The effect of brushing with nano calcium carbonate and calcium carbonate toothpaste on the surface roughness of nano-ionomer

NASA Astrophysics Data System (ADS)

Anisja, D. H.; Indrani, D. J.; Herda, E.

2017-08-01

Nanotechnology developments in dentistry have resulted in the development of nano-ionomer, a new restorative material. The surface roughness of restorative materials can increase bacteria adhesion and lead to poor oral hygiene. Abrasive agents in toothpaste can alter tooth and restorative material surfaces. The aim of this study is to identify the effect of brushing with nano calcium carbonate, and calcium carbonate toothpaste on surface roughness of nano-ionomer. Eighteen nano-ionomer specimens were brushed with Aquabidest (doubledistilled water), nano calcium carbonate and calcium carbonate toothpaste. Brushing lasted 30 minutes, and the roughness value (Ra) was measured after each 10 minute segment using a surface roughness tester. The data was analyzed using repeated ANOVA and one-way ANOVA test. The value of nano-ionomer surface roughness increased significantly (p<0.05) after 20 minutes of brushing with the nano calcium carbonate toothpaste. Brushing with calcium carbonate toothpaste leaves nano-ionomer surfaces more rugged than brushing with nano calcium carbonate toothpaste.

EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

DOEpatents

Furman, N.H.; Mundy, R.J.

1957-12-10

An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

Uranyl ion coordination

USGS Publications Warehouse

Evans, H.T.

1963-01-01

A review of the known crystal structures containing the uranyl ion shows that plane-pentagon coordination is equally as prevalent as plane-square or plane-hexagon. It is suggested that puckered-hexagon configurations of OH - or H2O about the uranyl group will tend to revert to plane-pentagon coordination. The concept of pentagonal coordination is invoked for possible explanations of the complex crystallography of the natural uranyl hydroxides and the unusual behavior of polynuclear ions in hydrolyzed uranyl solutions.

Proteomic analysis of a rare urinary stone composed of calcium carbonate and calcium oxalate dihydrate: a case report.

PubMed

Kaneko, Kiyoko; Matsuta, Yosuke; Moriyama, Manabu; Yasuda, Makoto; Chishima, Noriharu; Yamaoka, Noriko; Fukuuchi, Tomoko; Miyazawa, Katsuhito; Suzuki, Koji

2014-03-01

The objective of the present study was to investigate the matrix protein of a rare urinary stone that contained calcium carbonate. A urinary stone was extracted from a 34-year-old male patient with metabolic alkalosis. After X-ray diffractometry and infrared analysis of the stone, proteomic analysis was carried out. The resulting mass spectra were evaluated with protein search software, and matrix proteins were identified. X-ray diffraction and infrared analysis confirmed that the stone contained calcium carbonate and calcium oxalate dihydrate. Of the identified 53 proteins, 24 have not been previously reported from calcium oxalate- or calcium phosphate-containing stones. The protease inhibitors and several proteins related to cell adhesion or the cytoskeleton were identified for the first time. We analyzed in detail a rare urinary stone composed of calcium carbonate and calcium oxalate dihydrate. Considering the formation of a calcium carbonate stone, the new identified proteins should play an important role on the urolithiasis process in alkaline condition. © 2013 The Japanese Urological Association.

Water structure and aqueous uranyl(VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: results from molecular simulations.

PubMed

Greathouse, Jeffery A; Cygan, Randall T

2006-06-15

Molecular dynamics simulations were performed to provide a systematic study of aqueous uranyl adsorption onto the external surface of 2:1 dioctahedral clays. Our understanding of this key process is critical in predicting the fate of radioactive contaminants in natural groundwaters. These simulations provide atomistic detail to help explain experimental trends in uranyl adsorption onto natural media containing smectite clays. Aqueous uranyl concentrations ranged from 0.027 to 0.162 M. Sodium ions and carbonate ions (0.027-0.243 M) were also present in the aqueous regions to more faithfully model a stream of uranyl-containing groundwater contacting a mineral system comprised of Na-smectite. No adsorption occurred near the pyrophyllite surface, and there was little difference in uranyl adsorption onto the beidellite and montmorillonite, despite the difference in location of clay layer charge between the two. At low uranyl concentration, the pentaaquouranyl complex dominates in solution and readily adsorbs to the clay basal plane. At higher uranyl (and carbonate) concentrations, the mono(carbonato) complex forms in solution, and uranyl adsorption decreases. Sodium adsorption onto beidellite occurred both as inner- and outer-sphere surface complexes, again with little effect on uranyl adsorption. Uranyl surface complexes consisted primarily of the pentaaquo cation (85%) and to a lesser extent the mono(carbonato) species (15%). Speciation diagrams of the aqueous region indicate that the mono(carbonato)uranyl complex is abundant at high ionic strength. Oligomeric uranyl complexes are observed at high ionic strength, particularly near the pyrophyllite and montmorillonite surfaces. Atomic density profiles of water oxygen and hydrogen atoms are nearly identical near the beidellite and montmorillonite surfaces. Water structure therefore appears to be governed by the presence of adsorbed ions and not by the location of layer charge associated with the substrate. The water

Molecular Simulations of the Diffusion of Uranyl Carbonate Species in Nanosized Mineral Fractures

NASA Astrophysics Data System (ADS)

Kerisit, S.; Liu, C.

2010-12-01

water and that of the electrolyte ions differ significantly from those in bulk aqueous solutions. We will then present MD simulations of the diffusion of a series of alkaline-earth uranyl carbonate species in aqueous solutions [7]. The MD simulations show that the alkaline-earth uranyl carbonate complexes have distinct water exchange dynamics, which could lead to different reactivities. Finally, we will present recent results on the diffusion and adsorption of uranyl carbonate species in intragrain micropores, modeled with the feldspar-water interfaces mentioned in the above, to help interpret the diffusion behavior of uranium in contaminated sediments. [1] Liu C. et al. Geochim. Cosmochim. Acta 68 4519 (2004) [2] McKinley J. P. et al. Geochim. Cosmochim. Acta 70 1873 (2006) [3] Liu C. et al. Water Resour. Res. 42 W12420 (2006) [4] Ilton E. S. et al. Environ. Sci. Technol. 42 1565 (2009) [5] Kerisit S. et al. Geochim. Cosmochim. Acta 72 1481 (2008) [6] Kerisit S. and Liu C. Environ. Sci. Technol. 43 777 (2009) [7] Kerisit S. and Liu C. Geochim. Cosmochim. Acta 74 4937 (2010)

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

NASA Astrophysics Data System (ADS)

Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

2016-12-01

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

Expanding the Library of Uranyl Amide Derivatives: New Complexes Featuring the tert-Butyldimethylsilylamide Ligand.

PubMed

Pattenaude, Scott A; Coughlin, Ezra J; Collins, Tyler S; Zeller, Matthias; Bart, Suzanne C

2018-04-16

New uranyl derivatives featuring the amide ligand, -N(SiHMe 2 ) t Bu, were synthesized and characterized by X-ray crystallography, multinuclear NMR spectroscopy, and absorption spectroscopies. Steric properties of these complexes were also quantified using the computational program Solid-G. The increased basicity of the free ligand -N(SiHMe 2 ) t Bu was demonstrated by direct comparison to -N(SiMe 3 ) 2 , a popular supporting ligand for uranyl. Substitutional lability on a uranyl center was also demonstrated by exchange with the -N(SiMe 3 ) 2 ligand. The increased basicity of this ligand and diverse characterization handles discussed here will make these compounds useful synthons for future reactivity.

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes.

PubMed

Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

2016-12-01

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (U VI O 2 2+ ) coordinated by formate or acetate ligands. Anionic complexes containing U VI O 2 2+ and formate ligands fragment by decarboxylation and elimination of CH 2 =O, ultimately to produce an oxo-hydride species [U VI O 2 (O)(H)] - . Cationic species ultimately dissociate to make [U VI O 2 (OH)] + . Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH 3 CO 2 •, with associated reduction of uranyl to U V O 2 + . Subsequent CID steps cause elimination of CO 2 and CH 4 , ultimately to produce [U V O 2 (O)] - . Loss of CH 4 occurs by an intra-complex H + transfer process that leaves U V O 2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH 2 =C=O to leave [U V O 2 (O)] - . Elimination of CH 4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H 2 O. The reactions of other anionic species with gas-phase H 2 O create hydroxyl products, presumably through the elimination of H 2 . Graphical Abstract ᅟ.

Spectroscopy and DFT studies of uranyl carbonate, rutherfordine, UO2CO3: a model for uranium transport, carbon dioxide sequestration, and seawater species

NASA Astrophysics Data System (ADS)

Kalashnyk, N.; Perry, D. L.; Massuyeau, F.; Faulques, E.

2017-12-01

Several optical microprobe experiments of the anhydrous uranium carbonate—rutherfordine—are presented in this work and compared to periodic density functional theory results. Rutherfordine is the simplest uranyl carbonate and constitutes an ideal model system for the study of the rich uranium carbonate family relevant for environmental sustainability. Micro-Raman, micro-reflectance, and micro-photoluminescence (PL) spectroscopy studies have been carried out in situ on native, micrometer-sized crystals. The sensitivity of these techniques is sufficient to analyze minute amounts of samples in natural environments without using x-ray analysis. In addition, very intense micro-PL and micro-reflectance spectra that were not reported before add new results on the ground and excited states of this mineral. The optical gap value determined experimentally is found at about 2.6-2.8 eV. Optimized geometry, band structure, and phonon spectra have been calculated. The main vibrational lines are identified and predicted by this theoretical study. This work is pertinent for optical spectroscopy, for identification of uranyl species in various environmental settings, and for nuclear forensic analysis.

Transglutaminase-induced crosslinking of gelatin-calcium carbonate composite films.

PubMed

Wang, Yuemeng; Liu, Anjun; Ye, Ran; Wang, Wenhang; Li, Xin

2015-01-01

The effects of transglutaminase (TGase) on the rheological profiles and interactions of gelatin-calcium carbonate solutions were studied. In addition, mechanical properties, water vapour permeability and microstructures of gelatin-calcium carbonate films were also investigated and compared. Fluorescence data suggested that the interaction of TGase and gelation-calcium carbonate belonged to a static quenching mechanism, and merely one binding site between TGase and gelatin-calcium carbonate was identified. Moreover, differential scanning calorimetry (DSC), the mechanical properties and the water vapour permeability studies revealed that TGase favoured the strong intramolecular polymerisation of the peptides in gelatin. The microstructures of the surfaces and cross sections in gelatin-calcium carbonate films were shown by scanning electron microscope (SEM) micrographs. The results of the fourier transform infrared spectroscopy (FTIR) indicated that TGase caused conformational changes in the proteins films. Therefore, TGase successfully facilitated the formation of gelatin-calcium carbonate composite films. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermal stability of uranyl complexes with neutral oxygen-containing organic bases

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

Kobets, L.V.

1987-03-01

The thermal stability of uranyl chloride, nitrate, and oxalate with a series of neutral oxygen-containing organic ligands is discussed. It was found that the temperatures of removal of chlorine are higher than the stripping of the first molecule of the base in complexes UO/sub 2/Cl/sub 2/ x 2L. This is an indication of greater strength of the bonds of the Cl/sup -/ ions to the uranyl group in comparison with the investigated bases. It was shown that the temperatures of removal of a mole of neutral ligands depend little on the nature of the anions and exhibit a correlation withmore » the donor capacity of the bases: Ac < TBP < DMFA similarly ordered DMSO < TBPO similarly ordered PyO. The chemistry of the decomposition of the complexes and the strength of the binding of the acido- and neutral ligands in them are discussed.« less

21 CFR 184.1191 - Calcium carbonate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Calcium carbonate. 184.1191 Section 184.1191 Food... GRAS § 184.1191 Calcium carbonate. (a) Calcium carbonate (CaCO3, CAS Reg. No. 471-34-1) is prepared by... of calcium carbonate from calcium hydroxide in the “Carbonation process”; or (3) By precipitation of...

Calcium carbonate does not affect imatinib pharmacokinetics in healthy volunteers.

PubMed

Tawbi, Hussein; Christner, Susan M; Lin, Yan; Johnson, Matthew; Mowrey, Emily T; Cherrin, Craig; Chu, Edward; Lee, James J; Puhalla, Shannon; Stoller, Ronald; Appleman, Leonard R; Miller, Brian M; Beumer, Jan H

2014-01-01

Imatinib mesylate (Gleevec(®)/Glivec(®)) has revolutionized the treatment of chronic myeloid leukemias and gastrointestinal stromal tumors, and there is evidence for an exposure response relationship. Calcium carbonate is increasingly used as a calcium supplement and in the setting of gastric upset associated with imatinib therapy. Calcium carbonate could conceivably elevate gastric pH and complex imatinib, thereby influencing imatinib absorption and exposure. We aimed to evaluate whether use of calcium carbonate has a significant effect on imatinib pharmacokinetics. Eleven healthy subjects were enrolled in a 2-period, open-label, single-institution, randomized crossover, fixed-schedule study. In one period, each subject received 400 mg of imatinib p.o. In the other period, 4,000 mg calcium carbonate (Tums Ultra(®)) was administered p.o. 15 min before 400 mg of imatinib. Plasma concentrations of imatinib and its active N-desmethyl metabolite CGP74588 were assayed by LC-MS; data were analyzed non-compartmentally and compared after log transformation. Calcium carbonate administration did not significantly affect the imatinib area under the plasma concentration versus time curve (AUC) (41.2 μg/mL h alone vs. 40.8 μg/mL h with calcium carbonate, P = 0.99), maximum plasma concentration (C(max)) (2.35 μg/mL alone vs. 2.39 μg/mL with calcium carbonate, P = 0.89). Our results indicate that the use of calcium carbonate does not significantly affect imatinib pharmacokinetics.

Structure and reactivity of ferrihydrite-soil organic carbon-calcium ternary complexes

NASA Astrophysics Data System (ADS)

Yang, Y.; Adhikari, D.; Sowers, T.; Stuckey, J.; Poulson, S.; Sparks, D. L.

2017-12-01

Complete understanding about the interactions between soil organic carbon (SOC) and minerals is important for predicting the stability of SOC and its response to climate change. Recent studies have shown the importance of calcium (Ca)-bearing minerals and iron (Fe) oxide in associating with and stabilizing SOC. In this study, we have investigated the formation and reactivity of ferrihydrite-SOC-Ca ternary complexes. During the co-precipitation of ferrihydrite with SOC in the presence of Ca2+, 60% of SOC can be co-precipitated with ferrihydrite at a C/Fe (molar ratio) of up to 10, whereas the Ca/Fe ratio was saturated at 0.2. Increasing amount of Ca2+ did not affect the co-precipitation of SOC with ferrihydrite or the lability of ferrihydrite-bound SOC. In addition, microbial reduction of ferrihydrite and reductive release of ferrihydrite-bound SOC were not influenced by the presence of Ca, but the pathway for Fe mineral transformation during the reduction was affected by Ca. In the meantime, Fe reduction selectively released carboxylic-enriched SOC. As a comparison, the presence of SOC increased the incorporation of Ca into the structure of ferrihydrite. Our results indicate the formation of ferrihydrite-SOC-Ca complexes, with organic carbon bridging the ferrihydrite and Ca. Such ternary complexes potentially play an important role in regulating the interactions between SOC and mineral phases in soil.

Kinetics of triscarbonato uranyl reduction by aqueous ferrous iron: a theoretical study.

PubMed

Wander, Matthew C F; Kerisit, Sebastien; Rosso, Kevin M; Schoonen, Martin A A

2006-08-10

Uranium is a pollutant whose mobility is strongly dependent on its oxidation state. While U(VI) in the form of the uranyl cation is readily reduced by a range of natural reductants, by contrast complexation of uranyl by carbonate greatly reduces its reduction potential and imposes increased electron transfer (ET) distances. Very little is known about the elementary processes involved in uranium reduction from U(VI) to U(V) to U(IV) in general. In this study, we examine the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution. A combination of molecular dynamics (MD) simulations and density functional theory (DFT) electronic structure calculations is employed to compute the parameters that enter into Marcus' ET model, including the thermodynamic driving forces, reorganization energies, and electronic coupling matrix elements. MD simulations predict that two ferrous iron atoms will bind in an inner-sphere fashion to the three-membered carbonate ring of triscarbonato uranyl, forming the charge-neutral ternary Fe(2)UO(2)(CO(3))(3)(H(2)O)(8) complex. Through a sequential proton-coupled electron-transfer mechanism (PCET), the first ET step converting U(VI) to U(V) is predicted by DFT to occur with an electronic barrier that corresponds to a rate on the order of approximately 1 s(-1). The second ET step converting U(V) to U(IV) is predicted to be significantly endergonic. Therefore, U(V) is a stabilized end product in this ET system, in agreement with experiment.

Modification of the N-Terminus of a Calcium Carbonate Precipitating Peptide Affects Calcium Carbonate Mineralization.

PubMed

Usui, Kenji; Yokota, Shin-Ichiro; Ozaki, Makoto; Sakashita, Shungo; Imai, Takahito; Tomizaki, Kin-Ya

2018-01-01

A core sequence (the 9 C-terminal residues) of calcification-associated peptide (CAP- 1) isolated from the exoskeleton of the red swamp crayfish was previously shown to control calcium carbonate precipitation with chitin. In addition, a modified core sequence in which the phosphorylated serine at the N terminus is replaced with serine exhibits was also previously shown to alter precipitation characteristics with chitin. We focused on calcium carbonate precipitation and attempted to elucidate aspects of the mechanism underlying mineralization. We attempted to evaluate in detail the effects of modifying the N-terminus in the core sequence on calcium carbonate mineralization without chitin. The peptide modifications included phosphorylation, dephosphorylation, and a free or acetylated Nterminus. The peptides were synthesized manually on Wang resin using the DIPCI-DMAP method for the first residue, and Fmoc solid phase peptide synthesis with HBTU-HOBt for the subsequent residues. Prior to calcium carbonate precipitation, calcium carbonate was suspended in MilliQ water. Carbon dioxide gas was bubbled into the stirred suspension, then the remaining solid CaCO3 was removed by filtration. The concentration of calcium ions in the solution was determined by standard titration with ethylenediaminetetraacetate. Calcium carbonate precipitation was conducted in a micro tube for 3 h at 37°C. We used the micro-scale techniques AFM (atomic force microscopy) and TEM (transmission electron microscopy), and the macro-scale techniques chelate titration, HPLC, gel filtration, CD (circular dichroism) and DLS (dynamic light scattering). We determined the morphologies of the calcium carbonate deposits using AFM and TEM. The pS peptide provided the best control of the shape and size of the calcium carbonate round particles. The acetylated peptides (Ac-S and Ac-pS) provided bigger particles with various shapes. S peptide provided a mixture of bigger particles and amorphous particles. We

Calcium Carbonate.

PubMed

Al Omari, M M H; Rashid, I S; Qinna, N A; Jaber, A M; Badwan, A A

2016-01-01

Calcium carbonate is a chemical compound with the formula CaCO3 formed by three main elements: carbon, oxygen, and calcium. It is a common substance found in rocks in all parts of the world (most notably as limestone), and is the main component of shells of marine organisms, snails, coal balls, pearls, and eggshells. CaCO3 exists in different polymorphs, each with specific stability that depends on a diversity of variables. © 2016 Elsevier Inc. All rights reserved.

Precipitation and Dissolution of Uranyl Phosphates in a Microfluidic Pore Structure

NASA Astrophysics Data System (ADS)

Werth, C. J.; Fanizza, M.; Strathmann, T.; Finneran, K.; Oostrom, M.; Zhang, C.; Wietsma, T. W.; Hess, N. J.

2011-12-01

The abiotic precipitation of uranium (U(VI)) was evaluated in a microfluidic pore structure (i.e. micromodel) to assess the efficacy of using a phosphate amendment to immobilize uranium in groundwater and mitigate the risk of this contaminant to potential down-gradient receptor sites. U(VI) was mixed transverse to the direction of flow with hydrogen phosphate (HPO42-), in the presence or absence of calcium (Ca2+) or sulfate (SO42-), in order to identify precipitation rates, the morphology and types of minerals formed, and the stability of these minerals to dissolution with and without bicarbonate (HCO3-) present. Raman backscattering spectroscopy and micro X-ray diffraction (μ-XRD) results both showed that the only mineral precipitated was chernikovite (also known as hydrogen uranyl phosphate; UO2HPO4), even though the formation of other minerals were thermodynamically favored depending on the experimental conditions. Precipitation and dissolution rates varied with influent conditions. Relative to when only U(VI) and HPO42- were present, precipitation rates were 2.3 times slower when SO42- was present, and 1.4 times faster when Ca2+ was present. These rates were inversely related to the size of crystals formed during precipitation. Dissolution rates for chernikovite increased with increasing HCO3- concentrations, consistent with formation of uranyl carbonate complexes in aqueous solution, and they were the fastest for chernikovite formed in the presence of SO42-, and slowest for the chernikovite formed in the presence of Ca2+. These rates are related to the ratios of mineral-water interfacial area to mineral volume. Fluorescent tracer studies and laser confocal microscopy images showed that densely aggregated precipitates blocked pores and reduced permeability. The results suggest that changes in the solute conditions evaluated affect precipitation rates, crystal morphology, and crystal stability, but not mineral type.

Clonorcis sinensis eggs are associated with calcium carbonate gallbladder stones.

PubMed

Qiao, Tie; Ma, Rui-hong; Luo, Zhen-liang; Yang, Liu-qing; Luo, Xiao-bing; Zheng, Pei-ming

2014-10-01

Calcium carbonate gallbladder stones were easily neglected because they were previously reported as a rare stone type in adults. The aim of this study was to investigate the relationship between calcium carbonate stones and Clonorchis sinensis infection. A total of 598 gallbladder stones were studied. The stone types were identified by FTIR spectroscopy. The C. sinensis eggs and DNA were detected by microscopic examination and real-time fluorescent PCR respectively. And then, some egg-positive stones were randomly selected for further SEM examination. Corresponding clinical characteristics of patients with different types of stones were also statistically analyzed. The detection rate of C. sinensis eggs in calcium carbonate stone, pigment stone, mixed stone and cholesterol stone types, as well as other stone types was 60%, 44%, 36%, 6% and 30%, respectively, which was highest in calcium carbonate stone yet lowest in cholesterol stone. A total of 182 stones were egg-positive, 67 (37%) of which were calcium carbonate stones. The C. sinensis eggs were found adherent to calcium carbonate crystals by both light microscopy and scanning electron microscopy. Patients with calcium carbonate stones were mainly male between the ages of 30 and 60, the CO2 combining power of patients with calcium carbonate stones were higher than those with cholesterol stones. Calcium carbonate gallbladder stones are not rare, the formation of which may be associated with C. sinensis infection. Copyright © 2014 Elsevier B.V. All rights reserved.

Glycolytic intermediates induce amorphous calcium carbonate formation in crustaceans.

PubMed

Sato, Ai; Nagasaka, Seiji; Furihata, Kazuo; Nagata, Shinji; Arai, Isao; Saruwatari, Kazuko; Kogure, Toshihiro; Sakuda, Shohei; Nagasawa, Hiromichi

2011-04-01

It has been thought that phosphorus in biominerals made of amorphous calcium carbonate (ACC) might be related to ACC formation, but no such phosphorus-containing compounds have ever been identified. Crustaceans use ACC biominerals in exoskeleton and gastroliths so that they will have easy access to calcium carbonate inside the body before and after molting. We have identified phosphoenolpyruvate and 3-phosphoglycerate, intermediates of the glycolytic pathway, in exoskeleton and gastroliths and found them important for stabilizing ACC.

Calcium carbonate gallstones in children.

PubMed

Stringer, Mark D; Soloway, Roger D; Taylor, Donald R; Riyad, Kallingal; Toogood, Giles

2007-10-01

In the United States, cholesterol stones account for 70% to 95% of adult gallstones and black pigment stones for most of the remainder. Calcium carbonate stones are exceptionally rare. A previous analysis of a small number of pediatric gallstones from the north of England showed a remarkably high prevalence of calcium carbonate stones. The aims of this study were to analyze a much larger series of pediatric gallstones from our region and to compare their chemical composition with a series of adult gallstones from the same geographic area. A consecutive series of gallbladder stones from 63 children and 50 adults from the north of England were analyzed in detail using Fourier transform infrared microspectroscopy. Demographic and clinical data were collected on all patients. The relative proportions of each major stone component were assessed: cholesterol, protein and calcium salts of bilirubin, fatty acids, calcium carbonate, and hydroxyapatite. Thirty-nine (78%) adults had typical cholesterol stones, 7 (14%) had black pigment bilirubinate stones, and only 2 (4%) had calcium carbonate stones. In contrast, 30 (48%) children had black pigment stones, 13 (21%) had cholesterol stones, 15 (24%) had calcium carbonate stones, 3 (5%) had protein dominant stones, and 2 (3%) had brown pigment stones. In children, cholesterol stones were more likely in overweight adolescent girls with a family history of gallstones, whereas black pigment stones were equally common in boys and girls and associated with hemolysis, parenteral nutrition, and neonatal abdominal surgery. Calcium carbonate stones were more common in boys, and almost half had undergone neonatal abdominal surgery and/or required neonatal intensive care. The composition of pediatric gallstones differs significantly from that found in adults. In particular, one quarter of the children in this series had calcium carbonate stones, previously considered rare. Geographic differences are not the major reason for the high

Elemental calcium intake associated with calcium acetate/calcium carbonate in the treatment of hyperphosphatemia

PubMed Central

Wilson, Rosamund J; Copley, J Brian

2017-01-01

Background Calcium-based and non-calcium-based phosphate binders have similar efficacy in the treatment of hyperphosphatemia; however, calcium-based binders may be associated with hypercalcemia, vascular calcification, and adynamic bone disease. Scope A post hoc analysis was carried out of data from a 16-week, Phase IV study of patients with end-stage renal disease (ESRD) who switched to lanthanum carbonate monotherapy from baseline calcium acetate/calcium carbonate monotherapy. Of the intent-to-treat population (N=2520), 752 patients with recorded dose data for calcium acetate (n=551)/calcium carbonate (n=201) at baseline and lanthanum carbonate at week 16 were studied. Elemental calcium intake, serum phosphate, corrected serum calcium, and serum intact parathyroid hormone levels were analyzed. Findings Of the 551 patients with calcium acetate dose data, 271 (49.2%) had an elemental calcium intake of at least 1.5 g/day at baseline, and 142 (25.8%) had an intake of at least 2.0 g/day. Mean (95% confidence interval [CI]) serum phosphate levels were 6.1 (5.89, 6.21) mg/dL at baseline and 6.2 (6.04, 6.38) mg/dL at 16 weeks; mean (95% CI) corrected serum calcium levels were 9.3 (9.16, 9.44) mg/dL and 9.2 (9.06, 9.34) mg/dL, respectively. Of the 201 patients with calcium carbonate dose data, 117 (58.2%) had an elemental calcium intake of at least 1.5 g/day, and 76 (37.8%) had an intake of at least 2.0 g/day. Mean (95% CI) serum phosphate levels were 5.8 (5.52, 6.06) mg/dL at baseline and 5.8 (5.53, 6.05) mg/dL at week 16; mean (95% CI) corrected serum calcium levels were 9.7 (9.15, 10.25) mg/dL and 9.2 (9.06, 9.34) mg/dL, respectively. Conclusion Calcium acetate/calcium carbonate phosphate binders, taken to control serum phosphate levels, may result in high levels of elemental calcium intake. This may lead to complications related to calcium balance. PMID:28182142

Red mud carbonation using carbon dioxide: Effects of carbonate and calcium ions on goethite surface properties and settling.

PubMed

Liang, Gaojie; Chen, Wenmi; Nguyen, Anh V; Nguyen, Tuan A H

2018-05-01

Carbonation using CO 2 appears as an attractive solution for disposing of red mud suspensions, an aluminum industry hazardous waste since it also offers an option for CO 2 sequestration. Here we report the novel findings that CO 3 2- together with Ca 2+ can significantly affect the surface properties and settling of goethite, a major component of red mud. Specifically, their effects on the goethite surface chemistry, colloidal interaction forces and settling in alkaline solutions are investigated. The surface potential becomes more negative by the formation of carbonate inner-sphere complexes on goethite surface. It is consistent with the strong repulsion, decreased particle size and settling velocity with increased carbonate concentrations as measured by atomic force microscopy, particle size analysis, and particle settling. Adding Ca 2+ that forms outer-sphere complexes with pre-adsorbed carbonate changes goethite surface charge negligibly. Changing repulsion to the attraction between goethite surfaces by increasing calcium dosage indicates the surface bridging, in accordance with the increased settling velocity. The adverse effect of carbonate on goethite flocculation is probably due to its specific chemisorption and competition with flocculants. By forming outer-sphere complexes together with the flocculant-calcium bridging effect, calcium ions can eliminate the negative influence of carbonate and improve the flocculation of goethite particles. These findings contribute to a better understanding of goethite particle interaction with salt ions and flocculants in controlling the particle behavior in the handling processes, including the red mud carbonation. Copyright © 2018 Elsevier Inc. All rights reserved.

Structural, spectroscopic and redox properties of uranyl complexes with a maleonitrile containing ligand.

PubMed

Hardwick, Helen C; Royal, Drew S; Helliwell, Madeleine; Pope, Simon J A; Ashton, Lorna; Goodacre, Roy; Sharrad, Clint A

2011-06-14

The reaction of uranyl nitrate hexahydrate with the maleonitrile containing Schiff base 2,3-bis[(4-diethylamino-2-hydroxybenzylidene)amino]but-2-enedinitrile (salmnt((Et(2)N)(2))H(2)) in methanol produces [UO(2)(salmnt((Et2N)2))(H(2)O)] (1) where the uranyl equatorial coordination plane is completed by the N(2)O(2) tetradentate cavity of the (salmnt((Et(2)N)(2)))(2-) ligand and a water molecule. The coordinated water molecule readily undergoes exchange with pyridine (py), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF) and triphenylphosphine oxide (TPPO) to give a series of [UO(2)(salmnt((Et(2)N)(2)))(L)] complexes (L = py, DMSO, DMF, TPPO; 2-5, respectively). X-Ray crystallography of 1-5 show that the (salmnt((Et(2)N)(2)))(2-) ligand is distorted when coordinated to the uranyl moiety, in contrast to the planar structure observed for the free protonated ligand (salmnt((Et(2)N)(2))H(2)). The Raman spectra of 1-5 only display extremely weak bands (819-828 cm(-1)) that can be assigned to the typically symmetric O=U=O stretch. This stretching mode is also observed in the infrared spectra for all complexes 1-5 (818-826 cm(-1)) predominantly caused by the distortion of the tetradentate (salmnt((Et(2)N)(2)))(2-) ligand about the uranyl equatorial plane resulting in a change in dipole for this bond stretch. The solution behaviour of 2-5 was studied using NMR, electronic absorption and emission spectroscopy, and cyclic voltammetry. Complexes 2-5 exhibit intense absorptions in the visible region of the spectrum due to intramolecular charge transfer (ICT) transitions and the luminescence lifetimes (< 5 ns) indicate the emission arises from ligand-centred excited states. Reversible redox processes assigned to the {UO(2)}(2+)/{UO(2)}(+) couple are observed for complexes 2-5 (2: E(1/2) = -1.80 V; 3,5: E(1/2) = -1.78 V; 4: E(1/2) = -1.81 V : vs. ferrocenium/ferrocene {Fc(+)/Fc}, 0.1 M Bu(4)NPF(6)) in dichloromethane (DCM). These are some of the most negative half potentials

Calcium carbonate with magnesium overdose

MedlinePlus

The combination of calcium carbonate and magnesium is commonly found in antacids. These medicines provide heartburn relief. Calcium carbonate with magnesium overdose occurs when someone takes more than the ...

Calcium content of different compositions of gallstones and pathogenesis of calcium carbonate gallstones.

PubMed

Yu, Ji-Kuen; Pan, Huichin; Huang, Shing-Moo; Huang, Nan-Lan; Yao, Chung-Chin; Hsiao, Kuang-Ming; Wu, Chew-Wun

2013-01-01

Our aim was to investigate the calcium content of different gallstone compositions and the pathogenic mechanisms of calcium carbonate gallstones. Between August 2001 and July 2007, gallstones from 481 patients, including 68 calcium carbonate gallstones, were analyzed for total calcium content. Gallbladder bile samples from 33 cases and six controls were analyzed for pH, carbonate anion level, free-ionized calcium concentration and saturation index for calcium carbonate. Total calcium content averaged 75.6 %, 11.8 %, and 4.2 % for calcium carbonate, calcium bilirubinate and cholesterol gallstones. In 29.4 % of patients, chronic and/or intermittent cystic duct obstructions were caused by polypoid lesions in the neck region and 70.6 % were caused by stones. A total of 82 % of patients had chronic low-grade inflammation of the gallbladder wall and 18.0 % had acute inflammatory exacerbations. In the bile, we found the mean pH, mean carbonate anion, free-ionized calcium concentrations, and mean saturation index for calcium carbonate to be elevated in comparison to controls. From our study, we found chronic and/or intermittent cystic duct obstructions and low-grade GB wall inflammation lead to GB epithelium hydrogen secretion dysfunction. Increased calcium ion efflux into the GB lumen combined with increased carbonate anion presence increases SI_CaCO(3) from 1 to 22.4. Thus, in an alkaline milieu with pH 7.8, calcium carbonate begins to aggregate and precipitate. Copyright © 2012. Published by Elsevier B.V.

21 CFR 582.1191 - Calcium carbonate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Calcium carbonate. 582.1191 Section 582.1191 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use. This...

Induced calcium carbonate precipitation using Bacillus species.

PubMed

Seifan, Mostafa; Samani, Ali Khajeh; Berenjian, Aydin

2016-12-01

Microbially induced calcium carbonate precipitation is an emerging process for the production of self-healing concrete. This study was aimed to investigate the effects and optimum conditions on calcium carbonate biosynthesis. Bacillus licheniformis, Bacillus sphaericus, yeast extract, urea, calcium chloride and aeration were found to be the most significant factors affecting the biomineralization of calcium carbonate. It was noticed that the morphology of microbial calcium carbonate was mainly affected by the genera of bacteria (cell surface properties), the viscosity of the media and the type of electron acceptors (Ca 2+ ). The maximum calcium carbonate concentration of 33.78 g/L was achieved at the optimum conditions This value is the highest concentration reported in the literature.

Impregnating Coal With Calcium Carbonate

NASA Technical Reports Server (NTRS)

Sharma, Pramod K.; Voecks, Gerald E.; Gavalas, George R.

1991-01-01

Relatively inexpensive process proposed for impregnating coal with calcium carbonate to increase rates of gasification and combustion of coal and to reduce emission of sulfur by trapping sulfur in calcium sulfide. Process involves aqueous-phase reactions between carbon dioxide (contained within pore network of coal) and calcium acetate. Coal impregnated with CO2 by exposing it to CO2 at high pressure.

Aluminum hydroxide, calcium carbonate and calcium acetate in chronic intermittent hemodialysis patients.

PubMed

Janssen, M J; van der Kuy, A; ter Wee, P M; van Boven, W P

1996-02-01

Prevention of secondary hyperparathyroidism in uremia necessitates correction of hyperphosphatemia and hypocalcemia. In order to avoid aluminum toxicity, calcium containing phosphate binders are used increasingly, instead of aluminium hydroxide. Recent studies have shown that calcium acetate has many characteristics of an ideal phosphate binder. It is, for instance, a more readily soluble salt compared with calcium carbonate. This advantage might, however, disappear if calcium carbonate is taken on an empty stomach, a few minutes before meals. We examined the efficacy of three different phosphate binding agents in a randomized prospective study of 53 patients on regular hemodialysis. Bicarbonate dialyses were performed with a dialysate calcium concentration of 1.75 mmol/l. After a three-week wash-out period, patients received either aluminum hydroxide (control group), calcium acetate, or calcium carbonate as their phosphate binder. Patients were instructed to take the calcium salts a few minutes before meals on an empty stomach, and aluminum hydroxide during meals. Serum calcium, phosphate, intact parathormone, and alkaline phosphatase levels were determined every month. Patient compliance was estimated every month by asking the patients which phosphate binder and what daily dose they had used. Aluminum hydroxide tended to be the most effective phosphate binder. The mean +/- SEM required daily dose of calcium acetate at 12 months was 5.04 +/- 0.60 g, corresponding to 10.1 +/- 1.20 tablets of 500 mg. Co-medication with aluminum hydroxide, however, was needed (1.29 +/- 0.54 g per day, corresponding to 2.6 +/- 1.08 tablets of 500 mg). The required daily calcium carbonate dose appeared to be 2.71 +/- 0.48 g, corresponding to 5.4 +/- 0.95 capsules of 500 mg, with an adjuvant daily aluminum hydroxide dose of 0.69 +/- 0.27 g, corresponding to 1.4 +/- 0.55 tablets of 500 mg (p = 0.0055). Thus, the mean daily doses of elemental calcium were comparable between the calcium

Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

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

Medvedkov, Ya. A.; Serezhkina, L. B., E-mail: Lserezh@samsu.ru; Grigor’ev, M. S.

2016-05-15

Two new malonate-containing uranyl complexes with carbamide of the formulas [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}] (I) and [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 3}] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO{sub 2}(C{sub 2}O{sub 4})(Urea){sub 3}] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}]{sub ∞} belonging to the crystal-chemical group AT{sup 11}M{sub 2}{sup 1} (A = UO{sub 2}{sup 2+}, T{sup 11} = C{sub 3}H{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea) of uranyl complexes.more » Crystals II and III are composed of the molecular complexes [UO{sub 2}(L)(Urea){sub 3}], where L = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, belonging to the crystal-chemical group AB{sup 01}M{sub 3}{sup 1} (A = UO{sub 2}{sup 2+}, B{sup 01} = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.« less

Gravimetric Determination of Calcium as Calcium Carbonate Hydrate.

ERIC Educational Resources Information Center

Henrickson, Charles H.; Robinson, Paul R.

1979-01-01

The gravimetric determination of calcium as calcium carbonate is described. This experiment is suitable for undergraduate quantitative analysis laboratories. It is less expensive than determination of chloride as silver chloride. (BB)

Formic acid interaction with the uranyl(VI) ion: structural and photochemical characterization.

PubMed

Lucks, Christian; Rossberg, André; Tsushima, Satoru; Foerstendorf, Harald; Fahmy, Karim; Bernhard, Gert

2013-10-07

Complex formation between the uranyl(VI) ion and formic acid was studied by infrared absorption (IR) and X-ray absorption (EXAFS) spectroscopy as well as density functional theory (DFT) calculations. In contrast to the acetate ion which forms exclusively a bidentate complex with uranyl(VI), the formate ion binds to uranyl(VI) in a unidentate fashion. The photochemistry of the uranyl(VI)-formic acid system was explored by DFT calculations and photoreduction of uranyl(VI) in the presence of formic acid was found to occur via an intermolecular process, that is, hydrogen abstraction from hydrogenformate by the photo-excited uranyl(VI). There is no photo-induced decarboxylation of uranyl(VI) formate via an intramolecular process, presumably due to lack of a C=C double bond.

21 CFR 582.5191 - Calcium carbonate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use. This...

21 CFR 582.5191 - Calcium carbonate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use. This...

21 CFR 582.5191 - Calcium carbonate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use. This...

21 CFR 582.5191 - Calcium carbonate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use. This...

21 CFR 582.1191 - Calcium carbonate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... Additives § 582.1191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or feeding...

21 CFR 582.5191 - Calcium carbonate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use. This...

21 CFR 582.1191 - Calcium carbonate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... Additives § 582.1191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or feeding...

21 CFR 582.1191 - Calcium carbonate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... Additives § 582.1191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or feeding...

21 CFR 582.1191 - Calcium carbonate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... Additives § 582.1191 Calcium carbonate. (a) Product. Calcium carbonate. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or feeding...

Construction of Uranyl Selective Electrode Based on Complex of Uranyl Ion with New Ligand Carboxybenzotriazole in PVC Matrix Membrane

NASA Astrophysics Data System (ADS)

Abu-Dalo, M. A.; Al-Rawashdeh, N. A. F.; Al-Mheidat, I. R.; Nassory, N. S.

2015-10-01

In the present study uranyl selective electrodes in polyvinyl chloride (PVC) matrix membrane were prepared based on a complex of uranyl ion (UO2) with carboxybenzotriazole (CBT) as ligand. The effect of the nature of plasticizer in PVC matrix were evaluated using three different plasticizers, these are dibutyl phthalate (DBP), dioctyl phthalate (DOP) and bis(2-ethylhexyl) sebacate (BHS). The results of this study indicated that the best plasticizer could be used is the DBP, which may be attributed to its lowest viscosity value compared to DOP and BHS. The electrodes with DBP as plasticizer exhibits a Nernstian response with a slope of 28.0 mV/ decade, over a wide range of concentration from 3.0×10-5-6.0×10-2 M and a detection limit of 4.0×10-6 M. It can be used in the pH range of 4.0-10.0 with a response time of less than 10 s for DBP and 25 s for both DOP and BHS. The effects of ions interferences on the electrode response were evaluated. The di- and tri-valent cations were found to interfere less than univalent cations, which was attributed to the high diffusion and the exchange rate between the univalent ions and the uranyl ion solution. The electrodes were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron microscopy (SEM). The results of the standard addition method were satisfactory with errors less than 7%. The developed electrode was found to be fast, sensitive and reliable indicated its potential use in measuring the uranly ion concentration in the field.

Co-precipitation of dissolved organic matter by calcium carbonate in Pyramid Lake, Nevada

USGS Publications Warehouse

Leenheer, Jerry A.; Reddy, Michael M.

2008-01-01

Our previous research has demonstrated that dissolved organic matter (DOM) influences calcium carbonate mineral formation in surface and ground water. To better understand DOM mediation of carbonate precipitation and DOM co-precipitation and/or incorporation with carbonate minerals, we characterized the content and speciation of DOM in carbonate minerals and in the lake water of Pyramid Lake, Nevada, USA. A 400-gram block of precipitated calcium carbonate from the Pyramid Lake shore was dissolved in 8 liters of 10% acetic acid. Particulate matter not dissolved by acetic acid was removed by centrifugation. DOM from the carbonate rock was fractionated into nine portions using evaporation, dialysis, resin adsorption, and selective precipitations to remove acetic acid and inorganic constituents. The calcium carbonate rock contained 0.23% DOM by weight. This DOM was enriched in polycarboxylic proteinaceous acids and hydroxy-acids in comparison with the present lake water. DOM in lake water was composed of aliphatic, alicyclic polycarboxylic acids. These compound classes were found in previous studies to inhibit calcium carbonate precipitation. DOM fractions from the carbonate rock were 14C-age dated at about 3,100 to 3,500 years before present. The mechanism of DOM co-precipitation and/or physical incorporation in the calcium carbonate is believed to be due to formation of insoluble calcium complexes with polycarboxylic proteinaceous acids and hydroxy-acids that have moderately large stability constants at the alkaline pH of the lake. DOM co-precipitation with calcium carbonate and incorporation in precipitated carbonate minerals removes proteinaceous DOM, but nearly equivalent concentrations of neutral and acidic forms of organic nitrogen in DOM remain in solution. Calcium carbonate precipitation during lime softening pretreatment of drinking water may have practical applications for removal of proteinaceous disinfection by-product precursors.

Analysis of vibration frequencies of uranyl ion in complexes with neutral bases (in Russian)

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

Kobets, L.V.; Umreiko, D.S.

1986-12-01

It has been shown that any estimate of the changes in vibration frequencies of UO/sub 2//sup 2 +/ applies only to the series of isostructural compounds with similar stoichiometry. Either the same values of stretching vibration frequencies of uranyl correspond to complexes with ligands that have different donor abilities, or changes in these frequencies are not great and do not reflect the real increase in the donor ability of the bases with respect to proton-containing acceptors. When the acido ligands are replaced or the stoichiometry of the complexes is changed, no correlations can be carried out, since, besides the basicitiesmore » of donors, other parameters such as the dentateness of the ligand, and hence the symmetry and the structure of the compound, are also varied. In this paper, the authors evaluate the contributions of the ligands to the shift of the vibration frequencies of uranyl that have been made and do not take into account the characteristic features of the compounds which therefore led to very different values of the contributions for one and the same ligand in different compounds. To evaluate the shifts produced by the ligands, the value of 1065 cm/sup -1/ was taken as the vibration frequency of a hypothetical fee uranyl ion, not perturbed by bonds with equatorial ligands. The authors also evaluate the contributions of ions able to form polymer structures.« less

Hypoparathyroidism: what is the best calcium carbonate supplementation intake form?

PubMed

Gollino, Loraine; Biagioni, Maria Fernanda Giovanetti; Sabatini, Nathalia Regina; Tagliarini, José Vicente; Corrente, José Eduardo; Paiva, Sérgio Alberto Rupp de; Mazeto, Gláucia Maria Ferreira da Silva

2017-11-15

In hypoparathyroidism, calcium supplementation using calcium carbonate is necessary for the hypocalcemia control. The best calcium carbonate intake form is unknown, be it associated with feeding, juice or in fasting. The objective was to evaluate the calcium, phosphorus and Calcium×Phosphorus product serum levels of hypoparathyroidism women after total thyroidectomy, following calcium carbonate intake in three different forms. A crossover study was carried out with patients presenting definitive hypoparathyroidism, assessed in different situations (fasting, with water, orange juice, breakfast with a one-week washout). Through the review of clinical data records of tertiary hospital patients from 1994 to 2010, 12 adult women (18 50 years old) were identified and diagnosed with definitive post-thyroidectomy hypoparathyroidism. The laboratory results of calcium and phosphorus serum levels dosed before and every 30min were assessed, for 5h, after calcium carbonate intake (elementary calcium 500mg). The maximum peak average values for calcium, phosphorus and Calcium×Phosphorus product were 8.63mg/dL (water), 8.77mg/dL (orange juice) and 8.95mg/dL (breakfast); 4.04mg/dL (water), 4.03mg/dL (orange juice) and 4.12mg/dL (breakfast); 34.3mg 2 /dL 2 (water), 35.8mg 2 /dL 2 (orange juice) and 34.5mg 2 /dL 2 (breakfast), respectively, and the area under the curve 2433mg/dLmin (water), 2577mg/dLmin (orange juice) and 2506mg/dLmin (breakfast), 1203mg/dLmin (water), 1052mg/dLmin (orange juice) and 1128mg/dLmin (breakfast), respectively. There was no significant difference among the three different tests (p>0.05). The calcium, phosphorus and Calcium×Phosphorus product serum levels evolved in a similar fashion in the three calcium carbonate intake forms. Copyright © 2017 Associação Brasileira de Otorrinolaringologia e Cirurgia Cérvico-Facial. Published by Elsevier Editora Ltda. All rights reserved.

Identification of Uranyl Minerals Using Oxygen K-Edge X Ray Absorption Spectroscopy

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

Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.

2016-03-01

Uranium analysis is consistently needed throughout the fuel cycle, from mining to fuel fabrication to environmental monitoring. Although most of the world’s uranium is immobilized as pitchblende or uraninite, there exists a plethora of secondary uranium minerals, nearly all of which contain the uranyl cation. Analysis of uranyl compounds can provide clues as to a sample’s facility of origin and chemical history. X-ray absorption spectroscopy is one technique that could enhance our ability to identify uranium minerals. Although there is limited chemical information to be gained from the uranium X-ray absorption edges, recent studies have successfully used ligand NEXAFS tomore » study the physical chemistry of various uranium compounds. This study extends the use of ligand NEXAFS to analyze a suite of uranium minerals. We find that major classes of uranyl compounds (carbonate, oxyhydroxide, silicate, and phosphate) exhibit characteristic lineshapes in the oxygen K-edge absorption spectra. As a result, this work establishes a library of reference spectra that can be used to classify unknown uranyl minerals.« less

Ubiquitylation Functions in the Calcium Carbonate Biomineralization in the Extracellular Matrix

PubMed Central

Fang, Dong; Pan, Cong; Lin, Huijuan; Lin, Ya; Xu, Guangrui; Zhang, Guiyou; Wang, Hongzhong; Xie, Liping; Zhang, Rongqing

2012-01-01

Mollusks shell formation is mediated by matrix proteins and many of these proteins have been identified and characterized. However, the mechanisms of protein control remain unknown. Here, we report the ubiquitylation of matrix proteins in the prismatic layer of the pearl oyster, Pinctada fucata. The presence of ubiquitylated proteins in the prismatic layer of the shell was detected with a combination of western blot and immunogold assays. The coupled ubiquitins were separated and identified by Edman degradation and liquid chromatography/mass spectrometry (LC/MS). Antibody injection in vivo resulted in large amounts of calcium carbonate randomly accumulating on the surface of the nacreous layer. These ubiquitylated proteins could bind to specific faces of calcite and aragonite, which are the two main mineral components of the shell. In the in vitro calcium carbonate crystallization assay, they could reduce the rate of calcium carbonate precipitation and induce the calcite formation. Furthermore, when the attached ubiquitins were removed, the functions of the EDTA-soluble matrix of the prismatic layer were changed. Their potency to inhibit precipitation of calcium carbonate was decreased and their influence on the morphology of calcium carbonate crystals was changed. Taken together, ubiquitylation is involved in shell formation. Although the ubiquitylation is supposed to be involved in every aspect of biophysical processes, our work connected the biomineralization-related proteins and the ubiquitylation mechanism in the extracellular matrix for the first time. This would promote our understanding of the shell biomineralization and the ubiquitylation processes. PMID:22558208

Selective colorimetric and fluorescent quenching determination of uranyl ion via its complexation with curcumin

NASA Astrophysics Data System (ADS)

Zhu, Jing-Hui; Zhao, Xin; Yang, Jidong; Tan, Yu-Ting; Zhang, Lei; Liu, Shao-Pu; Liu, Zhong-Fang; Hu, Xiao-Li

2016-04-01

Under pH 4.0 HAc-NaAc buffer medium, curcumin alone possesses extraordinary weak fluorescence emission. Nevertheless, the introduction of Triton X-100 micelles can largely enhance the fluorescence intensity of curcumin. Uranyl ions can complex with micelles-capped curcumin, along with the slight red shift of curcumin fluorescence (about 1-7 nm), a clear decrement of absorbance (424 nm) and fluorescence (507 nm) intensities, and a distinct color change from bright yellow to orange. The fluorescence decrements (ΔF, 507 nm) are positively correlated to the amount of uranyl ions in the concentration range of 3.7 × 10- 6-1.4 × 10- 5 mol L- 1. The detection limit of this fluorescence quenching methods is 3.7 × 10- 6 mol L- 1, which is nearly 9000 times lower than the maximum allowable level in drinking water proposed by World Health Organization. Good selectivity is achieved because of a majority of co-existing substances (such as Ce4 +, La3 +, and Th4 +) do not affect the detection. The content of uranyl ions in tap water samples was determined by the proposed method with satisfactory results.

[Does carbonate originate from carbonate-calcium crystal component of the human urinary calculus?].

PubMed

Yuzawa, Masayuki; Nakano, Kazuhiko; Kumamaru, Takatoshi; Nukui, Akinori; Ikeda, Hitoshi; Suzuki, Kazumi; Kobayashi, Minoru; Sugaya, Yasuhiro; Morita, Tatsuo

2008-09-01

It gives important information in selecting the appropriate treatment for urolithiasis to confirm the component of urinary calculus. Presently component analysis of the urinary calculus is generally performed by infrared spectroscopy which is employed by companies providing laboratory testing services in Japan. The infrared spectroscopy determines the molecular components from the absorption spectra in consequence of atomic vibrations. It has the drawback that an accurate crystal structure cannot be analyzed compared with the X-ray diffraction method which analyzes the crystal constituent based on the diffraction of X-rays on crystal lattice. The components of the urinary calculus including carbonate are carbonate apatite and calcium carbonate such as calcite. Although the latter is reported to be very rare component in human urinary calculus, the results by infrared spectroscopy often show that calcium carbonate is included in calculus. The infrared spectroscopy can confirm the existence of carbonate but cannot determine whether carbonate is originated from carbonate apatite or calcium carbonate. Thus, it is not clear whether calcium carbonate is included in human urinary calculus component in Japan. In this study, we examined human urinary calculus including carbonate by use of X-ray structural analysis in order to elucidate the origin of carbonate in human urinary calculus. We examined 17 human calculi which were reported to contain calcium carbonate by infrared spectroscopy performed in the clinical laboratory. Fifteen calculi were obtained from urinary tract, and two were from gall bladder. The stones were analyzed by X-ray powder method after crushed finely. The reports from the clinical laboratory showed that all urinary culculi consisted of calcium carbonate and calcium phosphate, while the gallstones consisted of calcium carbonate. But the components of all urinary calculi were revealed to be carbonate apatite by X-ray diffraction. The components of

Structural characterization of environmentally relevant ternary uranyl citrate complexes present in aqueous solutions and solid state materials.

PubMed

Basile, Madeline; Unruh, Daniel K; Flores, Erin; Johns, Adam; Forbes, Tori Z

2015-02-14

Organic acids are important metal chelators in environmental systems and tend to form soluble complexes in aqueous solutions, ultimately influencing the transport and bioavailability of contaminants in surface and subsurface waters. This is particularly true for the formation of uranyl citrate complexes, which have been utilized in advanced photo- and bioremediation strategies for soils contaminated with nuclear materials. Given the complexity of environmental systems, the formation of ternary or heterometallic uranyl species in aqueous solutions are also expected, particularly with Al(iii) and Fe(iii) cations. These ternary forms are reported to be more stable in aqueous solutions, potentially enhancing contaminant mobility and uptake by organisms, but the exact coordination geometries of these soluble molecular complexes have not been elucidated. To provide insight into the nature of these species, we have developed a series of geochemical model compounds ([(UO(2))(2)Al(2)(C(6)H(4)O(7))(4)](6-) (U(2)Al(2)), [(UO(2))(2)Fe(2)(C(6)H(4)O(7))(4)](6-) (U(2)Fe(2)-1) and [(UO(2))(2)Fe(2)(C(6)H(4)O(7))(4)(H(2)O)(2)](6-) (U(2)Fe(2)-2) and [(UO(2))(2)Fe(4)(OH)(4)(C(6)H(4)O(7))(4)](8-) (U(2)Fe(4))) that were characterized by single-crystal X-ray diffraction and vibrational spectroscopy. Mass spectroscopy was then employed to compare the model compounds to species present in aqueous solutions to provide an enhanced understanding of the ternary uranyl citrate complexes that could be relevant in natural systems.

Perrhenate complexation by uranyl in traditional solvents and in ionic liquids: a joint molecular dynamics/spectroscopic study.

PubMed

Chaumont, Alain; Klimchuk, Olga; Gaillard, Clotilde; Billard, Isabelle; Ouadi, Ali; Hennig, Christoph; Wipff, Georges

2012-03-15

The complexation of perrhenate (ReO(4)(-)) anions by the uranyl (UO(2)(2+)) cation has been investigated by joint molecular dynamics simulations and spectroscopic (UV-vis, TRLFS, and EXAFS) studies in aqueous solution, acetonitrile, and three ionic liquids (ILs), namely, [Bmi][Tf(2)N], [Me(3)BuN][Tf(2)N], and [Bu(3)MeN][Tf(2)N] that are based on the same Tf(2)N(-) anion (bis(trifluoromethylsulfonyl)imide) and either Bmi(+) (1-butyl,3-methylimidazolium), Me(3)BuN(+), or Bu(3)MeN(+) cations. They show that ReO(4)(-) behaves as a weak ligand in aqueous solution and as a strong ligand in acetonitrile and in the ILs. According to MD simulations in aqueous solution, the UO(2)(ReO(4))(2) complex quickly dissociates to form UO(2)(H(2)O)(5)(2+), while in acetonitrile, a stable UO(2)(ReO(4))(5)(3-) species forms from dissociated ions. In the ILs, the UO(2)(ReO(4))(n)(2-n) complexes (n = 1 to 5) remained stable along the dynamics, and to assess their relative stabilities, we computed the free energy profiles for stepwise ReO(4)(-) complexation to uranyl. In the two studied ILs, complexation is favored, leading to the UO(2)(ReO(4))(5)(3-) species in [Bmi][Tf(2)N] and to UO(2)(ReO(4))(4)(2-) in [Bu(3)MeN][Tf(2)N]. Furthermore, in both acetonitrile and [Bmi][Tf(2)N] solutions, MD and PMF simulations support the formation of dimeric uranyl complexes [UO(2)(ReO(4))(4)](2)(4-) with two bridging ReO(4)(-) ligands. The simulation results are qualitatively consistent with spectroscopic observations in the different solvents, without firmly concluding, however, on the precise composition and structure of the complexes in the solutions. © 2012 American Chemical Society

Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

PubMed Central

2011-01-01

Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH4

Synthesis and characterization of heterometallic uranyl pyridinedicarboxylate compounds

NASA Astrophysics Data System (ADS)

Jayasinghe, Ashini S.; Payne, Maurice K.; Forbes, Tori Z.

2017-10-01

The incorporation of transition metals into hybrid uranyl materials can result in more diverse structural topologies and variations in physical and chemical properties. To explore the impact of transition metals on the uranyl cation, five uranium containing bimetallic chain compounds, [(UO2)M(PDC)2(H2O)4]·4(H2O) (PDC = 2,6 pyridinedicarboxylate; M = Ni2+, Co2+, Fe2+, Zn2+, and Cu2+) were synthesized by evaporation of aqueous solutions at room temperature. The uranyl cation is complex by two PDC ligands and the transition metal cations bond to the complex to form a one-dimensional chain topology. The presence of the transition metal leads to the presence of a stronger uranyl oxo bonds as shown by the single-crystal X-ray diffraction data and the Raman spectra. Solid state diffuse reflectance UV/Visible spectra confirmed the presence of the transition metals in the structure by the broad bands that appeared at relevant wavelengths.

21 CFR 73.1070 - Calcium carbonate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Calcium carbonate. 73.1070 Section 73.1070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF... mixtures for coloring drugs. (b) Specifications. Calcium carbonate shall meet the specifications for...

21 CFR 73.1070 - Calcium carbonate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Calcium carbonate. 73.1070 Section 73.1070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF... mixtures for coloring drugs. (b) Specifications. Calcium carbonate shall meet the specifications for...

Oral calcium carbonate affects calcium but not phosphorus balance in stage 3–4 chronic kidney disease

PubMed Central

Hill, Kathleen M.; Martin, Berdine R.; Wastney, Meryl; McCabe, George P.; Moe, Sharon M.; Weaver, Connie M.; Peacock, Munro

2014-01-01

Chronic kidney disease (CKD) patients are given calcium carbonate to bind dietary phosphorus and reduce phosphorus retention, and to prevent negative calcium balance. Data are limited on calcium and phosphorus balance in CKD to support this. The aim of this study was to determine calcium and phosphorus balance and calcium kinetics with and without calcium carbonate in CKD patients. Eight stage 3/4 CKD patients, eGFR 36 mL/min, participated in two 3-week balances in a randomized placebo-controlled cross-over study of calcium carbonate (1500 mg/d calcium). Calcium and phosphorus balance were determined on a controlled diet. Oral and intravenous 45calcium with blood sampling and urine and fecal collections were used for calcium kinetics. Fasting blood and urine were collected at baseline and end of each week of each balance period for biochemical analyses. Results showed that patients were in neutral calcium and phosphorus balance while on placebo. Calcium carbonate produced positive calcium balance, did not affect phosphorus balance, and produced only a modest reduction in urine phosphorus excretion compared with placebo. Calcium kinetics demonstrated positive net bone balance but less than overall calcium balance suggesting tissue deposition. Fasting biochemistries of calcium and phosphate homeostasis were unaffected by calcium carbonate. If they can be extrapolated to effects of chronic therapy, these data caution against the use of calcium carbonate as a phosphate binder. PMID:23254903

21 CFR 73.1070 - Calcium carbonate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Calcium carbonate. 73.1070 Section 73.1070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1070 Calcium carbonate. (a) Identity. (1) The color...

21 CFR 73.1070 - Calcium carbonate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Calcium carbonate. 73.1070 Section 73.1070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1070 Calcium carbonate. (a) Identity. (1) The color...

21 CFR 73.1070 - Calcium carbonate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Calcium carbonate. 73.1070 Section 73.1070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1070 Calcium carbonate. (a) Identity. (1) The color...

Testing Urey's carbonate-silicate cycle using the calcium isotopic composition of sedimentary carbonates

NASA Astrophysics Data System (ADS)

Blättler, Clara L.; Higgins, John A.

2017-12-01

Carbonate minerals constitute a major component of the sedimentary geological record and an archive of a fraction of the carbon and calcium cycled through the Earth's surface reservoirs for over three billion years. For calcium, carbonate minerals constitute the ultimate sink for almost all calcium liberated during continental and submarine weathering of silicate minerals. This study presents >500 stable isotope ratios of calcium in Precambrian carbonate sediments, both limestones and dolomites, in an attempt to characterize the isotope mass balance of the sedimentary carbonate reservoir through time. The mean of the dataset is indistinguishable from estimates of the calcium isotope ratio of bulk silicate Earth, consistent with the Urey cycle being the dominant mechanism exchanging calcium among surface reservoirs. The variability in bulk sediment calcium isotope ratios within each geological unit does not reflect changes in the global calcium cycle, but rather highlights the importance of local mineralogical and/or diagenetic effects in the carbonate record. This dataset demonstrates the potential for calcium isotope ratios to help assess these local effects, such as the former presence of aragonite, even in rocks with a history of neomorphism and recrystallization. Additionally, 29 calcium isotope measurements are presented from ODP (Ocean Drilling Program) Site 801 that contribute to the characterization of altered oceanic crust as an additional sink for calcium, and whose distinct isotopic signature places a limit on the importance of this subduction flux over Earth history.

Precipitation Rate Investigation on synthesis of precipitated calcium carbonate

NASA Astrophysics Data System (ADS)

Sulistiyono, E.; Handayani, M.; Firdiyono, F.; Fajariani, E. N.

2018-03-01

Study on the formation of precipitated calcium carbonate from natural limestone Sukabumi with the influenced of various parameters such as precipitation rate, concentration of CaCl2 and amplitudes were investigated. We also investigated the result with the precipitated calcium carbonate from Merck (p.a) for comparison. The higher concentration of CaCl2 would give effect to the lower of the precipitation rate. It was observed that precipitation rate of calcium carbonate from limestone Sukabumi at concentration of 0.08 molar was 3.66 cm/minutes and showing the optimum condition, while the precipitation rate of calcium carbonate Merck at the concentration 0.08 molar was 3.53 cm/minutes. The characterization of precipitated calcium carbonate was done using X-ray fluorescence (XRF) and scanning electron microscope (SEM). The characterization using XRF showed that CaO content of precipitated calcium carbonate from natural limestone Sukabumi had high purity of 99.16%. The particle distribution using scanning electron microscope (SEM) showed that precipitated calcium carbonate from natural limestone Sukabumi revealed 1.79 µm – 11.46 µm, meanwhile the particle distribution of precipitated calcium carbonate Merck showed larger particles with the size of 3.22 µm – 10.68 µm.

SECONDARY HYPERPARATHYROIDISM AFTER BARIATRIC SURGERY: TREATMENT IS WITH CALCIUM CARBONATE OR CALCIUM CITRATE?

PubMed Central

BARETTA, Giorgio Alfredo Pedroso; CAMBI, Maria Paula Carlini; RODRIGUES, Arieli Luz; MENDES, Silvana Aparecida

2015-01-01

Background : Bariatric surgery, especially Roux-en-Y gastric bypass, can cause serious nutritional complications arising from poor absorption of essential nutrients. Secondary hyperparathyroidism is one such complications that leads to increased parathyroid hormone levels due to a decrease in calcium and vitamin D, which may compromise bone health. Aim : To compare calcium carbonate and calcium citrate in the treatment of secondary hyperparathyroidism. Method : Patients were selected on the basis of their abnormal biochemical test and treatment was randomly done with citrate or calcium carbonate. Results : After 60 days of supplementation, biochemical tests were repeated, showing improvement in both groups. Conclusion : Supplementation with calcium (citrate or carbonate) and vitamin D is recommended after surgery for prevention of secondary hyperparathyroidism. PMID:26537273

Calcium carbonate overdose

MedlinePlus

Calcium carbonate is not very poisonous. Recovery is quite likely. But, long-term overuse is more serious than a single overdose, because it can cause kidney damage. Few people die from an antacid overdose. Keep ...

Oral calcium carbonate affects calcium but not phosphorus balance in stage 3-4 chronic kidney disease.

PubMed

Hill, Kathleen M; Martin, Berdine R; Wastney, Meryl E; McCabe, George P; Moe, Sharon M; Weaver, Connie M; Peacock, Munro

2013-05-01

Patients with chronic kidney disease (CKD) are given calcium carbonate to bind dietary phosphorus, reduce phosphorus retention, and prevent negative calcium balance; however, data are limited on calcium and phosphorus balance during CKD to support this. Here, we studied eight patients with stage 3 or 4 CKD (mean estimated glomerular filtration rate 36 ml/min) who received a controlled diet with or without a calcium carbonate supplement (1500 mg/day calcium) during two 3-week balance periods in a randomized placebo-controlled cross-over design. All feces and urine were collected during weeks 2 and 3 of each balance period and fasting blood, and urine was collected at baseline and at the end of each week. Calcium kinetics were determined using oral and intravenous (45)calcium. Patients were found to be in neutral calcium and phosphorus balance while on the placebo. Calcium carbonate supplementation produced positive calcium balance, did not affect phosphorus balance, and produced only a modest reduction in urine phosphorus excretion compared with placebo. Calcium kinetics demonstrated positive net bone balance but less than overall calcium balance, suggesting soft-tissue deposition. Fasting blood and urine biochemistries of calcium and phosphate homeostasis were unaffected by calcium carbonate. Thus, the positive calcium balance produced by calcium carbonate treatment within 3 weeks cautions against its use as a phosphate binder in patients with stage 3 or 4 CKD, if these findings can be extrapolated to long-term therapy.

Using Calcium Isotopic Composition of Calcium Carbonate Veins to Assess the Roles of Vein Formation and Seafloor Alteration in Regulation of the Carbon Cycle

NASA Astrophysics Data System (ADS)

Chen, F.; Coggon, R. M.; Teagle, D. A. H.; Turchyn, A. V.

2016-12-01

Calcium carbonate vein formation in the oceanic crust has been proposed as a climate-sensitive feedback mechanism that regulates the carbon cycle on million-year timescales. The suggestion has been that higher pCO2 levels may drive changes in ocean temperature and pH that increase seafloor alteration, releasing more calcium from oceanic basalt. This results in more removal of carbon from Earth's surface through calcium carbonate formation, which includes calcium carbonate vein formation in oceanic crust. The importance of this feedback mechanism remains enigmatic. Measurements of the δ44Ca of calcium carbonate veins in the oceanic crust may constrain the sources of calcium and timing of vein formation. Seawater and basalt are the only sources present shortly after crustal formation, whereas other sources, such as anhydrite dissolution and sedimentary carbonates become available when the crust ages, at which point carbonate veins may form far from the ridge axis. We report the calcium isotopic composition of 65 calcium carbonate veins, ranging from 108 to 1.2 million years old, in hydrothermally altered basalt from the Mid-Atlantic and Juan de Fuca ridges. We also present 43 δ44Ca measurements of 5.9 million year old basalts and dikes from the Costa Rica Rift that have undergone hydrothermal alteration over a range of conditions in upper crust. The δ44Ca of the calcium carbonate veins ranges from -1.59 to 1.01‰ (versus Bulk Silicate Earth), whereas the δ44Ca of altered basalts ranges from -0.18 to 0.28‰. Depth and temperature of formation seem to be major influences on calcium carbonate vein δ44Ca, with veins formed at cool, shallower depths having higher δ44Ca, closer to seawater. In contrast, we note no temporal variation in δ44Ca of calcium carbonate veins when comparing samples from older and younger crust. The majority of veins (54 out of 65) have δ44Ca between that of seawater and basalt, which implies that they may have formed quite soon after

Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions

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

Stewart, B.D.; Amos, R.T.; Nico, P.S.

2010-03-15

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate themore » impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl-calcium

Signaling complexes of voltage-gated calcium channels

PubMed Central

Turner, Ray W; Anderson, Dustin

2011-01-01

Voltage-gated calcium channels are key mediators of depolarization induced calcium entry into electrically excitable cells. There is increasing evidence that voltage-gated calcium channels, like many other types of ionic channels, do not operate in isolation, but instead form complexes with signaling molecules, G protein coupled receptors, and other types of ion channels. Furthermore, there appears to be bidirectional signaling within these protein complexes, thus allowing not only for efficient translation of calcium signals into cellular responses, but also for tight control of calcium entry per se. In this review, we will focus predominantly on signaling complexes between G protein-coupled receptors and high voltage activated calcium channels, and on complexes of voltage-gated calcium channels and members of the potassium channel superfamily. PMID:21832880

Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

NASA Astrophysics Data System (ADS)

Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.; Fendorf, Scott; Kumar, Naresh; Lowry, Gregory V.; Brown, Gordon E.

2017-10-01

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O22+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0-835 ppm) or Suwanee River Fulvic Acid (SRFA) (0-955 ppm). No evidence was found for reduction of uranyl by either form of NOM after 24 h of exposure. The following three size fractions were considered in this study: (1) ≥0.2 μm (Fh-NOM aggregates), (2) 0.02-0.2 μm (dispersed Fh nanoparticles and NOM macro-molecules), and (3) <0.02 μm (dissolved). The extent to which U(VI) is sorbed in aggregates or dispersed as colloids was assessed by comparing U, Fe, and NOM concentrations in these three size fractions. Partitioning of uranyl between Fh and NOM was determined in size fraction (1) using X-ray absorption spectroscopy (XAS). Uranyl sorption on Fh-NOM aggregates was affected by the presence of NOM in different ways depending on pH and type of NOM (ESHA vs. SRFA). The presence of ESHA in the uranyl-Fh-NOM ternary system at pH 4.6 enhanced uranyl uptake more than the presence of SRFA. In contrast, neither form of NOM affected uranyl sorption at pH 7.0 over most of the NOM concentration range examined (0-500 ppm); at the highest NOM concentrations (500-955 ppm) uranyl uptake in the aggregates was slightly inhibited at pH 7.0, which is interpreted as being due to the dispersion of Fh aggregates. XAS at the U LIII-edge was used to characterize molecular-level changes in uranyl complexation as a result of sorption to the Fh-NOM aggregates. In the absence of NOM, uranyl formed dominantly inner-sphere, mononuclear, bidentate sorption complexes on Fh. However, when NOM concentration was increased at pH 4.6, the

Phase transitions in biogenic amorphous calcium carbonate.

PubMed

Gong, Yutao U T; Killian, Christopher E; Olson, Ian C; Appathurai, Narayana P; Amasino, Audra L; Martin, Michael C; Holt, Liam J; Wilt, Fred H; Gilbert, P U P A

2012-04-17

Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC · H(2)O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC · H(2)O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC · H(2)O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC · H(2)O in vitro.

Influence of calcium on microbial reduction of solid phase uranium(VI).

PubMed

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M; Wang, Zheming

2007-08-15

The effect of calcium on the dissolution and microbial reduction of a representative solid phase uranyl [U(VI)], sodium boltwoodite (NaUO(2)SiO(3)OH . 1.5H(2)O), was investigated to evaluate the rate-limiting step of microbial reduction of the solid phase U(VI). Microbial reduction experiments were performed in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1, in a bicarbonate medium with lactate as electron donor at pH 6.8 buffered with PIPES. Calcium increased the rate of Na-boltwoodite dissolution and U(VI) bioavailability by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) collectively revealed that microbial reduction of solid phase U(VI) was a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. Under studied experimental conditions, the overall rate of microbial reduction of solid phase U(VI) was limited by U(VI) dissolution reactions in solutions without calcium and limited by microbial reduction in solutions with calcium. Generally, the overall rate of microbial reduction of solid phase U(VI) was determined by the coupling of solid phase U(VI) dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) that were all affected by calcium. (c) 2007 Wiley Periodicals, Inc.

Tris-amidoximate uranyl complexes via η2 binding mode coordinated in aqueous solution shown by X-ray absorption spectroscopy and density functional theory methods.

PubMed

Zhang, Linjuan; Qie, Meiying; Su, Jing; Zhang, Shuo; Zhou, Jing; Li, Jiong; Wang, Yu; Yang, Shitong; Wang, Shuao; Li, Jingye; Wu, Guozhong; Wang, Jian Qiang

2018-03-01

The present study sheds some light on the long-standing debate concerning the coordination properties between uranyl ions and the amidoxime ligand, which is a key ingredient for achieving efficient extraction of uranium. Using X-ray absorption fine structure combined with theoretical simulation methods, the binding mode and bonding nature of a uranyl-amidoxime complex in aqueous solution were determined for the first time. The results show that in a highly concentrated amidoxime solution the preferred binding mode between UO 2 2+ and the amidoxime ligand is η 2 coordination with tris-amidoximate species. In such a uranyl-amidoximate complex with η 2 binding motif, strong covalent interaction and orbital hybridization between U 5f/6d and (N, O) 2p should be responsible for the excellent binding ability of the amidoximate ligand to uranyl. The study was performed directly in aqueous solution to avoid the possible binding mode differences caused by crystallization of a single-crystal sample. This work also is an example of the simultaneous study of local structure and electronic structure in solution systems using combined diagnostic tools.

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

NASA Astrophysics Data System (ADS)

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; Chorover, Jon; O'Day, Peggy A.

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium (U) concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this work, the dissolution rates of K- and Na-compreignacite (K2(UO2)6O4(OH)6·8H2O and Na2(UO2)6O4(OH)6·8H2O, respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved carbonate concentration (ca. 0.2 and 2.8 mmol L-1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area, and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total U mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved U was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

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

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

DOE PAGES

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; ...

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered

Performance of a hydrogen uranyl phosphate-carbon double-layer solid capacitor

NASA Astrophysics Data System (ADS)

Pham-Thi, M.; Adet, Ph.; Velasco, G.; Colomban, Ph.

1986-05-01

A mixture of commercially available carbon black (C) powders and hydrogen uranyl phosphate (HUP) precipitate can be used as the electrode material for miniaturized double-layer capacitors. A solid cell of C-HUP/HUP/C-HUP has a capacitance of 1 F which, given the device area and thickness of 0.8 sq cm and 0.2 cm respectively, corresponds to an energy density of more than 5 J/cu cm. The charge x voltage factor is higher than 5 x 10 to the -6th s and the working voltage is over 1.6 V. The leakage current is lower than 3 microamps at room temperature. The electrolyte can be operated up to about 120 C if the device is hermetically sealed.

Gallbladder mucin production and calcium carbonate gallstones in children.

PubMed

Sayers, Craig; Wyatt, Judy; Soloway, Roger D; Taylor, Donald R; Stringer, Mark D

2007-03-01

In contrast to adults, calcium carbonate gallstones are relatively common in children. Their pathogenesis is poorly understood. Cystic duct obstruction promotes calcium carbonate formation in bile and increases gallbladder mucin production. We tested the hypothesis that mucin producing epithelial cells would be increased in gallbladders of children with calcium carbonate gallstones. Archival gallbladder specimens from 20 consecutive children who had undergone elective cholecystectomy for cholelithiasis were examined. In each case, gallstone composition was determined by Fourier transform infrared microspectroscopy. Gallbladder specimens from six children who had undergone cholecystectomy for conditions other than cholelithiasis during the same period were used as controls. Multiple sections were examined in a blinded fashion and scored semiquantitatively for mucin production using two stains (alcian blue and periodic acid-Schiff). Increased mucin staining was observed in 50% or more epithelial cells in five gallbladder specimens from seven children with calcium carbonate stones, compared to 5 of 13 with other stone types (P = 0.17) and none of the control gallbladders (P = 0.02). Gallbladders containing calcium carbonate stones were significantly more likely than those containing other stone types or controls to contain epithelial cells with the greatest mucin content (P = 0.03). Gallbladders containing calcium carbonate stones were also more likely to show the ulcer-associated cell lineage. These results demonstrate an increase in mucin producing epithelial cells in gallbladders from children containing calcium carbonate stones. This supports the hypothesis that cystic duct obstruction leading to increased gallbladder mucin production may play a role in the development of calcium carbonate gallstones in children.

Calcium acetate or calcium carbonate for hyperphosphatemia of hemodialysis patients: a meta-analysis.

PubMed

Wang, Yong; Xie, Guoqiang; Huang, Yuanhang; Zhang, Han; Yang, Bo; Mao, Zhiguo

2015-01-01

High levels of serum phosphorus both at baseline and during follow-up are associated with increased mortality in dialysis patients, and administration of phosphate binders was independently associated with improved survival among hemodialysis population. Calcium-based phosphate binders are the most commonly used phosphate binders in developing countries for their relatively low costs. To compare the efficacy and safety between calcium carbonate and calcium acetate in the treatment of hyperphosphatemia in hemodialysis patients. PubMed, EMBASE, Cochrane Library, Google scholar and Chinese databases (Wanfang, Weipu, National Knowledge Infrastructure of China) were searched for relevant studies published before March 2014. Reference lists of nephrology textbooks and review articles were checked. A meta-analysis of randomized controlled trials (RCTs) and quasi-RCTs that assessed the effects and adverse events of calcium acetate and calcium carbonate in adult patients with MHD was performed using Review Manager 5.0. A total of ten studies (625 participants) were included in this meta-analysis. There was insufficient data in all-cause mortality and cardiovascular events for meta-analysis. Compared with calcium carbonate group, the serum phosphorus was significantly lower in calcium acetate group after4 weeks' administration (MD -0.15 mmol/L, 95% CI -0.28 to -0.01) and after 8 weeks' administration (MD -0.25 mmol/L, 95% CI -0.40 to -0.11). There was no difference in serum calcium levels or the incidence of hypercalcemia between two groups at 4 weeks and 8 weeks. No statistical difference was found in parathyroid hormone (PTH) levels or serum calcium by phosphorus (Ca x P) product. There was significantly higher risk of intolerance with calcium acetate treatment (RR 3.46, 95% CI 1.48 to 8.26). For hyperphosphatemia treatment, calcium acetate showed better efficacy and with a higher incidence of intolerance compared with calcium carbonate. There are insufficient data to

Calcium Acetate or Calcium Carbonate for Hyperphosphatemia of Hemodialysis Patients: A Meta-Analysis

PubMed Central

Zhang, Han; Yang, Bo; Mao, Zhiguo

2015-01-01

Background High levels of serum phosphorus both at baseline and during follow-up are associated with increased mortality in dialysis patients, and administration of phosphate binders was independently associated with improved survival among hemodialysis population. Calcium-based phosphate binders are the most commonly used phosphate binders in developing countries for their relatively low costs. Objectives To compare the efficacy and safety between calcium carbonate and calcium acetate in the treatment of hyperphosphatemia in hemodialysis patients. Methods PubMed, EMBASE, Cochrane Library, Google scholar and Chinese databases (Wanfang, Weipu, National Knowledge Infrastructure of China) were searched for relevant studies published before March 2014. Reference lists of nephrology textbooks and review articles were checked. A meta-analysis of randomized controlled trials (RCTs) and quasi-RCTs that assessed the effects and adverse events of calcium acetate and calcium carbonate in adult patients with MHD was performed using Review Manager 5.0. Results A total of ten studies (625 participants) were included in this meta-analysis. There was insufficient data in all-cause mortality and cardiovascular events for meta-analysis. Compared with calcium carbonate group, the serum phosphorus was significantly lower in calcium acetate group after4 weeks’ administration (MD -0.15 mmol/L, 95% CI -0.28 to -0.01) and after 8 weeks’ administration (MD -0.25 mmol/L, 95% CI -0.40 to -0.11). There was no difference in serum calcium levels or the incidence of hypercalcemia between two groups at 4 weeks and 8 weeks. No statistical difference was found in parathyroid hormone (PTH) levels or serum calcium by phosphorus (Ca x P) product. There was significantly higher risk of intolerance with calcium acetate treatment (RR 3.46, 95% CI 1.48 to 8.26). Conclusions For hyperphosphatemia treatment, calcium acetate showed better efficacy and with a higher incidence of intolerance compared with

Phase transitions in biogenic amorphous calcium carbonate

NASA Astrophysics Data System (ADS)

Gong, Yutao

Geological calcium carbonate exists in both crystalline phases and amorphous phases. Compared with crystalline calcium carbonate, such as calcite, aragonite and vaterite, the amorphous calcium carbonate (ACC) is unstable. Unlike geological calcium carbonate crystals, crystalline sea urchin spicules (99.9 wt % calcium carbonate and 0.1 wt % proteins) do not present facets. To explain this property, crystal formation via amorphous precursors was proposed in theory. And previous research reported experimental evidence of ACC on the surface of forming sea urchin spicules. By using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), we studied cross-sections of fresh sea urchin spicules at different stages (36h, 48h and 72h after fertilization) and observed the transition sequence of three mineral phases: hydrated ACC → dehydrated ACC → biogenic calcite. In addition, we unexpectedly found hydrated ACC nanoparticles that are surrounded by biogenic calcite. This observation indicates the dehydration from hydrated ACC to dehydrated ACC is inhibited, resulting in stabilization of hydrated ACC nanoparticles. We thought that the dehydration was inhibited by protein matrix components occluded within the biomineral, and we designed an in vitro assay to test the hypothesis. By utilizing XANES-PEEM, we found that SM50, the most abundant occluded matrix protein in sea urchin spicules, has the function to stabilize hydrated ACC in vitro.

Phase transitions in biogenic amorphous calcium carbonate

PubMed Central

Gong, Yutao U. T.; Killian, Christopher E.; Olson, Ian C.; Appathurai, Narayana P.; Amasino, Audra L.; Martin, Michael C.; Holt, Liam J.; Wilt, Fred H.; Gilbert, P. U. P. A.

2012-01-01

Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC·H2O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC·H2O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC·H2O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC·H2O in vitro. PMID:22492931

Assessment of calcium addition on the removal of U(VI) in the alkaline conditions created by NH 3 gas

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

Katsenovich, Yelena; Cardona, Claudia; Szecsody, Jim

Remediation of uranium (U) contamination in the deep vadose zone (VZ) sediments abundant in calcite mineral is a challenging task considering the formation of highly stable and mobile uranyl complexes with carbonate and calcium in pore water composition. There is a concern that uranium contamination in the VZ can serve as a continued source for groundwater pollution, creating a risk to human health and the environment through the groundwater pathway. This requires in-situ remediation of the radionuclide-contaminated VZ to convert soluble U species to low solubility precipitates that are stable in the natural environment. Injection of reactive gasses (e.g., NHmore » 3) is a promising technology to decrease U mobility in the unsaturated zone without the addition of liquid amendments. The NH 3 injection creates alkaline conditions that can alter the sediment pore water composition due to a release of elements from minerals (via desorption and dissolution) that are present in the sediment. However, it is not known how VZ pore water constituents (Si, Al 3+, HCO 3 -, and Ca 2 +) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of major pore water constituents typically present in the arid and semi-arid environments of the western regions of the U.S and identified solid uranium-bearing phases that could potentially precipitate from solutions approximating pore water compositions after pH manipulations via ammonia gas injections. Triplicate samples were prepared using six Si (5, 50 100, 150, 200, and 250 mM), six HCO 3 - (0, 3, 25, 50, 75, and 100 mM), and two Ca 2+ (5 and 10 mM) concentrations. The concentration of aluminum and uranium was kept constant at 5 mM and 0.0084 mM, respectively, in all synthetic formulations tested. Results showed that the percentage of U(VI) removal was controlled by the Si/Al molar ratios and Ca 2+ concentrations. Regardless of the bicarbonate concentration tested, the percentage of U

Assessment of calcium addition on the removal of U(VI) in the alkaline conditions created by NH 3 gas

DOE PAGES

Katsenovich, Yelena; Cardona, Claudia; Szecsody, Jim; ...

2018-03-06

Remediation of uranium (U) contamination in the deep vadose zone (VZ) sediments abundant in calcite mineral is a challenging task considering the formation of highly stable and mobile uranyl complexes with carbonate and calcium in pore water composition. There is a concern that uranium contamination in the VZ can serve as a continued source for groundwater pollution, creating a risk to human health and the environment through the groundwater pathway. This requires in-situ remediation of the radionuclide-contaminated VZ to convert soluble U species to low solubility precipitates that are stable in the natural environment. Injection of reactive gasses (e.g., NHmore » 3) is a promising technology to decrease U mobility in the unsaturated zone without the addition of liquid amendments. The NH 3 injection creates alkaline conditions that can alter the sediment pore water composition due to a release of elements from minerals (via desorption and dissolution) that are present in the sediment. However, it is not known how VZ pore water constituents (Si, Al 3+, HCO 3 -, and Ca 2 +) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of major pore water constituents typically present in the arid and semi-arid environments of the western regions of the U.S and identified solid uranium-bearing phases that could potentially precipitate from solutions approximating pore water compositions after pH manipulations via ammonia gas injections. Triplicate samples were prepared using six Si (5, 50 100, 150, 200, and 250 mM), six HCO 3 - (0, 3, 25, 50, 75, and 100 mM), and two Ca 2+ (5 and 10 mM) concentrations. The concentration of aluminum and uranium was kept constant at 5 mM and 0.0084 mM, respectively, in all synthetic formulations tested. Results showed that the percentage of U(VI) removal was controlled by the Si/Al molar ratios and Ca 2+ concentrations. Regardless of the bicarbonate concentration tested, the percentage of U

A novel stable 3D luminescent uranyl complex for highly efficient and sensitive recognition of Ru3+ and biomolecules

NASA Astrophysics Data System (ADS)

Tian, Hong-Hong; Chen, Liang-Ting; Zhang, Rong-Lan; Zhao, Jian-She; Liu, Chi-Yang; Weng, Ng Seik

2018-02-01

A novel highly stable 3D luminescent uranyl coordination polymer, namely {[UO2(L)]·DMA}n (1), was assembled with uranyl salt and a glycine-derivative ligand [6-(carboxymethyl-amino)-4-oxo-4,5-dihydro-[1,3,5]triazin-2-ylamino]-acetic acid (H2L) under solvothermal reaction. Besides, It was found that complex 1 possesses excellent luminescent properties, particularly the efficient selectivity and sensitivity in the recognition of Ru3+, biomacromolecule bovine serum albumin (BSA), biological small molecules dopamine (DA), ascorbic acid (AA) and uric acid (UA) in the water solution based on a "turn-off" mechanism. Accordingly, the luminescent explorations also demonstrated that complex 1 could be acted as an efficient luminescent probe with high quenching efficiency and low detection limit for selectively detecting Ru3+ and biomolecules (DA, AA, UA and BSA). It was noted that the framework structure of complex 1 still remains highly stable after quenching, which was verified by powder X-ray diffraction (PXRD).

A Uranyl Peroxide Dimer in the Gas Phase

DOE PAGES

Dau, Phuong D.; Dau, Phuong V.; Rao, Linfeng; ...

2017-03-14

For this study, the gas-phase uranyl peroxide dimer, [(UO 2) 2(O2)(L) 2] 2+ where L = 2,2'-trifluoroethylazanediyl)bis(N,N'-dimethylacetamide), was synthesized by electrospray ionization of a solution of UO 2 2+ and L. Collision-induced dissociation of this dimer resulted in endothermic O atom elimination to give [(UO 2) 2(O)(L) 2] 2+, which was found to spontaneously react with water via exothermic hydrolytic chemisorption to yield [(UO 2) 2(OH) 2(L) 2] 2+. Density functional theory computations of the energies for the gas-phase reactions are in accord with observations. The structures of the observed uranyl dimer were computed, with that of the peroxide ofmore » particular interest, as a basis to evaluate the formation of condensed phase uranyl peroxides with bent structures. The computed dihedral angle in [(UO 2) 2(O 2)(L) 2] 2+ is 145°, indicating a substantial deviation from the planar structure with a dihedral angle of 180°. Energies needed to induce bending in the most elementary gas-phase uranyl peroxide complex, [(UO 2) 2(O 2)] 2+, were computed. It was found that bending from the lowest-energy planar structure to dihedral angles up to 140° required energies of <10 kJ/mol. The gas-phase results demonstrate the inherent stability of the uranyl peroxide moiety and support the notion that the uranyl-peroxide-uranyl structural unit is intrinsically planar, with only minor energy perturbations needed to form the bent structures found in studtite and uranyl peroxide nanostructures.« less

Seeded Growth Route to Noble Calcium Carbonate Nanocrystal.

PubMed

Islam, Aminul; Teo, Siow Hwa; Rahman, M Aminur; Taufiq-Yap, Yun Hin

2015-01-01

A solution-phase route has been considered as the most promising route to synthesize noble nanostructures. A majority of their synthesis approaches of calcium carbonate (CaCO3) are based on either using fungi or the CO2 bubbling methods. Here, we approached the preparation of nano-precipitated calcium carbonate single crystal from salmacis sphaeroides in the presence of zwitterionic or cationic biosurfactants without external source of CO2. The calcium carbonate crystals were rhombohedron structure and regularly shaped with side dimension ranging from 33-41 nm. The high degree of morphological control of CaCO3 nanocrystals suggested that surfactants are capable of strongly interacting with the CaCO3 surface and control the nucleation and growth direction of calcium carbonate nanocrystals. Finally, the mechanism of formation of nanocrystals in light of proposed routes was also discussed.

Seeded Growth Route to Noble Calcium Carbonate Nanocrystal

PubMed Central

Islam, Aminul; Teo, Siow Hwa; Rahman, M. Aminur; Taufiq-Yap, Yun Hin

2015-01-01

A solution-phase route has been considered as the most promising route to synthesize noble nanostructures. A majority of their synthesis approaches of calcium carbonate (CaCO3) are based on either using fungi or the CO2 bubbling methods. Here, we approached the preparation of nano-precipitated calcium carbonate single crystal from salmacis sphaeroides in the presence of zwitterionic or cationic biosurfactants without external source of CO2. The calcium carbonate crystals were rhombohedron structure and regularly shaped with side dimension ranging from 33–41 nm. The high degree of morphological control of CaCO3 nanocrystals suggested that surfactants are capable of strongly interacting with the CaCO3 surface and control the nucleation and growth direction of calcium carbonate nanocrystals. Finally, the mechanism of formation of nanocrystals in light of proposed routes was also discussed. PMID:26700479

Magnetically responsive calcium carbonate microcrystals.

PubMed

Fakhrullin, Rawil F; Bikmullin, Aidar G; Nurgaliev, Danis K

2009-09-01

Here we report the fabrication of magnetically responsive calcium carbonate microcrystals produced by coprecipitation of calcium carbonate in the presence of citrate-stabilized iron oxide nanoparticles. We demonstrate that the calcite microcrystals obtained possess superparamagnetic properties due to incorporated magnetite nanoparticles and can be manipulated by an external magnetic field. The microcrystals doped with magnetic nanoparticles were utilized as templates for the fabrication of hollow polyelectrolyte microcapsules, which retain the magnetic properties of the sacrificial cores and might be spatially manipulated using a permanent magnet, thus providing the magnetic-field-facilitated delivery and separation of materials templated on magnetically responsive calcite microcrystals.

Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents

DOE PAGES

Mehio, Nada; Ivanov, Alexander S.; Ladshaw, Austin P.; ...

2015-11-22

Poly(acrylamidoxime) fibers are the current state of the art adsorbent for mining uranium from seawater. However, the competition between uranyl (UO 2 2+) and vanadium ions poses a challenge to mining on the industrial scale. In this work, we employ density functional theory (DFT) and coupled-cluster methods (CCSD(T)) in the restricted formalism to investigate potential binding motifs of the oxovanadium(IV) ion (VO 2+) with the formamidoximate ligand. Consistent with experimental EXAFS data, the hydrated six-coordinate complex is predicted to be preferred over the hydrated five-coordinate complex. Here, our investigation of formamidoximate-VO 2+ complexes universally identified the most stable binding motifmore » formed by chelating a tautomerically rearranged imino hydroxylamine via the imino nitrogen and hydroxylamine oxygen. The alternative binding motifs for amidoxime chelation via a non-rearranged tautomer and 2 coordination are found to be ~11 kcal/mol less stable. Ultimately, the difference in the most stable VO 2+ and UO 2 2+ binding conformation has important implications for the design of more selective UO 2 2+ ligands.« less

Effect of carbonate and phosphate ratios on the transformation of calcium orthophosphates

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

Eliassi, Mohammad Daoud, E-mail: eliassi2007@gmail.com; Zhao, Wei; Tan, Wen Feng, E-mail: wenfeng.tan@hotmail.com

2014-07-01

Graphical abstract: Complexes among phosphate, carbonate and calcium have been prepared via a facile hydrothermal route. The synthesized product at the low (0.15) and the high (1.8) molar ratio of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} is calcium phosphate hydrate and hydroxylapatite (HAp), respectively. Molar ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} are effective on the reduction of carbonate activity during the crystallization of HAp. - Highlights: • Formation of different complexes from CO{sub 3}{sup 2−}, PO{sub 4}{sup 3−} and Ca{sup 2+} solutions at 60 °C. • Molar ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2} cause changes in phase and sizemore » of synthesized products. • Addition of PO{sub 4}{sup 3} inhibited the activity of CO{sub 3}{sup 2−} during bound with Ca{sup 2+}. • The phase transformation was completed, when CO{sub 3}{sup 2−} peaks disappeared in FTIR. • PO{sub 4}{sup 3−}, CO{sub 3}{sup 2−} and Ca{sup 2+} distributed heterogeneously on the surface of precipitation. - Abstract: Complexes among phosphate, carbonate and calcium have been synthesized by a designed hydrothermal method. Effects of carbonate and phosphate ratios on the transformation of calcium-orthophosphates were investigated. With X-ray diffraction measurement the synthesized product at the low (0.15) and the high (1.8) molar ratio of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} is calcium phosphate hydrate at pH 9.0, and hydroxylapatite (HAp) at pH 8.0, respectively. Fourier transform infrared spectroscopy of product at the high ratio (1.8) of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} shows that the CO{sub 3}{sup 2−} peaks disappear, and the strong peaks at 1412 and 1460 cm{sup −1} are assigned to the vibrations of PO{sub 4}{sup 3−} in HAp. {sup 31}P nuclear magnetic resonance spectra of products at the low (0.15–0.6) to the high (1.2–1.8) ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} are obtained at 2.9 and 2.7 ppm, respectively. Molar ratios

Influence of Calcium on Microbial Reduction of Solid Phase Uranium (VI)

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

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M.

2007-06-27

The effect of calcium on microbial reduction of a solid phase U(VI), sodium boltwoodite (NaUO2SiO3OH ∙1.5H2O), was evaluated in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. Batch experiments were performed in a non-growth bicarbonate medium with lactate as electron donor at pH 7 buffered with PIPES. Calcium increased both the rate and extent of Na-boltwoodite dissolution by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) revealed that microbial reductionmore » of solid phase U(VI) is a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. The overall rates of microbial reduction of solid phase U(VI) can be described by the coupled rates of dissolution and microbial reduction that were both influenced by calcium. The results demonstrated that dissolved U(VI) concentration during microbial reduction was a complex function of solid phase U(VI) dissolution kinetics, aqueous U(VI) speciation, and microbial activity.« less

Calcination of calcium carbonate and blend therefor

DOEpatents

Mallow, William A.; Dziuk, Jr., Jerome J.

1989-01-01

A method for calcination of a calcium carbonate material comprising heating the calcium carbonate material to a temperature and for a time sufficient to calcine the material to the degree desired while in the presence of a catalyst; said catalyst comprising at least one fused salt having the formula MCO.sub.3.CaCO.sub.3.CaO.H.sub.2 O.sub.x, wherein M is an alkali metal and x is 0 to 1 and formed by fusing MCO.sub.3 and CaCO.sub.3 in a molar ratio of about 1:2 to 2:1, and a blend adapted to be heated to CaO comprising a calcium carbonate material and at least one such fused salt.

Quantitative in vivo Analyses Reveal Calcium-dependent Phosphorylation Sites and Identifies a Novel Component of the Toxoplasma Invasion Motor Complex

PubMed Central

Nebl, Thomas; Prieto, Judith Helena; Kapp, Eugene; Smith, Brian J.; Williams, Melanie J.; Yates, John R.; Cowman, Alan F.; Tonkin, Christopher J.

2011-01-01

Apicomplexan parasites depend on the invasion of host cells for survival and proliferation. Calcium-dependent signaling pathways appear to be essential for micronemal release and gliding motility, yet the target of activated kinases remains largely unknown. We have characterized calcium-dependent phosphorylation events during Toxoplasma host cell invasion. Stimulation of live tachyzoites with Ca2+-mobilizing drugs leads to phosphorylation of numerous parasite proteins, as shown by differential 2-DE display of 32[P]-labeled protein extracts. Multi-dimensional Protein Identification Technology (MudPIT) identified ∼546 phosphorylation sites on over 300 Toxoplasma proteins, including 10 sites on the actomyosin invasion motor. Using a Stable Isotope of Amino Acids in Culture (SILAC)-based quantitative LC-MS/MS analyses we monitored changes in the abundance and phosphorylation of the invasion motor complex and defined Ca2+-dependent phosphorylation patterns on three of its components - GAP45, MLC1 and MyoA. Furthermore, calcium-dependent phosphorylation of six residues across GAP45, MLC1 and MyoA is correlated with invasion motor activity. By analyzing proteins that appear to associate more strongly with the invasion motor upon calcium stimulation we have also identified a novel 15-kDa Calmodulin-like protein that likely represents the MyoA Essential Light Chain of the Toxoplasma invasion motor. This suggests that invasion motor activity could be regulated not only by phosphorylation but also by the direct binding of calcium ions to this new component. PMID:21980283

Calcium carbonate does not affect nilotinib pharmacokinetics in healthy volunteers.

PubMed

Tawbi, Hussein A; Tran, An L; Christner, Susan M; Lin, Yan; Johnson, Matthew; Mowrey, Emily; Appleman, Leonard R; Stoller, Ronald; Miller, Brian M; Egorin, Merrill J; Beumer, Jan H

2013-11-01

Gastric upset is a common side effect of nilotinib therapy, and calcium carbonate is frequently used concomitantly, either as antacid or as calcium supplementation. With the increasing number of oral agents in cancer therapy, oral drug-drug interactions are becoming more relevant. Nilotinib has already been shown to be absorbed to a much lesser extent when co-administered with proton pump inhibitors. Because exposure to sub-therapeutic concentrations of anticancer drugs such as nilotinib may result in selection of resistant clones and ultimately relapse, we studied the effect of a calcium carbonate supplement (Tums Ultra 1000®) on nilotinib pharmacokinetics. Calcium carbonate may be co-administered with nilotinib without significantly affecting the pharmacokinetics of nilotinib and potentially impacting efficacy. Nilotinib is a second-generation oral tyrosine kinase inhibitor with superior efficacy compared with imatinib mesylate in the treatment for chronic phase chronic myelogenous leukemia. Calcium carbonate is commonly used as a source of calcium supplementation or as antacid to ameliorate the gastrointestinal side effects associated with nilotinib, which could have unknown effects on nilotinib absorption. The purpose of this study was to provide information on the effect of calcium carbonate on the PK of nilotinib in healthy volunteers. Healthy subjects were enrolled in a two-period, open-label, single-institution, randomized, cross-over, fixed-schedule study. In one period, each subject received 400 mg of nilotinib p.o. In the other period, 4,000 mg of calcium carbonate (4 X Tums Ultra 1000®) was administered p.o. 15 min prior to the nilotinib dose. Plasma samples were collected at specified timepoints, concentrations of nilotinib were quantitated by LC-MS, and data were analyzed non-compartmentally. Eleven subjects were evaluable. Calcium supplementation did not significantly affect nilotinib pharmacokinetic parameters including area under the plasma

Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions.

PubMed

Thuéry, Pierre; Harrowfield, Jack

2016-03-07

Twelve new complexes were obtained from reaction of uranyl ions with the aliphatic dicarboxylic acids HOOC-(CH2)n-2-COOH (H2Cn; n = 7-10 and 12) under solvo-hydrothermal conditions, in the presence of 3d-block metal ions (Mn(2+), Fe(3+), Co(2+), Ni(2+), and Cu(2+)) and 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen). In contrast to previously reported triple-stranded helicates obtained with C9(2-) and C12(2-), all these complexes crystallize as polymeric one-dimensional (1D) or two-dimensional (2D) species. [Fe(bipy)3][(UO2)2(C7)3]·3H2O (1), [Cu(phen)2]2[(UO2)3(C7)4(H2O)2]·2H2O (2), and [Cu(bipy)2]2[(UO2)2(C9)3] (6), in which the 3d cation was reduced in situ, are 1D ladderlike polymers displaying tetra- or hexanuclear rings, of sufficient width to encompass two counterions in 2 and 6. The three complexes [Co(phen)3][(UO2)3(C8)3(O)]·H2O (3), [Ni(phen)3][(UO2)3(C8)3(O)]·H2O (4) and [Co(phen)3][(UO2)3(C9)3(O)]·H2O (5) contain bis(μ3-oxo)-bridged tetranuclear secondary building units, and they crystallize as deeply furrowed 2D assemblies. Depending on the nature of the counterion, C10(2-) gives [Ni(bipy)3][(UO2)2(C10)3]·2H2O (7), a 2D network displaying elongated decanuclear rings containing the counterions, or [Mn(phen)3][(UO2)2(C10)3]·6H2O (8), [Co(phen)3][(UO2)2(C10)3]·7H2O (9), and [Ni(phen)3][(UO2)2(C10)3]·7H2O (10), which consist of 2D assemblies with honeycomb topology; the hexanuclear rings in 8-10 are chairlike and occupied by one counterion and two uranyl groups from neighboring layers. Two complexes of the ligand with the longest chain, C12(2-), are reported. [UO2(C12)(bipy)] (11) is a neutral 1D species in which bipy chelates the uranyl ion and plays an important role in the packing through π-stacking interactions. Two polymeric units, 1D and 2D, coexist in the complex [Ni(bipy)3][(UO2)2(C12)3][UO2(C12)(H2O)2]·H2O (12); the 2D network has the honeycomb topology, but the hexanuclear rings are markedly convoluted, with local features akin to

Solubility and bioavailability of stabilized amorphous calcium carbonate.

PubMed

Meiron, Oren E; Bar-David, Elad; Aflalo, Eliahu D; Shechter, Assaf; Stepensky, David; Berman, Amir; Sagi, Amir

2011-02-01

Since its role in the prevention of osteoporosis in humans was proven some 30 years ago, calcium bioavailability has been the subject of numerous scientific studies. Recent technology allowing the production of a stable amorphous calcium carbonate (ACC) now enables a bioavailability analysis of this unique form of calcium. This study thus compares the solubility and fractional absorption of ACC, ACC with chitosan (ACC-C), and crystalline calcium carbonate (CCC). Solubility was evaluated by dissolving these preparations in dilute phosphoric acid. The results demonstrated that both ACC and ACC-C are more soluble than CCC. Fractional absorption was evaluated by intrinsically labeling calcium carbonate preparations with (45)Ca, orally administrated to rats using gelatin capsules. Fractional absorption was determined by evaluating the percentage of the administrated radioactive dose per milliliter that was measured in the serum, calcium absorption in the femur, and whole-body retention over a 34-hour period. Calcium serum analysis revealed that calcium absorption from ACC and ACC-C preparations was up to 40% higher than from CCC, whereas retention of ACC and ACC-C was up to 26.5% higher than CCC. Absorbed calcium in the femurs of ACC-administrated rats was 30% higher than in CCC-treated animals, whereas 15% more calcium was absorbed following ACC-C treatment than following CCC treatment. This study demonstrates the enhanced solubility and bioavailability of ACC over CCC. The use of stable ACC as a highly bioavailable dietary source for calcium is proposed based on the findings of this study. Copyright © 2011 American Society for Bone and Mineral Research.

Granule fraction inhomogeneity of calcium carbonate/sorbitol in roller compacted granules.

PubMed

Bacher, C; Olsen, P M; Bertelsen, P; Sonnergaard, J M

2008-02-12

The granule fraction inhomogeneity of roller compacted granules was examined on mixtures of three different morphologic forms of calcium carbonate and three particle sizes of sorbitol. The granule fraction inhomogeneity was determined by the distribution of the calcium carbonate in each of the 10 size fractions between 0 and 2000 microm and by calculating the demixing potential. Significant inhomogeneous occurrence of calcium carbonate in the size fractions was demonstrated, depending mostly on the particles sizes of sorbitol but also on the morphological forms of calcium carbonate. The heterogeneous distribution of calcium carbonate was related to the decrease in compactibility of roller compacted granules in comparison to the ungranulated materials. This phenomenon was explained by a mechanism where fracturing of the ribbon during granulation occurred at the weakest interparticulate bonds (the calcium carbonate: calcium carbonate bonds) and consequently exposed the weakest areas of bond formation on the surface of the granules. Accordingly, the non-uniform allocation of the interparticulate attractive forces in a tablet would cause a lowering of the compactibility. Furthermore, the ability of the powder to agglomerate in the roller compactor was demonstrated to be related to the ability of the powder to be compacted into a tablet, thus the most compactable calcium carbonate and the smallest sized sorbitol improved the homogeneity by decreasing the demixing potential.

New agent to treat elevated phosphate levels: magnesium carbonate/calcium carbonate tablets.

PubMed

Meyer, Caitlin; Cameron, Karen; Battistella, Marisa

2012-01-01

In summary, Binaphos CM, a magnesium carbonate/calcium carbonate combination phosphate binder, is marketed for treating elevated phosphate levels in dialysis patients. Although studies using magnesium/calcium carbonate as a phosphate binder are short term with small numbers of patients, this phosphate binder has shown some promising results and may provide clinicians with an alternative for phosphate binding. Using a combination phosphate binder may reduce pill burden and encourage patient compliance. In addition to calcium and phosphate, it is imperative to diligently monitor magnesium levels in patients started on this medication, as magnesium levels may increase with longer duration of use. Additional randomized controlled trials are necessary to evaluate long-term efficacy and safety of this combination phosphate binder.

Increased calcium absorption from synthetic stable amorphous calcium carbonate: Double-blind randomized crossover clinical trial in post-menopausal women

USDA-ARS?s Scientific Manuscript database

Calcium supplementation is a widely recognized strategy for achieving adequate calcium intake. We designed this blinded, randomized, crossover interventional trial to compare the bioavailability of a new stable synthetic amorphous calcium carbonate (ACC) with that of crystalline calcium carbonate (C...

Presence and dehydration of ikaite, calcium carbonate hexahydrate, in frozen shrimp shell.

PubMed

Mikkelsen, A; Andersen, A B; Engelsen, S B; Hansen, H C; Larsen, O; Skibsted, L H

1999-03-01

Ikaite, calcium carbonate hexahydrate, has by means of X-ray diffraction analyses of frozen samples been identified as the mineral component of the white spots formed in the shell of frozen shrimp during storage. When the shrimp thaw and the shell material is dried and kept at room temperature, ikaite rapidly transforms into a mixture of anhydrous calcium carbonate forms. X-ray diffraction analyses and Raman spectra of synthetic ikaite as well as the dehydration product confirm the assignments, and the rate constant for dehydration is approximately 7 x 10(-)(4) s(-)(1) at ambient temperature. Differential scanning calorimetry showed that dehydration of synthetic ikaite is an entropy-driven, athermal process and confirms that a single first-order reaction is rate-determining. Ikaite is found to be stable in aqueous solution at temperatures below 5 degrees C and in the shell of frozen shrimps but decomposes on thawing to form anhydrous calcium carbonates.

Amorphous Calcium Carbonate in Biomineralization: Stable and Precursor Phases

NASA Astrophysics Data System (ADS)

Weiner, S.

2003-12-01

The biological formation of the crystalline polymorphs of calcium carbonate, aragonite and calcite, is widespread. The less stable polymorphs, vaterite and monohydrocalcite are also formed by some organisms. Surprisingly, the highly unstable phase, amorphous calcium carbonate (ACC), is formed by a variety of organisms from different phyla. Most of these are stable at least within the lifetime of the organism. The stable forms all have a stoichiometry of CaCO3.H2O. Despite the fact that they do not diffract X-rays. Studies of their short range order by EXAFS, reveal species specific variations in the number and distances of atoms that surround the calcium ion. Proteins extracted from stable biogenic ACC are able to stabilize the phase in vitro. ACC has also been identified as a transient precursor phase during the formation of the calcitic larval spicule of the sea urchin and the formation of the larval shell of a bivalve. The transient form has little or no water associated with the CaCO3. Preliminary EXAFS data suggest that the short range order of the sea urchin spicule transient ACC resembles calcite. Proteins extracted from these spicules are able to stabilize ACC provided Mg is present in the solution. As the mollusks and the echinoderms are on two different branches of the animal phylogenetic tree, it is conceivable that the strategy of using ACC as a precursor phase at least for larval mineralization may be widespread. It has yet to be shown that it is used by adults of either phylum. The manner in which organisms precipitate, stabilize and destabilize if necessary, this highly metastable phase of calcium carbonate presents many fascinating and enigmatic questions, whose solutions could well contribute to a better understanding of basic processes in biomineralization. For more details and references, see Addadi, L., Raz, S. and Weiner, S. (2003). Taking advantage of disorder: Amorphous calcium carbonate and its roles in biomineralization. Adv. Mat.15, 959-970.

Formate oxidation-driven calcium carbonate precipitation by Methylocystis parvus OBBP.

PubMed

Ganendra, Giovanni; De Muynck, Willem; Ho, Adrian; Arvaniti, Eleni Charalampous; Hosseinkhani, Baharak; Ramos, Jose Angel; Rahier, Hubert; Boon, Nico

2014-08-01

Microbially induced carbonate precipitation (MICP) applied in the construction industry poses several disadvantages such asammonia release to the air and nitric acid production. An alternative MICP from calcium formate by Methylocystis parvus OBBP is presented here to overcome these disadvantages. To induce calcium carbonate precipitation, M. parvus was incubated at different calcium formate concentrations and starting culture densities. Up to 91.4% ± 1.6% of the initial calcium was precipitated in the methane-amended cultures compared to 35.1% ± 11.9% when methane was not added. Because the bacteria could only utilize methane for growth, higher culture densities and subsequently calcium removals were exhibited in the cultures when methane was added. A higher calcium carbonate precipitate yield was obtained when higher culture densities were used but not necessarily when more calcium formate was added. This was mainly due to salt inhibition of the bacterial activity at a high calcium formate concentration. A maximum 0.67 ± 0.03 g of CaCO3 g of Ca(CHOOH)2(-1) calcium carbonate precipitate yield was obtained when a culture of 10(9) cells ml(-1) and 5 g of calcium formate liter(-)1 were used. Compared to the current strategy employing biogenic urea degradation as the basis for MICP, our approach presents significant improvements in the environmental sustainability of the application in the construction industry.

Formate Oxidation-Driven Calcium Carbonate Precipitation by Methylocystis parvus OBBP

PubMed Central

Ganendra, Giovanni; De Muynck, Willem; Ho, Adrian; Arvaniti, Eleni Charalampous; Hosseinkhani, Baharak; Ramos, Jose Angel; Rahier, Hubert

2014-01-01

Microbially induced carbonate precipitation (MICP) applied in the construction industry poses several disadvantages such as ammonia release to the air and nitric acid production. An alternative MICP from calcium formate by Methylocystis parvus OBBP is presented here to overcome these disadvantages. To induce calcium carbonate precipitation, M. parvus was incubated at different calcium formate concentrations and starting culture densities. Up to 91.4% ± 1.6% of the initial calcium was precipitated in the methane-amended cultures compared to 35.1% ± 11.9% when methane was not added. Because the bacteria could only utilize methane for growth, higher culture densities and subsequently calcium removals were exhibited in the cultures when methane was added. A higher calcium carbonate precipitate yield was obtained when higher culture densities were used but not necessarily when more calcium formate was added. This was mainly due to salt inhibition of the bacterial activity at a high calcium formate concentration. A maximum 0.67 ± 0.03 g of CaCO3 g of Ca(CHOOH)2−1 calcium carbonate precipitate yield was obtained when a culture of 109 cells ml−1 and 5 g of calcium formate liter−1 were used. Compared to the current strategy employing biogenic urea degradation as the basis for MICP, our approach presents significant improvements in the environmental sustainability of the application in the construction industry. PMID:24837386

40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Calcium Carbonate Production Subcategory § 415.300 Applicability; description of the calcium carbonate production subcategory. The provisions of this subpart are applicable to discharges...

40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Calcium Carbonate Production Subcategory § 415.300 Applicability; description of the calcium carbonate production subcategory. The provisions of this subpart are applicable to discharges...

40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Calcium Carbonate Production Subcategory § 415.300 Applicability; description of the calcium carbonate production subcategory. The provisions of this subpart are applicable to discharges...

40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Calcium Carbonate Production Subcategory § 415.300 Applicability; description of the calcium carbonate production subcategory. The provisions of this subpart are applicable to discharges...

40 CFR 415.300 - Applicability; description of the calcium carbonate production subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... calcium carbonate production subcategory. 415.300 Section 415.300 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Calcium Carbonate Production Subcategory § 415.300 Applicability; description of the calcium carbonate production subcategory. The provisions of this subpart are applicable to discharges...

Image-based Modeling of Biofilm-induced Calcium Carbonate Precipitation

NASA Astrophysics Data System (ADS)

Connolly, J. M.; Rothman, A.; Jackson, B.; Klapper, I.; Cunningham, A. B.; Gerlach, R.

2013-12-01

Pore scale biological processes in the subsurface environment are important to understand in relation to many engineering applications including environmental contaminant remediation, geologic carbon sequestration, and petroleum production. Specifically, biofilm induced calcium carbonate precipitation has been identified as an attractive option to reduce permeability in a lasting way in the subsurface. This technology may be able to replace typical cement-based grouting in some circumstances; however, pore-scale processes must be better understood for it to be applied in a controlled manor. The work presented will focus on efforts to observe biofilm growth and ureolysis-induced mineral precipitation in micro-fabricated flow cells combined with finite element modelling as a tool to predict local chemical gradients of interest (see figure). We have been able to observe this phenomenon over time using a novel model organism that is able to hydrolyse urea and express a fluorescent protein allowing for non-invasive observation over time with confocal microscopy. The results of this study show the likely existence of a wide range of local saturation indices even in a small (1 cm length scale) experimental system. Interestingly, the locations of high predicted index do not correspond to the locations of higher precipitation density, highlighting the need for further understanding. Figure 1 - A micro-fabricated flow cell containing biofilm-induced calcium carbonate precipitation. (A) Experimental results: Active biofilm is in green and dark circles are calcium carbonate crystals. Note the channeling behavior in the top of the image, leaving a large hydraulically inactive area in the biofilm mass. (B) Finite element model: The prediction of relative saturation of calcium carbonate (as calcite). Fluid enters the system at a low saturation state (blue) but areas of high supersaturation (red) are predicted within the hydraulically inactive area in the biofilm. If only effluent

In-Situ Production of Calcium Carbonate Nanoparticles in Fresh Concrete Using Pre-carbonation Method

NASA Astrophysics Data System (ADS)

Qian, Xin

To reduce the carbon footprint of ordinary Portland cement (OPC)-based concrete, a novel technique, pre-carbonation process, has been developed to produce CaCO3 nanoparticles in fresh concrete. In this technique, gaseous CO2 is first absorbed into a slurry of calcium-rich minerals which is then blended with other ingredients to produce mortar/concrete. The objective of this work is to obtain an in-depth understanding of the underlying scientific mechanisms associated with the enhancement of strength and durability of the concrete induced by the new method. A comprehensive research plan has been carried out to study the carbonated slaked lime slurry and the effect of carbonated slaked lime slurry on the performance of OPC-based concrete, and to evaluate the potentials of the pre-carbonation method. Experimental studies show that carbonating the calcium-rich mineral slurry with CO2 can produce CaCO3 nanoparticles and Ca(HCO 3)2 in the slurry, and these carbonation products were dictated by four parameters of the pre-carbonation method: the duration and temperature of the carbonation, the concentration of the calcium source slurry, and the stirring method of the calcium source slurry during the carbonation. The mechanical properties and durability of the mortar/concrete made with the carbonated slurry were significantly improved, which can be attributed to major mechanisms induced by the pre-carbonation method: promoted hydration of the cement and denser microstructure of the mortar/concrete. Calorimetry testing showed that the hydration of OPC was greatly improved by the pre-carbonation because of the extra heterogenous nucleation sites provided by the CaCO3 nanoparticles. XRD and TGA results revealed that more ettringite was produced in the mortar/concrete with pre-carbonated slaked lime slurry. The overall volume of the hydration products of the cement was increased by the pre-carbonation, leading to denser microstructure of the mortar/concrete. It has been found

Nacre-like calcium carbonate controlled by ionic liquid/graphene oxide composite template.

PubMed

Yao, Chengli; Xie, Anjian; Shen, Yuhua; Zhu, Jinmiao; Li, Hongying

2015-06-01

Nacre-like calcium carbonate nanostructures have been mediated by an ionic liquid (IL)-graphene oxide (GO) composite template. The resultant crystals were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, and X-ray powder diffractometry (XRD). The results showed that either 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4) or graphene oxide can act as a soft template for calcium carbonate formation with unusual morphologies. Based on the time-dependent morphology changes of calcium carbonate particles, it is concluded that nacre-like calcium carbonate nanostructures can be formed gradually utilizing [BMIM]BF4/GO composite template. During the process of calcium carbonate formation, [BMIM]BF4 acted not only as solvents but also as morphology templates for the fabrication of calcium carbonate materials with nacre-like morphology. Based on the observations, the possible mechanisms were also discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of Strength Enhancement of Soil Treated with Environment-Friendly Calcium Carbonate Powder

PubMed Central

Park, Kyungho; Jun, Sangju; Kim, Daehyeon

2014-01-01

This study aims to investigate the effects of the strength improvement of soft ground (sand) by producing calcium carbonate powder through microbial reactions. To analyze the cementation effect of calcium carbonate produced through microbial reaction for different weight ratios, four different types of specimens (untreated, calcium carbonate, cement, and calcium carbonate + cement) with different weight ratios (2%, 4%, 6%, and 8%) were produced and cured for a period of 3 days, 7 days, 14 days, 21 days, and 28 days to test them. The uniaxial compression strength of specimens was measured, and the components in the specimen depending on the curing period were analyzed by means of XRD analysis. The result revealed that higher weight ratios and longer curing period contributed to increased strength of calcium carbonate, cement, and calcium carbonate + cement specimens. The calcium carbonate and the calcium carbonate + cement specimens in the same condition showed the tendency of decreased strength approximately 3 times and two times in comparison with the 8% cement specimens cured for 28 days, but the tendency of increased strength was approximately 4 times and 6 times in comparison with the untreated specimen. PMID:24688401

Effect of strength enhancement of soil treated with environment-friendly calcium carbonate powder.

PubMed

Park, Kyungho; Jun, Sangju; Kim, Daehyeon

2014-01-01

This study aims to investigate the effects of the strength improvement of soft ground (sand) by producing calcium carbonate powder through microbial reactions. To analyze the cementation effect of calcium carbonate produced through microbial reaction for different weight ratios, four different types of specimens (untreated, calcium carbonate, cement, and calcium carbonate + cement) with different weight ratios (2%, 4%, 6%, and 8%) were produced and cured for a period of 3 days, 7 days, 14 days, 21 days, and 28 days to test them. The uniaxial compression strength of specimens was measured, and the components in the specimen depending on the curing period were analyzed by means of XRD analysis. The result revealed that higher weight ratios and longer curing period contributed to increased strength of calcium carbonate, cement, and calcium carbonate + cement specimens. The calcium carbonate and the calcium carbonate + cement specimens in the same condition showed the tendency of decreased strength approximately 3 times and two times in comparison with the 8% cement specimens cured for 28 days, but the tendency of increased strength was approximately 4 times and 6 times in comparison with the untreated specimen.

Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments

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

Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.

Scale-dependency of uranyl[U(VI)] surface complexation rates was investigated in stirred flow-cell and column systems using a U(VI)-contaminated sediment from the US Department of Energy, Hanford site, WA. The experimental results were used to estimate the apparent rate of U(VI) surface complexation at the grain-scale and in porous media. Numerical simulations using molecular, pore-scale, and continuum models were performed to provide insights into and to estimate the rate constants of U(VI) surface complexation at the different scales. The results showed that the grain-scale rate constant of U(VI) surface complexation was over 3 to 10 orders of magnitude smaller, dependent on themore » temporal scale, than the rate constant calculated using the molecular simulations. The grain-scale rate was faster initially and slower with time, showing the temporal scale-dependency. The largest rate constant at the grain-scale decreased additional 2 orders of magnitude when the rate was scaled to the porous media in the column. The scaling effect from the grain-scale to the porous media became less important for the slower sorption sites. Pore-scale simulations revealed the importance of coupled mass transport and reactions in both intragranular and inter-granular domains, which caused both spatial and temporal dependence of U(VI) surface complexation rates in the sediment. Pore-scale simulations also revealed a new rate-limiting mechanism in the intragranular porous domains that the rate of coupled diffusion and surface complexation reaction was slower than either process alone. The results provided important implications for developing models to scale geochemical/biogeochemical reactions.« less

Interfacial Interaction of Titania Nanoparticles and Ligated Uranyl Species: A Relativistic DFT Investigation.

PubMed

Zhao, Hong-Bo; Zheng, Ming; Schreckenbach, Georg; Pan, Qing-Jiang

2017-03-06

To understand interfacial behavior of actinides adsorbed onto mineral surfaces and unravel their structure-property relationship, the structures, electronic properties, and energetics of various ligated uranyl species adsorbed onto TiO 2 surface nanoparticle clusters (SNCs) were examined using relativistic density functional theory. Rutile (110) and anatase (101) titania surfaces, experimentally known to be stable, were fully optimized. For the former, models studied include clean and water-free Ti 27 O 64 H 20 (dry), partially hydrated (Ti 27 O 64 H 20 )(H 2 O) 8 (sol) and proton-saturated [(Ti 27 O 64 H 20 )(H 2 O) 8 (H) 2 ] 2+ (sat), while defect-free and defected anatase SNCs involving more than 38 TiO 2 units were considered. The aquouranyl sorption onto rutile SNCs is energetically preferred, with interaction energies of -8.54, -10.36, and -2.39 eV, respectively. Energy decomposition demonstrates that the sorption is dominated by orbital attractive interactions and modified by steric effects. Greater hydrogen-bonding involvement leads to increased orbital interactions (i.e., more negative energy) from dry to sol/sat complexes, while much larger steric interaction in the sat complex significantly reduces the sorption interaction (i.e., more positive energy). For dry SNC, adsorbates were varied from aquo to aquo-carbonato, to carbonato, to hydroxo uranyl species. Longer U-O surf /U-Ti distances and more positive sorption energies were calculated upon introducing carbonato and hydroxo ligands, indicative of weaker uranyl sorption onto the substrate. This is consistent with experimental observations that the uranyl sorption rate decreases upon raising solution pH value or adding carbon dioxide. Anatase SNCs adsorbing aquouranyl are even more exothermic, because more bonds are formed than in the case of rutile. Moreover, the anatase sorption can be tuned by surface defects as well as its Ti and O stoichiometry. All the aquouranyl-SNC complexes show similar

Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

NASA Astrophysics Data System (ADS)

Turchyn, Alexandra V.; DePaolo, Donald J.

2011-11-01

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ 44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ 44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ 44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ 44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these

A comparative study of calcium absorption following a single serving administration of calcium carbonate powder versus calcium citrate tablets in healthy premenopausal women

PubMed Central

Wang, Haiyuan; Bua, Peter; Capodice, Jillian

2014-01-01

Background Calcium is an essential mineral often taken as a daily, long-term nutritional supplement. Data suggests that once-daily dosing is important with regard to long-term compliance of both drugs and nutritional supplements. Objective This study was undertaken to compare the bioavailability of a single serving of two calcium supplements in healthy, premenopausal women. Design A two-period, crossover bioavailability study of a single serving of calcium citrate tablets (two tablets=500 mg calcium) versus a single serving of calcium carbonate powder (one packet of powder=1,000 mg calcium) was performed in healthy women aged between 25 and 45. All subjects were on a calcium-restricted diet 7 days prior to testing and fasted for 12 h before being evaluated at 0, 1, 2, and 4 h after oral administration of the test agents. Blood measurements for total and ionized calcium and parathyroid hormone were performed and adverse events were monitored. Results Twenty-three women were evaluable with a mean age of 33.2±8.71. Results showed that administration of a single serving of a calcium carbonate powder resulted in greater absorption in total and ionized calcium versus a single serving of calcium citrate tablets at 4 h (4.25±0.21 vs. 4.16±0.16, p=0.001). There were minimal side effects and no reported serious adverse events. Conclusions This study shows that a single serving of a calcium carbonate powder is more bioavailable than a single serving of calcium citrate tablets. This may be beneficial for long-term compliance. PMID:24772062

Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

USGS Publications Warehouse

Arai, Y.; McBeath, M.; Bargar, J.R.; Joye, J.; Davis, J.A.

2006-01-01

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ???7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 ??M, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and ?? charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in

An experimental model for calcium carbonate urolithiasis in goats

PubMed Central

Dominguez, Brandon J.; Deveau, Michael A.

2018-01-01

Background Calcium carbonate is a common urolith type in small ruminants with no high‐yield experimental model to evaluate animal susceptibility or preventative measure response. Hypothesis That novel plastic winged implants would allow accumulation and quantification of calcium carbonate calculus formation in goats on a high‐calcium diet and identify individual variation between goats in the mass of calculi produced. Animals Eight nonpregnant 3‐ and 4‐year‐old Boer‐cross does, weighing 22.3–39.5 kg, determined to be healthy based on physical examination, were used in these experiments. Methods Prospective cohort study for in vivo experimental model development. Implants were placed into the urinary bladder lumen in 8 goats over 2 evaluation periods. The alfalfa‐based ration had a total ration Ca : P of 3.29 and 3.84 : 1, respectively. Urine was collected at 0, 28, 56, and 84 days in the 1st experiment; blood and urine at those timepoints in the 2nd experiment. For each evaluation period, the implants were removed 84 days after implantation and weighed. Accumulated calculi mass was calculated and compared between goats and was analyzed for composition. Results Implant retention was 100% and 86% in the 2 studies. All goats with retained implants accumulated calcium carbonate at a mean implant gain per day across studies ranging from 0.44 to 57.45 mg. Two goats accumulated (0.44–7.65 mg/day and 33.64 & 57.45 mg/day) significantly more urolith material than the cohort across both studies (P = .047). No routine analytes on blood or urine were found to be explanatory for the difference observed. Conclusions and Clinical Importance These findings form a basis for implant and diet selection for use in future studies of urolithiasis development and for studies regarding individual susceptibility to urolithiasis. PMID:29524246

Randomized crossover study comparing the phosphate-binding efficacy of calcium ketoglutarate versus calcium carbonate in patients on chronic hemodialysis.

PubMed

Bro, S; Rasmussen, R A; Handberg, J; Olgaard, K; Feldt-Rasmussen, B

1998-02-01

The objective of the study was to evaluate the phosphate-binding efficacy, side effects, and cost of therapy of calcium ketoglutarate granulate as compared with calcium carbonate tablets in patients on chronic hemodialysis. The study design used was a randomized, crossover open trial, and the main outcome measurements were plasma ionized calcium levels, plasma phosphate levels, plasma intact parathyroid hormone (PTH) levels, requirements for supplemental aluminum-aminoacetate therapy, patient tolerance, and cost of therapy. Nineteen patients on chronic hemodialysis were treated with a dialysate calcium concentration of 1.25 mmol/L and a fixed alfacalcidol dose for at least 2 months. All had previously tolerated therapy with calcium carbonate. Of the 19 patients included, 10 completed both treatment arms. After 12 weeks of therapy, the mean (+/-SEM) plasma ionized calcium level was significantly lower in the ketoglutarate arm compared with the calcium carbonate arm (4.8+/-0.1 mg/dL v 5.2+/-0.1 mg/dL; P = 0.004), whereas the mean plasma phosphate (4.5+/-0.3 mg/dL v 5.1+/-0.1 mg/dL) and PTH levels (266+/-125 pg/mL v 301+/-148 pg/mL) did not differ significantly between the two treatment arms. Supplemental aluminum-aminoacetate was not required during calcium ketoglutarate treatment, while two patients needed this supplement when treated with calcium carbonate. Five of 17 (29%) patients were withdrawn from calcium ketoglutarate therapy within 1 to 2 weeks due to intolerance (anorexia, vomiting, diarrhea, general uneasiness), whereas the remaining 12 patients did not experience any side effects at all. The five patients with calcium ketoglutarate intolerance all had pre-existing gastrointestinal symptoms; four of them had received treatment with cimetidine or omeprazol before inclusion into the study. Calculations based on median doses after 12 weeks showed that the cost of the therapy in Denmark was 10 times higher for calcium ketoglutarate compared with calcium

A facile magnesium-containing calcium carbonate biomaterial as potential bone graft.

PubMed

He, Fupo; Zhang, Jing; Tian, Xiumei; Wu, Shanghua; Chen, Xiaoming

2015-12-01

The calcium carbonate is the main composition of coral which has been widely used as bone graft in clinic. Herein, we readily prepared novel magnesium-containing calcium carbonate biomaterials (MCCs) under the low-temperature conditions based on the dissolution-recrystallization reaction between unstable amorphous calcium carbonate (ACC) and metastable vaterite-type calcium carbonate with water involved. The content of magnesium in MCCs was tailored by adjusting the proportion of ACC starting material that was prepared using magnesium as stabilizer. The phase composition of MCCs with various amounts of magnesium was composed of one, two or three kinds of calcium carbonates (calcite, aragonite, and/or magnesian calcite). The different MCCs differed in topography. The in vitro degradation of MCCs accelerated with increasing amount of introduced magnesium. The MCCs with a certain amount of magnesium not only acquired higher compressive strength, but also promoted in vitro cell proliferation and osteogenic differentiation. Taken together, the facile MCCs shed light on their potential as bone graft. Copyright © 2015 Elsevier B.V. All rights reserved.

Calcium carbonate nucleation in an alkaline lake surface water, Pyramid Lake, Nevada, USA

USGS Publications Warehouse

Reddy, Michael M.; Hoch, Anthony

2012-01-01

Calcium concentration and calcite supersaturation (Ω) needed for calcium carbonate nucleation and crystal growth in Pyramid Lake (PL) surface water were determined during August of 1997, 2000, and 2001. PL surface water has Ω values of 10-16. Notwithstanding high Ω, calcium carbonate growth did not occur on aragonite single crystals suspended PL surface water for several months. However, calcium solution addition to PL surface-water samples caused reproducible calcium carbonate mineral nucleation and crystal growth. Mean PL surface-water calcium concentration at nucleation was 2.33 mM (n = 10), a value about nine times higher than the ambient PL surface-water calcium concentration (0.26 mM); mean Ω at nucleation (109 with a standard deviation of 8) is about eight times the PL surface-water Ω. Calcium concentration and Ω regulated the calcium carbonate formation in PL nucleation experiments and surface water. Unfiltered samples nucleated at lower Ω than filtered samples. Calcium concentration and Ω at nucleation for experiments in the presence of added particles were within one standard deviation of the mean for all samples. Calcium carbonate formation rates followed a simple rate expression of the form, rate (mM/min) = A (Ω) + B. The best fit rate equation "Rate (Δ mM/Δ min) = -0.0026 Ω + 0.0175 (r = 0.904, n = 10)" was statistically significant at greater than the 0.01 confidence level and gives, after rearrangement, Ω at zero rate of 6.7. Nucleation in PL surface water and morphology of calcium carbonate particles formed in PL nucleation experiments and in PL surface-water samples suggest crystal growth inhibition by multiple substances present in PL surface water mediates PL calcium carbonate formation, but there is insufficient information to determine the chemical nature of all inhibitors.

Calcium Carbonate Nucleation in an Alkaline Lake Surface Water, Pyramid Lake, Nevada, USA

USGS Publications Warehouse

Reddy, M.M.; Hoch, A.

2012-01-01

Calcium concentration and calcite supersaturation (??) needed for calcium carbonate nucleation and crystal growth in Pyramid Lake (PL) surface water were determined during August of 1997, 2000, and 2001. PL surface water has ?? values of 10-16. Notwithstanding high ??, calcium carbonate growth did not occur on aragonite single crystals suspended PL surface water for several months. However, calcium solution addition to PL surface-water samples caused reproducible calcium carbonate mineral nucleation and crystal growth. Mean PL surface-water calcium concentration at nucleation was 2.33 mM (n = 10), a value about nine times higher than the ambient PL surface-water calcium concentration (0.26 mM); mean ?? at nucleation (109 with a standard deviation of 8) is about eight times the PL surface-water ??. Calcium concentration and ?? regulated the calcium carbonate formation in PL nucleation experiments and surface water. Unfiltered samples nucleated at lower ?? than filtered samples. Calcium concentration and ?? at nucleation for experiments in the presence of added particles were within one standard deviation of the mean for all samples. Calcium carbonate formation rates followed a simple rate expression of the form, rate (mM/min) = A (??) + B. The best fit rate equation "Rate (?? mM/?? min) = -0.0026 ?? + 0.0175 (r = 0.904, n = 10)" was statistically significant at greater than the 0.01 confidence level and gives, after rearrangement, ?? at zero rate of 6.7. Nucleation in PL surface water and morphology of calcium carbonate particles formed in PL nucleation experiments and in PL surface-water samples suggest crystal growth inhibition by multiple substances present in PL surface water mediates PL calcium carbonate formation, but there is insufficient information to determine the chemical nature of all inhibitors. ?? 2011 U.S. Government.

On the structure of amorphous calcium carbonate--a detailed study by solid-state NMR spectroscopy.

PubMed

Nebel, Holger; Neumann, Markus; Mayer, Christian; Epple, Matthias

2008-09-01

The calcium carbonate phases calcite, aragonite, vaterite, monohydrocalcite (calcium carbonate monohydrate), and ikaite (calcium carbonate hexahydrate) were studied by solid-state NMR spectroscopy ( (1)H and (13)C). Further model compounds were sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium hydroxide. With the help of these data, the structure of synthetically prepared additive-free amorphous calcium carbonate (ACC) was analyzed. ACC contains molecular water (as H 2O), a small amount of mobile hydroxide, and no hydrogencarbonate. This supports the concept of ACC as a transient precursor in the formation of calcium carbonate biominerals.

Particle size of calcium carbonate does not affect apparent and standardized total tract digestibility of calcium, retention of calcium, or growth performance of growing pigs.

PubMed

Merriman, L A; Stein, H H

2016-09-01

Two experiments were conducted to evaluate particle size of calcium carbonate used in diets fed to growing pigs. Experiment 1 was conducted to determine apparent total tract digestibility (ATTD), standardized total tract digestibility (STTD), and retention of Ca among diets containing calcium carbonate produced to different particle sizes, and Exp. 2 was conducted to determine if growth performance of weanling pigs is affected by particle size of calcium carbonate. In Exp. 1, 4 diets based on corn and potato protein isolate were formulated to contain 0.70% Ca and 0.33% standardized total tract digestible P, but the calcium carbonate used in the diets was ground to 4 different particle sizes (200, 500, 700, or 1,125 μm). A Ca-free diet was formulated to determine basal endogenous losses of Ca. In Exp. 2, 4 diets were based on corn and soybean meal and the only difference among diets was that each diet contained calcium carbonate ground to the 4 particle sizes used in Exp. 1. In Exp. 1, 40 barrows (15.42 ± 0.70 kg initial BW) were allotted to the 5 diets with 8 replicate pigs per diet using a randomized complete block design, and in Exp. 2, 128 pigs with an initial BW of 9.61 ± 0.09 kg were randomly allotted to 4 experimental diets. Results of Exp. 1 indicated that basal endogenous losses of Ca were 0.329 g/kg DMI. The ATTD of Ca was 70.0 ± 3.2, 74.3 ± 2.7, 70.0 ± 2.9, and 72.1 ± 2.7 and the STTD of Ca was 74.2 ± 3.2, 78.5 ± 2.7, 74.1 ± 2.9, and 76.2 ± 2.7 for calcium carbonate ground to 200, 500, 700, or 1,125 μm, respectively. Retention of Ca was 67.4 ± 3.1, 70.4 ± 2.6, 63.9 ± 2.8, and 67.2 ± 2.2 for diets containing calcium carbonate ground to 200, 500, 700, or 1,125 μm, respectively. There were no differences among diets for ATTD of Ca, STTD of Ca, or retention of Ca. The ATTD of P was 64.5 ± 1.7, 66.8 ± 2.6, 64.2 ± 3.0, and 63.2 ± 1.7% and retention of P was 61.4 ± 1.4, 63.8 ± 2.8, 61.9 ± 2.8, and 60.9 ± 1.5 for diets containing calcium

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

PubMed

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

2017-12-01

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

Influence of Calcium Carbonate on Cobalt Phytoavailability in Fluvo-aquic Soil

NASA Astrophysics Data System (ADS)

Wang, Mengyuan; Liu, Borui; Ma, Yufei; Xue, Qianhui; Huang, Qing

2017-12-01

In order to study the efficacy of calcium carbonate for cobalt (Co) fixation, as well as its influence on chemical speciation of Co in fluvo-aquic soil, pakchoies were planted in the soil with different quantities of exogenous Co and calcium carbonate. Co concentrations in the mature plant shoots were analyzed, and the chemical speciation of Co were detected with the Tessier five-step sequential extraction. The results showed that the Co concentration in plants tended to decrease first and then get higher with the concentration of calcium carbonate increasing (0-12g/kg) in soil (P < 0.05). The proportion of Co in the exchangeable form in the soil followed the similar tendency (P < 0.05), which might transform from the exchangeable form into the carbonate-associated and organic-associated forms. A regression analysis showed that when the concentrations of calcium carbonate were in the range of 5.0 to 7.5 g/kg, Co concentration in the plant reached to the lowest point, while the proportion of Co in the exchangeable form reached the minimum. In conclusion, to get the optimum effect, the dosage of calcium carbonate should be kept in the range of 5.0 to 7.5 g/kg when it is applied to Co fixation.

Roles of Acetone and Diacetone Alcohol in Coordination and Dissociation Reactions of Uranyl Complexes

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

Rios, Daniel; Schoendorff, George E.; Van Stipdonk, Michael J.

2012-12-03

Combined collision-induced dissociation mass-spectrometry experiments and DFT calculations were employed to elucidate the molecular structure of "hypercoordinated" species and the energetics of water-elimination reactions of uranyl acetone complexes observed in earlier work (Rios, D.; Rutkowski, P. X.; Van Stipdonk, M. J.; Gibson, J. K. Inorg. Chem. 2011, 50, 4781). It is shown that the "hypercoordinated" species contain diacetone alcohol ligands bonded in either bidentate or monodentate fashion, which are indistinguishable from (acetone)2 in mass spectrometry. Calculations confirm that four diacetone ligands can form stable complexes, but that the effective number of atoms coordinating with uranium in the equatorial plane doesmore » not exceed five. Diacetone alcohol ligands are shown to form mesityl oxide ligands and alkoxide species through the elimination of water, providing an explanation for the observed water-elimination reactions.« less

Exaggerated levothyroxine malabsorption due to calcium carbonate supplementation in gastrointestinal disorders.

PubMed

Csako, G; McGriff, N J; Rotman-Pikielny, P; Sarlis, N J; Pucino, F

2001-12-01

To describe a patient with primary hypothyroidism in whom ingestion of levothyroxine with calcium carbonate led to markedly elevated serum thyrotropin concentrations. A 61-year-old white woman with primary hypothyroidism, systemic lupus erythematosus, celiac disease, and history of Whipple resection for pancreatic cancer was euthyroid with levothyroxine 175-188 micrograms/d. After taking a high dose of calcium carbonate (1250 mg three times daily) with levothyroxine, she developed biochemical evidence of hypothyroidism (thyrotropin up to 41.4 mU/L) while remaining clinically euthyroid. Delaying calcium carbonate administration by four hours returned her serum thyrotropin to a borderline high concentration (5.7 mU/L) within a month. Serum concentrations of unbound and total thyroxine and triiodothyronine tended to decrease, but remained borderline low to normal while the patient concomitantly received levothyroxine and calcium carbonate. Concomitant administration of levothyroxine and calcium carbonate often results in levothyroxine malabsorption. While in most patients the clinical consequences of this interaction, even with prolonged exposure, are relatively small, overt hypothyrodism may develop in patients with preexisting malabsorption disorders. However, as the current case illustrates, the clinical manifestations of the initial levothyroxine deficit may not always be apparent and, of all usual laboratory thyroid function tests, only thyrotropin measurement will reliably uncover the exaggerated levothyroxine malabsorption. Decreased absorption of levothyroxine when given with calcium carbonate may be particularly pronounced in patients with preexisting malabsorption disorders. Once recognized, a change in drug administration schedule usually minimizes or eliminates this interaction.

[Calcium carbonate for the treatment of hyperphosphatemia in chronic hemodialysis patients].

PubMed

Kiss, D; Battegay, M; Meier, C; Lyrer, A

1990-03-03

Hyperphosphatemia in chronic hemodialysis patients is usually treated with aluminium containing phosphate binders. In recent years there has been increasing evidence of serious complications due to aluminium accumulation. We have investigated a new calcium carbonate preparation with an HCl-resistant capsule designed to prevent gastrointestinal side effects. Its phosphate binding capacity in comparison to aluminium chloride hydroxide was investigated in 17 chronic hemodialysis patients. The dose of the phosphate binder was adjusted regularly so that the serum phosphorus levels were below 1.8 mmol/l. The mean dose of aluminium chloride hydroxide was 3.36 g/day and of calcium carbonate 4.96 g/day. The mean (+/- SD) serum calcium level was 2.58 +/- 0.11 mmol/l under aluminium chloride hydroxide and 2.50 +/- 0.25 mmol/l under calcium carbonate. The mean phosphorus level was 1.69 +/- 0.31 mmol/l under aluminium chloride hydroxide and 1.71 +/- 0.33 under calcium carbonate. Serum aluminium fell from 64.5 +/- 14.4 micrograms/l to 28.5 +/- 17.5 micrograms/l after 3 months.

Comparison of the Absorption of Calcium Carbonate and Calcium Citrate after Roux-en-Y Gastric Bypass

PubMed Central

Tondapu, P.; Provost, D.; Adams-Huet, B.; Sims, T.; Chang, C.; Sakhaee, K.

2015-01-01

Introduction Roux-en-Y gastric bypass (RYGB) restricts food intake. Consequently, patients consume less calcium. In addition, food no longer passes through the duodenum, the main site of calcium absorption. Therefore, calcium absorption is significantly impaired. The goal of this study is to compare two common calcium supplements in gastric bypass patients. Method Nineteen patients were enrolled in a randomized, double-blinded, crossover study comparing the absorption of calcium from calcium carbonate and calcium citrate salts. Serum and urine calcium levels were assessed for peak values (Cmax) and cumulative calcium increment (area under the curve [AUC]). Serum PTH was assessed for minimum values (PTHmin) and cumulative PTH decrement (AUC). Statistical analysis was performed using a repeated analysis of variance model. Results Eighteen subjects completed the study. Calcium citrate resulted in a significantly higher serum Cmax (9.4+0.4 mg/dl vs. 9.2+0.3 mg/dl, p=0.02) and serum AUC (55+2 mg/dl vs. 54+2 mg/dl, p=0.02). Calcium citrate resulted in a significantly lower PTHmin (24+11 pg/ml vs. 30+13 pg/ml, p=0.01) and a higher AUC (−32+51 pg/ml vs. −3+56 pg/ml, p=0.04). There was a non-significant trend for higher urinary AUC in the calcium citrate group (76.13+36.39 mg/6 h vs. 66.04+40.82, p=0.17). Conclusion Calcium citrate has superior bioavailability than calcium carbonate in RYGB patients. PMID:19437082

Amorphous Calcium Carbonate Based-Microparticles for Peptide Pulmonary Delivery.

PubMed

Tewes, Frederic; Gobbo, Oliviero L; Ehrhardt, Carsten; Healy, Anne Marie

2016-01-20

Amorphous calcium carbonate (ACC) is known to interact with proteins, for example, in biogenic ACC, to form stable amorphous phases. The control of amorphous/crystalline and inorganic/organic ratios in inhalable calcium carbonate microparticles may enable particle properties to be adapted to suit the requirements of dry powders for pulmonary delivery by oral inhalation. For example, an amorphous phase can immobilize and stabilize polypeptides in their native structure and amorphous and crystalline phases have different mechanical properties. Therefore, inhalable composite microparticles made of inorganic (i.e., calcium carbonate and calcium formate) and organic (i.e., hyaluronan (HA)) amorphous and crystalline phases were investigated for peptide and protein pulmonary aerosol delivery. The crystalline/amorphous ratio and polymorphic form of the inorganic component was altered by changing the microparticle drying rate and by changing the ammonium carbonate and HA initial concentration. The bioactivity of the model peptide, salmon calcitonin (sCT), coprocessed with alpha-1-antitrypsin (AAT), a model protein with peptidase inhibitor activity, was maintained during processing and the microparticles had excellent aerodynamic properties, making them suitable for pulmonary aerosol delivery. The bioavailability of sCT after aerosol delivery as sCT and AAT-loaded composite microparticles to rats was 4-times higher than that of sCT solution.

Preparation of Lentinula edodes polysaccharide-calcium complex and its immunoactivity.

PubMed

Cui, Yujiao; Yan, Huidan; Zhang, Xuewu

2015-01-01

Polysaccharide is a major bioactive component of mushrooms. In this study, for the first time, starting from a new Lentinula edodes polysaccharide L2, we prepared a novel L2-calcium complex and the process was optimized. Scanning electron microscopy and Fourier Transform infrared spectrometry were used for characterization. The immunostimulating activities of L2 and L2-calcium complex were measured by enhancing the production of two cytokines TNF-α and IL-6 in RAW264.7 cells. While L2-calcium complex significantly stimulates the secretions of TNF-α and IL-6 compared with the control, complex with calcium ion decreased the secretion of them. These facts indicate that calcium ion can modulate immune stimulating activity of Lentinula edodes polysaccharide L2.

Isolation and metagenomic characterization of bacteria associated with calcium carbonate and struvite precipitation in a pure moving bed biofilm reactor-membrane bioreactor.

PubMed

Gonzalez-Martinez, A; Leyva-Díaz, J C; Rodriguez-Sanchez, A; Muñoz-Palazon, B; Rivadeneyra, A; Poyatos, J M; Rivadeneyra, M A; Martinez-Toledo, M V

2015-01-01

A bench-scale pure moving bed bioreactor-membrane bioreactor (MBBR-MBR) used for the treatment of urban wastewater was analyzed for the identification of bacterial strains with the potential capacity for calcium carbonate and struvite biomineral formation. Isolation of mineral-forming strains on calcium carbonate and struvite media revealed six major colonies with a carbonate or struvite precipitation capacity in the biofouling on the membrane surface and showed that heterotrophic bacteria with the ability to precipitate calcium carbonate and struvite constituted ~7.5% of the total platable bacteria. These belonged to the genera Lysinibacillus, Trichococcus, Comamomas and Bacillus. Pyrosequencing analysis of the microbial communities in the suspended cells and membrane biofouling showed a high degree of similarity in all the samples collected with respect to bacterial assemblage. The study of operational taxonomic units (OTUs) identified through pyrosequencing suggested that ~21% of the total bacterial community identified in the biofouling could potentially form calcium carbonate or struvite crystals in the pure MBBR-MBR system used for the treatment of urban wastewater.

Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O=U=O]²⁺ Asymmetric Stretch

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

Gibson, John K.; Hu, Hanshi; Van Stipdonk, Michael J.

2015-04-09

The gas-phase complex UO₂(TMOGA)₂²⁺ (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700–1800 cm⁻¹ was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm⁻¹ (<1%) and a maximum deviation of 21 cm⁻¹ (<2%). The only IR peak assigned to the linear uranyl moiety was the asymmetric ν₃ mode, which appeared at 965 cm⁻¹ and was predicted by DFT as 953 cm⁻¹. This ν₃ frequency is red-shifted relative tomore » bare uranyl, UO₂²⁺, by ca. 150 cm⁻¹ due to electron donation from the TMOGA ligands. Based on the degree of red-shifting, it is inferred that two TMOGA oxygen-donor ligands have a greater effective gas basicity than the four monodentate acetone ligands in UO₂(acetone)₄²⁺. The uranyl ν₃ frequency was also computed for uranyl coordinated by two TMGA ligands, in which the central Oether of TMOGA has been replaced by CH₂. The computed ν₃ for UO₂(TMGA)₂²⁺, 950 cm⁻¹, is essentially the same as that for UO₂(TMOGA)₂²⁺, suggesting that electron donation to uranyl from the Oether of TMOGA is minor. The computed ν₃ asymmetric stretching frequencies for the three actinyl complexes, UO₂(TMOGA)₂²⁺, NpO₂(TMOGA)₂²⁺ and PuO₂(TMOGA)₂²⁺, are comparable. This similarity is discussed in the context of the relationship between ν₃ and intrinsic actinide-oxygen bond energies in actinyl complexes.« less

Mineralization of gellan gum hydrogels with calcium and magnesium carbonates by alternate soaking in solutions of calcium/magnesium and carbonate ion solutions.

PubMed

Lopez-Heredia, Marco A; Łapa, Agata; Reczyńska, Katarzyna; Pietryga, Krzysztof; Balcaen, Lieve; Mendes, Ana C; Schaubroeck, David; Van Der Voort, Pascal; Dokupil, Agnieszka; Plis, Agnieszka; Stevens, Chris V; Parakhonskiy, Bogdan V; Samal, Sangram Keshari; Vanhaecke, Frank; Chai, Feng; Chronakis, Ioannis S; Blanchemain, Nicolas; Pamuła, Elżbieta; Skirtach, Andre G; Douglas, Timothy E L

2018-04-27

Mineralization of hydrogels is desirable prior to applications in bone regeneration. CaCO 3 is a widely used bone regeneration material and Mg, when used as a component of calcium phosphate biomaterials, has promoted bone-forming cell adhesion and proliferation and bone regeneration. In this study, gellan gum (GG) hydrogels were mineralized with carbonates containing different amounts of calcium (Ca) and magnesium (Mg) by alternate soaking in, firstly, a calcium and/or magnesium ion solution and, secondly, a carbonate ion solution. This alternate soaking cycle was repeated five times. Five different calcium and/or magnesium ion solutions, containing different molar ratios of Ca to Mg ranging from Mg-free to Ca-free were compared. Carbonate mineral formed in all sample groups subjected to the Ca:Mg elemental ratio in the carbonate mineral formed was higher than in the respective mineralizing solution. Mineral formed in the absence of Mg was predominantly CaCO 3 in the form of a mixture of calcite and vaterite. Increasing the Mg content in the mineral formed led to the formation of magnesian calcite, decreased the total amount of the mineral formed and its crystallinity. Hydrogel mineralization and increasing Mg content in mineral formed did not obviously improve proliferation of MC3T3-E1 osteoblast-like cells or differentiation after 7 days. This article is protected by copyright. All rights reserved.

Uranyl mediated photofootprinting reveals strong E. coli RNA polymerase--DNA backbone contacts in the +10 region of the DeoP1 promoter open complex.

PubMed Central

Jeppesen, C; Nielsen, P E

1989-01-01

Employing a newly developed uranyl photofootprinting technique (Nielsen et al. (1988) FEBS Lett. 235, 122), we have analyzed the structure of the E. coli RNA polymerase deoP1 promoter open complex. The results show strong polymerase DNA backbone contacts in the -40, -10, and most notably in the +10 region. These results suggest that unwinding of the -12 to +3 region of the promoter in the open complex is mediated through polymerase DNA backbone contacts on both sides of this region. The pattern of bases that are hyperreactive towards KMnO4 or uranyl within the -12 to +3 region furthermore argues against a model in which this region is simply unwound and/or single stranded. The results indicate specific protein contacts and/or a fixed DNA conformation within the -12 to +3 region. Images PMID:2503811

Effect of calcium carbonate combined with calcitonin on hypercalcemia in hemodialysis patients.

PubMed

Wei, Yong; Kong, Xiang Lei; Li, Wen Bin; Wang, Zun Song

2014-12-01

This short-term study assessed the efficacy and safety of calcium carbonate combined with calcitonin in the treatment of hypercalcemia in hemodialysis patients. Patients (n=64) on hemodialysis for chronic kidney disease for more than 6 months were included based on total serum calcium more than 10.5 mg/dL. All patients were randomized (1:1) to receive calcium carbonate combined with calcitonin (Group I) or lanthanum carbonate (Group II) for 12 weeks. Blood levels of calcium, phosphorus and intact parathyroid hormone (iPTH) were measured every month, bone mass density (BMD) and coronary artery calcium scores (CACS) were measured at 3 months. During the study period, serum calcium decreased from 10.72 ± 0.39 to 10.09 ± 0.28 mg/dL (P < 0.05), serum phosphorus decreased from 6.79 ± 1.05 to 5.46 ± 1.18 mg/dL (P < 0.05), and serum iPTH levels in the Group I and Group II were not significantly different from the baseline. There were no significant differences in CACS in either group. There were no significant differences in the BMD values between Group I and baseline. In Group II, the BMD values at the lumbar spine and femoral neck were significantly lower than those before the trial and significantly lower than the corresponding values of Group I (P<0.05). Calcium carbonate combined with calcitonin and lanthanum carbonate were equally effective in the suppression of hypercalcemia in hemodialysis patients. There were no serious treatment-related adverse events in treatment with calcium carbonate combined with calcitonin. © 2014 The Authors. Therapeutic Apheresis and Dialysis © 2014 International Society for Apheresis.

Efficacy and Safety of Sucroferric Oxyhydroxide and Calcium Carbonate in Hemodialysis Patients.

PubMed

Koiwa, Fumihiko; Yokoyama, Keitaro; Fukagawa, Masafumi; Akizawa, Tadao

2018-01-01

In this phase III, open-label, single-arm, multi-center 12-week study, we evaluated the efficacy and safety of combination therapy with sucroferric oxyhydroxide (PA21) and calcium carbonate for hemodialysis patients with hyperphosphatemia. We enrolled 35 subjects aged ≥ 20 years with end-stage kidney disease and serum phosphorus 3.5-6.0 mg/dl who were undergoing hemodialysis 3 times weekly and taking calcium carbonate and sevelamer hydrochloride. Patients switched from sevelamer hydrochloride and calcium carbonate to sucroferric oxyhydroxide and calcium carbonate. Sucroferric oxyhydroxide was orally administered 3 times daily within 750 mg/d (250 mg per dose) to 3000 mg/d (1000 mg per dose), immediately before every meal, for 12 weeks. Calcium carbonate was orally administered 3 times daily after every meal. Outcomes were serum phosphorus concentration, safety, and satisfaction with bowel movements. Mean (SD) serum phosphorus concentrations were 5.01 (0.63) mg/dl at week 0 and 4.89 (1.14) mg/dl at the end of treatment, after patients switched from sevelamer hydrochloride to sucroferric oxyhydroxide. The incidence of adverse drug reactions was 31.4% (11/35), with diarrhea being the most frequent (31.4%). More sucroferric oxyhydroxide-treated patients were satisfied with their bowel movements. More patients with constipation, as well as those who experienced diarrhea, were satisfied with their bowel movements at the end of the study. Combined administration of sucroferric oxyhydroxide and calcium carbonate at low doses was effective in maintaining serum phosphorus concentrations within the target range, and patients' gastrointestinal status improved. Sucroferric oxyhydroxide maintained its serum phosphorus-lowering effect with a decreased pill burden, and its concomitant administration with calcium carbonate was well tolerated.

Methotrexate intercalated calcium carbonate nanostructures: Synthesis, phase transformation and bioassay study.

PubMed

Dai, Chao-Fan; Wang, Wei-Yuan; Wang, Lin; Zhou, Lei; Li, Shu-Ping; Li, Xiao-Dong

2016-12-01

The formation and stabilization of amorphous calcium carbonate (ACC) is an active area of research owing to the presence of stable ACC in various biogenic minerals. In this paper, the synthesis of calcium carbonate (CaCO3) under the participation of methotrexate (MTX) via a facile gas diffusion route was reported. The results indicated that the addition of MTX can result in the phase transformation of CaCO3, and then two kinds of hybrids, i.e., MTX-vaterite and stable MTX-ACC came into being. Interestingly, the functional agent MTX served as both the target anticancer drug loaded and effective complexation agents to modify and control the morphology of final samples. The examination of MTX-ACC biodegradation process revealed that the collapse of MTX-ACC nanoparticles was due to the synergistic effect of drug release and the phase transformation. Finally, our study also proved that MTX-ACC exhibited the most excellent suppressing function on the viability of cancer cells, especially after long-time duration. Copyright © 2016. Published by Elsevier B.V.

An experimental model for calcium carbonate urolithiasis in goats.

PubMed

Jones, Meredyth L; Dominguez, Brandon J; Deveau, Michael A

2018-05-01

Calcium carbonate is a common urolith type in small ruminants with no high-yield experimental model to evaluate animal susceptibility or preventative measure response. That novel plastic winged implants would allow accumulation and quantification of calcium carbonate calculus formation in goats on a high-calcium diet and identify individual variation between goats in the mass of calculi produced. Eight nonpregnant 3- and 4-year-old Boer-cross does, weighing 22.3-39.5 kg, determined to be healthy based on physical examination, were used in these experiments. Prospective cohort study for in vivo experimental model development. Implants were placed into the urinary bladder lumen in 8 goats over 2 evaluation periods. The alfalfa-based ration had a total ration Ca : P of 3.29 and 3.84 : 1, respectively. Urine was collected at 0, 28, 56, and 84 days in the 1st experiment; blood and urine at those timepoints in the 2nd experiment. For each evaluation period, the implants were removed 84 days after implantation and weighed. Accumulated calculi mass was calculated and compared between goats and was analyzed for composition. Implant retention was 100% and 86% in the 2 studies. All goats with retained implants accumulated calcium carbonate at a mean implant gain per day across studies ranging from 0.44 to 57.45 mg. Two goats accumulated (0.44-7.65 mg/day and 33.64 & 57.45 mg/day) significantly more urolith material than the cohort across both studies (P = .047). No routine analytes on blood or urine were found to be explanatory for the difference observed. These findings form a basis for implant and diet selection for use in future studies of urolithiasis development and for studies regarding individual susceptibility to urolithiasis. Copyright © 2018 The Authors. Journal of Veterinary Internal Medicine published by Wiley Periodicals, Inc. on behalf of the American College of Veterinary Internal Medicine.

[Study on solid dispersion of precipitated calcium carbonate-based oleanolic acid].

PubMed

Yan, Hong-mei; Zhang, Zhen-hai; Jia, Xiao-bin; Jiang, Yan-rong; Sun, E

2015-05-01

Oleanolic acid-precipitated calcium carbonate solid dispersion was prepared by using solvent evaporation method. The microscopic structure and physicochemical properties of solid dispersion were analyzed using differential scanning calorimetry and scanning electron microscopy (SEM). And its in vitro release also was investigated. The properties of the precipitated calcium carbonate was studied which was as a carrier of oleanolic acid solid dispersion. Differential scanning calorimetry analysis suggested that oleanolic acid may be present in solid dispersion as amorphous substance. The in vitro release determination results of oleanolic acid-precipitated calcium carbonate (1: 5) solid dispersion showed accumulated dissolution rate of.oleanolic acid was up to 90% at 45 min. Accelerating experiment showed that content and in vitro dissolution of oleanolic acid solid dispersion did not change after storing over 6 months. The results indicated that in vitro dissolution of oleanolic acid was improved greatly by the solid dispersion with precipitated calcium carbonate as a carrier. The solid dispersion is a stabilizing system which has actual applied value.

Calcium carbonate solubility: a reappraisal of scale formation and inhibition.

PubMed

Gal, J Y; Bollinger, J C; Tolosa, H; Gache, N

1996-09-01

Considerable disparity exists in the published thermodynamic data for selected species in the Ca(2+) /CO(2)/H(2)O system near 25 degrees C and 1 atm pressure. Some authors doubt the significance of CaCO(3)(0)aq) complexes although there is experimental evidence of their occurrence. Evaluation of all the published experimental and estimated data for aqueous calcium carbonate species confirms that the consistent set of constants given by Plummer and Busenberg in 1982 is the best available, and suggests a formation constant log beta = 3.22 for CaCO(3)(0)(aq). This value was confirmed by additional experimental data and calculations using a specially developed computer program. The solubility s and solubility product K(s) are critically evaluated for each solid polymorph (amorphous CaCO(3), ikaite, vaterite, aragonite and calcite) using a hydrated ion pair model and we give coherent explanations for the calcium carbonate precipitation/dissolution process and the existence of supersaturated waters. The practical cases of scale formation and its inhibition by phosphonate-type compounds are discussed and explained with the same model, taking into account the CaCO(3)(0)(aq) species.

Carbonate-H₂O₂ leaching for sequestering uranium from seawater.

PubMed

Pan, Horng-Bin; Liao, Weisheng; Wai, Chien M; Oyola, Yatsandra; Janke, Christopher J; Tian, Guoxin; Rao, Linfeng

2014-07-28

Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1 M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to the formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with minimal loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

Crystallization of Calcium Carbonate in a Large Scale Field Study

NASA Astrophysics Data System (ADS)

Ueckert, Martina; Wismeth, Carina; Baumann, Thomas

2017-04-01

The long term efficiency of geothermal facilities and aquifer thermal energy storage in the carbonaceous Malm aquifer in the Bavarian Molasse Basin is seriously affected by precipitations of carbonates. This is mainly caused by pressure and temperature changes leading to oversaturation during production. Crystallization starts with polymorphic nuclei of calcium carbonate and is often described as diffusion-reaction controlled. Here, calcite crystallization is favoured by high concentration gradients while aragonite crystallization is occurring at high reaction rates. The factors affecting the crystallization processes have been described for simplified, well controlled laboratory experiments, the knowledge about the behaviour in more complex natural systems is still limited. The crystallization process of the polymorphic forms of calcium carbonate were investigated during a heat storage test at our test site in the eastern part of the Bavarian Molasse Basin. Complementary laboratory experiments in an autoclave were run. Both, field and laboratory experiments were conducted with carbonaceous tap water. Within the laboratory experiments additionally ultra pure water was used. To avoid precipitations of the tap water, a calculated amount of {CO_2} was added prior to heating the water from 45 - 110°C (laboratory) resp. 65 - 110°C (field). A total water volume of 0.5 L (laboratory) resp. 1 L (field) was immediately sampled and filtrated through 10 - 0.1

Biomineralization of calcium carbonates and their engineered applications: a review

PubMed Central

Dhami, Navdeep K.; Reddy, M. Sudhakara; Mukherjee, Abhijit

2013-01-01

Microbially induced calcium carbonate precipitation (MICCP) is a naturally occurring biological process in which microbes produce inorganic materials as part of their basic metabolic activities. This technology has been widely explored and promising with potential in various technical applications. In the present review, the detailed mechanism of production of calcium carbonate biominerals by ureolytic bacteria has been discussed along with role of bacteria and the sectors where these biominerals are being used. The applications of bacterially produced carbonate biominerals for improving the durability of buildings, remediation of environment (water and soil), sequestration of atmospheric CO2 filler material in rubbers and plastics etc. are discussed. The study also sheds light on benefits of bacterial biominerals over traditional agents and also the issues that lie in the path of successful commercialization of the technology of microbially induced calcium carbonate precipitation from lab to field scale. PMID:24194735

FT-Raman spectroscopic study of calcium-rich and magnesium-rich carbonate minerals.

PubMed

Edwards, Howell G M; Villar, Susana E Jorge; Jehlicka, Jan; Munshi, Tasnim

2005-08-01

Calcium and magnesium carbonates are important minerals found in sedimentary environments. Although sandstones are the most common rock colonized by endolith organisms, the production of calcium and magnesium carbonates is important in survival strategies of organisms and as a source for the removal of oxalate ions. Extremophile organisms in some situations may convert or destroy carbonates of calcium and magnesium, which gives important information about the conditions under which these organisms can survive. The identification on the surface of Mars of 'White Rock' formations, in Juventae Chasma or Sabaea Terra, as possibly carbonate rocks makes the study of these minerals a prerequisite of remote Martian exploration. Here, we show the protocol for the identification by Raman spectroscopy of different calcium and magnesium carbonates and we present a database of relevance in the search for life, extinct or extant, on Mars; this will be useful for the assessment of data obtained from remote, miniaturized Raman spectrometers now proposed for Mars exploration.

Calcium carbonate crystals promote calcium oxalate crystallization by heterogeneous or epitaxial nucleation: possible involvement in the control of urinary lithogenesis.

PubMed

Geider, S; Dussol, B; Nitsche, S; Veesler, S; Berthézène, P; Dupuy, P; Astier, J P; Boistelle, R; Berland, Y; Dagorn, J C; Verdier, J M

1996-07-01

A large proportion of urinary stones have calcium oxalate (CaOx) as the major mineral phase. In these stones, CaOx is generally associated with minor amounts of other calcium salts. Several reports showing the presence of calcium carbonate (CaCO3) and calcium phosphate in renal stones suggested that crystals of those salts might be present in the early steps of stone formation. Such crystals might therefore promote CaOx crystallization from supersaturated urine by providing an appropriate substrate for heterogeneous nucleation. That possibility was investigated by seeding a metastable solution of 45Ca oxalate with vaterite or calcite crystallites. Accretion of CaOx was monitored by 45Ca incorporation. We showed that (1) seeds of vaterite (the hexagonal polymorph of CaCO3) and calcite (the rhomboedric form) could initiate calcium oxalate crystal growth; (2) in the presence of lithostathine, an inhibitor of CaCO3 crystal growth, such accretion was not observed. In addition, scanning electron microscopy demonstrated that growth occurred by epitaxy onto calcite seeds whereas no special orientation was observed onto vaterite. It was concluded that calcium carbonate crystals promote crystallization of calcium oxalate and that inhibitors controlling calcium carbonate crystal formation in Henle's loop might play an important role in the prevention of calcium oxalate stone formation.

Potential New Ligand Systems for Binding Uranyl Ions in Seawater Environments

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

Arnold, John

2014-12-13

Work began this quarter on a new project involving a combined computational and biosynthetic approach to selective recognition of uranyl ion in aqueous solution. This project exploits the results of computational studies to discover new ligand classes. Synthetic studies will follow to generate target systems for uranyl binding and determination of binding constants. The process will be iterative, with results from computation informing synthesis, and vice versa. The theme of the ligand classes to be examined initially will be biologically based. New phosphonate-containing α-amino acid N-carboxyanhydride (NCA) monomers were used recently to prepare well-defined phosphonate-containing poly-peptides and block copolypeptides. Ourmore » first approach is to utilize these phosphate- and phosphonate-containing NCAs for the coordination of uranyl. The work includes the laboratory-scale preparation of a series of NCAs and the full thermodynamic and spectroscopic characterization of the resulting uranyl complexes. We are also evaluating the sequestering activity in different physiological and environmental conditions of these copolymers as well as their biodegradability.« less

Calcium carbonate and calcium sulfate in Martian meteorite EETA79001

NASA Technical Reports Server (NTRS)

Gooding, J. L.; Wentworth, S. J.

1987-01-01

Chips of glassy Lithology C of EETA79001 were studied by scanning electron microscopy and energy dispersive X-ray spectroscopy to determine the mineralogy and petrogenesis of the glass that was shown by others to contain trapped Mars-like gases. Calcium carbonite was identified as massive to acicular crystals for which Ca, C, and O were the major elements. Calcium sulfate was identified as prismatic-acicular crystals with Ca and S as the major elements.

Uranyl coordination in ionic liquids: the competition between ionic liquid anions, uranyl counterions, and Cl- anions investigated by extended X-ray absorption fine structure and UV-visible spectroscopies and molecular dynamics simulations.

PubMed

Gaillard, C; Chaumont, A; Billard, I; Hennig, C; Ouadi, A; Wipff, G

2007-06-11

The first coordination sphere of the uranyl cation in room-temperature ionic liquids (ILs) results from the competition between its initially bound counterions, the IL anions, and other anions (e.g., present as impurities or added to the solution). We present a joined spectroscopic (UV-visible and extended X-ray absorption fine structure)-simulation study of the coordination of uranyl initially introduced either as UO2X2 salts (X-=nitrate NO3-, triflate TfO-, perchlorate ClO4-) or as UO2(SO4) in a series of imidazolium-based ILs (C4mimA, A-=PF6-, Tf2N-, BF4- and C4mim=1-methyl-3-butyl-imidazolium) as well as in the Me3NBuTf2N IL. The solubility and dissociation of the uranyl salts are found to depend on the nature of X- and A-. The addition of Cl- anions promotes the solubilization of the nitrate and triflate salts in the C4mimPF6 and the C4mimBF4 ILs via the formation of chloro complexes, also formed with other salts. The first coordination sphere of uranyl is further investigated by molecular dynamics (MD) simulations on associated versus dissociated forms of UO2X2 salts in C4mimA ILs as a function of A- and X- anions. Furthermore, the comparison of UO2Cl(4)2-, 2 X- complexes with dissociated X- anions, to the UO2X2, 4 Cl- complexes with dissociated chlorides, shows that the former is more stable. The case of fluoro complexes is also considered, as a possible result of fluorinated IL anion's degradation, showing that UO2F42- should be most stable in solution. In all cases, uranyl is found to be solvated as formally anionic UO2XnAmClp2-n-m-p complexes, embedded in a cage of stabilizing IL imidazolium or ammonium cations.

Multi-Functions of Carbonated Calcium Deficient Hydroxyapatite (CDHA)

NASA Astrophysics Data System (ADS)

Zhou, Huan

Natural bone is a complex composite mainly constituted of inorganic minerals and organic collagen molecules. Calcium phosphate (CaP) based materials have been proposed as the predominant bone substitute for bone tissue engineering applications due to their chemical similarity to bone mineral. Amorphous carbonated calcium deficient hydroxyapatite (CDHA) is an important compound among CaP materials because of the amorphous crystallite structure. The presence of extra ions in its lattice structure not only influences cell attachment and proliferation of osteoblasts, but also helps in bone metabolism. Biomimetic coating approach is the most widely used approach to produce CDHA coatings to implant. It is a process using simulated body fluid (SBF) to deposit bone-like CDHA coating to various material surfaces. The CDHA formation mechanism, SBF compositions and reacting conditions of biomimetic coating have already been sufficiently studied and compared in the past 20 years. It is an attempt in this thesis to explore new applications of SBF in biomedical research, focusing on different biomaterial applications: 1) based on the low temperature reaction condition of SBF, bisphosphonate incorporated CDHA coatings were deposited onto Ti6Al4V surface for the treatment of osteoporosis; 2) amorphous calcium phosphate nanospheres with extra elements in the lattice structure were prepared by a novel microwave assisted approach, providing a new potential of CaP materials production; 3) CDHA particles formed in SBF can be used as great fillers with biopolymers for preparing biocomposites for biomedical applications; 4) based on the high activity of CDHA amorphous structure and the stabilization ability of ethanol, yttrium and europium doped calcium phosphates were prepared using CDHA as a sacrificing template. In the end, future work based on these observations in the thesis is addressed, including areas of drug delivery, biocomposite fabrication and preparation of functionalized

Structure of complexes of uranyl succinate with carbamide and dimethylurea

NASA Astrophysics Data System (ADS)

Serezhkina, L. B.; Grigor'ev, M. S.; Seliverstova, N. V.; Serezhkin, V. N.

2017-09-01

Three new succinate-containing complexes of uranyl with carbamide ( Urea) and N,N'-dimethylurea ( s-Dmur) are synthesized and studied by IR spectroscopy and X-ray diffraction. Structures of the same type, [UO2( Urea)4(H2O)][(UO2)2(C4H4O4)3] · 3H2O and [UO2( Urea)4(H2O)][(UO2)2(C4H4O4)3] · 2 Urea contain two sorts of uranium-containing complex groups, namely, mononuclear [UO2( Urea)4(H2O)]2+ cations and two-dimensional [(UO2)2(C4H4O4)3]2- anions described by crystal-chemical formulas AM 5 1 and A 2 Q 3 02, respectively ( A = UO2 2+, M 1 = Urea or H2O, Q 02 = C4H4O4 2-), and differ only in the nature of noncoordinated molecules—water and carbamide. The main structural groups of the [(UO2)2(C4H4O4)2( s-Dmur)3] crystals are [(UO2)2(C4H4O4)2( s-Dmur)3] chains belonging to the A 2 Q 2 02 M 3 1 ( A = UO2 2+, Q 02 = C4H4O4 2-, M 1 = s-Dmur) crystal-chemical group. Specific features of intermolecular interactions in the crystal structures are revealed using the Voronoi-Dirichlet method of molecular polyhedra.

Equatorial coordination of uranyl: Correlating ligand charge donation with the O yl-U-O yl asymmetric stretch frequency

DOE PAGES

Gibson, John K.; de Jong, Wibe A.; van Stipdonk, Michael J.; ...

2017-10-14

In uranyl coordination complexes, UO 2(L) n 2+, uranium in the formally dipositive [O=U=O] 2+ moiety is coordinated by n neutral organic electron donor ligands, L. The extent of ligand electron donation, which results in partial reduction of uranyl and weakening of the U=O bonds, is revealed by the magnitude of the red-shift of the uranyl asymmetric stretch frequency, ν 3 . This phenomenon appears in gas-phase complexes in which uranyl is coordinated by electron donor ligands: the ν 3 red-shift increases as the number of ligands and their proton affinity (PA) increases. Because PA is a measure of themore » enthalpy change associated with a proton-ligand interaction, which is much stronger and of a different nature than metal ion-ligand bonding, it is not necessarily expected that ligand PAs should reliably predict uranyl-ligand bonding and the resulting ν 3 red-shift. In this study, ν 3 was measured for uranyl coordinated by ligands with a relatively broad range of PAs, revealing a surprisingly good correlation between PA and ν 3 frequency. From computed ν 3 frequencies for bare UO 2 cations and neutrals, it is inferred that the effective charge of uranyl in UO 2(L) n 2+ complexes can be reduced to near zero upon ligation by sufficiently strong charge-donor ligands. The basis for the correlation between ν 3 and ligand PAs, as well as limitations and deviations from it, are considered. It is demonstrated that the correlation evidently extends to a ligand that exhibits polydentate metal ion coordination.« less

Solid state and aqueous behavior of uranyl peroxide cage clusters

NASA Astrophysics Data System (ADS)

Pellegrini, Kristi Lynn

Uranyl peroxide cage clusters include a large family of more than 50 published clusters of a variety of sizes, which can incorporate various ligands including pyrophosphate and oxalate. Previous studies have reported that uranyl clusters can be used as a method to separate uranium from a solid matrix, with potential applications in reprocessing of irradiated nuclear fuel. Because of the potential applications of these novel structures in an advanced nuclear fuel cycle and their likely presence in areas of contamination, it is important to understand their behavior in both solid state and aqueous systems, including complex environments where other ions are present. In this thesis, I examine the aqueous behavior of U24Pp 12, as well as aqueous cluster systems with added mono-, di-, and trivalent cations. The resulting solutions were analyzed using dynamic light scattering and ultra-small angle X-ray scattering to evaluate the species in solution. Precipitates of these systems were analyzed using powder X-ray diffraction, X-ray fluorescence spectrometry, and Raman spectroscopy. The results of these analyses demonstrate the importance of cation size, charge, and concentration of added cations on the aqueous behavior of uranium macroions. Specifically, aggregates of various sizes and shapes form rapidly upon addition of cations, and in some cases these aggregates appear to precipitate into an X-ray amorphous material that still contains U24Pp12 clusters. In addition, I probe aggregation of U24Pp12 and U60, another uranyl peroxide cage cluster, in mixed solvent water-alcohol systems. The aggregation of uranyl clusters in water-alcohol systems is a result of hydrogen bonding with polar organic molecules and the reduction of the dielectric constant of the system. Studies of aggregation of uranyl clusters also allow for comparison between the newer uranyl polyoxometalate family and century-old transition metal polyoxometalates. To complement the solution studies of uranyl

Electrospinning of calcium carbonate fibers and their conversion to nanocrystalline hydroxyapatite.

PubMed

Holopainen, Jani; Santala, Eero; Heikkilä, Mikko; Ritala, Mikko

2014-12-01

Calcium carbonate (CaCO3) fibers were prepared by electrospinning followed by annealing. Solutions consisting of calcium nitrate tetrahydrate (Ca(NO3)2·4H2O) and polyvinylpyrrolidone (PVP) dissolved in ethanol or 2-methoxyethanol were used for the fiber preparation. By varying the precursor concentrations in the electrospinning solutions CaCO3 fibers with average diameters from 140 to 290 nm were obtained. After calcination the fibers were identified as calcite by X-ray diffraction (XRD). The calcination process was studied in detail with high temperature X-ray diffraction (HTXRD) and thermogravimetric analysis (TGA). The initially weak fiber-to-substrate adhesion was improved by adding a strengthening CaCO3 layer by spin or dip coating Ca(NO3)2/PVP precursor solution on the CaCO3 fibers followed by annealing of the gel formed inside the fiber layer. The CaCO3 fibers were converted to nanocrystalline hydroxyapatite (HA) fibers by treatment in a dilute phosphate solution. The resulting hydroxyapatite had a plate-like crystal structure with resemblance to bone mineral. The calcium carbonate and hydroxyapatite fibers are interesting materials for bone scaffolds and bioactive coatings. Copyright © 2014 Elsevier B.V. All rights reserved.

Carbonate-H2O2 Leaching for Sequestering Uranium from Seawater

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

Pan, Horng-Bin; Weisheng, Liao; Wai, Chien

Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with little loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

Increased calcium absorption from synthetic stable amorphous calcium carbonate: double-blind randomized crossover clinical trial in postmenopausal women.

PubMed

Vaisman, Nachum; Shaltiel, Galit; Daniely, Michal; Meiron, Oren E; Shechter, Assaf; Abrams, Steven A; Niv, Eva; Shapira, Yami; Sagi, Amir

2014-10-01

Calcium supplementation is a widely recognized strategy for achieving adequate calcium intake. We designed this blinded, randomized, crossover interventional trial to compare the bioavailability of a new stable synthetic amorphous calcium carbonate (ACC) with that of crystalline calcium carbonate (CCC) using the dual stable isotope technique. The study was conducted in the Unit of Clinical Nutrition, Tel Aviv Sourasky Medical Center, Israel. The study population included 15 early postmenopausal women aged 54.9 ± 2.8 (mean ± SD) years with no history of major medical illness or metabolic bone disorder, excess calcium intake, or vitamin D deficiency. Standardized breakfast was followed by randomly provided CCC or ACC capsules containing 192 mg elemental calcium labeled with 44Ca at intervals of at least 3 weeks. After swallowing the capsules, intravenous CaCl2 labeled with 42Ca on was administered on each occasion. Fractional calcium absorption (FCA) of ACC and CCC was calculated from the 24-hour urine collection following calcium administration. The results indicated that FCA of ACC was doubled (± 0.96 SD) on average compared to that of CCC (p < 0.02). The higher absorption of the synthetic stable ACC may serve as a more efficacious way of calcium supplementation. © 2014 American Society for Bone and Mineral Research.

Spectral features of biogenic calcium carbonates and implications for astrobiology

NASA Astrophysics Data System (ADS)

Berg, B. L.; Ronholm, J.; Applin, D. M.; Mann, P.; Izawa, M.; Cloutis, E. A.; Whyte, L. G.

2014-09-01

The ability to discriminate biogenic from abiogenic calcium carbonate (CaCO3) would be useful in the search for extant or extinct life, since CaCO3 can be produced by both biotic and abiotic processes on Earth. Bioprecipitated CaCO3 material was produced during the growth of heterotrophic microbial isolates on medium enriched with calcium acetate or calcium citrate. These biologically produced CaCO3, along with natural and synthetic non-biologically produced CaCO3 samples, were analysed by reflectance spectroscopy (0.35-2.5 μm), Raman spectroscopy (532 and 785 nm), and laser-induced fluorescence spectroscopy (365 and 405 nm excitation). Optimal instruments for the discrimination of biogenic from abiogenic CaCO3 were determined to be reflectance spectroscopy, and laser-induced fluorescence spectroscopy. Multiple absorption features in the visible light region occurred in reflectance spectra for most biogenic CaCO3 samples, which are likely due to organic pigments. Multiple fluorescence peaks occurred in emission spectra (405 nm excitation) of biogenic CaCO3 samples, which also are best attributed to the presence of organic compounds; however, further analyses must be performed in order to better determine the cause of these features to establish criteria for confirming the origin of a given CaCO3 sample. Raman spectroscopy was not useful for discrimination since any potential Raman peaks in spectra of biogenic carbonates collected by both the 532 and 785 nm lasers were overwhelmed by fluorescence. However, this also suggests that biogenic carbonates may be identified by the presence of this organic-associated fluorescence. No reliable spectroscopic differences in terms of parameters such as positions or widths of carbonate-associated absorption bands were found between the biogenic and abiogenic carbonate samples. These results indicate that the presence or absence of organic matter intimately associated with carbonate minerals is the only potentially useful

Immobilization of Pseudomonas sp. DG17 onto sodium alginate–attapulgite–calcium carbonate

PubMed Central

Wang, Hong Qi; Hua, Fei; Zhao, Yi Cun; Li, Yi; Wang, Xuan

2014-01-01

A strain of Pseudomonas sp. DG17, capable of degrading crude oil, was immobilized in sodium alginate–attapulgite–calcium carbonate for biodegradation of crude oil contaminated soil. In this work, proportion of independent variables, the laboratory immobilization parameters, the micromorphology and internal structure of the immobilized granule, as well as the crude oil biodegradation by sodium alginate–attapulgite–calcium carbonate immobilized cells and sodium alginate–attapulgite immobilized cells were studied to build the optimal immobilization carrier and granule-forming method. The results showed that the optimal concentrations of sodium alginate–attapulgite–calcium carbonate and calcium chloride were 2.5%–3.5%, 0.5%–1%, 3%–7% and 2%–4%, respectively. Meanwhile, the optimal bath temperature, embedding cell amount, reaction time and multiplication time were 50–60 °C, 2%, 18 h and 48 h, respectively. Moreover, biodegradation was enhanced by immobilized cells with a total petroleum hydrocarbon removal ranging from 33.56% ± 3.84% to 56.82% ± 3.26% after 20 days. The SEM results indicated that adding calcium carbonate was helpful to form internal honeycomb-like pores in the immobilized granules. PMID:26019567

Dehydration-induced amorphous phases of calcium carbonate.

PubMed

Saharay, Moumita; Yazaydin, A Ozgur; Kirkpatrick, R James

2013-03-28

Amorphous calcium carbonate (ACC) is a critical transient phase in the inorganic precipitation of CaCO3 and in biomineralization. The calcium carbonate crystallization pathway is thought to involve dehydration of more hydrated ACC to less hydrated ACC followed by the formation of anhydrous ACC. We present here computational studies of the transition of a hydrated ACC with a H2O/CaCO3 ratio of 1.0 to anhydrous ACC. During dehydration, ACC undergoes reorganization to a more ordered structure with a significant increase in density. The computed density of anhydrous ACC is similar to that of calcite, the stable crystalline phase. Compared to the crystalline CaCO3 phases, calcite, vaterite, and aragonite, the computed local structure of anhydrous ACC is most-similar to those of calcite and vaterite, but the overall structure is not well described by either. The strong hydrogen bond interaction between the carbonate ions and water molecules plays a crucial role in stabilizing the less hydrated ACC compositions compared to the more hydrated ones, leading to a progressively increasing hydration energy with decreasing water content.

Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

PubMed Central

Kubicki, James D; Halada, Gary P; Jha, Prashant; Phillips, Brian L

2009-01-01

Background Quantum mechanical calculations were performed on a variety of uranium species representing U(VI), U(V), U(IV), U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG), and U-2-Keto-3-doxyoctanoate (KDO) with explicit solvation by H2O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra. Results Agreement between experiment and theory is acceptable in most cases, and the reasons for discrepancies are discussed. Calculated Gibbs free energies are used to constrain which configurations are most likely to be stable under circumneutral pH conditions. Reduction of U(VI) to U(IV) is examined for the U-carbonate and U-catechol complexes. Conclusion Results on the potential energy differences between U(V)- and U(IV)-carbonate complexes suggest that the cause of slower disproportionation in this system is electrostatic repulsion between UO2 [CO3]35- ions that must approach one another to form U(VI) and U(IV) rather than a change in thermodynamic stability. Calculations on U-catechol species are consistent with the observation that UO22+ can oxidize catechol and form quinone-like species. In addition, outer-sphere complexation is predicted to be the most stable for U-catechol interactions based on calculated energies and comparison to 13C NMR spectra. Outer-sphere complexes (i.e., ion pairs bridged by water molecules) are predicted to be comparable in Gibbs free energy to inner-sphere complexes for a model carboxylic acid. Complexation of uranyl to phosphorus-containing groups in extracellular polymeric substances is predicted to favor phosphonate groups, such as that found in phosphorylated NAG, rather than phosphodiesters, such as those in nucleic acids. PMID:19689800

Morphology and phase identification of synthesized precipitated calcium carbonate from acetylene gas industry waste

NASA Astrophysics Data System (ADS)

Sabri, Siti Noorzidah Mohd; Othman, Rohaya; Othman, Anuar

2017-12-01

Precipitated calcium carbonate (PCC) is also known as synthetic calcium carbonate. In this paper, PCC was synthesized from carbide lime, which is the by-product from acetylene gas industry. The method used to produce PCC from carbide lime waste was ionic sucrose precipitation technique. The experiments were performed by varying the stirring rate. In this technique, carbide lime was first dissolved in ionic sucrose solution and then chilled at 10 °C for 24 hours before carbon dioxide gasses was introduced into the solution. The carbonation and precipitation process was took place and PCC was formed. The PCC was further filtered to obtain the solid PCC. The sample was then further characterised by using FESEM and XRD to determine the morphology and to identify the phase that exists in the synthesized compound respectively. The XRD and FESEM results clearly shown that the PCC obtained has mixed phases of calcite and vaterite, with mixtures of spherical and irregular shape morphologies formed. The irregular shapes corresponded to vaterite formation, meanwhile spherical shapes corresponded to calcite formation.

Aminotroponiminate calcium and strontium complexes.

PubMed

Datta, Simmi; Gamer, Michael T; Roesky, Peter W

2008-06-07

Heteroleptic aminotroponiminate complexes of calcium and strontium have been prepared. The monomeric calcium complex [((iPr)2ATI)CaI(THF)3] 1 ((iPr)2ATI = N-isopropyl-2-(isopropylamino)troponiminate) and the corresponding dimeric strontium compound [( (iPr)2ATI)SrI(THF)2]2 2 were obtained by reaction of [((iPr)2ATI)K] and MI2. Whereas the mixed ligand compound of composition [((iPr)2ATI)Ca(iPrAT)]2 3 (iPrAT = 2-(isopropylamino)troponate) was not obtained via a salt metathesis but by reaction of [Ca(N(SiMe3)2)2(THF)2] with ( (iPr)2ATI)H and (iPrAT)H, the diphosphanylamido complex [( (iPr)2ATI)Ca((Ph2P)2N)(THF)2] was obtained by reaction of CaI2 with the potassium compounds [( (iPr)2ATI)K] and [K(THF)n][N(PPh2)2]. The single crystal X-ray structures of all compounds were established and the latter compound shows a eta2-coordination mode of the ligand via the nitrogen and one phosphorus atom.

Density functional theory and molecular dynamics study of the uranyl ion (UO₂)²⁺.

PubMed

Rodríguez-Jeangros, Nicolás; Seminario, Jorge M

2014-03-01

The detection of uranium is very important, especially in water and, more importantly, in the form of uranyl ion (UO₂)²⁺, which is one of its most abundant moieties. Here, we report analyses and simulations of uranyl in water using ab initio modified force fields for water with improved parameters and charges of uranyl. We use a TIP4P model, which allows us to obtain accurate water properties such as the boiling point and the second and third shells of water molecules in the radial distribution function thanks to a fictitious charge that corrects the 3-point models by reproducing the exact dipole moment of the water molecule. We also introduced non-bonded interaction parameters for the water-uranyl intermolecular force field. Special care was taken in testing the effect of a range of uranyl charges on the structure of uranyl-water complexes. Atomic charges of the solvated ion in water were obtained using density functional theory (DFT) calculations taking into account the presence of nitrate ions in the solution, forming a neutral ensemble. DFT-based force fields were calculated in such a way that water properties, such as the boiling point or the pair distribution function stand. Finally, molecular dynamics simulations of a water box containing uranyl cations and nitrate anions are performed at room temperature. The three peaks in the oxygen-oxygen radial distribution function for water were found to be kept in the presence of uranyl thanks to the improvement of interaction parameters and charges. Also, we found three shells of water molecules surrounding the uranyl ion instead of two as was previously thought.

Reequilibration of fluid inclusions in low-temperature calcium-carbonate cement

NASA Astrophysics Data System (ADS)

Goldstein, Robert H.

1986-09-01

Calcium-carbonate cements precipitated in low-temperature, near-surface, vadose environments contain fluid inclusions of variable vapor-to-liquid ratios that yield variable homogenization temperatures. Cements precipitated in low-temperature, phreatic environments contain one-phase, all-liquid fluid inclusions. Neomorphism of unstable calcium-carbonate phases may cause reequilibration of fluid inclusions. Stable calcium-carbonate cements of low-temperature origin, which have been deeply buried, contain fluid inclusions of variable homogenization temperature and variable salt composition. Most inclusion fluids are not representative of the fluids present during cement growth and are more indicative of burial pore fluids. Therefore, low-temperature fluid inclusions probably reequilibrate with burial fluids during progressive burial. Reequilibration is likely caused by high internal pressures in inclusions which result in hydrofracturing. The resulting fluid-inclusion population could contain a nearly complete record of burial fluids in which a particular rock has been bathed. *Present address: Department of Geology, University of Kansas, Lawrence, Kansas 66045

Layer-by-Layer Assembled Nanotubes as Biomimetic Nanoreactors for Calcium Carbonate Deposition.

PubMed

He, Qiang; Möhwald, Helmuth; Li, Junbai

2009-09-17

Enzyme-loaded magnetic polyelectrolyte multilayer nanotubes prepared by layer-by-layer assembly combined with the porous template could be used as biomimetic nanoreactors. It is demonstrated that calcium carbonate can be biomimetically synthesized inside the cavities of the polyelectrolyte nanotubes by the catalysis of urease, and the size of the calcium carbonate precipitates was controlled by the cavity dimensions. The metastable structure of the calcium carbonate precipitates inside the nanotubes was protected by the outer shell of the polyelectrolyte multilayers. These features may allow polyelectrolyte nanotubes to be applied in the fields of nanomaterials synthesis, controlled release, and drug delivery. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conversion of calcium sulphide to calcium carbonate during the process of recovery of elemental sulphur from gypsum waste.

PubMed

de Beer, M; Maree, J P; Liebenberg, L; Doucet, F J

2014-11-01

The production of elemental sulphur and calcium carbonate (CaCO3) from gypsum waste can be achieved by thermally reducing the waste into calcium sulphide (CaS), which is then subjected to a direct aqueous carbonation step for the generation of hydrogen sulphide (H2S) and CaCO3. H2S can subsequently be converted to elemental sulphur via the commercially available chemical catalytic Claus process. This study investigated the carbonation of CaS by examining both the solution chemistry of the process and the properties of the formed carbonated product. CaS was successfully converted into CaCO3; however, the reaction yielded low-grade carbonate products (i.e. <90 mass% as CaCO3) which comprised a mixture of two CaCO3 polymorphs (calcite and vaterite), as well as trace minerals originating from the starting material. These products could replace the Sappi Enstra CaCO3 (69 mass% CaCO3), a by-product from the paper industry which is used in many full-scale AMD neutralisation plants but is becoming insufficient. The insight gained is now also being used to develop and optimize an indirect aqueous CaS carbonation process for the production of high-grade CaCO3 (i.e. >99 mass% as CaCO3) or precipitated calcium carbonate (PCC). Copyright © 2014 Elsevier Ltd. All rights reserved.

Epitaxial Relationships between Calcium Carbonate and Inorganic Substrates

PubMed Central

Yang, Taewook; Jho, Jae Young; Kim, Il Won

2014-01-01

The polymorph-selective crystallization of calcium carbonate has been studied in terms of epitaxial relationship between the inorganic substrates and the aragonite/calcite polymorphs with implication in bioinspired mineralization. EpiCalc software was employed to assess the previously published experimental results on two different groups of inorganic substrates: aragonitic carbonate crystals (SrCO3, PbCO3, and BaCO3) and a hexagonal crystal family (α-Al2O3, α-SiO2, and LiNbO3). The maximum size of the overlayer (aragonite or calcite) was calculated for each substrate based on a threshold value of the dimensionless potential to estimate the relative nucleation preference of the polymorphs of calcium carbonate. The results were in good agreement with previous experimental observations, although stereochemical effects between the overlayer and substrate should be separately considered when existed. In assessing the polymorph-selective nucleation, the current method appeared to provide a better tool than the oversimplified mismatch parameters without invoking time-consuming molecular simulation\\. PMID:25226539

The Skeletal Organic Matrix from Mediterranean Coral Balanophyllia europaea Influences Calcium Carbonate Precipitation

PubMed Central

Goffredo, Stefano; Vergni, Patrizia; Reggi, Michela; Caroselli, Erik; Sparla, Francesca; Levy, Oren; Dubinsky, Zvy; Falini, Giuseppe

2011-01-01

Scleractinian coral skeletons are made mainly of calcium carbonate in the form of aragonite. The mineral deposition occurs in a biological confined environment, but it is still a theme of discussion to what extent the calcification occurs under biological or environmental control. Hence, the shape, size and organization of skeletal crystals from the cellular level through the colony architecture, were attributed to factors as diverse as mineral supersaturation levels and organic mediation of crystal growth. The skeleton contains an intra-skeletal organic matrix (OM) of which only the water soluble component was chemically and physically characterized. In this work that OM from the skeleton of the Balanophyllia europaea, a solitary scleractinian coral endemic to the Mediterranean Sea, is studied in vitro with the aim of understanding its role in the mineralization of calcium carbonate. Mineralization of calcium carbonate was conducted by overgrowth experiments on coral skeleton and in calcium chloride solutions containing different ratios of water soluble and/or insoluble OM and of magnesium ions. The precipitates were characterized by diffractometric, spectroscopic and microscopic techniques. The results showed that both soluble and insoluble OM components influence calcium carbonate precipitation and that the effect is enhanced by their co-presence. The role of magnesium ions is also affected by the presence of the OM components. Thus, in vitro, OM influences calcium carbonate crystal morphology, aggregation and polymorphism as a function of its composition and of the content of magnesium ions in the precipitation media. This research, although does not resolve the controversy between environmental or biological control on the deposition of calcium carbonate in corals, sheds a light on the role of OM, which appears mediated by the presence of magnesium ions. PMID:21799830

Carbon nanopipettes characterize calcium release pathways in breast cancer cells

NASA Astrophysics Data System (ADS)

Schrlau, Michael G.; Brailoiu, Eugen; Patel, Sandip; Gogotsi, Yury; Dun, Nae J.; Bau, Haim H.

2008-08-01

Carbon-based nanoprobes are attractive for minimally invasive cell interrogation but their application in cell physiology has thus far been limited. We have developed carbon nanopipettes (CNPs) with nanoscopic tips and used them to inject calcium-mobilizing messengers into cells without compromising cell viability. We identify pathways sensitive to cyclic adenosine diphosphate ribose (cADPr) and nicotinic acid adenine dinucleotide phosphate (NAADP) in breast carcinoma cells. Our findings demonstrate the superior utility of CNPs for intracellular delivery of impermeant molecules and, more generally, for cell physiology studies. The CNPs do not appear to cause any lasting damage to cells. Their advantages over commonly used glass pipettes include smaller size, breakage and clogging resistance, and potential for multifunctionality such as in concurrent injection and electrical measurements.

Carbon nanopipettes characterize calcium release pathways in breast cancer cells.

PubMed

Schrlau, Michael G; Brailoiu, Eugen; Patel, Sandip; Gogotsi, Yury; Dun, Nae J; Bau, Haim H

2008-08-13

Carbon-based nanoprobes are attractive for minimally invasive cell interrogation but their application in cell physiology has thus far been limited. We have developed carbon nanopipettes (CNPs) with nanoscopic tips and used them to inject calcium-mobilizing messengers into cells without compromising cell viability. We identify pathways sensitive to cyclic adenosine diphosphate ribose (cADPr) and nicotinic acid adenine dinucleotide phosphate (NAADP) in breast carcinoma cells. Our findings demonstrate the superior utility of CNPs for intracellular delivery of impermeant molecules and, more generally, for cell physiology studies. The CNPs do not appear to cause any lasting damage to cells. Their advantages over commonly used glass pipettes include smaller size, breakage and clogging resistance, and potential for multifunctionality such as in concurrent injection and electrical measurements.

Perlwapin, an Abalone Nacre Protein with Three Four-Disulfide Core (Whey Acidic Protein) Domains, Inhibits the Growth of Calcium Carbonate Crystals

PubMed Central

Treccani, Laura; Mann, Karlheinz; Heinemann, Fabian; Fritz, Monika

2006-01-01

We have isolated a new protein from the nacreous layer of the shell of the sea snail Haliotis laevigata (abalone). Amino acid sequence analysis showed the protein to consist of 134 amino acids and to contain three sequence repeats of ∼40 amino acids which were very similar to the well-known whey acidic protein domains of other proteins. The new protein was therefore named perlwapin. In addition to the major sequence, we identified several minor variants. Atomic force microscopy was used to explore the interaction of perlwapin with calcite crystals. Monomolecular layers of calcite crystals dissolve very slowly in deionized water and recrystallize in supersaturated calcium carbonate solution. When perlwapin was dissolved in the supersaturated calcium carbonate solution, growth of the crystal was inhibited immediately. Perlwapin molecules bound tightly to distinct step edges, preventing the crystal layers from growing. Using lower concentrations of perlwapin in a saturated calcium carbonate solution, we could distinguish native, active perlwapin molecules from denaturated ones. These observations showed that perlwapin can act as a growth inhibitor for calcium carbonate crystals in saturated calcium carbonate solution. The function of perlwapin in nacre growth may be to inhibit the growth of certain crystallographic planes in the mineral phase of the polymer/mineral composite nacre. PMID:16861275

Europium, uranyl, and thorium-phenanthroline amide complexes in acetonitrile solution: an ESI-MS and DFT combined investigation.

PubMed

Xiao, Cheng-Liang; Wang, Cong-Zhi; Mei, Lei; Zhang, Xin-Rui; Wall, Nathalie; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

2015-08-28

The tetradentate N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) ligand with hard-soft donor atoms has been demonstrated to be promising for the group separation of actinides from highly acidic nuclear wastes. To identify the formed complexes of this ligand with actinides and lanthanides, electrospray ionization mass spectrometry (ESI-MS) combined with density functional theory (DFT) calculations was used to probe the possible complexation processes. The 1 : 2 Eu-L species ([EuL2(NO3)](2+)) can be observed in ESI-MS at low metal-to-ligand ([M]/[L]) ratios, whereas the 1 : 1 Eu-L species ([EuL(NO3)2](+)) can be observed when the [M]/[L] ratio is higher than 1.0. However, ([UO2L(NO3)](+)) is the only detected species for the uranyl complexes. The [ThL2(NO3)2](2+) species can be observed at low [M]/[L] ratios; the 1 : 2 species ([ThL2(NO3)](3+)) and a new 1 : 1 species ([ThL(NO3)3](+)) can be detected at high [M]/[L] ratios. Collision-induced dissociation (CID) results showed that Et-Tol-DAPhen ligands can coordinate strongly with metal ions, and the coordination moieties remain intact under CID conditions. Natural bond orbital (NBO), molecular electrostatic potential (MEP), electron localization function (ELF), atoms in molecules (AIM) and molecular orbital (MO) analyses indicated that the metal-ligand bonds of the actinide complexes exhibited more covalent character than those of the lanthanide complexes. In addition, according to thermodynamic analysis, the stable cationic M-L complexes in acetonitrile are found to be in good agreement with the ESI-MS results.

Molecular dynamics study of the solvation of calcium carbonate in water.

PubMed

Bruneval, Fabien; Donadio, Davide; Parrinello, Michele

2007-10-25

We performed molecular dynamics simulations of diluted solutions of calcium carbonate in water. To this end, we combined and tested previous polarizable models. The carbonate anion forms long-living hydrogen bonds with water and shows an amphiphilic character, in which the water molecules are expelled in a region close to its C(3) symmetry axis. The calcium cation forms a strongly bound ion pair with the carbonate. The first hydration shell around the CaCO(3) pair is found to be very similar to the location of the water molecules surrounding CaCO(3) in ikaite, the hydrated mineral.

An Exploration of the Calcium-Binding Mode of Egg White Peptide, Asp-His-Thr-Lys-Glu, and In Vitro Calcium Absorption Studies of Peptide-Calcium Complex.

PubMed

Sun, Na; Jin, Ziqi; Li, Dongmei; Yin, Hongjie; Lin, Songyi

2017-11-08

The binding mode between the pentapeptide (DHTKE) from egg white hydrolysates and calcium ions was elucidated upon its structural and thermodynamics characteristics. The present study demonstrated that the DHTKE peptide could spontaneously bind calcium with a 1:1 stoichiometry, and that the calcium-binding site corresponded to the carboxyl oxygen, amino nitrogen, and imidazole nitrogen atoms of the DHTKE peptide. Moreover, the effect of the DHTKE-calcium complex on improving the calcium absorption was investigated in vitro using Caco-2 cells. Results showed that the DHTKE-calcium complex could facilitate the calcium influx into the cytosol and further improve calcium absorption across Caco-2 cell monolayers by more than 7 times when compared to calcium-free control. This study facilitates the understanding about the binding mechanism between peptides and calcium ions as well as suggests a potential application of egg white peptides as nutraceuticals to improve calcium absorption.

Micro-SHINE Uranyl Sulfate Irradiations at the Linac

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

Youker, Amanda J.; Kalensky, Michael; Chemerisov, Sergey

2016-08-01

Peroxide formation due to water radiolysis in a uranyl sulfate solution is a concern for the SHINE Medical Technologies process in which Mo-99 is generated from the fission of dissolved low enriched uranium. To investigate the effects of power density and fission on peroxide formation and uranyl-peroxide precipitation, uranyl sulfate solutions were irradiated using a 50-MeV electron linac as part of the micro-SHINE experimental setup. Results are given for uranyl sulfate solutions with both high and low enriched uranium irradiated at different linac powers.

Fractional absorption of active absorbable algal calcium (AAACa) and calcium carbonate measured by a dual stable-isotope method

USDA-ARS?s Scientific Manuscript database

With the use of stable isotopes, this study aimed to compare the bioavailability of active absorbable algal calcium (AAACa), obtained from oyster shell powder heated to a high temperature, with an additional heated seaweed component (Heated Algal Ingredient, HAI), with that of calcium carbonate. In ...

Sea urchin spine calcite forms via a transient amorphous calcium carbonate phase.

PubMed

Politi, Yael; Arad, Talmon; Klein, Eugenia; Weiner, Steve; Addadi, Lia

2004-11-12

The skeletons of adult echinoderms comprise large single crystals of calcite with smooth convoluted fenestrated morphologies, raising many questions about how they form. By using water etching, infrared spectroscopy, electron diffraction, and environmental scanning electron microscopy, we show that sea urchin spine regeneration proceeds via the initial deposition of amorphous calcium carbonate. Because most echinoderms produce the same type of skeletal material, they probably all use this same mechanism. Deposition of transient amorphous phases as a strategy for producing single crystals with complex morphology may have interesting implications for the development of sophisticated materials.

Isolation of an acidic protein from cholesterol gallstones, which inhibits the precipitation of calcium carbonate in vitro.

PubMed Central

Shimizu, S; Sabsay, B; Veis, A; Ostrow, J D; Rege, R V; Dawes, L G

1989-01-01

In seeking to identify nucleating/antinucleating proteins involved in the pathogenesis of cholesterol gallstones, a major acidic protein was isolated from each of 13 samples of cholesterol gallstones. After the stones were extracted with methyl t-butyl ether to remove cholesterol, and methanol to remove bile salts and other lipids, they were demineralized with EDTA. The extracts were desalted with Sephadex-G25, and the proteins separated by PAGE. A protein was isolated, of molecular weight below 10 kD, which included firmly-bound diazo-positive yellow pigments and contained 24% acidic, but only 7% basic amino acid residues. The presence of N-acetyl glucosamine suggested that this was a glycoprotein. This protein at concentrations as low as 2 micrograms/ml, but neither human serum albumin nor its complex with bilirubin, inhibited calcium carbonate precipitation from a supersaturated solution in vitro. This protein could be precipitated from 0.15 M NaCl solution by the addition of 0.5 M calcium chloride. Considering that cholesterol gallstones contain calcium and pigment at their centers, and that small acidic proteins are important regulators in other biomineralization systems, this protein seems likely to play a role in the pathogenesis of cholesterol gallstones. Images PMID:2592569

Calcium carbonate scale control, effect of material and inhibitors.

PubMed

Macadam, J; Parsons, S A

2004-01-01

This paper focuses on developing a reproducible method for reducing calcium carbonate scale formation on heated surfaces where scaling can cause serious problems. It is known that calcium carbonate precipitation is sensitive to impurity ions, such as iron and zinc, even at trace concentration levels. In this paper two sets of experiments are reported. The first experiments were undertaken to investigate the effect of zinc, copper and iron dosing on CaCO3 nucleation and precipitation. Results from the experiments showed that the most effective inhibitor of CaCO3 precipitation was zinc and the effect was linked to dose levels and temperature. Copper and iron had little effect on precipitation in the dose range investigated. The second trial was undertaken to translate the precipitation data to scale formation. These tests were undertaken at 70 degrees C. 5 mg x L(-1) zinc dose reduced the scale formation by 35%. The effect of iron on calcium carbonate scaling rate was not significant. The physical nature of the material on which the scale is formed also influences the scaling. The scaling experiment was also used to investigate the effect of different surface material (stainless steel, copper and aluminium) on CaCO3 scale formation. Copper surface scaled the most.

D.C. electrical conductivity and conduction mechanism of some azo sulfonyl quinoline ligands and uranyl complexes.

PubMed

El-Ghamaz, N A; Diab, M A; El-Sonbati, A Z; Salem, O L

2011-12-01

Supramolecular coordination of dioxouranium(VI) heterochelates 5-sulphono-7-(4'-X phenylazo)-8-hydroxyquinoline HL(n) (n=1, X=CH(3); n=2, X=H; n=3, X=Cl; n=4, X=NO(2)) have been prepared and characterized with various physico-chemical techniques. The infrared spectral studies showed a monobasic bidentate behavior with the oxygen and azonitrogen donor system. The temperature dependence of the D.C. electrical conductivity of HL(n) ligands and their uranyl complexes has been studied in the temperature range 305-415 K. The thermal activation energies E(a) for HL(n) compounds were found to be in the range 0.44-0.9 eV depending on the nature of the substituent X. The complexation process decreased E(a) values to the range 0.043-045 eV. The electrical conduction mechanism has been investigated for all samples under investigation. It was found to obey the variable range hopping mechanism (VRH). Copyright © 2011 Elsevier B.V. All rights reserved.

Comparison of sevelamer and calcium carbonate on endothelial function and inflammation in patients on peritoneal dialysis.

PubMed

Chennasamudram, Sudha P; Noor, Tanjila; Vasylyeva, Tetyana L

2013-06-01

Hyperphosphataemia is a known independent risk factor for cardiovascular mortality. The objective of the study was to compare the effects of two phosphate binders, sevelamer carbonate and calcium carbonate on endothelial function (EF) and inflammation in patients on peritoneal dialysis (PD) with Type 2 diabetes mellitus (T2DM). Fifteen subjects with hyperphosphataemia discontinued all phosphate binders to undergo a two-week washout and were assigned to sevelamer carbonate or calcium carbonate treatments for eight weeks. After a second two-week washout period, subjects crossed over to either of the alternate treatments for another eight weeks. At the beginning and end of each treatment, biomarkers of EF, pro-inflammatory cytokines, serum albumin, calcium, phosphate and lipids were measured. Sevelamer carbonate significantly improved lipid profile compared with calcium carbonate. Amongst the EF and pro-inflammatory biomarkers, sevelamer carbonate decreased serum endothelin-1, plasminogen activator inhibitor-1, C-reactive protein and interleukin-6. Both phosphate binders were effective in decreasing serum phosphate but sevelamer had a positive effect on EF. Treatment with sevelamer carbonate has beneficial effects compared with calcium carbonate in decreasing inflammation and improving EF in patients with T2DM on PD. © 2013 European Dialysis and Transplant Nurses Association/European Renal Care Association.

Enzyme-accelerated and structure-guided crystallization of calcium carbonate: role of the carbonic anhydrase in the homologous system.

PubMed

Müller, Werner E G; Schlossmacher, Ute; Schröder, Heinz C; Lieberwirth, Ingo; Glasser, Gunnar; Korzhev, Michael; Neufurth, Meik; Wang, Xiaohong

2014-01-01

The calcareous spicules from sponges, e.g. from Sycon raphanus, are composed of almost pure calcium carbonate. In order to elucidate the formation of those structural skeletal elements, the function of the enzyme carbonic anhydrase (CA), isolated from this species, during the in vitro calcium carbonate-based spicule formation, was investigated. It is shown that the recombinant sponge CA substantially accelerates calcium carbonate formation in the in vitro diffusion assay. A stoichiometric calculation revealed that the turnover rate of the sponge CA during the calcification process amounts to 25 CO2s(-1) × molecule CA(-1). During this enzymatically driven process, initially pat-like particles are formed that are subsequently transformed to rhomboid/rhombohedroid crystals with a dimension of ~50 μm. The CA-catalyzed particles are smaller than those which are formed in the absence of the enzyme. The Martens hardness of the particles formed is ~4 GPa, a value which had been determined for other biogenic calcites. This conclusion is corroborated by energy-dispersive X-ray spectroscopy, which revealed that the particles synthesized are composed predominantly of the elements calcium, oxygen and carbon. Surprising was the finding, obtained by light and scanning electron microscopy, that the newly formed calcitic crystals associate with the calcareous spicules from S. raphanus in a highly ordered manner; the calcitic crystals almost perfectly arrange in an array orientation along the two opposing planes of the spicules, leaving the other two plane arrays uncovered. It is concluded that the CA is a key enzyme controlling the calcium carbonate biomineralization process, which directs the newly formed particles to existing calcareous spicular structures. It is expected that with the given tools new bioinspired materials can be fabricated. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Complete genome sequence of Lysinibacillus sphaericus LMG 22257, a strain with ureolytic activity inducing calcium carbonate precipitation.

PubMed

Yan, Wenkai; Xiao, Xiang; Zhang, Yu

2017-03-20

Microbiologically induced calcium carbonate precipitation shows the potential for use in bioremediation and construction consolidation, but the efficiency of this process must be improved. Lysinibacillus sphaericus LMG 22257 is a gram-positive ureolytic strain that has recently been applied for consolidating construction by mediating calcium carbonate precipitation. The complete genome sequence of L. sphaericus LMG 22257 is 3,436,578 base pairs with a GC content of 38.99%. The urea degradation pathway and genes related to extracellular polymeric substance biosynthesis were also identified. The strain can tolerate high alkalinity (pH up to 10) and high urea concentration (up to 3M). These findings provide insights into the microbiologically induced carbonate precipitation and extend the application of the metabolic potential of L. sphaericus LMG 22257 for bioremediation. Copyright © 2017 Elsevier B.V. All rights reserved.

Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite

NASA Astrophysics Data System (ADS)

Aufort, Julie; Ségalen, Loïc; Gervais, Christel; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne

2017-12-01

The stable isotope composition of biogenic apatite is an important geochemical marker that can record environmental parameters and is widely used to infer past climates, biomineralization processes, dietary preferences and habitat of vertebrates. In this study, theoretical equilibrium isotopic fractionation of oxygen, carbon and calcium in hydroxyapatite and carbonate-bearing hydroxyapatite is investigated using first-principles methods based on density-functional theory and compared to the theoretical isotopic fractionation properties of calcite, CO2 and H2O. Considering the variability of apatite crystal-chemistry, special attention is given to specific contributions of crystal sites to isotopic fractionation. Significant internal fractionation is calculated for oxygen and carbon isotopes in CO3 between the different structural sites occupied by carbonate groups in apatite (typically 7‰ for both 18O/16O and 13C/12C fractionation at 37 °C). Compared with calcite-water oxygen isotope fractionation, occurrence of A-type substitution in apatite structure, in addition to the main B-type substitution, could explain the larger temperature dependence of oxygen isotope fractionation measured at low temperature between carbonate in apatite and water. Theoretical internal fractionation of oxygen isotopes between carbonate and phosphate in B-type carbonated apatite (∼8‰ at 37 °C) is consistent with experimental values obtained from modern and well-preserved fossil bio-apatites. Concerning calcium, theoretical results suggest a small fractionation between apatite and calcite (-0.17‰ at 37 °C). Internal fractionation reaching 0.8‰ at 37 °C occurs between the two Ca sites in hydroxyapatite. Furthermore, the Ca isotopic fractionation properties of apatite are affected by the occurrence of carbonate groups, which could contribute to the variability observed on natural samples. Owing to the complexity of apatite crystal-chemistry and in light of the theoretical

Effects of iron and calcium carbonate on the variation and cycling of carbon source in integrated wastewater treatments.

PubMed

Zhimiao, Zhao; Xinshan, Song; Yufeng, Zhao; Yanping, Xiao; Yuhui, Wang; Junfeng, Wang; Denghua, Yan

2017-02-01

Iron and calcium carbonate were added in wastewater treatments as the adjusting agents to improve the contaminant removal performance and regulate the variation of carbon source in integrated treatments. At different temperatures, the addition of the adjusting agents obviously improved the nitrogen and phosphorous removals. TN and TP removals were respectively increased by 29.41% and 23.83% in AC-100 treatment under 1-day HRT. Carbon source from dead algae was supplied as green microbial carbon source and Fe 2+ was supplied as carbon source surrogate. COD concentration was increased to 30mg/L and above, so the problem of the shortage of carbon source was solved. Dead algae and Fe 2+ as carbon source supplement or surrogate played significant role, which was proved by microbial community analysis. According to the denitrification performance in the treatments, dead algae as green microbial carbon source combined with iron and calcium carbonate was the optimal supplement carbon source in wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Obtaining and Characterization of Polyolefin-Filled Calcium Carbonate Composites Modified with Stearic Acid

NASA Astrophysics Data System (ADS)

Croitoru, C.; Pascu, A.; Roata, I. C.; Stanciu, E. M.

2017-06-01

In order to obtain high performance calcium carbonate-reinforced HDPE and PP composites, the dispersibility and compatibility of the inorganic phase in the polymer has been achieved through surface treatment of the amorphous calcium carbonate filler with stearic acid. The surface coating of the inorganic phase has been proved by XRD and FTIR spectroscopy, through forming of an intermediate layer of calcium stearate which acts as a surfactant, efficient in providing an optimum compatibility with the dominatingly hydrophobic polymer matrix, as determined from the structural information obtained through samples cross-sections analysing.

Automatic photometric titrations of calcium and magnesium in carbonate rocks

USGS Publications Warehouse

Shapiro, L.; Brannock, W.W.

1955-01-01

Rapid nonsubjective methods have been developed for the determination of calcium and magnesium in carbonate rocks. From a single solution of the sample, calcium is titrated directly, and magnesium is titrated after a rapid removal of R2O3 and precipitation of calcium as the tungstate. A concentrated and a dilute solution of disodium ethylenediamine tetraacetate are used as titrants. The concentrated solution is added almost to the end point, then the weak solution is added in an automatic titrator to determine the end point precisely.

The effect of pigeon yolk sac fluid on the growth behavior of calcium carbonate crystals.

PubMed

Song, Juan; Cheng, Haixia; Shen, Xinyu; Tong, Hua

2015-03-01

Previous experiments have proved that thermodynamically unstable calcium carbonate vaterite can exist for long periods in the yolk sac of a pigeon embryo. The aim of this article was to demonstrate the effect of in vitro mineralization of yolk sac fluid on calcium carbonate by direct precipitation. Experiments were conducted using pigeon yolk sac fluid and using lecithin extracted from pigeon yolk sac fluid as a control to investigate the regulating effects of the organic components in the embryo on the formation of the calcium carbonate precipitate. Multiple characterization methods were employed to study the various morphological patterns, sizes, crystal growth, and crystal phase transformations of the calcium carbonate precipitates as regulated by the yolk sac fluid extracted at different stages of incubation. The experimental results demonstrate that as the incubation proceeds towards the later stages, the composition and environmental features of the yolk sac fluid become more favorable for the formation of relatively unstable calcium carbonate phases with high energies of the vaterite state. The experiments conducted with extracted lecithin as the template for crystal growth yielded similar results. A large amount of organic molecules with polar functional groups carried by the yolk sac fluid have strong effects and can both initially induce the crystallization and regulate the aggregation of calcium carbonate. Furthermore, this regulation process is found to be closely related to the lecithin contained in yolk sac fluid. These observations confirm the changes in yolk sac fluid composition during incubation have significant effects on the production of vaterite, which implicates the calcium transport during embryo growth. © 2015 Poultry Science Association Inc.

Chemical controls on uranyl citrate speciation and the self-assembly of nanoscale macrocycles and sandwich complexes in aqueous solutions.

PubMed

Basile, M; Unruh, D K; Gojdas, K; Flores, E; Streicher, L; Forbes, T Z

2015-03-28

Uranyl citrate forms trimeric species at pH > 5.5, but exact structural characteristics of these important oligomers have not previously been reported. Crystallization and structural characterization of the trimers suggests the self-assembly of the 3 : 3 and 3 : 2 U : Cit complexes into larger sandwich and macrocyclic molecules. Raman spectroscopy and ESI-MS have been utilized to investigate the relative abundance of these species in solution under varying pH and citrate concentrations. Additional dynamic light scattering experiments indicate that self-assembly of the larger molecules does occur in aqueous solution.

Microwave hydrothermal transformation of amorphous calcium carbonate nanospheres and application in protein adsorption.

PubMed

Qi, Chao; Zhu, Ying-Jie; Chen, Feng

2014-03-26

Calcium carbonate and calcium phosphate are the main components of biominerals. Among all of the forms of biominerals, amorphous calcium carbonate (ACC) and amorphous calcium phosphate (ACP) are the most important forms because they play a pivotal role in the process of biomineralization and are the precursors to the crystalline polymorphs. In this work, we first synthesized ACC in vitro using adenosine 5'-triphosphate disodium salt (ATP) as the stabilizer and investigated the transformation of the ACC under microwave hydrothermal conditions, and ACC/ACP composite nanospheres and carbonated hydroxyapatite (CHA) nanospheres were successfully prepared. In this novel strategy, ATP has two main functions: it serves as the stabilizer for ACC and the phosphorus source for ACP and CHA. Most importantly, the morphology and the size of the ACC precursor can be well-preserved after microwave heating, so it provides a new method for the preparation of calcium phosphate nanostructured materials using phosphorus-containing biomolecule-stabilized ACC as the precursor. Furthermore, the as-prepared ACC/ACP composite nanospheres have excellent biocompatibility and high protein adsorption capacity, indicating that they are promising for applications in biomedical fields such as drug delivery and protein adsorption.

Formation of ternary CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) complexes under neutral to weakly alkaline conditions.

PubMed

Lee, Jun-Yeop; Yun, Jong-Il

2013-07-21

The chemical behavior of ternary Ca-UO2-CO3 complexes was investigated by using time-resolved laser fluorescence spectroscopy (TRLFS) in combination with EDTA complexation at pH 7-9. A novel TRLFS revealed two distinct fluorescence lifetimes of 12.7 ± 0.2 ns and 29.2 ± 0.4 ns for uranyl complexes which were formed increasingly dependent upon the calcium ion concentration, even though nearly indistinguishable fluorescence peak shapes and positions were measured for both Ca-UO2-CO3 complexes. For identifying the stoichiometric number of complexed calcium ions, slope analysis in terms of relative fluorescence intensity versus calcium concentration was employed in a combination with the complexation reaction of CaEDTA(2-) by adding EDTA. The formation of CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) was identified under given conditions and their formation constants were determined at I = 0.1 M Na/HClO4 medium, and extrapolated to infinitely dilute solution using specific ion interaction theory (SIT). As a result, the formation constants for CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) were found to be log β113(0) = 27.27 ± 0.14 and log β213(0) = 29.81 ± 0.19, respectively, providing that the ternary Ca-UO2-CO3 complexes were predominant uranium(vi) species at neutral to weakly alkaline pH in the presence of Ca(2+) and CO3(2-) ions.

Amorphous calcium carbonate: A precursor phase for aragonite in shell disease of the pearl oyster.

PubMed

Huang, Jingliang; Liu, Chuang; Xie, Liping; Zhang, Rongqing

2018-02-26

Amorphous calcium carbonate (ACC) has long been shown to act as an important constituent or precursor phase for crystalline material in mollusks. However, the presence and the role of ACC in bivalve shell formation are not fully studied. In this study, we found that brown deposits containing heterogeneous calcium carbonates were precipitated when a shell disease occurred in the pearl oyster Pinctada fucata. Calcein-staining of the brown deposits indicated that numerous amorphous calcium deposits were present, which was further confirmed by Fourier-transform infrared spectroscopy (FTIR), Raman spectrum and X-ray difraction (XRD) analyses. So we speculate that ACC plays an important role in rapid calcium carbonate precipitation during shell repair process in diseased oysters. Copyright © 2018 Elsevier Inc. All rights reserved.

Preparation and characterization of carbonic anhydrase-conjugated liposomes for catalytic synthesis of calcium carbonate particles.

PubMed

Maeshima, Keisuke; Yoshimoto, Makoto

2017-10-01

The biomimetic approach using immobilized enzymes is useful for the synthesis of structurally defined inorganic materials. In this work, carbonic anhydrase (CA) from bovine erythrocytes was covalently conjugated at 25°C to the liposomes composed of 15mol% 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine-N-(glutaryl) (NG-POPE), and the zwitterionic and anionic phospholipids with the same acyl chains as NG-POPE. For the conjugation, the carboxyl groups of liposomal NG-POPE were activated with 11mM 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and 4.6mM N-hydroxysulfosuccinimide (sulfo-NHS). The carbonic anhydrase-conjugated liposomes (CALs) with the mean hydrodynamic diameter of 149nm showed the esterase activity corresponding to on average 5.5×10 2 free CA molecules per liposome. On the other hand, the intrinsic fluorescence and absorbance measurements consistently revealed that on average 1.4×10 3 CA molecules were conjugated to a liposome, suggesting that the molecular orientation of enzyme affected its activity. The formation of calcium carbonate particles was significantly accelerated by the CALs ([lipid]=50μ M) in the 0.3M Tris solution at 10-40°C with dissolved CO 2 (≈17mM) and CaCl 2 (46mM). The anionic CALs were adsorbed with calcium as revealed with the ζ-potential measurements. The CAL system offered the calcium-rich colloidal interface where the bicarbonate ions were catalytically produced by the liposome-conjugated CA molecules. The CALs also functioned in the external loop airlift bubble column operated with a model flue gas (10vol/vo% CO 2 ), yielding partly agglomerated calcium carbonate particles as observed with the scanning electron microscopy (SEM). Copyright © 2017 Elsevier Inc. All rights reserved.

Calcium and Oxygen Isotopic Composition of Calcium Carbonates

NASA Astrophysics Data System (ADS)

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

2016-04-01

Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40

Linear-dendritic block copolymers as a green scale inhibitor for calcium carbonate in cooling water systems.

PubMed

Liu, Guangqing; Xue, Mengwei; Liu, Qinpu; Zhou, Yuming

2017-01-01

Water-soluble monomer APEG-PG-(OH)n were produced and the Structure of APEG-PG-(OH)5 were identified by 1 H-NMR. APEG-PG-(OH)n were copolymerized with maleic anhydride (MA) to synthesize no phosphate and nitrogen free calcium carbonate inhibitor MA/APEG-PG-(OH)n. The structure and thermal property of MA/APEG-PG-(OH)5 were characterized and measured by 1 H-NMR, GPC and TGA. The observation shows that the dosage and n value of MA/APEG-PG-(OH)n plays an important role on CaCO 3 inhibition. MA/APEG-PG-(OH)5 displays superior ability to inhibit the precipitation of calcium carbonate, with approximately 97% inhibition at a level of 8 mg/L. The effect on formation of CaCO 3 was investigated with combination of SEM and XRD analysis.

Linear-dendritic block copolymers as a green scale inhibitor for calcium carbonate in cooling water systems

PubMed Central

Liu, Guangqing; Xue, Mengwei; Liu, Qinpu; Zhou, Yuming

2017-01-01

Abstract Water-soluble monomer APEG-PG-(OH)n were produced and the Structure of APEG-PG-(OH)5 were identified by 1H-NMR. APEG-PG-(OH)n were copolymerized with maleic anhydride (MA) to synthesize no phosphate and nitrogen free calcium carbonate inhibitor MA/APEG-PG-(OH)n. The structure and thermal property of MA/APEG-PG-(OH)5 were characterized and measured by 1H-NMR, GPC and TGA. The observation shows that the dosage and n value of MA/APEG-PG-(OH)n plays an important role on CaCO3 inhibition. MA/APEG-PG-(OH)5 displays superior ability to inhibit the precipitation of calcium carbonate, with approximately 97% inhibition at a level of 8 mg/L. The effect on formation of CaCO3 was investigated with combination of SEM and XRD analysis. PMID:29491811

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

PubMed

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

2007-07-01

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

XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

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

Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai

In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η 2 motifs proposed by small molecule andmore » computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ 2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.« less

XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

DOE PAGES

Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai; ...

2015-11-12

In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η 2 motifs proposed by small molecule andmore » computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ 2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.« less

Amorphous calcium carbonate associated with biofilms in hot spring deposits

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2012-08-01

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

Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

DOE PAGES

Martin-Diaconescu, Vlad; Gennari, Marcello; Gerey, Bertrand; ...

2014-12-10

Calcium K-edge pre-edges coupled with TD-DFT theoretical calculation of spectra provide a powerful approach for the characterization of complex calcium centers in inorganic and bioinorganic chemistry. Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodologymore » to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed.« less

Unexpected link between polyketide synthase and calcium carbonate biomineralization.

PubMed

Hojo, Motoki; Omi, Ai; Hamanaka, Gen; Shindo, Kazutoshi; Shimada, Atsuko; Kondo, Mariko; Narita, Takanori; Kiyomoto, Masato; Katsuyama, Yohei; Ohnishi, Yasuo; Irie, Naoki; Takeda, Hiroyuki

2015-01-01

Calcium carbonate biominerals participate in diverse physiological functions. Despite intensive studies, little is known about how mineralization is initiated in organisms. We analyzed the medaka spontaneous mutant, ha, defective in otolith (calcareous ear stone) formation. ha lacks a trigger for otolith mineralization, and the causative gene was found to encode polyketide synthase (pks), a multifunctional enzyme mainly found in bacteria, fungi, and plant. Subsequent experiments demonstrate that the products of medaka PKS, most likely polyketides or their derivatives, act as nucleation facilitators in otolith mineralization. The generality of this novel PKS function is supported by the essential role of echinoderm PKS in calcareous skeleton formation together with the presence of PKSs in a much wider range of animals from coral to vertebrates. The present study first links PKS to biomineralization and provides a genetic cue for biogeochemistry of carbon and calcium cycles.

On the origin of the cation templated self-assembly of uranyl-peroxide nanoclusters.

PubMed

Miró, Pere; Pierrefixe, Simon; Gicquel, Mickaël; Gil, Adrià; Bo, Carles

2010-12-22

Uranyl-peroxide nanoclusters display different topologies based on square, pentagonal and hexagonal building blocks. Computed complexation energies of different cations (Li(+), Na(+), K(+), Rb(+), and Cs(+)) with [UO(2)(O(2))(H(2)O)](n) (n = 4, 5, and 6) macrocycles suggest a strong cation templating effect. The inherent bent structure of a U-O(2)-U model dimer is demonstrated and justified through the analysis of its electronic structure, as well as of the inherent curvature of the four-, five-, and six-uranyl macrocyles. The curvature is enhaced by cation coordination, which is suggested to be the driving force for the self-assembly of the nanocapsules.

ATP-stabilized amorphous calcium carbonate nanospheres and their application in protein adsorption.

PubMed

Qi, Chao; Zhu, Ying-Jie; Lu, Bing-Qiang; Zhao, Xin-Yu; Zhao, Jing; Chen, Feng; Wu, Jin

2014-05-28

Calcium carbonate is a common substance found in rocks worldwide, and is the main biomineral formed in shells of marine organisms and snails, pearls and eggshells. Amorphous calcium carbonate (ACC) is the least stable polymorph of calcium carbonate, which is so unstable under normal conditions that it is difficult to be prepared in vitro because it rapidly crystallizes to form one of the more stable polymorphs in aqueous solution. Herein, we report the successful synthesis of highly stable ACC nanospheres in vitro using adenosine 5'-triphosphate disodium salt (ATP) as a stabilizer. The effect of ATP on the stability of ACC nanospheres is investigated. Our experiments show that ATP plays an unique role in the stabilization of ACC nanospheres in aqueous solution. Moreover, the as-prepared ACC nanospheres are highly stable in phosphate buffered saline for a relatively long period of time (12 days) even under relatively high concentrations of calcium and phosphate ions. The cytotoxicity tests show that the as-prepared highly stable ACC nanospheres have excellent biocompatibility. The highly stable ACC nanospheres have high protein adsorption capacity, implying that they are promising for applications in biomedical fields such as drug delivery and protein adsorption. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Genesis of kasolite associated with aplite-pegmatite at Jabal Sayid, Hijaz region, Kingdom of Saudi Arabia

NASA Astrophysics Data System (ADS)

Dawood, Yehia H.; Harbi, Hesham M.; Abd El-Naby, Hamdy H.

2010-01-01

In this study, we report kasolite Pb(UO 2)SiO 4·(H 2O) for the first time as a main uranyl mineral in the mineralized aplite-pegmatite of Jabal Sayid, Hijaz region. It commonly forms clusters of yellow acicular crystals in the voids and fractures. The mineral chemistry and mineralogical characteristics of kasolite were investigated using different techniques. Calcium, iron and phosphorus are detected in kasolite in addition to its major constituents; uranium, lead and silicon. Lead does not exist as a radiogenic product and not even as a substitute for uranium in the mineral structure. Alternatively, galena mineralization could be considered as a source for lead. The fluoride and carbonate complexes played a significant role in the formation of kasolite. High temperature hydrothermal solutions reacted with pre-existing uranium-bearing metamictized accessory minerals such as pyrochlore, U-rich thorite and zircon to form uranous fluoride complexes. These complexes are predominant in reducing environment and at pH 4. When the fluids approached the surface passing through fracture system, the oxygen fugacity ( fO 2) and the pH increased because of the loss of volatile components. At these conditions, uranous fluorides would convert to uranyl fluoride complexes UO 2F 3-. Further decrease in temperature was associated with the decay of the activity of fluorine ion by the dilution of hydrothermal solutions and precipitation of fluorite. At this condition, uranyl-carbonate complexes are favoured. These complexes were combined later with silica and lead to form kasolite.

Waste oil shale ash as a novel source of calcium for precipitated calcium carbonate: carbonation mechanism, modeling, and product characterization.

PubMed

Velts, O; Uibu, M; Kallas, J; Kuusik, R

2011-11-15

In this paper, a method for converting lime-containing oil shale waste ash into precipitated calcium carbonate (PCC), a valuable commodity is elucidated. The mechanism of ash leachates carbonation was experimentally investigated in a stirred semi-batch barboter-type reactor by varying the CO(2) partial pressure, gas flow rate, and agitation intensity. A consistent set of model equations and physical-chemical parameters is proposed to describe the CaCO(3) precipitation process from oil shale ash leachates of complex composition. The model enables the simulation of reactive species (Ca(2+), CaCO(3), SO(4)(2-), CaSO(4), OH(-), CO(2), HCO(3)(-), H(+), CO(3)(2-)) concentration profiles in the liquid, gas, and solid phases as well as prediction of the PCC formation rate. The presence of CaSO(4) in the product may also be evaluated and used to assess the purity of the PCC product. A detailed characterization of the PCC precipitates crystallized from oil shale ash leachates is also provided. High brightness PCC (containing up to ∼ 96% CaCO(3)) with mean particle sizes ranging from 4 to 10 μm and controllable morphology (such as rhombohedral calcite or coexisting calcite and spherical vaterite phases) was obtained under the conditions studied. Copyright © 2011 Elsevier B.V. All rights reserved.

The flame photometric determination of calcium in phosphate, carbonate, and silicate rocks

USGS Publications Warehouse

Kramer, H.

1957-01-01

A flame photometric method of determining calcium in phosphate, carbonate, and silicate locks has been developed Aluminum and phosphate interference was overcome by the addition of a large excess of magnesium. The method is rapid and suitable for routine analysis Results obtained are within ?? 2% of the calcium oxide content. ?? 1957.

Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

PubMed

Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

2012-09-17

Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

Uranyl sulfate irradiations at the Van de Graaff: A means to combat uranyl peroxide precipitation

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

Youker, Amanda J.; Kalensky, Michael; Quigley, Kevin J.

As part of an effort to support SHINE Medical Technologies in developing a process to produce Mo-99 by neutron-induced fission, a series of irradiation experiments was performed with a 3 MeV Van de Graaff accelerator to generate high radiation doses in 0.5–2 mL uranyl sulfate solutions. The purpose was to determine what conditions result in uranyl peroxide precipitation and what can be done to prevent its formation. The effects of temperature, dose rate, uranium concentration, and the addition of known catalysts for the destruction of peroxide were determined.

Coexistence of three calcium carbonate polymorphs in the shell of the Antarctic clam Laternula elliptica

NASA Astrophysics Data System (ADS)

Nehrke, Gernot; Poigner, Harald; Wilhelms-Dick, Dorothee; Brey, Thomas; Abele, Doris

2012-05-01

We analyzed shell cuts of five individuals of the Antarctic bivalve Laternula elliptica from three locations along the Antarctic Peninsula by means of Confocal Raman Microscopy (CRM) as well as Electron Microprobe (EMP). The shell of L. elliptica has been previously described as being composed of aragonite exclusively. Now, CRM mapping reveals that three polymorphs of calcium carbonate - aragonite, calcite, and vaterite - are present in the chondrophore region of the examined individuals. Annual shell growth layers continue through aragonite and vaterite, suggesting simultaneous mineralization of both polymorphs. Spatially congruent EMP scans showed that the calcium carbonate polymorph affects the distribution of magnesium and strontium within the chondrophore. This is, to our knowledge, the first report of the coexistence of these three calcium carbonate polymorphs within the mineralized structures of a marine calcifying organism. Particularly the presence of vaterite is unexpected, but shows striking similarities to some fish otoliths. The strong effect of the calcium carbonate polymorph on trace element incorporation restrict the suitability of magnesium and strontium based proxies for the chondrophore area of L. elliptica.

Precipitation of calcium carbonate in aqueous solutions in presence of ethylene glycol and dodecane.

NASA Astrophysics Data System (ADS)

Natsi, Panagiota D.; Rokidi, Stamatia; Koutsoukos, Petros G.

2015-04-01

The formation of calcium carbonate (CaCO3) in aqueous supersaturated solutions has been intensively studied over the past decades, because of its significance for a number of processes of industrial and environmental interest. In the oil and gas production industry the deposition of calcium carbonate affects adversely the productivity of the wells. Calcium carbonate scale deposits formation causes serious problems in water desalination, CO2 sequestration in subsoil wells, in geothermal systems and in heat exchangers because of the low thermal coefficient of the salt. Amelioration of the operational conditions is possible only when the mechanisms underlying nucleation and crystal growth of calcium carbonate in the aqueous fluids is clarified. Given the fact that in oil production processes water miscible and immiscible hydrocarbons are present the changes of the dielectric constant of the fluid phase has serious impact in the kinetics of calcium carbonate precipitation, which remains largely unknown. The problem becomes even more complicated if polymorphism exhibited by calcium carbonate is also taken into consideration. In the present work, the stability of aqueous solutions supersaturated with respect to all calcium carbonate polymorphs and the subsequent kinetics of calcium carbonate precipitation were measured. The measurements included aqueous solutions and solutions in the presence of water miscible (ethylene glycol, MEG) and water immiscible organics (n-dodecane). All measurements were done at conditions of sustained supersaturation using the glass/ Ag/AgCl combination electrode as a probe of the precipitation and pH as the master variable for the addition of titrant solutions with appropriate concentration needed to maintenance the solution supersaturation. Initially, the metastable zone width was determined from measurements of the effect of the solution supersaturation on the induction time preceding the onset of precipitation at free-drift conditions. The

Uranium: A Dentist's perspective

PubMed Central

Toor, R. S. S.; Brar, G. S.

2012-01-01

Uranium is a naturally occurring radionuclide found in granite and other mineral deposits. In its natural state, it consists of three isotopes (U-234, U-235 and U-238). On an average, 1% – 2% of ingested uranium is absorbed in the gastrointestinal tract in adults. The absorbed uranium rapidly enters the bloodstream and forms a diffusible ionic uranyl hydrogen carbonate complex (UO2HCO3+) which is in equilibrium with a nondiffusible uranyl albumin complex. In the skeleton, the uranyl ion replaces calcium in the hydroxyapatite complex of the bone crystal. Although in North India, there is a risk of radiological toxicity from orally ingested natural uranium, the principal health effects are chemical toxicity. The skeleton and kidney are the primary sites of uranium accumulation. Acute high dose of uranyl nitrate delays tooth eruption, and mandibular growth and development, probably due to its effect on target cells. Based on all previous research and recommendations, the role of a dentist is to educate the masses about the adverse effects of uranium on the overall as well as the dental health. The authors recommended that apart from the discontinuation of the addition of uranium to porcelain, the Public community water supplies must also comply with the Environmental Protection Agency (EPA) standards of uranium levels being not more than 30 ppb (parts per billion). PMID:24478959

Molecular dynamics simulations of uranyl adsorption and structure on the basal surface of muscovite

DOE PAGES

Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Cygan, Randall T.

2014-02-05

Anthropogenic activities have led to an increased concentration of uranium on the Earth’s surface and potentially in the subsurface with the development of nuclear waste repositories. Uranium is soluble in groundwater, and its mobility is strongly affected by the presence of clay minerals in soils and in subsurface sediments. We use molecular dynamics simulations to probe the adsorption of aqueous uranyl (UO 2 2+) ions onto the basal surface of muscovite, a suitable proxy for typically ultrafine-grained clay phases. Model systems include the competitive adsorption between potassium counterions and aqueous ions (0.1 M and 1.0 M UO 2Cl 2 ,more » 0.1 M NaCl). We find that for systems with potassium and uranyl ions present, potassium ions dominate the adsorption phenomenon. Potassium ions adsorb entirely as inner-sphere complexes associated with the ditrigonal cavity of the basal surface. Uranyl ions adsorb in two configurations when it is the only ion species present, and in a single configuration in the presence of potassium. Finally, the majority of adsorbed uranyl ions are tilted less than 45° relative to the muscovite surface, and are associated with the Si 4Al 2 rings near aluminum substitution sites.« less

Viral lysis of photosynthesizing microbes as a mechanism for calcium carbonate nucleation in seawater

USGS Publications Warehouse

Lisle, John T.; Robbins, Lisa L.

2016-01-01

Removal of carbon through the precipitation and burial of calcium carbonate in marine sediments constitutes over 70% of the total carbon on Earth and is partitioned between coastal and pelagic zones. The precipitation of authigenic calcium carbonate in seawater, however, has been hotly debated because despite being in a supersaturated state, there is an absence of persistent precipitation. One of the explanations for this paradox is the geochemical conditions in seawater cannot overcome the activation energy barrier for the first step in any precipitation reaction; nucleation. Here we show that virally induced rupturing of photosynthetic cyanobacterial cells releases cytoplasmic-associated bicarbonate at concentrations ~23-fold greater than in the surrounding seawater, thereby shifting the carbonate chemistry toward the homogenous nucleation of one or more of the calcium carbonate polymorphs. Using geochemical reaction energetics, we show the saturation states (Ω) in typical seawater for calcite (Ω = 4.3), aragonite (Ω = 3.1), and vaterite (Ω = 1.2) are significantly elevated following the release and diffusion of the cytoplasmic bicarbonate (Ωcalcite = 95.7; Ωaragonite = 68.5; Ωvaterite = 25.9). These increases in Ω significantly reduce the activation energy for nuclei formation thresholds for all three polymorphs, but only vaterite nucleation is energetically favored. In the post-lysis seawater, vaterite's nuclei formation activation energy is significantly reduced from 1.85 × 10−17 J to 3.85 × 10−20 J, which increases the nuclei formation rate from highly improbable (<<1.0 nuclei cm−3 s−1) to instantaneous (8.60 × 1025 nuclei cm−3 s−1). The proposed model for homogenous nucleation of calcium carbonate in seawater describes a mechanism through which the initial step in the production of carbonate sediments may proceed. It also presents an additional role of photosynthesizing microbes and their viruses in marine carbon cycles and

Thermal breakdown of calcium carbonate and constraints on its use as a biomarker

NASA Astrophysics Data System (ADS)

Thompson, Stephen P.; Parker, Julia E.; Tang, Chiu C.

2014-02-01

Observed differences in the thermal behaviour of calcium carbonates of biogenic and abiogenic origin (phase transformation and breakdown temperatures) are widely cited as potential biomarkers for whether life once existed on Mars. Although seemingly compelling, there has been no systematic investigation into the physical mechanism behind these apparent differences and therefore no direct proof that they are uniquely diagnostic of a biogenic versus abiogenic formation. In this paper we present a laboratory investigation into the thermal behaviour of two high purity calcium carbonates, one of which was produced in the presence of an amino acid as a biomimetic carbonate. In situ synchrotron X-ray powder diffraction measurements show the aragonite-to-calcite phase transition and calcite-to-oxide breakdown temperatures are significantly lower in the biomimetic carbonate. The observed thermal differences closely match reported differences between biogenic and geological abiogenic carbonates. The biomimetic carbonate exhibits a modified crystal morphology, with a highly strained internal crystal lattice, similar to biogenic carbonate structures. Since biogenic carbonates are formed in the presence of organic macromolecules such as amino acids, the induced microstrain appears to be the defining common factor as it adds an additional energy term to the carbonate lattice energy, which lowers the activation energy required for structural transformation or decomposition. Although produced via biomimetic means, the carbonate investigated here is nevertheless abiogenic in origin and we propose that given suitable localised conditions such as pooled water and a supply of organic molecules, naturally occurring biomimetic carbonates could have similarly formed on the martian surface and could therefore exhibit the same thermal characteristics as biogenic carbonate. Thus as a limiting case - without other supporting observations - the thermal behaviour of martian calcium carbonate

Evidence for the involvement of carbonic anhydrase and urease in calcium carbonate formation in the gravity-sensing organ of Aplysia californica

NASA Technical Reports Server (NTRS)

Pedrozo, H. A.; Schwartz, Z.; Dean, D. D.; Harrison, J. L.; Campbell, J. W.; Wiederhold, M. L.; Boyan, B. D.

1997-01-01

To better understand the mechanisms that could modulate the formation of otoconia, calcium carbonate granules in the inner ear of vertebrate species, we examined statoconia formation in the gravity-sensing organ, the statocyst, of the gastropod mollusk Aplysia californica using an in vitro organ culture model. We determined the type of calcium carbonate present in the statoconia and investigated the role of carbonic anhydrase (CA) and urease in regulating statocyst pH as well as the role of protein synthesis and urease in statoconia production and homeostasis in vitro. The type of mineral present in statoconia was found to be aragonitic calcium carbonate. When the CA inhibitor, acetazolamide (AZ), was added to cultures of statocysts, the pH initially (30 min) increased and then decreased. The urease inhibitor, acetohydroxamic acid (AHA), decreased statocyst pH. Simultaneous addition of AZ and AHA caused a decrease in pH. Inhibition of urease activity also reduced total statoconia number, but had no effect on statoconia volume. Inhibition of protein synthesis reduced statoconia production and increased statoconia volume. In a previous study, inhibition of CA was shown to decrease statoconia production. Taken together, these data show that urease and CA play a role in regulating statocyst pH and the formation and maintenance of statoconia. CA produces carbonate ion for calcium carbonate formation and urease neutralizes the acid formed due to CA action, by production of ammonia.

Development of Bio-Based Foams Prepared from Pbat/Pla Reinforced with Bio-Calcium Carbonate Compatibilized by Electron-Beam Radiation

NASA Astrophysics Data System (ADS)

Cardoso, Elizabeth Carvalho L.; Seixas, Marcus Vinicius S.; Wiebeck, Helio; Oliveira, René R.; Machado, Glauson Aparecido F.; Moura, Esperidiana A. B.

In Brazil, the food industry generates every year huge amounts of avian eggshell waste, an industrial byproduct containing 95% of calcium carbonate, and its disposal constitutes a serious environmental hazard. This study aims to the development of bio-foams from PBAT/PLA blends reinforced with bio-calcium carbonate from eggshells. Composites were obtained by melting extrusion process, blending PBAT/PLA (50/50) with 25% of bio-calcium carbonate, PBAT/PLA (50/45) with 25% of bio-calcium carbonate and 5 % of pre-irradiated PLA and PBAT/PLA (50/40) with 25% of bio-calcium carbonate and 10 % of pre-irradiated PLA. PLA was previously e-beam irradiated at 150kGy in air and used as compatibilizer agent. The composites were then extruded in a Rheomex 332p single special screw for foaming. Samples were submitted to Tensile and Compression tests, MFI, DSC, TGA, XRD and FEG/SEM, analyses.

The formation of web-like connection among electrospun chitosan/PVA fiber network by the reinforcement of ellipsoidal calcium carbonate.

PubMed

Sambudi, Nonni Soraya; Kim, Minjeong G; Park, Seung Bin

2016-03-01

The electrospun fibers consist of backbone fibers and nano-branch network are synthesized by loading of ellipsoidal calcium carbonate in the mixture of chitosan/poly(vinyl alcohol) (PVA) followed by electrospinning. The synthesized ellipsoidal calcium carbonate is in submicron size (730.7±152.4 nm for long axis and 212.6±51.3 nm for short axis). The electrospun backbone fibers experience an increasing in diameter by loading of calcium carbonate from 71.5±23.4 nm to 281.9±51.2 nm. The diameters of branch fibers in the web-network range from 15 nm to 65 nm with most distributions of fibers are in 30-35 nm. Calcium carbonate acts as reinforcing agent to improve the mechanical properties of fibers. The optimum value of Young's modulus is found at the incorporation of 3 wt.% of calcium carbonate in chitosan/PVA fibers, which is enhanced from 15.7±3 MPa to 432.4±94.3 MPa. On the other hand, the ultimate stress of fibers experiences a decrease. This result shows that the fiber network undergoes changes from flexible to more stiff by the inclusion of calcium carbonate. The thermal analysis results show that the crystallinity of polymer is changed by the existence of calcium carbonate in the fiber network. The immersion of fibers in simulated body fluid (SBF) results in the formation of apatite on the surface of fibers. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2012-06-01

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

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

PubMed Central

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

2012-01-01

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

Uranyl extraction by N,N-dialkylamide ligands studied using static and dynamic DFT simulations.

PubMed

Sieffert, Nicolas; Wipff, Georges

2015-02-14

We report DFT static and dynamic studies on uranyl complexes [UO(2)(NO(3))x(H(2)O)(y)L(z)](2-x) involved in the uranyl extraction from water to an "oil" phase (hexane) by an amide ligand L (N,N-dimethylacetamide). Static DFT results "in solution" (continuum SMD models for water and hexane) predict that the stepwise formation of [UO(2)(NO(3))(2)L(2)] from the UO(2)(H(2)O)(5)(2+) species is energetically favourable, and allow us to compare cis/trans isomers of penta- and hexa-coordinated complexes and key intermediates in the two solvents. DFT-MD simulations of [UO(2)(NO(3))(2)L(2)], [UO(2)(NO(3))(2)(H(2)O)L(2)], and [UO(2)(NO(3))(H(2)O)L(2)](+) species in explicit solvent environments (water, hexane, or the water/hexane interface) represented at the MM or full-DFT level reveal a versatile solvent dependent binding mode of nitrates, also evidenced by metadynamics simulations. In water and at the interface, the latter exchange from bi- to monodentate, via in plane rotational motions in some cases. Remarkably, structures of complexes at the interface are more "water-like" than gas phase- or hexane-like. Thus, the order of U-O(NO(3))/U-O(L) bond distances observed in the gas phase (U-O(nit) < U-OL) is inverted at the interface and in water. Overall, the results are consistent with the experimental observation of uranyl extraction from nitric acid solutions by amide analogues (bearing "fatty" substituents), and allow us to propose possible extraction mechanisms, involving complexation of L "right at the interface". They also point to the importance of the solvent environment and the dynamics on the structure and stability of the complexes.

Calcium and organic matter removal by carbonation process with waste incineration flue gas towards improvement of leachate biotreatment performance.

PubMed

Zhang, Cheng; Zhu, Xuedong; Wu, Liang; Li, Qingtao; Liu, Jianyong; Qian, Guangren

2017-09-01

Municipal solid wastes incineration (MSWI) flue gas was employed as the carbon source for in-situ calcium removal from MSWI leachate. Calcium removal efficiency was 95-97% with pH of 10.0-11.0 over 100min of flue gas aeration, with both bound Ca and free Ca being removed effectively. The fluorescence intensity of tryptophan, protein-like and humic acid-like compounds increased after carbonation process. The decrease of bound Ca with the increase of precipitate indicated that calcium was mainly converted to calcium carbonate precipitate. It suggested that the interaction between dissolved organic matter and Ca 2+ was weakened. Moreover, 10-16% of chemical oxygen demand removal and the decrease of ultraviolet absorption at 254nm indicated that some organics, especially aromatic compound decreased via adsorption onto the surface of calcium carbonate. The results indicate that introduce of waste incineration flue gas could be a feasible way for calcium removal from leachate. Copyright © 2017 Elsevier Ltd. All rights reserved.

Computer simulation of uranyl uptake by the rough lipopolysaccharide membrane of Pseudomonas aeruginosa.

PubMed

Lins, Roberto D; Vorpagel, Erich R; Guglielmi, Matteo; Straatsma, T P

2008-01-01

Heavy metal environmental contaminants cannot be destroyed but require containment, preferably in concentrated form, in a solid or immobile form for recycling or final disposal. Microorganisms are able to take up and deposit high levels of contaminant metals, including radioactive metals such as uranium and plutonium, into their cell wall. Consequently, these microbial systems are of great interest as the basis for potential environmental bioremediation technologies. The outer membranes of Gram-negative microbes are highly nonsymmetric and exhibit a significant electrostatic potential gradient across the membrane. This gradient has a significant effect on the uptake and transport of charged and dipolar compounds. However, the effectiveness of microbial systems for environmental remediation will depend strongly on specific properties that determine the uptake of targeted contaminants by a particular cell wall. To aid in the design of microbial remediation technologies, knowledge of the factors that determine the affinity of a particular bacterial outer membrane for the most common ionic species found in contaminated soils and groundwater is of great importance. Using our previously developed model for the lipopolysaccharide (LPS) membrane of Pseudomonas aeruginosa, this work presents the potentials of mean force as the estimate of the free energy profile for uptake of sodium, calcium, chloride, uranyl ions, and a water molecule by the bacterial LPS membrane. A compatible classical parameter set for uranyl has been developed and validated. Results show that the uptake of uranyl is energetically a favorable process relative to the other ions studied. At neutral pH, this nuclide is shown to be retained on the surface of the LPS membrane through chelation with the carboxyl and hydroxyl groups located in the outer core.

Climatically driven loss of calcium in steppe soil as a sink for atmospheric carbon

USGS Publications Warehouse

Lapenis, A.G.; Lawrence, G.B.; Bailey, S.W.; Aparin, B.F.; Shiklomanov, A.I.; Speranskaya, N.A.; Torn, M.S.; Calef, M.

2008-01-01

During the last several thousand years the semi-arid, cold climate of the Russian steppe formed highly fertile soils rich in organic carbon and calcium (classified as Chernozems in the Russian system). Analysis of archived soil samples collected in Kemannaya Steppe Preserve in 1920, 1947, 1970, and fresh samples collected in 1998 indicated that the native steppe Chernozems, however, lost 17-28 kg m-2 of calcium in the form of carbonates in 1970-1998. Here we demonstrate that the loss of calcium was caused by fundamental shift in the steppe hydrologic balance. Previously unleached soils where precipitation was less than potential evapotranspiration are now being leached due to increased precipitation and, possibly, due to decreased actual evapotranspiration. Because this region receives low levels of acidic deposition, the dissolution of carbonates involves the consumption of atmospheric CO2. Our estimates indicate that this climatically driven terrestrial sink of atmospheric CO2 is ???2.1-7.4 g C m-2 a-1. In addition to the net sink of atmospheric carbon, leaching of pedogenic carbonates significantly amplified seasonal amplitude of CO2 exchange between atmosphere and steppe soil. Copyright 2008 by the American Geophysical Union.

METHOD OF INHIBITING CORROSION IN URANYL SULFATE SOLUTIONS

DOEpatents

Bohlmann, E.G.; Griess, J.C. Jr.

1960-08-23

A method is given for treating a uranyl sulfate solution to inhibit the corrosiveness of the solution and elevate the phase separation temperature of the solution. Lithium sulfate is added to the solution in an amount ranging from 0.25 to 1.3 times the uranyl sulfate concentration. The corrosiveness of the solution with respect to stainless steel is substantially decreased by this means. This treatment also serves to raise the phase separation temperature of the solution (above 250 deg C), at which time the uranyl sulfate solution separates into two liquid phases of unequal uranium concentration and thus becomes unsuitable as nuclear reactor fuel.

Uranyl carboxyphosphonates that incorporate Cd(II)

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

Alsobrook, Andrea N.; Alekseev, Evgeny V.; Depmeier, Wulf

2011-05-15

The hydrothermal treatment of UO{sub 3}, Cd(CH{sub 3}CO{sub 2}){sub 2}.2H{sub 2}O, and triethyl phosphonoacetate results in the formation of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O (CdUPAA-1), [Cd{sub 3}(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 6}(H{sub 2}O){sub 13}].6H{sub 2}O (CdUPAA-2), and Cd(H{sub 2}O){sub 2}[(UO{sub 2})(PO{sub 3}CH{sub 2}CO{sub 2})(H{sub 2}O)]{sub 2} (CdUPAA-3). CdUPAA-1 adopts a cubic three-dimensional structure constructed from planar uranyl oxide clusters containing both UO{sub 7} pentagonal bipyramids and UO{sub 8} hexagonal bipyramids that are linked by Cd(II) cations and phosphonoacetate to yield large cavities approximately 16 A across that are filled with disordered watermore » molecules. CdUPAA-2 forms a rhombohedral three-dimensional channel structure that is assembled from UO{sub 7} pentagonal bipyramids that are bridged by phosphonoacetate. CdUPAA-3 is layered with the hydrated Cd(II) cations incorporated directly into the layers linking one-dimensional uranyl phosphonate substructures together. In this structure, there are complex networks of hydrogen bonds that exist within the sheets, and also stitch the sheets together. -- Graphical abstract: A view of part of the cubic structure of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O. Display Omitted highlights: > High symmetry uranyl compounds. > Three-dimensional structures. > Porous materials. > Heterobimetallic compounds.« less

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

PubMed

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

2015-06-01

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

Structural characterization of anion-calcium-humate complexes in phosphate-based fertilizers.

PubMed

Baigorri, Roberto; Urrutia, Oscar; Erro, Javier; Mandado, Marcos; Pérez-Juste, Ignacio; Garcia-Mina, José María

2013-07-01

Fertilizers based on phosphate-metal-humate complexes are a new family of compounds that represents a more sustainable and bioavailable phosphorus source. The characterization of this type of complex by using solid (31)P NMR in several fertilizers, based on single superphosphate (SSP) and triple superphosphate (TSP) matrices, yielded surprising and unexpected trends in the intensity and fine structure of the (31)P NMR peaks. Computational chemistry methods allowed the characterization of phosphate-calcium-humate complexes in both SSP and TSP matrices, but also predicted the formation of a stable sulfate-calcium-humate complex in the SSP fertilizers, which has not been described previously. The stability of this complex has been confirmed by using ultrafiltration techniques. Preference towards the humic substance for the sulfate-metal phase in SSP allowed the explanation of the opposing trends that were observed in the experimental (31)P NMR spectra of SSP and TSP samples. Additionally, computational chemistry has provided an assignment of the (31)P NMR signals to different phosphate ligands as well as valuable information about the relative strength of the phosphate-calcium interactions within the crystals. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphous Calcium Carbonate Precipitation by Cellular Biomineralization in Mantle Cell Cultures of Pinctada fucata

PubMed Central

Xiang, Liang; Kong, Wei; Su, Jingtan; Liang, Jian; Zhang, Guiyou; Xie, Liping; Zhang, Rongqing

2014-01-01

The growth of molluscan shell crystals is generally thought to be initiated from the extrapallial fluid by matrix proteins, however, the cellular mechanisms of shell formation pathway remain unknown. Here, we first report amorphous calcium carbonate (ACC) precipitation by cellular biomineralization in primary mantle cell cultures of Pinctada fucata. Through real-time PCR and western blot analyses, we demonstrate that mantle cells retain the ability to synthesize and secrete ACCBP, Pif80 and nacrein in vitro. In addition, the cells also maintained high levels of alkaline phosphatase and carbonic anhydrase activity, enzymes responsible for shell formation. On the basis of polarized light microscopy and scanning electron microscopy, we observed intracellular crystals production by mantle cells in vitro. Fourier transform infrared spectroscopy and X-ray diffraction analyses revealed the crystals to be ACC, and de novo biomineralization was confirmed by following the incorporation of Sr into calcium carbonate. Our results demonstrate the ability of mantle cells to perform fundamental biomineralization processes via amorphous calcium carbonate, and these cells may be directly involved in pearl oyster shell formation. PMID:25405357

The influence of electron discharge and magnetic field on calcium carbonate (CaCO{sub 3}) precipitation

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

Putro, Triswantoro, E-mail: tris@physics.its.ac.id; Endarko, E-mail: endarko@physics.its.ac.id

The influences of electron discharge and magnetic field on calcium carbonate (CaCO{sub 3}) precipitation in water have been successfully investigated. The study used three pairs of magnetic field 0.1 T whilst the electron discharge was generated from television flyback transformer type BW00607 and stainless steel SUS 304 as an electrode. The water sample with an initial condition of 230 mg/L placed in the reactor with flow rate 375 mL/minutes, result showed that the electron discharge can be reduced contain of calcium carbonate the water sample around 17.39% within 2 hours. Meanwhile for the same long period of treatment and flow rate, aroundmore » 56.69% from initial condition of 520 mg/L of calcium carbonate in the water sample can be achieved by three pairs of magnetic field 0.1 T. When the combination of three pairs of magnetic field 0.1 T and the electron discharge used for treatment, the result showed that the combination of electron discharge and magnetic field methods can be used to precipitate calcium carbonate in the water sample 300 mg/L around 76.66% for 2 hours of treatment. The study then investigated the influence of the polar position of the magnetic field on calcium carbonate precipitation. Two positions of magnetic field were tested namely the system with alternated polar magnetics and the system without inversion of the polar magnetics. The influence of the polar position showed that the percentage reduction in levels of calcium carbonate in the water sample (360 mg/L) is significant different. Result showed that the system without inversion of the polar magnetics is generally lower than the system with alternated polar magnetics, with reduction level at 30.55 and 57.69%, respectively.« less

Protein encapsulation and release from PEO-b-polyphosphoester templated calcium carbonate particles.

PubMed

Ergul Yilmaz, Zeynep; Cordonnier, Thomas; Debuigne, Antoine; Calvignac, Brice; Jerome, Christine; Boury, Frank

2016-11-20

Calcium carbonate particles are promising candidates as proteins carriers for their controlled delivery in the body. The present paper aims at investigating the protein encapsulation by in situ precipitation of calcium carbonate particles prepared by a process based on supercritical CO 2 and using a new type of degradable well-defined double hydrophilic block copolymers composed of poly(ethylene oxide) and polyphosphoester blocks acting as templating agent for the calcium carbonate. For this study, lysozyme was chosen as a model for therapeutic protein for its availability and ease of detection. It was found that by this green process, loading into the CaCO 3 microparticles with a diameter about 2μm can be obtained as determined by scanning electron microscopy. A protein loading up to 6.5% active lysozyme was measured by a specific bioassay (Micrococcus lysodeikticus). By encapsulating fluorescent-labelled lysozyme (lysozyme-FITC), the confocal microscopy images confirmed its encapsulation and suggested a core-shell distribution of lysozyme into CaCO 3 , leading to a release profile reaching a steady state at 59% of release after 90min. Copyright © 2016. Published by Elsevier B.V.

Biological Origin of Micro-laminated Calcium Carbonate Deposits on Antarctic Rock Surfaces

NASA Astrophysics Data System (ADS)

Farmer, M.; Stone, J. O.

2001-12-01

We have observed and sampled patchy encrustations of calcium carbonate on rock surfaces in East and West Antarctica. Individual disk-like deposits are up to 1 cm across and a few mm thick, but in places coalesce to form more extensive, colloform coatings. We have observed these deposits on substrates of granite, sandstone, and schist. Their distribution appears similar to that of Antarctic lichens and endolithic algae, extending up to ca. 1000m elevation, but has no consistent relationship to snow drifts, solar radiation, or prevailing winds. The morphology and position of the deposits are distinct from sub-glacial carbonate precipitates. In Marie Byrd Land, the encrustations occur on the surfaces exposed by deglaciation within the past 5000 yrs, and the sample from East Antarctica contains live C-14 (M. Mabin, pers. comm.), suggesting a possible biological origin Electron microprobe and SEM examination of cross-sectioned specimens reveals micron-scale layering of predominantly calcium carbonate, but with a number of bright laminae in SEM images, believed to be calcium fluoride. Sections closely resemble desert varnish in micro-morphology, though not in mineralogy. Isotopic analysis of an organic carbon extract (as opposed to C from the CaCO3 itself) gave a delta C-13 PDB value of -23.3 per mil, similar to values expected in carbon of biological origin. However, we have no proof yet that the carbon analyzed was produced by organisms within the encrustation, rather than being entrapped during an inorganic precipitation process. To investigate the possible biological origin of this material, we attempted to sequence the 16S segment of rRNA in the organic extract, but have not yet completed successful PCR replication. We are continuing attempts to isolate and analyze the pertinent genetic material. The micro-morphology, strongly negative delta C-13 and presence of live C-14 suggest a biological process for precipitation of these calcium carbonate deposits. We hope to

Rapid hydrothermal flow synthesis and characterisation of carbonate- and silicate-substituted calcium phosphates

PubMed Central

Knowles, Jonathan C; Rehman, Ihtesham; Darr, Jawwad A

2013-01-01

A range of crystalline and nano-sized carbonate- and silicate-substituted hydroxyapatite has been successfully produced by using continuous hydrothermal flow synthesis technology. Ion-substituted calcium phosphates are better candidates for bone replacement applications (due to improved bioactivity) as compared to phase-pure hydroxyapatite. Urea was used as a carbonate source for synthesising phase pure carbonated hydroxyapatite (CO3-HA) with ≈5 wt% substituted carbonate content (sample 7.5CO3-HA) and it was found that a further increase in urea concentration in solution resulted in biphasic mixtures of carbonate-substituted hydroxyapatite and calcium carbonate. Transmission electron microscopy images revealed that the particle size of hydroxyapatite decreased with increasing urea concentration. Energy-dispersive X-ray spectroscopy result revealed a calcium deficient apatite with Ca:P molar ratio of 1.45 (±0.04) in sample 7.5CO3-HA. For silicate-substituted hydroxyapatite (SiO4-HA) silicon acetate was used as a silicate ion source. It was observed that a substitution threshold of ∼1.1 wt% exists for synthesis of SiO4-HA in the continuous hydrothermal flow synthesis system, which could be due to the decreasing yields with progressive increase in silicon acetate concentration. All the as-precipitated powders (without any additional heat treatments) were analysed using techniques including Transmission electron microscopy, X-ray powder diffraction, Differential scanning calorimetry, Thermogravimetric analysis, Raman spectroscopy and Fourier transform infrared spectroscopy. PMID:22983020

Removal of toxic uranium from synthetic nuclear power reactor effluents using uranyl ion imprinted polymer particles.

PubMed

Preetha, Chandrika Ravindran; Gladis, Joseph Mary; Rao, Talasila Prasada; Venkateswaran, Gopala

2006-05-01

Major quantities of uranium find use as nuclear fuel in nuclear power reactors. In view of the extreme toxicity of uranium and consequent stringent limits fixed by WHO and various national governments, it is essential to remove uranium from nuclear power reactor effluents before discharge into environment. Ion imprinted polymer (IIP) materials have traditionally been used for the recovery of uranium from dilute aqueous solutions prior to detection or from seawater. We now describe the use of IIP materials for selective removal of uranium from a typical synthetic nuclear power reactor effluent. The IIP materials were prepared for uranyl ion (imprint ion) by forming binary salicylaldoxime (SALO) or 4-vinylpyridine (VP) or ternary SALO-VP complexes in 2-methoxyethanol (porogen) and copolymerizing in the presence of styrene (monomer), divinylbenzene (cross-linking monomer), and 2,2'-azobisisobutyronitrile (initiator). The resulting materials were then ground and sieved to obtain unleached polymer particles. Leached IIP particles were obtained by leaching the imprint ions with 6.0 M HCl. Control polymer particles were also prepared analogously without the imprint ion. The IIP particles obtained with ternary complex alone gave quantitative removal of uranyl ion in the pH range 3.5-5.0 with as low as 0.08 g. The retention capacity of uranyl IIP particles was found to be 98.50 mg/g of polymer. The present study successfully demonstrates the feasibility of removing uranyl ions selectively in the range 5 microg - 300 mg present in 500 mL of synthetic nuclear power reactor effluent containing a host of other inorganic species.

Results of the TTF-TCNQ and the calcium carbonate crystallization on the Long Duration Exposure Facility

NASA Technical Reports Server (NTRS)

Nielsen, Kjeld Flemming; Lind, M. David

1992-01-01

Experiment A0139A on the Long Duration Exposure Facility (LDEF) carried four large containers into orbit five years with crystal growth solutions for lead sulfide, calcium carbonate, and TTF-TCNQ. Although temperature data was lost, the experimental program had been working since the valves in all containers had been opened. All four experiments produced crystals of varying quality. The calcium carbonate crystals had the best appearance. The TTF-TCNQ crystals were packed together near the valve openings of the container. When taken apart, the single crystals showed some unusual morphological properties. X ray investigations as well as conductivity measurements on long duration space grown TTF-TCNQ crystals will be presented. Comparisons will be made with our previous space solution growth experiments. The TTF-TCNQ crystals are no longer of the highest interest, so this activity has been terminated in favor of calcium carbonate and calcium phosphate crystallizations.

Numerical investigation of the influence of electromagnetic treatment on calcium carbonate scaling rate in non-isothermal pipe flow

NASA Astrophysics Data System (ADS)

Kireev, Victor; Kovaleva, Liana; Isakov, Andrey; Alimbekova, Sofya

2017-11-01

In the present paper, an attempt to explain the mechanisms of the electromagnetic field influence on the process of formation and deposition of calcium carbonate from supersaturated brine solution has been made using numerical modeling. The one-dimensional mathematical model of the brine laminar flow through a cylindrical tube with non-uniform temperature field is written in the form of the system of transient convection-diffusion-reaction partial differential equations describing temperature field and chemical components concentrations (Ca2+, HCO3-, CaCO3). The influence of the temperature on the kinetics of formation of calcium carbonate is taken into account and it is described in accordance with the Arrhenius equation. The kinetics of the calcium carbonate precipitation on the wall of the pipe is given on the basis of the Henry isotherm. It has been established that the electromagnetic treatment of brine solution leads to a decrease of the adsorption rate constant and Henry's constant but it does not significantly influence on the chemical reaction rate of calcium carbonate formation. It also has been shown that treatment with electromagnetic field significantly reduces the amount of calcium carbonate deposits on the wall of the pipe.

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

NASA Astrophysics Data System (ADS)

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; Runde, W.; Roback, R.; Williams-Jones, A. E.

2018-02-01

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO22+, UO2Cl+, and UO2Cl2°. UO2Cl3- is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species show fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO2Cl42- and UO2Cl53- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T > 150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO2Cl2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO22+ + Cl- = UO2Cl+ are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO22+ + 2Cl- = UO2Cl2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.

Modification of nanostructured calcium carbonate for efficient gene delivery.

PubMed

Zhao, Dong; Wang, Chao-Qun; Zhuo, Ren-Xi; Cheng, Si-Xue

2014-06-01

In this study, a facile method to modify nanostructured calcium carbonate (CaCO3) gene delivery systems by adding calcium phosphate (CaP) component was developed. CaCO3/CaP/DNA nanoparticles were prepared by the co-precipitation of Ca(2+) ions with plasmid DNA in the presence of carbonate and phosphate ions. For comparison, CaCO3/DNA nanoparticles and CaP/DNA co-precipitates were also prepared. The effects of carbonate ion/phosphate ion (CO3(2-)/PO4(3-)) ratio on the particle size and gene delivery efficiency were investigated. With an appropriate CO3(2-)/PO4(3-) ratio, the co-existence of carbonate and phosphate ions could control the size of co-precipitates effectively, and CaCO3/CaP/DNA nanoparticles with a decreased size and improved stability could be obtained. The in vitro gene transfections mediated by different nanoparticles in 293T cells and HeLa cells were carried out, using pGL3-Luc as a reporter plasmid. The gene transfection efficiency of CaCO3/CaP/DNA nanoparticles could be significantly improved as compared with CaCO3/DNA nanoparticles and CaP/DNA co-precipitates. The confocal microscopy study indicated that the cellular uptake and nuclear localization of CaCO3/CaP/DNA nanoparticles were significantly enhanced as compared with unmodified CaCO3/DNA nanoparticles. Copyright © 2014 Elsevier B.V. All rights reserved.

Fractionated-combustion analysis of carbonate-containing phases in composite materials of the hydroxyapatite-calcium carbonate system

NASA Astrophysics Data System (ADS)

Goldberg, M. A.; Shibaeva, T. V.; Smirnov, V. V.; Kutsev, S. V.; Barinov, S. M.; Grigorovich, K. V.

2012-12-01

Materials in the hydroxyapatite (HA)-calcium carbonate (CC) system were synthesized by a precipitation method from aqueous solutions. According to the data of X-ray phase analysis and IR spectroscopy, the powders consisted of CC and AB-type carbonate-substituted HA (CHA). In order to determine the content of carbonate-containing phases in materials, the temperature-temporal mode of fractionated-combustion analysis of carbon was developed. The quantitative phase ratios and the degree of substitution of carbonate groups in CHA were determined. It was shown that the degree of substitution of carbonate groups in CHA increased from 2.47 to 5.31 wt % as the CC content increased from 13.50 to 88.33 wt %.

Pseudomonas, Pantoea and Cupriavidus isolates induce calcium carbonate precipitation for biorestoration of ornamental stone.

PubMed

Daskalakis, M I; Magoulas, A; Kotoulas, G; Catsikis, I; Bakolas, A; Karageorgis, A P; Mavridou, A; Doulia, D; Rigas, F

2013-08-01

Bacterially induced calcium carbonate precipitation from various isolates was investigated aiming at developing an environmentally friendly technique for ornamental stone protection and restoration. Micro-organisms isolated from stone samples and identified using 16S rDNA and biochemical tests promoted calcium carbonate precipitation in solid and novel liquid growth media. Biomineral morphology was studied on marble samples with scanning electron microscopy. Most isolates demonstrated specimen weight increase, covering partially or even completely the marble surfaces mainly with vaterite. The conditions under which vaterite precipitated and its stability throughout the experimental runs are presented. A growth medium that facilitated bacterial growth of different species and promoted biomineralization was formulated. Most isolates induced biomineralization of CaCO3 . Micro-organisms may actually be a milestone in the investigation of vaterite formation facilitating our understanding of geomicrobiological interactions. Pseudomonas, Pantoea and Cupriavidus strains could be candidates for bioconsolidation of ornamental stone protection. Characterization of biomineralization capacity of different bacterial species improves understanding of the bacterially induced mineralization processes and enriches the list of candidates for biorestoration applications. Knowledge of biomineral morphology assists in differentiating mineral from biologically induced precipitates. © 2013 The Society for Applied Microbiology.

Surface-functionalized cockle shell–based calcium carbonate aragonite polymorph as a drug nanocarrier

PubMed Central

Mohd Abd Ghafar, Syairah Liyana; Hussein, Mohd Zobir; Rukayadi, Yaya; Abu Bakar Zakaria, Md Zuki

2017-01-01

Calcium carbonate aragonite polymorph nanoparticles derived from cockle shells were prepared using surface functionalization method followed by purification steps. Size, morphology, and surface properties of the nanoparticles were characterized using transmission electron microscopy, field emission scanning electron microscopy, dynamic light scattering, zetasizer, X-ray powder diffraction, and Fourier transform infrared spectrometry techniques. The potential of surface-functionalized calcium carbonate aragonite polymorph nanoparticle as a drug-delivery agent were assessed through in vitro drug-loading test and drug-release test. Transmission electron microscopy, field emission scanning electron microscopy, and particle size distribution analyses revealed that size, morphology, and surface characterization had been improved after surface functionalization process. Zeta potential of the nanoparticles was found to be increased, thereby demonstrating better dispersion among the nanoparticles. Purification techniques showed a further improvement in the overall distribution of nanoparticles toward more refined size ranges <100 nm, which specifically favored drug-delivery applications. The purity of the aragonite phase and their chemical analyses were verified by X-ray powder diffraction and Fourier transform infrared spectrometry studies. In vitro biological response of hFOB 1.19 osteoblast cells showed that surface functionalization could improve the cytotoxicity of cockle shell–based calcium carbonate aragonite nanocarrier. The sample was also sensitive to pH changes and demonstrated good abilities to load and sustain in vitro drug. This study thus indicates that calcium carbonate aragonite polymorph nanoparticles derived from cockle shells, a natural biomaterial, with modified surface characteristics are promising and can be applied as efficient carriers for drug delivery. PMID:28572724

Development of poly(aspartic acid-co-malic acid) composites for calcium carbonate and sulphate scale inhibition.

PubMed

Mithil Kumar, N; Gupta, Sanjay Kumar; Jagadeesh, Dani; Kanny, K; Bux, F

2015-01-01

Polyaspartic acid (PSI) is suitable for the inhibition of inorganic scale deposition. To enhance its scale inhibition efficiency, PSI was modified by reacting aspartic acid with malic acid (MA) using thermal polycondensation polymerization. This reaction resulted in poly(aspartic acid-co-malic acid) (PSI-co-MA) dual polymer. The structural, chemical and thermal properties of the dual polymers were analysed by using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, differential scanning calorimetry and gel permeation chromatography. The effectiveness of six different molar ratios of PSI-co-MA dual polymer for calcium carbonate and calcium sulphate scale inhibition at laboratory scale batch experiments was evaluated with synthetic brine solution at selected doses of polymer at 65-70°C by the static scale test method. The performance of PSI-co-MA dual polymer for the inhibition of calcium carbonate and calcium sulphate precipitation was compared with that of a PSI single polymer. The PSI-co-MA exhibited excellent ability to control inorganic minerals, with approximately 85.36% calcium carbonate inhibition and 100% calcium sulphate inhibition at a level of 10 mg/L PSI-co-MA, respectively. Therefore, it may be reasonably concluded that PSI-co-MA is a highly effective scale inhibitor for cooling water treatment applications.

Incremental cost-utility of sevelamer relative to calcium carbonate for treatment of hyperphosphatemia among pre-dialysis chronic kidney disease patients.

PubMed

Nguyen, Hai V; Bose, Saideep; Finkelstein, Eric

2016-04-28

Sevelamer is an alternative to calcium carbonate for the treatment of hyperphosphatemia among non-dialysis dependent patients with chronic kidney disease (CKD). Although some studies show that it may reduce mortality and delay the onset of dialysis when compared to calcium carbonate, it is also significantly more expensive. Prior studies looking at the incremental cost-effectiveness of sevelamer versus calcium carbonate in pre-dialysis patients are based on data from a single clinical trial. The goal of our study is to use a wider range of clinical data to achieve a more contemporary and robust cost-effectiveness analysis. We used a Markov model to estimate the lifetime costs and quality-adjusted life years (QALYs) gained for treatment with sevelamer versus calcium carbonate. The model simulated transitions among three health states (CKD not requiring dialysis, end-stage renal disease, and death). Data on transition probabilities and utilities were obtained from the published literature. Costs were calculated from a third party payer perspective and included medication, hospitalization, and dialysis. Sensitivity analyses were also run to encompass a wide range of assumptions about the dose, costs, and effectiveness of sevelamer. Over a lifetime, the average cost per patient treated with sevelamer is S$180,724. The estimated cost for patients treated with calcium carbonate is S$152,988. A patient treated with sevelamer gains, on average, 6.34 QALYs relative to no treatment, whereas a patient taking calcium carbonate gains 5.81 QALYs. Therefore, sevelamer produces an incremental cost-effectiveness ratio (ICER) of S$51,756 per QALY gained relative to calcium carbonate. Based on established benchmarks for cost-effectiveness, sevelamer is cost effective relative to calcium carbonate for the treatment of hyperphosphatemia among patients with chronic kidney disease initially not on dialysis.

Intrinsically disordered and pliable Starmaker-like protein from medaka (Oryzias latipes) controls the formation of calcium carbonate crystals.

PubMed

Różycka, Mirosława; Wojtas, Magdalena; Jakób, Michał; Stigloher, Christian; Grzeszkowiak, Mikołaj; Mazur, Maciej; Ożyhar, Andrzej

2014-01-01

Fish otoliths, biominerals composed of calcium carbonate with a small amount of organic matrix, are involved in the functioning of the inner ear. Starmaker (Stm) from zebrafish (Danio rerio) was the first protein found to be capable of controlling the formation of otoliths. Recently, a gene was identified encoding the Starmaker-like (Stm-l) protein from medaka (Oryzias latipes), a putative homologue of Stm and human dentine sialophosphoprotein. Although there is no sequence similarity between Stm-l and Stm, Stm-l was suggested to be involved in the biomineralization of otoliths, as had been observed for Stm even before. The molecular properties and functioning of Stm-l as a putative regulatory protein in otolith formation have not been characterized yet. A comprehensive biochemical and biophysical analysis of recombinant Stm-l, along with in silico examinations, indicated that Stm-l exhibits properties of a coil-like intrinsically disordered protein. Stm-l possesses an elongated and pliable structure that is able to adopt a more ordered and rigid conformation under the influence of different factors. An in vitro assay of the biomineralization activity of Stm-l indicated that Stm-l affected the size, shape and number of calcium carbonate crystals. The functional significance of intrinsically disordered properties of Stm-l and the possible role of this protein in controlling the formation of calcium carbonate crystals is discussed.

Intrinsically Disordered and Pliable Starmaker-Like Protein from Medaka (Oryzias latipes) Controls the Formation of Calcium Carbonate Crystals

PubMed Central

Różycka, Mirosława; Wojtas, Magdalena; Jakób, Michał; Stigloher, Christian; Grzeszkowiak, Mikołaj; Mazur, Maciej; Ożyhar, Andrzej

2014-01-01

Fish otoliths, biominerals composed of calcium carbonate with a small amount of organic matrix, are involved in the functioning of the inner ear. Starmaker (Stm) from zebrafish (Danio rerio) was the first protein found to be capable of controlling the formation of otoliths. Recently, a gene was identified encoding the Starmaker-like (Stm-l) protein from medaka (Oryzias latipes), a putative homologue of Stm and human dentine sialophosphoprotein. Although there is no sequence similarity between Stm-l and Stm, Stm-l was suggested to be involved in the biomineralization of otoliths, as had been observed for Stm even before. The molecular properties and functioning of Stm-l as a putative regulatory protein in otolith formation have not been characterized yet. A comprehensive biochemical and biophysical analysis of recombinant Stm-l, along with in silico examinations, indicated that Stm-l exhibits properties of a coil-like intrinsically disordered protein. Stm-l possesses an elongated and pliable structure that is able to adopt a more ordered and rigid conformation under the influence of different factors. An in vitro assay of the biomineralization activity of Stm-l indicated that Stm-l affected the size, shape and number of calcium carbonate crystals. The functional significance of intrinsically disordered properties of Stm-l and the possible role of this protein in controlling the formation of calcium carbonate crystals is discussed. PMID:25490041

Nanoscale analysis of the morphology and surface stability of calcium carbonate polymorphs

NASA Astrophysics Data System (ADS)

Sekkal, W.; Zaoui, A.

2013-04-01

Under earth surface conditions, in ocean and natural water, calcium carbonate is ubiquitous, forming anhydrous and hydrous minerals. These hydrous phases are of considerable interest for their role as precursors to stable carbonate minerals. Atomistic simulation techniques have been employed here to perform a comprehensive and quantitative study of the structural and energetic stability of dry and hydrous surfaces of calcium carbonate polymorphs using two recently developed forcefields. Results show that the dry forms are prone to ductility; while hydrous phases are found to be brittle. The (001) surface of monohydrocalcite appears to be the most stable (0.99 J/m2) whereas for the ikaite phase, the (001) surface is the most stable. The corresponding value is 0.2 J/m2, i.e. even lower than the surface energy of the Beautiful computed morphology pictures are obtained with Xiao's model and are very similar to the observed SEM images.

First Cationic Uranyl-Organic Framework with Anion-Exchange Capabilities.

PubMed

Bai, Zhuanling; Wang, Yanlong; Li, Yuxiang; Liu, Wei; Chen, Lanhua; Sheng, Daopeng; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

2016-07-05

By controlling the extent of hydrolysis during the self-assembly process of a zwitterionic-based ligand with uranyl cations, we observed a structural evolution from the neutral uranyl-organic framework [(UO2)2(TTTPC)(OH)O(COOH)]·1.5DMF·7H2O (SCU-6) to the first cationic uranyl-organic framework with the formula of [(UO2)(HTTTPC)(OH)]Br·1.5DMF·4H2O (SCU-7). The crystal structures of SCU-6 and SCU-7 are layers built with tetranuclear and dinuclear uranyl clusters, respectively. Exchangeable halide anions are present in the interlaminar spaces balancing the positive charge of layers in SCU-7. Therefore, SCU-7 is able to effectively remove perrhenate anions from aqueous solution. Meanwhile, the H2PO4(-)-exchanged SCU-7 material exhibits a moderate proton conductivity of 8.70 × 10(-5) S cm(-1) at 50 °C and 90% relative humidity, representing nearly 80 times enhancement compared to the original material.

Micro and colloidal stickie pacification with precipitated calcium carbonate

Treesearch

John H. Klungness; Roland L. Gleisner; Marguerite Sykes

2004-01-01

The colloidal stickies which build up in mill process water during pulping are problematic and difficult to remove. The USDA Forestry Service examined precipitated calcium carbonate (PCC) as a means to ameliorate process water stickies, comparing: i) the effectiveness of PCC added directly into a slurry of deinked pulp with ii) in situ precipitation of PCC by the fibre...

Micro and colloidal stickie pacification with precipitated calcium carbonate

Treesearch

John H. Klungness; Roland L. Gleisner; Marguerite S. Sykes

2002-01-01

Colloidal stickies that build up in mill process water during pulping are problematic and difficult to remove. We examined precipitated calcium carbonate (PCC) as a means to ameliorate process water stickies. The effectiveness of PCC added directly into a slurry of deinked pulp was compared with in situ precipitation of PCC by the fiber loading method. We found that...

Microalgal bacterial flocs treating paper mill effluent: A sunlight-based approach for removing carbon, nitrogen, phosphorus, and calcium.

PubMed

Van Den Hende, Sofie; Rodrigues, André; Hamaekers, Helen; Sonnenholzner, Stanislaus; Vervaeren, Han; Boon, Nico

2017-10-25

Treatment of upflow anaerobic sludge blanket (UASB) effluent from a paper mill in aerated activated sludge reactors involves high aeration costs. Moreover, this calcium-rich effluent leads to problematic scale formation. Therefore, a novel strategy for the aerobic treatment of paper mill UASB effluent in microalgal bacterial floc sequencing batch reactors (MaB-floc SBRs) is proposed, in which oxygen is provided via photosynthesis, and calcium is removed via bio-mineralization. Based on the results of batch experiments in the course of this study, a MaB-floc SBR was operated at an initial neutral pH. This SBR removed 58±21% organic carbon, 27±8% inorganic carbon, 77±5% nitrogen, 73±2% phosphorus, and 27±11% calcium. MaB-flocs contained 10±3% calcium, including biologically-influenced calcite crystals. The removal of calcium and inorganic carbon by MaB-flocs significantly decreased when inhibiting extracellular carbonic anhydrase (CA), an enzyme that catalyses the hydration and dehydration of CO 2 . This study demonstrates the potential of MaB-floc SBRs for the alternative treatment of calcium-rich paper mill effluent, and highlights the importance of extracellular CA in this treatment process. Copyright © 2017 Elsevier B.V. All rights reserved.

The fate of calcium carbonate nanoparticles administered by oral route: absorption and their interaction with biological matrices.

PubMed

Lee, Jeong-A; Kim, Mi-Kyung; Kim, Hyoung-Mi; Lee, Jong Kwon; Jeong, Jayoung; Kim, Young-Rok; Oh, Jae-Min; Choi, Soo-Jin

2015-01-01

Orally administered particles rapidly interact with biological fluids containing proteins, enzymes, electrolytes, and other biomolecules to eventually form particles covered by a corona, and this corona potentially affects particle uptake, fate, absorption, distribution, and elimination in vivo. This study explored relationships between the biological interactions of calcium carbonate particles and their biokinetics. We examined the effects of food grade calcium carbonates of different particle size (nano [N-Cal] and bulk [B-Cal]: specific surface areas of 15.8 and 0.83 m(2)/g, respectively) on biological interactions in in vitro simulated physiological fluids, ex vivo biofluids, and in vivo in gastrointestinal fluid. Moreover, absorption and tissue distribution of calcium carbonates were evaluated following a single dose oral administration to rats. N-Cal interacted more with biomatrices than bulk materials in vitro and ex vivo, as evidenced by high fluorescence quenching ratios, but it did not interact more actively with biomatrices in vivo. Analysis of coronas revealed that immunoglobulin, apolipoprotein, thrombin, and fibrinogen, were the major corona proteins, regardless of particle size. A biokinetic study revealed that orally delivered N-Cal was more rapidly absorbed into the blood stream than B-Cal, but no significant differences were observed between the two in terms of absorption efficiencies or tissue distributions. Both calcium carbonates were primarily present as particulate forms in gastrointestinal fluids but enter the circulatory system in dissolved Ca(2+), although both types showed partial phase transformation to dicalcium phosphate dihydrate. Relatively low dissolution (about 4%), no remarkable protein-particle interaction, and the major particulate fate of calcium carbonate in vivo gastrointestinal fluids can explain its low oral absorption (about 4%) regardless of particle size. We conclude that calcium carbonate nanoparticles can act more

Selective Se-for-S substitution in Cs-bearing uranyl compounds

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

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Tyumentseva, Olga S.; Krivovichev, Sergey V.

Phase formation in the mixed sulfate-selenate aqueous system of uranyl nitrate and cesium nitrate has been investigated. Two types of crystalline compounds have been obtained and characterized using a number of experimental (single crystal XRD, FTIR, SEM) and theoretical (information-based complexity calculations, topological analysis) techniques. No miscibility gaps have been observed for Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se), which crystallizes in tetragonal system, P-42{sub 1}m, a =9.616(1)–9.856(2), c =8.105(1)–8.159(1) Å, V =749.6(2)–792.5(3) Å{sup 3}. Nine phases with variable amount of S and Se have been structurally characterized. The structures of the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]more » (T= S, Se) compounds are based upon the [(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]{sup 2-} layers of corner-sharing uranyl pentagonal bipyramids and TO{sub 4} tetrahedra. The layers contain two types of tetrahedral sites: T1 (3-connected, i.e. having three O atoms shared by adjacent uranyl polyhedra) and T2 (4-connected). The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded T2 site. Crystallization in the pure Se system starts with the formation of Cs{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) crystals, its subsequent dissolution and formation of Cs{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}]. The information-based structural complexity calculations for these two phases support the rule that more topologically complex structures form at the latest stages of crystallization. - Graphical abstract: Nine phases representing the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) solid solution series with variable amount of S and Se have been prepared by isothermal evaporation from aqueous solutions and characterized using a number of experimental and theoretical techniques. No immiscibility is observed

Calcium Isotope Fractionation during Carbonate Weathering in the Northern Guangdong, South China

NASA Astrophysics Data System (ADS)

Liu, F.; Mao, G.; Wei, G.; Zhang, Z.

2017-12-01

CO2 is consumed during the weathering of carbonates, whereas carbonates are precipitated rapidly in the oceans, which are pivotal to modulate atmospheric CO2, oceanic pH and climate. Calcium carbonate in limestone is one of the largest reservoirs of carbon at the Earth's surface, so calcium is an important element that links the lithosphere, hydrosphere, biosphere, and the atmosphere. Compared with silicate rocks, carbonate rocks have more rapid rates of physical and chemical erosions, so the carbonate weathering will respond more quickly to the climatic changes. In the southeast of China, enormous of carbonate rocks are widely distributed. Due to the influence of the subtropical monsoon climate, the rocks experienced strong chemical weathering and pedogenic process, resulting in red weathering crust of carbonate rocks. This type of weathering crust is geochemistry-sensitive and ecology-vulnerable, which can provide important insights into the recycle of supergene geochemistry in the karst areas. In this study, we report calcium isotopic compositions of saprolites from a weathering profile developed on argillaceous carbonate rocks in northern Guangdong, South China. The acid-leachable fraction, which was extracted by 1N hydrochloride acid, showed limited variation of δ44/40Ca(NIST 915a) spanning from 0.55 ± 0.06‰ (2SD) to 0.72 ± 0.05‰ (2SD) despite CaO content ranging from 0.01 wt.% to 45.7 wt.%, implying that Ca isotope didn't fractionate much which may due to the congruent dissolution of limestone minerals. In contrast, radiogenic 87Sr/86Sr ratios of the whole rocks changed with depth from 0.710086 ± 6 (2SE) at the base rock to 0.722164± 8 (2SE) at the top-soil, which are possibly attributed to the mixing effect between carbonate and silicate fractions. Sr is an analogue for Ca due to its similar ionic size and charge; however, these two systems can differ in certain respects. The coupled study of Ca and Sr will be helpful to verify sources of Ca and the

Transforming growth factor-beta1 accelerates resorption of a calcium carbonate biomaterial in periodontal defects.

PubMed

Koo, Ki-Tae; Susin, Cristiano; Wikesjö, Ulf M E; Choi, Seong-Ho; Kim, Chong-Kwan

2007-04-01

In a previous study, recombinant human transforming growth factor-beta1 (rhTGF-beta(1)) in a calcium carbonate carrier was implanted into critical-size, supraalveolar periodontal defects under conditions for guided tissue regeneration (GTR) to study whether rhTGF-beta(1) would enhance or accelerate periodontal regeneration. The results showed minimal benefits of rhTGF-beta(1), and a clear account for this could not be offered. One potential cause may be that the rhTGF-beta(1) formulation was biologically inactive. Several growth or differentiation factors have been suggested to accelerate degradation of biomaterials used as carriers. The objective of this study was to evaluate possible activity of rhTGF-beta(1) on biodegradation of the calcium carbonate carrier. rhTGF-beta(1) in a putty-formulated particulate calcium carbonate carrier was implanted into critical-size, supraalveolar periodontal defects under conditions for GTR in five beagle dogs. Contralateral defects received the calcium carbonate carrier combined with GTR without rhTGF-beta(1) (control). The animals were euthanized at week 4 post-surgery and block biopsies of the defect sites were collected for histologic and histometric analysis. Radiographs were obtained at defect creation and weeks 2 and 4 after defect creation. No statistically significant differences were observed in new bone formation (bone height and area) among the treatments. However, total residual carrier was significantly reduced in sites receiving rhTGF-beta(1) compared to control (P = 0.04). Similarly, carrier density was considerably reduced in sites receiving rhTGF-beta(1) compared to control; the difference was borderline statistically significant (P = 0.06). Within the limitations of the study, it may be concluded that rhTGF-beta(1) accelerates biodegradation of a particulate calcium carbonate biomaterial, indicating a biologic activity of the rhTGF-beta(1) formulation apparently not encompassing enhanced or accelerated

The effect of humic acid on uranyl sorption onto bentonite at trace uranium levels.

PubMed

Ivanov, Peter; Griffiths, Tamara; Bryan, Nick D; Bozhikov, Gospodin; Dmitriev, Serguei

2012-11-01

The effect of humic acid (HA) on U(VI) sorption on bentonite was studied in batch experiments at room temperature and ambient atmosphere at a (237)U(VI) concentration of 8.4 × 10(-11) M and HA concentration of 100 mg L(-1). The distribution of U(VI) between the liquid and solid phases was studied as a function of pH and ionic strength both in the absence and presence of HA. It was shown that the uranyl sorption on bentonite is strongly dependent on pH and the presence of humics, and the effect of the addition order was negligible. In the absence of HA an enhancement in the uptake with increasing pH was observed and a sharp sorption edge was found to take place between pH 3.2 and 4.2. The presence of HA slightly increases uranium(VI) sorption at low pH and curtails it at moderate pH, compared to the absence of HA. In the basic pH range for both the presence and absence of HA the sorption of uranium is significantly reduced, which could be attributed to the formation of soluble uranyl carbonate complexes. The influence of ionic strength on U(VI) and HA uptake by bentonite were investigated in the range of 0.01-1.0 M, and while there was an enhancement in the sorption of humic acid with increasing ionic strength, no significant effect of the ionic strength on the U(VI) sorption was observed in both the absence and presence of HA.

Determination of thermodynamic parameters for complexation of calcium and magnesium with chondroitin sulfate isomers using isothermal titration calorimetry: Implications for calcium kidney-stone research

NASA Astrophysics Data System (ADS)

Rodgers, Allen L.; Jackson, Graham E.

2017-04-01

Chondroitin sulfate (CS) occurs in human urine. It has several potential binding sites for calcium and as such may play an inhibitory role in calcium oxalate and calcium phosphate (kidney stone disease by reducing the supersaturation (SS) and crystallization of these salts. Urinary magnesium is also a role player in determining speciation in stone forming processes. This study was undertaken to determine the thermodynamic parameters for binding of the disaccharide unit of two different CS isomers with calcium and magnesium. These included the binding constant K. Experiments were performed using an isothermal titration calorimeter (ITC) at 3 different pH levels in the physiological range in human urine. Data showed that interactions between the CS isomers and calcium and magnesium occur via one binding site, thought to be sulfate, and that log K values are 1.17-1.93 and 1.77-1.80 for these two metals respectively. Binding was significantly stronger in Mg-CS than in Ca-CS complexes and was found to be dependent on pH in the latter but not in the former. Furthermore, binding in Ca-CS complexes was dependent on the location of the sulfate binding site. This was not the case in the Mg-CS complexes. Interactions were shown to be entropy driven and enthalpy unfavourable. These findings can be used in computational modeling studies to predict the effects of the calcium and magnesium CS complexes on the speciation of calcium and the SS of calcium salts in real urine samples.

Impact of pore size on the sorption of uranyl under seawater conditions

DOE PAGES

Mayes, Richard T.; Gorka, Joanna; Dai, Sheng

2016-04-05

The extraction of uranium from seawater has received significant interest recently, because of the possibility of a near-limitless supply of uranium to fuel the nuclear power industry. While sorbent development has focused primarily on polymeric sorbents, nanomaterials represent a new area that has the potential to surpass the current polymeric sorbents, because of the high surface areas that are possible. Mesoporous carbon materials are a stable, high-surface-area material capable of extracting various chemical species from a variety of environments. Herein, we report the use of a dual templating process to understand the effect of pore size on the adsorption ofmore » uranyl ions from a uranyl brine consisting of seawater-relevant sodium, chloride, and bicarbonate ions. It was found that pore size played a more significant role in the effective use of the grafted polymer, leading to higher uranium capacities than the surface area. Furthermore, the pore size must be tailored to meet the demands of the extraction medium and analyte metal to achieve efficacy as an adsorbent.« less

Neptunium incorporation into select uranyl phases and thermal analysis of select uranyl phases

NASA Astrophysics Data System (ADS)

Klingensmith, Amanda Leigh

Alteration of spent nuclear fuel in a geological repository under oxidizing conditions is likely to result in abundant uranyl compounds. The proposed repository at Yucca Mountain, Nevada is intended to store about 70,000 metric tons of spent nuclear fuel in the unsaturated zone of a welded tuff sequence. Following failure of canisters that encapsulate the waste, contents may be exposed both to air and water and undergo repetitive wetting and drying events. Incorporation of radionuclides into the uranyl alteration phases may significantly reduce their mobility, thereby impacting repository performance. Of particular interest is 237Np owing to its long half-life (2.14 x 106 years) and potential mobility in groundwater. Powders of the synthetic uranyl phase soddyite, (UO2) 2(SiO4)(H2O)2, a framework type structure, and uranophane, Ca[(UO2)(SiO3OH)]2(H 2O)5, kasolite, Pb[(UO2)(SiO4)]H 2O, Na compreignacite, Na2[(UO2)3O 2(OH)3]2(H2O)7, and becquerelite, Ca[(UO2)3O2(OH)3]2(H 2O)8, all of which are sheet type structures, were synthesized in the presence of Np5+ under varying temperature and pH conditions. Uranophane, kasolite, boltwoodite K[(UO2)(SiO3OH)](H 2O)1.5, and Na boltwoodite K,Na[(UO2)(SiO 3OH)](H2O)1.5 were synthesized in the presence of Np as well as P, Ca and/or Mg. Single crystals of Na metaschoepite, Na[(UO 2)4O2(OH)5]˙5H2O were synthesized in the presence of Np5+ and laser ablation verified that Np can be incorporated within the structure of a uranyl phase. Incorporation of Np5+ into soddyite increased steadily with synthesis temperature. Np incorporation into uranophane, becquerelite, and kasolite was not dependent on synthesis temperature. Np uptake in uranophane and kasolite was found to be dependent on synthesis pH, with an increase in Np uptake with higher pH. Uranophane, boltwoodite and Na boltwoodite showed an increase in Np incorporation in the presence of P. Boltwoodite showed an even higher Np uptake when Mg and P were both present in the

Calcium carbonate precipitation by strain Bacillus licheniformis AK01, newly isolated from loamy soil: a promising alternative for sealing cement-based materials.

PubMed

Vahabi, Ali; Ramezanianpour, Ali Akbar; Sharafi, Hakimeh; Zahiri, Hossein Shahbani; Vali, Hojatollah; Noghabi, Kambiz Akbari

2015-01-01

The relevant experiments were designed to determine the ability of indigenous bacterial strains isolated from limestone caves, mineral springs, and loamy soils to induce calcium carbonate precipitation. Among all isolates examined in this study, an efficient carbonate-precipitating soil bacterium was selected from among the isolates and identified by 16S rRNA gene sequences as Bacillus licheniformis AK01. The ureolytic isolate was able to grow well on alkaline carbonate-precipitation medium and precipitate calcium carbonate more than 1 g L(-1). Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) analyses, and scanning electron microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDX) examinations were performed in order to confirm the presence of calcium carbonate in the precipitate and to determine which polymorphs were present. The selected isolate was determined to be an appropriate candidate for application in a surface treatment of cement-based material to improve the properties of the mortar. Biodeposition of a layer of calcite on the surface of cement specimens resulted in filling in pore spaces. This could be an alternative method to improve the durability of the mortar. The kind of bacterial culture and medium composition had a profound impact on the resultant CaCO(3) crystal morphology. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Properties of calcium silicate-monobasic calcium phosphate materials for endodontics containing tantalum pentoxide and zirconium oxide.

PubMed

Zamparini, Fausto; Siboni, Francesco; Prati, Carlo; Taddei, Paola; Gandolfi, Maria Giovanna

2018-05-08

The aim of the study was to evaluate chemical-physical properties and apatite-forming ability of three premixed calcium silicate materials containing monobasic calcium phosphate (CaH 4 P 2 O 8 ) bioceramic, tantalum pentoxide and zirconium oxide, recently marketed for endodontics (TotalFill BC-Sealer, BC-RRM-Paste, BC-RRM-Putty). Microchemical and micromorphological analyses, radiopacity, initial and final setting times, calcium release and alkalising activity were tested. The nucleation of calcium phosphates (CaPs) and/or apatite after 28 days ageing was evaluated by ESEM-EDX and micro-Raman spectroscopy. BC-Sealer and BC-RRM-Paste showed similar initial (23 h), prolonged final (52 h) setting times and good radiopacity (> 7 mm Al); BC-RRM-Putty showed fast initial (2 h) and final setting times (27 h) and excellent radiopacity (> 9 mm Al). All materials induced a marked alkalisation (pH 11-12) up to 28 days and showed the release of calcium ions throughout the entire test period (cumulative calcium release 641-806 ppm). After 28 days ageing, a well-distributed mineral layer was present on all samples surface; EDX demonstrated relevant calcium and phosphorous peaks. B-type carbonated apatite and calcite deposits were identified by micro-Raman spectroscopy on all the 28-day-aged samples; the deposit thickness was higher on BC-RRM-Paste and BC-RRM-Putty, in agreement with calcium release data. These materials met the required chemical and physical standards and released biologically relevant ions. The CaSi-CaH 4 P 2 O 8 system present in the materials provided Ca and OH ions release with marked abilities to nucleate a layer of B-type carbonated apatite favoured/accelerated by the bioceramic presence. The ability to nucleate apatite may lead many clinical advantages: In orthograde endodontics, it may improve the sealing ability by the deposition of CaPs at the material-root dentine interface, and in endodontic surgery, it could promote bone and

Constraints on Biogenic Emplacement of Crystalline Calcium Carbonate and Dolomite

NASA Astrophysics Data System (ADS)

Colas, B.; Clark, S. M.; Jacob, D. E.

2015-12-01

Amorphous calcium carbonate (ACC) is a biogenic precursor of calcium carbonates forming shells and skeletons of marine organisms, which are key components of the whole marine environment. Understanding carbonate formation is an essential prerequisite to quantify the effect climate change and pollution have on marine population. Water is a critical component of the structure of ACC and the key component controlling the stability of the amorphous state. Addition of small amounts of magnesium (1-5% of the calcium content) is known to promote the stability of ACC presumably through stabilization of the hydrogen bonding network. Understanding the hydrogen bonding network in ACC is fundamental to understand the stability of ACC. Our approach is to use Monte-Carlo simulations constrained by X-ray and neutron scattering data to determine hydrogen bonding networks in ACC as a function of magnesium doping. We have already successfully developed a synthesis protocol to make ACC, and have collected X-ray data, which is suitable for determining Ca, Mg and O correlations, and have collected neutron data, which gives information on the hydrogen/deuterium (as the interaction of X-rays with hydrogen is too low for us to be able to constrain hydrogen atom positions with only X-rays). The X-ray and neutron data are used to constrain reverse Monte-Carlo modelling of the ACC structure using the Empirical Potential Structure Refinement program, in order to yield a complete structural model for ACC including water molecule positions. We will present details of our sample synthesis and characterization methods, X-ray and neutron scattering data, and reverse Monte-Carlo simulations results, together with a discussion of the role of hydrogen bonding in ACC stability.

Nanoscale analysis of the morphology and surface stability of calcium carbonate polymorphs

PubMed Central

Sekkal, W.; Zaoui, A.

2013-01-01

Under earth surface conditions, in ocean and natural water, calcium carbonate is ubiquitous, forming anhydrous and hydrous minerals. These hydrous phases are of considerable interest for their role as precursors to stable carbonate minerals. Atomistic simulation techniques have been employed here to perform a comprehensive and quantitative study of the structural and energetic stability of dry and hydrous surfaces of calcium carbonate polymorphs using two recently developed forcefields. Results show that the dry forms are prone to ductility; while hydrous phases are found to be brittle. The (001) surface of monohydrocalcite appears to be the most stable (0.99 J/m2) whereas for the ikaite phase, the (001) surface is the most stable. The corresponding value is 0.2 J/m2, i.e. even lower than the surface energy of the Beautiful computed morphology pictures are obtained with Xiao's model and are very similar to the observed SEM images. PMID:23545842

Nanoscale analysis of the morphology and surface stability of calcium carbonate polymorphs.

PubMed

Sekkal, W; Zaoui, A

2013-01-01

Under earth surface conditions, in ocean and natural water, calcium carbonate is ubiquitous, forming anhydrous and hydrous minerals. These hydrous phases are of considerable interest for their role as precursors to stable carbonate minerals. Atomistic simulation techniques have been employed here to perform a comprehensive and quantitative study of the structural and energetic stability of dry and hydrous surfaces of calcium carbonate polymorphs using two recently developed forcefields. Results show that the dry forms are prone to ductility; while hydrous phases are found to be brittle. The (001) surface of monohydrocalcite appears to be the most stable (0.99 J/m(2)) whereas for the ikaite phase, the (001) surface is the most stable. The corresponding value is 0.2 J/m(2), i.e. even lower than the surface energy of the Beautiful computed morphology pictures are obtained with Xiao's model and are very similar to the observed SEM images.

Characterization of calcium carbonate crystals in pigeon yolk sacs with different incubation times.

PubMed

Song, Juan; Cheng, Haixia; Shen, Xinyu; Hu, Jingxiao; Tong, Hua

2014-05-01

Calcium carbonate crystals are known to form in the yolk sacs of fertile pigeon eggs at late stages of incubation. The composition and structure of these crystals were investigated, the crystallization environment was inspected, and the physical chemistry constants of the yolk fluid were determined through the incubation period. Polarized light microscopy was used to observe the generation and distribution of calcium carbonate crystals in the yolk sac. In addition, X-ray diffraction was employed to analyze the composition and crystal phase of the yolk sac. A decalcification and deproteination method was established to analyze the ultrastructure and composition of the crystals, as well as the internal relationship between inorganic and organic phases of the crystals. Additionally, scanning electron microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, and Fourier transform infrared spectroscopy were used to evaluate the characteristics of the crystals. Our results demonstrated that the calcium carbonate crystals were mainly composed of vaterite and calcite, with vaterite being the major component. Vaterite, a type of biomaterial generated by an organic template control, presented as a concentric hierarchical spherical structure. The organic nature of the biomaterial prevented vaterite from transforming into calcite, which is more thermodynamically stable than vaterite. Additionally, the configuration, size, and aggregation of vaterite were also mediated by the organic template. This bio-vaterite was found during the incubation period and is valuable in calcium transport during embryonic development. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

PubMed

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

2011-07-01

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

Synthesis of microspheres of triuranium octaoxide by simultaneous water and nitrate extraction from ascorbate-uranyl sols.

PubMed

Brykala, M; Deptula, A; Rogowski, M; Lada, W; Olczak, T; Wawszczak, D; Smolinski, T; Wojtowicz, P; Modolo, G

A new method for synthesis of uranium oxide microspheres (diameter <100 μm) has been developed. It is a variant of our patented Complex Sol-Gel Process, which has been used to synthesize high-quality powders of a wide variety of complex oxides. Starting uranyl-nitrate-ascorbate sols were prepared by addition of ascorbic acid to uranyl nitrate hexahydrate solution and alkalizing by aqueous ammonium hydroxide and then emulsified in 2-ethylhexanol-1 containing 1v/o SPAN-80. Drops of emulsion were firstly gelled by extraction of water by the solvent. Destruction of the microspheres during thermal treatment, owing to highly reactive components in the gels, requires modification of the gelation step by Double Extraction Process-simultaneously extraction of water and nitrates using Primene JMT, which completely eliminates these problem. Final step was calcination in air of obtained microspheres of gels to triuranium octaoxide.

A review on the kinetics of microbially induced calcium carbonate precipitation by urea hydrolysis

NASA Astrophysics Data System (ADS)

van Paassen, L. A.

2017-12-01

In this study the kinetics of calcium carbonate precipitation induced by the ureolytic bacteria are reviewed based on experiments and mathematical modelling. The study shows how urea hydrolysis rate depends on the amount of bacteria and the conditions during growth, storage, hydrolysis and precipitation. The dynamics of Microbially Induced Carbonate Precipitation has been monitored in non-seeded liquid batch experiments. Results show that particulary for a fast hydrolysis of urea (>1 M-urea day-1) in a highly concentrated equimolar solution with calcium chloride (>0.25 M) the solubility product of CaCO3 is exceeded within a short period (less than 30 minutes), the supersaturation remains high for an exended period, resulting in prolonged periods of nucleation and crystal growth and extended growth of metastable precursor mineral phases. The pH, being a result of the speciation, quickly rises until critical supersaturation is reached and precipitation is initiated. Then pH drops (sometimes showing oscillating behaviour) to about neutral where it stays until all substrates are depleted. Higher hydrolysis rates lead to higher supersaturation and pH and relatively many small crystals, whereas higher concentrations of urea and calcium chloride mainly lead to lower pH values. The conversion can be reasonably monitored by electrical conductivity and reasonably predicted, using a simplified model based on a single reaction as long as the urea hydrolysis rate is known. Complex geochemical models, which include chemical speciciation through acid-base equilibria and kinetic equations to describe mineral precipitation, do not show significant difference from the simplified model regarding the bulk chemistry and the total amount of precipitates. However, experiments show that ureolytic MICP can result in a highly variable crystal morphologies with large variation in the affected hydraulic properties when applied in a porous medium. In order to calculate the number, size and

Synthesis of calcium carbonate using extract components of croaker gill as morphology and polymorph adjust control agent.

PubMed

Chen, Hao; Qing, Chengsong; Zheng, Jiaoling; Liu, Yuxi; Wu, Gang

2016-06-01

Biomimetic synthesis of calcium carbonate with various polymorphs, sizes and morphologies by using organic substrates has become an interesting topic for the last years. Calcium carbonate has been synthesized by the reaction of Na2CO3 and CaCl2 in the presence of extract components of croaker gill. The products were characterized by powder X-ray diffraction (PXRD) and Fourier transform infrared (FT-IR) spectrum, and particle morphologies were observed by scanning electron microscope (SEM). The results show that at lower concentration yellow croaker gill extract has no effect on calcium carbonate crystal polymorph. Calcite was obtained only. But the morphologies of calcite particle change with the increase of the concentration. The corners of the particle change from angular to curved. However, with the further increase of the concentration of yellow croaker gill extract, the calcium carbonate obtained is a mixture of calcite and vaterite. The vaterite component in the mixture rises with increasing concentration of extract solution, indicating that the proteins from the yellow croaker gill during growth play a crucial role in stabilizing and directing the crystal growth. Copyright © 2016 Elsevier B.V. All rights reserved.

Mechanisms of the inhibition of enzymatic hydrolysis of waste pulp fibers by calcium carbonate and the influence of nonionic surfactant for mitigation.

PubMed

Min, Byeong Cheol; Ramarao, Bandaru V

2017-06-01

Recycled paper mills produce large quantities of fibrous rejects and fines which are usually sent to landfills as solid waste. These cellulosic materials can be enzymatically hydrolyzed into sugars for the production of biofuels and biomaterials. Paper mill wastes also contain large amounts of calcium carbonate which inhibits cellulase activity. The calcium carbonate (30%, w/w) decreased 40-60% of sugar yield of unbleached softwood kraft pulp. The prime mechanisms for this are by pH variation, competitive and non-productive binding, and aggregation effect. Addition of acetic acid (pH adjustment) increased the sugar production from 19 to 22 g/L of paper mill waste fibers. Strong affinity of enzyme-calcium carbonate decreased free enzyme in solution and hindered sugar production. Electrostatic and hydrogen bond interactions are mainly possible mechanism of enzyme-calcium carbonate adsorption. The application of the nonionic surfactant Tween 80 alleviated the non-productive binding of enzyme with the higher affinity on calcium carbonate. Dissociated calcium ion also inhibited the hydrolysis by aggregation of enzyme.

Ocean acidification accelerates net calcium carbonate loss in a coral rubble community

NASA Astrophysics Data System (ADS)

Stubler, Amber D.; Peterson, Bradley J.

2016-09-01

Coral rubble communities are an important yet often overlooked component of a healthy reef ecosystem. The organisms inhabiting reef rubble are primarily bioeroders that contribute to the breakdown and dissolution of carbonate material. While the effects of ocean acidification on calcifying communities have been well studied, there are few studies investigating the response of bioeroding communities to future changes in pH and calcium carbonate saturation state. Using a flow-through pH-stat system, coral rubble pieces with a naturally occurring suite of organisms, along with bleached control rubble pieces, were subjected to three different levels of acidification over an 8-week period. Rates of net carbonate loss in bleached control rubble doubled in the acidification treatments (0.02 vs. 0.04% CaCO3 d-1 in ambient vs. moderate and high acidification), and living rubble communities experienced significantly increased rates of net carbonate loss from ambient to high acidification conditions (0.06 vs. 0.10% CaCO3 d-1, respectively). Although more experimentation is necessary to understand the long-term response and succession of coral rubble communities under projected conditions, these results suggest that rates of carbonate loss will increase in coral rubble as pH and calcium carbonate saturation states are reduced. This study demonstrates a need to thoroughly investigate the contribution of coral rubble to the overall carbonate budget, reef resilience, recovery, and function under future conditions.

Theoretical insights into the uranyl adsorption behavior on vanadium carbide MXene

NASA Astrophysics Data System (ADS)

Zhang, Yu-Juan; Zhou, Zhang-Jian; Lan, Jian-Hui; Ge, Chang-Chun; Chai, Zhi-Fang; Zhang, Peihong; Shi, Wei-Qun

2017-12-01

Remediation of the contamination by long-lived actinide wastes is extremely important but also challenging. Adsorption based techniques have attracted much research attention for their potential as low-cost and effective methods to reduce the radioactive waste from solution. In this work, we have investigated the adsorption behavior of uranyl species [with the general form UO2(L1)x(L2)y(L3)z, where L1, L2 and L3 stand for ligands H2O, OH and CO3, respectively] on hydroxylated vanadium carbide V2C(OH)2 MXene nanosheets using density functional theory based simulation methods We find that all studied uranyl species can stably bond to hydroxylated MXene with binding energies ranging from -3.3 to -4.6 eV, suggesting that MXenes could be effective adsorbers for uranyl ions. The strong adsorption is achieved by forming two Usbnd O bonds with the hydroxylated Mxene. In addition, the axial oxygen atoms from the uranyl ions form hydrogen bonds with the hydroxylated V2C, further strengthening the adsorption. We have also investigated the effects of F termination on the uranyl adsorption properties of V2C nanosheets. Usbnd F bonds are in general weaker than Usbnd O bonds on the adsorption site, suggesting that F terminated Mexne is less favorable for uranyl adsorption applications.

Long-term Kinetics of Uranyl Desorption from Sediments Under Advective Conditions

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

Shang, Jianying; Liu, Chongxuan; Wang, Zheming

2014-02-15

Long-term (> 4 months) column experiments were performed to investigate the kinetics of uranyl (U(VI)) desorption in sediments collected from the Integrated Field Research Challenge (IFRC) site at the US Department of Energy (DOE) Hanford 300 Area. The experimental results were used to evaluate alternative multi-rate surface complexation reaction (SCR) approaches to describe the short- and long-term kinetics of U(VI) desorption under flow conditions. The SCR stoichiometry, equilibrium constants, and multi-rate parameters were independently characterized in batch and stirred flow-cell reactors. Multi-rate SCR models that were either additively constructed using the SCRs for individual size fractions (e.g., Shang et al.,more » 2011), or composite in nature could effectively describe short-term U(VI) desorption under flow conditions. The long-term desorption results, however, revealed that using a labile U concentration measured by carbonate extraction under-estimated desorbable U(VI) and the long-term rate of U(VI) desorption. An alternative modeling approach using total U as the desorbable U(VI) concentration was proposed to overcome this difficulty. This study also found that the gravel size fraction (2-8 mm), which is typically treated as non-reactive in modeling U(VI) reactive transport because of low external surface area, can have an important effect on the U(VI) desorption in the sediment. This study demonstrates an approach to effectively extrapolate U(VI) desorption kinetics for field-scale application, and identifies important parameters and uncertainties affecting model predictions.« less

The fate of calcium carbonate nanoparticles administered by oral route: absorption and their interaction with biological matrices

PubMed Central

Lee, Jeong-A; Kim, Mi-Kyung; Kim, Hyoung-Mi; Lee, Jong Kwon; Jeong, Jayoung; Kim, Young-Rok; Oh, Jae-Min; Choi, Soo-Jin

2015-01-01

Background Orally administered particles rapidly interact with biological fluids containing proteins, enzymes, electrolytes, and other biomolecules to eventually form particles covered by a corona, and this corona potentially affects particle uptake, fate, absorption, distribution, and elimination in vivo. This study explored relationships between the biological interactions of calcium carbonate particles and their biokinetics. Methods We examined the effects of food grade calcium carbonates of different particle size (nano [N-Cal] and bulk [B-Cal]: specific surface areas of 15.8 and 0.83 m2/g, respectively) on biological interactions in in vitro simulated physiological fluids, ex vivo biofluids, and in vivo in gastrointestinal fluid. Moreover, absorption and tissue distribution of calcium carbonates were evaluated following a single dose oral administration to rats. Results N-Cal interacted more with biomatrices than bulk materials in vitro and ex vivo, as evidenced by high fluorescence quenching ratios, but it did not interact more actively with biomatrices in vivo. Analysis of coronas revealed that immunoglobulin, apolipoprotein, thrombin, and fibrinogen, were the major corona proteins, regardless of particle size. A biokinetic study revealed that orally delivered N-Cal was more rapidly absorbed into the blood stream than B-Cal, but no significant differences were observed between the two in terms of absorption efficiencies or tissue distributions. Both calcium carbonates were primarily present as particulate forms in gastrointestinal fluids but enter the circulatory system in dissolved Ca2+, although both types showed partial phase transformation to dicalcium phosphate dihydrate. Relatively low dissolution (about 4%), no remarkable protein–particle interaction, and the major particulate fate of calcium carbonate in vivo gastrointestinal fluids can explain its low oral absorption (about 4%) regardless of particle size. Conclusion We conclude that calcium

Calcium carbonate obstructive urolithiasis in a red kangaroo (Macropus rufus).

PubMed

Lindemann, Dana M; Gamble, Kathryn C; Corner, Sarah

2013-03-01

A 6-yr-old male red kangaroo (Macropus rufus) presented for a history of inappetance, abnormal behavior, and unconfirmed elimination for 6 hr prior to presentation. Based on abdominal ultrasound, abdominocentesis, and cystocentesis, a presumptive diagnosis of urinary tract obstruction with uroabdomen and hydronephrosis was reached. Abdominal radiographs did not assist in reaching an antemortem diagnosis. Postmortem examination confirmed a urinary bladder rupture secondary to urethral obstruction by a single urethrolith. Bilateral hydronephrosis and hydroureter were identified and determined to be a result of bilateral ureteroliths. Urolith analysis revealed a composition of 100% calcium carbonate. A dietary analysis was performed, implicating an increased Ca:P ratio from a food preparation miscommunication as a contributing factor. Appropriate husbandry changes were made, and mob surveillance procedures were performed, which resolved the urolithiasis risk for the remaining five animals.

Dynamic interplay between uranyl phosphate precipitation, sorption, and phase evolution

DOE PAGES

Munasinghe, P. Sumudu; Elwood Madden, Megan E.; Brooks, Scott C.; ...

2015-04-17

We report that natural examples demonstrate uranyl-phosphate minerals can maintain extremely low levels of aqueous uranium in groundwaters due to their low solubility. Thus, greater understanding of the geochemical factors leading to uranyl phosphate precipitation may lead to successful application of phosphate-based remediation methods. However, the solubility of uranyl phosphate phases varies over >3 orders of magnitude, with the most soluble phases typically observed in lab experiments. To understand the role of common soil/sediment mineral surfaces in the nucleation and transformation of uranyl phosphate minerals under environmentally relevant conditions, we carried out batch experiments with goethite and mica at pHmore » 6 in mixed electrolyte solutions ranging from 1–800 μM U and 1–800 μM P. All experiments ended with uranium concentrations below the USEPA MCL for U, but with 2–3 orders of magnitude difference in uranium concentrations.« less

Biocalcite, a multifunctional inorganic polymer: Building block for calcareous sponge spicules and bioseed for the synthesis of calcium phosphate-based bone

PubMed Central

Schröder, Heinz C; Müller, Werner E G

2014-01-01

Summary Calcium carbonate is the material that builds up the spicules of the calcareous sponges. Recent results revealed that the calcium carbonate/biocalcite-based spicular skeleton of these animals is formed through an enzymatic mechanism, such as the skeleton of the siliceous sponges, evolutionarily the oldest animals that consist of biosilica. The enzyme that mediates the calcium carbonate deposition has been identified as a carbonic anhydrase (CA) and has been cloned from the calcareous sponge species Sycon raphanus. Calcium carbonate deposits are also found in vertebrate bones besides the main constituent, calcium phosphate/hydroxyapatite (HA). Evidence has been presented that during the initial phase of HA synthesis poorly crystalline carbonated apatite is deposited. Recent data summarized here indicate that during early bone formation calcium carbonate deposits enzymatically formed by CA, act as potential bioseeds for the precipitation of calcium phosphate mineral onto bone-forming osteoblasts. Two different calcium carbonate phases have been found during CA-driven enzymatic calcium carbonate deposition in in vitro assays: calcite crystals and round-shaped vaterite deposits. The CA provides a new target of potential anabolic agents for treatment of bone diseases; a first CA activator stimulating the CA-driven calcium carbonate deposition has been identified. In addition, the CA-driven calcium carbonate crystal formation can be frozen at the vaterite state in the presence of silintaphin-2, an aspartic acid/glutamic acid-rich sponge-specific protein. The discovery that calcium carbonate crystals act as bioseeds in human bone formation may allow the development of novel biomimetic scaffolds for bone tissue engineering. Na-alginate hydrogels, enriched with biosilica, have recently been demonstrated as a suitable matrix to embed bone forming cells for rapid prototyping bioprinting/3D cell printing applications. PMID:24991497

Biocalcite, a multifunctional inorganic polymer: Building block for calcareous sponge spicules and bioseed for the synthesis of calcium phosphate-based bone.

PubMed

Wang, Xiaohong; Schröder, Heinz C; Müller, Werner E G

2014-01-01

Calcium carbonate is the material that builds up the spicules of the calcareous sponges. Recent results revealed that the calcium carbonate/biocalcite-based spicular skeleton of these animals is formed through an enzymatic mechanism, such as the skeleton of the siliceous sponges, evolutionarily the oldest animals that consist of biosilica. The enzyme that mediates the calcium carbonate deposition has been identified as a carbonic anhydrase (CA) and has been cloned from the calcareous sponge species Sycon raphanus. Calcium carbonate deposits are also found in vertebrate bones besides the main constituent, calcium phosphate/hydroxyapatite (HA). Evidence has been presented that during the initial phase of HA synthesis poorly crystalline carbonated apatite is deposited. Recent data summarized here indicate that during early bone formation calcium carbonate deposits enzymatically formed by CA, act as potential bioseeds for the precipitation of calcium phosphate mineral onto bone-forming osteoblasts. Two different calcium carbonate phases have been found during CA-driven enzymatic calcium carbonate deposition in in vitro assays: calcite crystals and round-shaped vaterite deposits. The CA provides a new target of potential anabolic agents for treatment of bone diseases; a first CA activator stimulating the CA-driven calcium carbonate deposition has been identified. In addition, the CA-driven calcium carbonate crystal formation can be frozen at the vaterite state in the presence of silintaphin-2, an aspartic acid/glutamic acid-rich sponge-specific protein. The discovery that calcium carbonate crystals act as bioseeds in human bone formation may allow the development of novel biomimetic scaffolds for bone tissue engineering. Na-alginate hydrogels, enriched with biosilica, have recently been demonstrated as a suitable matrix to embed bone forming cells for rapid prototyping bioprinting/3D cell printing applications.

Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase

DOE PAGES

Abergel, Rebecca J.; de Jong, Wibe A.; Deblonde, Gauthier J. -P.; ...

2017-10-11

Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U 6+ chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidence d by CID, using deuterium and 18O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theorymore » (DFT) computations predict that the overall reaction requires only 132 kJ/mol, with the first oxygen activation entailing about 107 kJ/mol. Here, combined with analysis of similar, but unreactive ligands, these results shed light on the chelation-driven mechanism of uranyl oxo bond cleavage, demonstrating its dependence on the presence of ligand hydroxyl protons available for direct interactions with the uranyl oxygens.« less

Transforming Growth Factor-β1 Accelerates Resorption of a Calcium Carbonate Biomaterial in Periodontal Defects.

PubMed

Koo, Ki-Tae; Susin, Cristiano; Wikesjö, Ulf M E; Choi, Seong-Ho; Kim, Chong-Kwan

2007-04-01

In a previous study, recombinant human transforming growth factor-beta1 (rhTGF-β 1 ) in a calcium carbonate carrier was implanted into critical-size, supraalveolar periodontal defects under conditions for guided tissue regeneration (GTR) to study whether rhTGF-β 1 would enhance or accelerate periodontal regeneration. The results showed minimal benefits of rhTGF-β 1 , and a clear account for this could not be offered. One potential cause may be that the rhTGF-β 1 formulation was biologically inactive. Several growth or differentiation factors have been suggested to accelerate degradation of biomaterials used as carriers. The objective of this study was to evaluate possible activity of rhTGF-β 1 on biodegradation of the calcium carbonate carrier. rhTGF-β 1 in a putty-formulated particulate calcium carbonate carrier was implanted into critical-size, supraalveolar periodontal defects under conditions for GTR in five beagle dogs. Contralateral defects received the calcium carbonate carrier combined with GTR without rhTGF-β 1 (control). The animals were euthanized at week 4 post-surgery and block biopsies of the defect sites were collected for histologic and histometric analysis. Radiographs were obtained at defect creation and weeks 2 and 4 after defect creation. No statistically significant differences were observed in new bone formation (bone height and area) among the treatments. However, total residual carrier was significantly reduced in sites receiving rhTGF-β 1 compared to control (P = 0.04). Similarly, carrier density was considerably reduced in sites receiving rhTGF-β 1 compared to control; the difference was borderline statistically significant (P = 0.06). Within the limitations of the study, it may be concluded that rhTGF-β 1 accelerates biodegradation of a particulate calcium carbonate biomaterial, indicating a biologic activity of the rhTGF-β 1 formulation apparently not encompassing enhanced or accelerated periodontal regeneration. © 2007

The influence of seawater carbonate chemistry, mineralogy, and diagenesis on calcium isotope variations in Lower-Middle Triassic carbonate rocks

DOE PAGES

Lau, Kimberly V.; Maher, Kate; Brown, Shaun T.; ...

2017-11-01

The geological calcium cycle is linked to the geological carbon cycle through the weathering and burial of carbonate rocks. As a result, calcium (Ca) isotope ratios ( 44 Ca/ 40 Ca, expressed as δ 44/40 Ca) can help to constrain ancient carbon cycle dynamics if Ca cycle behavior can be reconstructed. But, the δ 44/40 Ca of carbonate rocks is influenced not only by the δ 44/40 Ca of seawater but also by diagenetic processes and fractionation associated with carbonate precipitation. In this study, we investigate the dominant controls on carbonate δ 44/40 Ca in Upper Permian to Middle Triassicmore » limestones (ca. 253 to 244 Ma) from south China and Turkey. This time interval is ideal for assessing controls on Ca isotope ratios in carbonate rocks because fluctuations in seawater δ 44/40 Ca may be expected based on several large carbon isotope (δ 13 C) excursions ranging from -2 to + 8‰. Parallel negative δ 13 C and δ 44/40 Ca excursions were previously identified across the end-Permian extinction horizon. Here, we find a second negative excursion in δ 44/40 Ca of ~ 0.2‰ within Lower Triassic strata in both south China and Turkey; however, this excursion is not synchronous between regions and thus cannot be interpreted to reflect secular change in the δ 44/40 Ca of global seawater. Additionally, δ 44/40 Ca values from Turkey are consistently 0.3‰ lower than contemporaneous samples from south China, providing further support for local or regional influences. By measuring δ 44/40 Ca and Sr concentrations ([Sr]) in two stratigraphic sections located at opposite margins of the Paleo-Tethys Ocean, we can determine whether the data represent global conditions (e.g., secular variations in the δ 44/40 Ca of seawater) versus local controls (e.g., original mineralogy or diagenetic alteration). The [Sr] and δ 44/40 Ca data from this study are best described statistically by a log-linear correlation that also exists in many previously published datasets of

The influence of seawater carbonate chemistry, mineralogy, and diagenesis on calcium isotope variations in Lower-Middle Triassic carbonate rocks

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

Lau, Kimberly V.; Maher, Kate; Brown, Shaun T.

The geological calcium cycle is linked to the geological carbon cycle through the weathering and burial of carbonate rocks. As a result, calcium (Ca) isotope ratios ( 44 Ca/ 40 Ca, expressed as δ 44/40 Ca) can help to constrain ancient carbon cycle dynamics if Ca cycle behavior can be reconstructed. But, the δ 44/40 Ca of carbonate rocks is influenced not only by the δ 44/40 Ca of seawater but also by diagenetic processes and fractionation associated with carbonate precipitation. In this study, we investigate the dominant controls on carbonate δ 44/40 Ca in Upper Permian to Middle Triassicmore » limestones (ca. 253 to 244 Ma) from south China and Turkey. This time interval is ideal for assessing controls on Ca isotope ratios in carbonate rocks because fluctuations in seawater δ 44/40 Ca may be expected based on several large carbon isotope (δ 13 C) excursions ranging from -2 to + 8‰. Parallel negative δ 13 C and δ 44/40 Ca excursions were previously identified across the end-Permian extinction horizon. Here, we find a second negative excursion in δ 44/40 Ca of ~ 0.2‰ within Lower Triassic strata in both south China and Turkey; however, this excursion is not synchronous between regions and thus cannot be interpreted to reflect secular change in the δ 44/40 Ca of global seawater. Additionally, δ 44/40 Ca values from Turkey are consistently 0.3‰ lower than contemporaneous samples from south China, providing further support for local or regional influences. By measuring δ 44/40 Ca and Sr concentrations ([Sr]) in two stratigraphic sections located at opposite margins of the Paleo-Tethys Ocean, we can determine whether the data represent global conditions (e.g., secular variations in the δ 44/40 Ca of seawater) versus local controls (e.g., original mineralogy or diagenetic alteration). The [Sr] and δ 44/40 Ca data from this study are best described statistically by a log-linear correlation that also exists in many previously published datasets of

Synthesis and characterization of new ion-imprinted polymer for separation and preconcentration of uranyl (UO2(2+)) ions.

PubMed

Ahmadi, Seyed Javad; Noori-Kalkhoran, Omid; Shirvani-Arani, Simindokht

2010-03-15

UO(2)(2+) ion-imprinted polymer materials used for solid-phase extraction were prepared by copolymerization of a ternary complex of uranyl ions with styrene and divinyl benzene in the presence of 2,2'-azobisisobutyronitrile. The imprinted particles were leached by HCl 6M. Various parameters in polymerization steps such as DVB/STY ratio, time of polymerization and temperature of polymerization were varied to achieve the most efficient uranyl-imprinted polymer. X-ray diffraction (XRD), infra-red spectroscopy (IR), thermo gravimetric analysis (TGA), UV-vis and nitrogen sorption were used to characterize the polymer particles. The XRD results showed that uranyl ions were completely removed from the polymer after leaching process. IR Analysis indicated that the N,N'-ethylenebis(pyridoxylideneiminato) remained intact in the polymer even after leaching. Some parameters such as pH, weight of the polymer, elution time, eluent volume and aqueous phase volume which affects the efficiency of the polymer were studied. (c) 2009 Elsevier B.V. All rights reserved.

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

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

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

DOE PAGES

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; ...

2017-10-24

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

Uranyl(VI) nitrate salts: modeling thermodynamic properties using the binding mean spherical approximation theory and determination of "fictive" binary data.

PubMed

Ruas, Alexandre; Bernard, Olivier; Caniffi, Barbara; Simonin, Jean-Pierre; Turq, Pierre; Blum, Lesser; Moisy, Philippe

2006-02-23

This work is aimed at a description of the thermodynamic properties of highly concentrated aqueous solutions of uranyl nitrate at 25 degrees C. A new resolution of the binding mean spherical approximation (BIMSA) theory, taking into account 1-1 and also 1-2 complex formation, is developed and used to reproduce, from a simple procedure, experimental uranyl nitrate osmotic coefficient variation with concentration. For better consistency of the theory, binary uranyl perchlorate and chloride osmotic coefficients are also calculated. Comparison of calculated and experimental values is made. The possibility of regarding the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O as a "simple" solution (in the sense of Zdanovskii, Stokes, and Robinson) is examined from water activity and density measurements. Also, an analysis of existing uranyl nitrate binary data is proposed and compared with our obtained data. On the basis of the concept of "simple" solution, values for density and water activity for the binary system UO(2)(NO(3))(2)/H(2)O are proposed in a concentration range on which uranyl nitrate precipitates from measurements on concentrated solutions of the ternary system UO(2)(NO(3))(2)/HNO(3)/H(2)O. This new set of binary data is "fictive" in the sense that the real binary system is not stable chemically. Finally, a new, interesting predictive capability of the BIMSA theory is shown.

Experimental Comparison of Calcium Sulfate (CaSO(4)) Scale Deposition on Coated Carbon Steel and Titanium Surfaces

NASA Astrophysics Data System (ADS)

Al-Otaibi, Dhawi AbdulRahman

Calcium Sulfate (CaSO4) deposit reduces heat exchange in heat transfer equipment which adversely affects the equipment performance and plant production. This experimental study was conducted by using the Rotating Cylinder Electrode (RCE) equipment available in the university's Center for Engineering Research (CER/RI) to study and compare the effect of solution hydrodynamics on Calcium Sulfate (CaSO4) scale deposition on coated carbon steel and titanium surfaces. In addition, the Scanning Electron Microscopic was used to examine the morphology and distribution of Calcium Sulfate (CaSO 4) crystals deposited on titanium metal surfaces. In this study, the rotational speed was varied from 100 to 2000 RPM to study the behavior of Calcium Sulfate (CaSO4) accumulation on both materials. Based on the experimental results, Calcium Sulfate (CaSO4) scale obtained in the present study was almost constant on coated carbon steel in which the rate of scale deposition is equal to the rate of scale removal. However, the deposition of Calcium Sulfate (CaSO4) observed on titanium material was increased as the speed increased.

Results of the TTF-TCNQ- and the calcium carbonate-crystallization on the Long Duration Exposure Facility

NASA Technical Reports Server (NTRS)

Nielsen, Kjeld Flemming; Lind, M. David

1991-01-01

Experiment AO139A on the Long Duration Exposure Facility (LDEF) carried four large containers into orbit for five years with crystal growth solutions for lead sulfide, calcium carbonate, and tetra thiafulvalene- tetra cyanoquino methane (TTF-TCNQ). The LDEF was in excellent condition after the long orbital stay, and although the temperature data was lost, the experiment program had been working since the valves in all containers were opened. All four experiments produced crystals; however, they were of varying quality. The calcium carbonate crystals had the best appearance. The TTF-TCNQ crystals were packed together near the valve openings of the container. When taken apart, the single crystals showed some unusual morphological properties. X-ray investigations as well as conductivity measurements on the long duration space grown TTF-TCNQ crystals are presented, and pictures of the calcium carbonate are shown. Comparisons are made with previous space solution growth experiments on the European Spacelab Mission and the Apollo-Soyuz Test Project.

In vitro study of the effect of a dentifrice containing 8% arginine, calcium carbonate, and sodium monofluorophosphate on acid-softened enamel.

PubMed

Rege, Aarti; Heu, Rod; Stranick, Michael; Sullivan, Richard J

2014-01-01

To investigate the possible mode of action of a dentifrice containing 8% arginine and calcium carbonate (Pro-Argin Technology), and sodium monofluorophosphate in delivering the benefits of preventing acid erosion and rehardening acid-softened enamel. The surfaces of acid-softened bovine enamel specimens were evaluated after application of a dentifrice containing 8% arginine, calcium carbonate, and sodium monofluorophosphate in vitro. Scanning Electron Microscopy (SEM), Electronic Spectrometry for Chemical Analysis (ESCA), and Secondary Ion Mass Spectrometry (SIMS) were used to characterize the enamel surfaces. Exposure of pristine enamel surfaces to citric acid resulted in clear roughening of the surface. Multiple applications of a dentifrice containing 8% arginine, calcium carbonate, and sodium monofluorophosphate to the surface of the enamel resulted in the disappearance of the microscopic voids observed by SEM as a function of treatment applications. The ESCA analysis demonstrated that both the nitrogen and carbonate levels increased as the number of treatments increased, which provides evidence that arginine and calcium carbonate were bound to the surface. Observance of arginine's signature mass fragmentation pattern by SIMS analysis confirmed the identity of arginine on the enamel surface. A series of in vitro experiments has demonstrated a possible mode of action by which a dentifrice containing 8% arginine, calcium carbonate, and sodium monofluorophosphate delivers the benefits of preventing acid erosion and rehardening acid-softened enamel. The combination of arginine and calcium carbonate adheres to the enamel surface and helps to fill the microscopic gaps created by acid, which in turn helps repair the enamel and provides a protective coating against future acid attacks.

Bioprecipitation of Calcium Carbonate Crystals by Bacteria Isolated from Saline Environments Grown in Culture Media Amended with Seawater and Real Brine

PubMed Central

Silva-Castro, G. A.; Uad, I.; Gonzalez-Martinez, A.; Rivadeneyra, A.; Gonzalez-Lopez, J.; Rivadeneyra, M. A.

2015-01-01

The precipitation of calcium carbonate and calcium sulphate by isolated bacteria from seawater and real brine obtained in a desalination plant growth in culture media containing seawater and brine as mineral sources has been studied. However, only bioprecipitation was detected when the bacteria were grown in media with added organic matter. Biomineralization process started rapidly, crystal formation taking place in the beginning a few days after inoculation of media; roughly 90% of total cultivated bacteria showed. Six major colonies with carbonate precipitation capacity dominated bacterial community structure cultivated in heterotrophic platable bacteria medium. Taxonomic identification of these six strains through partial 16S rRNA gene sequences showed their affiliation with Gram-positive Bacillus and Virgibacillus genera. These strains were able to form calcium carbonate minerals, which precipitated as calcite and aragonite crystals and showed bacterial fingerprints or bacteria calcification. Also, carbonic anhydrase activity was observed in three of these isolated bacteria. The results of this research suggest that microbiota isolated from sea water and brine is capable of precipitation of carbonate biominerals, which can occur in situ with mediation of organic matter concentrations. Moreover, calcium carbonate precipitation ability of this microbiota could be of importance in bioremediation of CO2 and calcium in certain environments. PMID:26273646

Bioprecipitation of Calcium Carbonate Crystals by Bacteria Isolated from Saline Environments Grown in Culture Media Amended with Seawater and Real Brine.

PubMed

Silva-Castro, G A; Uad, I; Gonzalez-Martinez, A; Rivadeneyra, A; Gonzalez-Lopez, J; Rivadeneyra, M A

2015-01-01

The precipitation of calcium carbonate and calcium sulphate by isolated bacteria from seawater and real brine obtained in a desalination plant growth in culture media containing seawater and brine as mineral sources has been studied. However, only bioprecipitation was detected when the bacteria were grown in media with added organic matter. Biomineralization process started rapidly, crystal formation taking place in the beginning a few days after inoculation of media; roughly 90% of total cultivated bacteria showed. Six major colonies with carbonate precipitation capacity dominated bacterial community structure cultivated in heterotrophic platable bacteria medium. Taxonomic identification of these six strains through partial 16S rRNA gene sequences showed their affiliation with Gram-positive Bacillus and Virgibacillus genera. These strains were able to form calcium carbonate minerals, which precipitated as calcite and aragonite crystals and showed bacterial fingerprints or bacteria calcification. Also, carbonic anhydrase activity was observed in three of these isolated bacteria. The results of this research suggest that microbiota isolated from sea water and brine is capable of precipitation of carbonate biominerals, which can occur in situ with mediation of organic matter concentrations. Moreover, calcium carbonate precipitation ability of this microbiota could be of importance in bioremediation of CO2 and calcium in certain environments.

Increasing Soil Calcium Availability Alters Forest Soil Carbon Stocks

NASA Astrophysics Data System (ADS)

Melvin, A.; Goodale, C. L.

2011-12-01

Acid deposition in the Northeastern U.S. has been linked to a loss of soil base cations, especially calcium (Ca). While much research has addressed the effects of Ca depletion on soil and stream acidification, few studies have investigated its effects on ecosystem carbon (C) balance. We studied the long-term effects of increased Ca availability on C cycling in a northern hardwood forest in the Adirondack Park, NY. In 1989, calcium carbonate (lime) was added to ~ 100 ha of the Woods Lake Watershed to ameliorate the effects of soil Ca depletion. An additional 100 ha were maintained as controls. We hypothesized that the lime addition would improve forest health and that this improvement would be evident in increased tree biomass, leaf litter, and fine root production. Within the forest floor, we anticipated that the increased pH associated with liming would stimulate microbial activity resulting in increased decomposition and basal soil respiration, and reduced C stocks. Additionally, we hypothesized that increased Ca availability could enhance Ca-OM complexation in the upper mineral soils, leading to increased C stocks in these horizons. Eighteen years after liming, soil pH and exchangeable Ca pools remained elevated in the forest floor and upper mineral soil of the limed plots. Forest floor C stocks were significantly larger in limed plots (68 vs. 31 t C ha-1), and were driven primarily by greater C accumulation in the forest floor Oa horizon. Mineral soil C stocks did not differ between limed and control soils. Liming did not affect tree growth, however a net decline in biomass was observed across the entire watershed. There was a trend for larger fine root and foliar litter inputs in limed plots relative to controls, but the observed forest floor accumulation appears to be driven primarily by a suppression of decomposition. Liming reduced basal soil respiration rates by 17 and 43 % in the Oe and Oa horizons, respectively. This research suggests that Ca may

Calcium absorbability from milk products, an imitation milk, and calcium carbonate

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

Recker, R.R.; Bammi, A.; Barger-Lux, M.J.

Whole milk, chocolate milk, yogurt, imitation milk (prepared from dairy and nondairy products), cheese, and calcium carbonate were labeled with /sup 45/Ca and administered as a series of test meals to 10 healthy postmenopausal women. Carrier Ca content of the test meals was held constant at 250 mg and subjects fasted before each meal. The absorbability of Ca from the six sources was compared by measuring fractional absorption by the double isotope method. The mean absorption values for all six sources were tightly clustered between 21 and 26% and none was significantly different from the others using one-way analysis ofmore » variance. We conclude that none of the sources was significantly superior or inferior to the others.« less

Calcium carbonates: induced biomineralization with controlled macromorphology

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

The mineral phase in the cuticles of two species of Crustacea consists of magnesium calcite, amorphous calcium carbonate, and amorphous calcium phosphate.

PubMed

Becker, Alexander; Ziegler, Andreas; Epple, Matthias

2005-05-21

The cuticules (shells) of the woodlice Porcellio scaber and Armadillidium vulgare were analysed with respect to their content of inorganic material. It was found that the cuticles consist of crystalline magnesium calcite, amorphous calcium carbonate (ACC), and amorphous calcium phosphate (ACP), besides small amounts of water and an organic matrix. It is concluded that the cuticle, which constitutes a mineralized protective organ, is chemically adapted to the biological requirements by this combination of different materials.

Calcium Carbonate Precipitation by Bacillus and Sporosarcina Strains Isolated from Concrete and Analysis of the Bacterial Community of Concrete.

PubMed

Kim, Hyun Jung; Eom, Hyo Jung; Park, Chulwoo; Jung, Jaejoon; Shin, Bora; Kim, Wook; Chung, Namhyun; Choi, In-Geol; Park, Woojun

2016-03-01

Microbially induced calcium carbonate precipitation (CCP) is a long-standing but re-emerging environmental engineering process for production of self-healing concrete, bioremediation, and long-term storage of CO2. CCP-capable bacteria, two Bacillus strains (JH3 and JH7) and one Sporosarcina strain (HYO08), were isolated from two samples of concrete and characterized phylogenetically. Calcium carbonate crystals precipitated by the three strains were morphologically distinct according to field emission scanning electron microscopy. Energy dispersive X-ray spectrometry mapping confirmed biomineralization via extracellular calcium carbonate production. The three strains differed in their physiological characteristics: growth at alkali pH and high NaCl concentrations, and urease activity. Sporosarcina sp. HYO08 and Bacillus sp. JH7 were more alkali- and halotolerant, respectively. Analysis of the community from the same concrete samples using barcoded pyrosequencing revealed that the relative abundance of Bacillus and Sporosarcina species was low, which indicated low culturability of other dominant bacteria. This study suggests that calcium carbonate crystals with different properties can be produced by various CCP-capable strains, and other novel isolates await discovery.

Effects of copyrolysis of sludge with calcium carbonate and calcium hydrogen phosphate on chemical stability of carbon and release of toxic elements in the resultant biochars.

PubMed

Xu, Xuebin; Hu, Xin; Ding, Zhuhong; Chen, Yijun

2017-12-01

The potential release of toxic elements and the stability of carbon in sludge-based biochars are important on their application in soil remediation and wastewater treatment. In this study, municipal sludge was co-pyrolyzed with calcium carbonate (CaCO 3 ) and calcium dihydrogen phosphate [Ca(H 2 PO 4 ) 2 ] under 300 and 600 °C, respectively. The basic physicochemical properties of the resultant biochars were characterized and laboratory chemical oxidation and leaching experiments of toxic elements were conducted to evaluate the chemical stability of carbon in biochars and the potential release of toxic elements from biochars. Results show that the exogenous minerals changed the physico-chemical properties of the resultant biochars greatly. Biochars with exogenous minerals, especially Ca(H 2 PO 4 ) 2 , decreased the release of Zn, Cr, Ni, Cu, Pb, and As and the release ratios were less than 1%. Tessier's sequential extraction analysis revealed that labile toxic elements were transferred to residual fraction in the biochars with high pyrolysis temperature (600 °C) and exogenous minerals. Low risks for biochar-bound Pb, Zn, Cd, As, Cr, and Cu were confirmed according to risk assessment code (RAC) while the potential ecological risk index (PERI) revealed that the exogenous Ca(H 2 PO 4 ) 2 significantly decreased the risks from considerable to moderate level. Moreover, the exogenous minerals significantly increased the chemical stability of carbon in 600 °C-pyrolyzed biochars by 10-20%. These results indicated that the copyrolysis of sludge with phosphate and carbonate, especially phosphate, were effective methods to prepare the sludge-based biochars with immobilized toxic elements and enhanced chemical stability of carbon. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lithostathine, the presumed pancreatic stone inhibitor, does not interact specifically with calcium carbonate crystals.

PubMed

De Reggi, M; Gharib, B; Patard, L; Stoven, V

1998-02-27

Lithostathine (pancreatic stone protein, Reg protein) is, in addition to albumin, the major nonenzymatic protein of the pancreatic juice. It has been assumed to inhibit calcium carbonate precipitation and therefore to prevent stone formation in the pancreatic ducts. This function is, however, debatable. The assumption is based on the inhibition of in vitro crystal nucleation and growth by lithostathine. Considering that these phenomena occur only under certain critical conditions, we re-examined the question using a protein preparation where the purity and folding have been tested by mass spectroscopy and NMR in the absence of nonprotein contaminants. Under these conditions, we showed conclusively that lithostathine does not inhibit calcium carbonate nucleation and crystal growth. We demonstrated that previous findings on the alleged inhibition can be attributed to the uncontrolled presence of salts in the protein preparation used. Moreover, the affinity of lithostathine to calcite crystals, expressed as the half-life of bound iodinated protein in the presence of unlabeled competitor, was significantly lower than that of bovine serum albumin (8.8 and 11.2 h, respectively). Using glass microspheres instead of crystals did not significantly change the half-life of bound lithostathine (8.0 h). These findings are incompatible with the hypothesis of a specific interaction of lithostathine with calcium carbonate crystals. In conclusion, considering that components of pancreatic juice such as NaCl and phosphate ions are powerful inhibitors of calcium carbonate crystal growth, the mechanism of stone formation in pancreatic ducts must be reconsidered. The presence in normal pancreatic juice of small amounts of the 133-residue isoform of lithostathine (PSP-S1), which precipitates at physiological pH, should be noted, and the possibility should be considered that they form micro-precipitates that aggregate and are progressively calcified.

Vibrational Properties of Anhydrous and Partially Hydrated Uranyl Fluoride

DOE PAGES

Anderson, Brian B.; Kirkegaard, Marie C.; Miskowiec, Andrew J.; ...

2017-01-01

Uranyl fluoride (UO 2F 2) is a hygroscopic powder with two main structural phases: an anhydrous crystal and a partially hydrated crystal of the same R¯3m symmetry. The formally closed-shell electron structure of anhydrous UO 2F 2 is amenable to density functional theory calculations. We use density functional perturbation theory (DFPT) to calculate the vibrational frequencies of the anhydrous crystal structure and employ complementary inelastic neutron scattering and temperature-dependent Raman scattering to validate those frequencies. As a model closed-shell actinide, we investigated the effect of LDA, GGA, and non-local vdW functionals as well as the spherically-averaged Hubbard +U correction onmore » vibrational frequencies, electronic structure, and geometry of anhydrous UO 2F 2. A particular choice of U eff = 5.5 eV yields the correct U Oyl bond distance and vibrational frequencies for the characteristic Eg and A1g modes that are within the resolution of experiment. Inelastic neutron scattering and Raman scattering suggest a degree of water coupling to the lattice vibrations in the more experimentally accessible partially hydrated UO 2F 2 system, with the symmetric O-U-O stretching vibration shifted approximately 47 cm -1 lower in energy compared to the anhydrous structure. Evidence of water interaction with the uranyl ion is present from a two-peak decomposition of the uranyl stretching vibration in the Raman spectra and anion hydrogen stretching vibrations in the inelastic neutron scattering spectra. A first-order dehydration phase transition temperature is definitively identified to be 125 °C using temperature-dependent Raman scattering.« less

Engineered nano-magnetic iron oxide-urea-activated carbon nanolayer sorbent for potential removal of uranium (VI) from aqueous solution

NASA Astrophysics Data System (ADS)

Mahmoud, Mohamed E.; Khalifa, Mohamed A.; El Wakeel, Yasser M.; Header, Mennatllah S.; Abdel-Fattah, Tarek M.

2017-04-01

A novel magnetic nanosorbent was designed using chemical grafting of nano-magnetite (Nano-Fe3O4) with nanolayer of activated carbon (AC) via urea intermediate for the formation of Nano-Fe3O4-Urea-AC. Characterizing was carried out using FT-IR, SEM, HR-TEM, TGA, point of zero charge (Pzc) and surface area analysis. The designed sorbent maintained its magnetic properties and nanosized structure in the range of 8.7-14.1 nm. The surface area was identified as 389 m2/g based on the BET method. Sorption of uranyl ions from aqueous solutions was studied and evaluated in different experimental conditions. Removal of uranyl ions increased with increasing in pH value and the maximum percentage removal was established at pH 5.0. The removal and sorption processes of uranyl ions by Nano-Fe3O4-Urea-AC sorbent were studied and optimized using the batch technique. The key variables affecting removal of uranyl ions were studied including the effect of the contact time, dosage of Nano-Fe3O4-Urea-AC sorbent, reaction temperature, initial uranyl ions concentration and interfering anions and cations.

EPR investigation of UV light effect on calcium carbonate powders with different grain sizes.

PubMed

Kabacińska, Zuzanna; Krzyminiewski, Ryszard; Dobosz, Bernadeta

2014-06-01

This study is based on investigation of calcium carbonate powders with different grain sizes exposed to UV light. Calcium carbonate is widely used in many branches of industry, e.g. as a filler for polymer materials; therefore, knowing its properties, among them also its reaction to UV light, is essential. Samples of powdered calcium carbonate with average grain sizes of 69 and 300 nm and 2.1, 6, 16, 25 µm were used in this investigation. Measurements were performed at room temperature using EPR X-band spectrometer, and they have shown the additional signals induced by the light from Hg lamp. The effect of annealing of the micro-grain samples was also studied. The spectra of four micro-grain samples after irradiation are similar, but there are differences between them and the other two powders, which could be related to the different sizes of their grains. Further studies based on these preliminary results may prove useful in research of photodegradation of CaCO3-filled materials, as well as helpful in increasing the accuracy of dating of archaeological and geological objects. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Strontium hydroxyapatite and strontium carbonate as templates for the precipitation of calcium-phosphates in the absence and presence of fluoride

NASA Astrophysics Data System (ADS)

Sternitzke, Vanessa; Janousch, Markus; Heeb, Michèle B.; Hering, Janet G.; Johnson, C. Annette

2014-06-01

The heterogeneous precipitation of calcium-phosphates on calcium hydroxyapatite (Ca10(PO4)6(OH)2 or HAP) in the presence and absence of fluoride is important in the formation of bone and teeth, protection against tooth decay, dental and skeletal fluorosis and defluoridation of drinking water. Strontium hydroxyapatite (Sr10(PO4)6(OH)2 or SrHAP) and strontium carbonate (SrCO3) were used as calcium-free seed templates in precipitation experiments conducted with varying initial calcium-to-phosphate (Ca/P) or calcium-to-phosphate-to-fluoride (Ca/P/F) ratios. Suspensions of SrHAP or SrCO3 seed templates (which were calcium-limited for both templates and phosphate-limited in the case of SrCO3) were reacted at pH 7.3 (25 °C) over 3 days. The resulting solids were examined with Scanning Transmission Electron Microscopy (STEM), X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR), and X-ray Photoelectron Spectroscopy (XPS), X-ray Absorption Near Edge Structure (XANES), and Extended X-ray Absorption Fine Structure spectroscopy (EXAFS). Calcium apatite was the predominant phase identified by all techniques independent of the added Ca/P ratios and of the presence of fluoride. It was not possible to make an unambiguous distinction between HAP and fluorapatite (Ca10(PO4)6F2, FAP). The apatite was calcium-deficient and probably contained some strontium.

Mineralized alginate hydrogels using marine carbonates for bone tissue engineering applications.

PubMed

Diaz-Rodriguez, P; Garcia-Triñanes, P; Echezarreta López, M M; Santoveña, A; Landin, M

2018-09-01

The search for an ideal bone tissue replacement has led to the development of new composite materials designed to simulate the complex inorganic/organic structure of bone. The present work is focused on the development of mineralized calcium alginate hydrogels by the addition of marine derived calcium carbonate biomineral particles. Following a novel approach, we were able to obtain calcium carbonate particles of high purity and complex micro and nanostructure dependent on the source material. Three different types of alginates were selected to develop inorganic/organic scaffolds in order to correlate alginate composition with scaffold properties and cell behavior. The incorporation of calcium carbonates into alginate networks was able to promote extracellular matrix mineralization and osteoblastic differentiation of mesenchymal stem cells when added at 7 mg/ml. We demonstrated that the selection of the alginate type and calcium carbonate origin is crucial to obtain adequate systems for bone tissue engineering as they modulate the mechanical properties and cell differentiation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Non-ureolytic calcium carbonate precipitation by Lysinibacillus sp. YS11 isolated from the rhizosphere of Miscanthus sacchariflorus.

PubMed

Lee, Yun Suk; Kim, Hyun Jung; Park, Woojun

2017-06-01

Although microbially induced calcium carbonate precipitation (MICP) through ureolysis has been widely studied in environmental engineering fields, urea utilization might cause environmental problems as a result of ammonia and nitrate production. In this study, many non-ureolytic calcium carbonate-precipitating bacteria that induced an alkaline environment were isolated from the rhizosphere of Miscanthus sacchariflorus near an artificial stream and their ability to precipitate calcium carbonate minerals with the absence of urea was investigated. MICP was observed using a phase-contrast microscope and ion-selective electrode. Only Lysinibacillus sp. YS11 showed MICP in aerobic conditions. Energy dispersive X-ray spectrometry and X-ray diffraction confirmed the presence of calcium carbonate. Field emission scanning electron microscopy analysis indicated the formation of morphologically distinct minerals around cells under these conditions. Monitoring of bacterial growth, pH changes, and Ca 2+ concentrations under aerobic, hypoxia, and anaerobic conditions suggested that strain YS11 could induce alkaline conditions up to a pH of 8.9 and utilize 95% of free Ca 2+ only under aerobic conditions. Unusual Ca 2+ binding and its release from cells were observed under hypoxia conditions. Biofilm and extracellular polymeric substances (EPS) formation were enhanced during MICP. Strain YS11 has resistance at high pH and in high salt concentrations, as well as its spore-forming ability, which supports its potential application for self-healing concrete.

Constraining the cause of the end-Guadalupian extinction with coupled records of carbon and calcium isotopes

NASA Astrophysics Data System (ADS)

Jost, A. B.; Mundil, R.; He, B.; Brown, S. T.; Altiner, D.; Sun, Y.; DePaolo, D. J.; Payne, J.

2013-12-01

A negative δ13C excursion in carbonate sediments from Guadalupian (Middle Permian) and Lopingian (Late Permian) stratigraphic sections has been interpreted to result from a large carbon cycle disturbance during end-Guadalupian extinction event (ca. 260 Ma). However, the carbon isotope data alone are insufficient to uniquely determine the type and magnitude of perturbations to the global carbon cycle. The carbon and calcium cycles are coupled via CaCO3 burial, so changes in calcium isotopes can be used to constrain the cause of a carbon isotope excursion. In this study, we present coupled carbon and calcium isotope records from three Guadalupian-Lopingian (G/L) sections in China and Turkey. Isotope records among our studied sections are inconsistent in both their δ13C and δ44/40Ca records. Similar inconsistencies in δ13C among sections occur across previously published datasets. Sections with large (>3‰) changes in δ13C either show evidence for diagenetic alteration or do not show δ13C and δ44/40Ca changes consistent with severe volcanic degassing from Emeishan or methane clathrate destabilization. We conclude that the large isotopic changes are more likely the result of local burial conditions or diagenetic effects, rather than a large carbon cycle disturbance. Perturbations to the global carbon and calcium cycles appear to have been much smaller across the G/L transition than across the subsequent Permian-Triassic boundary. This finding is consistent with recent paleobiological data showing that the end-Guadalupian extinction was much less severe than previously believed, and was indistinguishable in magnitude from background intervals. However, selective extinction of marine animals with passive respiratory physiology indicates that the G/L extinction cannot simply be due to background extinction or sampling failure, and that it was triggered by some environmental event. Therefore, any environmental event must have been small enough to not generate large

The onset of calcium carbonate nucleation: a density functional theory molecular dynamics and hybrid microsolvation/continuum study.

PubMed

Di Tommaso, Devis; de Leeuw, Nora H

2008-06-12

Density functional theory (Perdew-Burke-Ernzerhof) based methods have been used to study the structure and hydration environment of the building blocks of CaCO 3 in aqueous solutions of calcium bicarbonate and calcium carbonate. Car-Parrinello molecular dynamics simulations of Ca(2+)/CO3(2-) and Ca (2+)/HCO3(-) in explicit water were performed to investigate the formation of CaCO3 and the hydration shell of the solvated hetero-ion pair. Our simulations show that the formation of the monomer of CaCO3 occurs with an associative mechanism and that the dominant building block of calcium (bi)carbonate in aqueous solution is Ca[eta(1)-(H)CO3](H2O)5, i.e., the preferred hydration number is five, while the (bi)carbonate is coordinated to the calcium in a monodentate mode. This result agrees with static calculations, where a hybrid approach using a combination of explicit solvent molecules and a polarizable continuum model has been applied to compute the solvation free energies of calcium bicarbonate species. Furthermore, the discrete-continuum calculations predict that the Ca(HCO3)2 and Ca(HCO3)3(-) species are stable in an aqueous environment preferentially as Ca(HCO3)2(H2O)4 and Ca(HCO3)3(H2O)2(-), respectively.

Restoration of parathyroid function after change of phosphate binder from calcium carbonate to lanthanum carbonate in hemodialysis patients with suppressed serum parathyroid hormone.

PubMed

Inaba, Masaaki; Okuno, Senji; Nagayama, Harumi; Yamada, Shinsuke; Ishimura, Eiji; Imanishi, Yasuo; Shoji, Shigeichi

2015-03-01

Control of phosphate is the most critical in the treatment of chronic kidney disease with mineral and bone disorder (CKD-MBD). Because calcium-containing phosphate binder to CKD patients is known to induce adynamic bone disease with ectopic calcification by increasing calcium load, we examined the effect of lanthanum carbonate (LaC), a non-calcium containing phosphate binder, to restore bone turnover in 27 hemodialysis patients with suppressed parathyroid function (serum intact parathyroid hormone [iPTH] ≦ 150 pg/mL). At the initiation of LaC administration, the dose of calcium-containing phosphate binder calcium carbonate (CaC) was withdrawn or reduced based on serum phosphate. After initiation of LaC administration, serum calcium and phosphate decreased significantly by 4 weeks, whereas whole PTH and iPTH increased. A significant and positive correlation between decreases of serum calcium, but not phosphate, with increases of whole PTH and iPTH, suggested that the decline in serum calcium with reduction of calcium load by LaC might increase parathyroid function. Serum bone resorption markers, such as serum tartrate-resistant acid phosphatase 5b, and N-telopeptide of type I collagen increased significantly by 4 weeks after LaC administration, which was followed by increases of serum bone formation markers including serum bone alkaline phosphatase, intact procollagen N-propeptide, and osteocalcin. Therefore, it was suggested that LaC attenuated CaC-induced suppression of parathyroid function and bone turnover by decreasing calcium load. In conclusion, replacement of CaC with LaC, either partially or totally, could increase parathyroid function and resultant bone turnover in hemodialysis patients with serum iPTH ≦ 150 pg/mL. Copyright © 2015 National Kidney Foundation, Inc. Published by Elsevier Inc. All rights reserved.

Influence of zinc on the calcium carbonate biomineralization of Halomonas halophila

PubMed Central

2012-01-01

Background The salt tolerance of halophilic bacteria make them promising candidates for technical applications, like isolation of salt tolerant enzymes or remediation of contaminated saline soils and waters. Furthermore, some halophilic bacteria synthesize inorganic solids resulting in organic–inorganic hybrids. This process is known as biomineralization, which is induced and/or controlled by the organism. The adaption of the soft and eco-friendly reaction conditions of this formation process to technical syntheses of inorganic nano materials is desirable. In addition, environmental contaminations can be entrapped in biomineralization products which facilitate the subsequent removal from waste waters. The moderately halophilic bacteria Halomonas halophila mineralize calcium carbonate in the calcite polymorph. The biomineralization process was investigated in the presence of zinc ions as a toxic model contaminant. In particular, the time course of the mineralization process and the influence of zinc on the mineralized inorganic materials have been focused in this study. Results H. halophila can adapt to zinc contaminated medium, maintaining the ability for biomineralization of calcium carbonate. Adapted cultures show only a low influence of zinc on the growth rate. In the time course of cultivation, zinc ions accumulated on the bacterial surface while the medium depleted in the zinc contamination. Intracellular zinc concentrations were below the detection limit, suggesting that zinc was mainly bound extracellular. Zinc ions influence the biomineralization process. In the presence of zinc, the polymorphs monohydrocalcite and vaterite were mineralized, instead of calcite which is synthesized in zinc-free medium. Conclusions We have demonstrated that the bacterial mineralization process can be influenced by zinc ions resulting in the modification of the synthesized calcium carbonate polymorph. In addition, the shape of the mineralized inorganic material is chancing

Calcium signaling in taste cells: regulation required.

PubMed

Medler, Kathryn F

2010-11-01

Peripheral taste receptor cells depend on distinct calcium signals to generate appropriate cellular responses that relay taste information to the central nervous system. Some taste cells have conventional chemical synapses and rely on calcium influx through voltage-gated calcium channels. Other taste cells lack these synapses and depend on calcium release from stores to formulate an output signal through a hemichannel. Despite the importance of calcium signaling in taste cells, little is known about how these signals are regulated. This review summarizes recent studies that have identified 2 calcium clearance mechanisms expressed in taste cells, including mitochondrial calcium uptake and sodium/calcium exchangers (NCXs). These studies identified a unique constitutive calcium influx that contributes to maintaining appropriate calcium homeostasis in taste cells and the role of the mitochondria and exchangers in this process. The additional role of NCXs in the regulation of evoked calcium responses is also discussed. Clearly, calcium signaling is a dynamic process in taste cells and appears to be more complex than has previously been appreciated.

Effects of dietary supplementation of arginine-silicate-inositol complex on absorption and metabolism of calcium of laying hens

PubMed Central

Orhan, Cemal; Tuzcu, Mehmet; Hayirli, Armagan; Komorowski, James R.; Sahin, Nurhan

2018-01-01

The effects of supplementation of arginine-silicate-inositol complex (ASI; 49.5–8.2–25 g/kg, respectively) to laying hens were investigated with respect to eggshell quality, calcium (Ca) balance, and expression of duodenal proteins related to Ca metabolism (calbindin and tight junction proteins). A total of 360 laying hens, 25 weeks old, were divided into 3 groups consisting of 6 replicate of cages, 20 birds per cage. The groups were fed a basal diet and the basal diet supplemented with 500 or 1000 mg ASI complex per kilogram for 90 days. Data were analyzed by ANCOVA using data during the first week of the adaptation period as covariates. As the ASI complex supplementation level increased, there were increases in feed intake (P < 0.0001), egg production (P < 0.001), egg weight (P < 0.0001) and eggshell weight (P < 0.001) weight, and shell thickness (P < 0.001) and decreases in feed conversion ratio and cracked egg percentage (P < 0.0001 for both). Concentrations of serum osteocalcin (P < 0.0001), vitamin D (P < 0.0001), calcium (P < 0.001), phosphorus (P < 0.001), and alkaline phosphatase (P < 0.008) as well as amounts of calcium retention (P < 0.0001) and eggshell calcium deposition (P < 0.001), and Ca balance (P < 0.0001) increased, whereas amount of calcium excretion (P < 0.001) decreased linearly in a dose-dependent manner. The ASI complex supplementation increased expressions of calcium transporters (calbindin-D28k, N sodium-calcium exchanger, plasma membrane calcium ATPase, and vitamin D receptor) and tight junction proteins (zonula occludens-1 and occludin) in the duodenum in a linear fashion (P < 0.0001 for all). In conclusion, provision of dietary ASI complex to laying hens during the peak laying period improved eggshell quality through improving calcium utilization as reflected by upregulation of genes related to the calcium metabolism. Further studies are needed to elucidate the contribution of each of the ASI complex ingredients. PMID:29360830

Influence of Structure, Charge, and Concentration on the Pectin-Calcium-Surfactant Complexes.

PubMed

Joshi, Nidhi; Rawat, Kamla; Bohidar, H B

2016-05-12

Polymer-surfactant complex formation of pectin with different types of surfactants, cationic (cetyltrimethylammonium bromide, CTAB and dodecyl trimethylammonium bromide, DTAB), anionic (sodium dodecyl sulfate, SDS), and neutral (Triton X-100, TX-100), was investigated at room temperature in the presence and absence of cross-linker calcium chloride using light scattering, zeta potential, rheology, and UV-vis spectroscopic measurements where the surfactant concentration was maintained below their critical micellar concentration (CMC). Results indicated that the interaction of cationic surfactant with pectin in the presence and absence of calcium chloride was much stronger compared to anionic and neutral surfactants. The neutral surfactant showed identifiable interaction despite the absence of any charged headgroup, while anionic surfactant showed feeble or very weak interaction with the polymer. The pectin-CTAB or DTAB complex formation was attributed to associative electrostatic and hydrophobic interactions. On comparison between the cationic surfactants, it was found that CTAB interacts strongly with pectin because of its long hydrocarbon chain. The morphology of complexes formed exhibited random coil structures while at higher concentration of surfactant, rod-like or extended random coil structures were noticed. Thus, functional characteristics of the complex could be tuned by varying the type of surfactant (charge and structure) and its concentration. The differential network rigidity (pectin-CTAB versus pectin-DTAB gels) obtained from rheology measurements showed that addition of a very small amount of surfactant (concentration ≪ CMC) was required for enhancing network strength, while the presence of a large amount of surfactant resulted in the formation of fragile gels. No gel formation occurred when the surfactant concentration was close to their CMC values. Considering the importance of pectin in food and pharmaceutical industry, this study is relevant.

KINETICS OF THE DISSOLUTION OF URANIUM DIOXIDE IN CARBONATE-BICARBONATE SOLUTIONS

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

Schortmann, W.E.; DeSesa, M.A.

The kinetics of the dissolution of uranium dioxide in sodium carbonate- sodium bicarbonate solutions were determined. The study was undertaken in order to obtain fundamental information about the commercial carbonate process for leaching uranium from its ores. A rate equation incorporating the effects of surface area oxygen partial pressure, temperature, and reagent concentrations was empirically developed. A mechanism consisting essentially of two consecutive reactions at steady state is proposed. These reactions are the oxidation of U/ sup 4+/ to U/sup 6+/ and the subsequent formation of the uranyl dicarbonate complexion. Depending on the conditions, either or both of these reactionsmore » can determine the over-all rate. The conversion of uranyl dicarbonate to the uranyl tricarbonate complexion is postulated to be very rapid. In the suggested mechanism, the rate-determining phase of the oxidation is the dissociation of adsorbed molecular oxygen. and both the carbonate and bicarbonate ions play equivalent roles in the formation of the uranyl dicarbonate. As indicated by their high activation energies of about 13 and 14 kcal per mole uranium, both reactions are chemical rather than diffusional processes. A mathematical examination of the proposed mechanism produced a rate equation consistent with the experimental information. The credibility of the mechanism was thereby strengthened. (auth)« less

Influence of calcium carbonate on extraction yield and quality of extra virgin oil from olive (Olea europaea L. cv. Coratina).

PubMed

Squeo, G; Silletti, R; Summo, C; Paradiso, V M; Pasqualone, A; Caponio, F

2016-10-15

The aim of the research was to evaluate the effect of calcium carbonate (1%, 2%, and 4% of addition) at two different particle sizes (2.7μm and 5.7μm), added at the beginning of the malaxation phase, on both the extraction yield and the quality of oil obtained from Coratina olives at different ripening index. The results showed that calcium carbonate significantly increased the extraction yield of olive oil, more than affecting chemical indices. In particular, for less ripened olives, 1-2% of larger particle size calcium carbonate addiction determined a significant increase of the extraction effectiveness, ranging from 4.0 to 4.9%, while more ripened olives required higher amounts of coadjuvant (2-4% when using the larger particle size and 4% when using the smaller one), with a significant increase of the extraction yield up to 5%. Moreover, an increase of pungent perception was observed in some cases when adding calcium carbonate to more ripened olives. Copyright © 2016 Elsevier Ltd. All rights reserved.

The determination of calcium in phosphate, carbonate, and silicate rocks by flame photometer

USGS Publications Warehouse

Kramer, Henry

1956-01-01

A method has been developed for the determination of calcium in phosphate, carbonate, and silicate rocks using the Beckman flame photometer, with photomultiplier attachement. The sample is dissolved in hydrofluoric, nitric, and perchloric acids, the hydrofluoric and nitric acids are expelled, a radiation buffer consisting of aluminum, magnesium, iron, sodium, potassium, phosphoric acid, and nitric acid is added, and the solution is atomized in an oxy-hydrogen flame with an instrument setting of 554 mµ. Measurements are made by comparison against calcium standards, prepared in the same manner, in the 0 to 50 ppm range. The suppression of calcium emission by aluminum and phosphate was overcome by the addition of a large excess of magnesium. This addition almost completely restores the standard curve obtained from a solution of calcium nitrate. Interference was noted when the iron concentration in the aspirated solution (including the iron from the buffer) exceeded 100 ppm iron. Other common rock-forming elements did not interfere. The results obtained by this procedure are within ± 2 percent of the calcium oxide values obtained by other methods in the range 1 to 95 percent calcium oxide. In the 0 to 1 percent calcium oxide range the method compares favorably with standard methods.

Comparison of efficacy of an arginine-calcium carbonate-MFP toothpaste to a calcium carbonate-MFP toothpaste in controlling supragingival calculus formation and gingivitis: a 6-month clinical study.

PubMed

Li, Yiming; Lee, Sean; Stephens, Joni; Mateo, Luis R; Zhang, Yun Po; DeVizio, William

2012-02-01

To investigate whether the long-term use (6 months) of an arginine-calcium carbonate-MFP toothpaste would affect calculus formation and/or gingivitis when compared to a calcium carbonate-MFP toothpaste. This was a double-blind clinical study. Eligible adult subjects (120) entered a 2-month pre-test phase of the study. After receiving an evaluation of oral tissue and a dental prophylaxis, the subjects were provided with a regular fluoride toothpaste, a soft-bristled adult toothbrush with instructions to brush their teeth for 1-minute twice daily (morning and evening) for 2 months. The subjects were then examined for baseline calculus using the Volpe-Manhold Calculus Index (VMI) and gingivitis using the Löe-Silness Gingival Index (GI), along with an oral tissue examination. Qualifying subjects were randomized to two treatment groups: (1) Colgate Sensitive Pro-Relief toothpaste containing 8.0% arginine, 1450 ppm MFP and calcium carbonate (Test group), or (2) Colgate Cavity Protection toothpaste containing 1450 ppm MFP and calcium carbonate (Control group). Subjects were stratified by the VMI score and gender. After a dental prophylaxis (VMI=0), the subjects entered a 6-month test phase. Each received the assigned toothpaste and a soft-bristled adult toothbrush for home use with instructions of brushing teeth for 1 minute twice daily (morning and evening). The examinations of VMI, Löe-Silness GI and oral tissues were conducted after 3 and 6 months. Prior to each study visit, subjects refrained from brushing their teeth as well as eating and drinking for 4 hours. 99 subjects complied with the study protocol and completed the 6-month test phase. No within-treatment comparison was performed for the VMI because it was brought down to zero after the prophylaxis at the baseline of the test phase. For the Löe-Silness GI, subjects of the Test group exhibited a significant difference from baseline at the 3- and 6-month examinations. The 3-month Löe-Silness GI of the Control

Cyanex based uranyl sensitive polymeric membrane electrodes.

PubMed

Badr, Ibrahim H A; Zidan, W I; Akl, Z F

2014-01-01

Novel uranyl selective polymeric membrane electrodes were prepared using three different low-cost and commercially available Cyanex extractants namely, bis(2,4,4-trimethylpentyl) phosphinic acid [L1], bis(2,4,4-trimethylpentyl) monothiophosphinic acid [L2] and bis(2,4,4-trimethylpentyl) dithiophosphinic acid [L3]. Optimization and performance characteristics of the developed Cyanex based polymer membrane electrodes were determined. The influence of membrane composition (e.g., amount and type of ionic sites, as well as type of plasticizer) on potentiometric responses of the prepared membrane electrodes was studied. Optimized Cyanex-based membrane electrodes exhibited Nernstian responses for UO₂(2+) ion over wide concentration ranges with fast response times. The optimized membrane electrodes based on L1, L2 and L3 exhibited Nernstian responses towards uranyl ion with slopes of 29.4, 28.0 and 29.3 mV decade(-1), respectively. The optimized membrane electrodes based on L1-L3 showed detection limits of 8.3 × 10(-5), 3.0 × 10(-5) and 3.3 × 10(-6) mol L(-1), respectively. The selectivity studies showed that the optimized membrane electrodes exhibited high selectivity towards UO₂(2+) ion over large number of other cations. Membrane electrodes based on L3 exhibited superior potentiometric response characteristics compared to those based on L1 and L2 (e.g., widest linear range and lowest detection limit). The analytical utility of uranyl membrane electrodes formulated with Cyanex extractant L3 was demonstrated by the analysis of uranyl ion in different real samples for nuclear safeguards verification purposes. The results obtained using direct potentiometry and flow-injection methods were compared with those measured using the standard UV-visible and inductively coupled plasma spectroscopic methods. © 2013 Published by Elsevier B.V.

Effect of silk sericin on morphology and structure of calcium carbonate crystal

NASA Astrophysics Data System (ADS)

Zhao, Rui-Bo; Han, Hua-Feng; Ding, Shao; Li, Ze-Hao; Kong, Xiang-Dong

2013-06-01

In this paper, silk sericin was employed to regulate the mineralization of calcium carbonate (CaCO3). CaCO3 composite particles were prepared by the precipitation reaction of sodium carbonate with calcium chloride solution in the presence of silk sericin. The as-prepared samples were collected at different reaction time to study the crystallization process of CaCO3 by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The results showed that silk sericin significantly affected the morphology and crystallographic polymorph of CaCO3. With increasing the reaction time, the crystal phase of CaCO3 transferred from calcite dominated to vaterite dominated mixtures, while the morphology of CaCO3 changed from disk-like calcite crystal to spherical vaterite crystal. These studies showed the potential of silk sericin used as a template molecule to control the growth of inorganic crystal.

Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite–selenates

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

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Kovrugin, Vadim M.; Tyumentseva, Olga S.

2015-09-15

Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (I), [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O)] (II), [C{sub 4}H{sub 15}N{sub 3}][H{sub 3}O]{sub 0.5}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 2.93}(SeO{sub 3}){sub 0.07}(H{sub 2}O)](NO{sub 3}){sub 0.5} (III), [C{sub 2}H{sub 8}N]{sub 3}[H{sub 5}O{sub 2}][(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub 2}(H{sub 2}O){sub 5} (IV), [C{sub 2}H{sub 8}N]{sub 2}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 4}(HSeO{sub 3})(H{sub 2}O)](H{sub 2}SeO{sub 3}){sub 0.2} (V), [C{sub 4}H{sub 12}N]{sub 3}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 5}(H{sub 2}O)] (VI), and [C{sub 2}H{sub 8}N]{sub 3}(C{sub 2}H{sub 7}N)[(UO{sub 2}){sub 3}(SeO{sub 4}){submore » 4}(HSeO{sub 3})(H{sub 2}O)] (VII) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite–selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U–O{sub br}–Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers. - Graphical abstract: Crystal structures of the seven novel Se-contaning uranyl oxysalts that contain protonated organic molecules as interlayer species have been investigated from the viewpoints of topology of interpolyhedral linkages, isomeric variations and flexibility of structural units. - Highlights: • Single crystals of seven novel uranyl oxysalts were prepared by evaporation method. • The graph theory

Novel morphology of calcium carbonate controlled by poly(L-lysine).

PubMed

Yao, Yuan; Dong, Wenyong; Zhu, Shenmin; Yu, Xinhai; Yan, Deyue

2009-11-17

The novel calcium carbonate (CaCO(3)) morphology, twin-sphere with an equatorial girdle, has been obtained under the control of poly(L-lysine) (PLys) through gas-diffusion method. The effect of the concentration of calcium cation and PLys, the reaction time, and the initial pH value are investigated, and various interesting morphologies, including twin-sphere, discus-like, hexagonal plate, and hallow structure are observed by using scanning electronic microscopy. Laser microscopic Raman spectroscopy studies indicated that all these CaCO(3) are vaterite. A possible mechanism is suggested to explain the formation of the twin-sphere based morphologies according to the results. It is proven that alkaline polypeptides can control the mineralization of CaCO(3) precisely as the reported acidic polypeptides and double hydrophilic block copolymers.

Effects of a low-radiotoxicity uranium salt (uranyl acetate) on biochemical and hematological parameters of the catfish, Clarias gariepinus

NASA Astrophysics Data System (ADS)

Al-Ghanim, Khalid A.; Ahmad, Zubair; Al-Kahem Al-Balawi, Hmoud F.; Al-Misned, Fahad; Maboob, Shahid; Suliman, El-Amin M.

2016-01-01

Specimens of Clarias gariepinus were treated with lethal (70, 75, 80, 85, 90, and 95 mg/L) and sub-lethal concentrations (8, 12 and 16 mg/L) of uranyl acetate, a low-radiotoxicity uranium salt. The LC 50 value was registered as 81.45 mg/L. The protein and glycogen concentrations in liver and muscles were decreased in the fish exposed to sub-lethal concentrations. The red blood cell (RBC) and white blood cell (WBC) counts, haemoglobin (Hb) concentration and haematocrit (Hct) values were decreased. Different blood indices like mean corpuscular volume (MCV), mean corpuscular haemoglobin (MCH) and mean corpuscular haemoglobin concentration (MCHC) were negatively affected. Level of plasma glucose was elevated whereas protein was decreased. The level of calcium concentration (Ca) was declined in the blood of exposed fish whereas magnesium (Mg) remains unchanged. The activity level of glutamic-oxaloacetic transaminase (GOT) and glutamic-pyruvic transaminase (GPT) was elevated in exposed fish. These effects were more pronounced in the last period of exposure and in higher concentrations. Results of the present study indicate that uranyl acetate has adverse effects on Clarias gariepinus and causes changes in the biochemical and hematological parameters of the fish.

Structure and Reactivity of X-ray Amorphous Uranyl Peroxide, U 2O 7

DOE PAGES

Odoh, Samuel O.; Shamblin, Jacob; Colla, Christopher A.; ...

2016-03-14

Recent accidents resulting in worker injury and radioactive contamination occurred due to pressurization of uranium yellowcake drums produced in the western USA. The drums contained an unexpected X-ray amorphous reactive form of uranium oxide, U 2O7. Heating hydrated uranyl peroxides produced during in situ mining unintentionally produced U 2O 7. It is a hygroscopic anhydrous uranyl peroxide that reacts rapidly with water to release O 2 gas and form metaschoepite, a uranyl-oxide hydrate. Quantum chemical calculations indicate that the most stable U 2O 7 conformer consists of two bent (UO 2) 2+ uranyl ions bridged by a peroxide group bidentatemore » and parallel to each uranyl ion, and a μ2-O atom, resulting in charge neutrality. A pair distribution function from neutron total scattering supports this structural model. The reactivity of U 2O 7 in water and with water in air is much higher than other uranium oxides, and this can be both hazardous and potentially advantageous in the nuclear fuel cycle.« less

Were kinetics of Archean calcium carbonate precipitation related to oxygen concentration?

NASA Technical Reports Server (NTRS)

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

1996-01-01

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

Selective Aliphatic Carbon-Carbon Bond Activation by Rhodium Porphyrin Complexes.

PubMed

To, Ching Tat; Chan, Kin Shing

2017-07-18

The carbon-carbon bond activation of organic molecules with transition metal complexes is an attractive transformation. These reactions form transition metal-carbon bonded intermediates, which contribute to fundamental understanding in organometallic chemistry. Alternatively, the metal-carbon bond in these intermediates can be further functionalized to construct new carbon-(hetero)atom bonds. This methodology promotes the concept that the carbon-carbon bond acts as a functional group, although carbon-carbon bonds are kinetically inert. In the past few decades, numerous efforts have been made to overcome the chemo-, regio- and, more recently, stereoselectivity obstacles. The synthetic usefulness of the selective carbon-carbon bond activation has been significantly expanded and is becoming increasingly practical: this technique covers a wide range of substrate scopes and transition metals. In the past 16 years, our laboratory has shown that rhodium porphyrin complexes effectively mediate the intermolecular stoichiometric and catalytic activation of both strained and nonstrained aliphatic carbon-carbon bonds. Rhodium(II) porphyrin metalloradicals readily activate the aliphatic carbon(sp 3 )-carbon(sp 3 ) bond in TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl) and its derivatives, nitriles, nonenolizable ketones, esters, and amides to produce rhodium(III) porphyrin alkyls. Recently, the cleavage of carbon-carbon σ-bonds in unfunctionalized and noncoordinating hydrocarbons with rhodium(II) porphyrin metalloradicals has been developed. The absence of carbon-hydrogen bond activation in these systems makes the reaction unique. Furthermore, rhodium(III) porphyrin hydroxide complexes can be generated in situ to selectively activate the carbon(α)-carbon(β) bond in ethers and the carbon(CO)-carbon(α) bond in ketones under mild conditions. The addition of PPh 3 promotes the reaction rate and yield of the carbon-carbon bond activation product. Thus, both rhodium

Characterization of bacteria isolated from palaeoproterozoic metasediments for sequestration of carbon dioxide and formation of calcium carbonate.

PubMed

Srivastava, Shaili; Bharti, Randhir K; Thakur, Indu Shekhar

2015-01-01

Bacterial community of palaeoproterozoic metasediments was enriched in the chemostat in the presence of different concentrations of NaHCO3. Six bacterial isolates were isolated from the chemostat on nutrient agar plates on the basis of distinct morphology. Denaturing gradient gel electrophoresis (DGGE) proved the presence of six operational taxonomic units (OTUs) at 50 and 100 mM NaHCO3. The OTU was reduced to three and one at enrichment concentration of 150 and 200 mM NaHCO3 respectively. These six isolates were tested for sequestration of carbon dioxide by (14)C metabolic labeling of NaH(14)CO3. Among the six isolates, one of the bacterium showed better potency to fix radiolabeled NaH(14)CO3. The isolate (ISTD04) was identified as Serratia sp. by 16S ribosomal RNA (16S rRNA) sequence analysis and was found to be same as the DGGE OTU sequence at 200-mM NaHCO3 concentration. The bacterium was tested for product formation in form of calcite crystals in presence of 5 % CO2. Scanning electron microscopy (SEM) of product formed by the bacterium revealed defined faceted rhombohedral structure which resembled calcite and vaterite phases of the crystal. Formation of calcium carbonate crystals was further confirmed by Fourier transform infrared (FTIR) spectroscopy as carbonate group showing strong vibration at 1,456 cm(-1). Major calcite phase diffraction peaks were determined by X-ray diffraction (XRD) analysis, and energy-dispersive X-ray (EDX) analysis showed the presence of CaO (72 %) and carbon (18 %). Bacterium use bicarbonate as carbon source for their growth as well as by-product formation in form of calcite shows carbon circulation and storage.

Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

PubMed

Armstrong, Christopher R; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E; Burns, Peter C; Navrotsky, Alexandra

2012-02-07

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.

Uranyl peroxide enhanced nuclear fuel corrosion in seawater

PubMed Central

Armstrong, Christopher R.; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E.; Burns, Peter C.; Navrotsky, Alexandra

2012-01-01

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances. PMID:22308442

Phosphine/Sulfoxide-Supported Carbon(0) Complex.

PubMed

Lozano González, Mariana; Bousquet, Laura; Hameury, Sophie; Alvarez Toledano, Cecilio; Saffon-Merceron, Nathalie; Branchadell, Vicenç; Maerten, Eddy; Baceiredo, Antoine

2018-02-21

A new carbon(0) complex 2 with two different L ligands, a phosphine and a sulfoxide, was synthesized and fully characterized. This new type of carbone exhibits excellent coordination ability, in contrast to the related phosphine/sulfide-supported carbon(0) complexes. Several organometallic complexes were isolated and, of special interest, the ν av (CO) value of Rh I -dicarbonyl complex indicates that 2 has a donor capability superior to classical NHCs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical immobilization of Pb, Cu, and Cd by phosphate materials and calcium carbonate in contaminated soils.

PubMed

Huang, Guoyong; Su, Xiaojuan; Rizwan, Muhammad Shahid; Zhu, Yifei; Hu, Hongqing

2016-08-01

Soil contamination with toxic metals has increasingly become a global concern over the past few decades. Phosphate and carbonate compounds are good passivation materials for Pb immobilization, while the effect of phosphate and carbonate on the immobilization of multiple heavy metals (Pb, Cu, and Cd) in contaminated soils was seldom investigated. In this study, bone meal (BM), phosphate rock (PR), oxalic acid-activated phosphate rock (APR), super phosphate (SP), and calcium carbonate (CC) were added to the contaminated soils to evaluate the effect of phosphate materials and calcium carbonate on the immobilization of Pb, Cu, and Cd. The results showed that the pH of the treated soils increased 1.3-2.7, except SP which decreased 0.5 at most. Compared to the control treatment, all phosphates and calcium carbonate added to the polluted soils increased the fraction of residual metals, and the application of APR, PR, BM, and CC significantly reduced exchangeable and carbonate-bound fraction metals. PR and APR were the most effective for the immobilization of Pb, Cu, and Cd in the soils among these materials. Moreover, the concentrations of all metals in the toxicity characteristic leaching procedure (TCLP) leachate decreased with increasing amounts of amendments, and the concentrations of Pb in the TCLP leachate for soils treated with PR and APR were below the nonhazardous regulatory limit of 5 mg L(-1) (US Environmental Protection Agency). Based on our results, phosphate rock and oxalic acid-activated phosphate rock are effective in the immobilization of multiple metals by reducing their mobility in the co-contaminated soils.

Biopharmaceutical characterisation of ciprofloxacin-metallic ion interactions: comparative study into the effect of aluminium, calcium, zinc and iron on drug solubility and dissolution.

PubMed

Stojković, Aleksandra; Tajber, Lidia; Paluch, Krzysztof J; Djurić, Zorica; Parojčić, Jelena; Corrigan, Owen I

2014-03-01

Ciprofloxacin bioavailability may be reduced when ciprofloxacin is co-administered with metallic ion containing preparations. In our previous study, physicochemical interaction between ciprofloxacin and ferrous sulphate was successfully simulated in vitro. In the present work, comparative in vitro ciprofloxacin solubility and dissolution studies were performed in the reactive media containing aluminium hydroxide, calcium carbonate or zinc sulphate. Solid phases collected from the dissolution vessel with aluminium hydroxide, calcium carbonate and zinc sulphate were investigated for their properties. The results obtained indicate that different types of adducts may form and retard ciprofloxacin solubility and dissolution. In the case of aluminium, no phase changes were observed. The solid phase generated in the presence of calcium carbonate was identified as hydrated ciprofloxacin base. Similarly to iron, a new complex consistent with Zn(SO4)2(Cl)2(ciprofloxacin)2 × nH2O stoichiometry was generated in the presence of relatively high concentrations of ciprofloxacin hydrochloride and zinc sulphate, indicating that small volume dissolution experiments can be useful for biorelevant dissolution tests.

Construction of two ureolytic model organisms for the study of microbially induced calcium carbonate precipitation.

PubMed

Connolly, James; Kaufman, Megan; Rothman, Adam; Gupta, Rashmi; Redden, George; Schuster, Martin; Colwell, Frederick; Gerlach, Robin

2013-09-01

Two bacterial strains, Pseudomonas aeruginosa MJK1 and Escherichia coli MJK2, were constructed that both express green fluorescent protein (GFP) and carry out ureolysis. These two novel model organisms are useful for studying bacterial carbonate mineral precipitation processes and specifically ureolysis-driven microbially induced calcium carbonate precipitation (MICP). The strains were constructed by adding plasmid-borne urease genes (ureABC, ureD and ureFG) to the strains P. aeruginosa AH298 and E. coli AF504gfp, both of which already carried unstable GFP derivatives. The ureolytic activities of the two new strains were compared to the common, non-GFP expressing, model organism Sporosarcina pasteurii in planktonic culture under standard laboratory growth conditions. It was found that the engineered strains exhibited a lower ureolysis rate per cell but were able to grow faster and to a higher population density under the conditions of this study. Both engineered strains were successfully grown as biofilms in capillary flow cell reactors and ureolysis-induced calcium carbonate mineral precipitation was observed microscopically. The undisturbed spatiotemporal distribution of biomass and calcium carbonate minerals were successfully resolved in 3D using confocal laser scanning microscopy. Observations of this nature were not possible previously because no obligate urease producer that expresses GFP had been available. Future observations using these organisms will allow researchers to further improve engineered application of MICP as well as study natural mineralization processes in model systems. © 2013.

Bacillus megaterium mediated mineralization of calcium carbonate as biogenic surface treatment of green building materials.

PubMed

Dhami, Navdeep Kaur; Reddy, M Sudhakara; Mukherjee, Abhijit

2013-12-01

Microbially induced calcium carbonate precipitation is a biomineralization process that has various applications in remediation and restoration of range of building materials. In the present study, calcifying bacteria, Bacillus megaterium SS3 isolated from calcareous soil was applied as biosealant to enhance the durability of low energy, green building materials (soil-cement blocks). This bacterial isolate produced high amounts of urease, carbonic anhydrase, extra polymeric substances and biofilm. The calcium carbonate polymorphs produced by B. megaterium SS3 were analyzed by scanning electron microscopy, confocal laser scanning microscopy, X-ray diffraction and Fourier transmission infra red spectroscopy. These results suggested that calcite is the most predominant carbonate formed by this bacteria followed by vaterite. Application of B. megaterium SS3 as biogenic surface treatment led to 40 % decrease in water absorption, 31 % decrease in porosity and 18 % increase in compressive strength of low energy building materials. From the present investigation, it is clear that surface treatment of building materials by B. megaterium SS3 is very effective and eco friendly way of biodeposition of coherent carbonates that enhances the durability of building materials.

Nanosized amorphous calcium carbonate stabilized by poly(ethylene oxide)-b-poly(acrylic acid) block copolymers.

PubMed

Guillemet, Baptiste; Faatz, Michael; Gröhn, Franziska; Wegner, Gerhard; Gnanou, Yves

2006-02-14

Particles of amorphous calcium carbonate (ACC), formed in situ from calcium chloride by the slow release of carbon dioxide by alkaline hydrolysis of dimethyl carbonate in water, are stabilized against coalescence in the presence of very small amounts of double hydrophilic block copolymers (DHBCs) composed of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blocks. Under optimized conditions, spherical particles of ACC with diameters less than 100 nm and narrow size distribution are obtained at a concentration of only 3 ppm of PEO-b-PAA as additive. Equivalent triblock or star DHBCs are compared to diblock copolymers. The results are interpreted assuming an interaction of the PAA blocks with the surface of the liquid droplets of the concentrated CaCO3 phase, formed by phase separation from the initially homogeneous reaction mixture. The adsorption layer of the block copolymer protects the liquid precursor of ACC from coalescence and/or coagulation.

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

PubMed

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

2006-08-15

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

Synthesis of size-controlled acid-resistant hybrid calcium carbonate microparticles as templates for fabricating "micelles-enhanced" polyelectrolyte capsules by the LBL technique.

PubMed

Li, Xiaodong; Hu, Qiaoling; Yue, Linhai; Shen, Jiacong

2006-07-24

Size-controlled, low-dispersed calcium carbonate microparticles were synthesized in the presence of the amphiphilic block copolymer polystyrene-b-poly(acrylic acid) (PS-b-PAA) by modulating the concentration of block copolymer in the reactive system. This type of hybrid microparticles have acid-resistant properties. By investigating the aggregation behaviors of PS-b-PAA micelles by transmission electron microscopy (TEM), the mechanism of hybrid calcium carbonate formation illustrated that the block copolymer served not only as "pseudonuclei" for the growth of calcium carbonate nanocrystals, but also forms the supramicelle congeries, a spherical framework, as templates for calcium carbonate nanocrystal growth into hybrid CaCO(3) particles. Moreover, this pilot study shows that the hybrid microparticle is a novel candidate as a template for fabricating multilayer polyelectrolyte capsules, in which the block copolymer is retained within the capsule interior after core removal under soft conditions. This not only facilitates the encapsulation of special materials, but also provides "micelles-enhanced" polyelectrolyte capsules.

Altered steady state pharmacokinetics of levofloxacin in adult cystic fibrosis patients receiving calcium carbonate.

PubMed

Pai, Manjunath P; Allen, Sarah E; Amsden, Guy W

2006-08-01

Levofloxacin is used in adult patients with cystic fibrosis but its pharmacokinetics is not well characterized in this population. Patients with cystic fibrosis use calcium routinely to prevent osteoporosis. A slower intestinal transit time is common in cystic fibrosis implying that the standard 2-h spacing of minerals and levofloxacin to prevent a chelation interaction may be insufficient. The objectives of this study were to characterize the steady state pharmacokinetics of oral levofloxacin 750 mg with and without 2-h spaced calcium carbonate in patients with cystic fibrosis compared to matched healthy volunteers. In an open-label, randomized, cross-over study of five patients with cystic fibrosis and five age, sex, race, and serum creatinine matched healthy volunteers received 750 mg of oral levofloxacin alone daily for 5 days and the same dose of levofloxacin with 2-h spaced calcium carbonate supplementation 500 mg po thrice daily with meals in random sequence. Blood was collected for plasma assay of levofloxacin pre-dose, 0.5, 1, 1.5, 2, 4, 8, 12, and 24h after the fifth levofloxacin dose. There was no significant interaction in healthy volunteers, however, when cystic fibrosis patients were given levofloxacin with 2-h spaced calcium, the maximum plasma concentration (Cmax) decreased by 19% and time to Cmax increased by 37% (p<0.05). This difference in peak concentrations resulted in a lack of bioequivalence (Cmax geometric mean ratio 81.6%, 90% confidence intervals: 71.8%, 91.4%) even when levofloxacin and calcium supplements were spaced by the standard 2h administration instruction in patients with cystic fibrosis. These results indicate that multivalent cations such as calcium should be maximally separated from oral levofloxacin administration in adult patients with cystic fibrosis to prevent this drug interaction, thereby better optimizing antibiotic efficacy and decreasing the potential for resistance development.

Biogenic Fish-gut Calcium Carbonate is a Stable Amorphous Phase in the Gilt-head Seabream, Sparus aurata

PubMed Central

Foran, Elizabeth; Weiner, Steve; Fine, Maoz

2013-01-01

The main source of calcium carbonate (CaCO3) in the ocean comes from the shells of calcifying planktonic organisms, but substantial amounts of CaCO3 are also produced in fish intestines. The precipitation of CaCO3 assists fish in intestinal water absorption and aids in whole body Ca2+ homeostasis. Here we report that the product formed in the intestinal lumen of the gilt-head seabream, Sparus aurata, is an amorphous calcium carbonate (ACC) phase. With FTIR spectroscopy and SEM imaging, our study shows that the fish-derived carbonates from S. aurata are maintained as a stable amorphous phase throughout the intestinal tract. Moreover, intestinal deposits contained up to 54 mol% Mg2+, the highest concentration yet reported in biogenic ACC. Mg is most likely responsible for stabilizing this inherently unstable mineral. The fish carbonates also displayed initial rapid dissolution when exposed to seawater, exhibiting a significant increase in carbonate concentration. PMID:23609008

Aqueous solubility of calcium L-lactate, calcium D-gluconate, and calcium D-lactobionate: importance of complex formation for solubility increase by hydroxycarboxylate mixtures.

PubMed

Vavrusova, Martina; Munk, Merete Bøgelund; Skibsted, Leif H

2013-08-28

Among the calcium hydroxycarboxylates important for cheese quality, D-lactobionate [Ksp = (7.0 ± 0.3) × 10(-3) mol(3) L(-3)] and L-lactate [Ksp = (5.8 ± 0.2) × 10(-3) mol(3) L(-3)] were found more soluble than D-gluconate [Ksp = (7.1 ± 0.2) × 10(-4) mol(3) L(-3)], as indicated by the solubility products determined electrochemically for aqueous 1.0 M NaCl at 25.0 °C. Still, solubility of calcium L-lactate increases by 45% in the presence of 0.50 M sodium D-gluconate and by 37% in the presence of 0.50 M sodium D-lactobionate, while solubility of calcium D-gluconate increases by 66 and 85% in the presence of 0.50 M sodium L-lactate and 0.50 M sodium D-lactobionate, respectively, as determined by complexometric titration. Sodium L-lactate and sodium D-gluconate have only little influence on solubility of calcium D-lactobionate. The increased solubility is described quantitatively by calcium binding to D-gluconate (K1 = 14 ± 3 mol(-1) L) in 1.0 M NaCl at 25 °C, D-lactobionate (K1 = 11 ± 2 mol(-1) L), and L-lactate (K1 = 8 ± 2 mol(-1) L), as indicated by the association constants determined electrochemically. In mixed hydroxycarboxylate solutions, calcium binding is quantitatively described by the geometric mean of the individual association constants for both aqueous 1.0 and 0.20 M NaCl, indicating a 1:1 stoichiometry for complex formation.

Structure of hydrated calcium carbonates: A first-principles study

NASA Astrophysics Data System (ADS)

Demichelis, Raffaella; Raiteri, Paolo; Gale, Julian D.

2014-09-01

The structures of both ikaite (CaCO3 · 6H2 O) and monohydrocalcite (CaCO3 ·H2 O) were computed at the PBE0 level of theory, using all electron Gaussian type basis sets. Correction for the long-range dispersion contribution was included for the oxygen-oxygen interactions by using an additive pairwise term with the atomic coefficients fitted against the calcite vs aragonite enthalpy difference. The potential chirality of monohydrocalcite is discussed, as well as the helical motifs created by the three-fold rototranslational axes parallel to the [001] direction. These elements represent a significant link between monohydrocalcite and vaterite, both appearing as intermediate species during CaCO3 crystallization from amorphous calcium carbonate. The hydrogen bond pattern, never fully discussed for monohydrocalcite, is here described and compared to the available experimental data. Both phases are characterized by the presence of hydrogen bonds of moderate to high strength. Water molecules in monohydrocalcite interact quite strongly with 2 CO32- units through such hydrogen bonds, whereas their interaction with each other is minor. On the contrary, water molecules in ikaite create a complex network of hydrogen bonds, where each water molecule is strongly hydrogen bonded to one CO32- anion and to one or two other water molecules.

Crystallization and preliminary crystallographic analysis of calcium-binding protein-2 from Entamoeba histolytica and its complexes with strontium and the IQ1 motif of myosin V

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

Gourinath, S., E-mail: sgourinath@mail.jnu.ac.in; Padhan, Narendra; Alam, Neelima

2005-04-01

Calcium-binding protein-2 (EhCaBP2) crystals were grown using MPD as a precipitant. EhCaBP2 also crystallized in complex with strontium (replacing calcium) at similar conditions. Preliminary data for EhCaBP2 crystals in complex with an IQ motif are also reported. Calcium plays a pivotal role in the pathogenesis of amoebiasis, a major disease caused by Entamoeba histolytica. Two domains with four canonical EF-hand-containing calcium-binding proteins (CaBPs) have been identified from E. histolytica. Even though they have very high sequence similarity, these bind to different target proteins in a Ca{sup 2+}-dependent manner, leading to different functional pathways. Calcium-binding protein-2 (EhCaBP2) crystals were grown usingmore » MPD as a precipitant. The crystals belong to space group P2{sub 1}, with unit-cell parameters a = 111.74, b = 68.83, c = 113.25 Å, β = 116.7°. EhCaBP2 also crystallized in complex with strontium (replacing calcium) at similar conditions. The crystals belong to space group P2{sub 1}, with unit-cell parameters a = 69.18, b = 112.03, c = 93.42 Å, β = 92.8°. Preliminary data for EhCaBP2 crystals in complex with an IQ motif are also reported. This complex was crystallized with MPD and ethanol as precipitating agents. These crystals belong to space group P2{sub 1}, with unit-cell parameters a = 60.5, b = 69.86, c = 86.5 Å, β = 97.9°.« less

Biomediated Precipitation of Calcium Carbonate in a Slightly Acidic Hot Spring

NASA Astrophysics Data System (ADS)

Jiang, L.

2015-12-01

A slightly acidic hot spring named "Female Tower" (T=73.5 °C, pH=6.64) is located in the Jifei Geothermal Field, Yunnan Province, Southwest China. The precipitates in the hot spring are composed of large amounts of calcite, aragonite, and sulfur. Scanning electron microscopy (SEM) analyses revealed that the microbial mats were formed of various coccoid, rod-shaped, and filamentous microbes. Transmission electron microscopy (TEM) showed that the intracellular sulfur granules were commonly associated with these microbes. A culture-independent molecular phylogenetic analysis demonstrated that the majority of the bacteria in the spring were sulfur-oxidizing bacteria. In the spring water, H2S concentration was up to 60 ppm, while SO42- concentration was only about 10 ppm. We speculated that H2S might be utilized by sulfur-oxidizing bacteria in this hot spring water, leading to the intracellular formation of sulfur granules. In the meantime, this reaction increased the pH in the micron-scale microdomains, which fostered the precipitation of calcium carbonate in the microbial mats. The results of this study indicated that the sulfur-oxidizing bacteria could play an important role in calcium carbonate precipitation in slightly acidic hot spring environments.

Grain-Size Based Additivity Models for Scaling Multi-rate Uranyl Surface Complexation in Subsurface Sediments

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

Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.

The additivity model assumed that field-scale reaction properties in a sediment including surface area, reactive site concentration, and reaction rate can be predicted from field-scale grain-size distribution by linearly adding reaction properties estimated in laboratory for individual grain-size fractions. This study evaluated the additivity model in scaling mass transfer-limited, multi-rate uranyl (U(VI)) surface complexation reactions in a contaminated sediment. Experimental data of rate-limited U(VI) desorption in a stirred flow-cell reactor were used to estimate the statistical properties of the rate constants for individual grain-size fractions, which were then used to predict rate-limited U(VI) desorption in the composite sediment. The resultmore » indicated that the additivity model with respect to the rate of U(VI) desorption provided a good prediction of U(VI) desorption in the composite sediment. However, the rate constants were not directly scalable using the additivity model. An approximate additivity model for directly scaling rate constants was subsequently proposed and evaluated. The result found that the approximate model provided a good prediction of the experimental results within statistical uncertainty. This study also found that a gravel-size fraction (2 to 8 mm), which is often ignored in modeling U(VI) sorption and desorption, is statistically significant to the U(VI) desorption in the sediment.« less

Effects of temperature during the irradiation of calcium carbonate.

PubMed

Negrón-Mendoza, Alicia; Camargo-Raya, Claudia; Gómez-Vidales, Virginia; Uribe, Roberto M; Ramos-Bernal, Sergio

2016-05-01

Calcium carbonate received gamma irradiation at different doses (0-309kGy) and temperature regimes (77-298K) to study the effects of irradiation temperature. The changes were followed by EPR spectroscopy. We observed the formation of a composite EPR spectrum, even at low radiation doses and temperature. There was a strong effect on the evaluation of the radicals formed as a function of irradiation temperature, probably due to the diffusion in the frozen powder and the recombination of some radicals at room temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.

Drivers of Water Column Calcium Carbonate Fluxes and Dissolution in the Gulf of Maine: Impacts on the Carbon Cycle

NASA Astrophysics Data System (ADS)

Pilskaln, C. H.; Wang, A. Z.; Lawson, G. L.; Hayashi, K.; Salisbury, J.

2016-02-01

Recent studies indicate that the U.S. Northeast coastal region, particularly the Gulf of Maine (GoME), may be more susceptible to ocean acidification (OA) than previously thought due to the low buffer capacity, low pH, and low calcium carbonate saturation measured in the region. In particular, sub-surface waters of the GoME already experience under-saturation with respect to aragonite in spring and summer and recent data suggest that water-column aragonite dissolution may occur throughout the year, even when aragonite is slightly over-saturated. This dissolution process appears associated with organic carbon remineralization in the extensive benthic nepheloid layers and may thus represent a major control over the calcium carbonate (CaCO3) budget of deep, near-bottom waters of the GoME. These findings are surprising for shallow, non-upwelling shelf systems and have important implications for the CaCO3 cycle, shell-building organisms, and the GoME planktonic ecosystem. Additionally, freshening of the GoME over the past several decades due to an increase in low-salinity water input originating in the Labrador Sea may further decrease seawater pH and aragonite saturation in the gulf. We present a variety of biogeochemical data that suggest linkages between potential water column CaCO3 dissolution and their impacts on the GoME carbon cycle.

Onsite defluoridation system for drinking water treatment using calcium carbonate.

PubMed

Wong, Elaine Y; Stenstrom, Michael K

2018-06-15

Fluoride in drinking water has several effects on teeth and bones. At concentrations of 1-1.5 mg/L, fluoride can strengthen enamel, improving dental health, but at concentrations above 1.5 to 4 mg/L can cause dental fluorosis. At concentrations of 4-10 mg/L, skeletal fluorosis can occur. There are many areas of the world that have excessive fluoride in drinking water, such as China, India, Sri Lanka, and the Rift Valley countries in Africa. Treatment solutions are needed, especially in poor areas where drinking water treatment plants are not available. On-site or individual treatment alternatives can be attractive if constructed from common materials and if simple enough to be constructed and maintained by users. Advanced on-site methods, such as under sink reserve osmosis units, can remove fluoride but are too expensive for developing areas. This paper investigates calcium carbonate as a cost effective sorbent for an onsite defluoridation drinking water system. Batch and column experiments were performed to characterize F - removal properties. Fluoride sorption was described by a Freundlich isotherm model, and it was found that the equilibrium time was approximately 3 h. Calcium carbonate was found to have comparable F - removal abilities as the commercial ion exchange resins and possessed higher removal effectiveness compared to calcium containing eggshells and seashells. It was also found that the anion Cl- did not compete with F - at typical drinking water concentrations, having little impact on the effectiveness of the treatment system. A fluoride removal system is proposed that can be used at home and can be maintained by users. Through this work, we can be a step closer to bringing safe drinking water to those that do not have access to it. Copyright © 2017 Elsevier Ltd. All rights reserved.

Calcium carbonate in human gallstones and total CO2 in bile.

PubMed Central

Sutor, D J; Wilkie, L I

1978-01-01

Measurement of total CO2 concentrations in bile from patients undergoing cholecystectomy because of gallstones has shown that the presence of calcium carbonate in the stones can be associated with a raised total CO2 concentration in the common duct bile. In bile from functioning and poorly-functioning gallbladders, total CO2 was nearly always related to pH irrespective of stone composition. PMID:631643

Adsorption of arsenic by activated carbon, calcium alginate and their composite beads.

PubMed

Hassan, A F; Abdel-Mohsen, A M; Elhadidy, H

2014-07-01

The present investigation deals with preparation of three different adsorbent materials namely; potassium hydroxide activated carbon based apricot stone (C), calcium alginate beads (G) and calcium alginate/activated carbon composite beads (GC) were used for the removal of arsenic. The prepared adsorbent materials were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), N2-adsorption at -196°C and point of zero charge. From the obtained results, it was found that the porosity, surface area and total pore volume of the adsorbent material C>GC>G respectively, however, the G adsorbent has more acidic function group than the other adsorbents. The influence of pH, time, temperature and initial concentration of arsenic(V) were studied and optimized. GC exhibits the maximum As(V) adsorption (66.7mg/g at 30°C). The adsorption of arsenic ions was observed to follow pseudo-second order mechanism as well as the thermodynamic parameters confirm also the endothermic spontaneous and a physisorption process. Copyright © 2014 Elsevier B.V. All rights reserved.

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.

2003-01-01

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U

A rare case of Mirizzi syndrome due to pure calcium carbonate stones (Limy Bile).

PubMed

Gilani, Nooman; Hanif, Muhammad Farooq; Karasek, Veronika

2016-06-01

We report the first case of Mirizzi syndrome in a patient who presented with biliary obstruction caused by pure calcium carbonate stones. A 61 years old male with history of portal vein thrombosis presented with rash, nausea and jaundice. An ultrasound of biliary tree showed gallstones with dilatation of hepatic duct and intrahepatic biliary tree. There was suspicion of a stone in proximal CBD. CT scan showed an opaque gallbladder with dense radio-opaque material in its lumen. An ERCP was then performed revealing external common hepatic duct obstruction at the neck of the gallbladder. A plastic biliary stent was placed across the obstruction, followed by a cholecystectomy. Resected gallbladder specimen revealed thick whitish paste like material, and formed stones filling the gallbladder lumen. Laboratory testing showed this material to be composed of 100% calcium carbonate crystals.

Calcium Signaling in Taste Cells

PubMed Central

Medler, Kathryn F.

2014-01-01

The sense of taste is a common ability shared by all organisms and is used to detect nutrients as well as potentially harmful compounds. Thus taste is critical to survival. Despite its importance, surprisingly little is known about the mechanisms generating and regulating responses to taste stimuli. All taste responses depend on calcium signals to generate appropriate responses which are relayed to the brain. Some taste cells have conventional synapses and rely on calcium influx through voltage-gated calcium channels. Other taste cells lack these synapses and depend on calcium release to formulate an output signal through a hemichannel. Beyond establishing these characteristics, few studies have focused on understanding how these calcium signals are formed. We identified multiple calcium clearance mechanisms that regulate calcium levels in taste cells as well as a calcium influx that contributes to maintaining appropriate calcium homeostasis in these cells. Multiple factors regulate the evoked taste signals with varying roles in different cell populations. Clearly, calcium signaling is a dynamic process in taste cells and is more complex than has previously been appreciated. PMID:25450977

Instant dentin hypersensitivity relief of a single topical application of an in-office desensitizing paste containing 8% arginine and calcium carbonate: a split-mouth, randomized-controlled study.

PubMed

Kapferer, Ines; Pflug, Claudia; Kisielewsky, Irene; Giesinger, Johannes; Beier, Ulrike S; Dumfahrt, Herbert

2013-01-01

The aim of this study was to evaluate the clinical efficacy of an in-office desensitizing paste containing 8% arginine and calcium carbonate relative to calcium carbonate alone in the reduction of dentin hypersensitivity in a randomized, double-blind, split-mouth clinical trial. Sixty teeth (30 subjects) with an air blast hypersensitivity score of 2 or 3 (Schiff Cold Air Sensitivity Scale) were randomly assigned to one of two treatment groups: (1) test paste containing 8% arginine and calcium carbonate (elmex sensitive professional desensitizing paste) and (2) control paste: paris white (calcium carbonate). Tactile and air blast dentin hypersensitivity examinations were performed at baseline, immediately after paste application and 4 and 12 weeks later. A statistically significant difference in air blast (p = 0.001) and tactile (p = 0.047) hypersensitivity reduction over time was observed between the two therapy modes. After 12-weeks, statistically significant differences were indicated between the test and control group with respect to baseline-adjusted mean tactile (41.94%; p = 0.038) and air blast hypersensitivity scores (46.5%; p = 0.017). The tested in-office desensitizing paste containing 8.0% arginine and calcium carbonate provides significantly greater hypersensitivity relief compared to calcium carbonate alone.

Investigating the Basis of Biogenic Calcium Carbonate Formation from an Amorphous Precursor: Nature of the Transformation to Calcite on Hydroxyl Functionalized Surfaces

NASA Astrophysics Data System (ADS)

Wang, D.; Lee, J. R.; Talley, C. E.; Murphy, K. E.; Han, T. Y.; Deyoreo, J. J.; Dove, P. M.

2006-12-01

Calcium carbonate biominerals are particularly significant because of their direct role in regulating the global carbon cycle, as well as their ubiquitous occurrence across earth environments. Biogenic carbonates are further distinguished by their broad phlyogenetic distribution; hence it has been suggested that unrelated eukaryotes must have used similar biochemical strategies to control mineralization. Recent studies have shown that an amorphous calcium carbonate (ACC) phase potentially plays a key role in the initial formation of carbonate minerals and in "shaping" them into complex morphologies widely seen in biominerals. Echinoderms, mollusks, and possibly many other organisms use ACC as a precursor phase that is first nucleated in cellularly controlled environments such as vesicles and subsequently transforms into a fully crystalline material. Recent studies on sea urchin embryos have shown that during transformation ACC develops short range that resembles calcite before fully crystallizing and serve as inspiration for our studies in synthetic systems. Self-assembled monolayers (SAM) on gold and silver have been used as simple model systems that approximate biological surfaces. Many studies have shown that thiol monolayers with hydroxyl termination stabilize a transitory ACC film that with prolonged exposure to aqueous solution transforms into calcite nucleated on {104} faces. Using Near Edge X-ray Absorption Fine Structure (NEXAFS) we studied SAM/mineral interactions with well ordered mercaptophenol monolayers showed that when these films are first exposed to calcium carbonate solutions, they become disordered and remain so after subsequent deposition of an ACC over-layer. Yet calcite nucleates and grows from the surface bound ACC with predominantly {104} orientation, which suggests a dynamic structural relationship between the SAMs and the mineral phase. While the monolayer/mineral phase interaction has been characterized, the mechanism for nucleating

Evaluation of ERTS data for certain oceanographic uses. [precipitation of calcium carbonate in Lake Michigan, Lake Erie, and Lake Ontario

NASA Technical Reports Server (NTRS)

Strong, A. E. (Principal Investigator)

1974-01-01

The author has identified the following significant results. According to Lake Michigan records, the pH levels have been steadily increasing as the lake becomes more eutrophic. Numerous upwellings during the summer of 1973, beginning with the late July event, appear to be triggering a chemical precipitation of calcium carbonate. The upwelling provides abundant carbon dioxide into the surface water and results in massive blooms of phytoplankton. As the CO2 is utilized by these microscopic plants the pH is increased (acidity decreases) and CaCO3 no longer is able to remain in solution. The precipitation takes place where the phytoplankton are living, near depths of 10 meters. Therefore, the whiting observed by ERTS-1 is only seen in the green band, as red cannot penetrate but a few meters. With these whitings, secci disc readings lower in July from 10-15 meters to 3-5 meters and green, milky water is observed by research vessels. It appears that whitings have been becoming more frequent since the middle 60's but until ERTS-1 the extent had never been realized. Calcium levels are too low, presently, for a similar precipitate in Lakes Huron or Superior. However, whitings have been seen by ERTS-1 in Lakes Erie and Ontario where the calcium ion and pH levels are more like those found in Lake Michigan.