and Th(IV) with Merck calcite was observed. Eu(III) and Th(IV) sorption kinetics were fast and the isotherms indicated a linear adsorption behaviour over the experimentally accessible concentration range. In the case of Eu(III), a decrease of the R d value with increasing solid to liquid (S:L) ratio was observed indicating that, along with adsorption, other processes might influence the immobilisation of this cation by Merck calcite under ACW conditions. In the case of Th(IV), however, changes in the S:L ratio had no effect on the sorption behaviour . High ISA and GLU concentrations in solution significantly affected the sorption of both Eu(III) and Th(IV): R d values for Eu(III) decreased significantly at ISA concentrations higher than 10 -5 M and at GLU concentrations higher than 10 -7 M. The sorption of Th(IV) was reduced at ISA concentrations above 2.10 -5 M and at GLU concentrations above 10 -6 M. The effects of ISA and GLU on the immobilisation of Eu(III) and Th(IV) were interpreted in terms of complex formation in solution. In the case of Eu(III) the metal ligand complexes were found to have a 1 : 1 stoichiometry. Complexation constants derived for the aqueous Eu(III)-ISA. and Eu(III)GLU complexes were determined to be logβ 0 EulSA = -31.1�

Rapid stepwise onset of Antarctic glaciation and deeper calcite compensation in the Pacific Ocean.

Science.gov (United States)

Coxall, Helen K; Wilson, Paul A; Pälike, Heiko; Lear, Caroline H; Backman, Jan

2005-01-06

The ocean depth at which the rate of calcium carbonate input from surface waters equals the rate of dissolution is termed the calcite compensation depth. At present, this depth is approximately 4,500 m, with some variation between and within ocean basins. The calcite compensation depth is linked to ocean acidity, which is in turn linked to atmospheric carbon dioxide concentrations and hence global climate. Geological records of changes in the calcite compensation depth show a prominent deepening of more than 1 km near the Eocene/Oligocene boundary (approximately 34 million years ago) when significant permanent ice sheets first appeared on Antarctica, but the relationship between these two events is poorly understood. Here we present ocean sediment records of calcium carbonate content as well as carbon and oxygen isotopic compositions from the tropical Pacific Ocean that cover the Eocene/Oligocene boundary. We find that the deepening of the calcite compensation depth was more rapid than previously documented and occurred in two jumps of about 40,000 years each, synchronous with the stepwise onset of Antarctic ice-sheet growth. The glaciation was initiated, after climatic preconditioning, by an interval when the Earth's orbit of the Sun favoured cool summers. The changes in oxygen-isotope composition across the Eocene/Oligocene boundary are too large to be explained by Antarctic ice-sheet growth alone and must therefore also indicate contemporaneous global cooling and/or Northern Hemisphere glaciation.

Texture development in Al-Mg alloys during high temperature annealing

International Nuclear Information System (INIS)

Saitou, T.; Inagaki, H.

2001-01-01

To clarify the effect of Mg content on annealing textures developed in Al-Mg alloys during high temperature annealing, Al-Mg alloys containing up to 9 wt.% Mg in supersaturated solid solution were cold rolled 95% and isothermally annealed at 450 C. Their textures were investigated with the orientation distribution function analysis. It was found that, in the recrystallization textures observed at complete recrystallization, addition of more than 1 wt.% Mg was sufficient to suppress the development of {100} left angle 001 right angle. With increasing Mg content, {100} left angle 001 right angle decreased remarkably, whereas {100} left angle 013 right angle and {103} left angle 321 right angle increased. Thus, {100} left angle 013 right angle and {103} left angle 321 right angle were found to be the main orientations of the recrystallization textures of Al-Mg alloys annealed at high temperatures. {100} left angle 013 right angle developed most remarkably at 4 wt.% Mg, while {103} left angle 321 right angle showed the maximum development at 7 wt.% Mg. During subsequent grain growth at 450 C, remarkable texture changes were observed only in the alloys containing Mg in the range between 2 and 4 wt.%. In these alloys, {100} left angle 013 right angle developed at the expense of {100} left angle 001 right angle at earlier stages of grain growth, whereas {103} left angle 321 right angle increased independently of these two orientations at later stages of grain growth. Reflecting these texture changes, grain growth occurred in these alloys discontinuously. Such a discontinuous grain growth with large texture changes is expected, if strong textures are already present before grain growth, and if recrystallized grains having similar orientations are distributed by forming large clusters before grain growth. (orig.)

Removal of trace elements from landfill leachate by calcite precipitation

Czech Academy of Sciences Publication Activity Database

Ettler, V.; Zelená, O.; Mihaljevič, M.; Šebek, O.; Strnad, L.; Coufal, P.; Bezdička, Petr

2006-01-01

Roč. 88, 1-3 (2006), s. 28-31 ISSN 0375-6742 R&D Projects: GA AV ČR(CZ) KJB3111402 Institutional research plan: CEZ:AV0Z40320502 Keywords : landfill leachate * calcite * scavenging Subject RIV: CA - Inorganic Chemistry Impact factor: 0.922, year: 2006

Calcite microcrystals in the pineal gland of the human brain: second harmonic generators and possible piezoelectric transducers

International Nuclear Information System (INIS)

Lang, S.B.

2004-01-01

Full text: A new form of biomineralization in the pineal gland of the human brain has been studied. It consists of small crystals that are less than 20 μm in length and that are completely distinct from the often-observed mulberry-type hydroxyapatite concretions. Cubic, hexagonal and cylindrical morphologies have been identified using scanning electron microscopy. Energy dispersive spectroscopy, selected-area electron diffraction and near infrared Raman spectroscopy established that the crystals were calcite. Experiments at the European Synchrotron Radiation Facility (ESRF) to study the biomineralization showed the presence of sulfur originating from both sugars and proteins. Other studies at the ESRF furnished information on the complex texture crystallization of the calcite. With the exception of the otoconia structure of the inner ear, this is the only known non-pathological occurrence of calcite in the human body. The calcite microcrystals are believed to be responsible for the previously observed second harmonic generation (SHG) in pineal tissue sections. There is a strong possibility that the complex twinned structure of the crystals may lower their symmetry and permit the existence of a piezoelectric effect

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

Science.gov (United States)

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.

Preparation of high quality superconducting thin MgB2 films for electronics

International Nuclear Information System (INIS)

Surdu, Andrei; Zdravkov, Vladimir; Sidorenko, Anatolie; Rossolenko, Anna; Ryazanov, Valerii; Bdikin, Igor; Kroemer, Oliver; Nold, Eberhard; Koch, Thomas; Schimmel, Thomas

2007-01-01

In this work we report the growth of high-Tc MgB 2 smooth films which are prepared in a two-step process: 1) deposition of the precursor films and 2) their annealing in Mg vapor with a specially designed, reusable reactor. Our method opens perspectives for the use of MgB 2 films in microelectronics, especially for high-frequency applications. (authors)

Strontium geochemistry and carbon and oxygen isotopic compositions of Lower Proterozoic dolomite and calcite marbles from the Marmorilik Formation, West Greenland

International Nuclear Information System (INIS)

Garde, A.A.

1979-01-01

The Marmorilik Formation, Rinkian mobile belt, West Greenland, is a large, Lower Proterozoic carbonate-rock sequence, deformed and metamorphosed under greenschist to amphibolite facies conditions. The pre-deformation thickness of the sequence is at least 2000 m, with about 1400 m of dolomite marble and 350 m of calcite marble. Strontium contents of forty-two dolomite and calcite marbles range from 30 to 100 ppm and 300 to 800 ppm, respectively, whereas samples with calcite of secondary origin have strontium contents between 80 ppm and 200 ppm. Carbon and oxygen isotope ratios were determined for forty calcite and dolomite marbles as -0.2+-1.0 per 1000 delta 13 C and -9.9+-1.5 per 1000 delta 18 O (vs. PDB) and are compatible with the isotopic compositions of unmetamorphosed carbonates of similar age. Calcite from eight calciumsilicate rocks, breccias and calcite veins is significantly more negative in delta 13 C and delta 18 O. Five 13 C analyses of graphite in marble range from -9.6 to -14 per 1000. Possible post-depositional changes in the strontium content and carbon and oxygen isotope compositions are discussed. It is concluded that (a) the calcite marbles are not dedolomites and are therefore of primary origin, (b) the delta 13 C and delta 18 O values of the marbles are primary or diagenetic (i.e., pre-metamorphic), and (c) the isotopic composition of the graphite is compatible with, though not necessarily evidence for, a biogenic origin. (Auth.)

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

Science.gov (United States)

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

2016-10-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1994-12-31

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-07-01

The reactivity of calcite, one of the most abundant minerals in the earth's crust, is determined by the molecular details of its interface with the contacting solution. Recently, it has been found that trace concentrations of NaNO{sub 3} severely affect calcite's (104) surface and its reactivity. Molecular dynamics (MD) simulations reveal density profiles of different ions near calcite's surface, with NO{sub 3}{sup -} able to reach closer to the surface than CO{sub 3}{sup 2-} and in higher concentrations. Additionally, incorporation of NO{sub 3}{sup -} into the surface significantly disturbs the water structure at the interface.

Hydrogen incorporation in high hole density GaN:Mg

Science.gov (United States)

Zvanut, M. E.; Uprety, Y.; Dashdorj, J.; Moseley, M.; Doolittle, W. Alan

2011-03-01

We investigate hydrogen passivation in heavily doped p-type GaN using electron paramagnetic resonance (EPR) spectroscopy. Samples include both conventionally grown GaN (1019 cm-3 Mg, 1017 cm-3 holes) and films grown by metal modulation epitaxy (MME), which yielded higher Mg (1- 4 x 1020 cm-3) and hole (1- 40 x 1018 cm-3) densities than found in conventionally grown GaN. The Mg acceptor signal is monitored throughout 30 minute annealing steps in N2 :H2 (92%:7%)) and subsequently pure N2 . N2 :H2 heat treatments of the lower hole density films begin to reduce the Mg EPR intensity at 750 o C, but quench the signal in high hole density films at 600 o C. Revival of the signal by subsequent N2 annealing occurs at 800 o C for the low hole density material and 600 o C in MME GaN. The present work highlights chemical differences between heavily Mg doped and lower doped films; however, it is unclear whether the difference is due to changes in hydrogen-Mg complex formation or hydrogen diffusion. The work at UAB is supported by the NSF.

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

Science.gov (United States)

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

An essential factor for high Mg2+ tolerance of Staphylococcus aureus

Directory of Open Access Journals (Sweden)

Joshua Armitano

2016-11-01

Full Text Available Internal bacterial concentration of Mg2+, the most abundant divalent cation in living cells, is estimated to be in the single millimolar range. However, many bacteria will thrive in media with only micromolars of Mg2+, by using a range of intensely studied and highly efficient import mechanisms, as well as in media with very high magnesium concentration, presumably mediated by currently unknown export mechanisms. Staphylococcus aureus has a particularly high Mg2+ tolerance for a pathogen, growing unimpaired in up to 770 mM Mg2+, and we here identify SA0657, a key factor in this tolerance. The predicted domain structure of SA0657 is shared with a large number of proteins in bacteria, archaea and even eukarya, for example CorB from Salmonella and the human CNNM protein family. One of the shared domains, a CBS pair potentially involved in Mg2+ sensing, contains the conserved Glycine326 which we establish to be a key residue for SA0657 function. In light of our findings, we propose the name MpfA, Magnesium Protection Factor A, for SA0657.

Relationship between 13C and 18O fractionation and changes in major element composition in a recent calcite-depositing spring - a model of chemical variations with inorganic CaCO3 precipitation

International Nuclear Information System (INIS)

Usdowski, E.; Hoefs, J.; Menschel, G.

1979-01-01

A theoretical model is derived in which isotopic fractionations can be calculated as a function of variations in dissolved carbonate species on CO 2 degassing and calcite precipitation. This model is tested by application to a calcite-depositing spring system near Westerhof, Germany. In agreement with the model, 13 C of the dissolved carbonate species changes systematically along the flow path. The difference in delta values between the upper and lower part of the stream is about 1%. The 13 C content of the precipitated calcite is different from that expected from the theoretical partitioning. The isotopic composition of the solid CaCO 3 is similar to that of the dissolved carbonate, though in theory it should be isotopically heavier by about 2.4%. The 18 O composition of dissolved carbonate and H 2 O is constant along the stream. Calculated calcite-water temperatures differ by about +5 0 C from the observed temperatures demonstrating isotopic disequilibrium between the water and precipitated solid. This is attributed to kinetic effects during CaCO 3 deposited from a highly supersaturated solution, in which precipitation is faster than equilibration with respect to isotopes. Plant populations in the water have virtually no influence on CO 2 degassing, calcite saturation and isotopic fractionation. Measurements of Psub(CO 2 ), Ssub(C) and 13 C within a diurnal cycle demonstrate that metabolic effects are below the detection limit in a system with a high supply-rate of dissolved carbonate species. The observed variations are due to differences in CO 2 degassing and calcite precipitation, caused by a continuously changing hydrodynamic conditions and carbonate nucleation rates. (Auth.)

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

Science.gov (United States)

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.

Prediction of superconducting ternary hydride MgGeH6: from divergent high-pressure formation routes.

Science.gov (United States)

Ma, Yanbin; Duan, Defang; Shao, Ziji; Li, Da; Wang, Liyuan; Yu, Hongyu; Tian, Fubo; Xie, Hui; Liu, Bingbing; Cui, Tian

2017-10-18

Invigorated by the high temperature superconductivity in some binary hydrogen-dominated compounds, we systematically explored high-pressure phase diagrams and superconductivity of a ternary Mg-Ge-H system using ab initio methods. Stoichiometric MgGeH 6 with high hydrogen content exhibiting Pm3[combining macron] symmetry was predicted from a series of high-pressure synthesis paths. We performed an in-depth study on three distinct formation routes to MgGeH 6 , i.e., Mg + Ge + 3H 2 → MgGeH 6 , MgGe + 3H 2 → MgGeH 6 and MgH 2 + GeH 4 → MgGeH 6 at high pressures. By directly squeezing three elemental solids Mg + Ge + 3H 2 , we obtained ternary MgGeH 6 at 200 GPa. By adding a little bit of the MgGe alloy into hydrogen, we found that MgGeH 6 can form and stabilize at about 200 GPa. More intriguingly, upon compressing MgH 2 and GeH 4 to 250 GPa, we also predicted the same MgGeH 6 . Electron structure calculations reveal that the cubic MgGeH 6 is a good metal and takes on ionic character. Electron-phonon coupling calculation reveals a large λ = 1.16 for MgGeH 6 at 200 GPa. In particular, we found that ternary MgGeH 6 could be a potential high temperature superconductor with a superconducting transition temperature T c of ∼67 K at 200 GPa.

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

Science.gov (United States)

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

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

DEFF Research Database (Denmark)

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

2015-01-01

The growth and nucleation of biominerals are directed and affected by associated biological molecules. In this paper, we investigate the influence of occluded biomolecules on biogenic calcite from the coccolithophorid Pleurochrysis carterae and from chalk, a rock composed predominantly of fossil....... Two heating cycles allow us to differentiate the effects of thermal agitation and organic molecules. Single peak analysis and Rietveld refinement were combined to show significant differences resulting from the occluded biomolecules on the mineral phase in biogenic calcite in the mollusk shell...

Neoproterozoic marine carbonates and their paleoceanographic significance

Science.gov (United States)

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2002-10-01

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

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

DEFF Research Database (Denmark)

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

2017-01-01

The structure and the strength of organic compound adsorption on mineral surfaces are of interest for a number of industrial and environmental applications, oil recovery, CO2 storage and contamination remediation. Biomineralised calcite plays an essential role in the function of many organisms...... that control crystal growth with organic macromolecules. Carbonate rocks, composed almost exclusively of calcite, host drinking water aquifers and oil reservoirs. In this study, we examined the ordering behaviour of several organic compounds and the thickness of the adsorbed layers formed on calcite {10...... monolayers. The results of this work indicate that adhered organic compounds from the surrounding environment can affect the surface behaviour, depending on properties of the organic compound....

Study of Raman Spectroscopy on Phase Relations of CaCO3 at High Temperature and High Pressure

Science.gov (United States)

Li, M.; Zheng, H.; Duan, T.

2006-05-01

Laser Raman Spectroscopy was used to study phase relations between calcite I, calcite II and aragonite at high pressure and high temperature. The experiment was performed in an externally heated Basselt type diamond anvil cell (DAC). Natural calcite (calcite I) was used as starting mineral. The sample and a small chip of quartz were loaded in a cavity (300 μm in diameter and 250 μm in depth) in a rhenium gasket. The Na2CO3 aqueous solution of 1mol/L was also loaded as a pressure medium to yield hydrostatic pressure. The whole assembly was pressurized first and then heated stepwise to 400°C. Pressure and temperature in the chamber were determined by the shift of Raman band at 464 cm-1 of quartz and by NiCr-NiSi thermocouple, respectively. The Raman spectra were measured by a Renishaw 1000 spetrometer with 50 mW of 514.5nm argon-ion laser as the excitation light source. The slit width was 50 μm and the corresponding resolution was ±1 cm-1. From the experiments, we observed the phase transitions between calcite I and calcite II, calcite I and aragonite, calcite II and aragonite, respectively. Our data showed a negative slope for the boundary between calcite I and calcite II, which was similar to Bridgman's result, although Hess et al. gave a positive slope. The boundary with a negative slope for calcite II and aragonite was also defined, which had never been done before. And all these data can yield a more complete phase diagram of CaCO3 than the studies of Hess et al. and Suito et al.Reference:Bridgeman P. W.(1939) Journal: American Journal of Science, Vol. 237, p. 7-18Bassett W. A. et al. (1993) Journal: Review of Scientific Instruments, Vol. 64, p. 2340-2345Suito K. et al. (2001) Journal: American Mineralogist, Vol. 86, p. 997- 1002Hess N. J. et al. (1991) In A. K. Singh, Ed., Recent Trends in High Pressure Research; Proc. X IIIth AIRAPT International Conference on High Pressure Science and Technology, p. 236-241. Oxford & IBH Publishing Co. Pvt, Ltd., New

Development of MgB2 superconductor wire with high critical current

International Nuclear Information System (INIS)

Kim, Chan Joong; Jun, Byung Hyuk; Park, Soon Dong; Kim, Nam Kyu; Kim, Yi Jeong; Yi, Ji Hye; Lee, Ji Hyun; Tan, Kai Sin

2009-07-01

The MgB 2 superconductor with smaller grain size could improve its critical properties by providing flux pinning centers with high grain boundary density. The effects of C doping such as charcoal, paper ash and glycerin on the superconducting properties was investigated for in situ processed MgB 2 samples using low purity semi-crystalline B powder. The results show a decrease in Tc and an enhancement of Jc at high fields for the C-doped samples as compared to the un-doped samples. A combined process of a mechanical ball milling and liquid glycerin (C 3 H 8 O 3 ) treatment of B powder has been conducted to enhance the superconducting properties of MgB 2 . The mechanical ball milling was effective for grain refinement, and a lattice disorder was easily achieved by glycerin addition. With the combined process, the critical properties was further increased due to a higher grain boundary density and a greater C substitution. To get fine grain structure of MgB 2 with high critical current properties, mechanical milling for as-received B powder and low temperature solid-state reaction of 550 or 600 .deg. C were attempted to in situ powder-in-tube processed MgB 2 /Fe wires. The critical current properties of the MgB 2 wires using the milled B powder were enhanced due to a smaller grain size and an increased volume of the superconducting phase. The solid-state reaction of a low temperature process for the samples using the milled B powder resulted in a poorer crystallinity with a smaller grain size, which improved superconducting properties. We established the system to measure the transport current properties of the MgB 2 wires. The field dependence of the transport Jc was evaluated for the MgB 2 wires heat-treated at different heat treatment conditions using ball-milled and glycerin-treated B powder. The MgB 2 magnet was developed and the AC loss of MgB 2 wire was also investigated. A conduction cooling device to cool the MgB 2 coil down to 4 K has been fabricated and the

Iodine-129 and Iodine-127 speciation in groundwater at the Hanford Site, U.S.: iodate incorporation into calcite

International Nuclear Information System (INIS)

Zhang, Saijin; Yeager, Chris; Wellman, Dawn M.; Santschi, Peter H.

2013-01-01

The Hanford Site, the most contaminated nuclear site in the United States, has large radioactive waste plumes containing high 129I levels. 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 accounts for up to 84%, followed by organo-iodine and minimal levels of iodide. The relatively high pH and oxidizing environment may have prevented iodate reduction. Our results identified that calcite precipitation caused by degassing of CO2 during deep groundwater sampling incorporated between 7 to 40% of dissolved iodine (including 127I and 129I) that was originally in the groundwater, transforming dissolved to particulate iodate during sampling. In order to understand the mechanisms underlying iodine incorporation by calcite, laboratory experiments were carried out to replicate this iodine sequestering processes. Two methods were utilized in this study, 1) addition of sodium carbonate; 2) addition of calcium chloride followed by sodium carbonate where the pH was well controlled at ~8.2, which is close to the average pH of Hanford Site groundwater. It was demonstrated that iodate was the main species incorporated into calcite and this incorporation process could be impeded by elevated pH and decreasing ionic strength in groundwater. This study provides critical information for predicting the long-term fate and transport of 129I at the Hanford Site and reveals a potential means for improved remediation strategies of 129I

A paired apatite and calcite clumped isotope thermometry approach to estimating Cambro-Ordovician seawater temperatures and isotopic composition

Science.gov (United States)

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.

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

Science.gov (United States)

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

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

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

Directory of Open Access Journals (Sweden)

Samer Farkh

2015-01-01

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

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

Science.gov (United States)

Jones, Brian; Peng, Xiaotong

2016-11-01

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

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

Science.gov (United States)

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.

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

Directory of Open Access Journals (Sweden)

A. Wackerbarth

2012-11-01

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

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

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

Microstructure and mechanical properties of an Al–Mg alloy solidified under high pressures

International Nuclear Information System (INIS)

Jie, J.C.; Zou, C.M.; Brosh, E.; Wang, H.W.; Wei, Z.J.; Li, T.J.

2013-01-01

Highlights: •Al–42.2Mg alloy was solidified under pressures of 1, 2, and 3 GPa and the microstructure analyzed. •A thermodynamic calculation of the Al–Mg phase diagram at high pressures was performed. •The phase content changes from predominantly γ-Al 12 Mg 17 at 1 GPa to FCC solid solution at 3 GPa. •The β-Al 3 Mg 2 is predicted to remain stable at low temperatures but is not observed. •The alloy solidified at high pressure has remarkably enhanced ultimate tensile strength. -- Abstract: Phase formation, the microstructure and its evolution, and the mechanical properties of an Al–42.2 at.% Mg alloy solidified under high pressures were investigated. After solidification at pressures of 1 GPa and 2 GPa, the main phase is the γ phase, richer in Al than in equilibrium condition. When the pressure is further increased to 3 GPa, the main phase is the supersaturated Al(Mg) solid solution with Mg solubility up to 41.6 at.%. Unlike in similar alloys solidified at ambient pressure, the β phase does not appear. Calculated high-pressure phase diagrams of the Al–Mg system show that although the stability range of the β phase is diminished with pressure, it is still thermodynamically stable at room temperature. Hence, the disappearance of the β phase is interpreted as kinetic suppression, due to the slow diffusion rate at high pressures, which inhibits solid–solid reactions. The Al–42.2 at.% Mg alloy solidified under 3 GPa has remarkably enhanced ultimate tensile strength compared to the alloy solidified under normal atmospheric pressure

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

DEFF Research Database (Denmark)

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

2008-01-01

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

Sturgeon and paddlefish (Acipenseridae) sagittal otoliths are composed of the calcium carbonate polymorphs vaterite and calcite.

Science.gov (United States)

Pracheil, B M; Chakoumakos, B C; Feygenson, M; Whitledge, G W; Koenigs, R P; Bruch, R M

2017-02-01

This study sought to resolve whether sturgeon (Acipenseridae) sagittae (otoliths) contain a non-vaterite fraction and to quantify how large a non-vaterite fraction is using neutron diffraction analysis. This study found that all otoliths examined had a calcite fraction that ranged from 18 ± 6 to 36 ± 3% by mass. This calcite fraction is most probably due to biological variation during otolith formation rather than an artefact of polymorph transformation during preparation. © 2016 The Fisheries Society of the British Isles.

Reclamation of acidic colliery spoil. III. Problems associated with the use of high rates of limestone

Energy Technology Data Exchange (ETDEWEB)

Costigan, P A [Univ. of Liverpool, England; Bradshaw, A D; Gemmell, R P

1982-04-01

Growth of Trifolium repens in acidic colliery spoil was suppressed by more than 90% when agricultural ground calcitic limestone was applied at above 5 t ha/sup -1/ whereas Lolium perenne was unaffected at rates up to 100 t ha/sup -1/. The inhibitory effect of ground limestone on T. repens was reduced by high phosphorus fertilization and disappeared within 34 weeks of treatment.There was some evidence that high liming caused an imbalance of the Ca/Mg ratio in freshly limed spoil, contribution to growth inhibition. Growth of L. perene was improved and the inhibitory effect on T. repens was alleviated by substituting magnesian limestone (dolomite) for calcitic limestone. Phosphate adsorption of spoil was similar after low and very high limestone applications but increased by 100% after liming at 25 t ha/sup -1/ to pH 5.1.It is suggested that phosphate adsorption at pH 5.1 is caused by freshly precipitated amorphous aluminium hydroxide. The practical implications of the results are discussed.

High temperature mechanical forming of Mg alloys

International Nuclear Information System (INIS)

Mwembela, A.; McQueen, H.J.; Myshlyaev, M.

2002-01-01

Mg alloys are hot worked in the range 180-450 o C and 0.0-10 s -1 ; the present project data are compared with a wide selection of published results. The flow stresses and their dependence on temperature and strain rate are fairly similar to simple Al alloys: however, the hot ductility is much lower (≤3 in torsion). Twinning plays a significant role in Mg alloys almost independently of temperature; the twins initiate at low strains in grains poorly oriented for basal slip and in consequence become well disposed for such slip. As T rises, there is increasing formation of subgrains that spread toward the grain centers from grain and twin boundaries: this is indicative of stress concentrations inducing non-basal sup which helps provide the geometrically necessary dislocations. Above about 240 o C, dynamic (DRX) nucleates at grain and twin boundaries, preferentially at intersections; this again is evidence of non-basal slip that provides the highly misoriented cells. The boundaries in which further strain concentrates producing further DRX. The microstructure remains very heterogeneous compared to the uniform dynamically recovered substructure in Al alloys, thus giving rise to the reduced ductility. These results are employed to interpret the mechanical and microstructural behavior of Mg alloys in extrusion, rolling and forging. (author)

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

Science.gov (United States)

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

2012-09-01

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

Thermoluminescent of induced calcite by gamma and ultraviolet radiation

International Nuclear Information System (INIS)

Lima, J.F. de.

1987-01-01

Samples of brazilian calcite, exposed to gamma radiation in laboratory and heated at constant rate of 2.7 0 C/s, showed three glow peaks at 150, 250 and 350 0 C in their thermoluminescent emission curves. The analysis of these peaks, using different models, indicated that they follow a second order kinetics; it has been obtained, for the activation energy, 1.3, 1.5 and 1.7 eV, and, for the pre-exponential factors, 8.1 x 10 14 , 6.8 x10 13 and 2.4 x 10 12 s -1 . Although the total thermoluminescent emission has stayed constant, the relative height of glow peaks has changed with the temperature of annealing in the range of 400 to 700 0 C. Exposed samples were also illuminated with ultraviolet light and the resultant curves showed partial or total bleaching or some glow peaks and the growth of peaks at lower temperatures. Samples of virgin calcite, submited to increasing exposures of gamma rays, showed a corresponding enhancement of the optical absorption bands in the range of 25000 to 47000 cm -1 A subsequent illumination of these samples with ultraviolet light produced a decrease of the optical absorption bands at the same range. (author) [pt

Effect of Mg/Ca ratios on microbially induced carbonate precipitation

Science.gov (United States)

Balci, Nurgul; Demirel, Cansu; Seref Sonmez, M.; Kurt, M. Ali

2016-04-01

Influence of Mg/Ca ratios on microbially induced carbonate mineralogy were investigated by series of experiments carried out under various environmental conditions (Mg/Ca ratio, temperature and salinity). Halophilic bacterial cultures used for biomineralization experiments were isolated from hypersaline Lake Acıgöl (Denizli, SW Turkey), displaying extreme water chemistry with an average pH around 8.6 (Balci eta l.,2015). Enriched bacterial culture used in the experiments consisted of Halomonas saccharevitans strain AJ275, Halomonas alimentaria strain L7B; Idiomarina sp. TBZ29, 98% Idiomarina seosensis strain CL-SP19. Biomineralization experiments were set up using above enriched culture with Mg/Ca ratios of 0.05, 1, 4 and 15 and salinity of 8% and 15% experiments at 30oC and 10oC. Additionally, long-term biomineralization experiments were set up to last for a year, for Mg/Ca=4 and Mg/Ca=15 experiments at 30oC. For each experimental condition abiotic experiments were also conducted. Solution chemistry throughout incubation was monitored for Na, K, Mg, Ca, bicarbonate, carbonate, ammonium and phosphate for a month. At the end of the experiments, precipitates were collected and morphology and mineralogy of the biominerals were investigated and results were evaluated using the software DIFFRAC.SUITE EVA. Overall the preliminary results showed chemical precipitation of calcite, halite, hydromagnesite and sylvite. Results obtained from biological experiments indicate that, low Mg/Ca ratios (0.05 and 1) favor chlorapatite precipitation, whereas higher Mg/Ca ratios favor struvite precipitation. Biomineralization of dolomite, huntite and magnesite is favorable at high Mg/Ca ratios (4 and 15), in the presence of halophilic bacteria. Moreover, results indicate that supersaturation with respect to Mg (Mg/Ca=15) combined with NaCl (15%) inhibits biomineralization and forms chemical precipitates. 15% salinity is shown to favor chemical precipitation of mineral phases more than

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

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

2017-04-01

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

Growth kinetics of racemic heptahelicene-2-carboxylic acid nanowires on calcite (104)

Czech Academy of Sciences Publication Activity Database

Einax, M.; Richter, T.; Nimmrich, M.; Rahe, P.; Stará, Irena G.; Starý, Ivo; Kühnle, A.; Maass, P.

2016-01-01

Roč. 145, č. 13 (2016), č. článku 134702. ISSN 0021-9606 Institutional support: RVO:61388963 Keywords : heptahelicene-2-carboxylic acid nanowires * nc-AFM * calcite * growth kinetics Subject RIV: CC - Organic Chemistry Impact factor: 2.965, year: 2016

14C-analyses of calcite coatings in open fractures from the Klipperaas study site, Southern Sweden

International Nuclear Information System (INIS)

Possnert, G.; Tullborg, E.L.

1989-11-01

Carbonate samples from open fractures in crystalline rock from the Klipperaas study site have been analysed for their 14 C contents using accelerator mass spectrometry. This technique makes it possible to analyse very small carbonate samples (c. 1 mg C). The analyses show low but varying contents of 14 C. However, contamination by CO 2 have taken place affecting small samples more than others. Attempts have been made to quantify the contamination and thus evaluate the analyses of the fracture samples. The obtained low 14 C values can be due to: 1. An effective retention of 14 C by sorption/fractionation forcing 14 C onto the calcite surfaces in the near-surface zone which means that the 14 C contribution to the deeper levels is diminished or 2. the penetration depth of surface groundwater is very shallow. The former is suggested as more probable based on evaluations of the hydrochemical conditions and the fracture mineral studies. (10 figs., 3 tabs., 9 refs.) (authors)

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

Directory of Open Access Journals (Sweden)

Mansour Rezaei Azizi

2015-04-01

for green, white and pink calcites were varied 0.087, 0.247 and 0.997 respectively. The low amounts of Eu anomaly for green and white calcites attributed to low rock/fluid ratio (Nesbitt et al., 1990 and relatively more pH value (Cheng et al., 2013, however, increasing the Eu anomaly may be due to high rock/fluid ratio and less pH value. Ce anomalies are 0.0241, 0.0113 and 0.0131 in pink, white and green calcites respectively. The most negative Ce anomaly values show that calcite have precipitated under reduction conditions (Nesbitt et al., 1990. Discussion Recently, multiple attributes decision-making techniques help scientist to solve decision-making problems related to various controlling factors (Zhijun et al., 2013. One of these techniques is a Technique for Order Preference by Similarity to Ideal Solution (TOPSIS which is a quantitative weighted method (Momenei 2006. The identified criteria are CaO abundant in solution (C1, Eu anomaly (C2, Ce anomaly (C3, Sr abundant (C4 and volume (C5. The Index-Rock matrix also includes A1, A2 and A3 alternatives; as pink, green and white calcite respectively. The weighted normalized decision matrix can be calculated by multiplying the normalized evaluation matrix with its associated weight to obtain the result. The result show that Eu anomaly, volume, Sr abundant and Ce anomaly in order have higher role to investigate the geochemical study of area. Calculation of the relative closeness to the ideal solution (Cl * for pink, green and white calcites are 0.837, 0.445 and 0.157 respectively. It can be deduced that the most preferable calcite to be sampled for investigating geochemically are pink and green calcites. References Cheng, D.L., Jiang-haob, L., Shou-pengc, Z., Lianga, L., Zhao-bina, Y., Guo-lina, G. and Tinga, L., 2013. Geochemical characteristics of calcite and dolomite in sandstone of Dongying Sinking, Shandong Province, China. Procedia Earth and Planetary Science, 7(4: 504 – 507. Eftekharnezhad, J., 1973

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

Science.gov (United States)

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) 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.

High-Strength Low-Alloy (HSLA) Mg-Zn-Ca Alloys with Excellent Biodegradation Performance

Science.gov (United States)

Hofstetter, J.; Becker, M.; Martinelli, E.; Weinberg, A. M.; Mingler, B.; Kilian, H.; Pogatscher, S.; Uggowitzer, P. J.; Löffler, J. F.

2014-04-01

This article deals with the development of fine-grained high-strength low-alloy (HSLA) magnesium alloys intended for use as biodegradable implant material. The alloys contain solely low amounts of Zn and Ca as alloying elements. We illustrate the development path starting from the high-Zn-containing ZX50 (MgZn5Ca0.25) alloy with conventional purity, to an ultrahigh-purity ZX50 modification, and further to the ultrahigh-purity Zn-lean alloy ZX10 (MgZn1Ca0.3). It is shown that alloys with high Zn-content are prone to biocorrosion in various environments, most probably because of the presence of the intermetallic phase Mg6Zn3Ca2. A reduction of the Zn content results in (Mg,Zn)2Ca phase formation. This phase is less noble than the Mg-matrix and therefore, in contrast to Mg6Zn3Ca2, does not act as cathodic site. A fine-grained microstructure is achieved by the controlled formation of fine and homogeneously distributed (Mg,Zn)2Ca precipitates, which influence dynamic recrystallization and grain growth during hot forming. Such design scheme is comparable to that of HSLA steels, where low amounts of alloying elements are intended to produce a very fine dispersion of particles to increase the material's strength by refining the grain size. Consequently our new, ultrapure ZX10 alloy exhibits high strength (yield strength R p = 240 MPa, ultimate tensile strength R m = 255 MPa) and simultaneously high ductility (elongation to fracture A = 27%), as well as low mechanical anisotropy. Because of the anodic nature of the (Mg,Zn)2Ca particles used in the HSLA concept, the in vivo degradation in a rat femur implantation study is very slow and homogeneous without clinically observable hydrogen evolution, making the ZX10 alloy a promising material for biodegradable implants.

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

Science.gov (United States)

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.

Transformation of amorphous calcium carbonate to rod-like single crystal calcite via "copying" collagen template.

Science.gov (United States)

Xue, Zhonghui; Hu, Binbin; Dai, Shuxi; Du, Zuliang

2015-10-01

Collagen Langmuir films were prepared by spreading the solution of collagen over deionized water, CaCl2 solution and Ca(HCO3)2 solution. Resultant collagen Langmuir monolayers were then compressed to a lateral pressure of 10 mN/m and held there for different duration, allowing the crystallization of CaCO3. The effect of crystallization time on the phase composition and microstructure of CaCO3 was investigated. It was found that amorphous calcium carbonate (ACC) was obtained at a crystallization time of 6 h. The amorphous CaCO3 was transformed to rod-like single crystal calcite crystals at an extended crystallization time of 12 h and 24 h, via "copying" the symmetry and dimensionalities of collagen fibers. Resultant calcite crystallites were well oriented along the longitudinal axis of collagen fibers. The ordered surface structure of collagen fibers and electrostatic interactions played key roles in tuning the oriented nucleation and growth of the calcite crystallites. The mineralized collagen possessing both desired mechanical properties of collagen fiber and good biocompatibility of calcium carbonate may be assembled into an ideal biomaterial for bone implants. Copyright © 2015. Published by Elsevier B.V.

Diagenetic conditions of fibrous calcite vein formation in black shales: Petrographic, chemical and isotopic evidence

Energy Technology Data Exchange (ETDEWEB)

Al-Aasm, I.S.; Muir, I. (Imperial Oil Resources, Calgary, AB (Canada)); Morad, S. (Windsor Univ., ON (Canada))

1992-03-01

Antiaxial fibrous calcite veins 2-6 cm thick outcrop parallel to bedding in the Bluefish Member of the Middle Devonian Hare Indian Formation in the Norman Wells area of the Northwest Territories. The Bluefish Member consists of dark brown to black laminated shales with total organic matter content in the 1.8-8.0 wt % range. The basal part of the Member, characterized by the presence of low diversity macrofossils, was deposited under anaerobic conditions on top of the drowned Hume carbonate platform. The pattern of incorporation of host-shale fragments and tiny inclusions into the fibrous calcite indicates repeated episodes of vein opening and sealing. The [delta][sup 13]C values and the low Mn and Fe contents indicate a dominantly marine source of carbonate ions was related to the dissolution of metastable skeletal carbonates in the host shales. The [delta][sup 18]O values suggest precipitation at 30-50[degree]C and burial depths of tens to hundreds of meters. The formation of finely crystalline non-stoichiometric Ca-rich dolomite disseminated in the shale inclusions occurred subsequent to the emplacement of fibrous calcite veins under elevated burial temperatures. 54 refs., 8 figs., 3 tabs.

The effect of fluids on the frictional behavior of calcite gouge

Science.gov (United States)

Rempe, M.; Di Toro, G.; Mitchell, T. M.; Hirose, T.; Smith, S. A. F.; Renner, J.

2016-12-01

The presence of fluids in fault zones affects the faults' strength and the nucleation and propagation of earthquakes due to mechanical or physico-chemical weakening effects. To better understand the effect of pore fluids on the frictional behavior of gouge-bearing faults, a series of intermediate- to high-velocity experiments was conducted using the Phv rotary-shear apparatus (Kochi Core Center, Japan) equipped with a servo-controlled pore-fluid pressure system. Calcite gouge was sheared up to several meters displacement at room-humidity (dry) and water-saturated conditions. The pore-fluid factor, λ=pf/σn, ranged from 0.15 to 0.7 and the effective normal stress, σn,eff=σn-pf, from 1 to 12 MPa. Sheared samples were analyzed using scanning electron microscopy and Raman spectroscopy. The steady-state shear stress is lower for saturated than for dry gouges sliding at V=1 mm/s, possibly due to higher intergranular lubrication and/or accelerated subcritical crack growth, as evidenced also by the observed higher degree of compaction. At V=1 m/s, dry gouges show a pronounced strengthening phase preceding the onset of dynamic weakening; saturated gouges weaken abruptly. The higher λ, the lower the peak and steady-state shear stress, but -counterintuitively- the less localized deformation. Degree of weakening and localization might be influenced by insufficient drainage at high λ. In undrained experiments, the shear stress is slightly decreased likely due to thermal pressurization of the pore fluid, but the onset of dynamic weakening is not accelerated, indicating that dynamic weakening is due to more efficient mechanisms. For example, amorphous carbon may lubricate the slip surfaces of dry and saturated calcite gouges and cause dynamic weakening, yet Raman spectra only show the presence of disordered carbon on the principal slip surface. Furthermore, the presence of small recrystallized grains suggests that strain accommodation during steady-state slip might occur by

Realisation of four-wave mixing phase matching for frequency components at intracavity stimulated Raman scattering in a calcite crystal

International Nuclear Information System (INIS)

Smetanin, Sergei N; Fedin, Aleksandr V; Shurygin, Anton S

2013-01-01

The possibilities of implementing four-wave mixing (FWM) phase matching at stimulated Raman scattering (SRS) in a birefringent SRS-active crystal placed in a cavity with highly reflecting mirrors have been theoretically and experimentally investigated. Phase-matching angles providing conditions for five types of phase matching are determined for a calcite crystal. These types are characterised by different combinations of polarisation directions for the interacting waves and ensure FWM generation of either an anti-Stokes wave or the second Stokes SRS component. In agreement with the calculation results, low-threshold generation of the second Stokes SRS component with a wavelength 0.602 μm was observed at angles of incidence on a calcite crystal of 4.8° and 18.2°, under SRS pumping at a wavelength of 0.532 μm. This generation is due to the FWM coupling of the first and second Stokes SRS components with the SRS-pump wave. (nonlinear optical phenomena)

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

Science.gov (United States)

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 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

Numerical Simulations of Urea Hydrolysis and Calcite Precipitation in Porous Media Using STOMP

International Nuclear Information System (INIS)

Guo, Luanjing; Huang, Hai; Hu, Bill X.

2010-01-01

Subsurface radionuclide and trace metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE's greatest challenges for long-term stewardship. One promising in situ immobilization approach of these contaminants is engineered mineral (co)precipitation of calcite driven by urea hydrolysis that is catalyzed by enzyme urease. The tight nonlinear coupling among flow, transport, reaction and reaction-induced property changes of media of this approach was studied by reactive transport simulations with systematically increasing level of complexities of reaction network and physical/chemical heterogeneities using a numerical simulator named STOMP. Sensitivity studies on the reaction rates of both urea hydrolysis and calcite precipitation are performed via controlling urease enzyme concentration and precipitation rate constant according to the rate models employed. We have found that the rate of ureolysis is a dominating factor in the amount of precipitated mineral; however, the spatial distribution of the precipitates depends on both rates of ureolysis and calcite precipitation. A maximum 5% reduction in the porosity was observed within the simulation time period of 6 pore volumes in our 1-dimensional (1D) column simulations. When a low permeability inclusion is considered in the 2D simulations, the altered flow fields redistribute mineral forming constituents, leading to a distorted precipitation reaction front. The simulations also indicate that mineral precipitation occurs along the boundary of the low permeability zone, which implies that contaminants in the low permeability zone could be encapsulated and isolated from the flow paths.

An isotopic and fluid inclusion study of fracture calcite from borehole OL-KR1 at the Olkiluoto site, Finland

International Nuclear Information System (INIS)

Blyth, A.; Frape, S.; Blomqvist, R.; Nissinen, P.; McNutt, R.

1998-04-01

A study of the geochemistry of fracture filling calcite in borehole OL-KR1 at the radioactive waste disposal investigation site Olkiluoto (in Finland) was undertaken in 1998. The purpose of the present study is to characterize the fracture calcite using mineralogy, oxygen, carbon and strontium isotopes, and fluid inclusions in order to determine past and present chemical and isotopic condition at the site

An isotopic and fluid inclusion study of fracture calcite from borehole OL-KR1 at the Olkiluoto site, Finland

Energy Technology Data Exchange (ETDEWEB)

Blyth, A.; Frape, S. [Univ. of Waterloo, ON (Canada); Blomqvist, R.; Nissinen, P. [Geological Survey of Finland, Espoo (Finland); McNutt, R. [McMaster Univ. of Hamilton, ON (Canada)

1998-04-01

A study of the geochemistry of fracture filling calcite in borehole OL-KR1 at the radioactive waste disposal investigation site Olkiluoto (in Finland) was undertaken in 1998. The purpose of the present study is to characterize the fracture calcite using mineralogy, oxygen, carbon and strontium isotopes, and fluid inclusions in order to determine past and present chemical and isotopic condition at the site 39 refs.

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

Directory of Open Access Journals (Sweden)

John P. Craddock

2016-02-01

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

Low-power, high-uniform, and forming-free resistive memory based on Mg-deficient amorphous MgO film with rough surface

Science.gov (United States)

Guo, Jiajun; Ren, Shuxia; Wu, Liqian; Kang, Xin; Chen, Wei; Zhao, Xu

2018-03-01

Saving energy and reducing operation parameter fluctuations remain crucial for enabling resistive random access memory (RRAM) to emerge as a universal memory. In this work, we report a resistive memory device based on an amorphous MgO (a-MgO) film that not only exhibits ultralow programming voltage (just 0.22 V) and low power consumption (less than 176.7 μW) but also shows excellent operative uniformity (the coefficient of variation is only 1.7% and 2.2% for SET and RESET voltage, respectively). Moreover, it also shows a forming-free characteristic. Further analysis indicates that these distinctive properties can be attributed to the unstable local structures and the rough surface of the Mg-deficient a-MgO film. These findings show the potential of using a-MgO in high-performance nonvolatile memory applications.

Aragonite→calcite transformation studied by EPR of Mn 2+ ions

Science.gov (United States)

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.

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

Science.gov (United States)

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

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

NARCIS (Netherlands)

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

2003-01-01

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

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

International Nuclear Information System (INIS)

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

2015-01-01

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 × 10"9 and 1 × 10"1"2 ions/cm"2 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 × 10"1"0 ions/cm"2, all existing bands decrease in intensity. Between 8 × 10"1"0 and 1 × 10"1"1 ions/cm"2 a broad Cu_2O 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 Cu_2O band, the carbon band vanished when further irradiating the sample. The installations as well as first in situ measurements at room temperature are presented.

Calcite Dissolution Kinetics

Science.gov (United States)

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

2016-12-01

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

Methodology to obtain exchange properties of the calcite surface-Application to major and trace elements: Ca(II), HCO3-, and Zn(II)

International Nuclear Information System (INIS)

Tertre, E.; Beaucaire, C.; Juery, A.; Ly, J.; Tertre, E.; Beaucaire, C.; Juery, A.; Ly, J.

2010-01-01

Sorption of inorganic elements onto carbonate minerals has been intensively described in the literature by two reaction steps: (1) a first one rapid and completed within a few hours and (2) a second one slower, eventually irreversible, and occurring at a constant rate. The first step is often attributed to an ion-exchange process, but its reversibility is rarely investigated. Consequently, discrimination of the global sorption phenomenon into two different mechanisms is not always justified. In this study, we investigated, by batch experiments, both sorption and desorption of Ca(II), HCO 3 - , and Zn(II), radiolabeled with isotopes 45 Ca(II), H 14 CO 3 - , and 65 Zn(II), respectively, onto synthetic pure calcite. Solutions were pre-equilibrated with atmospheric p(CO 2 ) and saturated with respect to calcite. Therefore, our purpose was to: (1) obtain experimental distribution coefficients of major elements (Ca(II) and HCO 3 - ) and a trace element (Zn(II)) onto calcite from sorption and desorption experiments, (2) test the validity of a first-occurring ion-exchange process generally noted in the literature, by calculating distribution coefficients for the 'sole' exchange process, and (3) quantify the amounts of Ca(II), HCO 3 - , and Zn(II) sorbed on the calcite surface by the sole 'exchange process' and compare them with surface crystallochemical data. Ca(II) or HCO 3 - sorption experimental data suggest that a significant fraction of these two elements was sorbed irreversibly onto or in the calcite. By using a method based on isotopic ratios, the Ca(II) or HCO 3 - concentrations, which are reversibly adsorbed on the calcite, have been quantified. These concentrations are respectively estimated at 4. 0 ± 2. 0 * 10 -4 and 7. 0 ± 1. 5 * 10 -4 mol/kg. The obtained Ca(II) surface concentration value is one order of magnitude lower than the one obtained from isotopic measurement by former authors [Geochim. Cosmochim. Acta 55 (1991) 1549; Geochim. Cosmochim. Acta 51

Superhard MgB sub 2 bulk material prepared by high-pressure sintering

CERN Document Server

Ma, H A; Chen, L X; Zhu, P W; Ren, G Z; Guo, W L; Fu, X Q; Zou Guang Tian; Ren, Z A; Che, G C; Zhao, Z X

2002-01-01

Superhard MgB sub 2 bulk material with a golden metallic shine was synthesized by high-pressure sintering for 8 h at 5.5 GPa and different temperatures. Appropriate pressure and temperature conditions for synthesizing polycrystalline MgB sub 2 with high hardness were investigated. The samples were characterized by means of atomic force microscopy and x-ray diffraction. The Vickers hardness, bulk density, and electrical resistivity were measured at room temperature.

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

Energy Technology Data Exchange (ETDEWEB)

Riechers, Shawn L.; Kerisit, Sebastien N.

2017-12-18

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

Incorporation of Eu(III) into calcite under recrystallization conditions

International Nuclear Information System (INIS)

Hellebrandt, S.E.; Jordan, Norbert; Barkleit, Astrid; Schmidt, Moritz; Hofmann, S.

2017-01-01

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

Incorporation of Eu(III) into calcite under recrystallization conditions

Energy Technology Data Exchange (ETDEWEB)

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

2017-06-01

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

Criteria for the recognition of pedogenic/supergene and nonpedogenic/hypogene deposits and their relationship to the origin of calcite/opal deposits at Yucca Mountain. Special report No. 14

International Nuclear Information System (INIS)

Hill, C.A.; Schluter, C.M.; Monger, H.C.

1993-10-01

This study is part of the research program of the Yucca Mountain Project intended to provide the State of Nevada with a detailed assessment of the geology and geochemistry of Yucca Mountain and adjacent regions. The purpose of this report is to try and establish criteria for the recognition of pedogenic/supergene deposits of calcite/opal versus non-pedogenic/hypogene deposits of calcite/opal. Far from being of esoteric concern, this subject is of paramount importance to the pedogenic-hypogene debate which rages around the suitability of Yucca Mountain as a high-level radioactive waste repository site

Influence of solution chemistry on the boron content in inorganic calcite grown in artificial seawater

Science.gov (United States)

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

2017-12-01

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

Magnetic anisotropy of thin sputtered MgB2 films on MgO substrates in high magnetic fields

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Savio Fabretti

2014-03-01

Full Text Available We investigated the magnetic anisotropy ratio of thin sputtered polycrystalline MgB2 films on MgO substrates. Using high magnetic field measurements, we estimated an anisotropy ratio of 1.35 for T = 0 K with an upper critical field of 31.74 T in the parallel case and 23.5 T in the perpendicular case. Direct measurements of a magnetic-field sweep at 4.2 K show a linear behavior, confirmed by a linear fit for magnetic fields perpendicular to the film plane. Furthermore, we observed a change of up to 12% of the anisotropy ratio in dependence of the film thickness.

The effect of heat treatment on the thermoluminescence of naturally-occurring calcites and their use as a gamma-ray dosimeter

International Nuclear Information System (INIS)

Engin, Birol; Gueven, Olgun

2000-01-01

The feasibility of using naturally-occurring calcite for gamma-ray dosimetry was investigated. Anneal treatment above 350 deg. C increased the sensitivity of all radiation-induced TL peaks except the glow peaks above 300 deg. C. On the other hand, annealing in air, at a temperature of 700 deg. C caused a collapse in the TL sensitivity. The increase in TL efficiency was found to depend on the annealing temperature and time. Heating at 600 deg. C for 5 h and quenching in ambient air are the optimum conditions for TL sensitivity enhancement in the calcite materials investigated. These results are explained using the energy scheme of the pre-dose model of and in terms of the impurity rearrangements in the crystal lattice induced by heating. It was found that the values of the kinetic parameters E, s and b for TL glow peaks remained unchanged for annealed samples. The TL dose-response curves for stable dosimetric peaks of annealed and unannealed calcite samples could be fitted to the same linear mathematical function. This implies that the annealing process probably does not change the nature of the trapping centers except the low temperature TL peaks at 125 and 160 deg. C of flowstone. The TL dosimetric parameters of calcite samples annealed, including glow curves, fading characteristics, dose-responses, dose-rate responses and energy responses, have also been studied in detail. The response to gamma-rays of annealed calcite samples was found to be linear from 0.05 to 10 4 Gy. The lower limit of observable doses for each calcite sample was about 0.05 Gy. This offers the possibility of applying the investigated materials for gamma-ray dosimetry within this useful range. These dosimeters can be used in various applications, such as, in industries related to chemical technology (polymerization), food processing and in determining the dose received by the patient during medical examination and treatment

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

Science.gov (United States)

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

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

African Journals Online (AJOL)

The point of zero charge values of 9.57 and 8.20 were obtained by mass titration method for synthetic and natural calcite, respectively. The maximum adsorption capacities of 200 mg/g and 150 mg/g Pb(II) of synthetic calcite and natural calcite were obtained at initial lead loading of 1200 mg/L at 25±2 °C, respectively.

Mechanics, microstructure and AMS evolution of a synthetic porphyritic calcite aggregate deformed in torsion

Czech Academy of Sciences Publication Activity Database

Marques, F. O.; Machek, Matěj; Roxerová, Zuzana; Burg, J.-P.; Almqvist, B. S. G.

2015-01-01

Roč. 655, August (2015), s. 41-57 ISSN 0040-1951 Institutional support: RVO:67985530 Keywords : experimental rock deformation * porphyritic calcite aggregate * EBSD and plastic deformation Subject RIV: DB - Geology ; Mineralogy Impact factor: 2.650, year: 2015

Assessing the effect of dissolved organic ligands on mineral dissolution rates: An example from calcite dissolution

International Nuclear Information System (INIS)

DeMaio, T.; Grandstaff, D.E.

1997-01-01

Experiments suggest that dissolved organic ligands may primarily modify mineral dissolution rates by three mechanisms: (1) metal-ligand (M-L) complex formation in solution, which increases the degree of undersaturation, (2) formation of surface M-L complexes that attack the surface, and (3) formation of surface complexes which passivate or protect the surface. Mechanisms (1) and (2) increase the dissolution rate and the third decreases it compared with organic-free solutions. The types and importance of these mechanisms may be assessed from plots of dissolution rate versus degree of undersaturation. To illustrate this technique, calcite, a common repository cementing and vein-filling mineral, was dissolved at pH 7.8 and 22 C in Na-Ca-HCO 3 -Cl solutions with low concentrations of three organic ligands. Low citrate concentrations (50 microM) increased the dissolution rate consistent with mechanism (1). Oxalate decreased the rate, consistent with mechanism (3). Low phthalate concentration (<50 microM) decreased calcite dissolution rates; however, higher concentrations increased the dissolution rates, which became faster than in inorganic solutions. Thus, phthalate exhibits both mechanisms (2) and (3) at different concentrations. In such cases linear extrapolations of dissolution rates from high organic ligand concentrations may not be valid

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

Science.gov (United States)

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

2007-09-01

BIOSOPE cruise achieved an oceanographic transect from the Marquise Islands to the Peru-Chili upwelling (PCU) via the centre of the South Pacific Gyre (SPG). Water samples from 6 depths in the euphotic zone were collected at 20 stations. The concentrations of suspended calcite particles, coccolithophores cells and detached coccoliths were estimated together with size and weight using an automatic polarizing microscope, a digital camera, and a collection of softwares performing morphometry and pattern recognition. Some of these softwares are new and described here for the first time. The coccolithophores standing stocks are usually low and reach maxima west of the PCU. The coccoliths of Emiliania huxleyi, Gephyrocapsa spp. and Crenalithus spp. (Order Isochrysidales) represent 50% of all the suspended calcite particles detected in the size range 0.1-46 μm (21% of PIC in term of the calcite weight). The latter species are found to grow preferentially in the Chlorophyll maximum zone. In the SPG their maximum concentrations was found to occur between 150 and 200 m, which is very deep for these taxa. The weight and size of coccoliths and coccospheres are correlated. Large and heavy coccoliths and coccospheres are found in the regions with relative higher fertility in the Marquises Island and in the PCU. Small and light coccoliths and coccospheres are found west of the PCU. This distribution may correspond to that of the concentration of calcium and carbonate ions.

Experimental evidences for reducing Mg activation energy in high Al-content AlGaN alloy by MgGa δ doping in (AlN)m/(GaN)n superlattice

Science.gov (United States)

Wang, Xiao; Wang, Wei; Wang, Jingli; Wu, Hao; Liu, Chang

2017-03-01

P-type doping in high Al-content AlGaN alloys is a main challenge for realizing AlGaN-based deep ultraviolet optoelectronics devices. According to the first-principles calculations, Mg activation energy may be reduced so that a high hole concentration can be obtained by introducing nanoscale (AlN)5/(GaN)1 superlattice (SL) in Al0.83Ga0.17N disorder alloy. In this work, experimental evidences were achieved by analyzing Mg doped high Al-content AlGaN alloys and Mg doped AlGaN SLs as well as MgGa δ doped AlGaN SLs. Mg acceptor activation energy was significantly reduced from 0.378 to 0.331 eV by using MgGa δ doping in SLs instead of traditional doping in alloys. This new process was confirmed to be able to realize high p-type doping in high Al-content AlGaN.

Improvement of IBAD-MgO texturing for high throughput of buffered substrate

International Nuclear Information System (INIS)

Ito, T.; Takahashi, Y.; Matsuse, K.; Kuriki, R.; Tokumaru, M.; Yoshizumi, M.; Izumi, T.

2011-01-01

The requirements from the market on two important factors of performance and cost need to be satisfied for commercialization of the coated conductors. Highly biaxially grain texturing with high production rate should be realized from the perspective of buffer layers processing. IBAD-MgO process is one of the major techniques which are possible to satisfy those requirements. The structure of our buffered substrate is IBS-GZO/IBAD-MgO/RFsputter-LaMnO 3 /PLD-CeO 2 . The PLD-CeO 2 process is the rate limiting and cost dominant one in this architecture. It is proposed that the self-texturing CeO 2 layer thickness could be reduced by optimization of the MgO processing due to higher MgO texturing and/or effective growth of self-texturing CeO 2 . Influence of the IBAD beam conditions and deposition time has been studied to optimize the IBAD conditions. Optimized IBAD conditions were decided from the viewpoints of in-plane grain texturing and the stability to obtain high texturing on fabrication. The Δφ value of CeO 2 layer was improved from 4-5 o to 3-3.5 o by the optimization. This buffered substrate gave high and uniform I c values of 524-565 A/cm-width for 50 m long GdBCO (1.5 μm) tape, indicating uniform distribution of Δφ(CeO 2 ). This improvement of Δφ(CeO 2 ) enables to reduce the CeO 2 thickness down to 300 nm without making Δφ(CeO 2 ) > 5 o , which improves CeO 2 throughput from 10 m/h to 30 m/h. A 50 m long patch sample showed more uniform Δφ distribution around 4 o even by high speed of 30 m/h as CeO 2 through-put. Highly and uniformly textured CeO 2 buffered substrate was obtained in 100 m long cost-effectively by optimization of IBAD-MgO processing.

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

International Nuclear Information System (INIS)

Winograd, I.J.; Coplen, T.B.; Landwehr, J.M.; Revesz, K.M.; Riggs, A.C.; Ludwig, K.R.; Szabo, B.J.; Kolesar, P.T.

1992-01-01

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

High-Mg basalts as a Signal of Magma System Replenishment at Lopevi Island, Vanuatu

Science.gov (United States)

Stewart, R. B.; Smith, I. E.; Turner, M. B.; Cronin, S. J.

2007-05-01

Lopevi is is a basalt to basaltic andesite island stratovolcano in central Vanuatu and is part of a long-lived, mature Island Arc chain. Central Vanuatu is tectonically influenced by the subduction of the D'Entrecasteaux zone. Primitive rock types that have been identified from the arc include picrites, ankaramites and high MgO basalts. High MgO rocks are generally considered to be a relatively rare component of arc-type magma suites but as detailed sequence sampling of individual volcanoes occurs, they have been identified more often. Here we report on the occurrence of high-Mg basalts in a sequence of lavas erupted in the last 100 years from Lopevi volcano. Activity at Lopevi is characteristically intermittent with eruptive sequences occurring over a c. 6 year period, separated by longer periods of repose. A major eruptive episode in 1939 caused evacuation of the island and the next eruptive episode in the 1960's also led to evacuation. The 1960's cycle of activity ended in 1982. The most recent phase of activity commenced in 1998 with a return to eruption of more siliceous, high alumina basaltic andesite. Geochemical data show that the 1960's lavas were different from those erupted earlier and later. They are olivine basalts with up to 9 wt percent MgO, 70 ppm Ni and 300 ppm Cr; Al2O3 content is about 12 wt percent. The 2003 lavas and pre-1960's lavas, in contrast, are basaltic andesites with c. 4 wt percent MgO, less than 25 ppm Ni, less than 100 ppm Cr and c. 20 wt percent Al2O3. The 1960's Lopevi sequence of eruptions represents an injection of a more primitive, high MgO magma at the end of a 21 year quiescent period after the major eruptions of 1939. Injection of small batches of more primitive magmas over decadal time periods at Lopevi marks the initiation of a new magmatic cycle. The occurrence of high MgO magmas as part of a cycle that includes typically low MgO arc type rocks demonstrates a consanguineous relationship and shows that high MgO arc type

Structure and interactions of calcite spherulites with α-chitin in the brown shrimp (Penaeus aztecus) shell

International Nuclear Information System (INIS)

Heredia, A.; Aguilar-Franco, M.; Magana, C.; Flores, C.; Pina, C.; Velazquez, R.; Schaeffer, T.E.; Bucio, L.; Basiuk, V.A.

2007-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-01-15

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

Reversal of rocuronium-induced (1.2 mg kg-1) profound neuromuscular block by accidental high dose of sugammadex (40 mg kg-1).

NARCIS (Netherlands)

Molina, A.L.; Boer, H.D. de; Klimek, M.; Heeringa, M.; Klein, J.

2007-01-01

Sugammadex is the first selective relaxant binding agent and reverses rocuronium-induced neuromuscular block. A case is reported in which a patient accidentally received a high dose of sugammadex (40 mg kg-1) to reverse a rocuronium-induced (1.2 mg kg-1) profound neuromuscular block. A fast and

Cryogenic cave calcite from several Central European caves: age, carbon and a genetic model

Czech Academy of Sciences Publication Activity Database

Žák, K.; Urban, J.; Cílek, Václav; Hercman, H.

2004-01-01

Roč. 206, 1/2 (2004), s. 119-136 ISSN 0009-2541 R&D Projects: GA ČR(CZ) GA205/02/0449 Keywords : cryogenic calcite * periglacial zone Subject RIV: DB - Geology ; Mineralogy Impact factor: 3.174, year: 2004

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

Science.gov (United States)

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.

Calcite dissolution along a transect in the western tropical Indian Ocean: A multiproxy approach

Digital Repository Service at National Institute of Oceanography (India)

Naik, S.S.; Naidu, P.D.

Three paleocarbonate ion proxies, size index, planktonic foraminifera shell weight, and calcite crystallinity, have been employed here to a set of core top samples from the western tropical Indian Ocean in the water depth ranges from 1086 to 4730 m...

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

Science.gov (United States)

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

2011-12-23

Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of high-surface-area spinel-type MgAl2O4 nanoparticles ...

Indian Academy of Sciences (India)

Home; Journals; Bulletin of Materials Science; Volume 40; Issue 1. Synthesis of high-surface-area spinel-type MgAl 2 O 4 nanoparticles by [Al(sal) 2 (H 2 O) 2 ] 2 [Mg(dipic) 2 ] and [Mg(H 2 O) 6 ][Al(ox) 2 (H 2 O) 2 ] 2 ·5H 2 O: influence of inorganic precursor type. Volume 40 Issue 1 February 2017 pp 45-53 ...

Relationship between oxygen isotopes in rainfall, cave percolation waters and speleothem calcite at Waitomo, New Zealand

International Nuclear Information System (INIS)

Williams, P.W.; Fowler, A.

2002-01-01

The relationship between the δ 18 O values of rainfall, vadose percolation water, and speleothem calcite was investigated in a cave at Waitomo. Water samples were obtained approximately monthly for two years from a storage rain gauge on the surface and from stored seepage from three stalactites underground. Rain water δ 18 O SMOW values varied considerably throughout the observation period, with a precipitation-weighted mean of -5.3 permille. Seasonal variability was evident, with winter values being more negative than summer values. Cave seepage waters had a mean of about -5 permille and showed very little variability and no discernible annual variation. This is explained by thorough mixing in the soil and subcutaneous zone stores. Given the average cave temperature (12.8 degrees C) and the δ 18 O SMOW value determined for seepage water, the δ 18 O PDB value of calcite that is actively depositing in isotopic equilibrium on speleothems at Waitomo should fall in the range of -4.1 to -4.6 permille. Observed delta-values of modern speleothem calcites overlap the positive end of this range of theoretical values, indicating that some growing speleothems are not in isotopic equilibrium with seepage waters, but are experiencing either evaporation or kinetic fractionation. (author). 32 refs., 8 figs

Structure in continuously cored, deep drill holes at Yucca Mountain, Nevada, with notes on calcite occurrence

International Nuclear Information System (INIS)

Carr, W.J.

1992-12-01

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

Genesis of Cenozoic intraplate high Mg# andesites in Northeast China

Science.gov (United States)

Liu, J. Q.; Chen, L. H.; Zhong, Y.; Wang, X. J.

2017-12-01

High-Mg# andesites (HMAs) are usually generated in the converged plate boundary and have genetic relationships with slab subduction. However, it still remained controversial about the origin of those HMAs erupted in the intra-plate setting. Here we present major, trace element, and Sr-Nd-Pb-Hf isotopic compositions for the Cenozoic intra-plate HMAs from Northeast China to constrain their origin and formation process. Cenozoic Xunke volcanic rocks are located in the northern Lesser Khingan Range, covering an area of about 3, 000 km2. These volcanic rocks are mainly basaltic andesite and basaltic trachyandesite, with only several classified as trachyandesite and andesites. They have high SiO2 contents (54.3-57.4 wt%) and Mg# (49.6-57.8), falling into the scope of high Mg# andesites. The Xunke HMAs are enriched in large ion lithophile elements but depleted in high field strength elements, with positive Ba, K, Sr and negative Zr-Hf, and Ti anomalies. Their trace element absolute concentrations are between those of potassic basalts and Wuchagou HMAs. The Xunke HMAs have relatively enriched Sr-Nd-Hf isotopes (87Sr/86Sr = 0.705398-0.705764, ɛNd=-8.8-3.8, ɛHf=0.5-11.7), and low radiogenic Pb isotopes (206Pb/204Pb = 16.701-17.198), towards to the EM1 end-member, which indicates that they are ultimately derived from ancient, recycled crustal components. Primitive silica-rich melts were generated from higher degrees of partial melting of recycled crustal materials (relative to potassic basalts) and then interacted with the peridotite to produce the Xunke HMAs.

First-principle Calculations of Mechanical Properties of Al2Cu, Al2CuMg and MgZn2 Intermetallics in High Strength Aluminum Alloys

Directory of Open Access Journals (Sweden)

LIAO Fei

2016-12-01

Full Text Available Structural stabilities, mechanical properties and electronic structures of Al2Cu, Al2CuMg and MgZn2 intermetallics in Al-Zn-Mg-Cu aluminum alloys were determined from the first-principle calculations by VASP based on the density functional theory. The results show that the cohesive energy (Ecoh decreases in the order MgZn2 > Al2CuMg > Al2Cu, whereas the formation enthalpy (ΔH decreases in the order MgZn2 > Al2Cu > Al2CuMg. Al2Cu can act as a strengthening phase for its ductile and high Young's modulus. The Al2CuMg phase exhibits elastic anisotropy and may act as a crack initiation point. MgZn2 has good plasticity and low melting point, which is the main strengthening phase in the Al-Zn-Mg-Cu aluminum alloys. Metallic bonding mode coexists with a fractional ionic interaction in Al2Cu, Al2CuMg and MgZn2, and that improves the structural stability. In order to improve the alloys' performance further, the generation of MgZn2 phase should be promoted by increasing Zn content while Mg and Cu contents are decreased properly.

Improvement of IBAD-MgO texturing for high throughput of buffered substrate

Energy Technology Data Exchange (ETDEWEB)

Ito, T., E-mail: t-ito@istec.or.jp [Superconductivity Research Laboratory, ISTEC, 1-10-13, Shinonome, Koto-ku, Tokyo 135-0062 (Japan); Takahashi, Y.; Matsuse, K.; Kuriki, R.; Tokumaru, M.; Yoshizumi, M.; Izumi, T. [Superconductivity Research Laboratory, ISTEC, 1-10-13, Shinonome, Koto-ku, Tokyo 135-0062 (Japan)

2011-11-15

The requirements from the market on two important factors of performance and cost need to be satisfied for commercialization of the coated conductors. Highly biaxially grain texturing with high production rate should be realized from the perspective of buffer layers processing. IBAD-MgO process is one of the major techniques which are possible to satisfy those requirements. The structure of our buffered substrate is IBS-GZO/IBAD-MgO/RFsputter-LaMnO{sub 3}/PLD-CeO{sub 2}. The PLD-CeO{sub 2} process is the rate limiting and cost dominant one in this architecture. It is proposed that the self-texturing CeO{sub 2} layer thickness could be reduced by optimization of the MgO processing due to higher MgO texturing and/or effective growth of self-texturing CeO{sub 2}. Influence of the IBAD beam conditions and deposition time has been studied to optimize the IBAD conditions. Optimized IBAD conditions were decided from the viewpoints of in-plane grain texturing and the stability to obtain high texturing on fabrication. The {Delta}{phi} value of CeO{sub 2} layer was improved from 4-5{sup o} to 3-3.5{sup o} by the optimization. This buffered substrate gave high and uniform I{sub c} values of 524-565 A/cm-width for 50 m long GdBCO (1.5 {mu}m) tape, indicating uniform distribution of {Delta}{phi}(CeO{sub 2}). This improvement of {Delta}{phi}(CeO{sub 2}) enables to reduce the CeO{sub 2} thickness down to 300 nm without making {Delta}{phi}(CeO{sub 2}) > 5{sup o}, which improves CeO{sub 2} throughput from 10 m/h to 30 m/h. A 50 m long patch sample showed more uniform {Delta}{phi} distribution around 4{sup o} even by high speed of 30 m/h as CeO{sub 2} through-put. Highly and uniformly textured CeO{sub 2} buffered substrate was obtained in 100 m long cost-effectively by optimization of IBAD-MgO processing.

Origin, distribution and transformation of authigenic carbonates in loessic soils

Directory of Open Access Journals (Sweden)

Martin Kolesár

2015-01-01

Full Text Available Processes of authigenic carbonates formation are component part of terrestrial biogeochemical cycle of carbon, which starts with co-accumulation of oxalic acid and Ca in Ca- oxalates. After plant decay are these biominerals slowly transformed under the influence of microbial processes into authigenic carbonates (calcites, depending on soil condition. The formation of authigenic calcites runs over in soil system where is rather high Ca and Mg concentration, presence of oxalomorphic plants and sufficient oxalotrophic stability of microorganisms. In addition to Ca-oxalates, Ca and Mg ions necessary for carbonate formation comes also from air (precipitation, dust, mineral weathering, subsurface water flow and decaying organic matter. The distribution pattern of authigenic calcites with depth, the size and shape of individual forms of calcites on loessic soils of SW Slovakia, as it is resulted from micromorphological study indicate that through the historical development of that soils as landscape units, soil water regime has played decisive role at vertical redistribution of forms (size, shape of authigenic calcites. To this witness the depth of variation of needle calcite zones and horizons of micritic calcites occurrence depending on soil types (leaching. Needle shape calcite zones which approach closest to the soil surface, gradually coalescence to the horizons of micritic calcites with the depth. Micritic calcites are without, or with microsparitic domains. Our study concurrently support the ideas of their inorganic origin depending on evaporitic soil regime. This formations have its own historic dynamics on which depends also the preservation of calcaric nature of soils.

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-01-01

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

Mg/Ca Ratios in Coralline Red Algae as Temperature Proxies for Reconstructing Labrador Current Variability

Science.gov (United States)

Gamboa, G.; Hetzinger, S.; Halfar, J.; Zack, T.; Kunz, B.; Adey, W.

2009-05-01

Marine ecosystems and fishery productivity in the Northwestern Atlantic have been considerably affected by regional climate and oceanographic changes. Fluctuations of North Atlantic marine climate have been linked in part to a dominant pattern of atmospheric circulation known as the North Atlantic Oscillation, which has a strong influence on transport variability of the Labrador Current (LC). The cold LC originates in the Labrador Sea and flows southbound along the Eastern Canadian coastline causing an important cooling effect on marine waters off the Canadian Atlantic provinces. Although interdecadal and interannual variability of sea surface temperatures (SST) in the LC system have been documented, a long-term pattern has not been identified. In order to better understand the observed ecosystem changes and their relationship with climate variability in the Northwestern Atlantic, a century-scale reconstruction of spatial and temporal variations of the LC is needed. This, however, requires reliable long-term and high-resolution SST records, which are not available from short instrumental observations. Here we present the first century-scale SST reconstructions from the Northwest Atlantic using long-lived coralline red algae. Coralline red algae have a high-Mg calcite skeleton, live in shallow water worldwide and develop annual growth bands. It has previously been demonstrated that subannual resolution SSTs can be obtained from coralline red algal Mg/Ca ratios, a commonly used paleotemperature proxy. Specimens of the long-lived coralline red algae Clathromorphum compactum were collected alive in August 2008 along a latitudinal transect spanning the southern extent of LC flow in Nova Scotia and Newfoundland. This collection is supplemented with specimens from the same region collected in the 1960's. In order to reconstruct spatial and temporal patterns of the LC, selected samples of C. compactum were analyzed for Mg/Ca using Laser Ablation Inductively-Coupled Plasma

Experimental evidences for reducing Mg activation energy in high Al-content AlGaN alloy by MgGa δ doping in (AlN)m/(GaN)n superlattice

OpenAIRE

Xiao Wang; Wei Wang; Jingli Wang; Hao Wu; Chang Liu

2017-01-01

P-type doping in high Al-content AlGaN alloys is a main challenge for realizing AlGaN-based deep ultraviolet optoelectronics devices. According to the first-principles calculations, Mg activation energy may be reduced so that a high hole concentration can be obtained by introducing nanoscale (AlN)5/(GaN)1 superlattice (SL) in Al0.83Ga0.17N disorder alloy. In this work, experimental evidences were achieved by analyzing Mg doped high Al-content AlGaN alloys and Mg doped AlGaN SLs as well as MgG...

Precipitation in Al–Mg solid solution prepared by solidification under high pressure

International Nuclear Information System (INIS)

Jie, J.C.; Wang, H.W.; Zou, C.M.; Wei, Z.J.; Li, T.J.

2014-01-01

The precipitation in Al–Mg solid solution containing 21.6 at.% Mg prepared by solidification under 2 GPa was investigated. The results show that the γ-Al 12 Mg 17 phase is formed and the β′ phase cannot be observed in the solid solution during ageing process. The precipitation of γ and β phases takes place in a non-uniform manner during heating process, i.e. the γ and β phases are first formed in the interdendritic region, which is caused by the inhomogeneous distribution of Mg atoms in the solid solution solidified under high pressure. Peak splitting of X-ray diffraction patterns of Al(Mg) solid solution appears, and then disappears when the samples are aged at 423 K for different times, due to the non-uniform precipitation in Al–Mg solid solution. The direct transformation from the γ to β phase is observed after ageing at 423 K for 24 h. It is considered that the β phase is formed through a peritectoid reaction of α + γ → β which needs the diffusion of Mg atoms across the interface of α/γ phases. - Highlights: • The γ phase is formed and the β′ phase is be observed in Al(Mg) solid solution. • Peak splitting of XRD pattern of Al(Mg) solid solution appears during aged at 150 °C. • The β phase is formed through a peritectoid reaction of α + γ → β

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

Science.gov (United States)

Bell, M. S.

2016-01-01

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

Bacterial bio-mediated calcite precipitation for monumental stones conservation: methods of evaluation.

Science.gov (United States)

Tiano, P; Biagiotti, L; Mastromei, G

1999-05-01

The weathering of monumental stones is a complex process inserted in the more general 'matter transformation cycle' operated by physical, chemical and biological factors. The consequence of these combined actions is a loss of cohesion with dwindling and scaling of stone material and the induction of a progressive mineral matrix dissolution. In the case of calcareous stones, calcite leaching increases the material porosity and decreases its mechanical features with a general weakening of the superficial structural strength. Attempts to stop, or at least to slow down, deterioration of monumental stones has been made by conservative treatments with both inorganic or organic products. More recent studies show a new approach to hinder these phenomena by inducing a bio-mediated precipitation of calcite directly inside the stone porosity. This can be achieved either through the application of organic matrix macromolecules extracted from sea shells or of living bacteria. The effectiveness of the treatment using calcinogenic bacteria has been evaluated with laboratory tests specifically developed to evaluate the parameters such as : porosity, superficial strength and chromatic changes, influenced by the treatment itself. The results obtained seem to indicate that this type of treatment might not be suitable for monumental stone conservation.

Highly efficient green light harvesting from Mg doped ZnO nanoparticles: Structural and optical studies

Energy Technology Data Exchange (ETDEWEB)

Sharma, Sarla, E-mail: mail2sarlasharma@gmail.com [Department of Physics, University of Rajasthan, Jaipur 302055 (India); Vyas, Rishi [Department of Physics, Malaviya National Institute of Technology, Jaipur 302017 (India); Sharma, Neha [Department of Physics, University of Rajasthan, Jaipur 302055 (India); Singh, Vidyadhar [Okinawa Institute of Science and Technology, Graduate University, Okinawa 9040495 (Japan); Singh, Arvind [Department of Physics, Institute of Chemical Technology, Mumbai 400 019 (India); Kataria, Vanjula; Gupta, Bipin Kumar [National Physical Laboratory (CSIR), New Delhi 110012 (India); Vijay, Y.K. [Department of Physics, University of Rajasthan, Jaipur 302055 (India)

2013-03-05

Graphical abstract: Demonstration of highly efficient green light emission harvesting from Mg doped ZnO nanoparticles were synthesized via facile wet chemical route with an average particle size ∼15 nm. The resulted nanoparticles exhibit intense green emission peaking at 530 nm upon 325 nm excitation. The photoluminescence (PL) intensity of visible emission depends upon the doping concentration of Mg. The PL intensity was found maximum up to 4% doping of Mg and beyond it exhibits a decrees in emission. The obtained highly luminescent green emission of ZnO nanoparticle would be an ultimate choice for next generation optoelectronics device materials. Highlights: ► Zn{sub 1−x}Mg{sub x}O nanoparticles were prepared by mechanochemical processing. ► High blue emission intensity was observed contrary to previous reports. ► Blue emission is suggested to be originating from the high density of defects. ► Defect density in as-milled condition is very high resulting in high emission. ► Mg promoted non-radiative recombination and lowered intensities. -- Abstract: Highly efficient green light emission was observed from Mg doped ZnO nanoparticles synthesized via facile wet chemical route with an average particle size ∼15 nm. The XRD analysis confirmed the growth of wurtzite phase of ZnO nanoparticles. Moreover, the optical properties of these nanoparticles were investigated by different spectroscopic techniques. The resulted nanoparticles exhibit intense green emission peaking at 530 nm (2.34 eV) upon 325 nm (3.81 eV) excitation. The photoluminescence (PL) intensity of visible emission depends upon the doping concentration of Mg. The PL intensity was found maximum up to 4% doping of Mg, and beyond it exhibits a decrees in emission. Furthermore, by varying the band gap from 3.50 to 3.61 eV, the PL spectra showed a near band edge (NBE) emission at wavelength around 370 nm (3.35 eV) and a broad deep level emission in the visible region. The obtained highly

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

Science.gov (United States)

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

2017-07-01

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

Calcite Twin Analysis in the Central Andes of Northern Argentina and Southern Bolivia

Science.gov (United States)

Hardesty, E.; Hindle, D.

2005-12-01

The use of calcite twinning to infer compression directions and strain axes patterns has been applied widely in both fold and thrust belts, and continental interiors. Calcite twinning is noted to be one of the most precise methods for determining the internal strain of deformed rocks. Until now, such data from the deformed plate boundary of the Central Andes were lacking. This study has examined twinning orientations along the deformed Andean foreland (southern Bolivia and northern Argentina) from -25 to -20 latitude. In the Central Andes, we find an abundance of calcite twins in intervals of the Cretaceous age Yacorite limestone. Twin samples were collected, measured for orientation and type (I and II can be best used for strain analysis), and processed using the Groshong method, to give resultant strain tensors. The orientations of the twin short axes trend mostly NE-SW, which is close to the plate convergence direction. However, in a limited number of samples from the north, adjacent to the southern culmination of the active Subandean fold thrust belt, they trend NW-SE. This difference may be related to the more active, or more recent, shortening of the southern portion of the Eastern Cordillera, south of the culmination of the Subandean belt. This implies that twin short axes vary consistently with respect to geographic location and local tectonic regime. NW-SE trends in the northern region match well with fault kinematic studies in rocks pre-dating the San Juan del Oro unconformity (9-10 Ma). NE-SW trends in the south could correspond to much younger (~1-3 Ma) fault kinematic trends. In the Eastern Cordillera, where there is present day tectonic activity, the plunges of the twin short axes are found to be almost horizontal. This suggests that the twins were formed after folding occurred.

Emission polarization study on quartz and calcite.

Science.gov (United States)

Vincent, R. K.

1972-01-01

Calculation of the spectral emission polarization of quartz and calcite polished plates for observation angles of 20 and 70 deg by the substitution of complex index of refraction values for each mineral into Fresnel's equations. The emission polarization is shown to be quite wavelength-dependent, demonstrating that selected narrow or medium-width spectral bands exhibit a significantly higher percentage of polarization than a broad spectral band for these two minerals. Field measurements with a broadband infrared radiometer yield polarizations on the order of 2% for a coarse-grained granite rock and beach sand (both quartz-rich). This implies that a more sensitive detector with a selected medium-width filter may be capable of measuring emission polarization accurately enough to make this parameter useful as a remote sensing tool for discrimination among rocks on the basis of texture.

Assessment of the potential for dating secondary calcite and quartz in fault zones

International Nuclear Information System (INIS)

Morency, Maurice

1982-03-01

Calcite and quartz occur frequently as secondary minerals in faults. In many instances these minerals are not deformed. Calcite, for example, often exhibits an undisturbed fibrous habit or appears as euhedral crystals. Direct dating of euhedral crystals would provide a minimum age of the last movement along a fault, whereas dating of fibrous crystals would furnish the real age of the last movement. This information would be essential in the evaluation and selection of sites for both nuclear power reactors and nuclear waste disposal. In the Canadian context, to be successful, the technique should be able to date minerals as old as tens of millions of years. In this study both isotopic and radioactive damage techniques were considered. It was found that thermoluminescence, thermally stimulated current, and electron spin resonance offer possibilities. Recent electron spin resonance studies of ancient flints have yielded dates of several hundred million years. It is anticipated that in the near future a combination of the above techniques will be extensively used in the field of geochronology

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

Energy Technology Data Exchange (ETDEWEB)

Whittaker, Michael L.; Joester, Derk (NWU)

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 sites 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.

Petrology, geochemistry and zirconology of impure calcite marbles from the Precambrian metamorphic basement at the southeastern margin of the North China Craton

Science.gov (United States)

Liu, Yi-Can; Zhang, Pin-Gang; Wang, Cheng-Cheng; Groppo, Chiara; Rolfo, Franco; Yang, Yang; Li, Yuan; Deng, Liang-Peng; Song, Biao

2017-10-01

Impure calcite marbles from the Precambrian metamorphic basement of the Wuhe Complex, southeastern margin of the North China Craton, provide an exceptional opportunity to understand the depositional processes during the Late Archean and the subsequent Palaeoproterozoic metamorphic evolution of one of the oldest cratons in the world. The studied marbles are characterized by the assemblage calcite + clinopyroxene + plagioclase + K-feldspar + quartz + rutile ± biotite ± white mica. Based on petrography and geochemistry, the marbles can be broadly divided into two main types. The first type (type 1) is rich in REE with a negative Eu anomaly, whereas the second type (type 2) is relatively poor in REE with a positive Eu anomaly. Notably, all marbles exhibit remarkably uniform REE patterns with moderate LREE/HREE fractionation, suggesting a close genetic relationship. Cathodoluminescence imaging, trace elements and mineral inclusions reveal that most zircons from two dated samples display distinct core-rim structures. Zircon cores show typical igneous features with oscillatory growth zoning and high Th/U ratios (mostly in the range 0.3-0.7) and give ages of 2.53 - 2.48 Ga, thus dating the maximum age of deposition of the protolith. Zircon rims overgrew during granulite-facies metamorphism, as evidenced by calcite + clinopyroxene + rutile + plagioclase + quartz inclusions, by Ti-in-zircon temperatures in the range 660-743 °C and by the low Th/U (mostly marbles are ascribed to syn-depositional felsic hydrothermal activity which occurred at 2.53 - 2.48 Ga. Our results, together with other published data and the inferred tectonic setting, suggest that the marbles' protolith is an impure limestone, rich in detrital silicates of igneous origin, deposited in a back-arc basin within an active continental margin during the late Archean and affected by synchronous high-T hydrothermalism at the southeastern margin of the North China Craton.

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

DEFF Research Database (Denmark)

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

2001-01-01

adsorption characteristics of selected pesticides. Investigated mineral phases included quartz, calcite, kaolinite, and alpha -alumina. Selected pesticides comprised atrazine (6-chloro-N-2-ethyl-N-4-isopropyl-1,3,5-triazine-2,4-diamine isoproturon [3-(4-isopropyl-phenyl)-1,1-dimethylurea)], mecoprop [(RS)-2...... due to formation of Ca-pesticide-surface complexes. Adsorption of the uncharged pesticides (atrazine and isoproturon) was detected only on kaolinite. The lack of adsorption on alpha -alumina indicates that the uncharged pesticides have a greater affinity for the silanol surface sites (= SiOH) than...

Dramatically enhanced ultraviolet photosensing mechanism in a n-ZnO nanowires/i-MgO/n-Si structure with highly dense nanowires and ultrathin MgO layers

International Nuclear Information System (INIS)

Kim, Dong Chan; Jung, Byung Oh; Cho, Hyung Koun; Lee, Ju Ho; Lee, Jeong Yong; Lee, Jun Hee

2011-01-01

This study reports that the visible-blind ultraviolet (UV) photodetecting properties of ZnO nanowire based photodetectors were remarkably improved by introducing ultrathin insulating MgO layers between the ZnO nanowires and Si substrates. All layers were grown without pause by metal organic chemical vapor deposition and the density and vertical arrangement of the ZnO nanowires were strongly dependent on the thickness of the MgO layers. The sample in which an MgO layer with a thickness of 8 nm was inserted had high density nanowires with a vertical alignment and showed dramatically improved UV photosensing performance (photo-to-dark current ratio = 1344.5 and recovery time = 350 ms). The photoresponse spectrum revealed good visible-blind UV detectivity with a sharp cut off at 378 nm and a high UV/visible rejection ratio. A detailed discussion regarding the developed UV photosensing mechanism from the introduction of the i-MgO layers and highly dense nanowires in the n-ZnO nanowires/i-MgO/n-Si substrates structure is presented in this work.

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

Science.gov (United States)

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-04-28

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

Mechanically activated self-propagated high-temperature synthesis of nanometer-structured MgB2

International Nuclear Information System (INIS)

Radev, D.D.; Marinov, M.; Tumbalev, V.; Radev, I.; Konstantinov, L.

2005-01-01

Nanometer-sized MgB 2 was prepared via a two-step modification of the mechanically activated self-propagated high-temperature synthesis. The experimental conditions and some structural and phase characteristics of the synthesized product are reported. It is shown that a single-phase material can be prepared after 2 h of intense mechanical treatment of the starting magnesium and boron powders and a synthesis induced at a current-pulse density of 30 A cm -2 . The average size of MgB 2 particles synthesized in this way is 70-80 nm. It is also shown that using the same reagents and the 'classic' high-temperature interaction at 850 deg C with a protective atmosphere of pure Ar, mean particle size of the MgB 2 obtained is 50 μm

Late-stage anhydrite-gypsum-siderite-dolomite-calcite assemblages record the transition from a deep to a shallow hydrothermal system in the Schwarzwald mining district, SW Germany

Science.gov (United States)

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

2018-02-01

The majority of hydrothermal vein systems of economic interest occur at relatively shallow crustal levels, although many of them formed at significantly greater depths. Their present position is a consequence of uplift and erosion. Although, many aspects of their formation are well constrained, the temporal chemical evolution of such systems during uplift and erosion is still poorly understood. These vein minerals comprise calcite, dolomite-ankerite, siderite-magnesite, anhydrite and gypsum forming the last gangue assemblages in Jurassic and Tertiary sulphide-fluorite-quartz-barite veins of the Schwarzwald mining district, SW Germany. Mineral textures of samples from nine localities reveal that in these sequences, mineral precipitation follows a recurring pattern: early calcite is followed by anhydrite or gypsum, siderite and/or dolomite. This succession may repeat up to three times. In-situ (LA-ICP-MS) U-Pb age dating of 15 carbonates from three subsequent generations of the late-stage vein assemblage yield robust ages between 20 and 0.6 Ma. Each mineral sequence forms in a distinctive period of about 2-5 Ma. These ages clearly relate these late-stage mineral phases to the youngest geological episode of the Schwarzwald, which is associated with the Cenozoic Rhine Graben rifting and basement uplift. Based on thermodynamic modelling, the formation of the observed mineral assemblages required an deeply sourced Mg-, Fe- and SO4-rich fluid (b), which was episodically mixed with a shallow crustal HCO3-rich fluid (a). As a consequence of fluid mixing, concentrations of Mg, Fe and SO4 temporarily increased and initiated the formation of the observed sulphate-carbonate mineral sequences. This discontinuous large-scale vertical fluid mixing was presumably directly related to episodes of active tectonics associated with the Cenozoic strike-slip regime of the Upper Rhine Graben. Analogously, episodic fluid mixing is a major key in the formation of older (Jurassic to early

Mg doping induced high structural quality of sol–gel ZnO nanocrystals: Application in photocatalysis

Energy Technology Data Exchange (ETDEWEB)

Abed, Chayma; Bouzidi, Chaker [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National de Recherches en Sciences des Matériaux, BP 95, Hammam-Lif 2050 (Tunisia); Elhouichet, Habib, E-mail: Habib.elhouichet@fst.rnu.tn [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National de Recherches en Sciences des Matériaux, BP 95, Hammam-Lif 2050 (Tunisia); Département de Physique, Faculté des Sciences de Tunis, Université Tunis El Manar, Tunis 2092 (Tunisia); Gelloz, Bernard [Graduate School of Engineering, Nagoya University, 2-24-16 Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan); Ferid, Mokhtar [Laboratoire de Physico-chimie des Matériaux Minéraux et leurs Applications, Centre National de Recherches en Sciences des Matériaux, BP 95, Hammam-Lif 2050 (Tunisia)

2015-09-15

Highlights: • ZnO nancrystals doped with Mg were prepared from sol–gel method. • Structural and optical properties of ZnO:Mg nanocrystals were investigated. • Good crystalline quality of ZnO nanocrystals was reported after Mg doping. • Good photocatalytic activity of Mg doped ZnO nanocrystals was demonstrated under sun light illumination. - Abstract: Undoped and Mg doped ZnO nanocrystals (NCs) ZnO:x%Mg (x = 1, 2, 3, and 5) were synthesized using sol–gel method. The structural and optical properties were investigated by X-ray diffraction (XRD), Raman spectroscopy, diffuse reflectivity, and photoluminescence (PL). XRD analysis demonstrates that all prepared samples present pure hexagonal wurtzite structure without any Mg related phases. The NCs size varies from 26.82 nm to 42.96 nm with Mg concentrations; it presents an optimal value for 2% of Mg. The Raman spectra are dominated by the E{sub 2high} mode. For highly Mg doping (5%), the occurrence of silent B{sub 1(low)} mode suggested that the Mg ions do substitute at Zn sites in the ZnO lattice The band gap energy was estimated from both Tauc and Urbach methods and found to be 3.39 eV for ZnO:2%Mg. The PL spectra exhibit two emission bands in the UV and visible range. Their evolution with Mg doping reveals the reduction of defect density in ZnO at low Mg doping by filling Zn vacancies. In addition, it was found that further Mg doping, above 2%, improves the photocatalytic activity of ZnO NCs for photodegradation of Rhodamine B (RhB) under sunlight irradiation. The efficient electron–hole separation is the main factor responsible for the enhancement of photocatalytic performance of Mg doped ZnO NCs. Through this work, we show that by varying the Mg contents in ZnO, this material can be a potential candidate for both optoelectronic and photocatalytic applications.

Role of Mg{sub x}Ca{sub 1−x}CO{sub 3} on the physical–chemical properties and cyclic CO{sub 2} capture performance of dolomite by two-step calcination

Energy Technology Data Exchange (ETDEWEB)

Wang, Ke; Han, Dongtai, E-mail: handongtai@cumt.edu.cn; Zhao, Pengfei, E-mail: zhaopfcumt@163.com; Hu, Xiumeng; Yin, Zeguang; Wu, Di

2015-08-20

Highlights: • Two-step calcination treated dolomite sorbent was prepared and characterized. • An intermediate phase (Mg{sub x}Ca{sub 1−x}CO{sub 3}) was observed by TG and XRD results. • Mg-calcite hindered the de-mixing of Ca and Mg. • Smaller grains, larger specific surface area and pore volume were obtained. • This favorable structure resulted in a high and stable CO{sub 2} capture performance. - Abstract: Two-step calcination (CO{sub 2} and N{sub 2} atmospheres) was used to modify the microstructure of natural dolomite for high-temperature CO{sub 2} capture. Two other one-step calcinations (CO{sub 2} or N{sub 2} atmosphere) were provided for comparison. Different morphological characterizations (thermal decomposition, phase composition, morphology, and nitrogen adsorption) were performed, followed by an analysis of 30 carbonation/calcination cycles in a fixed bed reactor. During primary calcination in a CO{sub 2} atmosphere, an intermediate phase (Mg{sub x}Ca{sub 1−x}CO{sub 3}) was observed by TG and XRD results, which hindered the de-mixing of CaO and MgO in the secondary calcination in a N{sub 2} atmosphere. Therefore, two-step calcination produced smaller grains (CaO: 45.2 nm; MgO: 32.6 nm), larger specific surface area (21.08 m{sup 2}/g) and pore volume (0.082 cm{sup 3}/g) and uniform distribution of CaO and MgO, which resulted in a higher and more stable uptake of CO{sub 2} compared to the results from one-step calcinations.

The surface destabilization effect of nitrate on the calcite (104). Water interface and yttrium(III) sorption thereon

Energy Technology Data Exchange (ETDEWEB)

Hellebrandt, S.E.; Hofmann, Sascha; Schmidt, Moritz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Surface Processes; Stubbs, J.E.; Eng, P.J. [Chicago Univ., IL (United States). Center for Advanced Radiation Sources; Stumpf, Thorsten [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology

2016-07-01

Calcite, as a most abundant mineral on earth, was studied with X-ray reflectivity under the influence of NaNO{sub 3} [1]. The calcite (104) surface undergoes significant destabilization effects in the presence of NaNO{sub 3}, which occurs as partial dissolution and the formation of an amorphous layer at the interface. The disordering of the surface reaches more than 15 Aa into the crystal bulk. Furthermore, this surface modification has also an effect on the sorption behavior of the rare earth element Y. Without NaNO{sub 3} Y{sup 3+} adsorbs as both inner and outer sphere complexes, this was verified with resonant anomalous X-ray reflectivity (RAXR). If NaNO{sub 3} is present, both species desorbs from the surface completely.

Graphite content and isotopic fractionation between calcite-graphite pairs in metasediments from the Mgama Hills, Southern Kenya

International Nuclear Information System (INIS)

Arneth, J.D.; Schidlowski, M.; Sarbas, B.; Goerg, U.; Amstutz, G.C.

1985-01-01

Amphibolite-grade metasediments from the Mgama Hills region, Kenya, contain conspicuous quantities of graphite, most probably derived from organic progenitor materials,. The highest graphite contents are found in schists whereas calcite marbles intercalated in the sequence contain relatively low amounts. The graphitic constituents are consistently enriched in 13 C relative to common sedimentary organic material, with the highest isotopic ratios in graphite from the marbles. Carbon isotope fractionations between calcite and graphite mostly vary between 3.3 and 7.1 per mille, which comes close to both empirically recorded and thermodynamically calculated fractionations in the temperature range of the upper amphibolite facies. However, larger values occasionally encountered in the marbles suggest that complete isotopic equilibrium is not always attained in amphibolite-facies metamorphism. (author)

Assessing the potential for using biogenic calcites as dosemeters for luminescence dating

International Nuclear Information System (INIS)

Duller, G.A.T.; Penkman, K.E.H.; Wintle, A.G.

2009-01-01

Calcium carbonate emits an intense thermoluminescence (TL) signal and previous work has explored the potential of using this signal to date both inorganic carbonates such as limestones and stalagmites and biogenic calcite produced by marine organisms. Luminescence analysis of biogenic calcites directly dates the secretion of the mineral by the organism and is therefore not reliant upon exposure of the sample to daylight. A method is outlined for using the TL signals from slug plates, from the Limacidae family, and opercula from the snail Bithynia tentaculata to construct a single-aliquot regenerative-dose growth curve. Analysis of slug plates from a number of Quaternary sites show that the equivalent dose (D e ) of a late Holocene sample is close to zero and that the D e increases with age over the last 500 ka. The TL signal from snail opercula is shown to increase up to doses over 4000 Gy. Replicate measurements from 16 opercula from a site ∼220 ka show a broad distribution. Potential causes of this scatter are discussed along with recommendations about how it could be reduced. The major challenge which remains to be solved before slug plates or snail opercula could be used to calculate ages is to develop methods for calculating the dose rate received during burial.

Ostracod calcite records the 18O/16O ratio of the bicarbonate and carbonate ions in water

Science.gov (United States)

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

2017-10-01

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

High-precision masses of 29-33Mg and the N=20 shell ''closure''

International Nuclear Information System (INIS)

Lunney, D.; Audi, G.; Gaulard, C.; Saint Simon, M. de; Thibault, C.; Vieira, N.

2006-01-01

High-precision mass measurements have been performed on the exotic magnesium isotopes 29-33 Mg using the MISTRAL radiofrequency spectrometer, especially suited for very short-lived nuclides. This method, combined with the powerful tool of resonant laser ionization at ISOLDE, has provided a significant reduction of uncertainty for the masses of the most exotic Mg isotopes: a relative error of 7 x 10 -7 was achieved for the weakly produced 33 Mg that has a half-life of only 90 ms. Moreover, the mass of 33 Mg is found to change by over 250 keV. Verifying and minimizing binding energy uncertainties in this region of the nuclear chart is important for understanding the lack of binding energy that is normally associated with magic numbers. (orig.)

MgB_{2} nonlinear properties investigated under localized high rf magnetic field excitation

Directory of Open Access Journals (Sweden)

Tamin Tai

2012-12-01

Full Text Available The high transition temperature and low surface resistance of MgB_{2} attracts interest in its potential application in superconducting radio frequency accelerating cavities. However, compared to traditional Nb cavities, the viability of MgB_{2} at high rf fields is still open to question. Our approach is to study the nonlinear electrodynamics of the material under localized rf magnetic fields. Because of the presence of the small superconducting gap in the π band, the nonlinear response of MgB_{2} at low temperature is potentially complicated compared to a single-gap s-wave superconductor such as Nb. Understanding the mechanisms of nonlinearity coming from the two-band structure of MgB_{2}, as well as extrinsic sources of nonlinearity, is an urgent requirement. A localized and strong rf magnetic field, created by a magnetic write head, is integrated into our nonlinear-Meissner-effect scanning microwave microscope [T. Tai et al., IEEE Trans. Appl. Supercond. 21, 2615 (2011ITASE91051-822310.1109/TASC.2010.2096531]. MgB_{2} films with thickness 50 nm, fabricated by a hybrid physical-chemical vapor deposition technique on dielectric substrates, are measured at a fixed location and show a strongly temperature-dependent third harmonic response. We propose that several possible mechanisms are responsible for this nonlinear response.

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

Directory of Open Access Journals (Sweden)

Florea Lee J.

2011-07-01

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

Mass spectrometric 230Th-234U-238U dating of the Devils Hole calcite vein

International Nuclear Information System (INIS)

Ludwig, K.R.; Simmons, K.R.; Szabo, B.J.; Riggs, A.C.; Winograd, I.J.; Landwehr, J.M.; Hoffman, R.J.

1992-01-01

The Devils Hole calcite vein contains a long-term climatic record, but requires accurate chronologic control for its interpretation. Mass-spectrometric U-series ages for samples from core DH-11 yielding 230 Th ages with precisions ranging from less than 1,000 years (2σ) for samples younger than ∼140 ka (thousands of years ago) to less than 50,000 years for the oldest samples (∼566 ka). The 234 U/ 238 U ages could be determined to a precision of ∼20,000 years for all ages. Calcite accumulated continuously from 566 ka until ∼60 ka at an average rate of 0.7 millimeter per 10 3 years. The precise agreement between replicate analyses and the concordance of the 230 Th/ 238 U and 234 U/ 238 U ages for the oldest samples indicate that the DH-11 samples were closed systems and validate the dating technique in general

Endogenic carbonate sedimentation in Bear Lake, Utah and Idaho, over the last two glacial-interglacial cycles

Science.gov (United States)

Dean, W.E.

2009-01-01

Sediments deposited over the past 220,000 years in Bear Lake, Utah and Idaho, are predominantly calcareous silty clay, with calcite as the dominant carbonate mineral. The abundance of siliciclastic sediment indicates that the Bear River usually was connected to Bear Lake. However, three marl intervals containing more than 50% CaCO3 were deposited during the Holocene and the last two interglacial intervals, equivalent to marine oxygen isotope stages (MIS) 5 and 7, indicating times when the Bear River was not connected to the lake. Aragonite is the dominant mineral in two of these three high-carbonate intervals. The high-carbonate, aragonitic intervals coincide with warm interglacial continental climates and warm Pacific sea-surface temperatures. Aragonite also is the dominant mineral in a carbonate-cemented microbialite mound that formed in the southwestern part of the lake over the last several thousand years. The history of carbonate sedimentation in Bear Lake is documented through the study of isotopic ratios of oxygen, carbon, and strontium, organic carbon content, CaCO3 content, X-ray diffraction mineralogy, and HCl-leach chemistry on samples from sediment traps, gravity cores, piston cores, drill cores, and microbialites. Sediment-trap studies show that the carbonate mineral that precipitates in the surface waters of the lake today is high-Mg calcite. The lake began to precipitate high-Mg calcite sometime in the mid-twentieth century after the artificial diversion of Bear River into Bear Lake that began in 1911. This diversion drastically reduced the salinity and Mg2+:Ca2+ of the lake water and changed the primary carbonate precipitate from aragonite to high-Mg calcite. However, sediment-trap and core studies show that aragonite is the dominant mineral accumulating on the lake floor today, even though it is not precipitating in surface waters. The isotopic studies show that this aragonite is derived from reworking and redistribution of shallow-water sediment

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

Science.gov (United States)

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

2012-10-01

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

Phase controlled synthesis of (Mg, Ca, Ba)-ferrite magnetic nanoparticles with high uniformity

International Nuclear Information System (INIS)

Wang, S.F.; Li, Q.; Zu, X.T.; Xiang, X.; Liu, W.; Li, S.

2016-01-01

(Mg, Ca, Ba)-ferrite magnetic nanoparticles were successfully synthesized through modifying the atomic ratio of polysaccharide and chelating agent at an optimal sintering temperature. In the process, the polysaccharide plays an important role in drastically shrinking the precursor during the gel drying process. In the metal-complex structure, M"2"+ ion active sites were coordinated by −OH of the water molecules except for EDTA anions. The MFe_2O_4 magnetic nanoparticles exhibited enhanced magnetic properties when compared with nano-MFe_2O_4 of similar particle size synthesized by other synthesis route reported in the literature. In particular, the sintering temperature improves the crystallinity and increases the hysteresis loop squareness ratio of (Mg, Ca, Ba)-ferrite nanoparticles significantly. - Graphical abstract: Schematic representation of the proposed model for MFe_2O_4 nanoparticle synthesis, starting from EDTA-chelated M"2"+ (M=Mg, Ca, or Ba) cations (left). High dispersion (Mg, Ca, Ba)-ferrite magnetic nanoparticles were prepared by a modified polyacrylamide gel route. Optimized utilization of polysaccharide, chelating agent, and sintering temperature allowed the formation of (Mg, Ca, Ba)-ferrite nanoparticles with a narrow diameter distribution. - Highlights: • We report a modified polyacrylamide gel route to synthesize (Mg, Ca, Ba)-ferrite magnetic nanoparticles. • Chelate mechanism of metal ions (Mg, Ca, Ba) and EDTA has been discussed. • Phase transformation process of (Mg, Ca, Ba)-ferrites has been discussed. • The preparation method increases the hysteresis loop squareness ratio of (Mg, Ca, Ba)-ferrite nanoparticles.

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

Science.gov (United States)

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

2015-04-01

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

Up-scaling mineral-aqueous interfacial processes that govern isotope and trace element partitioning during calcite growth

Science.gov (United States)

Lammers, L. N.

2014-12-01

The dependence of the isotopic and trace element composition of calcium carbonate minerals on growth conditions including temperature, pH, and salinity is widely used to infer paleoclimate conditions. These inferences rely heavily on phenomenological observations of biogenic and inorganic precipitation both in and ex situ, where only limited variability in solution conditions can be explored. Ionic fluxes between the mineral surface and aqueous growth solution govern the net uptake of both stoichiometric and trace species during calcification, so developing a mechanistic understanding of the reactions governing these fluxes is critical to refine existing proxies and to develop new ones. The micro-scale mechanisms of calcite precipitation from aqueous solution have been extensively studied, and net ionic uptake post-nucleation is known to occur primarily at monomolecular kink sites along step edges at the mineral surface. In this talk, I will present a theoretical framework that uses the quasi-elementary ion attachment and detachment reactions governing ion uptake at kink sites to simultaneously model bulk mineral growth kinetics and tracer partitioning during calcite precipitation. Several distinct processes occur during ion uptake at kink sites that can influence the distribution of trace species, directly impacting the composition of various carbonate paleoproxies including δ44Ca, δ18O, Sr/Ca and Mg/Ca. The distribution of these trace species will be shown to depend on (1) the relative rates of ion desolvation during attachment to kink sites, (2) the relative rates of bond breaking during detachment from kink sites, and (3) the equilibrium partitioning of trace aqueous species. This model accounts for the impact of solution conditions on net ion fluxes and surface speciation, which in turn controls the population of kink sites available for direct ion exchange with the aqueous phase. The impacts of solution variables including pH, temperature and salinity can

Growth of high quality large area MgB2 thin films by reactive evaporation

OpenAIRE

Moeckly, Brian H.; Ruby, Ward S.

2006-01-01

We report a new in-situ reactive deposition thin film growth technique for the production of MgB2 thin films which offers several advantages over all existing methods and is the first deposition method to enable the production of high-quality MgB2 films for real-world applications. We have used this growth method, which incorporates a rotating pocket heater, to deposit MgB2 films on a variety of substrates, including single-crystalline, polycrystalline, metallic, and semiconductor materials u...

Biomineralization of carbonate and phosphate by moderately halophilic bacteria

NARCIS (Netherlands)

Sánchez-Román, Mónica; Rivadeneyra, Maria A.; Vasconcelos, Crisogono; McKenzie, Judith A.

We investigated the precipitation of carbonate and phosphate minerals by 19 species of moderately halophilic bacteria using media with variable Mg 2+/Ca2+ ratios. The precipitated minerals were calcite, magnesium (Mg) calcite, and struvite (MgNH4PO4· 6H2O) in variable proportions depending on the

Production of high specific activity 27Mg by fast neutron irradiation and recoil-aided leaching

International Nuclear Information System (INIS)

Wierczinski, B.; Goeij, J.J.M. de; Volkers, K.J.

2000-01-01

High specific activity 27 Mg was produced via recoil-aided leaching from alumina in aqueous medium during irradiation with fast neutrons from a nuclear reactor. After irradiation the aqueous medium was passed through an IC-chelate column, the 24 Na formed during irradiation was removed by elution with 0.25 ml . l -1 sodium acetate and subsequently the 27 Mg was eluted with 2 mol . l -1 hydrochloric acid. Irradiation of alumina with a particle size of 3 μm and a specific surface area of 100 m 2 . g -1 in Milli-Q Plus Water yielded 90% of the total 27 Mg activity produced. Under standard conditions activities of about 8 . 10 5 Bq and specific activities of ca. 10 13 Bq . mol -1 were obtained at the end of irradiation. The standard working conditions involved irradiation of 200 mg alumina dispersed in 0.5 ml liquid in a fast neutron flux of 3 . 10 15 m -2 . s -1 for 15 min, a waiting time of 10 min, and a processing time of 15 minutes. Various alumina samples with different particle sizes and specific surfaces were tested, and the 27 Mg yields were fitted to a mathematical function. Since the high leaching yields cannot only be explained by recoil only, other phenomena such as diffusion and leaching aided by the high hydration energy of the Mg 2+ ion are probably involved. (orig.)

X-ray Raman scattering study of MgSiO₃ glass at high pressure: Implication for triclustered MgSiO₃ melt in Earth's mantle

Energy Technology Data Exchange (ETDEWEB)

Lee, Sung Keun; Lin, Jung-Fu; Cai, Yong Q.; Hiraoka, Nozomu; Eng, Peter J.; Okuchi, Takuo; Mao, Ho-kwang; Meng, Yue; Hu, Michael Y.; Chow, Paul; Shu, Jinfu; Li, Baosheng; Fukui, Hiroshi; Lee, Bum Han; Kim, Hyun Na; Yoo, Choong-Shik [SNU; (LLNL); (NSRRC); (Okayama); (UC); (CIW); (Wash State U); (Nagoya); (SBU)

2015-02-09

Silicate melts at the top of the transition zone and the core-mantle boundary have significant influences on the dynamics and properties of Earth's interior. MgSiO₃-rich silicate melts were among the primary components of the magma ocean and thus played essential roles in the chemical differentiation of the early Earth. Diverse macroscopic properties of silicate melts in Earth's interior, such as density, viscosity, and crystal-melt partitioning, depend on their electronic and short-range local structures at high pressures and temperatures. Despite essential roles of silicate melts in many geophysical and geodynamic problems, little is known about their nature under the conditions of Earth's interior, including the densification mechanisms and the atomistic origins of the macroscopic properties at high pressures. Here, we have probed local electronic structures of MgSiO₃ glass (as a precursor to Mg-silicate melts), using high-pressure x-ray Raman spectroscopy up to 39 GPa, in which high-pressure oxygen K-edge features suggest the formation of tricluster oxygens (oxygen coordinated with three Si frameworks; ^[3]O) between 12 and 20 GPa. Our results indicate that the densification in MgSiO₃ melt is thus likely to be accompanied with the formation of triculster, in addition to a reduction in nonbridging oxygens. The pressure-induced increase in the fraction of oxygen triclusters >20 GPa would result in enhanced density, viscosity, and crystal-melt partitioning, and reduced element diffusivity in the MgSiO₃ melt toward deeper part of the Earth's lower mantle.

Phase controlled synthesis of (Mg, Ca, Ba)-ferrite magnetic nanoparticles with high uniformity

Energy Technology Data Exchange (ETDEWEB)

Wang, S.F., E-mail: wangshifa2006@yeah.net [School of Physical Electronics, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan (China); Science and technology on vacuum technology and physics laboratory, Lanzhou Institute of Physics, Lanzhou 730000, Gansu (China); Li, Q. [School of Physical Electronics, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan (China); Zu, X.T., E-mail: xtzu@uestc.edu.cn [Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan (China); Xiang, X.; Liu, W. [School of Physical Electronics, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan (China); Li, S., E-mail: sean.li@unsw.edu.au [School of Material Science and Engineering, University of New South Wales, Sydney 2052 (Australia)

2016-12-01

(Mg, Ca, Ba)-ferrite magnetic nanoparticles were successfully synthesized through modifying the atomic ratio of polysaccharide and chelating agent at an optimal sintering temperature. In the process, the polysaccharide plays an important role in drastically shrinking the precursor during the gel drying process. In the metal-complex structure, M{sup 2+} ion active sites were coordinated by −OH of the water molecules except for EDTA anions. The MFe{sub 2}O{sub 4} magnetic nanoparticles exhibited enhanced magnetic properties when compared with nano-MFe{sub 2}O{sub 4} of similar particle size synthesized by other synthesis route reported in the literature. In particular, the sintering temperature improves the crystallinity and increases the hysteresis loop squareness ratio of (Mg, Ca, Ba)-ferrite nanoparticles significantly. - Graphical abstract: Schematic representation of the proposed model for MFe{sub 2}O{sub 4} nanoparticle synthesis, starting from EDTA-chelated M{sup 2+} (M=Mg, Ca, or Ba) cations (left). High dispersion (Mg, Ca, Ba)-ferrite magnetic nanoparticles were prepared by a modified polyacrylamide gel route. Optimized utilization of polysaccharide, chelating agent, and sintering temperature allowed the formation of (Mg, Ca, Ba)-ferrite nanoparticles with a narrow diameter distribution. - Highlights: • We report a modified polyacrylamide gel route to synthesize (Mg, Ca, Ba)-ferrite magnetic nanoparticles. • Chelate mechanism of metal ions (Mg, Ca, Ba) and EDTA has been discussed. • Phase transformation process of (Mg, Ca, Ba)-ferrites has been discussed. • The preparation method increases the hysteresis loop squareness ratio of (Mg, Ca, Ba)-ferrite nanoparticles.

High Coke-Resistance Pt/Mg1-xNixO Catalyst for Dry Reforming of Methane.

Directory of Open Access Journals (Sweden)

Faris A J Al-Doghachi

Full Text Available A highly active and stable nano structured Pt/Mg1-xNixO catalysts was developed by a simple co-precipitation method. The obtained Pt/Mg1-xNixO catalyst exhibited cubic structure nanocatalyst with a size of 50-80 nm and realized CH4 and CO2 conversions as high as 98% at 900°C with excellent stability in the dry reforming of methane. The characterization of catalyst was performed using various kinds of analytical techniques including XRD, BET, XRF, TPR-H2, TGA, TEM, FESEM, FT-IR, and XPS analyses. Characterization of spent catalyst further confirms that Pt/Mg1-xNixO catalyst has high coke-resistance for dry reforming. Thus, the catalyst demonstrated in this study, offers a promising catalyst for resolving the dilemma between dispersion and reducibility of supported metal, as well as activity and stability during high temperature reactions.

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

Energy Technology Data Exchange (ETDEWEB)

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

2018-09-15

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. In 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

High-MgO Vitric Ash in Upper Kulanaokuaiki Tephra, Kilauea Volcano, Hawai`i: A Preliminary Description

Science.gov (United States)

Rose, T. R.; Fiske, R. S.; Swanson, D.

2011-12-01

Small, well-formed Pele's tears containing anomalously high values of MgO were recently discovered in outcrops of the upper Kulanaokuaiki Tephra at and near the base of Uwekahuna Bluff, the western wall of Kilauea Caldera. Electron microprobe analyses of more than 60 high-MgO tears, which are 1-3 mm in diameter, show that most contain 11 to 12 wt. % MgO with a few approaching 13 % MgO. Separate microprobe analyses for sulfur and chlorine of 20 grains revealed no appreciable amounts of either, indicating the magma was largely degassed. Polished-section studies employing an analytical scanning electron microscope show most tears are composed of pure microvesicular glass with scattered skeletal olivine crystals and rare chromite. The abundance of skeletal olivine appears to increase with decreasing MgO content of the glass. These tears contain among the highest known MgO values of any material erupted subaerially from Kilauea. The high-MgO tears occur in a 1-6 cm thick layer of medium-coarse lithic-crystal-vitric ash. The top of this layer consists of 2-3 mm of very fine lithic-crystal ash. The lithics and many of the olivine crystals in this layer are highly oxidized. This deposit is at the top of a sequence of several lithic beds that are interspersed with thinner vitric units totaling about 75 cm in thickness. It is overlain by 9-13 cm of medium pumice lapilli and coarse vitric ash at the top of the "Bluff base" and "mid-Bluff" tephra sections described by Fiske et al. (2009). This high-MgO glass layer has been found thus far in only one other locality, a 2 m-deep soils study pit within Kipuka Puaulu, 3.5 km northwest of the caldera. Based upon stratigraphic relationships and preliminary microprobe data, a few other likely exposures of the high-MgO deposit have been identified north and west of the caldera. The high-MgO vitric ash in the upper Kulanaokuaiki Tephra has a primitive composition that suggests little if any shallow level storage of magma. Instead, the

High output power of differently cut Nd:MgO:LiTaO3 CW lasers

Science.gov (United States)

Sun, D. H.; Liu, S. D.; Wang, D. Z.; Sang, Y. H.; Kang, X. L.; Liu, H.; Bi, Y.; Yan, B. X.; He, J. L.; Wang, J. Y.

2013-04-01

A high-quality Nd3+ and Mg2+ co-doped LiTaO3 (Nd:MgO:LT) crystal was grown by the Czochralski method. The polarized absorption spectra and fluorescence spectra were studied, and the absorption cross section was calculated by Judd-Ofelt (J-O) theory. The laser performance with different sample cuts of the crystal was investigated for the first time, and it was found that Nd:MgO:LT crystal with different cutting directions (a and c) exhibits different laser properties. By optimizing a partial reflectivity mirror in the laser experimental setting, a high continuous wave output power of 3.58 W was obtained at 1092 and 1076 nm with an optical-to-optical conversion efficiency of 22.78% and slope efficiency of 26.06%. The results indicate that Nd:MgO:LT crystal is a promising candidate for the manufacture of Nd3+ doped periodically poled MgO:LiTaO3 crystal (Nd:PPMgOLT), which should have considerable applications in self-frequency doubling and optical parametric oscillation laser devices.

High output power of differently cut Nd:MgO:LiTaO3 CW lasers

International Nuclear Information System (INIS)

Sun, D H; Liu, S D; Wang, D Z; Sang, Y H; Kang, X L; Liu, H; He, J L; Wang, J Y; Bi, Y; Yan, B X

2013-01-01

A high-quality Nd 3+ and Mg 2+ co-doped LiTaO 3 (Nd:MgO:LT) crystal was grown by the Czochralski method. The polarized absorption spectra and fluorescence spectra were studied, and the absorption cross section was calculated by Judd–Ofelt (J–O) theory. The laser performance with different sample cuts of the crystal was investigated for the first time, and it was found that Nd:MgO:LT crystal with different cutting directions (a and c) exhibits different laser properties. By optimizing a partial reflectivity mirror in the laser experimental setting, a high continuous wave output power of 3.58 W was obtained at 1092 and 1076 nm with an optical-to-optical conversion efficiency of 22.78% and slope efficiency of 26.06%. The results indicate that Nd:MgO:LT crystal is a promising candidate for the manufacture of Nd 3+ doped periodically poled MgO:LiTaO 3 crystal (Nd:PPMgOLT), which should have considerable applications in self-frequency doubling and optical parametric oscillation laser devices. (paper)

Efficient MgO-based mesoporous CO2 trapper and its performance at high temperature.

Science.gov (United States)

Han, Kun Kun; Zhou, Yu; Chun, Yuan; Zhu, Jian Hua

2012-02-15

A novel MgO-based porous adsorbent has been synthesized in a facile co-precipitation method for the first time, in order to provide a candidate for trapping CO(2) in flue gas at high temperature. The resulting composite exhibits a mesoporous structure with a wide pore size distribution, due to the even dispersion and distribution of microcrystalline MgO in the framework of alumina to form a concrete-like structure. These sorbents can capture CO(2) at high temperature (150-400°C), possessing high reactivity and stability in cyclic adsorption-desorption processes, providing competitive candidates to control CO(2) emission. Copyright © 2011 Elsevier B.V. All rights reserved.

Quasicrystal-reinforced Mg alloys.

Science.gov (United States)

Kyun Kim, Young; Tae Kim, Won; Hyang Kim, Do

2014-04-01

The formation of the icosahedral phase (I-phase) as a secondary solidification phase in Mg-Zn-Y and Mg-Zn-Al base systems provides useful advantages in designing high performance wrought magnesium alloys. The strengthening in two-phase composites (I-phase + α -Mg) can be explained by dispersion hardening due to the presence of I-phase particles and by the strong bonding property at the I-phase/matrix interface. The presence of an additional secondary solidification phase can further enhance formability and mechanical properties. In Mg-Zn-Y alloys, the co-presence of I and Ca 2 Mg 6 Zn 3 phases by addition of Ca can significantly enhance formability, while in Mg-Zn-Al alloys, the co-presence of the I-phase and Mg 2 Sn phase leads to the enhancement of mechanical properties. Dynamic and static recrystallization are significantly accelerated by addition of Ca in Mg-Zn-Y alloy, resulting in much smaller grain size and more random texture. The high strength of Mg-Zn-Al-Sn alloys is attributed to the presence of finely distributed Mg 2 Sn and I-phase particles embedded in the α -Mg matrix.

Ionic Conductivity of the Perovskites, NaMgF3MgF3 and KZnF3 at High Temperatures

DEFF Research Database (Denmark)

Andersen, N. H.; Kjems, Jørgen; Hayes, W.

1985-01-01

We have carried out a study of the ionic conductivity of NaMgF3, KMgF3 and KZnF3 up to temperatures close to the melting point. Our results, in contrast to previous reports in the literature, show no abnormal ionic conductivity at high temperatures. Care in interpretation of results is required...... because of surface electronic conduction....

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

Science.gov (United States)

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

2017-04-01

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