Science.gov

Sample records for apatites

  1. Triclinic apatites.

    PubMed

    Baikie, Tom; Mercier, Patrick H J; Elcombe, Margaret M; Kim, Jean Y; Le Page, Yvon; Mitchell, Lyndon D; White, T J; Whitfield, Pamela S

    2007-04-01

    Apatites commonly adopt P6(3)/m hexagonal symmetry. More rarely, monoclinic chemical analogues have been recognized, including the biologically significant hydroxyapatite, Ca(10)(PO(4))(6)(OH)(2), but the driving force towards lower symmetry has not been systematically examined. A combination of diffraction observations and ab initio calculations for Ca(10)(AsO(4))(6)F(2) and Ca(10)(VO(4))(6)F(2) show these materials are triclinic P\\bar 1 apatites in which the AsO(4) and VO(4) tetrahedra tilt to relieve stress at the metal and metalloid sites to yield reasonable bond-valence sums. An analysis of the triclinic non-stoichiometric apatites La(10 - x)(GeO(4))(6)O(3 - 1.5x) and Ca(10)(PO(4))(6)(OH)(2 - x)O(x/2) confirms this scheme of tetrahedral rotations, while Cd(10)(PO(4))(6)F(2) and Ca(10)(CrO(4))(6)F(2) are predicted to be isostructural. These distortions are in contrast to the better known P112(1)/b monoclinic dimorphs of chloroapatite and hydroxyapatite, where the impetus for symmetry reduction is ordered anion (OH(-) and Cl(-)) displacements which are necessary to obtain acceptable bond lengths. These results are important for designing apatites with specific structural and crystal-chemical characteristics.

  2. Radionuclide removal by apatite

    SciTech Connect

    Rigali, Mark J.; Brady, Patrick V.; Moore, Robert C.

    2016-12-01

    In this study, a growing body of research supports widespread future reliance on apatite for radioactive waste cleanup. Apatite is a multi-functional radionuclide sorbent that lowers dissolved radionuclide concentrations by surface sorption, ion exchange, surface precipitation, and by providing phosphate to precipitate low-solubility radionuclide-containing minerals. Natural apatites are rich in trace elements, and apatite’s stability in the geologic record suggest that radionuclides incorporated into apatite, whether in a permeable reactive barrier or a waste form, are likely to remain isolated from the biosphere for long periods of time. Here we outline the mineralogic and surface origins of apatite-radionuclide reactivity and show how apatites might be used to environmental advantage in the future.

  3. Radionuclide removal by apatite

    DOE PAGES

    Rigali, Mark J.; Brady, Patrick V.; Moore, Robert C.

    2016-12-01

    In this study, a growing body of research supports widespread future reliance on apatite for radioactive waste cleanup. Apatite is a multi-functional radionuclide sorbent that lowers dissolved radionuclide concentrations by surface sorption, ion exchange, surface precipitation, and by providing phosphate to precipitate low-solubility radionuclide-containing minerals. Natural apatites are rich in trace elements, and apatite’s stability in the geologic record suggest that radionuclides incorporated into apatite, whether in a permeable reactive barrier or a waste form, are likely to remain isolated from the biosphere for long periods of time. Here we outline the mineralogic and surface origins of apatite-radionuclide reactivity andmore » show how apatites might be used to environmental advantage in the future.« less

  4. The lunar apatite paradox.

    PubMed

    Boyce, J W; Tomlinson, S M; McCubbin, F M; Greenwood, J P; Treiman, A H

    2014-04-25

    Recent discoveries of water-rich lunar apatite are more consistent with the hydrous magmas of Earth than the otherwise volatile-depleted rocks of the Moon. Paradoxically, this requires H-rich minerals to form in rocks that are otherwise nearly anhydrous. We modeled existing data from the literature, finding that nominally anhydrous minerals do not sufficiently fractionate H from F and Cl to generate H-rich apatite. Hydrous apatites are explained as the products of apatite-induced low magmatic fluorine, which increases the H/F ratio in melt and apatite. Mare basalts may contain hydrogen-rich apatite, but lunar magmas were most likely poor in hydrogen, in agreement with the volatile depletion that is both observed in lunar rocks and required for canonical giant-impact models of the formation of the Moon.

  5. Hanford Apatite Treatability Test Report Errata: Apatite Mass Loading Calculation

    SciTech Connect

    Szecsody, James E.; Vermeul, Vincent R.; Williams, Mark D.; Truex, Michael J.

    2014-05-19

    The objective of this errata report is to document an error in the apatite loading (i.e., treatment capacity) estimate reported in previous apatite treatability test reports and provide additional calculation details for estimating apatite loading and barrier longevity. The apatite treatability test final report (PNNL-19572; Vermeul et al. 2010) documents the results of the first field-scale evaluation of the injectable apatite PRB technology. The apatite loading value in units of milligram-apatite per gram-sediment is incorrect in this and some other previous reports. The apatite loading in units of milligram phosphate per gram-sediment, however, is correct, and this is the unit used for comparison to field core sample measurements.

  6. Photoluminescence of annealed biomimetic apatites.

    PubMed

    Zollfrank, Cordt; Müller, Lenka; Greil, Peter; Müller, Frank A

    2005-11-01

    Biomimetic apatite coatings are widely used in orthopaedic applications to provide bioinert material surfaces with bioactive behaviour by means of initiating bone growth at the implant surface. In this study we manufactured biomimetic calcium phosphate coatings consisting of a calcium deficient carbonated apatite by immersing activated titanium platelets into simulated body fluid. The development of the crystal phases was monitored by X-ray diffractometry in addition to Fourier-transform infrared spectroscopy. The microstructure of the biomimetic apatites and phase composition was analysed using scanning and transmission electron microscopy as well as attached energy dispersive X-ray spectrometry. The samples were annealed in air yielding in an inherent luminescence of the biomimetic apatite up to temperatures of 600 degrees C. The photo-induced emission spectra were recorded in the range from 400 to 750 nm at excitation wavelengths ranging 310-450 nm. A blue (437 nm) and a green (561 nm) emission were found between 200 and 600 degrees C visually appearing white. Photoluminescence of annealed biomimetic apatites might be of interest for histological probing and monitoring of bone re-modelling. The results are discussed in terms of chemical and crystallographic changes in the calcium phosphate layer during heat treatment.

  7. Factors controlling sulfur concentrations in volcanic apatite

    USGS Publications Warehouse

    Peng, G.; Luhr, J.F.; McGee, J.J.

    1997-01-01

    Apatite crystals from two types of samples were analyzed by electron microprobe for 15 major and trace elements: (1) apatite in H2O- and S-saturated experimental charges of the 1982 El Chicho??n trachyandesite and (2) apatite in volcanic rocks erupted from 20 volcanoes. The SO3 contents of the experimental apatite increase with increasing oxygen fugacity (fo2), from ???0.04 wt% in reduced charges buffered by fayalite-magnetite-quartz (FMQ), to 1.0-2.6 wt% in oxidized charges buffered by manganosite-hausmanite (MNH) or magnetite-hematite (MTH). The SO3 contents of MNH- and MTH-buffered apatite also generally increase with increasing pressure from 2 to 4 kbar and decreasing temperature from 950 to 800??C. The partition coefficient for SO3 between apatite and oxidized melt increases with decreasing temperature but appears to be independent of pressure. Apatites in volcanic rocks show a wide range of SO3 contents (<0.04 to 0.63 wt%). Our sample set includes one group known to contain primary anhydrite and a second group inferred to have been free of primary anhydrite. No systematic differences in apatite S contents are observed between these two groups. Our study was initiated to define the factors controlling S contents in apatite and to evaluate the hypothesis that high S contents in apatite could be characteristic of S-rich anhydrite-bearing magmas such as those erupted from El Chicho??n in 1982 and Pinatubo in 1991. This hypothesis is shown to be invalid, probably chiefly a consequence of the slow intra-crystaline diffusion that limits re-equilibration between early formed apatite and the evolving silicate melt. Contributing factors include early crystallization of most apatite over a relatively small temperature interval, common late-stage magmatic enrichment of S, progressive oxidation during magmatic evolution, and strong controls on S contents in apatite exerted fo2, temperature, and pressure.

  8. U-Pb Ages of Lunar Apatites

    NASA Technical Reports Server (NTRS)

    Vaughan, J.; Nemchin, A. A.; Pidgeon, R. T.; Meyer, Charles

    2006-01-01

    Apatite is one of the minerals that is rarely utilized in U-Pb geochronology, compared to some other U-rich accessory phases. Relatively low U concentration, commonly high proportion of common Pb and low closure temperature of U-Pb system of apatite inhibit its application as geochronological tool when other minerals such as zircon are widely available. However, zircon appear to be restricted to certain type of lunar rocks, carrying so called KREEP signature, whereas apatite (and whitlockite) is a common accessory mineral in the lunar samples. Therefore, utilizing apatite for lunar chronology may increase the pool of rocks that are available for U-Pb dating. The low stability of U-Pb systematics of apatite may also result in the resetting of the system during meteoritic bombardment, in which case apatite may provide an additional tool for the study of the impact history of the Moon. In order to investigate these possibilities, we have analysed apatites and zircons from two breccia samples collected during the Apollo 14 mission. Both samples were collected within the Fra Mauro formation, which is interpreted as a material ejected during the impact that formed the Imbrium Basin.

  9. Phosphorus removal from wastewater by mineral apatite.

    PubMed

    Bellier, Nathalie; Chazarenc, Florent; Comeau, Yves

    2006-08-01

    Natural apatite has emerged as potentially effective for phosphorus (P) removal from wastewater. The retention capacity of apatite is attributed to a lower activation energy barrier required to form hydroxyapatite (HAP) by crystallization. The aim of our study was to test the P removal potential of four apatites found in North America. Minerals were collected from two geologically different formations: sedimentary apatites from Florida and igneous apatites from Quebec. A granular size ranging from 2.5 to 10mm to prevent clogging in wastewater applications was used. Isotherms (24 and 96 h) were drawn after batch tests using the Langmuir model which indicated that sedimentary apatites presented a higher P-affinity (K(L)=0.009 L/g) than igneous apatites (K(L) approximately 0.004 L/g). The higher density of igneous material probably explained this difference. P-retention capacities were determined to be around 0.3mg P/g apatite (24 h). A 30 mg P/L synthetic effluent was fed during 39 days to four lab-scale columns. A mixture of sedimentary material (apatite and limestone 50-50%, w/w) showed a complete P-retention during 15 days which then declined to 65% until the end of the 39 days lab scale test period. A limitation in calcium may have limited nucleation processes. The same mixture used in a field scale test showed 60% P-retention from a secondary effluent (30 mg COD/L, 10 mg Pt/L) during 65 days without clogging.

  10. Apatite-Melt Partitioning at 1 Bar: An Assessment of Apatite-Melt Exchange Equilibria Resulting from Non-Ideal Mixing of F and Cl in Apatite

    NASA Technical Reports Server (NTRS)

    McCubbin, F. M.; Ustunisik, G.; Vander Kaaden, K. E.

    2016-01-01

    The mineral apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to precisely determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multi-component silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al. recently reported that the exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing. In the present study, we conducted apatite-melt partitioning experiments in evacuated, sealed silica-glass tubes at approximately 1 bar and 950-1050 degrees Centigrade on a synthetic Martian basalt composition equivalent to the basaltic shergottite Queen Alexandria Range (QUE) 94201. These experiments were conducted dry, at low pressure, to assess the effects of temperature and apatite composition on the partitioning behavior of F and Cl between apatite and basaltic melt along the F-Cl apatite binary join, where there is non-ideal mixing of F and Cl

  11. Ion exchanges in apatites for biomedical application.

    PubMed

    Cazalbou, S; Eichert, D; Ranz, X; Drouet, C; Combes, C; Harmand, M F; Rey, C

    2005-05-01

    The modification of the composition of apatite materials can be made by several processes corresponding to ion exchange reactions which can conveniently be adapted to current coatings and ceramics and are an alternative to setting up of new synthesis methods. In addition to high temperature thermal treatments, which can partly or almost totally replace the monovalent OH- anion of stoichiometric hydroxyapatite by any halogen ion or carbonate, aqueous processes corresponding to dissolution-reprecipitation reactions have also been proposed and used. However, the most interesting possibilities are provided by aqueous ion exchange reactions involving nanocrystalline apatites. These apatites are characterised by the existence on the crystal surface of a hydrated layer of loosely bound mineral ions which can be easily exchanged in solution. This layer offers a possibility to trap mineral ions and possibly active molecules which can modify the apatite properties. Such processes are involved in mineralised tissues and could be used in biomaterials for the release of active mineral species.

  12. Water-mediated structuring of bone apatite.

    PubMed

    Wang, Yan; Von Euw, Stanislas; Fernandes, Francisco M; Cassaignon, Sophie; Selmane, Mohamed; Laurent, Guillaume; Pehau-Arnaudet, Gérard; Coelho, Cristina; Bonhomme-Coury, Laure; Giraud-Guille, Marie-Madeleine; Babonneau, Florence; Azaïs, Thierry; Nassif, Nadine

    2013-12-01

    It is well known that organic molecules from the vertebrate extracellular matrix of calcifying tissues are essential in structuring the apatite mineral. Here, we show that water also plays a structuring role. By using solid-state nuclear magnetic resonance, wide-angle X-ray scattering and cryogenic transmission electron microscopy to characterize the structure and organization of crystalline and biomimetic apatite nanoparticles as well as intact bone samples, we demonstrate that water orients apatite crystals through an amorphous calcium phosphate-like layer that coats the crystalline core of bone apatite. This disordered layer is reminiscent of those found around the crystalline core of calcified biominerals in various natural composite materials in vivo. This work provides an extended local model of bone biomineralization.

  13. Apatite formation: why it may not work as planned, and how to conclusively identify apatite compounds.

    PubMed

    Drouet, Christophe

    2013-01-01

    Calcium phosphate apatites are inorganic compounds encountered in many different mineralized tissues. Bone mineral, for example, is constituted of nanocrystalline nonstoichiometric apatite, and the production of "analogs" through a variety of methods is frequently reported. In another context, the ability of solid surfaces to favor the nucleation and growth of "bone-like" apatite upon immersion in supersaturated fluids such as SFB is commonly used as one evaluation index of the "bioactivity" of such surfaces. Yet, the compounds or deposits obtained are not always thoroughly characterized, and their apatitic nature is sometimes not firmly assessed by appropriate physicochemical analyses. Of particular importance are the "actual" conditions in which the precipitation takes place. The precipitation of a white solid does not automatically indicate the formation of a "bone-like carbonate apatite layer" as is sometimes too hastily concluded: "all that glitters is not gold." The identification of an apatite phase should be carefully demonstrated by appropriate characterization, preferably using complementary techniques. This review considers the fundamentals of calcium phosphate apatite characterization discussing several techniques: electron microscopy/EDX, XRD, FTIR/Raman spectroscopies, chemical analyses, and solid state NMR. It also underlines frequent problems that should be kept in mind when making "bone-like apatites."

  14. Apatite Formation: Why It May Not Work as Planned, and How to Conclusively Identify Apatite Compounds

    PubMed Central

    2013-01-01

    Calcium phosphate apatites are inorganic compounds encountered in many different mineralized tissues. Bone mineral, for example, is constituted of nanocrystalline nonstoichiometric apatite, and the production of “analogs” through a variety of methods is frequently reported. In another context, the ability of solid surfaces to favor the nucleation and growth of “bone-like” apatite upon immersion in supersaturated fluids such as SFB is commonly used as one evaluation index of the “bioactivity” of such surfaces. Yet, the compounds or deposits obtained are not always thoroughly characterized, and their apatitic nature is sometimes not firmly assessed by appropriate physicochemical analyses. Of particular importance are the “actual” conditions in which the precipitation takes place. The precipitation of a white solid does not automatically indicate the formation of a “bone-like carbonate apatite layer” as is sometimes too hastily concluded: “all that glitters is not gold.” The identification of an apatite phase should be carefully demonstrated by appropriate characterization, preferably using complementary techniques. This review considers the fundamentals of calcium phosphate apatite characterization discussing several techniques: electron microscopy/EDX, XRD, FTIR/Raman spectroscopies, chemical analyses, and solid state NMR. It also underlines frequent problems that should be kept in mind when making “bone-like apatites.” PMID:23984373

  15. From biomimetic apatites to biologically inspired composites.

    PubMed

    Tampieri, A; Celotti, G; Landi, E

    2005-02-01

    Hydroxyapatite is an elective material for bone substitution. In this outline of our recent activity the crucial role of nanostructured ceramics in the design and preparation of ceramic scaffolds will be described, focussing on our more recent interest in biomimetic apatites, in particular apatites containing HPO42- CO32- and Mg2+ which are similar to the mineral component of bone. The paper describes such nanostructured products and, in particular, innovative synthetic techniques capable of yielding powders with higher reactivity and bioactivity. However, so far the characteristics of artificial bone tissues have been shown to be very different from those of natural bone, mainly because of the absence of the peculiar self-organizing interaction between apatites and the protein component. This causes modification of the structure of apatites and of the features of the overall composite forming human bone tissue. Therefore, attempts to mimic the features and structure of natural bone tissue, leading toward so-called bio-inspired materials, will be speculated upon. New techniques used to reproduce a composite in which a nanosize blade-like crystal of hydroxyapatite (HA) grows in contact with self-assembling fibres of natural polymer will be presented. In this specific case, the amazing ability of biological systems to store and process information at the molecular level, nucleating nanosize apatites (bio-inspired material), is exploited.

  16. The volatile content of Vesta: Clues from apatite in eucrites

    NASA Astrophysics Data System (ADS)

    Sarafian, Adam Robert; Roden, Michael F.; PatiñO-Douce, Alberto E.

    2013-11-01

    Apatite was analyzed by electron microprobe in 3 cumulate and 10 basaltic eucrites. Eucritic apatite is fluorine-rich with minor chlorine and hydroxyl (calculated by difference). We confirmed the hydroxyl content by measuring hydroxyl directly in apatites from three representative eucrites using secondary ionization mass spectroscopy. Overall, most eucritic apatites resemble fluorine-rich lunar mare apatites, but intriguing OH- and Cl-rich apatites suggest a role for water and/or hydrothermal fluids in the Vestan interior or on other related differentiated asteroids. Most late-stage apatite found in mesostasis has little hydroxyl or chlorine and is thought to have crystallized from a degassed magma; however, several apatites exhibit atypical compositions and/or textural characteristics. For example, the isotopically anomalous basaltic eucrite Pasamonte has apatite in the mesostasis with significant OH. Apatites in Juvinas also have significant OH and occur as veinlets crosscutting silicates. Euhedral apatites in the Moore County cumulate eucrite occur as inclusions in pyroxene and are also hydroxyl-rich (0.62 wt% OH). The OH was confirmed by SIMS analysis and this apatite clearly points to the presence of water, at least locally, in the Vestan interior. Portions of Elephant Moraine (EET) 90020 have large and abundant apatites, which may be the product of apatite accumulation in a zone of melt-rock reaction. Relatively chlorine-rich apatites occur in basaltic eucrite Graves Nunataks (GRA) 98098 (approximately 1 wt% Cl). Particularly striking is the compositional similarity between apatite in GRA 98098 and apatites in lunar KREEP, which may indicate the presence of residual magmas from an asteroid-wide magma ocean on Vesta.

  17. IN SITU LEAD IMMOBILIZATION BY APATITE

    EPA Science Inventory

    Lead contamination is of environmental concern due to its effect on human health. The purpose of this study was to develop a technology to immobilize Pb in situ in contaminated soils and wastes using apatite. Hydroxyapatite [Ca10(PO4)6(O...

  18. Can Polyphosphate Biochemistry Affect Biological Apatite Saturation?

    NASA Astrophysics Data System (ADS)

    Omelon, S. J.; Matsuura, N.; Gorelikov, I.; Wynnyckyj, C.; Grynpas, M. D.

    2010-12-01

    Phosphorus (P) is an important and limiting element for life. One strategy for storing ortho phosphates (Pi) is polymerization. Polymerized Pi's (polyphosphates: (PO3-)n: polyPs) serve as a Pi bank, as well as a catiion chelator, energy source, & regulator of responses to stresses in the stationary phase of culture growth and development1. PolyP biochemistry has been investigated in yeasts, bacteria & plants2. Bigeochemical cycling of P includes the condensation of Pi into pyro (P2O7-4), & polyPs, & the release of Pi from these compounds by the hydrolytic degradation of Pi from phosphomonoester bonds. Alkaline phosphatase (ALP) is one of the predominate enzymes for regenerating Pi in aquatic systems3, & it cleaves Pi from polyPs. ALP is also the enzyme associated with apatite biomineralization in vertebrates4. PolyP was proposed to be the ALP substrate in bone mineralization5. Where calcium ions are plentiful in many aquatic environments, there is no requirement for aquatic life to generate Ca-stores. However, terrestrial vertebrates benefit from a bioavailable Ca-store such as apatite. The Pi storage strategy of polymerizing PO4-3 into polyPs dovetails well with Ca-banking, as polyPs sequester Ca, forming a neutral calcium polyphosphate (Ca-polyP: (Ca(PO3)2)n) complex. This neutral complex represents a high total [Ca+2] & [PO4-3], without the threat of inadvertent apatite precipitation, as the free [Ca+2] & [PO4-3], and therefore apatite saturation, are zero. Recent identification of polyP in regions of bone resorption & calcifying cartilage5 suggests that vertebrates may use polyP chemistry to bank Ca+2 and PO4-3. In vitro experiments with nanoparticulate Ca-polyP & ALP were undertaken to determine if carbonated apatite could precipitate from 1M Ca-polyP in Pi-free “physiological fluid” (0.1 M NaCl, 2 mM Ca+2, 0.8 mM Mg+2, pH ~8.0 ±0.5, 37 °C), as this is estimated to generate the [Ca+2] & [PO4-3] required to form the apatite content of bone tissue

  19. Magnesium and carbonate in enamel and synthetic apatites.

    PubMed

    LeGeros, R Z; Sakae, T; Bautista, C; Retino, M; LeGeros, J P

    1996-11-01

    This study aimed to: determine the Mg and CO3 distribution in the outer (surface), middle, and inner (closest to the enamel-dentin junction, EDJ) layers of human enamel; and determine the factors affecting the incorporation of Mg into synthetic apatites and the consequence of such incorporation on the properties of the apatites. Results demonstrated that the concentrations of Mg, CO3, and organic components increased from the surface to the inner layers close to the EDJ and a difference in crystallinity from the outer to the inner layers. Initial results indicated that the extent of dissolution of the inner layer enamel is greater than that in the outer or surface enamel. Results on synthetic apatites showed the following: (1) Limited Mg incorporation into apatite was dependent on solution [Mg/Ca] molar ratio, temperature, pH, and the presence of CO3 or fluoride (F); (2) incorporation of Mg causes reduction in crystallinity and an increase in the extent of dissolution of the apatite; (3) the negative effect of Mg on the properties of apatites is synergistic to that of CO3 and antagonistic to that of F; and (4) exposure to acid of Mg-containing apatites causes the dissolution of Mg-rich apatite and precipitation of Mg-poor apatite. The observed decrease in the [Mg/Ca] of enamel and synthetic apatites after acid exposure may explain the observed 'preferential loss' of Mg and CO3 in the initial stages of caries.

  20. The determination of uranium (IV) in apatite

    USGS Publications Warehouse

    Clarke, Roy S.; Altschuler, Zalman S.

    1956-01-01

    Geologic and mineralogic evidence indicate that the uranium present in apatite may proxy for calcium in the mineral structure as U(IV). An experimental investigation was conducted and chemical evidence was obtained that establishes the presence of U(IV) in apatite. The following analytical procedure was developed for the determination of U(IV). Carbonate-fluorapatite is dissolved in cold 1.5M orthophosphoric acid and fluorapatite is dissolved in cold 1.2M hydrochloric acid containing 1.5 g of hydroxylamine hydrochloride per 100 ml. Uranium (IV) is precipitated by cupferron using titanium as a carrier. The uranium in the precipitate is separated by use of the ethyl acetate extraction procedure and determined fluorimetrically. The validity and the limitations of the method have been established by spike experiments.

  1. Calcium Apatite Deposition Disease: Diagnosis and Treatment

    PubMed Central

    2016-01-01

    Calcium apatite deposition disease (CADD) is a common entity characterized by deposition of calcium apatite crystals within and around connective tissues, usually in a periarticular location. CADD most frequently involves the rotator cuff. However, it can theoretically occur in almost any location in the musculoskeletal system, and many different locations of CADD have been described. When CADD presents in an unexpected location it can pose a diagnostic challenge, particularly when associated with pain or swelling, and can be confused with other pathologic processes, such as infection or malignancy. However, CADD has typical imaging characteristics that usually allows for a correct diagnosis to be made without additional imaging or laboratory workup, even when presenting in unusual locations. This is a review of the common and uncommon presentations of CADD in the appendicular and axial skeleton as well as an updated review of pathophysiology of CADD and current treatments. PMID:28042481

  2. Selenite sorption by carbonate substituted apatite

    SciTech Connect

    Moore, Robert C.; Rigali, Mark J.; Brady, Patrick

    2016-08-31

    The sorption of selenite, SeO32–, by carbonate substituted hydroxylapatite was investigated using batch kinetic and equilibrium experiments. The carbonate substituted hydroxylapatite was prepared by a precipitation method and characterized by SEM, XRD, FT-IR, TGA, BET and solubility measurements. The material is poorly crystalline, contains approximately 9.4% carbonate by weight and has a surface area of 210.2 m2/g. Uptake of selenite by the carbonated hydroxylapatite was approximately an order of magnitude higher than the uptake by uncarbonated hydroxylapatite reported in the literature. Distribution coefficients, Kd, determined for the carbonated apatite in this work ranged from approximately 4200 to over 14,000 L/kg. A comparison of the results from kinetic experiments performed in this work and literature kinetic data indicates the carbonated apatite synthesized in this study sorbed selenite 23 times faster than uncarbonated hydroxylapatite based on values normalized to the surface area of each material. Furthermore, the results indicate carbonated apatite is a potential candidate for use as a sorbent for pump-and-treat technologies, soil amendments or for use in permeable reactive barriers for the remediation of selenium contaminated sediments and groundwaters.

  3. Selenite sorption by carbonate substituted apatite

    DOE PAGES

    Moore, Robert C.; Rigali, Mark J.; Brady, Patrick

    2016-08-31

    The sorption of selenite, SeO32–, by carbonate substituted hydroxylapatite was investigated using batch kinetic and equilibrium experiments. The carbonate substituted hydroxylapatite was prepared by a precipitation method and characterized by SEM, XRD, FT-IR, TGA, BET and solubility measurements. The material is poorly crystalline, contains approximately 9.4% carbonate by weight and has a surface area of 210.2 m2/g. Uptake of selenite by the carbonated hydroxylapatite was approximately an order of magnitude higher than the uptake by uncarbonated hydroxylapatite reported in the literature. Distribution coefficients, Kd, determined for the carbonated apatite in this work ranged from approximately 4200 to over 14,000 L/kg.more » A comparison of the results from kinetic experiments performed in this work and literature kinetic data indicates the carbonated apatite synthesized in this study sorbed selenite 23 times faster than uncarbonated hydroxylapatite based on values normalized to the surface area of each material. Furthermore, the results indicate carbonated apatite is a potential candidate for use as a sorbent for pump-and-treat technologies, soil amendments or for use in permeable reactive barriers for the remediation of selenium contaminated sediments and groundwaters.« less

  4. Lunar apatite with terrestrial volatile abundances.

    PubMed

    Boyce, Jeremy W; Liu, Yang; Rossman, George R; Guan, Yunbin; Eiler, John M; Stolper, Edward M; Taylor, Lawrence A

    2010-07-22

    The Moon is thought to be depleted relative to the Earth in volatile elements such as H, Cl and the alkalis. Nevertheless, evidence for lunar explosive volcanism has been used to infer that some lunar magmas exsolved a CO-rich and CO(2)-rich vapour phase before or during eruption. Although there is also evidence for other volatile species on glass spherules, until recently there had been no unambiguous reports of indigenous H in lunar rocks. Here we report quantitative ion microprobe measurements of late-stage apatite from lunar basalt 14053 that document concentrations of H, Cl and S that are indistinguishable from apatites in common terrestrial igneous rocks. These volatile contents could reflect post-magmatic metamorphic volatile addition or growth from a late-stage, interstitial, sulphide-saturated melt that contained approximately 1,600 parts per million H(2)O and approximately 3,500 parts per million Cl. Both metamorphic and igneous models of apatite formation suggest a volatile inventory for at least some lunar materials that is similar to comparable terrestrial materials. One possible implication is that portions of the lunar mantle or crust are more volatile-rich than previously thought.

  5. The expanded amelogenin polyproline region preferentially binds to apatite versus carbonate and promotes apatite crystal elongation

    PubMed Central

    Gopinathan, Gokul; Jin, Tianquan; Liu, Min; Li, Steve; Atsawasuwan, Phimon; Galang, Maria-Therese; Allen, Michael; Luan, Xianghong; Diekwisch, Thomas G. H.

    2014-01-01

    The transition from invertebrate calcium carbonate-based calcite and aragonite exo- and endoskeletons to the calcium phosphate-based vertebrate backbones and jaws composed of microscopic hydroxyapatite crystals is one of the great revolutions in the evolution of terrestrial organisms. To identify potential factors that might have played a role in such a transition, three key domains of the vertebrate tooth enamel protein amelogenin were probed for calcium mineral/protein interactions and their ability to promote calcium phosphate and calcium carbonate crystal growth. Under calcium phosphate crystal growth conditions, only the carboxy-terminus augmented polyproline repeat peptide, but not the N-terminal peptide nor the polyproline repeat peptide alone, promoted the formation of thin and parallel crystallites resembling those of bone and initial enamel. In contrast, under calcium carbonate crystal growth conditions, all three amelogenin-derived polypeptides caused calcium carbonate to form fused crystalline conglomerates. When examined for long-term crystal growth, polyproline repeat peptides of increasing length promoted the growth of shorter calcium carbonate crystals with broader basis, contrary to the positive correlation between polyproline repeat element length and apatite mineralization published earlier. To determine whether the positive correlation between polyproline repeat element length and apatite crystal growth versus the inverse correlation between polyproline repeat length and calcium carbonate crystal growth were related to the binding affinity of the polyproline domain to either apatite or carbonate, a parallel series of calcium carbonate and calcium phosphate/apatite protein binding studies was conducted. These studies demonstrated a remarkable binding affinity between the augmented amelogenin polyproline repeat region and calcium phosphates, and almost no binding to calcium carbonates. In contrast, the amelogenin N-terminus bound to both carbonate

  6. The chemistry of five accessory rock-forming apatites

    USGS Publications Warehouse

    Lee, Donald E.; Rose, Harry J.; Brandt, Elaine L. Munson; Van Loenen, Richard E.

    1973-01-01

    Chemical and physical data are given for five samples of rock-forming apatite from diverse geologic environments in Nevada and Colorado.  Four of these apatites contain rare-earth assemblages in which the cerium group is well represented but the yttrium group predominates.  The fifth apatite contains a highly fractionated assemblage of the lighter (cerium group) rare earths similar to the assemblage typical of alkulic rocks.

  7. Distribution of halogens during fluid-mediated apatite replacement

    NASA Astrophysics Data System (ADS)

    Kusebauch, Christof; John, Timm; Whitehouse, Martin J.

    2016-04-01

    Apatite (Ca5(PO4)3(F,Cl,OH)) is one the most abundant halogen containing minerals in the crust. It is present in many different rock types and stable up to P-T conditions of the mantle. Although probably not relevant for the halogen budget of the mantle, apatite is potentially a carrier phase of halogens into the mantle via subduction processes and therefore important for the global halogen cycle. Different partitioning behavior of the halogens between apatite and melt/fluids causes fractionation of these elements. In hydrothermal environments apatite reacts via a coupled dissolution-reprecipitation process that leads to apatite halogen compositions which are in (local) equilibrium with the hydrothermal fluid. This behavior enables apatite to be used as fluid probe and as a tool for tracking fluid evolution during fluid-rock interaction. Here, we present a combined experimental and field related study focused on replacement of apatite under hydrothermal conditions, to investigate the partitioning of halogens between apatite and fluids. Experiments were conducted in a cold seal pressure apparatus at 0.2 GPa and temperatures ranging from 400-700°C using halogen bearing solutions of different composition (KOH, NaF, NaCl, NaBr, NaI) to promote the replacement of Cl-apatite. The halogen composition of reacted apatite was analyzed by electron microprobe (EMPA) and secondary ion mass spectrometry (SIMS). The data was used to calculate partition coefficients of halogens between fluid and apatite. Our new partitioning data show that fluorine is the most compatible halogen followed by chlorine, bromine and iodine. Comparison between partition coefficients of the apatite-fluid system and coefficients derived in the apatite-melt system reveals values for F that are one to two orders of magnitude higher. In contrast, Cl and Br show a similar partition behavior in fluid and melt systems. Consequently, apatite that formed by fluid-rock interaction will fractionate F from Cl more

  8. Time and the crystallization of apatite in seawater

    USGS Publications Warehouse

    Gulbrandsen, R.A.; Roberson, C.E.; Neil, S.T.

    1984-01-01

    Carbonate fluorapatite has been synthesized in seawater in an experiment of nearly 10-years duration. The addition of phosphate to seawater whose fluoride concentration had been increased to 7.6 mg/l brought about an initial amorphous phosphate precipitate. After 20 months, a crystalline magnesium phosphate phase developed within the amorphous phosphate. Crystallization of apatite, which occurred during the last 3 years of the experiment, was accompanied by dissolution of the crystalline magnesium phosphate phase. The MgO content of the apatite (1.9 percent) is high in comparison to Tertiary and older apatite but similar to some young apatite; the CO2 content (3.6 percent) is medium, and the fluorine content (2.2 percent) is low but again similar to some young apatite. The hydroxyl ion (OH-) likely fills the need for additional fluorine-position atoms. The mole ratio of Ca plus substituent elements to P plus substituent elements (1.50) is low in comparison to the expected ratio of 1.67. The substitution of the hydronium ion (H3O+) for Ca may account for this difference. The synthesis of apatite in seawater demonstrates that the factor of time overcomes the well known inhibiting effect of magnesium upon the crystallization of apatite. It also implies that given an adequate supply of phosphate, apatite can form in most ocean environments and likely plays a major pan in the control of the phosphate content of seawater. ?? 1984.

  9. In Situ Immobilization of Heavy Metals in Apatite Mineral Formulations

    DTIC Science & Technology

    1995-04-01

    radionuclides. In the Milestone One Report, we reported the characteristics of various lead- contaminated soils, phosphate-containing materials, and... characteristics of apatite slurries. Several candidate emplacement strategies, their applicability, and their advantages and disadvantages are also... characteristics of apatite slurries. Several candidate emplacement strategies are explained, including injection, auguring, horizontal drilling

  10. Ab-initio study of hexagonal apatites

    NASA Astrophysics Data System (ADS)

    Calderin, Lazaro; Stott, Malcom J.

    2001-03-01

    A silicon stabilized mixture of calcium phosphate phases has been recognized as playing an important role in actively resorbable coatings and in ceramics as bone materials. The nature of this material is being investigated using a variety of techniques including a combination of crystallographic analysis of measured x-ray diffraction spectra, and ab initio quantum mechanics simulations. We have used all-electron, density functional based calculations to investigate a group of hexagonal apatites. The fully relaxed crystallographic structures of hydroxyapatite, and related apatites have been obtained. We will present the results and discuss the nature of the bonding in these materials. The x-ray diffraction pattern and the infra-red spectra have also been obtained and will be compared with experiment. Acknowledgments:This work is part of a collaboration with the Applied Ceramics group of M.Sayer, and with Millenium Biologix Inc. Support of the NSERC of Canada through the award of a Co-operative R & D grant to the collaboration is acknowledged.

  11. Preparation and Evaluation of Two Apatites with Spherical Nanocrystal Morphology.

    PubMed

    Zhang, Yali; Li, Qihong; Li, Xiaojie; Li, Yong; Wang, Chunhui; Zhao, Yantao; Song, Yingliang; Liu, Yanpu

    2016-03-01

    Spherical nanocrystal of apatite has been proved to be beneficial for osteoblast growth. Two apatites with spherical nanocrystal morphology were prepared in this study by chemical wet method and further sintering process. SEM exhibited that both apatites had spherical nanocrystal morphology. The crystal morphology and size was approaching to each other. XRD showed the apatites separately were hydroxyapatite and tricalcium phosphate phases. The cellular biocompatibility was evaluated by osteoblasts for these two spherical nanocrstal apatites. The MTT result indicated a higher cell proliferation rate for spherical tricalcium phosphate group. The ALP activity assay also strongly favored the tricalcium phosphate group. RT-PCR results indicated that Collagen I had a higher transcription level on the spherical tricalcium phosphate group. SEM results showed robust cell growth on the materials. It was concluded that the spherical nanophase tricalcium phosphate was superior to the cellular biocompatibility of spherical nanophase hydroxyapatite and the results were helpful in the manufacture of more suitable tissue engineering scaffolds.

  12. Strongly bound citrate stabilizes the apatite nanocrystals in bone

    SciTech Connect

    Hu, Y.-Y.; Rawal, A.; Schmidt-Rohr, K.

    2010-10-12

    Nanocrystals of apatitic calcium phosphate impart the organic-inorganic nanocomposite in bone with favorable mechanical properties. So far, the factors preventing crystal growth beyond the favorable thickness of ca. 3 nm have not been identified. Here we show that the apatite surfaces are studded with strongly bound citrate molecules, whose signals have been identified unambiguously by multinuclear magnetic resonance (NMR) analysis. NMR reveals that bound citrate accounts for 5.5 wt% of the organic matter in bone and covers apatite at a density of about 1 molecule per (2 nm){sup 2}, with its three carboxylate groups at distances of 0.3 to 0.45 nm from the apatite surface. Bound citrate is highly conserved, being found in fish, avian, and mammalian bone, which indicates its critical role in interfering with crystal thickening and stabilizing the apatite nanocrystals in bone

  13. Apatite as a Tool for Tracking Magmatic CO2 Contents

    NASA Astrophysics Data System (ADS)

    Riker, J.; Humphreys, M.; Brooker, R. A.

    2014-12-01

    CO2 plays a fundamental role in the evolution of magmatic and volcanic systems, but its low solubility in silicate melts means that direct records of magmatic CO2 concentrations remain elusive. The phosphate mineral apatite is unique among igneous minerals in its capacity to accommodate all major magmatic volatiles (H2O, F, Cl, CO2 and S). Although interest in apatite as a tool for tracking magmatic volatile contents (namely H2O, F, and Cl) has increased in recent years, its potential as a record of magmatic CO2contents remains untapped. We present the results of high-temperature, high-pressure experiments investigating the partitioning behaviour of CO2 between apatite and basaltic melt. Experiments were run in piston cylinder apparatus at 1 GPa and 1250 °C, with a slow initial cooling ramp employed to facilitate crystal growth. Each charge contained the starting basaltic powder doped with Ca-phosphate and variable proportions of H2O, CO2, and F. Run products are glass-rich charges containing 15-25 vol% large, euhedral apatite crystals (± cpx and minor biotite). Experimental apatites and glasses have been characterised by BSE imaging, electron microprobe, and ion microprobe. Apatites range in composition from near-endmember fluorapatite (3.0 wt% F), to near-endmember hydroxyapatite (1.7 wt% H2O), to carbon-rich apatite containing up to 1.6 wt% CO2. Apatite compositions are stoichiometric if all anions (F-, OH-, and CO32—) lie in the channel site, suggesting an "A-type" substitution under these conditions (i.e. CO32— + [] = 2X—, where X is another channel anion and [] is a vacancy; e.g. Fleet et al. 2004). Importantly, CO2 partitions readily into apatite at all fluid compositions considered here. CO2 is also more compatible in apatite than water at our run conditions, with calculated H2O-CO2 exchange coefficients close to or greater than 1. Our results indicate that when channel ions are primarily occupied by H2O and CO2 (i.e. F- and Cl-poor magmatic systems

  14. Fabrication of hydroxycarbonate apatite coatings with hierarchically porous structures.

    PubMed

    Guo, Yaping; Zhou, Yu; Jia, Dechang

    2008-03-01

    Hierarchically porous hydroxycarbonate apatite is known to have a high bioactivity to regenerate bone, but its application in bone graft substitutes has been restricted due to its poor mechanical properties. This drawback has been addressed by (i) depositing calcium carbonate coatings on Ti6Al4V substrates by electrophoresis; and (ii) converting the coatings to hydroxycarbonate apatite coatings with hierarchically porous structures by treatment with a phosphate buffer solution (PBS). After soaking calcium carbonate coatings in PBS for 1 day, calcium-deficient hydroxycarbonate apatite nanocrystals are deposited on the surfaces of calcium carbonate particles via a dissolution-precipitation reaction. The aggregation of the nanocrystals produces plate-like hydroxycarbonate apatite. Mesopores with a pore size of approximately 3.8nm and macropores or apertures with an aperture size of approximately 1 microm are formed within and among the plates, respectively. After soaking for 9 days, the pore size of mesopores decreases and the mesopores disappear partly due to the crystal growth of hydroxycarbonate apatite. Simulated body fluid immersion tests reveal that the good in vitro bioactivity of hydroxycarbonate apatite coatings is attributed to the calcium deficiencies in apatite lattice and the hierarchically porous structures.

  15. The compressibility of a natural apatite

    NASA Astrophysics Data System (ADS)

    Matsukage, K. N.; Ono, S.; Kawamoto, T.; Kikegawa, T.

    2004-12-01

    In-situ synchrotron X-ray diffraction (XRD) experiments of a natural apatite with the formula of Ca5(PO4)3F0.94Cl0.06 were carried out using a diamond anvil cell and angle-dispersive technique at Photon Factory (PF), Japan. Pressure volume data were collected up to 7.12 GPa at 300 K. The pressures were determined from the ruby fluorescence spectra shift. The unit-cell parameters and volume decreased systematically with increasing pressure, and a reliable isothermal bulk modulus and its pressure derivative were obtained in this study. The third-order Birch Murnaghan equation of state yielded the isothermal bulk modulus of KT=91.5(38) GPa, its pressure derivative KT‧= 4.0(11), and the zero-pressure volume V0=524.2(3) Å3.

  16. UV photofunctionalization promotes nano-biomimetic apatite deposition on titanium

    PubMed Central

    Saita, Makiko; Ikeda, Takayuki; Yamada, Masahiro; Kimoto, Katsuhiko; Lee, Masaichi Chang-Il; Ogawa, Takahiro

    2016-01-01

    Background Although biomimetic apatite coating is a promising way to provide titanium with osteoconductivity, the efficiency and quality of deposition is often poor. Most titanium implants have microscale surface morphology, and an addition of nanoscale features while preserving the micromorphology may provide further biological benefit. Here, we examined the effect of ultraviolet (UV) light treatment of titanium, or photofunctionalization, on the efficacy of biomimetic apatite deposition on titanium and its biological capability. Methods and results Micro-roughed titanium disks were prepared by acid-etching with sulfuric acid. Micro-roughened disks with or without photofunctionalization (20-minute exposure to UV light) were immersed in simulated body fluid (SBF) for 1 or 5 days. Photofunctionalized titanium disks were superhydrophilic and did not form surface air bubbles when immersed in SBF, whereas non-photofunctionalized disks were hydrophobic and largely covered with air bubbles during immersion. An apatite-related signal was observed by X-ray diffraction on photofunctionalized titanium after 1 day of SBF immersion, which was equivalent to the one observed after 5 days of immersion of control titanium. Scanning electron microscopy revealed nodular apatite deposition in the valleys and at the inclines of micro-roughened structures without affecting the existing micro-configuration. Micro-roughened titanium and apatite-deposited titanium surfaces had similar roughness values. The attachment, spreading, settling, proliferation, and alkaline phosphate activity of bone marrow-derived osteoblasts were promoted on apatite-coated titanium with photofunctionalization. Conclusion UV-photofunctionalization of titanium enabled faster deposition of nanoscale biomimetic apatite, resulting in the improved biological capability compared to the similarly prepared apatite-deposited titanium without photofunctionalization. Photofunctionalization-assisted biomimetic apatite

  17. Properties of heterogeneous apatites containing magnesium, fluoride, and carbonate.

    PubMed

    Okazaki, M; LeGeros, R Z

    1996-11-01

    Biological apatites present in the mineral phases of normal and pathological calcifications contain magnesium, Mg, and carbonate, CO3. As a consequence of fluctuations in the composition of the micro-environment, these apatites may sometimes form by heterogeneous precipitation. The purpose of this study was to investigate the properties of (Mg, CO3)-apatites formed heterogeneously in the presence of fluoride, F. Two types of fluoridated (Mg, CO3)-apatites formed from solutions with low and high levels of Mg were prepared at 80 degrees C, pH 7.4. We prepared FMgCO3-MgCO3AP (Type 1) by adding the F-containing solution to those containing calcium, Mg, and phosphate ions during the first half of the precipitation period. We prepared MgCO3-FMgCO3Ap (Type 2) by adding the F-containing solution during the final half of the period. The apatites were analyzed by x-ray diffraction (XRD), infrared absorption spectroscopy, and scanning electron microscopy (SEM). SEM and XRD analyses showed evidence of mixed crystals in the heterogeneous apatites. The presence of Mg inhibits, while F promotes, apatite crystal growth. In addition, Mg incorporation increased with increasing fluoride concentration. The extent of dissolution in acid buffer of both types of heterogeneous apatites increased with Mg: Type 1 > Type 2. These results suggest that the crystal and dissolution properties of heterogeneous fluoridated (Mg, CO3)-apatites are greatly affected by the mode of F incorporation and Mg concentrations in the environment.

  18. Electron Microprobe Analysis Techniques for Accurate Measurements of Apatite

    NASA Astrophysics Data System (ADS)

    Goldoff, B. A.; Webster, J. D.; Harlov, D. E.

    2010-12-01

    Apatite [Ca5(PO4)3(F, Cl, OH)] is a ubiquitous accessory mineral in igneous, metamorphic, and sedimentary rocks. The mineral contains halogens and hydroxyl ions, which can provide important constraints on fugacities of volatile components in fluids and other phases in igneous and metamorphic environments in which apatite has equilibrated. Accurate measurements of these components in apatite are therefore necessary. Analyzing apatite by electron microprobe (EMPA), which is a commonly used geochemical analytical technique, has often been found to be problematic and previous studies have identified sources of error. For example, Stormer et al. (1993) demonstrated that the orientation of an apatite grain relative to the incident electron beam could significantly affect the concentration results. In this study, a variety of alternative EMPA operating conditions for apatite analysis were investigated: a range of electron beam settings, count times, crystal grain orientations, and calibration standards were tested. Twenty synthetic anhydrous apatite samples that span the fluorapatite-chlorapatite solid solution series, and whose halogen concentrations were determined by wet chemistry, were analyzed. Accurate measurements of these samples were obtained with many EMPA techniques. One effective method includes setting a static electron beam to 10-15nA, 15kV, and 10 microns in diameter. Additionally, the apatite sample is oriented with the crystal’s c-axis parallel to the slide surface and the count times are moderate. Importantly, the F and Cl EMPA concentrations are in extremely good agreement with the wet-chemical data. We also present EMPA operating conditions and techniques that are problematic and should be avoided. J.C. Stormer, Jr. et al., Am. Mineral. 78 (1993) 641-648.

  19. EPR properties of synthetic apatites, deorganified dentine, and enamel.

    PubMed

    Kenner, G H; Haskell, E H; Hayes, R B; Baig, A; Higuchi, W I

    1998-05-01

    Electron paramagnetic resonance spectroscopy (EPR) was used to study synthetic hydroxyapatite and approximately 1, 2, and 6% synthetic carbonated apatites, deorganified dentine, and enamel. The carbonated apatites were synthesized by hydrolysis of dicalcium phosphate. Comparisons were made with spectra from enamel and deorganified dentine. Microwave power saturation and dose responses were determined for the synthetic materials. The Marquardt version of the Levenberg decomposition method was used to extract individual signals from the apatite data. Two samples of dentine were irradiated with 25 and 100 Gy, respectively, from a 60Co source. The first sample was then deorganified at 200 degreesC using the Soxhlet extraction technique. A third sample was irradiated with 100 Gy after deorganification. The resulting EPR spectra were then compared. It was determined that the dosimetric signal of 2% synthetic carbonated apatite was approximately the same as that of enamel. It was also verified that the dosimetric signal saturates at about 2% in synthetic carbonated apatites. The study established that the precenters responsible for the dosimetric signal (g perpendicular = 2.0018, g parallel = 1.9985) are preferentially concentrated in the surface-accessible region of the mineral component, as shown by the approximately 80% attenuation of the dosimetric signal in dentine following deorganification. The precenters responsible are not destroyed by the deorganification since the magnitude of the dosimetric signal from the dentine specimen irradiated following deorganification was approximately twice that of the comparable untreated, irradiated sample. Finally, the dose response of 2 and 6% synthetic carbonated apatites was determined.

  20. Insight into Biological Apatite: Physiochemical Properties and Preparation Approaches

    PubMed Central

    Liu, Quan; Matinlinna, Jukka Pekka; Chen, Zhuofan; Pan, Haobo

    2013-01-01

    Biological apatite is an inorganic calcium phosphate salt in apatite form and nano size with a biological derivation. It is also the main inorganic component of biological hard tissues such as bones and teeth of vertebrates. Consequently, biological apatite has a wide application in dentistry and orthopedics by using as dental fillers and bone substitutes for bone reconstruction and regeneration. Given this, it is of great significance to obtain a comprehensive understanding of its physiochemical and biological properties. However, upon the previous studies, inconsistent and inadequate data of such basic properties as the morphology, crystal size, chemical compositions, and solubility of biological apatite were reported. This may be ascribed to the differences in the source of raw materials that biological apatite are made from, as well as the effect of the preparation approaches. Hence, this paper is to provide some insights rather than a thorough review of the physiochemical properties as well as the advantages and drawbacks of various preparation methods of biological apatite. PMID:24078928

  1. Modeling biominerals formed by apatites and DNA.

    PubMed

    Revilla-López, Guillermo; Casanovas, Jordi; Bertran, Oscar; Turon, Pau; Puiggalí, Jordi; Alemán, Carlos

    2013-12-01

    Different aspects of biominerals formed by apatite and DNA have been investigated using computer modeling tools. Firstly, the structure and stability of biominerals in which DNA molecules are embedded into hydroxyapatite and fluoroapatite nanopores have been examined by combining different molecular mechanics methods. After this, the early processes in the nucleation of hydroxyapatite at a DNA template have been investigated using molecular dynamics simulations. Results indicate that duplexes of DNA adopting a B double helix can be encapsulated inside nanopores of hydroxyapatite without undergoing significant distortions in the inter-strand hydrogen bonds and the intra-strand stacking. This ability of hydroxyapatite is practically independent of the DNA sequence, which has been attributed to the stabilizing role of the interactions between the calcium atoms of the mineral and the phosphate groups of the biomolecule. In contrast, the fluorine atoms of fluoroapatite induce pronounced structural distortions in the double helix when embedded in a pore of the same dimensions, resulting in the loss of its most relevant characteristics. On the other hand, molecular dynamics simulations have allowed us to observe the formation of calcium phosphate clusters at the surface of the B-DNA template. Electrostatic interactions between the phosphate groups of DNA and Ca(2+) have been found to essential for the formation of stable ion complexes, which were the starting point of calcium phosphate clusters by incorporating PO3(4) from the solution.

  2. Apatite mineralization in elasmobranch skeletons via a polyphosphate intermediate

    NASA Astrophysics Data System (ADS)

    Omelon, Sidney; Lacroix, Nicolas; Lildhar, Levannia; Variola, Fabio; Dean, Mason

    2014-05-01

    All vertebrate skeletons are stiffened with apatite, a calcium phosphate mineral. Control of apatite mineralization is essential to the growth and repair of the biology of these skeletons, ensuring that apatite is deposited in the correct tissue location at the desired time. The mechanism of this biochemical control remains debated, but must involve increasing the localized apatite saturation state. It was theorized in 1923 that alkaline phosphatase (ALP) activity provides this control mechanism by increasing the inorganic phosphate (Pi) concentration via dephosphorylation of phosphorylated molecules. The ALP substrate for biological apatite is not known. We propose that polyphosphates (polyPs) produced by mitochondria may be the substrate for biological apatite formation by ALP activity. PolyPs (PO3-)n, also known as condensed phosphates, represent a concentrated, bioavailable Pi-storage strategy. Mitochondria import Pi and synthesize phosphate polymers through an unknown biochemical mechanism. When chelated with calcium and/or other cations, the effective P-concentration of these neutrally charged, amorphous, polyP species can be very high (~ 0.5 M), without inducing phosphate mineral crystallization. This P-concentration in the low Pi-concentration biological environment offers a method of concentrating P well above an apatite supersaturation required for nucleation. Bone is the most studied mineralized skeletal tissue. However, locating and analyzing active mineralizing areas is challenging. We studied calcified cartilage skeletons of elasmobranch fishes (sharks, stingrays and relatives) to analyse the phosphate chemistry in this continually mineralizing skeleton. Although the majority of the elasmobranch skeleton is unmineralized cartilage, it is wrapped in an outer layer of mineralized tissue comprised of small tiles called tesserae. These calcified tesserae continually grow through the formation of new mineral on their borders. Co-localization of ALP and

  3. Apatite at Olympic Dam, South Australia: A petrogenetic tool

    NASA Astrophysics Data System (ADS)

    Krneta, Sasha; Ciobanu, Cristiana L.; Cook, Nigel J.; Ehrig, Kathy; Kontonikas-Charos, Alkis

    2016-10-01

    The > 10,000 million tonne Olympic Dam Cu-Au-U-Ag deposit, (eastern Gawler Craton, South Australia) is one of the largest orebodies in the World. The deposit is hosted within the Olympic Dam Breccia Complex, placed at the centre of, and resulting from multiple brecciation and Fe-metasomatism of the Roxby Downs Granite (RDG). The latter is part of a larger batholith emplaced at 1.6 Ga. Apatite petrography and chemistry were studied in non-mineralised RDG and coeval granitoids and dolerites, as well as in mineralised RDG from deep (> 2 km) and distal (2.7 km to NE) locations. In both latter cases, although the mineralisation corresponds to the same, early chalcopyrite-pyrite-magnetite ± hematite stage identified in the outer and deeper zones of the deposit itself, the character of granite alteration differs: sericite-chlorite alteration with all feldspar replaced in the deep location; and red-stained K-feldspar on top of prevailing albitization in the distal location. Close-to end-member fluorapatite is a key accessory mineral in all igneous rocks and a common product of early hydrothermal alteration within mineralised granite. Variations in habit, morphology and textures correlate with chemical trends expressed as evolving Cl/F ratios, and concentrations of REE + Y (hereafter REY), Sr, Mn, S, Si and Na. Magmatic apatite is unzoned in the dolerite but features core to REY-enriched rim zonation in the granitoids. Increases in Cl- and Sr-contents correlate with rock basicity. Calculation of Cl in the vapour phase relative to melt at the apatite saturation temperature for zoned apatite in the RDG shows higher values for grains with inclusion-rich cores associated with mafic enclaves, concordant with assimilation of exotic material during magma crystallisation. Hydrothermal alteration of magmatic apatite is most varied in the dolerite where interaction with fluids is expressed as subtle changes in Cl- versus F- and REY-enrichment, and most importantly, S-enrichment in

  4. Transformation of apatite phosphorus and non-apatite inorganic phosphorus during incineration of sewage sludge.

    PubMed

    Li, Rundong; Zhang, Ziheng; Li, Yanlong; Teng, Wenchao; Wang, Weiyun; Yang, Tianhua

    2015-12-01

    The recovery of phosphorus from incinerated sewage sludge ash (SSA) is assumed to be economical. Transformation from non-apatite inorganic phosphorus (NAIP) to apatite phosphorus (AP), which has a higher bioavailability and more extensive industrial applications, was studied at 750-950°C by sewage sludge incineration and model compound incineration with a calcium oxide (CaO) additive. Thermogravimetric differential scanning calorimetry analysis and X-ray diffraction measurements were used to analyze the reactions between NAIP with CaO and crystallized phases in SSA. High temperatures stimulated the volatilization of NAIP instead of AP. Sewage sludge incineration with CaO transformed NAIP into AP, and the percentage of AP from the total phosphorus reached 99% at 950°C. Aluminum phosphate reacted with CaO, forming Ca2P2O7 and Ca3(PO4)2 at 750-950°C. Reactions between iron phosphate and CaO occurred at lower temperatures, forming Ca(PO3)2 before reaching 850°C.

  5. Interaction between a bisphosphonate, tiludronate, and biomimetic nanocrystalline apatites.

    PubMed

    Pascaud, Patricia; Gras, Pierre; Coppel, Yannick; Rey, Christian; Sarda, Stéphanie

    2013-02-19

    Bisphosphonates (BPs) are well established as successful antiresorptive agents for the prevention and treatment of bone diseases such as osteoporosis and Paget's disease. The aim of this work was to clarify the reaction mechanisms between a BP molecule, tiludronate, and the nanocrystalline apatite surface. The adsorption of tiludronate on well-characterized synthetic biomimetic nanocrystalline apatites with homogeneous but different compositions and surface characteristics was investigated to determine the effect of the nanocrystalline apatite substrate on the adsorption behavior. The results show that the adsorption of tiludronate on nanocrystalline biomimetic apatite surfaces varies over a large range. The most immature apatitic samples exhibited the highest affinity and the greatest amount adsorbed at saturation. Maturation of the nanocrystals induces a decrease of these values. The amount of phosphate ion released per adsorbed BP molecule varied, depending on the nanocrystalline substrate considered. The adsorption mechanism, although associated with a release of phosphate ions, cannot be considered as a simple ion exchange process involving one or two phosphate ions on the surface. A two-step process is proposed consisting of a surface binding of BP groups to calcium ions associated with a proton release inducing the protonation of surface orthophosphate ions and their eventual solubilization.

  6. The Perils of Electron Microprobe Analysis of Apatite

    NASA Astrophysics Data System (ADS)

    Henderson, C. E.; Essene, E. J.; Wang, K. L.; Zhang, Y.

    2010-12-01

    Accurate electron microprobe analysis of apatite is problematic, especially for F and Cl, whose concentrations are essential in calculating a non-analyzable OH component. The issues include beam-induced sample damage and temporal variation of F and Cl X-rays; both effects are mainly dependent on beam current, beam spot size and apatite orientation [1]. To establish a rigorous analytical procedure, several oriented apatite samples, including the well-known Durango and Wilberforce fluorapatites, were analyzed for a large suite of elements, including oxygen. Careful X-ray spectroscopy was performed, including selection of appropriate analytical standards, background measurement positions and comparison of area peak factors. Polarized infrared spectra on oriented apatite samples were also collected for complementary information. The results show that when apatite samples are oriented with the c-axis parallel to the electron beam, there is significant nonlinear variation (an increase or decrease, depending on measurement conditions) of F and Cl X-ray intensities during analyses, and systematically higher-than-expected F apparent concentrations, despite the careful selection of electron beam conditions from a series of X-ray time scans and zero-time count rate extrapolation. On the other hand, when the electron beam is oriented perpendicular to the c-axis, with a ≤ 15 nA beam current and a ≥ 5 µm diameter defocused beam, F and Cl X-ray intensities do not vary or vary slowly and predictably with time, yielding quantitative analysis results for the Durango and Wilberforce apatites (both containing little OH) which are in good agreement with published wet chemical analyses. Furthermore, the OH and CO2 contents inferred for three other analyzed apatite samples are roughly consistent with infrared analyses. For example, for an apatite from Silver Crater Mine in Ontario, significant deficiency in the P site, as well as extra F, was inferred from microprobe analyses

  7. Formation of an ascorbate-apatite composite layer on titanium.

    PubMed

    Ito, Atsuo; Sogo, Yu; Ebihara, Yuko; Onoguchi, Masahiro; Oyane, Ayako; Ichinose, Noboru

    2007-09-01

    An ascorbate-apatite composite layer was successfully formed on NaOH- and heat-treated titanium by coprecipitating L-ascorbic acid phosphate and low-crystalline apatite in a supersaturated calcium phosphate solution at 37 degrees C for 48 h. The supersaturated calcium phosphate solutions used have chemical compositions attainable by mixing infusion fluids officially approved for clinical use. The amount of immobilized L-ascorbic acid phosphate ranged from 1.0 to 2.3 microg mm(-2), which is most likely to be sufficient for the in vitro osteogenic differentiation of mesenchymal stem cells on titanium. Since ascorbate is important for the collagen synthesis and subsequent osteogenesis of mesenchymal stem cells, titanium coated with the ascorbate-apatite composite layer would be useful as a scaffold in bone tissue engineering and as a bone substitute.

  8. Tetracycline-loaded biomimetic apatite: an adsorption study.

    PubMed

    Cazalbou, Sophie; Bertrand, Ghislaine; Drouet, Christophe

    2015-02-19

    Biomimetic apatites are appealing compounds for the elaboration of bioactive bone-repair scaffolds due to their intrinsic similarity to bone mineral. Bone surgeries are however often heavy procedures, and the infiltration of pathogens may not be totally avoided. To prevent their development, systemic antibiotic prophylaxis is widespread but does not specifically target surgical sites and involves doses not always optimized. A relevant alternative is a preliminary functionalization by an infection-fighting agent. In this work, we investigated from a physicochemical viewpoint the association of a wide-spectrum antibiotic, tetracycline (TC), and a biomimetic nanocrystalline apatite previously characterized. TC adsorption kinetics and isotherm were thoroughly explored. Kinetic data were fitted to various models (pseudo-first-order, pseudo-second-order, general kinetic model of order n, Elovich, double-exponential, and purely diffusive models). The best fit was found for a double-exponential kinetic model or with a decimal reaction order of 1.4, highlighting a complex process with such TC molecules which do not expose high-affinity end groups for the surface of apatite. The adsorption isotherm was perfectly fitted to the Sips (Langmuir-Freundlich) model, while other models failed to describe it, and the Sips exponent greater than unity (1.08) suggested a joint impact of surface heterogeneity and positive cooperativity between adsorbed molecules. Finally, preliminary insights on TC release from pelletized nanocrystalline apatite, in aqueous medium and neutral pH, were obtained using a recirculation cell, indicating a release profile mainly following a Higuchi-like diffusion-limited rate. This work is intended to shed more light on the interaction between polar molecules not exhibiting high-affinity end groups and biomimetic apatites and is a starting point in view of the elaboration of biomimetic apatite-based bone scaffolds functionalized with polar organic drugs for a

  9. Apatite: A new redox proxy for silicic magmas?

    NASA Astrophysics Data System (ADS)

    Miles, A. J.; Graham, C. M.; Hawkesworth, C. J.; Gillespie, M. R.; Hinton, R. W.; Bromiley, G. D.

    2014-05-01

    The oxidation states of magmas provide valuable information about the release and speciation of volatile elements during volcanic eruptions, metallogenesis, source rock compositions, open system magmatic processes, tectonic settings and potentially titanium (Ti) activity in chemical systems used for Ti-dependent geothermometers and geobarometers. In this paper we explore the use of Mn in apatite as an oxybarometer in intermediate and silicic igneous rocks. Increased Mn concentrations in apatite in granitic rocks from the zoned Criffell granitic pluton (southern Scotland) correlate with decreasing Fe2O3 (Fe3+) and Mn in the whole-rock and likely reflect increased Mn2+/Mn3+ and greater compatibility of Mn2+ relative to Mn3+ in apatite under reduced conditions. Fe3+/Fe2+ ratios in biotites have previously been used to calculate oxygen fugacities (fO2) in the outer zone granodiorites and inner zone granites where redox conditions have been shown to change from close to the magnetite-hematite buffer to close to the nickel-nickel oxide buffer respectively (Stephens et al., 1985). This trend is apparent in apatite Mn concentrations from a range of intermediate to silicic volcanic rocks that exhibit varying redox states and are shown to vary linearly and negatively with log fO2, such that logfO=-0.0022(±0.0003)Mn(ppm)-9.75(±0.46) Variations in the Mn concentration of apatites appear to be largely independent of differences in the Mn concentration of the melt. Apatite Mn concentrations may therefore provide an independent oxybarometer that is amenable to experimental calibration, with major relevance to studies on detrital mineral suites, particularly those containing a record of early Earth redox conditions, and on the climatic impact of historic volcanic eruptions.

  10. Characterization, physicochemical properties and biocompatibility of La-incorporated apatites.

    PubMed

    Guo, D G; Wang, A H; Han, Y; Xu, K W

    2009-11-01

    In this study, the physicochemical properties and biocompatibilities of La-containing apatites were intensively investigated together with their characterizations in terms of composition, structure, valent state and morphology using X-ray diffraction, Fourier-transform infrared spectra, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy, respectively. The results indicate that the La(3+) ion can be incorporated into the crystal lattice of hydroxyapatite resulting in the production of La-incorporated apatites (La(x)Ca(10-x)(PO(4))(6)(OH)(2+x-2y)O(y square y-x) (x> or =0.5, y<1+x/2) or La(x)Ca(10-x)(PO(4))(6)O(y square y-x) (0.5apatites. In contrast to La-free apatite, La-incorporated apatites possess a series of attractive properties, including higher thermal stability, higher flexural strength, lower dissolution rate, larger alkaline phosphatase activity, preferable osteoblast morphology and comparable cytotoxicity. In particular, the sintered La-incorporated apatite block achieves a maximal flexure strength of 66.69+/-0.98 MPa at 5% La content (confidence coefficient 0.95), increased 320% in comparison with the La-free apatite. The present study suggests that the La-incorporated apatite possesses application potential in developing a new type of bioactive coating material for metal implants and also as a promising La carrier for further exploring the beneficial functions of La in the human body.

  11. Composition dependent thermal annealing behaviour of ion tracks in apatite

    NASA Astrophysics Data System (ADS)

    Nadzri, A.; Schauries, D.; Mota-Santiago, P.; Muradoglu, S.; Trautmann, C.; Gleadow, A. J. W.; Hawley, A.; Kluth, P.

    2016-07-01

    Natural apatite samples with different F/Cl content from a variety of geological locations (Durango, Mexico; Mud Tank, Australia; and Snarum, Norway) were irradiated with swift heavy ions to simulate fission tracks. The annealing kinetics of the resulting ion tracks was investigated using synchrotron-based small-angle X-ray scattering (SAXS) combined with ex situ annealing. The activation energies for track recrystallization were extracted and consistent with previous studies using track-etching, tracks in the chlorine-rich Snarum apatite are more resistant to annealing than in the other compositions.

  12. Calibration for Infrared Measurements of OH in Apatite

    NASA Astrophysics Data System (ADS)

    Wang, K. L.; Naab, F.; Zhang, Y.

    2010-12-01

    Apatite is a common accessory mineral, and OH in apatite can indicate the fluid conditions of crystal formation. Previously, water (OH) concentration in apatite has often been estimated through electron microprobe analyses combined with mineral stoichiometry. However, the detection limit, precision, and accuracy of this method are not high. In this work, we calibrated the infrared spectroscopy (IR) method for measurement of OH concentration in apatite by using elastic recoil detection (ERD) analysis to obtain the absolute OH concentration. Large apatite wafers were cut perpendicular to the c-axis of each crystal and doubly polished. ERD measurements were carried out in the Michigan Ion Beam Laboratory at the University of Michigan to determine the hydrogen concentration in each sample. Each ERD spectrum was fitted and a hydrogen standard was used to quantify the hydrogen concentrations. Polarized transmission IR was used on apatite sections that were cut parallel to the c-axis, and doubly polished. IR measurements were made for E-vector parallel to the c-axis. Because the OH peak is intense, very thin samples must be used to avoid absorbance saturation; the thinnest sample (corresponding to the highest OH content) used was 17 µm thick. Four different apatite crystals were successfully analyzed using both the IR and ERD methods. Two were from Durango, Mexico; one from Imilchil, High Atlas Mountains, Morocco; and one from an unknown locality, purchased online from gem dealers. The OH peak near 3550 cm-1 was a relatively simple peak in all four samples. Therefore peak height was used for the absorbance value, A. Using the Beer-Lambert Law, a calibration line was established (R2= 0.95, for IR aperture of 50 µm x 50 µm) where the weight % of H2O is 0.013 times A/d, where d is the thickness in mm. The detection limit of H2O concentration in apatite by IR approaches ppm level for 0.1 mm wafers, the precision is better than 1% relative (depending on H2O content), and

  13. Carbon and oxygen isotopes in apatite CO/sub 2/ and co-existing calcite

    SciTech Connect

    Kolodny, Y.; Kaplan, I. R.

    1981-04-01

    Carbon and oxygen isotopes were analyzed in carbonate apatite CO/sub 2/ and in co-existing calcite. Both C and O in apatite CO/sub 2/ are enriched in the respective light isotopes relative to calcite. These results confirm the proposition that carbonate is part of the apatite structure.

  14. Inverted Apatite (U-Th)/He and Fission-track Dates from the Rae craton, Baffin Island, Canada and Implications for Apatite Radiation Damage-He Diffusivity Models

    NASA Astrophysics Data System (ADS)

    Ault, A. K.; Reiners, P. W.; Thomson, S. N.; Miller, G. H.

    2015-12-01

    Coupled apatite (U-Th)/He and fission-track (AFT) thermochronology data from the same sample can be used to decipher complex low temperature thermal histories and evaluate compatibility between these two methods. Existing apatite He damage-diffusivity models parameterize radiation damage annealing as fission-track annealing and yield inverted apatite He and AFT dates for samples with prolonged residence in the He partial retention zone. Apatite chemistry also impacts radiation damage and fission-track annealing, temperature sensitivity, and dates in both systems. We present inverted apatite He and AFT dates from the Rae craton, Baffin Island, Canada, that cannot be explained by apatite chemistry or existing damage-diffusivity and fission track models. Apatite He dates from 34 individual analyses from 6 samples range from 237 ± 44 Ma to 511 ± 25 Ma and collectively define a positive date-eU relationship. AFT dates from these same samples are 238 ± 15 Ma to 350 ± 20 Ma. These dates and associated track length data are inversely correlated and define the left segment of a boomerang diagram. Three of the six samples with 20-90 ppm eU apatite grains yield apatite He and AFT dates inverted by 300 million years. These samples have average apatite Cl chemistry of ≤0.02 wt.%, with no correlation between Cl content and Dpar. Thermal history simulations using geologic constraints, an apatite He radiation damage accumulation and annealing model, apatite He dates with the range of eU values, and AFT date and track length data, do not yield any viable time-temperature paths. Apatite He and AFT data modeled separately predict thermal histories with Paleozoic-Mesozoic peaks reheating temperatures differing by ≥15 °C. By modifying the parameter controlling damage annealing (Rmr0) from the canonical 0.83 to 0.5-0.6, forward models reproduce the apatite He date-eU correlation and AFT dates with a common thermal history. Results imply apatite radiation damage anneals at

  15. Biomimetic nanocrystalline apatites: Emerging perspectives in cancer diagnosis and treatment.

    PubMed

    Al-Kattan, Ahmed; Girod-Fullana, Sophie; Charvillat, Cédric; Ternet-Fontebasso, Hélène; Dufour, Pascal; Dexpert-Ghys, Jeannette; Santran, Véronique; Bordère, Julie; Pipy, Bernard; Bernad, José; Drouet, Christophe

    2012-02-14

    Nanocrystalline calcium phosphate apatites constitute the mineral part of hard tissues, and the synthesis of biomimetic analogs is now well-mastered at the lab-scale. Recent advances in the fine physico-chemical characterization of these phases enable one to envision original applications in the medical field along with a better understanding of the underlying chemistry and related pharmacological features. In this contribution, we specifically focused on applications of biomimetic apatites in the field of cancer diagnosis or treatment. We first report on the production and first biological evaluations (cytotoxicity, pro-inflammatory potential, internalization by ZR-75-1 breast cancer cells) of individualized luminescent nanoparticles based on Eu-doped apatites, eventually associated with folic acid, for medical imaging purposes. We then detail, in a first approach, the preparation of tridimensional constructs associating nanocrystalline apatite aqueous gels and drug-loaded pectin microspheres. Sustained releases of a fluorescein analog (erythrosin) used as model molecule were obtained over 7 days, in comparison with the ceramic or microsphere reference compounds. Such systems could constitute original bone-filling materials for in situ delivery of anticancer drugs.

  16. Fabrication of synthetic apatites by solid-state reactions.

    PubMed

    Fazan, F; Shahida, K B N

    2004-05-01

    The paper presents a method of producing synthetic Hydroxyapatite (HA) Ca10(PO4)6(OH)2 and other apatites for biological use by solid-state reaction. The solid-state reaction involves mix-grinding dry powders of beta-tricalcium phosphate powder (TCP) and either calcium hydroxide (Ca(OH)2) or calcium carbonate (CaCO3) or combination thereof, from pure commercial chemicals or derived from natural limestone or from seashells, of total calcium/phosphorus molar ratio between 1.5 to 2.0, to particle size of less than 10 microns, and firing the resultant powder to temperature between 600 degrees C - 1250 degrees C in atmosphere or in controlled atmospheric condition. The resultant apatites formed were characterised using XRD, SEM-EDX and FTIR. The presented reaction process was found to be much simpler compared to conventional methods of producing synthetic apatites since it involves only dry mix-grinding of the reactants before firing at high temperatures based on the required levels of purity. It can also produce synthetic apatites with good reproducibility in a shorter time. Thus the presented method has a great industrial value.

  17. In Situ Immobilization of Heavy Metals in Apatite Mineral Formulations

    DTIC Science & Technology

    1995-09-01

    Metals into Apatites Milestone Five Report September, 1995 119 PTI Environmental Services. 1994. "Bioavailability of Lead." Rai, D., Felmy , A.R. and Moore...crystalline CdCO 3 . Journal of Solution Chemistry, v. 20, p. 1169- 1187. Rai, D., Felmy , A.R. and Szelmeczka, R.W. 1991a. Hydrolysis constants and

  18. Trace Element Abundances in Extraterrestrial Apatite and Merrillite

    NASA Astrophysics Data System (ADS)

    Ward, D.; Bischoff, A.; Roszjar, J.; Berndt, J.; Whitehouse, M. J.

    2016-08-01

    The trace element abundances (Sc, Ti, V, Cr, Mn, Co, As, Rb, Sr, Y, Zr, Nb, Ba, Hf, Ta, Pb, Th, U, as well as the REE) of 133 apatite and 163 merrillite grains from 24 meteorites, covering 9 different classes were analyzed by LA-ICP-MS and SIMS.

  19. Apatite: a new redox proxy for silicic magmas?

    NASA Astrophysics Data System (ADS)

    Miles, Andrew; Graham, Colin; Hawkesworth, Chris; Gillespie, Martin; Bromiley, Geoff; Hinton, Richard

    2015-04-01

    The oxidation states of magmas provide valuable information about the release and speciation of volatile elements during volcanic eruptions, metallogenesis, source rock compositions, open system magmatic processes, tectonic settings and potentially titanium (Ti) activity in chemical systems used for Ti-dependent geothermometers and geobarometers. In this presentation we explore the use of Mn in apatite as an oxybarometer in intermediate and silicic igneous rocks. Increased Mn concentrations in apatite in granitic rocks from the zoned Criffell granitic pluton (southern Scotland) correlate with decreasing Fe2O3 (Fe3+) and Mn in the whole-rock and likely reflect increased Mn2+/Mn3+and greater compatibility of Mn2+ relative to Mn3+ in apatite under reduced conditions. Fe3+/Fe2+ ratios in biotites have previously been used to calculate oxygen fugacities (fO2) in the outer zone granodiorites and inner zone granites where redox conditions have been shown to change from close to the magnetite-hematite buffer to close to the nickel-nickel oxide buffer respectively[1]. This trend is apparent in apatite Mn concentrations from a range of intermediate to silicic volcanic rocks that exhibit varying redox states and are shown to vary linearly and negatively with log fO2, such that logfO2=-0.0022(±0.0003)Mn(ppm)-9.75(±0.46) Variations in the Mn concentration of apatites appear to be largely independent of differences in the Mn concentration of the melt. Apatite Mn concentrations may therefore provide an independent oxybarometer that is amenable to experimental calibration, with major relevance to studies on detrital mineral suites, particularly those containing a record of early Earth redox conditions, and on the climatic impact of historic volcanic eruptions[2]. [1] Stephens, W. E., Whitley, J. E., Thirlwall, M. F. and Halliday, A. N. (1985) The Criffell zoned pluton: correlated behaviour of rare earth element abundances with isotopic systems. Contributions to Mineralogy and

  20. Thermodynamic basis for evolution of apatite in calcified tissues (Invited)

    NASA Astrophysics Data System (ADS)

    Navrotsky, A.; Drouet, C.; Rollin-Martinet, S.; Champion, E.; Grossin, D.

    2013-12-01

    Bone remodeling and tooth enamel maturation are biological processes which alter the physico-chemical features of biominerals with time. However, although the ubiquity of bone remodeling is clear, why is well crystallized bone mineral systematically replaced by immature nanocrystalline inorganic material? In enamel, a clear evolution is also seen from the first mineral formed during the secretory stage to its mature well crystalline form, which then changes little in the adult tooth. This contribution provides the thermodynamic basis underlying these biological processes. We determined the energetics of biomimetic apatites corresponding to an increasing degree of maturation. Our data point out the progressive evolution of the enthalpy (ΔHf°) and free energy (ΔGf°) of formation toward more negative values upon maturation. Entropy contributions to ΔGf° values are small compared to enthalpy contributions. ΔHf° varies from -12058.9 × 12.2 to -12771.0 × 21.4 kJ/mol for maturation times increasing from 20 min to 3 weeks, approaching the value for stoichiometric hydroxyapatite, -13431.0 × 22.7 kJ/mol. Apatite thermodynamic stability increases as its composition moved toward stoichiometry. These findings imply diminishing aqueous solubility of calcium and phosphate ions as well as decreased surface reactivity. Such thermodynamically-driven maturation is favorable for enamel maturation since this biomineral must resist external aggressions such as contact with acids. In contrast, maintaining a metastable highly reactive and soluble form of apatite is essential to the effective participation of bone as a source of calcium and phosphate for homeostasis. Therefore our data strongly suggest that, far from being trivial, the intrinsic thermodynamic properties of apatite represent a critical driving force for continuous bone remodeling, in contrast to current views favoring a purely biologically driven cycle. These thermodynamic data may prove helpful in other domains

  1. Ascorbate-apatite composite and ascorbate-FGF-2-apatite composite layers formed on external fixation rods and their effects on cell activity in vitro.

    PubMed

    Wang, Xiupeng; Ito, Atsuo; Sogo, Yu; Li, Xia; Tsurushima, Hideo; Oyane, Ayako

    2009-09-01

    Ascorbate-apatite and ascorbate-fibroblast growth factor-2 (FGF-2)-apatite composite layers were successfully formed on anodically oxidized Ti rods clinically used for external fixation by a one-step procedure at 25 degrees C, using a metastable supersaturated calcium phosphate solution supplemented with l-ascorbic acid phosphate magnesium salt n-hydrate (AsMg) and FGF-2. The AsMg-apatite and AsMg-FGF-2-apatite composite layers were evaluated in vitro using fibroblastic NIH3T3 and osteoblastic MC3T3-E1 cells. The AsMg-FGF-2-apatite composite layer markedly enhanced the NIH3T3 cell proliferation and procollagen type capital I, Ukrainian gene expression. Without FGF-2, the AsMg-apatite composite layer whose ascorbate content was 3.64+/-1.27microgcm(-2) obviously enhanced osteoblastic proliferation and differentiation. However, the AsMg-FGF-2-apatite composite layers whose FGF-2 contents were from 0.15+/-0.03 to 0.31+/-0.04microgcm(-2) inhibited osteoblastic differentiation in vitro. Thus, the AsMg-FGF-2-apatite composite layer should be precipitated on the surface of external fixators attached to skin and soft tissue. On the other hand, the AsMg-apatite composite layer should be precipitated at the part attached to bone tissue.

  2. Dependence of ion concentration in simulated body fluid on apatite precipitation on titania surface

    NASA Astrophysics Data System (ADS)

    Sakaguchi, Akira; Nakano, Masayuki; Hieda, Junko; Ohtake, Naoto; Akasaka, Hiroki

    2015-08-01

    Titanium and its alloys are used as biomaterials, because of their high biocompatibility. Apatite precipitates on a titania surface in vivo, and living bone and titanium alloy are coupled through the thin apatite layer. The initial precipitation behavior of apatite on titania in simulated body fluid (SBF) solutions was evaluated and the effect of inorganic ions in the SBF was investigated. Measurement using the SPR phenomenon was used to evaluate the initial apatite precipitation. An SBF containing approximately equal ion concentrations to those in blood plasma was added to a titania surface and the SPR profile was obtained, from which the initial apatite precipitation rate was found to be 1.14 nm/h. Furthermore, the relationship between the inorganic concentration and the precipitation rate was determined for SBFs with different Na+ and Ca2+ concentrations. Apatite precipitation did not occur in the SBF with a low Na+ concentration, whereas the initial apatite precipitation rate in the SBF that did not contain Ca2+ was 0.32 nm/h. According to these results, Ca2+ has little effect on the initial apatite precipitation. In the initial reaction of apatite precipitation, sodium titanate is formed by the absorption of Na+. Next, calcium titanate precipitates upon the substitution of Na+ with Ca2+. Finally, Na+, phosphate ions and hydroxyl ions are attracted to the surface and apatite is formed. Thus, the rate-limiting factor in the initial nucleation of apatite is the Na+ concentration.

  3. Biomimetic synthesis and biocompatibility evaluation of carbonated apatites template-mediated by heparin.

    PubMed

    Deng, Yi; Sun, Yuhua; Chen, Xiaofang; Zhu, Peizhi; Wei, Shicheng

    2013-07-01

    Biomimetic synthesis of carbonated apatites with good biocompatibility is a promising strategy for the broadening application of apatites for bone tissue engineering. Most researchers were interested in collagen or gelatin-based templates for synthesis of apatite minerals. Inspired by recent findings about the important role of polysaccharides in bone biomineralization, here we reported that heparin, a mucopolysaccharide, was used to synthesize carbonated apatites in vitro. The results indicated that the Ca/P ratio, carbon content, crystallinity and morphology of the apatites varied depending on the heparin concentration and the initial pH value. The morphology of apatite changed from flake-shaped to needle-shaped, and the degree of crystallinity decreased with the increasing of heparin concentration. Biocompatibility of the apatites was tested by proliferation and alkaline phosphatase activity of MC3T3-E1 cells. The results suggested that carbonated apatites synthesized in the presence of heparin were more favorable to the proliferation and differentiation of MC3T3-E1 cells compared with traditional method. In summary, the heparin concentration and the initial pH value play a key role in the chemical constitution and morphology, as well as biological properties of apatites. These biocompatible nano-apatite crystals hold great potential to be applied as bioactive materials for bone tissue engineering.

  4. Removal of lead by apatite and its stability in the presence of organic acids.

    PubMed

    Katoh, Masahiko; Makimura, Akihiko; Sato, Takeshi

    2016-12-01

    In this study, lead sorption and desorption tests were conducted with apatite and organic acids (i.e. citric, malic, and formic acids) to understand lead removal by apatite in the presence of an organic acid and lead dissolution from the lead- and organic-acid-sorbed apatite by such organic acid exposure. The lead sorption test showed that the amount of lead removed by apatite in the presence of organic acid varied depending on the type of acid used. The molar amounts of calcium dissolved from apatite in the presence and absence of organic acid were exactly the same as those of lead removed even under different pH conditions as well as different organic acid concentrations, indicating that the varying amount of lead removal in the presence of different organic acids resulted from the magnitude of the dissolution of apatite and the precipitation of lead phosphate minerals. The percentages of lead dissolved from the organic-acid-sorbed and non-organic-acid-sorbed apatite by all the organic acid extractions were equal and higher than those by water extraction. In particular, the highest extractions were observed in the non-organic-acid-sorbed apatite by citric and malic acids. These results suggest that to immobilize lead by the use of apatite in the presence of organic acids, much more apatite must be added than in the absence of organic acid, and that measures must be taken to ensure that the immobilized lead is not dissolved.

  5. Situ formation of apatite for sequestering radionuclides and heavy metals

    DOEpatents

    Moore, Robert C.

    2003-07-15

    Methods for in situ formation in soil of a permeable reactive barrier or zone comprising a phosphate precipitate, such as apatite or hydroxyapatite, which is capable of selectively trapping and removing radionuclides and heavy metal contaminants from the soil, while allowing water or other compounds to pass through. A preparation of a phosphate reagent and a chelated calcium reagent is mixed aboveground and injected into the soil. Subsequently, the chelated calcium reagent biodegrades and slowly releases free calcium. The free calcium reacts with the phosphate reagent to form a phosphate precipitate. Under the proper chemical conditions, apatite or hydroxyapatite can form. Radionuclide and heavy metal contaminants, including lead, strontium, lanthanides, and uranium are then selectively sequestered by sorbing them onto the phosphate precipitate. A reducing agent can be added for reduction and selective sequestration of technetium or selenium contaminants.

  6. Synthesis and characterization of strontium-lanthanum apatites

    SciTech Connect

    Boughzala, K.; Salem, E. Ben; Chrifa, A. Ben; Gaudin, E.; Bouzouita, K. . E-mail: khaled.bouzouita@ipeim.rnu.tn

    2007-07-03

    Two series of strontium-lanthanum apatites, Sr{sub 10-x}La {sub x}(PO{sub 4}){sub 6-x}(SiO{sub 4}) {sub x}F{sub 2} and Sr{sub 10-x}La {sub x}(PO{sub 4}){sub 6-x}(SiO{sub 4}) {sub x}O with 0 {<=} x {<=} 6, were synthesized by solid state reaction in the temperature range of 1200-1400 deg. C. The obtained materials were characterized by powder X-ray diffraction, infrared absorption spectroscopy and solid {sup 31}P Nuclear Magnetic Resonance. Pure solid solutions were obtained within a limited range of unsubstituted phosphate and silicate apatites. A variation of the lattice parameters was observed, with an increase of a and a decrease of c parameters, related to the radius of the corresponding substituted ions.

  7. Collagen-apatite nanocomposite membranes for guided bone regeneration.

    PubMed

    Song, Ju-Ha; Kim, Hyoun-Ee; Kim, Hae-Won

    2007-10-01

    Collagen-apatite nanocomposite is regarded as a potential biomaterial because of its composition and structure, which are similar to those of human hard tissues. However, there have been few investigations of its mechanical and biological benefits in direct comparison with a collagen equivalent. Herein, we successfully produced a biomedical membrane made of a nanocomposite, and systemically evaluated the mechanical, chemical, and biological properties of the nanocomposite in comparison with those of pure collagen. The results showed that significant improvements were achieved by the nanocomposite approach, particularly in terms of the mechanical strength and chemical stability. The present findings point to the potential usefulness of the collagen-apatite nanocomposite membrane in the field of guided bone regeneration (GBR).

  8. The biomimetic apatite-cefalotin coatings on modified titanium.

    PubMed

    Kang, Min-Kyung; Lee, Sang-Bae; Moon, Seung-Kyun; Kim, Kwang-Mahn; Kim, Kyoung-Nam

    2012-02-03

    Dental implant failure often occurs due to oral bacterial infection. The aim of this study was to demonstrate that antibiotic efficacy could be enhanced with modified titanium. First, the titanium was modified by anodization and heat-treatment. Then, a biomimetic coating process was completed in two steps. Surface characterization was performed with scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. Release of antibiotic was evaluated by UV/VIS spectrometry, and the antibacterial effect was evaluated on Streptococcus mutans. After the second coating step, we observed a thick homogeneous apatite layer that contained the antibiotic, cefalotin. The titanium formed a rutile phase after the heat treatment, and a carbonated apatite phase appeared after biomimetic coating. We found that the modified titanium increased the loading of cefalotin onto the hydroxyapatite coated surface. The results suggested that modified titanium coated with a cefalotin using biomimetic coating method might be useful for preventing local post-surgical implant infections.

  9. Thermodynamic Mixing Behavior Of F-OH Apatite Crystalline Solutions

    NASA Astrophysics Data System (ADS)

    Hovis, G. L.

    2011-12-01

    It is important to establish a thermodynamic data base for accessory minerals and mineral series that are useful in determining fluid composition during petrologic processes. As a starting point for apatite-system thermodynamics, Hovis and Harlov (2010, American Mineralogist 95, 946-952) reported enthalpies of mixing for a F-Cl apatite series. Harlov synthesized all such crystalline solutions at the GFZ-Potsdam using a slow-cooled molten-flux method. In order to expand thermodynamic characterization of the F-Cl-OH apatite system, a new study has been initiated along the F-OH apatite binary. Synthesis of this new series made use of National Institute of Standards and Technology (NIST) 2910a hydroxylapatite, a standard reference material made at NIST "by solution reaction of calcium hydroxide with phosphoric acid." Synthesis efforts at Lafayette College have been successful in producing fluorapatite through ion exchange between hydroxylapatite 2910a and fluorite. In these experiments, a thin layer of hydroxylapatite powder was placed on a polished CaF2 disc (obtained from a supplier of high-purity crystals for spectroscopy), pressed firmly against the disc, then annealed at 750 °C (1 bar) for three days. Longer annealing times did not produce further change in unit-cell dimensions of the resulting fluorapatite, but it is uncertain at this time whether this procedure produces a pure-F end member (chemical analyses to be performed in the near future). It is clear from the unit-cell dimensions, however, that the newly synthesized apatite contains a high percentage of fluorine, probably greater than 90 mol % F. Intermediate compositions for a F-OH apatite series were made by combining 2910a hydroxylapatite powder with the newly synthesized fluorapatite in various proportions, then conducting chemical homogenization experiments at 750 °C on each mixture. X-ray powder diffraction data indicated that these experiments were successful in producing chemically homogeneous

  10. Partition coefficients of Hf, Zr, and REE between zircon, apatite, and liquid

    USGS Publications Warehouse

    Fujimaki, H.

    1986-01-01

    Concentration ratios of Hf, Zr, and REE between zircon, apatite, and liquid were determined for three igneous compositions: two andesites and a diorite. The concentration ratios of these elements between zircon and corresponding liquid can approximate the partition coefficient. Although the concentration ratios between apatite and andesite groundmass can be considered as partition coefficients, those for the apatite in the diorite may deviate from the partition coefficients. The HREE partition coefficients between zircon and liquid are very large (100 for Er to 500 for Lu), and the Hf partition coefficient is even larger. The REE partition coefficients between apatite and liquid are convex upward, and large (D=10-100), whereas the Hf and Zr partition coefficients are less than 1. The large differences between partition coefficients of Lu and Hf for zircon-liquid and for apatite-liquid are confirmed. These partition coefficients are useful for petrogenetic models involving zircon and apatite. ?? 1986 Springer-Verlag.

  11. [Age and gender changes of apatites from human hard tooth tissues].

    PubMed

    Pikhur, O L; Ryzhak, G A; Iordanishvili, A K; Iankovskiĭ, V V; D'iakonov, M M

    2014-01-01

    Apatites of hard tissues of teeth of persons of different sex and age were studied in detail. It is shown that the crystal structure of apatites depends on changes in the composition of the enamel that happen during a person's life. Limits of the variations of the crystal lattice parameters of the enamel apatites connected with the complicate processes of de- and remineralization have been determined. On the basis of the identified correlations between chemical composition, crystal lattice parameters and age of patients, the complicated interrelated isomorphic replacements occurring in the crystal structure of apatites of hard tooth tissues during aging were analysed.

  12. Molecular functionalization of tantalum oxide surface towards development of apatite growth

    NASA Astrophysics Data System (ADS)

    Aubry, D.; Volcke, C.; Arnould, Ch.; Humbert, C.; Thiry, P. A.; Delhalle, J.; Mekhalif, Z.

    2009-02-01

    We have studied the apatite growth dynamics on tantalum oxide surfaces. This nucleation is obtained via an organosilane intermediate layer between the apatite and the substrate surface. Four organosilane layers (differing by their terminal functionality) were investigated. Their characterization with atomic force microscopy and other techniques such as X-ray photoelectron spectroscopy (XPS) and wetting measurements highlighted the influence of the organosilane terminal groups on the apatite growth rates. Results revealed that apatite is indeed growing faster on phosphate terminal groups than on the three other groups studied (vinyl, hydroxyl and carboxyl).

  13. Lu-Hf and PbSL geochronology of apatites from Proterozoic terranes: A first look at Lu-Hf isotopic closure in metamorphic apatite

    NASA Astrophysics Data System (ADS)

    Barfod, Gry Hoffmann; Krogstad, Eirik Jens; Frei, Robert; Albarède, Francis

    2005-04-01

    The mineral apatite is characterized by elevated and highly variable Lu/Hf ratios that, in some cases, allow for single-crystal dating by the Lu-Hf isotopic system. Apatites from the Adirondack Lowlands and Otter Lake area in the Grenville Province, and from the Black Hills, South Dakota, yield Lu-Hf ages that are consistently older than their respective Pb step leaching ages. Isotopic closure for the Lu-Hf system, therefore, occurs before U-Pb system closure in this mineral. In the Adirondack Lowlands, where H 2O activity was low, Lu-Hf systematics of cm-sized apatite crystals remained undisturbed during upper amphibolite facies metamorphism (˜700 to 675 °C) at 1170-1130 Ma. The relatively old Lu-Hf ages of 1270 and 1230 Ma observed for these apatites correlate with decreasing crystal size. In contrast, apatite from the fluid-rich Otter Lake area and Black Hills yields unrealistically low apparent Lu-Hf closure temperatures, implying that in these apatites, fluids facilitated late exchange. The Lu-Hf ages for the metamorphic apatites were thus controlled either by the prevailing temperature and grain size, or by fluid activity.

  14. Biomimetic apatite coatings--carbonate substitution and preferred growth orientation.

    PubMed

    Müller, Lenka; Conforto, Egle; Caillard, Daniel; Müller, Frank A

    2007-11-01

    Biomimetic apatite coatings were obtained by soaking chemically treated titanium in SBF with different HCO(3)(-) concentration. XRD, FTIR and Raman analyses were used to characterize phase composition and degree of carbonate substitution. The microstructure, elemental composition and preferred alignment of biomimetically precipitated crystallites were characterized by cross-sectional TEM analyses. According to XRD, the phase composition of precipitated coatings on chemically pre-treated titanium after exposure to SBF was identified as hydroxy carbonated apatite (HCA). A preferred c-axis orientation of the deposited crystals can be supposed due to the high relative peak intensities of the (002) diffraction line at 2theta=26 degrees compared to the 100% intensity peak of the (211) plane at 2theta=32 degrees . The crystallite size in direction of the c-axis of HCA decreased from 26 nm in SBF5 with a HCO(3)(-) concentration of 5 mmol/l to 19 nm in SBF27 with a HCO(3)(-) concentration of 27 mmol/l. Cross-sectional TEM analyses revealed that all distances correspond exactly to the hexagonal structure of hydroxyapatite. The HCO(3)(-) content in SBF also influences the composition of precipitated calcium phosphates. Biomimetic apatites were shown to have a general formula of Ca(10-x-y)Mg(y)(HPO(4))(x-z)(CO(3))(z)(PO(4))(6-x)(OH)(2-x-w)(CO(3))(w/2). According to FTIR and Raman analyses, it can be supposed that as long as the HCO(3)(-) concentration in the testing solutions is below 20 mmol/l, only B-type HCA (0

  15. Thermal expansion of solid solutions in apatite binary systems

    SciTech Connect

    Knyazev, Alexander V.; Bulanov, Evgeny N. Korokin, Vitaly Zh.

    2015-01-15

    Graphical abstract: Thermal dependencies of volume thermal expansion parameter for with thermal expansion diagrams for Pb{sub 5}(PO{sub 4}){sub 3}F{sub x}Cl{sub 1−x}. - Highlights: • Solid solutions in three apatitic binary systems were investigated via HT-XRD. • Thermal expansion coefficients of solid solutions in the systems were calculated. • Features of the thermal deformation of the apatites were described. • Termoroentgenography is a sensitive method for the investigation of isomorphism. - Abstract: High-temperature insitu X-ray diffraction was used to investigate isomorphism and the thermal expansion of apatite-structured compounds in three binary systems in the entire temperature range of the existence of its hexagonal modifications. Most of the studied compounds are highly expandable (α{sub l} > 8 × 10{sup 6} (K{sup −1})). In Pb{sub 5}(PO{sub 4}){sub 3}F–Pb{sub 5}(PO{sub 4}){sub 3}Cl system, volume thermal expansion coefficient is independence from the composition at 573 K. In Pb{sub 5}(PO{sub 4}){sub 3}Cl–Pb{sub 5}(VO{sub 4}){sub 3}Cl, the compound with equimolar ratio of substituted atoms has constant volume thermal expansion coefficient in temperature range 298–973 K. Ca{sub 5}(PO{sub 4}){sub 3}Cl–Pb{sub 5}(PO{sub 4}){sub 3}Cl system is characterized by the most thermal sensitive composition, in which there is an equal ratio of isomorphic substituted atoms.

  16. Crystal Chemistry of Th in Apatite: Geochemistry and Environmental Implications

    NASA Astrophysics Data System (ADS)

    Luo, Y.; Rakovan, J.; Elzinga, E.; Pan, Y.; Hughes, J.

    2006-05-01

    Understanding the crystal chemistry of nuclear waste forms is critical to proper evaluation of their potential use and stability. Because of apatite's ability to incorporate rare earth elements and actinides, there is great interest in it as a solid nuclear waste form and an engineered contaminant barrier. However, the crystal chemistry of actinides in the apatite structure is still poorly understood. Through the complementary use of single crystal X-ray diffraction and X-ray absorption spectroscopy, we present here the first direct results on the site occupancy of thorium in apatite structure and the structural distortion created by its substitution. Single crystal X-ray diffraction data were used to refine the structure and site occupancies of a synthetic fluorapatite with approximately 2 wt% Th in the structure. The structure refinements of three separate crystals with R = 0.0167-0.0217 indicate that Th substitutes almost extensively into the Ca2 site. The value of ThCa(2)/ThCa(1), calculated per individual site to account for the different multiplicity of the two Ca sites, is 6.5. X-ray absorption spectroscopy was used to probe the local structure of Th in this synthetic fluorapatite (single crystal form), as well as Th in a natural fluorapatite (powder form) from Mineville, NY with the Th concentration of approximately 2000 ppm. The results from extend X-ray absorption fine structure (EXAFS) also indicate that Th partitions into the Ca2 site and yields Th specific bond distances which are not obtainable from single crystal X-ray diffraction.

  17. Annealing kinetics of latent particle tracks in Durango apatite

    SciTech Connect

    Afra, B.; Rodriguez, M. D.; Giulian, R.; Kluth, P.; Lang, M.; Zhang, J.; Ewing, R. C.; Kirby, N.; Trautmann, C.; Toulemonde, M.

    2011-02-01

    Using synchrotron small-angle x-ray scattering we determine the ''latent'' track morphology and the track annealing kinetics in the Durango apatite. The latter, measured during ex situ and in situ annealing experiments, suggests structural relaxation followed by recrystallization of the damaged material. The resolution of fractions of a nanometer with which the track radii are determined, as well as the nondestructive, artefact-free measurement methodology shown here, provides an effective means for in-depth studies of ion-track formation in natural minerals under a wide variety of geological conditions.

  18. H-Isotopic Composition of Apatite in Northwest Africa 7034

    NASA Technical Reports Server (NTRS)

    McCubbin, F. M.; Barnes, J. J.; Santos, A. R.; Boyce, J. W.; Anand, M.; Franchi, I. A.; Agee, C. B.

    2016-01-01

    Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to estimates of Mars' bulk crust composition [1]. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the crustal composition of components that cannot be measured directly by remote sensing. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034.

  19. Fundamental Study of Bone-Mimicking Phantom Using Apatite

    NASA Astrophysics Data System (ADS)

    Hirai, Takuya; Ohdaira, Etsuzo; Masuzawa, Nobuyoshi; Itoh, Katsuhiko; Matozaki, Takeshi

    2001-05-01

    Because of the success of the ultrasonic method for diagnosing osteoporosis, the challenge to obtain ultrasonic images of the inner part of bone has begun. Since ultrasonic imaging of the inner part of bone is very difficult, further research is necessary. The goal of this study is to develop a bone-mimicking phantom for use in the visualization of bone by ultrasound. The developed phantom using apatite and polyvinyl alcohol (PVA) as materials with consideration of the periosteum showed fairly good agreement with real bone.

  20. Lepidocrocite, an apatite mineral, and magnetic in teeth of chitons (Polyplacophora).

    PubMed

    Lowenstam, H A

    1967-06-09

    X-ray diffraction patterns show that the mature denticles of three extant chiton species are composed of the mineral lepidocrocite and an apatite mineral, probably francolite, in addition to magnetite. Each of the three minerals forms a discrete microarchitectural unit of the chiton denticles. This is the first indication that lepidocrocite is precipitated by marine organisms and an apatite mineral by chitons.

  1. Behaviour of apatite during partial melting of metapelites and consequences for prograde suprasolidus monazite growth

    NASA Astrophysics Data System (ADS)

    Yakymchuk, Chris

    2017-03-01

    The suprasolidus behaviour of apatite and monazite is examined for an average metapelite composition using phase equilibria modelling coupled with solubility equations of these minerals. Both closed- and open-system scenarios are considered. Partial melting above the solidus requires apatite and monazite breakdown in order to saturate the anatectic melt in phosphorus and the light rare earth elements. In general, melt loss is predicted to increase the stability of apatite and monazite at high temperature. Most apatite is predicted to survive up to ultrahigh temperature conditions except for rocks with low bulk phosphorus concentrations. By contrast, most monazite is expected to be consumed by UHT conditions. Thorium substitution in monazite is expected to increase the stability of monazite to higher temperatures. The presence of LREE-rich apatite decreases the stability of monazite above the solidus, but the breakdown of this apatite during anatexis may generate prograde monazite at the apatite-melt interface in local pockets of melt oversaturation. However, prograde suprasolidus monazite along grain boundaries is expected to be consumed during further partial melting or during melt homogenization when an interconnected melt network develops. Anatectic melts are predicted to be saturated with respect to apatite except at UHT conditions and for rocks with low initial P2O5 bulk concentrations.

  2. Apatite bone cement reinforced with calcium silicate fibers.

    PubMed

    Motisuke, Mariana; Santos, Verônica R; Bazanini, Naiana C; Bertran, Celso A

    2014-10-01

    Several research efforts have been made in the attempt to reinforce calcium phosphate cements (CPCs) with polymeric and carbon fibers. Due to their low compatibility with the cement matrix, results were not satisfactory. In this context, calcium silicate fibers (CaSiO3) may be an alternative material to overcome the main drawback of reinforced CPCs since, despite of their good mechanical properties, they may interact chemically with the CPC matrix. In this work CaSiO3 fibers, with aspect ratio of 9.6, were synthesized by a reactive molten salt synthesis and used as reinforcement in apatite cement. 5 wt.% of reinforcement addition has increased the compressive strength of the CPC by 250% (from 14.5 to 50.4 MPa) without preventing the cement to set. Ca and Si release in samples containing fibers could be explained by CaSiO3 partial hydrolysis which leads to a quick increase in Ca concentration and in silica gel precipitation. The latter may be responsible for apatite precipitation in needle like form during cement setting reaction. The material developed presents potential properties to be employed in bone repair treatment.

  3. Fluoride incorporation into apatite crystals delays amelogenin hydrolysis

    PubMed Central

    DenBesten, Pamela; Zhu, Li; Li, Wu; Tanimoto, Kotaro; Liu, Haichuan; Witkowska, Halina Ewa

    2012-01-01

    Enamel fluorosis has been related to an increase in the amount of amelogenin in fluorosed enamel as compared to normal enamel in the maturation stage. In this study we tested the hypothesis that fluoride incorporated into carbonated apatite alters amelogenin hydrolysis. Recombinant human amelogenin (rh174) was allowed to bind to 0.15 mg of carbonated hydroxyapatite (CAP) or fluoride-containing carbonated hydroxyapatite (F-CAP) synthesized to contain 100, 1000 or 4000 ppm F-. After 3 h digestion with recombinant human MMP20 or KLK4, bound protein was characterized by reverse-phase HPLC. Proteolytic fragments formed after 24 h digestion of amelogenin, were identified by LC tandem mass spectrometry (LCMS/MS). The hydrolysis of amelogenin bound to F100-CAP by both MMP20 and KLK4 was significantly reduced in a dose dependent manner as compared to CAP. After 24 h hydrolysis, the number of cleavage sites in bound amelogenin by MMP20 were similar in CAP and F100-CAP, whereas there were 24 fewer cleavage sites identified for the KLK4 hydrolysis on F100-CAP as compared to CAP. These results suggest that the reduced hydrolysis of amelogenins in fluorosed enamel may be partially due to the increased fluoride content in fluoride containing apatite, contributing to the hypomineralized enamel matrix phenotype observed in fluorosed enamel. PMID:22243219

  4. Structural analysis of a series of strontium-substituted apatites.

    PubMed

    O'Donnell, M D; Fredholm, Y; de Rouffignac, A; Hill, R G

    2008-09-01

    A series of Sr-substituted hydroxyapatites, (Sr(x)Ca(1-)(x))(5)(PO(4))(3)OH, where x=0.00, 0.25, 0.50, 0.75 and 1.00, were made by a standard wet chemical route and investigated using X-ray diffraction (XRD), Rietveld refinement and Raman spectroscopy. We report apatites manufactured by two synthesis routes under 90 degrees C, and only the fully Sr-substituted sample had a small amount of an impurity phase, which is believed to be strontium pyrophosphate. Lattice parameters (a and c), unit cell volume and density were shown to increase linearly with strontium addition and were consistent with the addition of a slightly larger and heavier ion (Sr) in place of Ca. XRD Lorentzian peak widths increased to a maximum at x=0.50, then decreased with increasing Sr content. This indicated an increase in crystallite size when moving away from the x=0.50 composition (d approximately 9.4nm). There was a slight preference for strontium to enter the Ca(II) site in the mixed apatites (6 to 12% depending on composition). The position of the Raman band attributed to v(1)PO(4)(3-) at around 963cm(-1) in hydroxyapatite decreased linearly to 949cm(-1) at full Sr-substitution. The full width at half maximum of this peak also correlated well and increased linearly with increasing crystallite size calculated from XRD.

  5. Ambi-site substitution of Mn in lanthanum germanate apatites

    SciTech Connect

    Kendrick, E.; Knight, K.S.; Slater, P.R.

    2009-08-05

    A neutron diffraction study at 4 K of the Mn doped lanthanum germanate apatite-type oxide ion conductor of nominal starting composition 'La{sub 9.5}Mn{sub 0.5}(GeO{sub 4}){sub 6}O{sub 2.75}' is reported. The structure was refined in space group P6{sub 3}/m, although high thermal displacement parameters were observed for the oxide ion sites (particularly O3, and O4). Reduced thermal displacement parameters were obtained by splitting the O3 site, and allowing the O4 oxygen to move off site, which may indicate local regions of lower symmetry within the structure. In addition, the data suggested ambi-site substitution of Mn, with it being present on both the Ge site and the La site. Assuming no change in La:Mn:Ge ratio, a composition of La{sub 9.18}Mn{sub 0.28}(GeO{sub 4}){sub 5.8}(MnO{sub 4}){sub 0.2}O{sub 2} was determined. As such there are nominally no interstitial oxide ions, but rather cation vacancies on the La site. Therefore, the high conductivity for this sample is most likely related to the introduction of Frenkel-type defects at higher temperature, as previously proposed for other apatite-type systems containing vacancies on the La site.

  6. TREATMENT OF ACID MINE DRAINAGE USING FISHBONE APATITE IITM

    SciTech Connect

    Neal A. Yancey

    2006-10-01

    ABSTRACT. In 2000, a reactive barrier was installed on the East Fork of Ninemile Creek near Wallace, Idaho to treat acid mine discharge. The barrier was filled with fishbone derived Apatite IITM to remove the contaminants of concern (Zn, Pb, and Cd) and raise the pH of the acidic mine discharge. Metal removal has been achieved by a combination of chemical, biological, and physical precipitation. Flow for the water ranges from 5 to 35 gallons per minute. The water is successfully being treated, but the system experienced varying degrees of plugging. In 2002, gravel was mixed with the Apatite IITM to help control plugging. In 2003 the Idaho National Laboratory was ask to provide technical support to the Coeur d’Alene Basin Commission to help identify a remedy to the plugging issue. Air sparging was employed to treat the plugging issues. Plastic packing rings were added in the fall of 2005, which have increased the void space in the media and increased flows during the 10 months of operation since the improvements were made.

  7. Evaluation of calcium titanate as apatite growth promoter.

    PubMed

    Coreño, J; Coreño, O

    2005-11-01

    Calcium titanate (CaTiO(3), perovskite) has been used to determine its apatite nucleation ability and propose a possible nucleation initial step. Measurements of calcium leaching from the calcium titanate surface and phosphate adsorption experiments were carried out separately by using commercial calcium titanate suspensions at room temperature. Adsorption behaviour determined by zeta potential measurements shows that phosphate is strongly adsorbed on the calcium titanate surface. It was found that the higher the pH, the higher the Ca present on the calcium titanate surface, but phosphate adsorption followed this trend only up to pH 7.4. Results suggest that phosphate ions are not adsorbed only on Ca sites but also on TiO(2) groups sites of the surface, formed after calcium leaching from the surface. When both ions are simultaneously added in a modified simulated body fluid containing calcium titanate, at 37 degrees C, apatite growth occurs on its surface after 1 week of immersion.

  8. Apatite precipitation on a novel fast-setting calcium silicate cement containing fluoride

    PubMed Central

    Ranjkesh, Bahram; Chevallier, Jacques; Salehi, Hamideh; Cuisinier, Frédéric; Isidor, Flemming; Løvschall, Henrik

    2016-01-01

    Abstract Aim: Calcium silicate cements are widely used in endodontics. Novel fast-setting calcium silicate cement with fluoride (Protooth) has been developed for potential applications in teeth crowns including cavity lining and cementation. Objective: To evaluate the surface apatite-forming ability of Protooth compositions as a function of fluoride content and immersion time in phosphate-buffered saline (PBS). Material and methods: Three cement compositions were tested: Protooth (3.5% fluoride and 10% radiocontrast), ultrafast Protooth (3.5% fluoride and 20% radiocontrast), and high fluoride Protooth (15% fluoride and 25% radiocontrast). Powders were cap-mixed with liquid, filled to the molds and immersed in PBS. Scanning electron microscopy, energy dispersive X-ray analysis, and Raman spectroscopy were used to characterize the precipitations morphology and composition after 1, 7, 28, and 56 days. Apatite/belite Raman peak height indicated the apatite thickness. Results: Spherical calcium phosphate precipitations with acicular crystallites were formed after 1-day immersion in PBS and Raman spectra disclosed the phosphate band at 965 cm−1, supporting the apatite formation over Protooth compositions. The apatite deposition continued and more voluminous precipitations were observed after 56 days over the surface of all cements. Raman bands suggested the formation of β-type carbonated apatite over Protooth compositions. High fluoride Protooth showed the most compact deposition with significantly higher apatite/belite ratio compared to Protooth and ultrafast Protooth after 28 and 56 days. Conclusions: Calcium phosphate precipitations (apatite) were formed over Protooth compositions after immersion in PBS with increasing apatite formation as a function of time. High fluoride Protooth exhibited thicker apatite deposition. PMID:27335901

  9. Endogenous Lunar Volatiles: Insights into the Abundances of Volatiles in the Moon from Lunar Apatite

    NASA Technical Reports Server (NTRS)

    McCubbin, Francis

    2016-01-01

    At the time of publication of New Views of the Moon, it was thought that the Moon was bone dry with less than about 1 ppb H2O. However in 2007, initial reports at the 38th Lunar and Planetary Science Conference speculated that H-species were present in both apatites and pyroclastic volcanic lunar glasses. These early reports were later confirmed through peer-review, which motivated many subsequent studies on magmatic volatiles in and on the Moon within the last decade. Some of these studies have cast into question the post-Apollo view of lunar formation, the distribution and sources of volatiles in the Earth-Moon system, and the thermal and magmatic evolution of the Moon. The mineral apatite has been one of the pillars of this new field of study, and it will be the primary focus of this abstract. Although apatite has been used both to understand the abundances of volatiles in lunar systems as well as the isotopic compositions of those volatiles, the focus here will be on the abundances of F, Cl, and H2O. This work demonstrates the utility of apatite in advancing our understanding of lunar volatiles, hence apatite should be among the topics covered in the endogenous lunar volatile chapter in NVM II. Truncated ternary plot of apatite X-site occupancy (mol%) from highlands apatite and mare basalt apatite plotted on the relative volatile abundance diagram from. The solid black lines delineate fields of relative abundances of F, Cl, and H2O (on a weight basis) in the melt from which the apatite crystallized. The diagram was constructed using available apatite/melt partitioning data for fluorine, chlorine, and hydroxyl.

  10. Apatite as probe for the halogen composition of metamorphic fluids (Bamble Sector, SE Norway)

    NASA Astrophysics Data System (ADS)

    Kusebauch, Christof; John, Timm; Whitehouse, Martin J.; Engvik, Ane K.

    2015-10-01

    Halogen composition of replaced apatite formed during a regional metasomatic event (Bamble Sector, SE Norway) reveals information about the composition and evolution of the hydrothermal fluid. Infiltration and pervasive fluid flow of highly saline fluids into gabbroic bodies lead to scapolitization and amphibolitization, where magmatic Cl-rich apatite reacts with the hydrothermal fluid to form OH- and/or F-rich apatite. Apatite from highly altered samples adjacent to the shear zone has highest F (up to 15,000 µg/g) and lowest Br (4-25 µg/g) concentrations, whereas apatite from least altered samples has very low F (30-200 µg/g) and high Br (30-85 µg/g). In addition, individual replaced apatite grains show a zonation in F with high concentrations along rims and cracks and low F in core regions. Iodine concentrations remain rather constant as low values of 0.18-0.70 µg/g. We interpret all observed compositional features of replaced apatite to be the result of a continuous evolution of the fluid during fluid-rock interaction. Due to its high compatibility, F from the infiltrating fluid is incorporated early into recrystallized apatite (close to shear zone and rims of individual apatite grains). In contrast, Br as an incompatible halogen becomes enriched in the fluid and is highest in the most evolved fluid. Using experimental partition data between replaced apatite and fluid, we calculated F concentrations of the evolving fluid to decrease from 60 to <1 µg/g and Br to increase from ~1200 to ~5000 µg/g; I concentrations of the fluid are constant in the order of 370 µg/g. Although Cl is expected to show a similar behavior as Br, replaced apatite has constant Cl concentrations throughout the alteration sequence (~1 wt.%), which is likely the result of a rather constant Cl activity in the fluid. Chlorine stable isotope values of individual apatite grains are heterogeneous and range from -1.2 to +3.7 ‰. High δ 37Cl values are generally correlated with OH

  11. Biomimetic apatite-based composite materials obtained by spark plasma sintering (SPS): physicochemical and mechanical characterizations.

    PubMed

    Brouillet, Fabien; Laurencin, Danielle; Grossin, David; Drouet, Christophe; Estournes, Claude; Chevallier, Geoffroy; Rey, Christian

    2015-08-01

    Nanocrystalline calcium phosphate apatites are biomimetic compounds analogous to bone mineral and are at the origin of the bioactivity of most biomaterials used as bone substitutes. Their unique surface reactivity originates from the presence of a hydrated layer containing labile ions (mostly divalent ones). So the setup of 3D biocompatible apatite-based bioceramics exhibiting a high reactivity requests the development of «low» temperature consolidation processes such as spark plasma sintering (SPS), in order to preserve the characteristics of the hydrated nanocrystals. However, mechanical performances may still need to be improved for such nanocrystalline apatite bioceramics, especially in view of load-bearing applications. The reinforcement by association with biopolymers represents an appealing approach, while preserving the advantageous biological properties of biomimetic apatites. Herein, we report the preparation of composites based on biomimetic apatite associated with various quantities of microcrystalline cellulose (MCC, 1-20 wt%), a natural fibrous polymer. The SPS-consolidated composites were analyzed from both physicochemical (X-ray diffraction, Fourier transform infrared, solid state NMR) and mechanical (Brazilian test) viewpoints. The preservation of the physicochemical characteristics of apatite and cellulose in the final material was observed. Mechanical properties of the composite materials were found to be directly related to the polymer/apatite ratios and a maximum crushing strength was reached for 10 wt% of MCC.

  12. In vitro growth of bioactive nanostructured apatites via agar-gelatin hybrid hydrogel.

    PubMed

    Deng, Yi; Zhao, Xianghui; Zhou, Yongsheng; Zhu, Peizhi; Zhang, Li; Wei, Shicheng

    2013-12-01

    Biomimetic synthesis of bone-like carbonated apatite with good biocompatibility is a promising strategy for the development of novel biomaterials for bone engineering applications. Most research efforts have been focused on only protein-based or only polysaccharide-based template for synthesis of apatite minerals. To understand the cooperative roles of gelatin and polysaccharide playing in the biomineralization, agar hydrogel, gelatin and agar-gelatin hybrid hydrogel were respectively introduced as mineralization matrix for the in vitro growth of apatite in the study. It was shown that bundle-like carbonated apatite was successfully prepared in agar-gelatin hybrid hydrogel for the first time, through the interaction between apatite and matrix macromolecule under physiological temperature. Moreover, the in vitro biocompatibility of the prepared nanostructured apatite crystals was investigated using CCK-8 assay and alkaline phosphatase activity of osteoblast-like MC3T3-E1. Compared with HA synthesized by traditional method, the obtained apatite in agar-gelatin hybrid hydrogel could provide significantly higher cell viability and alkaline phosphatase activity. Through the study, we could better understand the role of gelatin and polysaccharide in bone formation process, and the product is a promising candidate to be used in bone tissue engineering.

  13. Transformation of nacre coatings into apatite coatings in phosphate buffer solution at low temperature.

    PubMed

    Guo, Yaping; Zhou, Yu

    2008-08-01

    Nacre coatings were deposited on Ti6Al4V substrates by electrophoretic technique, and subsequently converted into apatite coatings with hierarchical porous structures by treatment with a phosphate buffer solution. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma optical emission spectroscopy, X-ray photoelectron spectroscopy (XPS), and N(2) adsorption-desorption isotherms. The results show that the nacre coatings are converted into the plate-like apatite coatings via a dissolution-precipitation reaction, while the organic components of the nacre are reserved. The mesopores with pore size of 4.4 nm are formed within the plate-like structure, and the macropores are formed among the plate-like structure. Simulated body fluid (SBF) immersion tests reveal that the apatite coatings have a good in vitro bioactivity. Bone-like apatite crystals are formed on the surfaces of the apatite coatings after soaking in SBF for 12 h, and fill up the macropores on the coatings with increasing the soaking time. In addition, XPS indicates that a TiO(x) layer and PO(4) (3-) ions appear on the substrate surfaces by pretreatment with a H(3)PO(4)/HF solution. The TiO(x) layer and PO(4) (3-) ions can induce the formation of apatite crystals, resulting in a composition gradient from the oxide layer to the external apatite layer.

  14. Calcium Solubility In Zeolite Synthetic-Apatite Mixtures

    NASA Technical Reports Server (NTRS)

    Beiersdorfer, R.; Ming, D. W.

    1999-01-01

    Life support systems at a lunar or martian outpost will require the ability to produce food growing in 1) treated lunar or martian regolith; 2) a synthetic soil, or 3) some combination of both. Zeoponic soil, composed of NH4 (-) and K-exchanged clinoptilolite (Cp) and synthetic apatite (Ap), can provide slow-release fertilization via dissolution and ion-exchange. Equilibrium studies indicate that KNH4, P, and Mg are available to plants at sufficient levels, however, Ca is deficient. Ca availability can be increased by adding a second Ca-bearing mineral: calcite (Cal); dolomite (Dol); or wollastonite (Wol). Additions of Cal, Dol, and Wol systematically change the concentrations of Ca and P in solution. Cal has the greatest effect, Dol the least, and Wol is intermediate.

  15. Apatite mineralization in teeth of the chiton Acanthopleura echinata.

    PubMed

    Lee, A P; Brooker, L R; Macey, D J; van Bronswijk, W; Webb, J

    2000-11-01

    Raman spectroscopy has been used to demonstrate, for the first time, that calcium mineralization in the core of the major lateral teeth of the chiton Acanthopleura echinata takes place as an ordered process, with crystalline carbonated apatite being the first mineral deposited. Deposition begins at the top of the tooth core, under the so-called tab region, progresses down the interior surface of the tab and lepidocrocite layer, and then extends outwards to the anterior surface. Mineralization is not initiated until the lepidocrocite layer has isolated the core of the tooth from the magnetite cap. The last region to be infiltrated is the anterior basal region of the tooth cusp, immediately above the junction zone. The junction zone is also a region of high ion density, as determined by energy dispersive spectroscopy (EDS) analysis, but we show here for the first time that it is free of mineral deposits, acting instead as a transfer and storage region.

  16. Radionuclide Incorporation and Long Term Performance of Apatite Waste Forms

    SciTech Connect

    Wang, Jianwei; Lian, Jie; Gao, Fei

    2016-01-04

    This project aims to combines state-of-the-art experimental and characterization techniques with atomistic simulations based on density functional theory (DFT) and molecular dynamics (MD) simulations. With an initial focus on long-lived I-129 and other radionuclides such as Cs, Sr in apatite structure, specific research objectives include the atomic scale understanding of: (1) incorporation behavior of the radionuclides and their effects on the crystal chemistry and phase stability; (2) stability and microstructure evolution of designed waste forms under coupled temperature and radiation environments; (3) incorporation and migration energetics of radionuclides and release behaviors as probed by DFT and molecular dynamics (MD) simulations; and (4) chemical durability as measured in dissolution experiments for long term performance evaluation and model validation.

  17. Magnetic apatite for structural insights on the plasma membrane.

    PubMed

    Stanca, Sarmiza E; Müller, Robert; Dellith, Jan; Nietzsche, Sandor; Stöckel, Stephan; Biskup, Christoph; Deckert, Volker; Krafft, Christoph; Popp, Jürgen; Fritzsche, Wolfgang

    2015-01-21

    The iron oxide-hydroxyapatite (FeOxHA) nanoparticles reported here differ from those reported before by their advantage of homogeneity and simple preparation; moreover, the presence of carboxymethyldextran (CMD), together with hydroxyapatite (HA), allows access to the cellular membrane, which makes our magnetic apatite unique. These nanoparticles combine magnetic behavior, Raman label ability and the property of interaction with the cellular membrane; they therefore represent an interesting material for structural differentiation of the cell membrane. It was observed by Raman spectroscopy, scanning electron microscopy (SEM) and fluorescence microscopy that FeOxHA adheres to the plasma membrane and does not penetrate the membrane. These insights make the nanoparticles a promising material for magnetic cell sorting, e.g. in microfluidic device applications.

  18. Magnetic apatite for structural insights on the plasma membrane

    NASA Astrophysics Data System (ADS)

    Stanca, Sarmiza E.; Müller, Robert; Dellith, Jan; Nietzsche, Sandor; Stöckel, Stephan; Biskup, Christoph; Deckert, Volker; Krafft, Christoph; Popp, Jürgen; Fritzsche, Wolfgang

    2015-01-01

    The iron oxide-hydroxyapatite (FeOxHA) nanoparticles reported here differ from those reported before by their advantage of homogeneity and simple preparation; moreover, the presence of carboxymethyldextran (CMD), together with hydroxyapatite (HA), allows access to the cellular membrane, which makes our magnetic apatite unique. These nanoparticles combine magnetic behavior, Raman label ability and the property of interaction with the cellular membrane; they therefore represent an interesting material for structural differentiation of the cell membrane. It was observed by Raman spectroscopy, scanning electron microscopy (SEM) and fluorescence microscopy that FeOxHA adheres to the plasma membrane and does not penetrate the membrane. These insights make the nanoparticles a promising material for magnetic cell sorting, e.g. in microfluidic device applications.

  19. Remediation of copper contaminated soil by using different particle sizes of apatite: a field experiment.

    PubMed

    Xing, Jinfeng; Hu, Tiantian; Cang, Long; Zhou, Dongmei

    2016-01-01

    The particle size of apatite is one of the critical factors that influence the adsorption of heavy metals on apatite in the remediation of heavy metal contaminated soils using apatite. However, little research has been done evaluating the impact of different particle sizes of apatite on immobilization remediation of heavy metal polluted soils in field. In this study, the adsorption isothermal experiments of copper on three kinds of apatite was tested, and the field experiment by using different particle sizes apatite [nano-hydroxyapatite (NAP), micro-hydroxyapatite (MAP), ordinary particle apatite (OAP)] at a same dosage of 25.8 t/ha (1.16 %, W/W) was also conducted. Ryegrass was chosen as the test plant. The ryegrass biomass, the copper contents in ryegrass and the copper fractionations in soil were determined after field experiments. Results of adsorption experiments showed that the adsorption amounts of copper on OAP was the lowest among different particles. The adsorption amounts of copper on MAP was higher than NAP at high copper equilibrium concentration (>1 mmol L(-1)), an opposite trend was obtained at low copper concentration (<1 mmol L(-1)). In the field experiment, we found that the application of different apatites could effectively increase the soil pH, decrease the available copper concentration in soil, provide more nutrient phosphate and promote the growth of ryegrass. The ryegrass biomass and the copper accumulation in ryegrass were the highest in MAP among all treatments. The effective order of apatite in phytoremediation of copper contaminated field soil was MAP > NAP > OAP, which was attributed to the high adsorption capacity of copper and the strong releasing of phosphate by MAP.

  20. Biomimetic magnesium-carbonate-apatite nanocrystals endowed with strontium ions as anti-osteoporotic trigger.

    PubMed

    Iafisco, Michele; Ruffini, Andrea; Adamiano, Alessio; Sprio, Simone; Tampieri, Anna

    2014-02-01

    The present work investigates the preparation of biomimetic nanocrystalline apatites co-substituted with Mg, CO3 and Sr to be used as starting materials for the development of nanostructured bio-devices for regeneration of osteoporotic bone. Biological-like amounts of Mg and CO3 ions were inserted in the apatite structure to mimic the composition of bone apatite, whereas the addition of increasing quantities of Sr ions, from 0 up to 12 wt.%, as anti-osteoporotic agent, was evaluated. The chemical-physical features, the morphology, the degradation rates, the ion release kinetics as well as the in vitro bioactivity of the as-prepared apatites were fully evaluated. The results indicated that the incorporation of 12 wt.% of Sr can be viewed as a threshold for the structural stability of Mg-CO3-apatite. Indeed, incorporation of lower quantity of Sr did not induce considerable variations in the chemical structure of Mg-CO3-apatite, while when the Sr doping extent reached 12 wt.%, a dramatically destabilizing effect was detected on the crystal structure thus yielding alteration of the symmetry and distortion of the PO4. As a consequence, this apatite exhibited the fastest degradation kinetic and the highest amount of Sr ions released when tested in physiological conditions. In this respect, the surface crystallization of new calcium phosphate phase when immersed in physiological-like solution occurred by different mechanisms and extents due to the different structural chemistry of the variously doped apatites. Nevertheless, all the apatites synthesized in this work exhibited in vitro bioactivity demonstrating their potential use to develop biomedical devices with anti-osteoporotic functionality.

  1. Adsorption of nucleotides on biomimetic apatite: The case of adenosine 5‧ monophosphate (AMP)

    NASA Astrophysics Data System (ADS)

    Hammami, K.; Feki, H. El; Marsan, O.; Drouet, C.

    2015-10-01

    This work investigates the interaction between the nucleotide adenosine 5‧ monophosphate molecule (AMP) and a biomimetic nanocrystalline carbonated apatite as a model for bone mineral. The analogy of the apatite phase used in this work with biological apatite was first pointed out by complementary techniques. AMP adsorption isotherms were then investigated. Obtained data were fitted to a Sips isotherm with an exponent greater than one suggesting positive cooperativity among adsorbed molecules. The data were compared to a previous study relative to the adsorption of another nucleotide, cytidine monophosphate (CMP) onto a similar substrate, evidencing some effect of the chemical nature of the nucleic base. An enhanced adsorption was observed under acidic (pH 6) conditions as opposed to pH 7.4, which parallels the case of DNA adsorption on biomimetic apatite. An estimated standard Gibbs free energy associated to the adsorption process (ΔG°ads ≅ -22 kJ/mol) intermediate between "physisorption" and "chemisorption" was found. The analysis of the solids after adsorption pointed to the preservation of the main characteristics of the apatite substrate but shifts or enhancements of Raman bands attributed to AMP showed the existence of chemical interactions involving both the phosphate and adenine parts of AMP. This contribution adds to the works conducted in view of better understanding the interaction of DNA/RNA and their constitutive nucleotides and the surface of biomimetic apatites. It could prove helpful in disciplines such as bone diagenesis (DNA/apatite interface in aged bones) or nanomedicine (setup of DNA- or RNA-loaded apatite systems). Also, the adsorption of nucleic acids on minerals like apatites could have played a role in the preservation of such biomolecules in the varying conditions known to exist at the origin of life on Earth, underlining the importance of dedicated adsorption studies.

  2. Fluoride incorporation into apatite crystals delays amelogenin hydrolysis.

    PubMed

    DenBesten, Pamela K; Zhu, Li; Li, Wu; Tanimoto, Kotaro; Liu, Haichuan; Witkowska, Halina E

    2011-12-01

    Enamel fluorosis has been related to an increase in the amount of amelogenin in fluorosed enamel compared with normal enamel in the maturation stage. In this study we tested the hypothesis that fluoride incorporated into carbonated apatite alters amelogenin hydrolysis. Recombinant human amelogenin (rh174) was allowed to bind to 0.15 mg of carbonated hydroxyapatite (CAP) or to fluoride-containing carbonated hydroxyapatite (F-CAP) synthesized to contain 100, 1,000, or 4,000 ppm F(-). After 3 h of digestion with recombinant human matrix metalloproteinase 20 (MMP20) or kallikrein-related peptidase 4 (KLK4), bound protein was characterized by reverse-phase high-performance liquid chromatography (HPLC). Proteolytic fragments of amelogenin formed after 24h of digestion with MMP20 of KLK 4 were identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The hydrolysis, by both MMP20 and KLK4, of amelogenin bound to F100-CAP was significantly reduced in a dose-dependent manner compared with the hydrolysis of amelogenin bound to CAP. After 24 h of hydrolysis, a similar number of MMP20 cleavage sites was found for amelogenin bound to CAP and amelogenin bound to F100-CAP; however, 24 fewer KLK4 cleavage sites were identified for amelogenin bound to F100-CAP than for amelogenin bound to CAP. These results suggest that the reduced hydrolysis of amelogenins in fluorosed enamel may be partially caused by the increased fluoride content in fluoride-containing apatite, contributing to the hypomineralized enamel matrix phenotype observed in fluorosed enamel.

  3. Cell surface receptor targeted biomimetic apatite nanocrystals for cancer therapy.

    PubMed

    Iafisco, Michele; Delgado-Lopez, Josè Manuel; Varoni, Elena Maria; Tampieri, Anna; Rimondini, Lia; Gomez-Morales, Jaime; Prat, Maria

    2013-11-25

    Nanosized drug carriers functionalized with moieties specifically targeting tumor cells are promising tools in cancer therapy, due to their ability to circulate in the bloodstream for longer periods and their selectivity for tumor cells, enabling the sparing of healthy tissues. Because of its biocompatibility, high bioresorbability, and responsiveness to pH changes, synthetic biomimetic nanocrystalline apatites are used as nanocarriers to produce multifunctional nanoparticles, by coupling them with the chemotherapeutic drug doxorubicin (DOXO) and the DO-24 monoclonal antibody (mAb) directed against the Met/Hepatocyte Growth Factor receptor (Met/HGFR), which is over-expressed on different types of carcinomas and thus represents a useful tumor target. The chemical-physical features of the nanoparticles are fully investigated and their interaction with cells expressing (GTL-16 gastric carcinoma line) or not expressing (NIH-3T3 fibroblasts) the Met/HGFR is analyzed. Functionalized nanoparticles specifically bind to and are internalized in cells expressing the receptor (GTL-16) but not in the ones that do not express it (NIH-3T3). Moreover they discharge DOXO in the targeted GTL-16 cells that reach the nucleus and display cytotoxicity as assessed in an MTT assay. Two different types of ternary nanoparticles are prepared, differing for the sequence of the functionalization steps (adsorption of DOXO first and then mAb or vice versa), and it is found that the ones in which mAb is adsorbed first are more efficient under all the examined aspects (binding, internalization, cytotoxicity), possibly because of a better mAb orientation on the nanoparticle surface. These multifunctional nanoparticles could thus be useful instruments for targeted local or systemic drug delivery, allowing a reduction in the therapeutic dose of the drug and thus adverse side effects. Moreover, this work opens new perspectives in the use of nanocrystalline apatites as a new platform for theranostic

  4. Quantification of octacalcium phosphate, authigenic apatite and detrital apatite in coastal sediments using differential dissolution and standard addition

    NASA Astrophysics Data System (ADS)

    Oxmann, J. F.; Schwendenmann, L.

    2014-01-01

    Knowledge of calcium phosphate (Ca-P) solubility is crucial for understanding temporal and spatial variations of phosphorus (P) concentrations in water bodies and sedimentary reservoirs. In-situ relationships between liquid and solid-phase levels cannot be fully explained by dissolved analytes alone and need to be verified by determination of particular sediment P species. Lack of quantification methods for these species limits the knowledge of the P cycle. To address this issue, we (i) optimized a specifically developed conversion-extraction (CONVEX) method for P species quantification using standard additions; and (ii) simultaneously determined solubilities of Ca-P standards by measuring their pH-dependent contents in the sediment matrix. Ca-P minerals including various carbonate fluorapatite (CFAP) specimens from different localities, fluorapatite (FAP), fish bone apatite, synthetic hydroxylapatite (HAP) and octacalcium phosphate (OCP) were characterized by XRD, Raman, FTIR and elemental analysis. Sediment samples were incubated with and without these reference minerals and then sequentially extracted to quantify Ca-P species by their differential dissolution at pH values between 3 and 8. The quantification of solid-phase phosphates at varying pH revealed solubilities in the following order: OCP > HAP > CFAP (4.5% CO3) > CFAP (3.4% CO3) > CFAP (2.2% CO3) > FAP. Thus, CFAP was less soluble in sediment than HAP, and CFAP solubility increased with carbonate content. Unspiked sediment analyses together with standard addition analyses indicated consistent differential dissolution of natural sediment species vs. added reference species and therefore verified the applicability of the CONVEX method in separately determining the most prevalent Ca-P minerals. We found surprisingly high OCP contents in the analyzed coastal sediments which supports the hypothesis of apatite formation by an OCP precursor.

  5. Quantification of octacalcium phosphate, authigenic apatite and detrital apatite in coastal sediments using differential dissolution and standard addition

    NASA Astrophysics Data System (ADS)

    Oxmann, J. F.; Schwendenmann, L.

    2014-06-01

    Knowledge of calcium phosphate (Ca-P) solubility is crucial for understanding temporal and spatial variations of phosphorus (P) concentrations in water bodies and sedimentary reservoirs. In situ relationships between liquid- and solid-phase levels cannot be fully explained by dissolved analytes alone and need to be verified by determining particular sediment P species. Lack of quantification methods for these species limits the knowledge of the P cycle. To address this issue, we (i) optimized a specifically developed conversion-extraction (CONVEX) method for P species quantification using standard additions, and (ii) simultaneously determined solubilities of Ca-P standards by measuring their pH-dependent contents in the sediment matrix. Ca-P minerals including various carbonate fluorapatite (CFAP) specimens from different localities, fluorapatite (FAP), fish bone apatite, synthetic hydroxylapatite (HAP) and octacalcium phosphate (OCP) were characterized by XRD, Raman, FTIR and elemental analysis. Sediment samples were incubated with and without these reference minerals and then sequentially extracted to quantify Ca-P species by their differential dissolution at pH values between 3 and 8. The quantification of solid-phase phosphates at varying pH revealed solubilities in the following order: OCP > HAP > CFAP (4.5% CO3) > CFAP (3.4% CO3) > CFAP (2.2% CO3) > FAP. Thus, CFAP was less soluble in sediment than HAP, and CFAP solubility increased with carbonate content. Unspiked sediment analyses together with standard addition analyses indicated consistent differential dissolution of natural sediment species vs. added reference species and therefore verified the applicability of the CONVEX method in separately determining the most prevalent Ca-P minerals. We found surprisingly high OCP contents in the coastal sediments analyzed, which supports the hypothesis of apatite formation by an OCP precursor mechanism.

  6. Physico-chemical and thermochemical studies of the hydrolytic conversion of amorphous tricalcium phosphate into apatite

    SciTech Connect

    Somrani, Saida; Banu, Mihai; Jemal, Mohamed; Rey, Christian . E-mail: christian.rey@ensiacet.fr

    2005-05-15

    The conversion of amorphous tricalcium phosphate with different hydration ratio into apatite in water at 25 deg. C has been studied by microcalorimetry and several physical-chemical methods. The hydrolytic transformation was dominated by two strong exothermic events. A fast, relatively weak, wetting process and a very slow but strong heat release assigned to a slow internal rehydration and the crystallization of the amorphous phase into an apatite. The exothermic phenomenon related to the rehydration exceeded the crystalline transformation enthalpy. Rehydration occurred before the conversion of the amorphous phase into apatite and determined the advancement of the hydrolytic reaction. The apatitic phases formed evolved slightly with time after their formation. The crystallinity increased whereas the amount of HPO{sub 4}{sup 2-} ion decreased. These data allow a better understanding of the behavior of biomaterials involving amorphous phases such as hydroxyapatite plasma-sprayed coatings.

  7. In Situ Formation of Calcium Apatite in Soil for Sequestering Contaminants in Soil and Groundwater

    ScienceCinema

    Moore, Robert; Szecsody, Jim; Thompson, Mike

    2016-07-12

    A new method for in situ formation of a calcium apatite permeable reactive barrier that is a groundbreaking technology for containing radioactive/heavy metal contaminants threatening groundwater supplies.

  8. Effects of calcium phosphate precipitation method on acid resistance to apatite powder and bovine tooth.

    PubMed

    Suge, Toshiyuki; Kawasaki, Akiko; Ishikawa, Kunio; Matsuo, Takashi; Ebisu, Shigeyuki

    2008-07-01

    The aims of this study were to evaluate the effects of CPP method on the crystallinity of apatite powder and on the acid resistance of bovine enamel. Crystallinity degrees of apatite powder before and after CPP treatment were measured by powder X-ray diffraction analysis. Polished bovine enamel specimens treated with CPP method or NaF were immersed in a lactic acid solution for up to five days. The demineralized depth of enamel was measured with a surface roughness analyzer. XRD peaks became sharper after the CPP treatment, indicating an increased crystallinity of the apatite powder. The demineralized depth of bovine enamel treated with CPP method was shallower than that of enamel treated with NaF. Results of this study revealed that the CPP method increased the crystallinity of apatite powder and the acid resistance of enamel. Therefore, the CPP method would be useful not only for treating dentin hypersensitivity, but also for the prevention of dental caries.

  9. Preparation of low-crystalline apatite nanoparticles and their coating onto quartz substrates.

    PubMed

    Kawashita, Masakazu; Taninai, Koji; Li, Zhixia; Ishikawa, Kunio; Yoshida, Yasuhiro

    2012-06-01

    We prepared low-crystalline apatite nanoparticles and coated them onto a surface of a Au/Cr-plated quartz substrate by the electrophoretic deposition (EPD) method or by using a self-assembled monolayer of 11-mercaptoundecanoic acid (SAM method). Low-crystalline apatite nanoparticles around 10 nm in size with extremely low contents of undesirable residual products were obtained by adding (NH(4))(2)HPO(4) aqueous droplets into a modified synthetic body fluid solution that contained Ca(CH(3)COO)(2). The apatite nanoparticles were successfully coated by either the EPD method or the SAM method; the nanoparticle coating achieved by the SAM method was more uniform than that achieved by the EPD method. The present SAM method is expected to be a promising technique for obtaining a quartz substrate coated with apatite nanoparticles, which can be used as a quartz crystal microbalance device.

  10. Synthesis and characterization of nanocrystalline apatites from eggshells at different Ca/P ratios.

    PubMed

    Siddharthan, A; Kumar, T S Sampath; Seshadri, S K

    2009-08-01

    Nanocrystalline apatites with different Ca/P ratios were synthesized using eggshell as a calcium source by microwave processing. The apatites were found to have a minor amount of Mg, Sr, Si and Na ions inherited from the eggshells. The presence of several foreign ions results in a perturbed lattice structure indicated by an increase in lattice constants and shift in vibrational frequencies of the functional groups. The apatites were heat treated to investigate the influence of foreign ions on thermal stability. The minor amounts of ions do not affect the thermal stability. The differences in thermal behaviour of these apatites were due to the presence of HPO(2-)(4) ions only and not due to other ions because of their low content.

  11. Detoxification of a highly toxic lead-loaded industrial solid waste by stabilization using apatites.

    PubMed

    Ioannidis, T A; Zouboulis, A I

    2003-02-28

    Apatites are known for their properties to immobilize lead contained in aqueous solutions or contaminated soils. In this study, apatites were examined as stabilization additives for lead-loaded industrial solid toxic wastes. The specific waste was the residue, obtained after thermal treatment of sludges (incineration), which was derived from tetraethyl lead fuel storage tanks. It was found to contain around 30 wt.% lead and 33 wt.% iron. Standard leaching tests (according to DIN 38414 S-4) were applied for the determination of leachability of metals from the ash and, thus, of chemical toxicity; the proposed leaching tests examined both initial and stabilized products in order to evaluate the effectiveness of the applied additives. The results obtained demonstrate the fact that lead concentrations in leachates, after the application of the proposed leaching tests using apatites as additives and with a ratio of 50% solid waste-50 wt.% apatite, could be reduced to the range of 1mg/l.

  12. Dissolution mechanism of calcium apatites in acids: A review of literature.

    PubMed

    Dorozhkin, Sergey V

    2012-02-26

    Eight dissolution models of calcium apatites (both fluorapatite and hydroxyapatite) in acids were drawn from the published literature, analyzed and discussed. Major limitations and drawbacks of the models were conversed in details. The models were shown to deal with different aspects of apatite dissolution phenomenon and none of them was able to describe the dissolution process in general. Therefore, an attempt to combine the findings obtained by different researchers was performed which resulted in creation of the general description of apatite dissolution in acids. For this purpose, eight dissolution models were assumed to complement each other and provide the correct description of the specific aspects of apatite dissolution. The general description considers all possible dissolution stages involved and points out to some missing and unclear phenomena to be experimentally studied and verified in future. This creates a new methodological approach to investigate reaction mechanisms based on sets of affine data, obtained by various research groups under dissimilar experimental conditions.

  13. In Situ Formation of Calcium Apatite in Soil for Sequestering Contaminants in Soil and Groundwater

    SciTech Connect

    Moore, Robert; Szecsody, Jim; Thompson, Mike

    2015-10-20

    A new method for in situ formation of a calcium apatite permeable reactive barrier that is a groundbreaking technology for containing radioactive/heavy metal contaminants threatening groundwater supplies.

  14. Geochemistry of Apatite in Climactic and Pre-Climactic Tephra from Mt. Mazama, Crater Lake, Oregon

    NASA Astrophysics Data System (ADS)

    Mandeville, C. W.; Langstaff, M.

    2007-12-01

    Apatite is a common accessory mineral in arc volcanic rocks that potentially records information about the dissolved volatile (S,Cl,F,OH) and trace-element concentrations (Sr, Ba, REEs) of the melt from which it crystallized. In a previous study of apatite from arc and convergent margin volcanic rocks, Peng et al. (1997) reported 0.63 wt.% SO3 in Mazama apatite grains with a corresponding SrO content of 0.18 wt.%, comprising some of the highest SO3 and SrO values in their data. Our electron microprobe study of apatite in climactic and pre-climactic Mazama tephra was done in order to assess possible correlation of apatite SO3 with Sr content of low-Sr and high-Sr recharge magmas identified based on whole-rock and matrix glass data (Bacon and Druitt, 1988) and Sr content of plagioclase (Druitt and Bacon 1989). Samples chosen represent all magmatic components erupted during the ca. 7700 year before present climactic eruption and precursor Llao Rock and Cleetwood eruptions. We compare the S, Cl, and F content of Mazama apatites with recent experimental data for S, Cl, and F partitioning between apatite and melt and with dissolved volatiles previously measured in melt inclusions from corresponding or similar Mazama samples. Our electron microprobe data confirm the presence of rare Mazama apatites with up to 0.78 wt.% SO3 and 0.12 wt.% SrO in Llao Rock, Cleetwood, and climactic scoria and pumice samples. However, high SO3 and SrO apatites are not restricted to high-Sr scoria hosts, but have been observed in low-Sr scoria, in Llao Rock rhyodacitic pumices and in Cleetwood rhyodacitic pumices, thus indicating significant magma mixing prior to the Llao Rock, Cleetwood and climactic eruptions. Most apatite SO3 and SrO data falls within the 0.06 to 0.36 wt.% and 0.04 to 0.12 wt.% range, respectively. Experimental data on SO3 partitioning between apatite and melt and maximum sulfur contents of 300 to 350 ppm measured in climactic and Cleetwood rhyodacitic melt inclusions

  15. U-Th-Pb Systematics in Zircon and Apatite from the Chicxulub Crater, Mexico

    NASA Astrophysics Data System (ADS)

    Kring, D. A.; Shaulis, B. J.; Schmieder, M.; Lapen, T. J.

    2016-08-01

    We probe the U-Th-Pb systematics in zircon and apatite to determine if post-impact hydrothermal activity produced discernible effects that are related to the duration, thermal evolution, and chemistry of the hydrothermal system.

  16. Feasibility of using natural fishbone apatite as a substitute for hydroxyapatite in remediating aqueous heavy metals.

    PubMed

    Admassu, W; Breese, T

    1999-10-29

    Fishbone, a natural, apatite rich substance, was examined for suitability as a substitute for hydroxyapatite in the sequestering of aqueous divalent heavy metal ions. The fishbone exhibited lower metal removal capacity than pure hydroxyapatite, due primarily to its purity ( approximately 70% apatite equivalent). In other ways the fishbone behaves in a similar manner as pure hydroxyapatite in the sequestration process. It was observed that it can remove all Pb(2+), Cu(2+), Cd(2+) and Ni(2+) to below detectable levels as measured by inductively coupled plasma atomic absorption, and the rate of reaction with either Zn(2+), Ni(2+), or Pb(2+) was also found to be similar to hydroxyapatite. Also, a two level, three variable full factorial design was performed for the Pb/apatite reaction and both apatites performed similarly. The main difference, besides capacity, was on exposure to high (2.4 mM) Pb concentrations. The fishbone removed less of the Pb(2+) than capacity correction predicted.

  17. Fluoride enhances transfection activity of carbonate apatite by increasing cytoplasmic stability of plasmid DNA

    SciTech Connect

    Chowdhury, E.H.

    2011-06-17

    Highlights: {yields} Cytoplasmic stability of plasmid DNA is enhanced by fluoride incorporation into carbonate apatite carrier. {yields} Fluoridated carbonate apatite promotes a robust increase in transgene expression. {yields} Controlled dissolution of fluoridated carbonate apatite in endosomal acidic environment might buffer the endosomes and prevent degradation of the released DNA. -- Abstract: Intracellular delivery of a functional gene or a nucleic acid sequence to specifically knockdown a harmful gene is a potential approach to precisely treat a critical human disease. The intensive efforts in the last few decades led to the development of a number of viral and non-viral synthetic vectors. However, an ideal delivery tool in terms of the safety and efficacy has yet to be established. Recently, we have developed pH-sensing inorganic nanocrystals of carbonate apatite for efficient and cell-targeted delivery of gene and gene-silencing RNA. Here we show that addition of very low level of fluoride to the particle-forming medium facilitates a robust increase in transgene expression following post-incubation of the particles with HeLa cells. Confocal microscopic observation and Southern blotting prove the cytoplasmic existence of plasmid DNA delivered by likely formed fluoridated carbonate apatite particles while degradation of plasmid DNA presumably by cytoplasmic nucleases was noticed following delivery with apatite particles alone. The beneficial role of fluoride in enhancing carbonate apatite-mediated gene expression might be due to the buffering potential of generated fluoridated apatite in endosomal acidic environment, thereby increasing the half-life of delivered plasmid DNA.

  18. New insights into structural alteration of enamel apatite induced by citric acid and sodium fluoride solutions.

    PubMed

    Wang, Xiaojie; Klocke, Arndt; Mihailova, Boriana; Tosheva, Lubomira; Bismayer, Ulrich

    2008-07-24

    Attenuated total reflectance infrared spectroscopy and complementary scanning electron microscopy were applied to analyze the surface structure of enamel apatite exposed to citric acid and to investigate the protective potential of fluorine-containing reagents against citric acid-induced erosion. Enamel and, for comparison, geological hydroxylapatite samples were treated with aqueous solutions of citric acid and sodium fluoride of different concentrations, ranging from 0.01 to 0.5 mol/L for citric acid solutions and from 0.5 to 2.0% for fluoride solutions. The two solutions were applied either simultaneously or consecutively. The citric acid-induced structural modification of apatite increases with the increase in the citric acid concentration and the number of treatments. The application of sodium fluoride alone does not suppress the atomic level changes in apatite exposed to acidic agents. The addition of sodium fluoride to citric acid solutions leads to formation of surface CaF2 and considerably reduces the changes in the apatite P-O-Ca framework. However, the CaF2 globules deposited on the enamel surface seem to be insufficient to prevent the alteration of the apatite structure upon further exposure to acidic agents. No evidence for fluorine-induced recovery of the apatite structure was found.

  19. Apatite deposition on titanium surfaces--the role of albumin adsorption.

    PubMed

    Serro, A P; Fernandes, A C; Saramago, B; Lima, J; Barbosa, M A

    1997-07-01

    Titanium implant surfaces are known to spontaneously nucleate apatite layers when in contact with simulated body fluids. However, adsorption of proteins may influence the process of apatite layer formation. In this study the role of bovine serum albumin (BSA) adsorption in the process of apatite deposition on titanium substrates is investigated. Deposition of calcium phosphate was induced by immersing titanium substrates in a Hank's balanced salt solution (HBSS) for times ranging from 1 to 23 days. The resulting substrates were studied by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), wettability measurements and electrochemical impedance determinations. All these methods indicate the presence of a calcium phosphate layer. The same procedure was repeated substituting HBSS with a solution of BSA in HBSS. Although SEM, EDS and electrochemical impedance spectra do not reveal the presence of an apatite layer, XPS analysis strongly indicates that the inhibition of apatite formation by BSA is only partial. The competition between BSA adsorption and apatite deposition seems to lead to a mixed film where the protein co-exists with calcium phosphate. Wettability studies suggest that this surface film is heterogeneous and porous, similar to the thicker films formed in albumin-free HBSS.

  20. Micro-CT of Porous Apatite Fiber Scaffolds Studied by Projection X-ray Microscopy

    NASA Astrophysics Data System (ADS)

    Moriya, J.; Aizawa, M.; Yoshimura, H.

    2011-09-01

    Hydroxyapatite (HAp) has been widely used as a scaffold for repairing fractured bone. For bone regeneration, the crystal structure, crystal orientation, and composition of HAp as well as the morphology of apatite scaffold are considered to be important. The apatite scaffold constructed by single-crystal fibers with pores showed good results for cellular response. Especially, apatite fiber scaffold (AFS) with large pores, 100 to 250 μm, was found to enhance cell activities such as cell proliferation and differentiation. Here, the three-dimensional (3-D) structure of apatite scaffolds was investigated by means of x-ray computed tomography (x-ray CT) using a scanning electron microscope (SEM) modified projection x-ray microscope. The 3-D structures of apatite fiber scaffolds (AFS) were reconstructed from a series of 180 x-ray projection images taken around a single rotation axis using the Feldkamp-based cone-beam reconstruction method. Extracted cross sections from CT data revealed a network-structure of apatite fibers. The distribution of pores inside the AFS in different preparations was compared.

  1. The lanthanides and yttrium in minerals of the apatite group; a review

    USGS Publications Warehouse

    Fleischer, Michael; Altschuler, Z.S.

    1982-01-01

    More than 1000 analyses have been tabulated of the distribution of the lanthanides and yttrium in minerals of the apatite group, recalculated to atomic percentages. Average compositions have been calculated for apatites from 14 types of rocks. These show a progressive change of composition from apatites of granitic pegmatites, highest in the heavy lanthanides and yttrium, to those from alkalic pegmatites, highest in the light lanthanides and lowest in yttrium. This progression is clearly shown in plots of S (= at % La+Ce+Pr) vs the ratio La/Nd and of S vs the ratio 100Y/(Y+Ln), where Ln is the sum of the lanthanides. Apatites of sedimentary phosphorites occupy a special position, being relatively depleted in Ce and relatively enriched in yttrium and the heavy lanthanides, consequences of deposition from sea water. Apatites associated with iron ores are close in composition to apatites of carbonatites, alkalic ultramafic, and ultramafic rocks, being enriched in the light lanthanides and depleted in the heavy lanthanides. Their compositions do not support the hypothesis of Parak that the Kiruna-type ores are of sedimentary origin. Table 9 and Figures 1-3 show the dependence of lanthanide distribution on the nature of the host rock. Although a given analysis of the lanthanides does not unequivocally permit certain identification of the host rock, it can indicate a choice of highly probable host rocks.

  2. Diagenetic uptake of rare earth elements by conodont apatite

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Algeo, T. J.; Cao, L.; Zhao, L.; Chen, Z. Q.; Li, Z.

    2015-12-01

    The rare earth element (REE) composition of bioapatite has long been used as a proxy for ancient seawater chemistry and paleomarine environmental reconstruction, based on the assumption of preservation of a hydrogenous (seawater-derived) REE signal. Recent work, however, has begun to question the provenance of REEs in conodonts, emphasizing the importance of REEs released by the lithogenous fraction of the sediment and subsequently adsorbed onto conodont apatite in the burial environment. Here, we investigate patterns of REE and trace-element abundance in conodonts and their host sediments from the Early to Late Ordovician Huanghuachang and Chenjiahe sections of Hubei Province, South China. Several lines of evidence indicate that REEs in the conodont samples were acquired mainly from clay minerals in the host sediment during burial diagenesis: (1) REEs in conodonts show a strong positive correlation to Th and other lithogenic elements; (2) conodonts and whole-rock samples show general patterns of REE and trace-element enrichment that are highly similar to each other and bear no resemblance to seawater elemental concentrations; (3) similar patterns are observed in Triassic conodonts and whole-rock samples; and (4) Y/Ho ratios in conodonts are mostly <40 (mean ~33), values that are consistent with derivation of >90% of REEs from lithogenous sources. Conodonts show pronounced middle rare earth element (MREE) enrichment, a pattern that is unambiguously of diagenetic origin owing to its association with lower Y/Ho ratios. With increasing MREE enrichment of conodont samples, U concentrations and LaN/YbN ratios shift from high to low, and Mn concentrations from low to high. These patterns suggest that conodont diagenesis was initiated at shallow burial depths under suboxic conditions (i.e., in the zone of Mn(IV) and Fe(III) reduction) but continued at greater burial depths, with most acquisition of secondary REEs at later diagenetic stages. Our findings indicate that (1

  3. Combined apatite fission track and U-Pb dating by LA-ICPMS

    NASA Astrophysics Data System (ADS)

    Chew, D. M.; Donelick, R. A.

    2012-04-01

    Apatite is a common accessory mineral in igneous, metamorphic and clastic sedimentary rocks. It is a nearly ubiquitous accessory phase in igneous rocks, is common in metamorphic rocks of pelitic, carbonate, basaltic, and ultramafic composition and is virtually ubiquitous in clastic sedimentary rocks. In contrast to the polycyclic behavior of the stable heavy mineral zircon, apatite is unstable in acidic groundwaters and has limited mechanical stability in sedimentary transport systems. Apatite has many potential applications in provenance studies, particularly as it likely represents first-cycle detritus. Fission track and U-Pb dating are very powerful techniques in apatite provenance studies. They yield complementary information, with the apatite fission-track system yielding low-temperature exhumation ages and the U-Pb system yielding high-temperature cooling ages which constrain the timing of apatite crystallization. This study focuses on integrating apatite fission track and U-Pb dating by the LA-ICPMS method. Our approach is intentionally broad in scope, and is applicable to any quadrupole or rapid-scanning magnetic-sector LA-ICPMS system. Calculating uranium concentrations in fission-track dating by LA-ICPMS increases the speed of analysis and sample throughput compared to the conventional external detector method and avoids the need for neutron irradiation (Hasebe et al., 2004). LA-ICPMS-based uranium measurements in apatite are measured relative to an internal concentration standard (typically 43Ca). Ca in apatite is not always stochiometric as minor cations (Mn2+, Sr2+, Ba2+ and Fe2+) and REE can substitute with Ca2+. These substitutions must be quantified by multi-elemental LA-ICPMS analyses. Such data are also useful for discriminating between different apatite populations in sedimentary or volcaniclastic rocks based on their trace-element chemistry. Low U, Th and radiogenic Pb concentrations, elevated common Pb / radiogenic Pb ratios and U-Pb elemental

  4. New ytterbium-doped apatite crystals for flexible laser design

    SciTech Connect

    Payne, S.A.; DeLoach, L.D.; Smith, L.K.; Krupke, W.F.; Chai, B.H.T.; Loutts, G.

    1994-03-01

    A new class of Yb-lasers is summarized in this article. The apatite family of crystals has been found to impose favorable spectroscopic and laser properties on the Yb{sup 3+} activator ion. Crystals of Yb-doped Ca{sub 5}(PO{sub 4}){sub 3}F, Sr{sub 5}(PO{sub 4}){sub 3}F, Ca{sub x}Sr{sub 5{minus}x}(PO{sub 4}){sub 3}F, and Sr{sub 5}(VO{sub 4}){sub 3}F have been grown and investigated. Several useful laser crystals have been identified which offer a variety of fundamental laser parameters for designing diode-pumped systems. In general, this class of materials is characterized by high emission cross sections (3.6--13.1 {times} 10{sup {minus}20} cm{sup 2}), useful emission lifetimes (0.59--1.26 msec), a strong pump band ({sigma}{sub abs} = 2.0--10.0 {times} 10{sup {minus}20} cm{sup 2}) and pump and extraction wavelengths near 900 and 1,045 nm, respectively. Efficient lasing has been demonstrated for several of the members of this class of materials, and high optical quality crystals have been grown by the Czochralski method.

  5. Constant composition kinetics study of carbonated apatite dissolution

    NASA Astrophysics Data System (ADS)

    Tang, Ruikang; Henneman, Zachary J.; Nancollas, George H.

    2003-03-01

    The carbonated apatites (CAP) may be more suitable models for biominerals such as bone and dental hard tissues than is pure hydroxyapatite (HAP) since they have similar chemical compositions. Although they contain only a relatively small amount of carbonate, the solubility and dissolution properties are different. The solubility product of the CAP particles used in this dissolution study, 2.88×10 -112 mol 18 l -18, was significantly greater than that of HAP, 5.52×10 -118 mol 18 l -18. The kinetics of dissolution of CAP has been studied using the constant composition (CC) method. At low undersaturations, the dissolution reaction appeared to be controlled mainly by surface diffusion with an effective reaction order of 1.9±0.1 with respect to the relative undersaturation. These results together with those obtained by scanning electron microscopy (SEM) suggest a dissolution model. Based on the surface diffusion theory of Burton, Cabrera and Frank (BCF). The interfacial tension between CAP and the aqueous phase calculated from this dissolution model, 9.0 m J m -2, was consistent with its relatively low solubility. An abnormal but interesting dissolution behavior is that the CAP dissolution rate was relatively insensitive to changes in calcium and phosphate concentrations at higher undersaturations, suggesting the importance of the carbonate component under these conditions.

  6. Arsenate substitution in lead hydroxyl apatites: A Raman spectroscopic study.

    PubMed

    Giera, Alicja; Manecki, Maciej; Bajda, Tomasz; Rakovan, John; Kwaśniak-Kominek, Monika; Marchlewski, Tomasz

    2016-01-05

    A total of seven compounds of the hydroxylpyromorphite Pb10(PO4)6(OH)2 - hydroxylmimetite Pb10(AsO4)6(OH)2 (HPY-HMI) solid solution series were synthesized at 80°C from aqueous solutions and characterized using Raman spectroscopy. The positions of the bands in all spectra of the series depend on the content of arsenates and phosphates shifting to lower wavenumbers with substitution of (AsO4)(3-) for (PO4)(3-). This shift results from the decreasing bond strength of X-O (where X=P, As) and higher atomic mass of As than P. The position and intensity of major (PO4)(3-) and (AsO4)(3-) bands in Raman spectra exhibit linear correlation with As content, while the ratio of the intensities of these peaks shows exponential correlation. This results due to different polarizability of (PO4)(3-) and (AsO4)(3-) molecules. A small carbonate band develops with increasing As content indicating that hydroxyl lead apatites adopt the (CO3)(2-) ions, particularly at the arsenate end of the series.

  7. Infrared spectra of carbonate apatites: v2-Region bands.

    PubMed

    Fleet, Michael E

    2009-03-01

    The proportions of A and B carbonate ions in a selection of AB carbonate apatites, including hydroxyapatite (CHAP), chlorapatite (CCLAP) and fluorapatite (CFAP), have been obtained using the out-of-plane bend (nu(2)) bands of Fourier transform infrared (FTIR) spectra. Band area ratios (B/A) are in very good agreement with site occupancies from single-crystal X-ray structure refinement; the correlation is linear (1:1) for B/A values ranging up to three. Most compositions have nu(2) spectra with one band for A carbonate (at 878-880 cm(-1)) and one for B (at 870-872 cm(-1)). Na-free AB CHAP has a third prominent band at 862 cm(-1), which is assigned to the stuffed channel species (A2), and Na-bearing CFAP has a third band at 864 cm(-1), which is assigned to a second B carbonate environment (B2). The A2 and B2 assignments are based largely on spectral changes in annealed samples.

  8. Fabrication of bone cement that fully transforms to carbonate apatite.

    PubMed

    Cahyanto, Arief; Maruta, Michito; Tsuru, Kanji; Matsuya, Shigeki; Ishikawa, Kunio

    2015-01-01

    The objective of this study was to fabricate a type of bone cement that could fully transform to carbonate apatite (CO3Ap) in physiological conditions. A combination of calcium carbonate (CaCO3) and dicalcium phosphate anhydrous was chosen as the powder phase and mixed with one of three kinds of sodium phosphate solutions: NaH2PO4, Na2HPO4, or Na3PO4. The cement that fully transformed to CO3Ap was fabricated using vaterite, instead of calcite, as a CaCO3 source. Their stability in aqueous solutions was different, regardless of the type of sodium phosphate solution. Rate of transformation to CO3Ap in descending order was Na3PO4>Na2HPO4>NaH2PO4. Transformation rate could be affected by the pH of solution. Results of this study showed that it was advantageous to use vaterite to fabricate CO3Ap-forming cement.

  9. Pseudomorphic 2A--> 2M--> 2H phase transitions in lanthanum strontium germanate electrolyte apatites.

    PubMed

    Pramana, Stevin S; White, T J; Schreyer, Martin K; Ferraris, Cristiano; Slater, Peter R; Orera, Alodia; Bastow, T J; Mangold, Stefan; Doyle, Stephen; Liu, Tao; Fajar, Andika; Srinivasan, Madhavi; Baikie, Tom

    2009-10-21

    Apatite-like materials are of considerable interest as potential solid oxide fuel cell electrolytes, although their structural vagaries continue to attract significant discussion. Understanding these features is crucial both to explain the oxide ion conduction process and to optimise it. As the composition of putative P6(3)/m apatites with ideal formula [A(I)(4)][A(II)(6)][(BO(4))(6)][X](2) is varied the [A(I)(4)(BO(4))(6)] framework will flex to better accommodate the [A(II)(6)X(2)] tunnel component through adjustment of the A(I)O(6) metaprism twist angle (varphi). The space group theory prescribes that framework adaptation during phase changes must lead to one of the maximal non-isomorphic subgroups of P6(3)/m (P2(1), P2(1)/m, P1[combining macron]). These adaptations correlate with oxygen ion conduction, and become crucial especially when the tunnels are filled by relatively small ions and/or partially occupied, and if interstitial oxygens are located in the framework. Detecting and completely describing these lower symmetry structures can be challenging, as it is difficult to precisely control apatite stoichiometry and small departures from the hexagonal metric may be near the limits of detection. Using a combination of diffraction and spectroscopic techniques it is shown that lanthanum strontium germanate oxide electrolytes crystallise as triclinic (A), monoclinic (M) and hexagonal (H) bi-layer pseudomorphs with the composition ranges: [La(10-x)Sr(x)][(GeO(4))(5+x/2)(GeO(5))(1-x/2)][O(2)] (0 apatite-2A[La(10-x)Sr(x)][(GeO(4))(5+x/2)(GeO(5))(1-x/2)][O(2)] (1 apatite-2M[La(10-x)Sr(x)][(GeO(4))(6)][O(2)][H(delta)] (2 apatite-2M[La(10-x)Sr(x)][(GeO(4))(6)][O(2)][H(delta)] (2.96 apatite-2HFurthermore, at typical fuel cell operating temperatures apatite-2A and apatite-2M will transform to apatite-2H, with the latter showing the highest conduction. The results show that small twist angles and high symmetry

  10. Ion substitutions and non-stoichiometry of carbonated apatite-(CaOH) synthesised by precipitation and hydrothermal methods

    NASA Astrophysics Data System (ADS)

    Frank-Kamenetskaya, Olga; Kol'tsov, Alexander; Kuz'mina, Maria; Zorina, Maina; Poritskaya, Lilya

    2011-04-01

    Apatite-(CaOH), either carbonate-free or with different concentrations of carbonate ions of the predominantly (not less than 60%) B type, was synthesised by precipitation from solutions, by hydrothermal methods from solid compounds and by hydrothermal treatment of calcite. In B type apatite, the concentration of CO32- ions could be up to 20.5 wt.%. The reverse precipitation method and hydrothermal treatment of calcite obtained monophase samples with a maximal concentration of CO32- ions of 10.3-10.5 wt.%. In apatites of a mixed type, the total concentration of CO32- ions did not exceed 8 wt.%. The synthesised apatites could be divided into three groups according to the degree and origin of non-stoichiometry: Apatite of nearly stoichiometric composition. Apatite of this type was synthesised by all methods. Calcium-deficient apatite. The Ca deficit was mainly due to CO32- incorporation. Monophase samples with maximal concentrations of CO32- ions were synthesised by the reverse precipitation method and by hydrothermal treatment of calcite. Calcium-deficient apatite. The Ca deficit was mainly due to a deficit of OH - ions and resulted in the incorporation of water into channels of the crystal structure. This group was synthesised by reverse precipitation and hydrothermal methods. This apatite was a crystal chemical analogue of the apatite formed in the hard tissues of the human body such as teeth, bone and different stones. Apatites formed by the precipitation methods revealed higher variations in composition (including variations in the concentration of CO32- ions), compared to hydrothermally-synthesised samples. The observed effect of aqueous solution composition on the ion substitution and apatite composition was stronger than previously reported.

  11. Plant-driven weathering of apatite--the role of an ectomycorrhizal fungus.

    PubMed

    Smits, M M; Bonneville, S; Benning, L G; Banwart, S A; Leake, J R

    2012-09-01

    Ectomycorrhizal (EcM) fungi are increasingly recognized as important agents of mineral weathering and soil development, with far-reaching impacts on biogeochemical cycles. Because EcM fungi live in a symbiotic relationship with trees and in close contact with bacteria and archaea, it is difficult to distinguish between the weathering effects of the fungus, host tree and other micro-organisms. Here, we quantified mineral weathering by the fungus Paxillus involutus, growing in symbiosis with Pinus sylvestris under sterile conditions. The mycorrhizal trees were grown in specially designed sterile microcosms in which the supply of soluble phosphorus (P) in the bulk media was varied and grains of the calcium phosphate mineral apatite mixed with quartz, or quartz alone, were provided in plastic wells that were only accessed by their fungal partner. Under P limitation, pulse labelling of plants with (14)CO(2) revealed plant-to-fungus allocation of photosynthates, with 17 times more (14)C transferred into the apatite wells compared with wells with only quartz. Fungal colonization increased the release of P from apatite by almost a factor of three, from 7.5 (±1.1) × 10(-10) mol m(-2) s(-1) to 2.2 (±0.52) × 10(-9) mol m(-2) s(-1). On increasing the P supply in the microcosms from no added P, through apatite alone, to both apatite and orthophosphate, the proportion of biomass in roots progressively increased at the expense of the fungus. These three observations, (i) proportionately more plant energy investment in the fungal partner under P limitation, (ii) preferential fungal transport of photosynthate-derived carbon towards patches of apatite grains and (iii) fungal enhancement of weathering rate, reveal the tightly coupled plant-fungal interactions underpinning enhanced EcM weathering of apatite and its utilization as P source.

  12. Fabrication and in vitro characterization of magnetic hydroxycarbonate apatite coatings with hierarchically porous structures.

    PubMed

    Guo, Yaping; Zhou, Yu; Jia, Dechang; Meng, Qingchang

    2008-07-01

    Hydroxycarbonate apatite/Fe(3)O(4) composite coatings (MHACs) with hierarchically porous structures were fabricated by electrophoretic deposition of CaCO(3)/Fe(3)O(4) particles on Ti6Al4V substrates followed by treatment with phosphate buffer solution (PBS) at 37 degrees C. The effects of Fe(3)O(4) on the conversion rate of calcium carbonate to hydroxycarbonate apatite and the porous structures and in vitro bioactivity of MHACs were investigated. After soaking CaCO(3)/Fe(3)O(4) coatings in PBS, hydroxycarbonate apatite nucleates heterogeneously on the surfaces of CaCO(3)/Fe(3)O(4) particles and forms a plate-like structure. Fe(3)O(4) increases the velocity of nucleus formation of hydroxycarbonate apatite. After soaking for 1day, the percentage of unreacted calcium carbonate for MHACs is approximately 9.1%, lower than the approximately 41.0% for hydroxycarbonate apatite coatings (HCACs). As the CaCO(3)/Fe(3)O(4) coatings are converted to MHACs, macropores with a pore size of approximately 4mum on the coatings and mesopores with a pore size of approximately 3.9nm within the hydroxycarbonate apatite plates are formed. The mesopores remain in the MHACs after treatment with PBS for 9 days, while they disappear in the HCACs. Simulated body fluid immersion tests reveal that Fe(3)O(4) improves the in vitro bioactivity of biocoatings. The amount of bone-like apatite precipitated on the surfaces of MHACs is greater than that on the surfaces of HCACs.

  13. Amelogenin as a promoter of nucleation and crystal growth of apatite

    NASA Astrophysics Data System (ADS)

    Uskoković, Vuk; Li, Wu; Habelitz, Stefan

    2011-02-01

    Human dental enamel forms over a period of 2-4 years by substituting the enamel matrix, a protein gel mostly composed of a single protein, amelogenin with fibrous apatite nanocrystals. Self-assembly of amelogenin and the products of its selective proteolytic digestion are presumed to direct the growth of apatite fibers and their organization into bundles that eventually comprise the mature enamel, the hardest tissue in the mammalian body. This work aimed to establish the physicochemical and biochemical conditions for the growth of apatite crystals under the control of a recombinant amelogenin matrix (rH174) in combination with a programmable titration system. The growth of apatite substrates was initiated in the presence of self-assembling amelogenin particles. A series of constant titration rate experiments was performed that allowed for a gradual increase of the calcium and/or phosphate concentrations in the protein suspensions. We observed a significant amount of apatite crystals formed on the substrates following the titration of rH174 sols that comprised the initial supersaturation ratio equal to zero. The protein layers adsorbed onto the substrate apatite crystals were shown to act as promoters of nucleation and growth of calcium phosphates subsequently formed on the substrate surface. Nucleation lag time experiments have showed that rH174 tends to accelerate precipitation from metastable calcium phosphate solutions in proportion to its concentration. Despite their mainly hydrophobic nature, amelogenin nanospheres, the size and surface charge properties of which were analyzed using dynamic light scattering, acted as a nucleating agent for the crystallization of apatite. The biomimetic experimental setting applied in this study proves as convenient for gaining insight into the fundamental nature of the process of amelogenesis.

  14. Selective protein adsorption and blood compatibility of hydroxy-carbonate apatites.

    PubMed

    Takemoto, Shinji; Kusudo, Yuko; Tsuru, Kanji; Hayakawa, Satoshi; Osaka, Akiyoshi; Takashima, Seisuke

    2004-06-01

    We examined the blood compatibility and protein adsorption on hydroxyapatite and hydroxy-carbonate apatite. Those apatites were synthesized under a 0, 5, or 15% CO(2)-containing N(2) atmosphere by a wet-chemical method with a strong ammonia alkali solution of calcium nitrate and diammonium hydrogen phosphate (5:3 in molar ratio) and subsequent calcination in the range of 105-700 degrees C. From infrared (IR) analysis, the carbonate ions substituted both phosphate ions and hydroxyl ions in the hydroxyapatite lattice; the intensities of IR bands assignable to phosphate ions and hydroxyl ions were reduced on calcinations. The specific surface areas of synthesized apatites decreased with increasing calcination temperature. Blood-clotting properties were evaluated in terms of active partial thromboplastin time, prothrombin time, and the amount of fibrinogen for the plasma in contact with the apatites, indicating that all the apatites barely influenced the blood clotting system. The apatites were in contact with a solution containing both bovine serum albumin (BSA) and beta(2)-microglobulin (beta(2)-MG), and the amounts of those proteins adsorbed on them were examined: the amount of absorbed BSA and beta(2)-MG gradually increased with the calcination temperature below 500 degrees C, while it showed a sudden increase when more than 600 degrees C. Hydroxy-carbonate apatite synthesized under a 15% CO(2)-containing N(2) atmosphere and calcined below 400 degrees C had the greatest selectivity in adsorbing beta(2)-MG. Thus, a higher selectivity for beta(2)-MG adsorption was empirically correlated to carbonate ions incorporated in the hydroxyapatite lattice.

  15. Poorly crystalline apatites: evolution and maturation in vitro and in vivo.

    PubMed

    Cazalbou, Sophie; Combes, Christèle; Eichert, Diane; Rey, Christian; Glimcher, Melvin J

    2004-01-01

    Poorly crystalline apatites (PCA) are the major mineral component of mineralized tissues in vertebrates. Their physical-chemical properties are, however, not very well known due to their relative instability and the difficulties to characterize nanocrystalline compounds. Several studies using spectroscopic techniques (Fourier transform infrared [FTIR]; 31P nuclear magnetic resonance [NMR]) have demonstrated the existence, both in precipitated and biological PCA, of labile non-apatitic environments of the mineral ions. These environments are involved in the high surface reactivity and evolution ability of PCA and they are believed to form a hydrated layer at the surface of the nanocrystals in aqueous media. The extent of the hydrated layer may vary considerably depending on the conditions of precipitation and maturation time. As PCA age, the decrease of the non-apatitic environments proportion is associated with a decrease of intracrystalline disorder and an increase of stable apatitic domains. For synthetic and biological apatites, the carbonation rate of the mineral and the uptake of essential or toxic trace elements can be related to the maturation processes. The mineral ions of the hydrated layer can be easily and reversibly substituted by other ions which can either be included in the growing stable apatite lattice during maturation or remain in the hydrated layer. In addition, the non-apatitic environments seem to be involved in the binding of soluble non-collagenic proteins. This phenomenon could be related to calcium phosphate formation; we showed that, at an albumin concentration close to that in human serum, this protein has an inhibitory effect on octacalcium phosphate crystallization on collagen in vitro.

  16. Interrogating the Effects of Radiation Damage Annealing on Helium Diffusion Kinetics in Apatite

    NASA Astrophysics Data System (ADS)

    Willett, C. D.; Fox, M.; Shuster, D. L.

    2015-12-01

    Apatite (U-Th)/He thermochronology is commonly used to study landscape evolution and potential links between climate, erosion and tectonics. The technique relies on a quantitative understanding of (i) helium diffusion kinetics in apatite, (ii) an evolving 4He concentration, (iii) accumulating damage to the crystal lattice caused by radioactive decay[1], and (iv) the thermal annealing of such damage[2],[3], which are each functions of both time and temperature. Uncertainty in existing models of helium diffusion kinetics has resulted in conflicting conclusions, especially in settings involving burial heating through geologic time. The effects of alpha recoil damage annealing are currently assumed to follow the kinetics of fission track annealing (e.g., reference [3]), although this assumption is difficult to fully validate. Here, we present results of modeling exercises and a suite of experiments designed to interrogate the effects of damage annealing on He diffusivity in apatite that are independent of empirical calibrations of fission track annealing. We use the existing experimental results for Durango apatite[2] to develop and calibrate a new function that predicts the effects of annealing temperature and duration on measured diffusivity. We also present a suite of experiments conducted on apatite from Sierra Nevada, CA granite to establish whether apatites with different chemical compositions have the same behavior as Durango apatite. Crystals were heated under vacuum to temperatures between 250 and 500°C for 1, 10, or 100 hours. The samples were then irradiated with ~220 MeV protons to produce spallogenic 3He, the diffusant then used in step-heating diffusion experiments. We compare the results of these experiments and model calibrations to existing models. Citations: [1]Shuster, D., Flowers R., and Farley K., (2006), EPSL 249(3-4), 148-161; [2]Shuster, D. and Farley, K., (2009), GCA 73 (1), 6183-6196; [3]Flowers, R., Ketcham, R., Shuster, D. and Farley, K

  17. Volatile History of the Bishop Tuff from Apatite Phenocrysts and Inclusions

    NASA Astrophysics Data System (ADS)

    Walowski, K. J.; Boyce, J. W.

    2009-12-01

    Apatite is a common mineral found in a wide variety of volcanic rocks and contains all of the volatile elements within its structure as either major or minor components. Such characteristics make apatite a useful tool for developing a better understanding of complex magmatic systems and their evolution. For some elements, such as F, Cl, and OH, an apatite phenocryst can participate in chemical exchange within the magma chamber on very short timescales (Brenan, 1993, Chem. Geol.), thus giving insight into the volatiles in the system immediately prior to eruption. For other elements (including S), natural and experimental data indicate that variations can be preserved for longer timescales, potentially providing a different, yet equally interesting record. With an especially well-studied ignimbrite and air fall sequence and previously published melt inclusion work, the Bishop Tuff is an ideal system in which to test the utility of apatite crystals for studying volatile evolution of a large volume magma body. The Bishop Tuff has a nine unit air fall sequence (Wilson and Hildreth, 1997, 2003, J. Geol.) from which three units were chosen to represent early (unit #2), middle (#5), and late (#8) air fall periods. Along with apatite phenocrysts, apatite inclusions within zircon phenocrysts were used to investigate the prospect that a host could protect the crystal from volatile exchange with the melt in a manner analogous to melt inclusions. This would potentially extend the record deeper into the history of the magma. Fifty analyses of volatile, major, and trace elements were performed at UCLA using the JOEL JXA-8200 electron microprobe. Apatite phenocrysts from the Bishop Tuff are very poor in Cl with measured values (<200 ppm), often within error of zero. In these same crystals, we observe S-depleted rims (<2000 ppm) and S-rich cores (>4500 ppm), possibly representing an earlier magmatic phase, or xenocrystic remnants. Interestingly, we observe similar S variations in

  18. Magnetite-apatite mineralization in Khanlogh iron deposit, northwest of Neyshaboor, NE Iran

    NASA Astrophysics Data System (ADS)

    Najafzadeh Tehrani, Parvin; Asghar Calagari, Ali; Velasco Roldan, Francisco; Simmonds, Vartan; Siahcheshm, Kamal

    2016-04-01

    Khanlogh iron deposit lies on Sabzehvar-Ghoochan Cenozoic magmatic belt in northwest of Neyshaboor, NE Iran. The lithologic units in this area include a series of sub-volcanic intrusive rocks like diorite porphyry, quartz-diorite porphyry, and micro-granodiorite of Oligocene age. Mineralization in this area occurred as veins, dissemination, and open space filling in brecciated zones within the host sub-volcanic intrusive bodies. Three distinct types of mineral associations can be distinguished, (1) diopside-magnetite, (2) magnetite-apatite, and (3) apatite-calcite. Microscopic examinations along with SEM and EPMA studies demonstrated that magnetite is the most common ore mineral occurring as solitary crystals. The euhedral magnetite crystals are accompanied by lamellar destabilized ilmenite and granular fluorapatite in magnetite-apatite ores. The results of EPMA revealed that the lamellar ilmenite, relative to host magnetite crystal, is notably enriched in MgO and MnO (average of 3.3 and 2.6 wt%, respectively; n=5), whereas magnetite is slighter enriched in Ti (TiO2 around 1.8 wt%) being average of MgO, MnO and V2O3 of 0.6wt%, 0.2wt%, and 0.6 wt% (respectively; n=20). Minerals such as chlorapatite, calcite, and chalcedony are also present in the magnetite-apatite ores. The samples from apatite-calcite ores contain coarse crystals of apatite and rhomboedral calcite. The plot of the EPMA data of Khanlogh iron ore samples on diagram of TiO2-V2O5 (Hou et al, 2011) illustrated that the data points lies between the well-known Kiruna and El Laco (Chile) iron deposits. The magnetite crystals in the sub-volcanic host rocks were possibly formed by immiscible iron oxide fluids during magmatic stage. However, the magnetite and apatite existing in the veins and breccia zones may have developed by high temperature hydrothermal fluids. Studies done by Purtov and Kotelnikova (1993) proved that the proportion of Ti in magnetite is related to fluoride complex in the hydrothermal

  19. Apatite formation behaviour during metasomatism in the Bathtub Intrusion (Babbitt deposit, Duluth Complex, USA)

    NASA Astrophysics Data System (ADS)

    Raič, Sara; Mogessie, Aberra; Krenn, Kurt; Hauzenberger, Christoph A.; Tropper, Peter

    2016-04-01

    The mineralized troctolitic Bathtub intrusion (Duluth Complex, NE-Minnesota) is known for its famous Cu-Ni-Sulfide±PGM Babbitt deposit, where platinum group minerals (PGMs) are either hosted by primary magmatic sulfides (base metal sulfides) or associated with hydrothermally altered portions. This secondary generation of PGMs is present in alteration patches and suggests the involvement of hydrothermal fluids in the mobilization of platinum-group elements (PGEs). Accessory fluorapatite in these samples reveals besides H2O- and CO2-rich primary fluid inclusions, textural and compositional variations that also record magmatic and metasomatic events. Based on detailed back-scattered electron imaging (BSE) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICPMS), a primary magmatic origin is reflected by homogeneous or zoned grains, where zoning patterns are either concentric or oscillatory, with respect to LREE. Late magmatic to hydrothermal processes are indicated by grains with bright LREE-enriched rims or conversion textures with REE-enriched patches in the interior of the apatite. A metasomatic formation of monazite from apatite is documented by the presence of monazite inclusions in apatite and newly grown monazite at altered apatite rims. They formed by the release of REEs from the apatite during a fluid-induced alteration, based on the coupled substitution Ca2+ + P5+ = REE3+ + Si4+ (Rønsbo 1989; Rønsbo 2008). Samples with monazite inclusions in apatite further display occurrences of PGMs associated with hydrothermal alteration patches (chlorite + amphibole). The presence of H2O- and CO2-rich fluid inclusions in apatite, the metasomatically induced monazite growth, as well as the occurrence of PGMs in hydrothermally alteration zones, also suggest the involvement of aqueous chloride complexes in a H2O dominated fluid in the transportation of LREE and redistribution of the second generation of PGEs. Rønsbo, J.G. (1989): Coupled substitutions

  20. Challenges Associated with Apatite Remediation of Uranium in the 300 Area Aquifer

    SciTech Connect

    Wellman, Dawn M.; Fruchter, Jonathan S.; Vermeul, Vincent R.; Williams, Mark D.

    2008-05-01

    Sequestration of uranium as insoluble phosphate phases appears to be a promising alternative for treating the uranium-contaminated groundwater at the Hanford 300 Area. The proposed approach involves both the direct formation of autunite by the application of a polyphosphate mixture, as well as the formation of apatite in the aquifer as a continuing source of phosphate for long-term treatment of uranium. After a series of bench-scale tests, a field treatability test was conducted in a well at the 300 Area. The objective of the treatability test was to evaluate the efficacy of using polyphosphate injections to treat uranium-contaminated groundwater in situ. A test site consisting of an injection well and 15 monitoring wells was installed in the 300 Area near the process trenches that had previously received uranium-bearing effluents. The results indicated that while the direct formation of autunite appears to have been successful, the outcome of the apatite formation of the test was more limited. Two separate overarching issues impact the efficacy of apatite remediation for uranium sequestration within the 300 Area: 1) the efficacy of apatite for sequestering uranium under the present geochemical and hydrodynamic conditions, and 2) the formation and emplacement of apatite via polyphosphate technology. This paper summarizes these issues.

  1. Crystallinity in apatites: how can a truly disordered fraction be distinguished from nanosize crystalline domains?

    PubMed

    Celotti, Giancarlo; Tampieri, Anna; Sprio, Simone; Landi, Elena; Bertinetti, Luca; Martra, Gianmario; Ducati, Caterina

    2006-11-01

    In the last decade synthetic apatites mimicking the human natural one have been widely prepared and characterized from the physico-chemical point of view; however a shading zone is still remaining related to the evaluation and distinction of the less crystalline part, almost amorphous, and the crystallographically well ordered, nano-sized part, inside the apatite itself. Actually natural apatite forming bone tissue can include both types of crystals whose prevalence is dependent from the specific bone evolution stage and the specialized tissue performance. The quantitative description of such a combination usually represents a puzzling problem, but the result can also clarify the definition of "crystallinity in apatite" that appears still controversial. Many different synthetic apatites, including those nucleated on organic templates, were analyzed with different techniques (X-ray diffraction, transmission electron microscopy, and so on) to clarify the true nature of the disordered part. The results, manipulated by the classical methodologies devised for substances with highly perturbed structural order, led to establish that only specifically prepared amorphous calcium phosphate is really a glass, while the distorted portion coexisting with more or less crystalline regions is simply nanocrystalline. Moreover, at the conceptual limit of crystallinity tending to zero, the two models surprisingly cease to be conflicting.

  2. Enzyme-functionalized biomimetic apatites: concept and perspectives in view of innovative medical approaches.

    PubMed

    Weber, Christina G; Mueller, Michaela; Vandecandelaere, Nicolas; Trick, Iris; Burger-Kentischer, Anke; Maucher, Tanja; Drouet, Christophe

    2014-03-01

    Biomimetic nanocrystalline calcium-deficient apatite compounds are particularly attractive for the setup of bioactive bone-repair scaffolds due to their high similarity to bone mineral in terms of chemical composition, structural and substructural features. As such, along with the increasingly appealing development of moderate temperature engineered routes for sample processing, they have widened the armamentarium of orthopedic and maxillofacial surgeons in the field of bone tissue engineering. This was made possible by exploiting the exceptional surface reactivity of biomimetic apatite nanocrystals, capable of easily exchanging ions or adsorbing (bio)molecules, thus leading to highly-versatile drug delivery systems. In this contribution we focus on the preparation of hybrid materials combining biomimetic nanocrystalline apatites and enzymes (lysozyme and subtilisin). This paper reports physico-chemical data as well as cytotoxicity evaluations towards Cal-72 osteoblast-like cells and finally antimicrobial assessments towards selected strains of interest in bone surgery. Biomimetic apatite/enzyme hybrids could be prepared in varying buffers. They were found to be non-cytotoxic toward osteoblastic cells and the enzymes retained their biological activity (e.g. bond cleavage or antibacterial properties) despite the immobilization and drying processes. Release properties were also examined. Beyond these illustrative examples, the concept of biomimetic apatites functionalized with enzymes is thus shown to be useable in practice, e.g. for antimicrobial purposes, thus widening possible therapeutic perspectives.

  3. Fabrication and apatite inducing ability of different porous titania structures by PEO treatment.

    PubMed

    Rao, X; Chu, C L; Sun, Q; Zheng, Y Y

    2016-09-01

    Plasma electrolytic oxidation (PEO) was employed to grow different porous titania structures on Ti6Al4V alloy (TC4) substrate using various parameters. It was found that the PEO voltage and working frequency could affect the morphology, the pore size, the pore density, the thickness and the phase composition of titania structures. Thereafter, three typical porous titania structures with nanosize pores, microsize pores and microsize grooves were respectively selected to estimate their bioactivity using SBF immersion test. After soaking at different durations (3-28d), the surface morphology, the chemical composition as well as the phase structure of deposited apatite layers on porous titania were evaluated using SEM, EDS, and XRD. The formation of various biomimetic apatite layers indicated the different influence due to the characteristics of porous titania structures. The porous titania structure with nanosize pores could induce a fast apatite growth at the early immersion stage (~7d), while the one with microsize pores exhibited the best apatite inducing ability at long term immersion (~28d). Based on the experimental results, the formation mechanism of biomimetic apatite affected by the pore structure of titania was discussed as well.

  4. Apatite fission-track thermochronology of the southern Appalachian Basin: Maryland, West Virginia, and Virginia

    SciTech Connect

    Roden, M.K. )

    1991-01-01

    Apatite fission-track apparent ages (246 {plus minus} 37 to 95 {plus minus} 18 Ma) for 26 samples of upper Devonian (Hampshire and Chemung Formations) and middle Devonian age (Tioga Ash Bed) from the southern Appalachian Basin of Maryland, Virginia, and West Virginia, along with confined track length distributions for 13 of these samples, suggest that uplift was contemporaneous with Triassic-Jurassic extension along the Atlantic continental margin. Uplift, as measured by apatite fission-track analysis, began earliest in the northwestern section on the Cumberland Plateau at {approximately}225 {plus minus} 25 Ma. This area probably required the least amount of erosional unroofing ({approximately}3.1 km). Samples from the Valley and Ridge Province of northern West Virginia, Virginia, and Maryland yield progressively younger apatite fission-track apparent ages to the east (ranging from 163 {plus minus} 10 to 95 {plus minus} 18 Ma). This is consistent with deeper burial in the eastern Appalachian Basin as indicated by increasing CAI indices and geodynamic modeling. The southwestern Virginia samples yield a mean apatite fission-track apparent age of 176 {plus minus} 11 Ma, which agrees with the Middle Jurassic apatite fission-track ages to the north.

  5. Experimental effects of pressure and fluorine on apatite saturation in mafic magmas, with reference to layered intrusions and massif anorthosites

    NASA Astrophysics Data System (ADS)

    Tollari, N.; Baker, D. R.; Barnes, S.-J.

    2008-08-01

    Apatite is a cumulate phase in the upper parts of some mafic layered intrusions and anorthositic complexes. We investigated the effect of pressure and fluorine on apatite saturation in mafic magmas to better understand under which conditions this mineral crystallizes. Apatite saturation gives information about the formation of silicate rocks, and is of interest in explaining the formation of apatite-oxide-rich rocks (e.g. nelsonites comprising approximately, one-third apatite and two-third Fe-Ti oxide). Two models of formation are proposed for this rock type: crystal fractionation followed by accumulation of apatite and Fe-Ti oxides and liquid immiscibility. New experiments carried out with mafic compositions at 500 MPa confirm that the most important variables on phosphate saturation are SiO2 and CaO. Fluorine addition leads to apatite saturation at lower SiO2 and higher CaO concentrations. Comparison of our results with those of previous experimental studies on liquid-liquid immiscibility at upper-to-mid-crustal conditions allows us to investigate the relative importance of apatite saturation versus liquid-liquid immiscibility in the petrogenesis of nelsonites and similar rocks. The liquid line of descent of three natural examples studied (the Sept-Îles intrusive suite, the anorthositic Complex of the Lac-St-Jean and the Skaergaard layered intrusion) do not cross the liquid-liquid immiscibility field before they reach apatite saturation. Thus, the apatite-oxide-rich rock associated with these three intrusive suites are best explained by crystal fractionation followed by accumulation of apatite and Fe-Ti oxides.

  6. Amelogenin Promotes the Formation of Elongated Apatite Microstructures in a Controlled Crystallization System

    PubMed Central

    Wang, Lijun; Guan, Xiangying; Du, Chang; Moradian-Oldak, Janet; Nancollas, George H.

    2009-01-01

    The organic matrix in forming enamel consists largely of the amelogenin protein self-assembled into nanospheres that play a pivotal role in controlling the oriented and elongated growth of highly ordered apatitic crystals during enamel biomineralization. However, the mechanisms of amelogenin-mediated mineralization have not yet been fully elucidated. Here we report that amelogenin dramatically accelerates the nucleation kinetics by decreasing the induction time in a dose-dependent manner in a controlled constant composition (CC) in vitro crystallization system. Remarkably, at very low protein concentrations, elongated microstructures which are similar in appearance to apatitic crystals in enamel were formed at relatively low supersaturations, through interfacial structural match/synergy between structured amelogenin assemblies and apatite nanocrystallites. This heterogeneous crystallization study provides experimental evidence to support the concept that templating by amelogenin very early in the crystallization process facilitates the formation of developing enamel crystals. PMID:20333260

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

    USGS Publications Warehouse

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

    1951-01-01

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

  8. Young asteroidal fluid activity revealed by absolute age from apatite in carbonaceous chondrite.

    PubMed

    Zhang, Ai-Cheng; Li, Qiu-Li; Yurimoto, Hisayoshi; Sakamoto, Naoya; Li, Xian-Hua; Hu, Sen; Lin, Yang-Ting; Wang, Ru-Cheng

    2016-09-29

    Chondritic meteorites, consisting of the materials that have formed in the early solar system (ESS), have been affected by late thermal events and fluid activity to various degrees. Determining the timing of fluid activity in ESS is of fundamental importance for understanding the nature, formation, evolution and significance of fluid activity in ESS. Previous investigations have determined the relative ages of fluid activity with short-lived isotope systematics. Here we report an absolute (207)Pb/(206)Pb isochron age (4,450±50 Ma) of apatite from Dar al Gani (DaG) 978, a type ∼3.5, ungrouped carbonaceous chondrite. The petrographic, mineralogical and geochemical features suggest that the apatite in DaG 978 should have formed during metamorphism in the presence of a fluid. Therefore, the apatite age represents an absolute age for fluid activity in an asteroidal setting. An impact event could have provided the heat to activate this young fluid activity in ESS.

  9. Young asteroidal fluid activity revealed by absolute age from apatite in carbonaceous chondrite

    NASA Astrophysics Data System (ADS)

    Zhang, Ai-Cheng; Li, Qiu-Li; Yurimoto, Hisayoshi; Sakamoto, Naoya; Li, Xian-Hua; Hu, Sen; Lin, Yang-Ting; Wang, Ru-Cheng

    2016-09-01

    Chondritic meteorites, consisting of the materials that have formed in the early solar system (ESS), have been affected by late thermal events and fluid activity to various degrees. Determining the timing of fluid activity in ESS is of fundamental importance for understanding the nature, formation, evolution and significance of fluid activity in ESS. Previous investigations have determined the relative ages of fluid activity with short-lived isotope systematics. Here we report an absolute 207Pb/206Pb isochron age (4,450+/-50 Ma) of apatite from Dar al Gani (DaG) 978, a type ~3.5, ungrouped carbonaceous chondrite. The petrographic, mineralogical and geochemical features suggest that the apatite in DaG 978 should have formed during metamorphism in the presence of a fluid. Therefore, the apatite age represents an absolute age for fluid activity in an asteroidal setting. An impact event could have provided the heat to activate this young fluid activity in ESS.

  10. Apatite in carbonatitic rocks: Compositional variation, zoning, element partitioning and petrogenetic significance

    NASA Astrophysics Data System (ADS)

    Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Zaitsev, Anatoly N.; Couëslan, Christopher; Xu, Cheng; Kynický, Jindřich; Mumin, A. Hamid; Yang, Panseok

    2017-03-01

    Apatite-group phosphates are nearly ubiquitous in carbonatites, but our understanding of these minerals is inadequate, particularly in the areas of element partitioning and petrogenetic interpretation of their compositional variation among spatially associated rocks and within individual crystals. In the present work, the mode of occurrence, and major- and trace-element chemistry of apatite (sensu lato) from calcite and dolomite carbonatites, their associated cumulate rocks (including phoscorites) and hydrothermal parageneses were studied using a set of 80 samples from 50 localities worldwide. The majority of this set represents material for which no analytical data are available in the literature. Electron-microprobe and laser-ablation mass-spectrometry data ( 600 and 400 analyses, respectively), accompanied by back-scattered-electron and cathodoluminescence images and Raman spectra, were used to identify the key compositional characteristics and zoning patterns of carbonatitic apatite. These data are placed in the context of phosphorus geochemistry in carbonatitic systems and carbonatite evolution, and compared to the models proposed by previous workers. The documented variations in apatite morphology and zoning represent a detailed record of a wide range of evolutionary processes, both magmatic and fluid-driven. The majority of igneous apatite from the examined rocks is Cl-poor fluorapatite or F-rich hydroxylapatite (≥ 0.3 apfu F) with 0.2-2.7 wt.% SrO, 0-4.5 wt.% LREE2O3, 0-0.8 wt.% Na2O, and low levels of other cations accommodated in the Ca site (up to 1000 ppm Mn, 2300 ppm Fe, 200 ppm Ba, 150 ppm Pb, 700 ppm Th and 150 ppm U), none of which show meaningful correlation with the host-rock type. Silicate, (SO4)2 - and (VO4)3 - anions, substituting for (PO4)3 -, tend to occur in greater abundance in crystals from calcite carbonatites (up to 4.2 wt.% SiO2, 1.5 wt.% SO3 and 660 ppm V). Although (CO3)2 - groups are very likely present in some samples, Raman micro

  11. Fourier transform infrared determination of CO2 evolved from carbonate in carbonated apatites.

    PubMed

    Cassella, A R; de Campos, R C; Garrigues, S; de la Guardia, M; Rossi, A

    2000-07-01

    A quantitative method based on FTIR has been developed to determine carbonate in synthetic apatites. The method measures the evolved CO2 after reaction of 50 mg apatite with 2 mL of hydrochloric acid (0.5 M) in a reaction vessel, heated to 40 degrees C. The CO2 evolved was swept by a carrier of nitrogen to a laboratory-made infrared gas cell of 39 mm pathlength and 490 microL volume. The signals were recorded as a function of time and the areas of the chemigram peaks obtained from the measurements in the wavenumber range of 2,500-2,150 cm(-1), were interpolated using a calibration curve. The method can be used to study apatites with carbonate contents below 0.2% with a sampling frequency of 8 h(-1).

  12. Uptake of cadmium by synthetic mica and apatite: Observation by micro-PIXE

    NASA Astrophysics Data System (ADS)

    Kozai, Naofumi; Ohnuki, Toshihiko; Komarneni, Sridhar; Kamiya, Tomihiro; Sakai, Takuro; Oikawa, Masakazu; Satoh, Takahiro

    2003-09-01

    This study investigated the uptake of Cd by a mixture containing equal mass of two powerful sorbents for Cd, a synthetic mica named 'Na-4-mica' and an apatite, by micro-particle-induced X-ray emission (micro-PIXE) analysis. Divalent Cd ions were found to be selectively taken up by the apatite from the mixture even though it has one order of magnitude lower distribution coefficient for Cd 2+ than Na-4-mica. This was mainly attributed to the fact that the kinetics of uptake by the apatite were more rapid than those by Na-4-mica. Regarding the uptake of Cd colloids containing hydroxides and carbonates, no clear selectivity for solid phases was observed and Cd colloids appeared to be preferentially taken up by smaller particles of solid phases.

  13. Échange terres rares légères Ca dans l'apatite

    NASA Astrophysics Data System (ADS)

    Iqdari, Abderrahmane; Velde, Bruce; Benalioulhaj, Noureddine; Dujon, Saint-Clair; El Yamine, Nacer

    2003-04-01

    Diffusion experiments were carried out on natural apatite crystals that were immersed in molten light rare earth element (REE) chloride salt at temperatures between 900 and 1150 °C for periods up to 35 days. Electron microprobe analysis of the crystals showed that light REEs replaced Ca according to electronic balance, i.e. 2 REE3+ for 3 Ca2+. These diffusion profiles indicate that a maximum amount of substitution in the structure occurs when two of the ten Ca ions in apatite are replaced by the REE diffusing elements. Anisotropic diffusion is observed between a and c crystallographic directions. Comparison of maximum distance indicates that the larger ions move more easily in the apatite structure. We conclude that the light REEs diffuse within the channel structures of the mineral, and that this diffusion is controlled by the substitution type of elements in the calcium sites. To cite this article: A. Iqdari et al., C. R. Geoscience 335 (2003).

  14. PNNL Apatite Investigation at 100-NR-2 Quality Assurance Project Plan

    SciTech Connect

    Fix, N. J.

    2009-04-02

    In 2004, the U.S. Department of Energy, Fluor Hanford, Inc., Pacific Northwest National Laboratory (PNNL), and the Washington Department of Ecology agreed that the long-term strategy for groundwater remediation at the 100-N Area would include apatite sequestration as the primary treatment, followed by a secondary treatment if necessary. Since then, the agencies have worked together to agree on which apatite sequestration technology has the greatest chance of reducing strontium-90 flux to the Columbia River. This Quality Assurance Project Plan provides the quality assurance requirements and processes that will be followed by staff working on the PNNL Apatite Investigation at 100-NR-2 Project. The plan is designed to be used exclusively by project staff.

  15. Biomimetic apatite formation on Ultra-High Molecular Weight Polyethylene (UHMWPE) using modified biomimetic solution.

    PubMed

    Aparecida, Anahi H; Fook, Marcus V L; Guastaldi, Antonio C

    2009-06-01

    Modifications were performed on a biomimetic solution (SBF), according to previous knowledge on the behavior of ions present in its composition, in order to obtain apatite coatings onto Ultra-High Molecular Weight Polyethylene (UHMWPE) without having to use polymer pre-treatments that could compromise its properties. UHMWPE substrates were immersed into a 30% H(2)O(2) solution for a 24-h period and then submitted to a biomimetic coating method using standard SBF and two other modified SBF solutions. Apatite coatings were only obtained onto UHMWPE when the modified SBF solutions were used. Based on these results, apatite coatings of biological importance (calcium-deficient hydroxyapatite-CDHA, amorphous calcium phosphate-ACP, octacalcium phosphate-OCP, and carbonated HA) can be obtained onto UHMWPE substrates, allowing an adequate conciliation between bonelike mechanical properties and bioactivity.

  16. Apatite (U-Th)/He thermochronology dataset interpretation: New insights from physical point of view

    NASA Astrophysics Data System (ADS)

    Gautheron, Cécile; Mbongo-Djimbi, Duval; Gerin, Chloé; Roques, Jérôme; Bachelet, Cyril; Oliviero, Erwan; Tassan-Got, Laurent

    2015-04-01

    The apatite (U-Th)/He (AHe) system has rapidly become a very popular thermochronometer to constrain burial and exhumation phases in a variety of geological contexts. However, the interpretation of AHe data depends on a precise knowledge of He diffusion in apatite. Several studies suggest that radiation damage generated by U and Th decay can create traps for He atoms, increasing He retention for irradiated minerals. The radiation damage also anneals with temperature and the amount of damage in an apatite crystal is at any time a balance between production and annealing, controlled by U-Th concentration, grain chemistry and thermal history (Flowers et al., 2009; Gautheron et al., 2009; 2013). However the models are not well constrained and do not fully explain the mechanism of He retention. In order to have a deeper insight on this issue, multidisciplinary studies on apatite combining diffusion experiments by Elastic Recoil Diffusion Analysis (ERDA) with a multi-scale theoretical diffusion calculation based on Density Functional Theory (DFT) and Kinetic Monte Carlo were performed. ERDA experiments were conducted on different macro-crystals, and we probed the shape of a He profile implanted into a planar and polished surface of the crystal. The helium profile evolves with temperature and allows quantifying the He diffusivity and damage impact. Additionally, DFT calculations of a damage-free crystal of apatite with different F and Cl compositions, in similar proportion as natural ones, have been run to find the favored paths of a helium atom between interstitial sites, leading to a computation of the activation energy and the diffusion coefficient. We show that damage free apatite crystals are characterized by low retention behavior and closure temperature range from 33-36°C for pure F-apatite to higher value for Cl riche apatite (up to 12°C higher), for typical grain size and cooling rate (Mbongo-Djimbi et al., in review). Using ERDA and DFT approaches, we

  17. Adsorption of nucleotides on biomimetic apatite: The case of adenosine 5⿲ triphosphate (ATP)

    NASA Astrophysics Data System (ADS)

    Hammami, Khaled; El-Feki, Hafed; Marsan, Olivier; Drouet, Christophe

    2016-01-01

    ATP is a well-known energy supplier in cells. The idea to associate ATP to pharmaceutical formulations/biotechnological devices to promote cells activity by potentially modulating their microenvironment thus appears as an appealing novel approach. Since biomimetic nanocrystalline apatites have shown great promise for biomedical applications (bone regeneration, cells diagnostics/therapeutics, ⿦), thanks to a high surface reactivity and an intrinsically high biocompatibility, the present contribution was aimed at exploring ATP/apatite interactions. ATP adsorption on a synthetic carbonated nanocrystalline apatite preliminarily characterized (by XRD, FTIR, Raman, TG-DTA and SEM-EDX) was investigated in detail, pointing out a good agreement with Sips isothermal features. Adsorption characteristics were compared to those previously obtained on monophosphate nucleotides (AMP, CMP), unveiling some specificities. ATP was found to adsorb effectively onto biomimetic apatite: despite smaller values of the affinity constant KS and the exponential factor m, larger adsorbed amounts were reached for ATP as compared to AMP for any given concentration in solution. m < 1 suggests that the ATP/apatite adsorption process is mostly guided by direct surface bonding rather than through stabilizing intermolecular interactions. Although standard οGads ° was estimated to only ⿿4 kJ/mol, the large value of Nmax led to significantly negative effective οGads values down to ⿿33 kJ/mol, reflecting the spontaneous character of adsorption process. Vibrational spectroscopy data (FTIR and Raman) pointed out spectral modifications upon adsorption, confirming chemical-like interactions where both the triphosphate group of ATP and its nucleic base were involved. The present study is intended to serve as a basis for future research works involving ATP and apatite nanocrystals/nanoparticles in view of biomedical applications (e.g. bone tissue engineering, intracellular drug delivery, ⿦).

  18. Green apatites: hydride ions, electrons and their interconversion in the crystallographic channel.

    PubMed

    Hayashi, Katsuro; Hosono, Hideo

    2016-03-21

    Hydride (H(-)) ions and electrons in channel sites of the lattice of calcium phosphate apatites are characterized. Solid-state chemical reduction using TiH2 is effective for doping of H(-) ions into apatites. Irradiation of the H(-) ion-doped apatite with ultraviolet (UV) light induces green coloration. Electron paramagnetic resonance (EPR) reveals that this colour centre is attributed to electrons captured at a vacant anion site in the crystallographic channel, forming F(+) centres. Transient H(0) atoms are detected at low temperatures by EPR. The concentration of UV-induced electrons in the apatite at room temperature decays according to second-order kinetics because of the chemical reactions involving two electrons; overall, electron generation and thermal decay can be described as: H(-) + O(2-) ↔ 2e(-) + OH(-). (1)H magic angle spinning nuclear magnetic resonance spectroscopy is used to identify H(-) ions in the apatite, which are characterized by a chemical shift of +3.4 ppm. Various types of O-H groups including OH(-) ions in the channel and protons bound to phosphate groups are concurrently formed, and are identified by considering the relationship between the O-H stretching frequency and the (1)H chemical shift. The complementary results obtained by EPR and NMR reveal that the H(-) ions and transient H(0) atoms are located at the centre of Ca3 triangles in the apatite, while the electrons are located in the centre of Ca6 octahedra. These findings provide an effective approach for identifying new classes of mixed-oxide-hydride or -electride crystals.

  19. Adsorption of nucleotides on biomimetic apatite: The case of cytidine 5' monophosphate (CMP).

    PubMed

    Choimet, Maëla; Tourrette, Audrey; Drouet, Christophe

    2015-10-15

    The chemical interaction between DNA macromolecules and hard tissues in vertebrate is of foremost importance in paleogenetics, as bones and teeth represent a major substrate for the genetic material after cell death. Recently, the empirical hypothesis of DNA "protection" over time thanks to its adsorption on hard tissues was revisited from a physico-chemical viewpoint. In particular, the existence of a strong interaction between phosphate groups of DNA backbone and the surface of apatite nanocrystals (mimicking bone/dentin mineral) was evidenced on an experimental basis. In the field of nanomedicine, DNA or RNA can be used for gene transport into cells, and apatite nanocarriers then appear promising. In order to shed some more light on interactions between DNA molecules and apatite, the present study focuses on the adsorption of a "model" nucleotide, cytidine 5' monophosphate (CMP), on a carbonated biomimetic apatite sample. The follow-up of CMP kinetics of adsorption pointed out the rapidity of interaction with stabilization reached within few minutes. The adsorption isotherm could be realistically fitted to the Sips model (Langmuir-Freundlich) suggesting the influence of surface heterogeneities and adsorption cooperativity in the adsorption process. The desorption study pointed out the reversible character of CMP adsorption on biomimetic apatite. This contribution is intended to prove helpful in view of better apprehending the molecular interaction of DNA fragments and apatite compounds, independently of the application domain, such as bone diagenesis or nanomedicine. This study may also appear informative for researchers interested in the origins of life on Earth and the occurrence and behavior of primitive biomolecules.

  20. Relationships among carbonated apatite solubility, crystallite size, and microstrain parameters.

    PubMed

    Baig, A A; Fox, J L; Young, R A; Wang, Z; Hsu, J; Higuchi, W I; Chhettry, A; Zhuang, H; Otsuka, M

    1999-05-01

    The use of the metastable equilibrium solubility (MES) concept to describe the solubility properties of carbonated apatites (CAPs) and human dental enamel (HE) has been well established in previous studies using a range of CAPs with varying carbonate contents and crystallinities. It was shown in these studies that the mean value of the CAP MES is directly related to the broadening parameter full width at half maximum (FWHM) of the 002 reflection of the X-ray diffraction profile. The apparent solubility of the CAPs increased monotonically with an increase in the broadening of the diffraction peaks, and when this peak broadening was taken into account, carbonate had no additional effect upon the MES. The broadening of the diffraction peaks has been used as an indicator of crystallinity, and is generally influenced by both crystallite size and microstrain. The purpose of the present study was to extract the crystallite size and microstrain parameters separately from the X-ray diffraction peaks and then to determine their relationships to the corresponding MES values. The samples studied were CAPs synthesized by precipitation from Ca(NO3)2 and NaH2PO4 solutions in carbonate containing media at temperatures of 95, 80, and 70 degrees C, and powdered HE. The crystallite size and microstrain parameters were determined simultaneously with the refinement of the structural parameters with the Rietveld method of whole-pattern-fitting structure-refinement. A modified pseudo-Voigt function was used to model the observed peak profiles. The MES distributions for the CAPs and HE were determined by a previously described method. The results of this study showed that the CAPs possessed an MES distribution and therefore provided further support that MES distribution is a common phenomenon, regardless of the method of CAP synthesis. The crystallite size decreased and the microstrain increased with increasing carbonate content and decreasing temperature of synthesis of the CAPs. A plot

  1. Mineralogy and geochemistry of Fe-Ti oxide and apatite (nelsonite) deposits and evaluation of the liquid immiscibility hypothesis.

    USGS Publications Warehouse

    Kolker, A.

    1982-01-01

    The modal mineralogy for 32 Fe-Ti oxides and apatites supports the 2:1 oxide:apatite ratio for these samples from New York, Quebec, Norway and Sweden. Accessory minerals include: biotite, clinoamphibole, spinel, zircon and sulphides, oxygen fugacities range from 10-11 to 10-20, and T 600o to 1000oC. - K.A.R.

  2. Theoretical stability assessment of uranyl phosphates and apatites: selection of amendments for in situ remediation of uranium.

    PubMed

    Raicevic, S; Wright, J V; Veljkovic, V; Conca, J L

    2006-02-15

    Addition of an amendment or reagent to soil/sediment is a technique that can decrease mobility and reduce bioavailability of uranium (U) and other heavy metals in the contaminated site. According to data from literature and results obtained in field studies, the general mineral class of apatites was selected as a most promising amendment for in situ immobilization/remediation of U. In this work we presented theoretical assessment of stability of U(VI) in four apatite systems (hydroxyapatite (HAP), North Carolina Apatite (NCA), Lisina Apatite (LA), and Apatite II) in order to determine an optimal apatite soil amendment which could be used for in situ remediation of uranium. In this analysis we used a theoretical criterion which is based on calculation of the ion-ion interaction potential, representing the main term of the cohesive energy of the matrix/pollutant system. The presented results of this analysis indicate (i) that the mechanism of immobilization of U by natural apatites depends on their chemical composition and (ii) that all analyzed apatites represent, from the point of view of stability, promising materials which could be used in field remediation of U-contaminated sites.

  3. A new glance at ruthenium sorption mechanism on hydroxy, carbonate, and fluor apatites: Analytical and structural studies.

    PubMed

    Tõnsuaadu, K; Gruselle, M; Villain, F; Thouvenot, R; Peld, M; Mikli, V; Traksmaa, R; Gredin, P; Carrier, X; Salles, L

    2006-12-15

    The sorption mechanism of Ru3+ ions on hydroxy (HAp), carbonate (CO3HAp), and fluor apatites (FAp) has been studied in detail. Ru apatites were obtained by reaction of the apatites with RuCl3 in aqueous solution. The structure and composition of the ruthenium-modified apatites were studied by several techniques: elemental analysis, XRD, EXAFS, IR, NMR, SEM-EDS, TEM, and thermal analysis. The amount of Ru in the modified apatite varies from 7.8 to 10.5 wt% and is not related to the initial composition or the specific surface area of the apatite. The different characterization techniques show that in the Ru-modified apatites Ru is surrounded by six oxygen atoms and do not contain any chlorine. For Ru-HAp and Ru-CO3HAp the new phase is amorphous whereas it is crystalline for FAp. The catalytic oxidation ability is higher for Ru-HAp and Ru-CO3HAp compared to Ru-FAp apatite in the oxidation of benzylic alcohol.

  4. Pacific Northwest National Laboratory Apatite Investigation at the 100-NR-2 Quality Assurance Project Plan

    SciTech Connect

    Fix, N. J.

    2008-03-28

    This Quality Assurance Project Plan provides the quality assurance requirements and processes that will be followed by staff working on the 100-NR-2 Apatite Project. The U.S. Department of Energy, Fluor Hanford, Inc., Pacific Northwest National Laboratory, and the Washington Department of Ecology agreed that the long-term strategy for groundwater remediation at 100-N would include apatite sequestration as the primary treatment, followed by a secondary treatment. The scope of this project covers the technical support needed before, during, and after treatment of the targeted subsurface environment using a new high-concentration formulation.

  5. Growth of apatite on chitosan-multiwall carbon nanotube composite membranes

    NASA Astrophysics Data System (ADS)

    Yang, Jun; Yao, Zhiwen; Tang, Changyu; Darvell, B. W.; Zhang, Hualin; Pan, Lingzhan; Liu, Jingsong; Chen, Zhiqing

    2009-07-01

    Bioactive membranes for guided tissue regeneration would be of value for periodontal therapy. Chitosan-multiwall carbon nanotube (CS-MWNT) composites were treated to deposit nanoscopic apatite for MWNT proportions of 0-4 mass%. Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, and X-ray diffraction were used for characterization. Apatite was formed on the CS-MWNT composites at low MWNT concentrations, but the dispersion of the MWNT affects the crystallite size and the Ca/P molar ratio of the composite. The smallest crystallite size was 9 nm at 1 mass% MWNT.

  6. In vitro apatite formation on organic polymers modified with a silane coupling reagent.

    PubMed

    Shirosaki, Yuki; Kubo, Masaaki; Takashima, Seisuke; Tsuru, Kanji; Hayakawa, Satoshi; Osaka, Akiyoshi

    2005-09-22

    Gamma-methacryloxypropyltrimethoxysilane (gamma-MPS) was grafted to high-density polyethylene, polyamide and silicone rubber substrates by the emulsion polymerization procedure in order to provide these organic polymers with in vitro apatite-forming ability. The contact angles towards distilled water of the gamma-MPS-grafted specimens were lower than those of the original organic polymer specimens, indicating that the grafted substrates were more hydrophilic. The in vitro apatite formation in a simulated body fluid (Kokubo solution) was confirmed for several of the gamma-MPS-grafted specimens.

  7. In vitro apatite formation on organic polymers modified with a silane coupling reagent

    PubMed Central

    Shirosaki, Yuki; Kubo, Masaaki; Takashima, Seisuke; Tsuru, Kanji; Hayakawa, Satoshi; Osaka, Akiyoshi

    2005-01-01

    γ-Methacryloxypropyltrimethoxysilane (γ-MPS) was grafted to high-density polyethylene, polyamide and silicone rubber substrates by the emulsion polymerization procedure in order to provide these organic polymers with in vitro apatite-forming ability. The contact angles towards distilled water of the γ-MPS-grafted specimens were lower than those of the original organic polymer specimens, indicating that the grafted substrates were more hydrophilic. The in vitro apatite formation in a simulated body fluid (Kokubo solution) was confirmed for several of the γ-MPS-grafted specimens. PMID:16849191

  8. Apatite: A New Tool For Understanding The Temporal Variability Of Magmatic Volatile Contents

    NASA Astrophysics Data System (ADS)

    Stock, M. J.; Humphreys, M.; Smith, V.; Pyle, D. M.; Isaia, R.

    2015-12-01

    The apatite crystal structure is capable of incorporating H2O, F and Cl, as well as trace CO2 and sulphur. These can be related to parental magma compositions through application of a series of pressure and temperature-dependent exchange reactions (Piccoli and Candela, 1994), permitting apatite crystals to preserve a record of all major volatile species in the melt. Furthermore, due to the general incompatibility of P in other rock-forming minerals, apatite is ubiquitous in igneous systems and often begins crystallising early, such that apatite inclusions within phenocrysts record melt volatile contents throughout magmatic differentiation. In this work, we compare the compositions of apatite inclusions and microphenocrysts with pyroxene-hosted melt inclusions from the Astroni 1 eruption of Campi Flegrei, Italy. These data are coupled with magmatic differentiation models (Gualda et al., 2012), experimental volatile solubility data (Webster et al., 2014) and thermodynamic models of apatite compositional variations (Piccoli and Candela, 1994) to determine a time-series of magmatic volatile evolution in the build-up to eruption. We find that apatite halogen/OH ratios decreased through magmatic differentiation, while melt inclusion F and Cl concentrations increased. Melt inclusion H2O contents are constant at ~2.5 wt%. These data are best explained by volatile-undersaturated differentiation over most of the crystallisation history of the Astroni 1 melt, with melt inclusion H2O contents reset during ascent, due to rapid H diffusion through the phenocryst hosts (Woods et al., 2000). Given the rapid diffusivity of volatiles in apatite (Brenan, 1993), preservation of undersaturated compositions in microphenocrysts suggests that saturation was only achieved a few days to months before eruption and that it may have been the transition into a volatile-saturated state that ultimately triggered eruption. Piccoli and Candela, 1994. Am. J. of Sc., 294, 92-135. Gualda et al., 2012

  9. Simultaneous incorporation of carbonate and fluoride in synthetic apatites: Effect on crystallographic and physico-chemical properties.

    PubMed

    Yao, Fang; LeGeros, John P; LeGeros, Racquel Z

    2009-07-01

    The mineral in bone is an impure hydroxyapatite, with carbonate as the chief minor substituent. Fluoride has been shown to stimulate osteoblastic activity and inhibit osteoclastic resorption in vitro. CO(3)- and F-substituted apatite (CFA) has been considered as potential bone graft material for orthopedic and dental applications. The objective of this study was to determine the effects of simultaneously incorporated CO(3) and F on the crystallographic physico-chemical properties of apatite. The results showed that increasing CO(3) and Na content in apatites with relatively constant F concentration caused a decrease in crystallite size and an increase in the extent of calcium release; increasing F content in apatites with relatively constant CO(3) concentration caused an increase in crystallite size and a decrease in the extent of Ca release. These findings suggest that CFAs as bone graft materials of desired solubility can be prepared by manipulating the relative concentrations of CO(3) and F incorporated in the apatite.

  10. In Vitro Biocompability/Osteogenesis and In Vivo Bone Formation Evalution of Peptide-Decorated Apatite Nanocomposites Assisted via Polydopamine.

    PubMed

    Deng, Yi; Sun, Yuhua; Bai, Yanjie; Gao, Xiang; Zhang, Huan; Xu, Anxiu; Huang, Enyi; Deng, Feng; Wei, Shicheng

    2016-04-01

    Enhancing the biocompatibility and osteogenic activity of nano-apatite for applications in bone graft substitutes and bone tissue engineering have been the current challenge in regeneration of lost bone. Inspired by mussels, here we have developed facile biomimetic approaches for preparation of two types of peptide-conjugated apatite nanocompsoties assisted by polydopamine (pDA). We exploited polydopamine chemistry for the modification of nano-apatite crystals: polydopamine coated apatite (HA-c-pDA) and polydopamine template-mediated apatite (HA-t-pDA), on which bone forming peptide was subsequently immobilized under weakly basic conditions to obtain peptide-conjugated apatite nanocomposites (HA-c-pep and HA-t-pep, respectively). TEM images revealed that HA-c-pDA displayed typically rod-like morphology, while HA-t-pDA was sponge-like structure where pDA sheets were decorated by needle-like apatite crystals with low degree of crystallinity. In the cell culture experiments, HA-t-pep nanocomposite exhibited higher cell proliferation, spreading, and alkaline phosphatase activity as well as calcium nodule-formation, compared with pristine nano-HA and HA-c-pep nanocomposite. We then implanted the peptide-decorated apatite into rabbit calvarial defects and analyzed bone formation after 2 months. The data revealed that HA-t-pep group exhibited remarkably enhanced bioactivity and bone formation in vivo. Based on these results, our biomimetic approach could be a promising tool to develop peptide-conjugated apatites for bone regeneration. Meanwhile, the excellent biocompatibility and high osteogenesis of the peptide-conjugated apatite nanocomposite might confer its great potentials in bone repair, bone augmentation, as well as coating of biomedical implants.

  11. Compositional Variation of Terrestrial Mantle Apatites and Implications for the Halogen and Water Budgets of the Terrestrial Mantle

    NASA Astrophysics Data System (ADS)

    Roden, M.; Patino Douce, A. E.; Chaumba, J. B.; Fleisher, C.; Yogodzinski, G. M.

    2011-12-01

    Apatite in ultramafic xenoliths from various tectonic enviroments including arc (Kamchatka), plume (Hawaii), and intraplate (Lunar Crater, Nunivak, Colorado Plateau) were analyzed by electron microprobe with the aim of characterizing the Cl and F contents, and from these measured compositions to infer the nature of fluids/melts that the apatites equilibrated with. The impetus for the study derived from the generalization of O'Reilly and Griffin (1) that mantle-derived metasomatic apatites tend to be Cl-rich and mantle-derived igneous apatites tend to be F-rich. Our work largely corroborates their generalization with Cl- and/or H2O-rich compositions characterizing the apatites from Nunivak and Kamchatka while apatites from igneous or Group II xenoliths tend to be Cl-poor and be either nearly pure fluorapatite or a mix of hydroxylapatite and fluorapatite. We attribute the Cl-rich nature of the Kamchatka apatites to formation from Cl-rich fluids generated from subducted lithosphere; however the Nunivak occurrence is far removed from subducted lithosphere and may reflect a deep seated source for Cl as also indicated by brine inclusions in diamonds, Cl-rich apatites in carbonate-bearing xenoliths and a Cl-rich signature in some plumes such as Iceland, Azores and Samoa. One curious aspect of mantle-derived apatite compositions is that xenoliths with evidence of carbonatitic metasomatism commonly have Cl-rich apatites while apatites from carbonatites are invariably Cl-poor - perhaps reflecting loss of Cl in fluids evolved from the carbonatitic magma. Apatites from Group II xenoliths at Hawaii are solid solutions between fluorapatite and hydroxylapatite and show no evidence for deep-seated Cl at Hawaii. Samples of the terrestrial mantle are almost uniformly characterized by mineral assemblages with a single Ca-rich phosphate phase but the mantles of Mars, Vesta and the Moon have two Ca-rich phosphates, apatite and volatile-poor merrillite - apatite compositions existing

  12. Ab initio simulation on the crystal structure and elastic properties of carbonated apatite.

    PubMed

    Ren, Fuzeng; Lu, Xiong; Leng, Yang

    2013-10-01

    Ab initio quantum mechanical (QM) calculations were employed to study the crystal structure and elastic properties of carbonated apatite (CAp). Two locations for the carbonate ion in the apatite lattice were considered: carbonate substituting for OH(-) ion (type-A), and for PO4(3-) ion (type-B) with possible charge compensation mechanisms. A combined type-AB substitution (two carbonate ions replacing one phosphate group and one hydroxyl group, respectively) was also investigated. The results show that the most energetically stable substitution is type-AB, followed by type-A and then type-B. The most stable configuration of type-A has its carbonate triangular plane almost parallel to c-axis at z=0.46. The lowest energy configuration of type-B is that with a sodium ion substituting for a calcium ion for charge balance and the carbonate lying on the b/c-plane of apatite. Lattice parameter changes after carbonate substitution in hydroxyapatite (HA) agree with reported experimental results qualitatively: for type-A, lattice parameter a increases but c decreases; and for type-B, lattice parameter a decreases but c increases. Using the calculated CAp stable structures, we also calculated the elastic properties of CAp and compared them with those of HA and biological apatites.

  13. From supernova to Solar System: Few years only; first Solar System components apatite and spinel determined

    NASA Astrophysics Data System (ADS)

    Jungck, Matthias H. A.; Niederer, Franz R.

    2017-03-01

    We show data for the very first years of our Solar System development after an interaction between undisturbed, cold interstellar dust and supernova type II explosion gases. All manual work was done in 1976-1982 as part of 3 theses works but fundamentally new data interpretation was reached within the last three years. From the CI1 meteorite Orgueil, we are able to separate 1.4 per mill of material containing supernova related noble gases He, Ne and Ar as well as P. We separate minerals using essentially density gradient centrifugation followed by stepwise heating noble gas analysis. Our procedure loses nearly no material and is in sharp contrast to the otherwise used dissolution of >99% of material to obtain single presolar grains (Anders and Zinner, 1993). Our method safeguards minerals considerably more fragile than SiC or TiC presolar grains, such as apatite, Mg-Al-spinel, graphite clusters and even apatite coated graphite clusters. We find graphite, apatite and Mg-Al-spinel containing highly anomalous noble gases. For the first time, apatite, containing anomalous Ar with an isotope ratio for 38Ar/36Ar of 0.35, twice the normal ratio, is reported. Such a ratio is produced by a 20 solar mass type II supernova in the C-O-Ne-burning shell. Unmatched pure Ne-E from 22Na measured in the same samples sets the timeframe for this interaction to a maximum of only a few years.

  14. Apatite coating of electrospun PLGA fibers using a PVA vehicle system carrying calcium ions.

    PubMed

    Kim, In Ae; Rhee, Sang-Hoon

    2010-01-01

    A novel method to coat electrospun poly(D,L-lactic-co-glycolic acid) (PLGA) fiber surfaces evenly and efficiently with low-crystalline carbonate apatite crystals using a poly(vinyl alcohol) (PVA) vehicle system carrying calcium ions was presented. A non-woven PLGA fabric was prepared by electrospinning: a 10 wt% PLGA solution was prepared using 1,1,3,3-hexafluoro-2-propanol as a solvent and electrospun under a electrical field of 1 kV/cm using a syringe pump with a flowing rate of 3 ml/h. The non-woven PLGA fabric, 12 mm in diameter and 1 mm in thickness, was cut and then coated with a PVA solution containing calcium chloride dihydrate (specimen PPC). As controls, pure non-woven PLGA fabric (specimen P) and fabric coated with a calcium chloride dihydrate solution without PVA (specimen PC) were also prepared. Three specimens were exposed to simulated body fluid for 1 week and this exposure led to form uniform and complete apatite coating layer on the fiber surfaces of specimen PPC. However, no apatite had formed to the fiber surfaces of specimen P and only inhomogeneous coating occurred on the fiber surfaces of specimen PC. These results were explained in terms of the calcium chelating and adhesive properties of PVA vehicle system. The practical implication of the results is that this method provides a simple but efficient technique for coating the fiber surface of an initially non-bioactive material with low-crystalline carbonate apatite.

  15. Preparation of fluoride substituted apatite cements as the building blocks for tooth enamel restoration

    NASA Astrophysics Data System (ADS)

    Wei, Jie; Wang, Jiecheng; Liu, Xiaochen; Ma, Jian; Liu, Changsheng; Fang, Jing; Wei, Shicheng

    2011-06-01

    Fluoride substituted apatite cement (fs-AC) was synthesized by using the cement powders of tetracalcium phosphate (TTCP) and sodium fluoride (NaF), and the cement powders were mixed with diluted phosphoric acid (H 3PO 4) as cement liquid to form fs-AC paste. The fs-AC paste could be directly filled into the carious cavities to repair damaged dental enamel. The results indicated that the fs-AC paste was changed into fluorapatite crystals with the atom molar ratio for calcium to phosphorus of 1.66 and the F ion amount of 3 wt% after self-hardening for 2 days. The solubility of fs-AC in Tris-HCl solution (pH 6) was slightly lower than hydroxyapatite cement (HAC) that was similar to the apatite in enamel, indicating the fs-AC was much insensitive to the weakly acidic solution than the apatite in enamel. The fs-AC was tightly combined with the enamel surface because of the chemical reaction between the fs-AC and the apatite in enamel after the caries cavities was filled with fs-AC. The extracts of fs-AC caused no cytotoxicity on L929 cells, which satisfied the relevant criterion on dental biomaterials, revealing good cytocompatibility. The fs-AC had potential prospect for the reconstitution of carious lesion of dental enamel.

  16. The impact of bacteria of circulating water on apatite-nepheline ore flotation.

    PubMed

    Evdokimova, G A; Gershenkop, A Sh; Fokina, N V

    2012-01-01

    A new phenomenon has been identified and studied-the impact of bacteria on the benefication process of non-sulphide ores using circulating water supply-a case study of apatite-nepheline ore. It is shown that bacteria deteriorate the floatability of apatite due to their interaction with active centres of calcium-containing minerals and intense flocculation, resulting in a decrease of the flotation process selectivity thus deteriorating the quality of concentrate. Based on the comparative analysis of primary sequences of 16S rRNA genes, there have been identified dominating bacteria species, recovered from the circulating water used at apatite-nepheline concentrating mills, and their phylogenetic position has been determined. All the bacteria were related to γ-Proteobacteria, including the Acinetobacter species, Pseudomonas alcaliphila, Ps. plecoglossicida, Stenotrophomonas rhizophila. A method of non-sulphide ores flotation has been developed with consideration of the bacterial factor. It consists in use of small concentrations of sodium hypochlorite, which inhibits the development of bacteria in the flotation of apatite-nepheline ores.

  17. Effect of fluoride-substituted apatite on in vivo bone formation.

    PubMed

    Inoue, Miho; Rodriguez, Andrea P; Nagai, Noriyuki; Nagatsuka, Hitoshi; LeGeros, Racquel Z; Tsujigiwa, Hidetsugu; Inoue, Masahisa; Kishimoto, Etsuo; Takagi, Shin

    2011-05-01

    Biological apatites are characterized by the presence of minor constituents such as magnesium (Mg), chloride (Cl), or fluoride (F) ions. These ions affect cell proliferation and osteoblastic differentiation during bone tissue formation. F-substituted apatites are being explored as potential bonegraft materials. The aim of the present study is to investigate the mechanism of bone formation induced by fluoride-substituted apatite (FAp) by analyzing the effect of FAp on the process of in vivo bone formation. FAps containing different F concentrations (l-FAp: 0.48 wt%, m-FAp: 0.91 wt%, h-FAp: 2.23 wt%) and calcium-deficient apatite (CDA), as positive control, were implanted in rat tibia and bone formation was evaluated by histological examination, immuhistochemistry, in situ hybridization and tartrate-resistant acid phosphatase examinations. The results showed that l-FAp, m-FAp, h-FAp, and CDA biomaterials allowed migration of macrophages, attachment, proliferation, and phenotypic expression of bone cells leading to new bone formation in direct apposition to the particles. However, the l-FAp preparation allowed faster bone conduction compared to the other experimental materials. These results suggest that FAp with low F concentration may be an efficient bonegraft material for dental and medical application.

  18. Infrared, Raman and NMR investigations of risedronate adsorption on nanocrystalline apatites.

    PubMed

    Errassifi, F; Sarda, S; Barroug, A; Legrouri, A; Sfihi, H; Rey, C

    2014-04-15

    The aim of the current work was to study the physico-chemical interactions of a bisphosphonate molecule, risedronate, with a well-characterised synthetic nanocrystalline apatite (NCA) as a model bone mineral. We adopted a global approach, using complementary physico-chemical techniques such as FTIR, RAMAN and NMR spectroscopies in order to learn more about the interaction process of risedronate with the apatitic surface. The results obtained suggest that risedronate adsorption corresponds to an ion substitution reaction with phosphate ions occurring at the crystal surface. This mechanism explains the greater amount adsorbed (N) for NCA, compared to well crystallised stoichiometric hydroxyapatite, attributable to the well-developed hydrated layer at the surface of the nanocrystals. However, most calcium ions remain attached to the solid phase and the formation of insoluble risedronate calcium salts must also be considered as a competitive reaction to the adsorption. Thus a calcium risedronate salt was synthesised and fully characterised for comparison to the solids after adsorption. Following spectroscopic results, it can be concluded that a strong interaction was established between risedronate ions and calcium ions at the apatitic surface. However, under these experimental conditions there is no nucleation of a distinct calcium risedronate salt and the apatite crystals retain their integrity.

  19. Evidence of hydroxyl-ion deficiency in bone apatites: an inelastic neutron-scattering study.

    PubMed

    Loong, C K; Rey, C; Kuhn, L T; Combes, C; Wu, Y; Chen, S; Glimcher, M J

    2000-06-01

    The novelty of very large neutron-scattering intensity from the nuclear-spin incoherence in hydrogen has permitted the determination of atomic motion of hydrogen in synthetic hydroxyapatite and in deproteinated isolated apatite crystals of bovine and rat bone without the interference of vibrational modes from other structural units. From an inelastic neutron-scattering experiment, we found no sharp excitations characteristic of the vibrational mode and stretch vibrations of OH ions around 80 and 450 meV (645 and 3630 cm(-1)), respectively, in the isolated, deproteinated crystals of bone apatites; such salient features were clearly seen in micron- and nanometer-size crystals of pure hydroxyapatite powders. Thus, the data provide additional definitive evidence for the lack of OH(-) ions in the crystals of bone apatite. Weak features at 160-180 and 376 meV, which are clearly observed in the apatite crystals of rat bone and possibly in adult mature bovine bone, but to a much lesser degree, but not in the synthetic hydroxyapatite, are assigned to the deformation and stretch modes of OH ions belonging to HPO(4)-like species.

  20. The role of collagen in bone apatite formation in the presence of hydroxyapatite nucleation inhibitors.

    PubMed

    Nudelman, Fabio; Pieterse, Koen; George, Anne; Bomans, Paul H H; Friedrich, Heiner; Brylka, Laura J; Hilbers, Peter A J; de With, Gijsbertus; Sommerdijk, Nico A J M

    2010-12-01

    Bone is a composite material in which collagen fibrils form a scaffold for a highly organized arrangement of uniaxially oriented apatite crystals. In the periodic 67 nm cross-striated pattern of the collagen fibril, the less dense 40-nm-long gap zone has been implicated as the place where apatite crystals nucleate from an amorphous phase, and subsequently grow. This process is believed to be directed by highly acidic non-collagenous proteins; however, the role of the collagen matrix during bone apatite mineralization remains unknown. Here, combining nanometre-scale resolution cryogenic transmission electron microscopy and cryogenic electron tomography with molecular modelling, we show that collagen functions in synergy with inhibitors of hydroxyapatite nucleation to actively control mineralization. The positive net charge close to the C-terminal end of the collagen molecules promotes the infiltration of the fibrils with amorphous calcium phosphate (ACP). Furthermore, the clusters of charged amino acids, both in gap and overlap regions, form nucleation sites controlling the conversion of ACP into a parallel array of oriented apatite crystals. We developed a model describing the mechanisms through which the structure, supramolecular assembly and charge distribution of collagen can control mineralization in the presence of inhibitors of hydroxyapatite nucleation.

  1. COMPARISON OF APATITE II™ TREATMENT SYSTEM AT TWO MINES FOR METALS REMOVAL

    EPA Science Inventory

    Two abandoned lead-zinc mine sites, the Nevada Stewart Mine (NSM) and Success Mine, are located within the Coeur d'Alene Mining District, in northern Idaho. An Apatite II™ Treatment System (ATS) was implemented at each site to treat metal-laden water, mainly zinc. In the ATS, f...

  2. Photoexcited formation of bone apatite-like coatings on micro-arc oxidized titanium.

    PubMed

    Han, Yong; Xu, Kewei

    2004-12-15

    A novel method to rapidly deposit bone apatite-like coatings on titanium implants in simulated body fluid (SBF) is proposed in this article. The processing was composed of two steps; for example, micro-arc oxidation (MAO) of titanium to form titania films, and UV-light illumination of the titania-coated titanium in SBF. The morphology, crystalline structure, and bond strength of the MAO films were investigated as a function of the applied voltage (in the range of 250-400 V) by using scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectrometry, Fourier transform infrared spectroscopy, adhesion-tensile test, and scratch test. Results showed that the MAO films were porous and nanocrystalline with pore sizes varying from 1 to 3 microm and grain sizes varying from 10-20 to 70-80 nm; the predominant phase in titania films changed from anatase to rutile, and the bond strength of the films decreased from 43.4 to 32.9 MPa as the applied voltage increased from 250 to 400 V. After UV-light illumination of the films in SBF for 2 h, bone apatite-like coating was deposited on the MAO film formed at 250 V. The bond strength of the apatite/titania bilayer was about 44.2 MPa. However, no apatite was observed on the MAO film formed at 400 V after UV-light illumination.

  3. New evolutionary insights into granite genesis preserved in the trace element compositions of apatite and zircon

    NASA Astrophysics Data System (ADS)

    Miles, A.; Graham, C.; Gillespie, M.; Hawkesworth, C. J.; Hinton, R. W.

    2010-12-01

    The chemical architecture of key accessory minerals like zircon and apatite has proved pivotal in assessing the early mechanisms of crustal growth and differentiation. However, the exact stages at which they crystallise during the evolution of granite plutons and the processes they record remain poorly constrained. We present a combined micro-analytical and petrological study of these important accessory minerals. The results reveal the significance of early and previously unrecognised incremental assembly of intermediate zones in the I-type (margins) to S-type (centre) zoned Scottish Caledonian pluton, Criffel. Within intermediate zones, two distinct I- and S-type trends are seen in trace element compositions of apatites enclosed by zircon and other major phases respectively (Fig. 1). The fluorine concentrations of apatite included within different phases have been used as a proxy for the degree of melt differentiation and S-type melt involvement, and indicate that zircon-hosted apatite compositions often preserve the earliest and most primitive record of I-type magmas. Together with textural evidence, this provides some of the first geochemical evidence that zircon started crystallising at a relatively early stage of magma evolution, placing important constraints on the interpretations of zircon O and Hf isotopic data. The systematic increase in δ18O from ~6‰ to >8‰ recorded by zircon from progressively more central zones of the pluton requires additions of an 18O-enriched component to the magma. Near-Gaussian zircon 18O probability distributions indicate effective magma mixing prior to zircon crystallisation, yet differences of up to 4‰ between zircon and their host whole-rock δ18O values demonstrate isotopic disequilibrium and early crystallisation of zircon from a magma of lower δ18O. Thus, the earliest records of magmatic processes indicate that final intermediate bulk compositions are primarily the product of both I- and S-type magma components

  4. Partitioning behavior of chlorine and fluorine in the system apatite-silicate melt-fluid

    NASA Astrophysics Data System (ADS)

    Mathez, Edmond A.; Webster, James D.

    2005-03-01

    The partitioning behavior of Cl among apatite, mafic silicate melt, and aqueous fluid and of F between apatite and melt have been determined in experiments conducted at 1066 to 1150 °C and 199-205 MPa. The value of D Clapatite/melt (wt. fraction of Cl in apatite/Cl in melt) ≈0.8 for silicate melt containing less than ˜3.8 wt.% Cl. At higher melt Cl contents, small increases in melt Cl concentration are accompanied by large increases in apatite Cl concentration, forcing D Clapatite/melt to increase as well. Melt containing less than 3.8% Cl coexists with water-rich vapor; that containing more Cl coexists with saline fluid, the salinity of which increases rapidly with small increases in melt Cl content, analogous to the dependency of apatite composition on melt Cl content. This behavior is due to the fact that the solubility of Cl in silicate melt depends strongly on the composition of the melt, particularly its Mg, Ca, Fe, and Si contents. Once the melt becomes "saturated" in Cl, additional Cl must be accommodated by coexisting fluid, apatite, or other phases rather than the melt itself. Because Cl solubility depends on composition, the Cl concentration at which D Clapatite/melt and D Clfluid/melt begin to increase also depends on composition. The experiments reveal that D Fapatite/melt ≈3.4. In contrast to Cl, the concentration of F in silicate melt is only weakly dependent on composition (mainly on melt Ca contents), so D Fapatite/melt is constant for a wide range of composition. The experimental data demonstrate that the fluids present in the waning stages of the solidification of the Stillwater and Bushveld complexes were highly saline. The Cl-rich apatite in these bodies crystallized from interstitial melt with high Cl/(F + OH) ratio. The latter was generated by the combined processes of fractional crystallization and dehydration by its reaction with the relatively large mass of initially anhydrous pyroxene through which it percolated.

  5. The formation of Luoboling porphyry Cu-Mo deposit: Constraints from zircon and apatite

    NASA Astrophysics Data System (ADS)

    Li, Cong-ying; Hao, Xi-luo; Liu, Ji-qiang; Ling, Ming-xing; Ding, Xing; Zhang, Hong; Sun, Wei-dong

    2017-02-01

    The Luobuling porphyry Cu-Mo deposit belongs to the Late Cretaceous Zijinshan Cu-Au-Mo mineralization field in southeastern China. Due to intensive hydrothermal alteration and weathering, it is very difficult to collect fresh whole rock samples for geochemical and isotopic studies in Luobuling. Zircon and apatite are accessory minerals that are resistant to hydrothermal alterations. In this study, we compared the trace element and isotope compositions of zircon and apatite from ore-bearing and barren samples to understand the formation of the Luoboling Cu-Mo deposit. Zircon U-Pb LA-ICP-MS dating shows that the Luoboling porphyries formed at 100 Ma (100.3 ± 1.2 Ma, 100.6 ± 1.5 Ma and 98.6 ± 1.2 Ma), which belongs to the late stage mineralization of the Zijinshan mineralization field. Zhongliao porphyritic granodiorite has the same age as the deposit (99.5 ± 1.6 Ma). The age of barren Sifang granodiorite is slightly older (109.7 ± 0.8 Ma). All these zircon grains have high Ce4+/Ce3+ ratios, indicating high oxygen fugacities. The ore-bearing samples show variable εHf(t) of - 7.3 to 0.2, suggesting either heterogeneous sources or mixing of two different magmas. Interestingly, the Hf isotope composition of barren samples is systematically higher (εHf(t) of - 3.6 to 5.5), implying a lower contribution of crustal materials. The OH mole percent of apatite grains from barren samples (LBL22-03 and SF09-05) is 0.5, which is higher than that of apatite from the ore-bearing samples (LBL20-01 LBL20-02 and LBL22-02), indicating lower F, Cl contents or higher water contents in the magma. In apatite from the ore-bearing samples, Sr is high, indicating the absence of plagioclase crystallization. In contrast, barren samples have varied and lower Sr, indicating that apatite crystallization was accompanied by plagioclase. These patterns were controlled by water contents because the crystallization of plagioclase is suppressed by high water contents in magmas. It also suggests

  6. Arsenic in hydrothermal apatite: Oxidation state, mechanism of uptake, and comparison between experiments and nature

    NASA Astrophysics Data System (ADS)

    Liu, Weihua; Mei, Yuan; Etschmann, Barbara; Brugger, Joël; Pearce, Mark; Ryan, Chris G.; Borg, Stacey; Wykes, Jeremey; Kappen, Peter; Paterson, David; Boesenberg, Ulrike; Garrevoet, Jan; Moorhead, Gareth; Falkenberg, Gerald

    2017-01-01

    Element substitution that occurs during fluid-rock interaction permits assessment of fluid composition and interaction conditions in ancient geological systems, and provides a way to fix contaminants from aqueous solutions. We conducted a series of hydrothermal mineral replacement experiments to determine whether a relationship can be established between arsenic (As) distribution in apatite and fluid chemistry. Calcite crystals were reacted with phosphate solutions spiked with As(V), As(III), and mixed As(III)/As(V) species at 250 °C and water-saturated pressure. Arsenic-bearing apatite rims formed in several hours, and within 48 h the calcite grains were fully replaced. X-ray Absorption Near-edge Spectroscopy (XANES) data show that As retained the trivalent oxidation state in the fully-reacted apatite grown from solutions containing only As(III). Extended X-ray Fine Spectroscopy (EXAFS) data reveal that these As(III) ions are surrounded by about three oxygen atoms at an Assbnd O bond length close to that of an arsenate group (AsO43-), indicating that they occupy tetrahedral phosphate sites. The three-coordinated As(III)-O3 structure, with three oxygen atoms and one lone electron pair around As(III), was confirmed by geometry optimization using ab initio molecular simulations. The micro-XANES imaging data show that apatite formed from solutions spiked with mixed As(III) and As(V) retained only As(V) after completion of the replacement reaction; in contrast, partially reacted samples revealed a complex distribution of As(V)/As(III) ratios, with As(V) concentrated in the center of the grain and As(III) towards the rim. Most natural apatites from the Ernest Henry iron oxide copper gold deposit, Australia, show predominantly As(V), but two grains retained some As(III) in their core. The As-anomalous amphibolite-facies gneiss from Binntal, Switzerland, only revealed As(V), despite the fact that these apatites in both cases formed under conditions where As(III) is

  7. Isotope dilution analysis of Ca and Zr in apatite and zircon (U-Th)/He chronometry

    NASA Astrophysics Data System (ADS)

    Guenthner, William R.; Reiners, Peter W.; Chowdhury, Uttam

    2016-05-01

    Because radiation damage influences He diffusivity, correlations between (U-Th)/He ages and effective uranium (eU, eU = U + 0.235 × Th) concentrations of single apatite and zircon grains are important for understanding thermal histories. Here we describe a method for quantifying eU concentrations in apatite and zircon grains using isotope dilution ICP-MS measurements of Zr and Ca and stoichiometry of zircon (ZrSiO4) and apatite (Ca5(PO4)3F) to obtain grain masses. Combined with independent U and Th measurements, these yield eU concentrations not based on the traditional morphologic measurements and assumptions. Additional benefits of this method include correct identification of an apatite or zircon and volume estimates for crystal shards. In some cases, this method gives eU concentrations consistent with those calculated with the morphologic approach, but often significant differences are observed between concentrations calculated from the two methods. Differences in eU concentrations for our apatite grains are greater and less than morphology estimates, and the majority are between 0.7 and 31%. With the exception of two grains, all of our zircon grains have differences between 3 and 34% less than morphology estimates. These differences could result from incorrect grain width measurements, mischaracterized grain shape, or incorrect volume calculations of the pure mineral phase due to inclusions. These morphologic errors—combined with evidence for the accuracy of our isotope dilution method from analyses of reference materials—suggest that eU concentrations calculated from morphology may often be significantly inaccurate. Finally, we demonstrate that differences between the two measurements of eU cause age-eU correlation variations for representative thermal histories.

  8. Atom probe tomography of apatites and bone-type mineralized tissues.

    PubMed

    Gordon, Lyle M; Tran, Lawrence; Joester, Derk

    2012-12-21

    Nanocrystalline biological apatites constitute the mineral phase of vertebrate bone and teeth. Beyond their central importance to the mechanical function of our skeleton, their extraordinarily large surface acts as the most important ion exchanger for essential and toxic ions in our body. However, the nanoscale structural and chemical complexity of apatite-based mineralized tissues is a formidable challenge to quantitative imaging. For example, even energy-filtered electron microscopy is not suitable for detection of small quantities of low atomic number elements typical for biological materials. Herein we show that laser-pulsed atom probe tomography, a technique that combines subnanometer spatial resolution with unbiased chemical sensitivity, is uniquely suited to the task. Common apatite end members share a number of features, but can clearly be distinguished by their spectrometric fingerprint. This fingerprint and the formation of molecular ions during field evaporation can be explained based on the chemistry of the apatite channel ion. Using end members for reference, we are able to interpret the spectra of bone and dentin samples, and generate the first three-dimensional reconstruction of 1.2 × 10(7) atoms in a dentin sample. The fibrous nature of the collagenous organic matrix in dentin is clearly recognizable in the reconstruction. Surprisingly, some fibers show selectivity in binding for sodium ions over magnesium ions, implying that an additional, chemical level of hierarchy is necessary to describe dentin structure. Furthermore, segregation of inorganic ions or small organic molecules to homophase interfaces (grain boundaries) is not apparent. This has implications for the platelet model for apatite biominerals.

  9. The status of strontium in biological apatites: an XANES investigation.

    PubMed

    Bazin, D; Daudon, M; Chappard, Ch; Rehr, J J; Thiaudière, D; Reguer, S

    2011-11-01

    Osteoporosis represents a major public health problem and increases patient morbidity through its association with fragility fractures. Among the different treatments proposed, strontium-based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk. While the localization of Sr(2+) cations in the bone matrix has been extensively studied, little is known regarding the status of Sr(2+) cations in natural biological apatite. In this investigation the local environment of Sr(2+) cations has been investigated through XANES (X-ray absorption near-edge structure) spectroscopy in a set of pathological and physiological apatites. To assess the localization of Sr(2+) cations in these biological apatites, numerical simulations using the ab initio FEFF9 X-ray spectroscopy program have been performed. The complete set of data show that the XANES part of the absorption spectra may be used as a fingerprint to determine the localization of Sr(2+) cations versus the mineral part of calcifications. More precisely, it appears that a relationship exists between some features present in the XANES part and a Sr(2+)/Ca(2+) substitution process in site (I) of crystal apatite. Regarding the data, further experiments are needed to confirm a possible link between the relationship between the preparation mode of the calcification (cellular activity for physiological calcification and precipitation for the pathological one) and the adsorption mode of Sr(2+) cations (simple adsorption or insertion). Is it possible to draw a line between life and chemistry through the localization of Sr in apatite? The question is open for discussion. A better structural description of these physiological and pathological calcifications will help to develop specific therapies targeting the demineralization process in the case of osteoporosis.

  10. High carbonate level of apatite in kidney stones implies infection, but is it predictive?

    PubMed

    Englert, Kate M; McAteer, James A; Lingeman, James E; Williams, James C

    2013-10-01

    The presence of infectious microorganisms in urinary stones is commonly inferred from stone composition, especially by the presence of struvite in a stone. The presence of highly carbonated apatite has also been proposed as a marker of the presence of bacteria within a stone. We retrospectively studied 368 patients who had undergone percutaneous nephrolithotomy (PCNL), and who also had culture results for both stone and urine. Urine culture showed no association with stone mineral content, but stone culture was more often positive in struvite-containing stones (73 % positive) and majority apatite stones (65 %) than in other stone types (54 %, lower than the others, P < 0.02). In 51 patients in whom the carbonate content of apatite could be measured, carbonate in the apatite was weakly predictive of positive stone culture with an optimal cutoff value of 13.5 % carbonate (sensitivity 0.61, specificity 0.80). In positive cultures of stones (all mineral types combined), organisms that characteristically produce urease were present in 71 % of the cases, with no difference in this proportion among different types of stone. In summary, the type of mineral in the stone was predictive of positive stone culture, but this correlation is imperfect, as over half of non-struvite, non-apatite stones were found to harbor culturable organisms. We conclude that mineral type is an inadequate predictor of whether a stone contains infectious organisms, and that stone culture is more likely to provide information useful to the management of patients undergoing PCNL.

  11. Controlled release of insulin in blood from strontium-substituted carbonate apatite complexes.

    PubMed

    Ahmad, Aiman; Othman, Iekhsan; Md Zain, Anuar Zaini; Chowdhury, Ezharul Hoque

    2015-01-01

    Diabetes mellitus is a chronic disease accompanied by a multitude of problems worldwide with subcutaneously administered insulin being the most common therapy currently. Controlledrelease insulin is assumed to be of high importance for long-term glycaemic control by reducing the number of daily injections. Long-acting insulin also mimics the basal insulin levels in normal individuals that may be lacking in diabetic patients. Nanoparticles of carbonate apatite as established for efficient intracellular transport of DNA and siRNA have the potential to be used for sustained release of insulin as responsive nano-carriers. The flexibility in the synthesis of the particles over a wide range of pHs with eventual adjustment of pH-dependent particle dissolution and the manageable variability of particle-integrity by incorporating selective ions into the apatite structure are the promising features that could help in the development of sustained release formulations for insulin. In particular strontium-incorporated carbonate apatite particles were formulated and compared with those of unsubstituted apatite in the context of insulin binding and subsequent release kinetics in DMEM, simulated buffer and finally human blood over a period of 20 hours. Clearly, the former demonstated to have a stronger electrostatic affinity towards the acidic insulin molecules and facilitate to some extent sustained release of insulin by preventing the initial burst effect at physiological pH in comparison with the latter. Thus, our findings suggest that optimization of the carbonate apatite particle composition and structure would serve to design an ideal insulin nano-carrier with a controlled release profile.

  12. Hydrogen and carbon abundances and isotopic ratios in apatite from alkaline intrusive complexes, with a focus on carbonatites

    SciTech Connect

    Nadeau, S.L.; Epstein, S.; Stolper, E.

    1999-06-01

    The authors report H and C contents and {delta}D and {delta}{sup 13}C values of apatites from 15 alkaline intrusive complexes ranging in age from 110 Ma to 2.6 Ga. Sampling focused on carbonatites, but included silicate rocks as well. Heating temperatures up to 1,500 C is needed to extract fully H{sub 2}O and CO{sub 2} from these apatites. Apatites from carbonatite-rich intrusive complexes contain 0.2--1.1 wt% H{sub 2}O and 0.05--0.70 wt% CO{sub 2}; apatites from two silicate-rich alkaline complexes with little or no carbonatite are generally poorer in both volatile components (0.1--0.2% H{sub 2}O and 0.01--0.11% CO{sub 2}). D/H ratios in apatites from these rocks are bimodally distributed. The authors suggest that the {delta}D values of group I apatites represent primitive, mantle-derived values and that the group II apatites crystallized from degassed magmas, resulting in lower H{sub 2}O contents and {delta}D values. In contrast to H{sub 2}O contents and {delta}D values, CO{sub 2} contents and {delta}{sup 13}C values of gas released at high temperatures from multiple aliquots of these apatite samples are variable. This suggests the presence of more than one C-bearing component in these apatites, one of which is proposed to be dissolved carbonate; the other could be associated with hydrocarbons.

  13. Postmagmatic magnetite-apatite assemblage in mafic intrusions: a case study of dolerite at Olympic Dam, South Australia

    NASA Astrophysics Data System (ADS)

    Apukhtina, Olga B.; Kamenetsky, Vadim S.; Ehrig, Kathy; Kamenetsky, Maya B.; McPhie, Jocelyn; Maas, Roland; Meffre, Sebastien; Goemann, Karsten; Rodemann, Thomas; Cook, Nigel J.; Ciobanu, Cristiana L.

    2016-01-01

    An assemblage of magnetite and apatite is common worldwide in different ore deposit types, including disparate members of the iron-oxide copper-gold (IOCG) clan. The Kiruna-type iron oxide-apatite deposits, a subtype of the IOCG family, are recognized as economic targets as well. A wide range of competing genetic models exists for magnetite-apatite deposits, including magmatic, magmatic-hydrothermal, hydrothermal(-metasomatic), and sedimentary(-exhalative). The sources and mechanisms of transport and deposition of Fe and P remain highly debatable. This study reports petrographic and geochemical features of the magnetite-apatite-rich vein assemblages in the dolerite dykes of the Gairdner Dyke Swarm (~0.82 Ga) that intruded the Roxby Downs Granite (~0.59 Ga), the host of the supergiant Olympic Dam IOCG deposit. These symmetrical, only few mm narrow veins are prevalent in such dykes and comprise besides usually colloform magnetite and prismatic apatite also further minerals (e.g., calcite, quartz). The genetic relationships between the veins and host dolerite are implied based on alteration in the immediate vicinity (~4 mm) of the veins. In particular, Ti-magnetite-ilmenite is partially to completely transformed to titanite and magmatic apatite disappears. We conclude that the mafic dykes were a local source of Fe and P re-concentrated in the magnetite-apatite veins. Uranium-Pb ages for vein apatite and titanite associated with the vein in this case study suggest that alteration of the dolerite and healing of the fractures occurred shortly after dyke emplacement. We propose that in this particular case the origin of the magnetite-apatite assemblage is clearly related to hydrothermal alteration of the host mafic magmatic rocks.

  14. A fast method for apatite selective leaching from granitic rocks followed through rare earth elements and phosphorus determination by inductively coupled plasma optical emission spectrometry.

    PubMed

    Gásquez, José A; DeLima, Edmilson; Olsina, Roberto A; Martinez, Luis D; de la Guardia, Miguel

    2005-10-15

    Rare earth elements (REE) and phosphorus (P) in apatite were determined using inductively coupled plasma optical emission spectrometry (ICP-OES) after partial dissolution of the granitic rocks and pure apatite. The dissolution was performed with nitric acid in an open system and the matrix elements were separated by a cation exchange procedure. Samples of pure apatite from granitic rocks were dissolved with, 0.14 mol L(-1) nitric acid. The results showed that the release of REE is due to apatite leaching because it could be assessed by comparing the chondrite-normalised pattern corresponding to the rocks and the pure apatite. Similar results were found for absolute REE abundance from the partial dissolution of the rocks and pure apatite. This simple and rapid method can be applied for the determination of REE in apatite as an indicator for mineral exploration, although its use in petrology could be possible.

  15. Reduction And Stabilization (Immobilization) Of Pertechnetate To An Immobile Reduced Technetium Species Using Tin(II) Apatite

    SciTech Connect

    Duncan, J. B.

    2012-11-02

    Synthetic tin(II)apatite reduces pertechnetate from the mobile +7 to a non-mobile oxidation state and sequesters the technetium, preventing re-oxidization to mobile +7 state under acidic or oxygenated conditions. Previous work indicated technetium reacted Sn(II)apatite can achieve an ANSI leachability index of 12.8 in Cast Stone. An effect by pH is observed on the distribution coefficient, the highest distribution coefficient being l70,900 observed at pH levels of 2.5 to 10.2. The tin apatite was resistant to releasing technetium under test conditions.

  16. Partitioning of F and Cl Between Apatite and a Synthetic Shergottite Liquid (QUE 94201) at 4 Gpa from 1300 TO 1500 C

    NASA Technical Reports Server (NTRS)

    McCubbin, F. M.; Barnes, J. J.; Vander Kaaden, K. E.; Boyce, J. W.

    2017-01-01

    Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (Xsite), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to accurately determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multicomponent silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al., recently reported that the exchange coefficients vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing, and McCubbin et al. reported substantial deviations in the Cl-F exchange Kd along the F-Cl apatite join that could be explained by the preferential incorporation of F into apatite. In the present study, we assess the effect of apatite crystal chemistry on F-Cl exchange equilibria between apatite and melt at 4 GPa over the temperature range of 1300-1500 C. The goal of these experiments is to assess the variation in the Ap-melt Cl-F exchange Kd over a broad range of F:Cl ratios in apatite. The results of these experiments could be used to understand at what

  17. Influence of vacancy damage on He diffusion in apatite, investigated at atomic to mineralogical scales

    NASA Astrophysics Data System (ADS)

    Gerin, Chloé; Gautheron, Cécile; Oliviero, Erwan; Bachelet, Cyril; Mbongo Djimbi, Duval; Seydoux-Guillaume, Anne-Magali; Tassan-Got, Laurent; Sarda, Philippe; Roques, Jérôme; Garrido, Frédérico

    2017-01-01

    Helium diffusion in U-Th-rich minerals, especially apatite, is considered as strongly impacted by damage, even at low U-Th content. To get direct evidence and better understand the impact of damage on He diffusion, we conducted a study on vacancy damage in apatite, at nanometric to atomic scales, using different methodologies. Firstly, damage was created on apatite crystals by He implantation at different He fluences ranging from 2 × 1015 to 1 × 1017 He/cm2, corresponding to atomic displacement ranging from 12 to more than 100% of the total structure in the first 200 nm below the surface. Transmission Electron Microscopy (TEM) was used to image the damage structure, for the lowest He fluence. TEM images present no visible damage zone at nano-scale, implying that the created damage corresponds well to Frenkel defects (vacancies and interstitials). Secondly, diffusion experiments were performed on those samples by mapping He concentration vs. depth profiles using Elastic Recoil Detection Analysis (ERDA). After measurement of implanted-He profiles and He concentrations, the samples were heated in order to diffuse the implanted profile during 15-45 h at temperatures from 145 to 250 °C. The obtained He vs. depth heated profiles and He concentrations reveal the impact of damage on He diffusivity. The results can only be explained by a model where diffusion depends on damage dose, taking into account He trapping in vacancies and damage interconnectivity at higher damage dose. Thirdly, Density Functional Theory (DFT) calculations were performed to simulate a vacancy in a F-apatite crystal. The structure becomes slightly deformed by the vacancy and the insertion energy of a He atom in the vacancy is lower than for an usual insertion site. Accordingly, the additional energy for a He atom to jump out of the vacancy is ΔEa ≈ 30-40 kJ/mol, in good agreement with published estimates. This calculation thus shows that small modifications of the structure due to the presence

  18. LABORATORY REPORT ON THE REDUCTION AND STABILIZATION (IMMOBILIZATION) OF PERTECHNETATE TO TECHNETIUM DIOXIDE USING TIN(II)APATITE

    SciTech Connect

    DUNCAN JB; HAGERTY K; MOORE WP; RHODES RN; JOHNSON JM; MOORE RC

    2012-06-01

    This effort is part of the technetium management initiative and provides data for the handling and disposition of technetium. To that end, the objective of this effort was to challenge tin(II)apatite (Sn(II)apatite) against double-shell tank 241-AN-105 simulant spiked with pertechnetate (TcO{sub 4}{sup -}). The Sn(II)apatite used in this effort was synthesized on site using a recipe developed at and provided by Sandia National Laboratories; the synthesis provides a high quality product while requiring minimal laboratory effort. The Sn(II)apatite reduces pertechnetate from the mobile +7 oxidation state to the non-mobile +4 oxidation state. It also sequesters the technetium and does not allow for re-oxidization to the mo bile +7 state under acidic or oxygenated conditions within the tested period oftime (6 weeks). Previous work (RPP-RPT-39195, Assessment of Technetium Leachability in Cement-Stabilized Basin 43 Groundwater Brine) indicated that the Sn(II)apatite can achieve an ANSI leachability index in Cast Stone of 12.8. The technetium distribution coefficient for Sn(II)apatite exhibits a direct correlation with the pH of the contaminated media. Table A shows Sn(II)apatite distribution coefficients as a function of pH. The asterisked numbers indicate that the lower detection limit of the analytical instrument was used to calculate the distribution coefficient as the concentration of technetium left in solution was less than the detection limit. The loaded sample (200 mg of Sn(II)apatite loaded with O.311 mg of Tc-99) was subjected to different molarities of nitric acid to determine if the Sn(II)apatite would release the sequestered technetium. The acid was allowed to contact for 1 minute with gentle shaking ('1st wash'); the aqueous solution was then filtered, and the filtrate was analyzed for Tc-99. Table B shows the results ofthe nitric acid exposure. Another portion of acid was added, shaken for a minute, and filtered ('2nd wash'). The technetium-loaded Sn(II)apatite

  19. Local structure investigation of oxide ion and proton defects in Ge-apatites by pair distribution function analysis.

    PubMed

    Malavasi, Lorenzo; Orera, Alodia; Slater, Peter R; Panchmatia, Pooja M; Islam, M Saiful; Siewenie, Joan

    2011-01-07

    In this communication we provide a direct insight into the local structure and defects of oxygen excess Ge-apatites, in both dry and deuterated states, by means of pair distribution function analysis.

  20. Estimation of the specific surface area of apatites in human mineralized tissues using 31P MAS NMR.

    PubMed

    Kolmas, Joanna; Slósarczyk, Anna; Wojtowicz, Andrzej; Kolodziejski, Waclaw

    2007-10-01

    Specific surface areas of apatites in whole human mineralized tissues were estimated from (31)P MAS NMR linewidths: 77 m(2)g(-1) for enamel and 94 m(2)g(-1) for dentin, dental cementum and cortical bone.

  1. A temporal record of pre-eruptive magmatic volatile contents at Campi Flegrei: Insights from texturally-constrained apatite analyses

    NASA Astrophysics Data System (ADS)

    Stock, Michael J.; Isaia, Roberto; Humphreys, Madeleine C. S.; Smith, Victoria C.; Pyle, David M.

    2016-04-01

    Apatite is capable of incorporating all major magmatic volatile species (H2O, CO2, S, Cl and F) into its crystal structure. Analysis of apatite volatile contents can be related to parental magma compositions through the application of pressure and temperature-dependent exchange reactions (Piccoli and Candela, 1994). Once included within phenocrysts, apatite inclusions are isolated from the melt and preserve a temporal record of magmatic volatile contents in the build-up to eruption. In this work, we measured the volatile compositions of apatite inclusions, apatite microphenocrysts and pyroxene-hosted melt inclusions from the Astroni 1 eruption of Campi Flegrei, Italy (Stock et al. 2016). These data are coupled with magmatic differentiation models (Gualda et al., 2012), experimental volatile solubility data (Webster et al., 2014) and thermodynamic models of apatite compositional variations (Piccoli and Candela, 1994) to decipher pre-eruptive magmatic processes. We find that apatite halogen/OH ratios decreased through magmatic differentiation, while melt inclusion F and Cl concentrations increased. Melt inclusion H2O contents are constant at ~2.5 wt%. These data are best explained by volatile-undersaturated differentiation over most of the crystallisation history of the Astroni 1 melt, with melt inclusion H2O contents reset at shallow levels during ascent. Given the high diffusivity of volatiles in apatite (Brenan, 1993), the preservation of volatile-undersaturated melt compositions in microphenocrysts suggests that saturation was only achieved 10 - 103 days before eruption. We suggest that late-stage transition into a volatile-saturated state caused an increase in magma chamber overpressure, which ultimately triggered the Astroni 1 eruption. This has major implications for monitoring of Campi Flegrei and other similar volcanic systems. Piccoli and Candela, 1994. Am. J. of Sc., 294, 92-135. Stock et al., 2016, Nat. Geosci. Gualda et al., 2012. J. Pet., 53, 875

  2. Phosphate-induced metal stabilization: Use of apatite and bone char for the removal of soluble radionuclides in authentic and simulated DOE groundwater

    SciTech Connect

    Bostick, W.D.; Jarabek, R.J.; Conca, J.L.

    1999-07-01

    The apatite group of minerals is a family of calcium phosphate phases. Apatite is the principal component of bone tissue, and it also occurs naturally as mineral deposits in the geosphere. Bone char is calcined (coked) animal bone, containing activated carbon as well as calcium phosphate mineral phases. Apatite II{trademark} is a more reactive form of apatite, supplied by UFA Ventures, Inc., at a cost of approximately 1/4 that of commercial bone char. Apatite is shown to be effective for the removal of select heavy metal impurities in groundwater. Previous investigations have demonstrated that apatite is an effective medium for the stabilization of soluble lead, cadmium, and zinc from mine waste leachate by the formation of highly insoluble precipitate phases. The performance of bone char and apatite II are compared with other candidate sorption media (including granular activated carbon and anion exchange resin) for the removal of soluble uranyl ion in synthetic DOE Site groundwater supplemented with varying levels of interfering nitrate ion. Apatite II has a greater affinity for U(VI), especially in the presence of nitrate ion, as evidenced by a larger value for the conditional distribution coefficient (Kd) in batch test experiments. Contact of uranyl nitrate solution with apatite II is shown to produce highly insoluble mineral phases of the autunite group (calcium uranyl phosphate hydrates). Apatite II is also demonstrated to be moderately effective for the removal of soluble radioactive isotopes of strontium, but not cesium, when these ions are supplemented into authentic DOE Site groundwater.

  3. Determination of the oxidation state of uranium in apatite and phosphorite deposits

    USGS Publications Warehouse

    Clarke, R.S.; Altschuler, Z.S.

    1958-01-01

    Geological and mineralogical evidence indicate that the uranium present in apatite may proxy for calcium in the mineral structure as U(IV). An experimental investigation was conducted and chemical evidence was obtained that establishes the presence of U(IV) in apatite. The following analytical procedure was developed for the determination of U(IV). Carbonatefluorapatite is dissolved in 1.5 M orthophosphoric acid at a temperature of 5??C or slightly below and fluorapatite is dissolved in cold 1.2 M hydrochloric acid (approximately 5??C) containing 1.5 g of hydroxylamine hydrochloride per 100 ml. Uranium(IV) is precipitated by cupferron using titanium as a carrier. The uranium in the precipitate is separated by use of the ethyl acetate extraction procedure and determined fluorimetrically. The validity and the limitations of the method have been established by spike experiments. ?? 1958.

  4. [A study on the formation of apatite crystallized with gel method].

    PubMed

    Endo, T; Amano, N; Yoshida, M; Murakami, H; Kosuge, N; Ohmi, Y; Kameda, A

    1989-10-01

    About apatite produced with a silicahydro gel method using calcium nitrate (group I) or calcium chloride (group II) and a gelatin gel method by use of calcium nitrate (group III) or calcium chloride (group IV), the formative volume as well as the formative condition of a periodic-layered precipitate (Liesegang ring), the pH measurement, calculation of Ca/P ratio, an estimation of the chlorine ion, morphological observation with a scanning electron microscope, qualitative analyses by X-ray diffraction (identification, crystallite size, lattice imperfections, lattice constants) and the composition analysis by infrared absorption spectroscopy were carried out to elucidate the formation of apatite using the gel method. The result showed that there were no distinct differences between group I-II and group III-IV, and it is suggested that it is possible to form satisfact fluorapatite with a gel method using calcium chloride as well as calcium nitrate.

  5. Incorporation of uranium into a biomimetic apatite: physicochemical and biological aspects.

    PubMed

    Chatelain, Grégory; Bourgeois, Damien; Ravaux, Johann; Averseng, Olivier; Vidaud, Claude; Meyer, Daniel

    2015-04-01

    Bone is the main target organ for the storage of several toxic metals, including uranium. But the mode of action of uranium on bones remains poorly understood. To better assess the impact of uranium on bone cells, synthetic biomimetic apatites encompassing a controlled amount of uranium were prepared and analyzed. This study revealed the physicochemical impact of uranium on apatite mineralization: the presence of the metal induces a loss of crystallinity and a lower mineralization rate. The prepared samples were then used as substrates for bone cell culture. Osteoblasts were not sensitive to the presence of uranium in the support, whereas previous results showed a deleterious effect of uranium introduced into a cell culture solution. This work should therefore have some original prospects within the context of toxicological studies concerning the effect of metallic cations on bone cell systems.

  6. Carbonate loss from two magnesium-substituted carbonated apatites prepared by different synthesis techniques

    SciTech Connect

    Barinov, S.M. . E-mail: barinov_s@mail.ru; Rau, J.V.; Fadeeva, I.V.; Cesaro, S. Nunziante; Ferro, D.; Trionfetti, G.; Komlev, V.S.; Bibikov, V.Yu.

    2006-03-09

    This study was aimed at the investigation of the thermal stability of Mg-substituted carbonated apatites over the wide temperature range. Two different apatites were studied, which were prepared by either precipitation from aqueous solution or by solid-liquid interaction. The following methods were employed: FTIR spectroscopy of the condensed gas phase to evaluate the CO and CO{sub 2} release with increasing temperature, FTIR of the solid residue after heating, XRD analysis, thermogravimetry and scanning electron microscopy. Decomposition behavior was shown to depend significantly on the synthesis method. Wet-synthesized powders are significantly less thermally stable compared with those prepared by solid-liquid interaction. Intensive release of carbon oxides from the former was observed at 300 deg. C, whereas the latter powder was relatively stable up to temperature about 1000 deg. C.

  7. Apatite 4He/3He and (U-Th)/He evidence for an ancient Grand Canyon.

    PubMed

    Flowers, R M; Farley, K A

    2012-12-21

    The Grand Canyon is one of the most dramatic features on Earth, yet when and why it was carved have been controversial topics for more than 150 years. Here, we present apatite (4)He/(3)He thermochronometry data from the Grand Canyon basement that tightly constrain the near-surface cooling history associated with canyon incision. (4)He/(3)He spectra for eastern Grand Canyon apatites of differing He date, radiation damage, and U-Th zonation yield a self-consistent cooling history that substantially validates the He diffusion kinetic model applied here. Similar data for the western Grand Canyon provide evidence that it was excavated to within a few hundred meters of modern depths by ~70 million years ago (Ma), in contrast to the conventional model in which the entire canyon was carved since 5 to 6 Ma.

  8. Influence of disodium EDTA on the nucleation and growth of struvite and carbonate apatite

    NASA Astrophysics Data System (ADS)

    Prywer, Jolanta; Olszynski, Marcin

    2013-07-01

    The effect of disodium EDTA, as an additive, on the crystallization of struvite and carbonate apatite was studied. The growth of struvite crystals and carbonate apatite occurred in the solution of artificial urine at 37 °C and at the condition emulating real urinary tract infection. The results demonstrate that the addition of disodium EDTA increases the induction time and decreases the growth efficiency compared to the baseline (without disodium EDTA). The struvite crystal mean and median diameters were found to decrease in the presence of disodium EDTA but the crystal morphology and habit remain almost unchanged. Disodium EDTA has demonstrated its potential to be further investigated in the presence of bacteria and in vivo conditions.

  9. Electrospun Nanostructured Fibers of Collagen-Biomimetic Apatite on Titanium Alloy

    PubMed Central

    Iafisco, Michele; Foltran, Ismaela; Sabbatini, Simona; Tosi, Giorgio; Roveri, Norberto

    2012-01-01

    Titanium and its alloys are currently the mainly used materials to manufacture orthopaedic implants due to their excellent mechanical properties and corrosion resistance. Although these materials are bioinert, the improvement of biological properties (e.g., bone implant contact) can be obtained by the application of a material that mimics the bone extracellular matrix. To this aim, this work describes a new method to produce nanostructured collagen-apatite composites on titanium alloy substrate, by combining electrospinning and biomimetic mineralization. The characterization results showed that the obtained mineralized scaffolds have morphological, structural, and chemical compositional features similar to natural bone extracellular matrix. Finally, the topographic distribution of the chemical composition in the mineralized matrix evaluated by Fourier Transform Infrared microspectroscopy demonstrated that the apatite nanocrystals cover the collagen fibers assembled by the electrospinning. PMID:22400013

  10. Synthesis of hexagonal lanthanum germanate apatites through site selective isovalent doping with yttrium

    SciTech Connect

    Kendrick, E.; Slater, P.R.

    2008-08-04

    Apatite-type lanthanum silicates/germanates have been attracting considerable interest as a new class of oxide ion conductors, whose conductivity is mediated by oxide ion interstitials. For the germanates, it has been shown that, depending on composition, the cell can be either hexagonal or triclinic, with evidence for reduced low-temperature conductivities for the latter, attributed to increased defect trapping in this lower symmetry cell. In this paper we show that site selective doping of Y into the triclinic apatite-type oxide ion conductors, La{sub 9.33+z}(GeO{sub 4}){sub 6}O{sub 2+3z/2} (0.33 {<=} z {<=} 0.67) results in a hexagonal lattice for the complete series with correspondingly enhanced low-temperature conductivity.

  11. Biological control of apatite growth in simulated body fluid and human blood serum.

    PubMed

    Juhasz, Judith A; Best, Serena M; Auffret, Antony D; Bonfield, William

    2008-04-01

    The surface transformation reactions of bioactive ceramics were studied in vitro in standard K9-SBF solution and in human blood serum (HBS)-containing simulated body fluid (SBF). The calcium phosphate ceramics used for this study were stoichiometric hydroxyapatite (HA), beta-tricalcium phosphate (beta-TCP) and brushite. Immersion of each calcium phosphate tested in this study, in simulated body fluid, led to immediate surface precipitation of apatite. The use of HBS resulted in a delay in the onset of precipitation and a significant inhibition of the dissolution reaction normally observed for brushite in solution. However, apatite formation still occurred. The use of HBS and SBF in this investigation, which has shown the ability to induce similar crystal growth as that observed in vivo, suggests that there is scope for the use of serum proteins in simulated body fluid in order to create a protein-rich surface coating on biomedical substrates.

  12. Fabrication of carbonate apatite block based on internal dissolution-precipitation reaction of dicalcium phosphate and calcium carbonate.

    PubMed

    Daitou, Fumikazu; Maruta, Michito; Kawachi, Giichiro; Tsuru, Kanji; Matsuya, Shigeki; Terada, Yoshihiro; Ishikawa, Kunio

    2010-05-01

    In this study, we investigated a novel method for fabrication of carbonate apatite block without ionic movement between precursor and solution by using precursor that includes all constituent ions of carbonate apatite. A powder mixture prepared from dicalcium phosphate anhydrous and calcite at appropriate Ca/P ratios (1.5, 1.67, and 1.8) was used as starting material. For preparation of specimens, the slurry made from the powder mixture and distilled water was packed in a split stainless steel mold and heat - treated, ranging from 60 degrees C to 100 degrees C up to 48 hours at 100% humidity. It appeared that carbonate apatite could be obtained above 70 degrees C and monophasic carbonate apatite could be obtained from the powder mixture at Ca/P ratio of 1.67. Carbonate content of the specimen was about 5-7%. Diametral tensile strength of the carbonate apatite blocks slightly decreased with increasing treatment temperature. The decrease in diametral tensile strength is thought to be related to the crystal size of the carbonate apatite formed.

  13. Hanford 100-N Area In Situ Apatite and Phosphate Emplacement by Groundwater and Jet Injection: Geochemical and Physical Core Analysis

    SciTech Connect

    Szecsody, James E.; Vermeul, Vincent R.; Fruchter, Jonathan S.; Williams, Mark D.; Rockhold, Mark L.; Qafoku, Nikolla; Phillips, Jerry L.

    2010-07-01

    The purpose of this study is to evaluate emplacement of phosphate into subsurface sediments in the Hanford Site 100-N Area by two different technologies: groundwater injection of a Ca-citrate-PO4 solution and water-jet injection of sodium phosphate and/or fish-bone apatite. In situ emplacement of phosphate and apatite adsorbs, then incorporates Sr-90 into the apatite structure by substitution for calcium. Overall, both technologies (groundwater injection of Ca-citrate-PO4) and water-jet injection of sodium phosphate/fish-bone apatite) delivered sufficient phosphate to subsur¬face sediments in the 100-N Area. Over years to decades, additional Sr-90 will incorporate into the apatite precipitate. Therefore, high pressure water jetting is a viable technology to emplace phosphate or apatite in shallow subsurface sediments difficult to emplace by Ca-citrate-PO4 groundwater injections, but further analysis is needed to quantify the relevant areal extent of phosphate deposition (in the 5- to 15-ft distance from injection points) and cause of the high deposition in finer grained sediments.

  14. An evaluation of the reactivity of synthetic and natural apatites in the presence of aqueous metals.

    PubMed

    Dybowska, Agnieszka; Manning, David A C; Collins, Matthew J; Wess, Timothy; Woodgate, Stephen; Valsami-Jones, Eugenia

    2009-04-01

    Metal removal from contaminated effluents was examined following reaction with natural apatites of biological and geological origin or a synthetic hydroxylapatite (HAP). Mammalian meat and bone meal (MBM), a by-product from meat industry, was the biological apatite source. The effect of incineration on metal removal capacity of MBM and HAP was also examined. The reactivity of apatites for all tested metals (Pb, Cd, Cu and Zn) followed the general order: synthetic > biological > mineral. For all apatites tested, Pb was removed best and preferentially from multi-metal solutions. MBM and HAP (0.5 g solid) removed Pb completely from both highly concentrated single metal solutions (50 ml, 1000 mg/L Pb) and from multi-metal solutions (50 ml) with 100 mg/L each of Cd, Cu and Zn in addition to Pb. The incineration of MBM (725 degrees C and 850 degrees C) reduced significantly its capacity for removal of Zn (by 47%, from 56 mg/g to 9 mg/g) and Cd (by 38%, from 53 mg/g to 13 mg/g) in particular and to a lesser extent for Cu (by 14%, from 61 mg/g to 46 mg/g) while the removal of Pb was not affected (100 mg/g). The same pattern was observed for incinerated HAP. SEM and XRD analysis indicated that HAP reacted with the metals by precipitation of pure metal phosphates--Pb hydroxylapatite, Zn phosphate (hopeite), a Cd phosphate (identified only by ED-SEM) and Cu phosphate (libenthenite).

  15. pH-responsive delivery of doxorubicin from citrate-apatite nanocrystals with tailored carbonate content.

    PubMed

    Rodríguez-Ruiz, Isaac; Delgado-López, José Manuel; Durán-Olivencia, Miguel A; Iafisco, Michele; Tampieri, Anna; Colangelo, Donato; Prat, Maria; Gómez-Morales, Jaime

    2013-07-02

    In this work, the efficiency of bioinspired citrate-functionalized nanocrystalline apatites as nanocarriers for delivery of doxorubicin (DOXO) has been assessed. The nanoparticles were synthesized by thermal decomplexing of metastable calcium/citrate/phosphate solutions both in the absence (Ap) and in the presence (cAp) of carbonate ions. The presence of citrate and carbonate ions in the solution allowed us to tailor the size, shape, carbonate content, and surface chemistry of the nanoparticles. The drug-loading efficiency of the two types of apatite was evaluated by means of the adsorption isotherms, which were found to fit a Langmuir-Freundlich behavior. A model describing the interaction between apatite surface and DOXO is proposed from adsorption isotherms and ζ-potential measurements. DOXO is adsorbed as a dimer by means of a positively charged amino group that electrostatically interacts with negatively charged surface groups of nanoparticles. The drug-release profiles were explored at pHs 7.4 and 5.0, mimicking the physiological pH in the blood circulation and the more acidic pH in the endosome-lysosome intracellular compartment, respectively. After 7 days at pH 7.4, cAp-DOXO released around 42% less drug than Ap-DOXO. However, at acidic pH, both nanoassemblies released similar amounts of DOXO. In vitro assays analyzed by confocal microscopy showed that both drug-loaded apatites were internalized within GTL-16 human carcinoma cells and could release DOXO, which accumulated in the nucleus in short times and exerted cytotoxic activity with the same efficiency. cAp are thus expected to be a more promising nanocarrier for experiments in vivo, in situations where intravenous injection of nanoparticles are required to reach the targeted tumor, after circulating in the bloodstream.

  16. Apatite and Chitin Amendments Promote Microbial Activity and Augment Metal Removal in Marine Sediments

    DTIC Science & Technology

    2013-07-01

    geotextile mats, apatite, organoclay , and chitin. Inorganic amend- ments help to immobilize several toxic metals such as lead, zinc, and cadmium by...to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data...needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection

  17. Apatite-forming PEEK with TiO2 surface layer coating.

    PubMed

    Kizuki, Takashi; Matsushita, Tomiharu; Kokubo, Tadashi

    2015-01-01

    Polyetheretherketone (PEEK) is widely used in orthopedic implants, such as spinal fusion devices, because of its moderate elastic modulus, as well as relatively high mechanical strength. However, it does not bond to living bone, and hence it needs autograft to be fixed to the bone. In this study, we attempted to add bone-bonding properties to PEEK by coating with TiO2 synthesized by the sol-gel process. When a TiO2 sol solution consisting of titanium isopropoxide, water, ethanol, and nitric acid was deposited on a PEEK substrate without any pretreatment, the formed TiO2 gel layer was easily peeled off after subsequent treatments. However, when the same solution was deposited on PEEK that was preliminarily subjected to UV or O2 plasma treatment, the deposited TiO2 gel layer strongly adhered to the substrate even after subsequent treatments. The strong adhesion was attributed to the interaction among the C-O, C=O, and O-C=O groups on the PEEK owing to the UV or O2 plasma treatment and the Ti-O bond of the TiO2 gel. Apatite did not form on the as-formed TiO2 gel layer in a simulated body fluid (SBF) even within 3 days; however, apatite formed after soaking in 0.1 M HCl solution at 80 °C for 24 h. This apatite formation was attributed to positive surface charge of the TiO2 gel layer induced by the acid treatment. The PEEK with the TiO2 gel layer coating formed by the proposed process is expected to bond to living bone, because a positively charged titanium oxide which facilitates the formation of apatite in SBF within a short period is known to bond to living bone.

  18. An Injectable Apatite Permeable Reactive Barrier for In Situ 90Sr Immobilization

    SciTech Connect

    Vermeul, Vincent R.; Szecsody, James E.; Fritz, Brad G.; Williams, Mark D.; Moore, Robert C.; Fruchter, Jonathan S.

    2014-04-16

    An injectable permeable reactive barrier (PRB) technology was developed to sequester 90Sr in groundwater through the in situ formation of calcium-phosphate mineral phases, specifically apatite that incorporates 90Sr into the chemical structure. An integrated, multi-scale development and testing approach was used that included laboratory bench-scale experiments, an initial pilot-scale field test, and the emplacement and evaluation of a 300-ft-long treatability-test-scale PRB. Standard groundwater wells were used for emplacement of the treatment zone, allowing treatment of contaminants too deep below ground surface for trench-and-fill type PRB technologies. The apatite amendment formulation uses two separate precursor solutions, one containing a Ca-citrate complex and the other a Na-phosphate solution, to form apatite precipitate in situ. Citrate is needed to keep calcium in solution long enough to achieve a more uniform and areally extensive distribution of precipitate formation. In the summer of 2008, the apatite PRB technology was applied as a 91-m (300-ft) -long permeable reactive barrier on the downgradient edge of a 90Sr plume beneath the Hanford Site in Washington State. The technology was deployed to reduce 90Sr flux discharging to the Columbia River. Performance assessment monitoring data collected to date indicate the barrier is meeting performance objectives. The average reduction in 90Sr concentrations at four downgradient compliance monitoring locations was 95% relative to the high end of the baseline range approximately 1 year after treatment, and continues to meet remedial objectives more than 4 years after treatment.

  19. Fabrication of DNA-antibody-apatite composite layers for cell-targeted gene transfer

    NASA Astrophysics Data System (ADS)

    Yazaki, Yushin; Oyane, Ayako; Araki, Hiroko; Sogo, Yu; Ito, Atsuo; Yamazaki, Atsushi; Tsurushima, Hideo

    2012-12-01

    Surface-mediated gene transfer systems using apatite (Ap)-based composite layers have received increased attention in tissue engineering applications owing to their safety, biocompatibility and relatively high efficiency. In this study, DNA-antibody-apatite composite layers (DA-Ap layers), in which DNA and antibody molecules are immobilized within a matrix of apatite nanocrystals, were fabricated using a biomimetic coating process. They were then assayed for their gene transfer capability for application in a specific cell-targeted gene transfer. A DA-Ap layer that was fabricated with an anti-CD49f antibody showed a higher gene transfer capability to the CD49f-positive CHO-K1 cells than a DNA-apatite composite layer (D-Ap layer). The antibody facilitated the gene transfer capability of the DA-Ap layer only to the specific cells that were expressing corresponding antigens. When the DA-Ap layer was fabricated with an anti-N-cadherin antibody, a higher gene transfer capability compared with the D-Ap layer was found in the N-cadherin-positive P19CL6 cells, but not in the N-cadherin-negative UV♀2 cells or in the P19CL6 cells that were pre-blocked with anti-N-cadherin. Therefore, the antigen-antibody binding that takes place at the cell-layer interface should be responsible for the higher gene transfer capability of the DA-Ap than D-Ap layer. These results suggest that the DA-Ap layer works as a mediator in a specific cell-targeted gene transfer system.

  20. Fabrication of DNA-antibody-apatite composite layers for cell-targeted gene transfer.

    PubMed

    Yazaki, Yushin; Oyane, Ayako; Araki, Hiroko; Sogo, Yu; Ito, Atsuo; Yamazaki, Atsushi; Tsurushima, Hideo

    2012-12-01

    Surface-mediated gene transfer systems using apatite (Ap)-based composite layers have received increased attention in tissue engineering applications owing to their safety, biocompatibility and relatively high efficiency. In this study, DNA-antibody-apatite composite layers (DA-Ap layers), in which DNA and antibody molecules are immobilized within a matrix of apatite nanocrystals, were fabricated using a biomimetic coating process. They were then assayed for their gene transfer capability for application in a specific cell-targeted gene transfer. A DA-Ap layer that was fabricated with an anti-CD49f antibody showed a higher gene transfer capability to the CD49f-positive CHO-K1 cells than a DNA-apatite composite layer (D-Ap layer). The antibody facilitated the gene transfer capability of the DA-Ap layer only to the specific cells that were expressing corresponding antigens. When the DA-Ap layer was fabricated with an anti-N-cadherin antibody, a higher gene transfer capability compared with the D-Ap layer was found in the N-cadherin-positive P19CL6 cells, but not in the N-cadherin-negative UV♀2 cells or in the P19CL6 cells that were pre-blocked with anti-N-cadherin. Therefore, the antigen-antibody binding that takes place at the cell-layer interface should be responsible for the higher gene transfer capability of the DA-Ap than D-Ap layer. These results suggest that the DA-Ap layer works as a mediator in a specific cell-targeted gene transfer system.

  1. Bone-like apatite coating on functionalized poly(etheretherketone) surface via tailored silanization layers technique.

    PubMed

    Zheng, Yanyan; Xiong, Chengdong; Zhang, Shenglan; Li, Xiaoyu; Zhang, Lifang

    2015-10-01

    Poly(etheretherketone) (PEEK) is a rigid semi-crystalline polymer with outstanding mechanical properties, bone-like stiffness and suitable biocompatibility that has attracted much interest as a biomaterial for orthopedic and dental implants. However, the bio-inert surface of PEEK limits its biomedical applications when direct osteointegration between the implants and the host tissue is desired. In this work, -PO4H2, -COOH and -OH groups were introduced on the PEEK surface by further chemical treatments of the vinyl-terminated silanization layers formed on the hydroxylation-pretreated PEEK surface. Both the surface-functionalized and pristine specimens were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and water contact angle measurements. When placed in 1.5 strength simulated body fluid (SBF) solution, apatite was observed to form uniformly on the functionalized PEEK surface and firmly attach to the substrate. The characterized results demonstrated that the coating was constituted by poorly crystallized bone-like apatite and the effect of surface functional groups on coating formation was also discussed in detail. In addition, in vitro biocompatibility of PEEK, in terms of pre-osteoblast cell (MC3T3-E1) attachment, spreading and proliferation, was remarkably enhanced by the bone-like apatite coating. Thus, this study provides a method to enhance the bioactivity of PEEK and expand its applications in orthopedic and dental implants.

  2. The development of carbonate-containing apatite/collagen composite for osteoconductive apical barrier material.

    PubMed

    Takenaka, Yoshihiro; Iijima, Mayumi; Kawano, Satoshi; Akita, Yasumitsu; Yoshida, Takakazu; Doi, Yutaka; Sekine, Ichiro

    2008-09-01

    The current report describes the properties of a new apical barrier material formulated from carbonate-containing apatite (CAp) and collagen. CAp particles of around 50 nm were deposited on reconstituted collagen fibers. CAp/col with about 60 wt % CAp (corresponding to apatite content of bone) was obtained after 1 day of calcification. CAp content increased up to about 80 wt % in a 15-day calcification reaction. CAp/col was composed of fine calcified collagen fibers. The crystallinity and Ca/PO(4) ratio of CAp were comparable to those of bone apatite. The mixture of CAp/col and saline reached a pH of about 9. The optimum powder-to-liquid ratio (P/L) to set into a root canal was determined to be 1.2. Furthermore, the mixture (P/L = 1.2) condensed in a root canal was liquid permeable. Thus, the CAp/col was expected as an apical barrier material with osteoconductivity.

  3. Synthetic apatite nanoparticles as a phosphorus fertilizer for soybean (Glycine max).

    PubMed

    Liu, Ruiqiang; Lal, Rattan

    2014-07-14

    Some soluble phosphate salts, heavily used in agriculture as highly effective phosphorus (P) fertilizers, cause surface water eutrophication, while solid phosphates are less effective in supplying the nutrient P. In contrast, synthetic apatite nanoparticles could hypothetically supply sufficient P nutrients to crops but with less mobility in the environment and with less bioavailable P to algae in comparison to the soluble counterparts. Thus, a greenhouse experiment was conducted to assess the fertilizing effect of synthetic apatite nanoparticles on soybean (Glycine max). The particles, prepared using one-step wet chemical method, were spherical in shape with diameters of 15.8 ± 7.4 nm and the chemical composition was pure hydroxyapatite. The data show that application of the nanoparticles increased the growth rate and seed yield by 32.6% and 20.4%, respectively, compared to those of soybeans treated with a regular P fertilizer (Ca(H2PO4)2). Biomass productions were enhanced by 18.2% (above-ground) and 41.2% (below-ground). Using apatite nanoparticles as a new class of P fertilizer can potentially enhance agronomical yield and reduce risks of water eutrophication.

  4. Influence of fluoride in poly(d,l-lactide)/apatite composites on bone formation.

    PubMed

    Luo, X; Barbieri, D; Passanisi, G; Yuan, H; de Bruijn, J D

    2015-05-01

    The influence of fluoride in poly(d,l-lactide)/apatite composites on ectopic bone formation was evaluated in sheep. Nano-apatite powders with different replacement levels of OH groups by fluoride (F) (0% (F0), 50% (F50), 100% (F100), and excessive (F200)) were co-extruded with poly (d,l-lactide) at a weight ratio of 1:1. Fluoride release from the composites (CF0, CF50, CF100, and CF200) was evaluated in vitro and bone formation was assessed after intramuscular implantation in sheep. After 24 weeks in simulated physiological solution, CF0 and CF50 showed negligible fluoride release, whereas it was considerable from the CF100 and CF200 composites. Histology showed that the incidence of de novo bone formation decreased in implants with increasing fluoride content indicating a negative influence of fluoride on ectopic bone formation. Furthermore, a significant decrease in resorption of the high fluoride-content composites and a reduction in the number of multinucleated giant cells were seen. These results show that instead of promoting, the presence of fluoride in poly(d,l-lactide)/apatite composites seemed to suppresses their resorption and osteoinductive potential in non-osseous sites.

  5. Synthetic apatite nanoparticles as a phosphorus fertilizer for soybean (Glycine max)

    NASA Astrophysics Data System (ADS)

    Liu, Ruiqiang; Lal, Rattan

    2014-07-01

    Some soluble phosphate salts, heavily used in agriculture as highly effective phosphorus (P) fertilizers, cause surface water eutrophication, while solid phosphates are less effective in supplying the nutrient P. In contrast, synthetic apatite nanoparticles could hypothetically supply sufficient P nutrients to crops but with less mobility in the environment and with less bioavailable P to algae in comparison to the soluble counterparts. Thus, a greenhouse experiment was conducted to assess the fertilizing effect of synthetic apatite nanoparticles on soybean (Glycine max). The particles, prepared using one-step wet chemical method, were spherical in shape with diameters of 15.8 +/- 7.4 nm and the chemical composition was pure hydroxyapatite. The data show that application of the nanoparticles increased the growth rate and seed yield by 32.6% and 20.4%, respectively, compared to those of soybeans treated with a regular P fertilizer (Ca(H2PO4)2). Biomass productions were enhanced by 18.2% (above-ground) and 41.2% (below-ground). Using apatite nanoparticles as a new class of P fertilizer can potentially enhance agronomical yield and reduce risks of water eutrophication.

  6. Removal of cadmium, copper, nickel, cobalt and mercury from water by Apatite II™: column experiments.

    PubMed

    Oliva, Josep; De Pablo, Joan; Cortina, José-Luis; Cama, Jordi; Ayora, Carlos

    2011-10-30

    Apatite II™, a biogenic hydroxyapatite, was evaluated as a reactive material for heavy metal (Cd, Cu, Co, Ni and Hg) removal in passive treatments. Apatite II™ reacts with acid water by releasing phosphates that increase the pH up to 6.5-7.5, complexing and inducing metals to precipitate as metal phosphates. The evolution of the solution concentration of calcium, phosphate and metals together with SEM-EDS and XRD examinations were used to identify the retention mechanisms. SEM observation shows low-crystalline precipitate layers composed of P, O and M. Only in the case of Hg and Co were small amounts of crystalline phases detected. Solubility data values were used to predict the measured column experiment values and to support the removal process based on the dissolution of hydroxyapatite, the formation of metal-phosphate species in solution and the precipitation of metal phosphate. Cd(5)(PO(4))(3)OH(s), Cu(2)(PO(4))OH(s), Ni(3)(PO(4))(2)(s), Co(3)(PO(4))(2)8H(2)O(s) and Hg(3)(PO(4))(2)(s) are proposed as the possible mineral phases responsible for the removal processes. The results of the column experiments show that Apatite II™ is a suitable filling for permeable reactive barriers.

  7. Fission-track dating of apatite and zircon: An interlaboratory comparison

    USGS Publications Warehouse

    Naeser, C.W.; Zimmermann, R.A.; Cebula, G.T.

    1981-01-01

    Apatite and zircon separates from the Fish Canyon Tuff (K-Ar age, 27.9??0.7 Myr), San Juan Mtns., Colorado, have been given to over 50 laboratories for fission-track dating. Nineteen laboratories have reported fission-track ages that they have determined for apatites. Nine laboratories have reported their analysis of the zircons. The principal difference between the results reported by the laboratories reflects their choice of the decay constant. The laboratories which use a value of ??f ??? 7.0 ?? 10-17 yr-1 for the spontaneous-fission decay constant of 238U, report an average age for the apatite of 28.5??0.7 Myr, and those using ??f ??? = 8.4 ?? 10-17 yr-1 report an average age of 23.6??1.0 Myr. The average fission-track age for the zircons is 28.4??0.7 Myr. Only laboratories which use ??f ??? 7.0 ?? 10-17 yr-1 reported zircon data. ?? 1981.

  8. Deposition of substituted apatites with anticolonizing properties onto titanium surfaces using a novel blasting process.

    PubMed

    O'Sullivan, C; O'Hare, P; O'Leary, N D; Crean, A M; Ryan, K; Dobson, A D W; O'Neill, L

    2010-10-01

    A series of doped apatites have been deposited onto titanium (V) substrates using a novel ambient temperature blasting process. The potential of these deposited doped apatites as non-colonizing osteoconductive coatings has been evaluated in vitro. XPS, EDX, and gravimetric analysis demonstrated that a high degree of coating incorporation was observed for each material. The modified surfaces were found to produce osteoblast proliferation comparable to, or better than, a hydroxyapatite finish. Promising levels of initial microbial inhibition were observed from the Sr- and Ag-doped surfaces, with the strontium showing prolonged ability to reduce bacteria numbers over a 30-day period. Ion elution profiles have been characterized and linked to the microbial response and based on the results obtained, mechanisms of kill have been suggested. In this study, the direct contact of coated substrate surfaces with microbes was observed to be a significant contributing factor to the antimicrobial performance and the anticolonizing activity. The silver substituted apatite was observed to out-perform both the SrA and ZnA in terms of biofilm inhibition.

  9. Synthesis and distribution of cations in substituted lead phosphate lacunar apatites

    SciTech Connect

    Hamdi, Besma; Feki, Hafed El; Savariault, Jean-Michel . E-mail: savariau@cemes.fr; Salah, Abdelhamid Ben

    2007-02-15

    Synthesis of apatites, Pb{sub 7.4}Bi{sub 0.3}Na{sub 2.3}(PO{sub 4}){sub 6} (I), Pb{sub 7.36}Bi{sub 0.32}Na{sub 2.08}Li{sub 0.24}(PO{sub 4}){sub 6} (II) and Pb{sub 5.78}Bi{sub 0.81}Ca{sub 0.60}Na{sub 2.81}(PO{sub 4}){sub 6} (III), with anion vacancy were carried out during solid state reactions. The three compounds of apatite-type structure crystallize in the hexagonal system, space group P6{sub 3}/m. In every compound, a preferential occupation of the (6h) site by Pb and Bi cations is shown revealing the influence of their lone electronic pair. The introduction of calcium increases the quantity of bismuth in these apatites. Alkaline metals occupy mainly the (4f) site. Infrared spectroscopy is correlated to the bonding scheme. A connection between the cations occupying (4f) sites and the c cell parameters is presented.

  10. Alternate dipping preparation of biomimetic apatite layers in the presence of carbonate ions.

    PubMed

    Chatelain, Grégory; Bourgeois, Damien; Ravaux, Johann; Averseng, Olivier; Vidaud, Claude; Meyer, Daniel

    2014-02-01

    The classical simulated body fluids method cannot be employed to prepare biomimetic apatites encompassing metallic ions that lead to very stable phosphates. This is the case for heavy metals such as uranium, whose presence in bone mineral after contamination deserves toxicological study. We have demonstrated that existing methods, based on alternate dipping into calcium and phosphate ions solutions, can be adapted to achieve this aim. We have also especially studied the impact of the presence of carbonate ions in the medium as these are necessary to avoid hydrolysis of the contaminating metallic cations. Both the apatite-collagen complex method and a standard chemical (STD) method employing only mineral solutions lead to biomimetic apatites when calcium and carbonate ions are introduced simultaneously. The obtained materials were fully characterized and we established that the STD method tolerates the presence of carbonate ions much better, and this leads to homogeneous samples. Emphasis was set on the repeatability of the method to ensure the relevancy of further work performed on series of samples. Finally, osteoblasts cultured on these samples also proved a similar yield and standard-deviation in their adenosine triphosphate content when compared to commercially available substrates designed to study of such cell cultures.

  11. Young asteroidal fluid activity revealed by absolute age from apatite in carbonaceous chondrite

    PubMed Central

    Zhang, Ai-Cheng; Li, Qiu-Li; Yurimoto, Hisayoshi; Sakamoto, Naoya; Li, Xian-Hua; Hu, Sen; Lin, Yang-Ting; Wang, Ru-Cheng

    2016-01-01

    Chondritic meteorites, consisting of the materials that have formed in the early solar system (ESS), have been affected by late thermal events and fluid activity to various degrees. Determining the timing of fluid activity in ESS is of fundamental importance for understanding the nature, formation, evolution and significance of fluid activity in ESS. Previous investigations have determined the relative ages of fluid activity with short-lived isotope systematics. Here we report an absolute 207Pb/206Pb isochron age (4,450±50 Ma) of apatite from Dar al Gani (DaG) 978, a type ∼3.5, ungrouped carbonaceous chondrite. The petrographic, mineralogical and geochemical features suggest that the apatite in DaG 978 should have formed during metamorphism in the presence of a fluid. Therefore, the apatite age represents an absolute age for fluid activity in an asteroidal setting. An impact event could have provided the heat to activate this young fluid activity in ESS. PMID:27682449

  12. Synthetic apatite nanoparticles as a phosphorus fertilizer for soybean (Glycine max)

    PubMed Central

    Liu, Ruiqiang; Lal, Rattan

    2014-01-01

    Some soluble phosphate salts, heavily used in agriculture as highly effective phosphorus (P) fertilizers, cause surface water eutrophication, while solid phosphates are less effective in supplying the nutrient P. In contrast, synthetic apatite nanoparticles could hypothetically supply sufficient P nutrients to crops but with less mobility in the environment and with less bioavailable P to algae in comparison to the soluble counterparts. Thus, a greenhouse experiment was conducted to assess the fertilizing effect of synthetic apatite nanoparticles on soybean (Glycine max). The particles, prepared using one-step wet chemical method, were spherical in shape with diameters of 15.8 ± 7.4 nm and the chemical composition was pure hydroxyapatite. The data show that application of the nanoparticles increased the growth rate and seed yield by 32.6% and 20.4%, respectively, compared to those of soybeans treated with a regular P fertilizer (Ca(H2PO4)2). Biomass productions were enhanced by 18.2% (above-ground) and 41.2% (below-ground). Using apatite nanoparticles as a new class of P fertilizer can potentially enhance agronomical yield and reduce risks of water eutrophication. PMID:25023201

  13. Modification of bone-like apatite nanoparticle size and growth kinetics by alizarin red S

    NASA Astrophysics Data System (ADS)

    Ibsen, Casper Jon Steenberg; Birkedal, Henrik

    2010-11-01

    The formation of nanocrystals in biomineralization such as in bone occurs under the influence of organic molecules. Prompted by this fact, the effect of alizarin red S, a dye used in in vivo bone labeling methods, on bone-like carbonated apatite nanocrystal formation was investigated as a function of alizarin red S additive concentration. The obtained nanoparticles were investigated by powder X-ray diffraction (XRD), FTIR as well thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) while the kinetics of nanoparticle formation was investigated by in situ pH and synchrotron XRD measurements. Increasing alizarin red S concentration lead to amorphous particles over a threshold concentration and to smaller crystallites in a dose-dependent fashion. Alizarin red S induced a macroscopic lattice strain that scaled linearly with the alizarin red S concentration; this effect is reminiscent of that seen in biogenic calcium carbonates. TGA showed that the amorphous particles contained significantly more water than the crystalline samples and the DSC data showed that crystallization occurs after loss of most of the included organic material. The in situ studies showed that the formation of apatite goes via the very rapid formation of an amorphous precursor that after a certain nucleation time crystallizes into apatite. This nucleation time increased exponentially with alizarin red S concentration showing that this additive strongly stabilizes the amorphous precursor phase.

  14. Using Apatite to Model Chlorine Contents of High SiO2 Magmas: An Enhanced Methodological Approach

    NASA Astrophysics Data System (ADS)

    Flesch, R.; Webster, J. D.; Nadeau, P. A.

    2015-12-01

    Hydrothermal experiments were conducted on high-silica (73-75 wt% SiO2), fluid-saturated melts at 844-862°C and ca. 50 MPa using crushed glass of the Los Posos rhyolite. Water and salts including NaCl, KCl, Ca(OH)2, and CaHPO4 and HCl were added proportionally to the experiments to restrict the variability of the aluminosity of the melt. The Durango apatite, which contains 3.53 wt% F and 0.41% Cl, was added as "seeds"<5µm in diameter to stimulate apatite growth during the experiments. Samples were loaded into gold capsules and run in cold-seal pressure vessels for durations of 286-1008 hours. Temperature was cycled at ±20˚C to promote apatite crystallization. Electron microprobe analyses of run-product glasses and embedded apatite grains support calculation of a range of partition coefficients ( = wt% Cl in apatite/wt% Cl in melt) of 4.7 to 15.9. The mole fraction of Cl in experimental apatites, or XCl, ranges from 0.19 to 0.56, while XF ranges from 0.08 to 0.63. The computed values for XOH range from 0.24 to 0.38. We find that normalizing XCl to XOH of apatites dramatically improves the precision when using apatite compositions to model Cl contents of melts. We compare our Los Posos rhyolite experiments with published data on 50 MPa rhyodacite experiments and find that Cl partitioning is significantly different in each system. Given the importance of chlorine in fluid equilibria, ore transport, and magma evolution, applications of apatite as a proxy for Cl contents in melts are unbounded. It is found that in order to accurately use the volatile composition of natural and synthetic apatites to calculate the volatile composition of melts in felsic systems, several chemical factors, including wt% SiO2 and the aluminosity/alkalinity of melts, should be incorporated as parameters to enhance relevant modeling. This allows geochemists to place better constraints on processes associated with crystallizing Cl-bearing magmatic systems.

  15. Monazite, iron oxide and barite exsolutions in apatite aggregates from CCSD drillhole eclogites and their geological implications

    NASA Astrophysics Data System (ADS)

    Sun, Xiaoming; Tang, Qian; Sun, Weidong; Xu, Li; Zhai, Wei; Liang, Jinlong; Liang, Yeheng; Shen, Kun; Zhang, Zeming; Zhou, Bing; Wang, Fangyue

    2007-06-01

    We have identified abundant exsolutions in apatite aggregates from eclogitic drillhole samples of the Chinese Continental Scientific Drilling (CCSD) project. Electron microscope and laser Raman spectroscopy analyses show that the apatite is fluorapatite, whereas exsolutions that can be classified into four types: (A) platy to rhombic monazite exsolutions; (B) needle-like hematite exsolutions; (C) irregular magnetite and hematite intergrowths; and (D) needle-like strontian barite exsolutions. The widths and lengths of type A monazite exsolutions range from about 6-10 μm (mostly 6 μm) and about 50-75 μm, respectively. Type B exsolutions are parallel with the C axis of apatite, with widths ranging from 0.5 to 2 μm, with most around 1.5 μm, and lengths that vary dramatically from 6 to 50 μm. Type C exsolutions are also parallel with the C axis of apatite, with lengths of ˜30-150 μm and widths of ˜10 to 50 μm. Type D strontian barite exsolutions coexist mostly with type B hematite exsolutions, with widths of about 9 μm and lengths of about 60-70 μm. Exsolutions of types B, C and D have never been reported in apatites before. Most of the exsolutions are parallel with the C axis of apatite, implying that they were probably exsolved at roughly the same time. Dating by the chemical Th-U-total Pb isochron method (CHIME) yields an U-Pb isochron age of 202 ± 28 Ma for monazite exsolutions, suggesting that these exsolutions were formed during recrystallization and retrograde metamorphism of the exhumed ultrahigh pressure (UHP) rocks. Quartz veins hosting apatite aggregates were probably formed slightly earlier than 202 Ma. Abundant hematite exsolutions, as well as coexistence of magnetite/hematite and barite/hematite in the apatite, suggest that the oxygen fugacity of apatite aggregates is well above the sulfide-sulfur oxide buffer (SSO). Given that quartz veins host these apatite aggregates, they were probably deposited from SiO 2-rich hydrous fluids formed during

  16. A taxonomy of apatite frameworks for the crystal chemical design of fuel cell electrolytes

    SciTech Connect

    Pramana, Stevin S.; Klooster, Wim T.; White, Timothy J.

    2008-08-15

    Apatite framework taxonomy succinctly rationalises the crystallographic modifications of this structural family as a function of chemical composition. Taking the neutral apatite [La{sub 8}Sr{sub 2}][(GeO{sub 4}){sub 6}]O{sub 2} as a prototype electrolyte, this classification scheme correctly predicted that 'excess' oxygen in La{sub 9}SrGe{sub 6}O{sub 26.5} is tenanted in the framework as [La{sub 9}Sr][(GeO{sub 4}){sub 5.5}(GeO{sub 5}){sub 0.5}]O{sub 2}, rather than the presumptive tunnel location of [La{sub 9}Sr][(GeO{sub 4}){sub 6}]O{sub 2.5}. The implication of this approach is that in addition to the three known apatite genera-A{sub 10}(BO{sub 3}){sub 6}X{sub 2}, A{sub 10}(BO{sub 4}){sub 6}X{sub 2}, A{sub 10}(BO{sub 5}){sub 6}X{sub 2}-hybrid electrolytes of the types A{sub 10}(BO{sub 3}/BO{sub 4}/BO{sub 5}){sub 6}X{sub 2} can be designed, with potentially superior low-temperature ion conduction, mediated by the introduction of oxygen to the framework reservoir. - Graphical abstract: Apatite framework taxonomy succinctly rationalises the crystallographic modifications of this structural family as a function of chemical composition. Neutron diffraction identified that the excess oxygen in La{sub 9}SrGe{sub 6}O{sub 26.5} is tenanted in the framework as [La{sub 9}Sr][(GeO{sub 4}){sub 5.5}(GeO{sub 5}){sub 0.5}]O{sub 2}. The implication of this approach is that in addition to the three known apatite genera-A{sub 10}(BO{sub 3}){sub 6}X{sub 2}, A{sub 10}(BO{sub 4}){sub 6}X{sub 2}, A{sub 10}(BO{sub 5}){sub 6}X{sub 2}-hybrid electrolytes of the types A{sub 10}(BO{sub 3}/BO{sub 4}/BO{sub 5}){sub 6}X{sub 2} can be designed.

  17. Biological Apatite Formed from Polyphosphate and Alkaline Phosphatase May Exchange Oxygen Isotopes from Water through Carbonate

    NASA Astrophysics Data System (ADS)

    Omelon, S. J.; Stanley, S. Y.; Gorelikov, I.; Matsuura, N.

    2011-12-01

    The oxygen isotopic composition in bone mineral phosphate is known to reflect the local water composition, environmental humidity, and diet1. Once ingested, biochemical processes presumably equilibrate PO43- with "body water" by the many biochemical reactions involving PO43- 2. Blake et al. demonstrated that enzymatic release of PO43- from organophosphorus compounds, and microbial metabolism of dissolved orthophosphate, significantly exchange the oxygen in precipitated apatite within environmental water3,4, which otherwise does not exchange with water at low temperatures. One of the enzymes that can cleave phosphates from organic substrates is alkaline phosphastase5, the enzyme also associated with bone mineralization. The literature often states that the mineral in bone in hydroxylapatite, however the mineral in bone is carbonated apatite that also contains some fluoride6. Deprotonation of HPO32- occurs at pH 12, which is impossibly high for biological system, and the predominate carbonate species in solution at neutral pH is HCO3-. To produce an apatite mineral without a significant hydroxyl content, it is possible that apatite biomineralization occurs through a polyphosphate pathway, where the oxygen atom required to transform polyphosphate into individual phosphate ions is from carbonate: [PO3-]n + CO32- -> [PO3-]n-1 + PO43- + CO2. Alkaline phosphatase can depolymerise polyphosphate into orthophosphate5. If alkaline phosphatase cleaves an oxygen atom from a calcium-carbonate complex, then there is no requirement for removing a hydrogen atom from the HCO3- or HPO43- ions of body water to form bioapatite. A mix of 1 mL of 1 M calcium polyphosphate hydogel, or nano-particles of calcium polyphosphate, and amorphous calcium carbonate were reacted with alkaline phosphatase, and maintained at neutral to basic pH. After two weeks, carbonated apatite and other calcium phosphate minerals were identified by powder x-ray diffraction. Orthophosphate and unreacted

  18. Mechanism and kinetics of apatite formation on nanocrystalline TiO2 coatings: a quartz crystal microbalance study.

    PubMed

    Yang, Zhengpeng; Si, Shihui; Zeng, Xiaoming; Zhang, Chunjing; Dai, Hongjuan

    2008-05-01

    Apatite (Ca5(PO4)3OH) has long been considered as an excellent biomaterial to promote bone repairs and implant. Apatite formation induced by negatively charged nanocrystalline TiO2 coatings soaked in simulated body fluid (SBF) was investigated using in situ quartz crystal microbalance (QCM), scanning electron microscopy (SEM), Fourier-transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX) techniques, and factors affecting its formation such as pH, size of TiO2 particles and thickness of TiO2 coatings, were discussed in detail. Two different stages were clearly observed in the process of apatite precipitation, indicating two different kinetic processes. At the first stage, the calcium ions in SBF were initially attracted to the negatively charged TiO2 surface, and then the calcium titanate formed at the interface combined with phosphate ions, consequently forming apatite nuclei. After the nucleation, the calcium ions, phosphate ions and other minor ions (i.e. CO3(2-) and Mg2+) in supersaturated SBF deposited spontaneously on the original apatite coatings to form apatite precipitates. In terms of the in situ frequency shifts, the growth-rate constants of apatite (K1 and K2) were estimated, respectively, at two different stages, and the results were (1.96+/-0.14)x10(-3)s(-1) and (1.28+/-0.10)x10(-4)s(-1), respectively, in 1.5 SBF solution. It was found that the reaction rate at the first stage is obviously higher than that at the second stage.

  19. Inter- and intra-crystal REE variations in apatite from the Bob Ingersoll pegmatite, Black Hills, South Dakota

    SciTech Connect

    Jolliff, B.L.; Papike, J.J.; Shearer, C.K. ); Shimizu, N. )

    1989-02-01

    Concentrations of rare earth elements (REE) have been measured on a suite of apatite crystals from an internally zoned granitic pegmatite enriched in Li, B, Be, F, Nb, Ta, Sn and U with a Cameca IMS 3f ion microprobe using energy filtering. An apatite specimen from the Tin Mountain pegmatite, analyzed previously by isotope dilution, was used as a standard. The chondrite-normalized pattern determined with the ion microprobe closely matches the pattern determined by isotope dilution, with maxima at Sm and Dy, and minima at Nd and Er. Apatite samples from the Bob Ingersoll pegmatite show a large range of REE patterns and concentrations. In one case, apatite crystals within millimeters show differences in REE concentrations and pattern shapes, including a switch from positive to negative Eu anomalies. These effects may be coupled with non-ideal partitioning of REE in a heterogeneous mixture of melt, aqueous fluid and crystals. REE concentrations in apatite samples from the different pegmatite zones indicate a large variation in outer zones, high concentrations near the pegmatite core, and very low concentration in the core. Patterns are flat to slightly inclined (Ce/Yb: 1 to 5), and most samples have positive Eu anomalies. The magnitude of positive Eu anomalies decreases with inward position in the pegmatite, possibly indicating a progressive increase in {line integral}O{sub 2}, and a sharp increase may be indicated by systematic Ce depletion in apatite from the pegmatite core. REE-specific volatile complexes may contribute to variations, including unusual kinks, observed in REE patterns of apatite from mineral assemblages in upper parts of the pegmatite.

  20. Facile preparation of apatite-type lanthanum silicate by a new water-based sol–gel process

    SciTech Connect

    Yamagata, Chieko; Elias, Daniel R.; Paiva, Mayara R.S.; Misso, Agatha M.; Castanho, Sonia R.H. Mello

    2013-06-01

    Highlights: ► We use a Na{sub 2}SiO{sub 3} waste solution as source of Si. ► We present a simple, rapid and low temperature method of lanthanum silicate apatite preparation. ► TEOS, a high cost reagent, was successfully substituted by a cheap price Na{sub 2}SiO{sub 3}, to obtain pure La{sub 9.56}(SiO{sub 4})6O{sub 2.33} lanthanum silicate apatite. - Abstract: In recent years, apatite-type lanthanum silicates ([Ln{sub 10−x}(XO{sub 4})6O{sub 3–1.5x}] (X = Si or Ge)) have been studied for use in SOFC (solid oxide fuel cells), at low temperature (600–800 °C), due to its ionic conductivity which is higher than that of YSZ (Yttrium Stabilized Zirconia) electrolyte. For this reason they are very promising materials as solid electrolyte for SOFCs. Synthesis of functional nanoparticles is a challenge in the nanotechnology. In this work, apatite-type lanthanum silicate nanoparticles were synthesized by a water-based sol–gel process, i.e., sol–gel technique followed by chemical precipitation of lanthanum hydroxide on the gel of the silica. Na{sub 2}SiO{sub 3} waste solution was used as silica source. Spherical aerogel silica was prepared by acid catalyzed reaction, followed by precipitation of lanthanum hydroxide to obtain the precursor of apatite-type lanthanum silicate. Powders of apatite-type lanthanum silicate achieved from the precursor were characterized by thermal analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific surface area measurements (BET). The apatite phase was formed at 900 °C.

  1. The high PT stability of apatite and Cl partitioning between apatite and hydrous potassic phases in peridotite: an experimental study to 19 GPa with implications for the transport of P, Cl and K in the upper mantle

    NASA Astrophysics Data System (ADS)

    Konzett, Jürgen; Rhede, Dieter; Frost, Daniel J.

    2012-02-01

    High PT experiments were performed in the range 2.5-19 GPa and 800-1,500°C using a synthetic peridotite doped with trace elements and OH-apatite or with Cl-apatite + phlogopite. The aim of the study was (1) to investigate the stability and phase relations of apatite and its high PT breakdown products, (2) to study the compositional evolution with P and T of phosphate and coexisting silicate phases and (3) to measure the Cl-OH partitioning between apatite and coexisting calcic amphibole, phlogopite and K-richterite. Apatite is stable in a garnet-lherzolite assemblage in the range 2.5-8.7 GPa and 800-1,100°C. The high-P breakdown product of apatite is tuite γ-Ca3 (PO4)2, which is stable in the range 8-15 GPa and 1,100-1,300°C. Coexisting apatite and tuite were observed at 8 GPa/1,050°C and 8.7 GPa/1,000°C. MgO in apatite increases with P from 0.8 wt% at 2.5 GPa to 3.2 wt% at 8.7 GPa. Both apatite and tuite may contain significant Na, Sr and REE with a correlation indicating 2 Ca2+=Na+ + REE3+. Tuite has always higher Sr and REE and lower Fe and Mg than apatite. Phosphorus in the peridotite phases decreases in the order Pmelt ≫ Pgrt ≫ PMg2SiO4 > Pcpx > Popx. The phosphate-saturated P2O5 content of garnet increases from 0.07 wt% at 2.5 GPa to 1.5 wt% at 12.8 GPa. Due to the low bulk Na content of the peridotite, [8]Na[4]P[8]M2+ -1 [4]Si-1 only plays a minor role in controlling the phosphorus content of garnet. Instead, element correlations indicate a major contribution of [6]M2+[4]P[6]M3+ -1 [4]Si-1. Pyroxenes contain ~200-500 ppm P and olivine has 0.14-0.23 wt% P2O5 in the P range 4-8.7 GPa without correlation with P, T or XMg. At ≥12.7 GPa, all Mg2SiO4 polymorphs have <200 ppm P. Coexisting olivine and wadsleyite show an equal preference for phosphorus. In case of coexisting wadsleyite and ringwoodite, the latter fractionates phosphorus. Although garnet shows by far the highest phosphorus concentrations of any peridotite silicate phase, olivine is no less

  2. Interaction between a bisphosphonate, tiludronate and nanocrystalline apatite: in vitro viability and proliferation of HOP and HBMSC cells.

    PubMed

    Pascaud, P; Bareille, R; Bourget, C; Amédée, J; Rey, C; Sarda, S

    2012-10-01

    Nanocrystalline apatites (NCA) are the inorganic components of mineralized tissues and they have been recently proposed as biomaterials for drug delivery systems. Bisphosphonates (BPs) are currently the reference drugs used to treat diseases involving bone disorders such as osteoporosis. Nevertheless, the interaction phenomena between BP molecules and apatite nanocrystals of bone are not well understood. Therefore, the adsorption characteristics have been examined and cellular activity of tiludronate molecules on NCA as models of bone mineral has been investigated. Adsorption experiments of tiludronate onto NCA were carried out and revealed a Langmuir-type adsorption isotherm. The uptake of tiludronate molecules is associated with a release of phosphate ions, indicating that the main reaction is an ion exchange process involving surface anions. The results evidence the strong affinity of BP molecules for the apatitic surface. The interactions of NCA-tiludronate associations with human osteoprogenitor cells and human bone marrow stromal cells do not reveal any cytotoxicity and evidence the activity of adsorbed tiludronate molecules. Moreover, an evolution of the physico-chemical characteristics of the apatitic substrate during biological study was observed, highlighting the existence of dynamic interactions. This work contributes to clarifying the reaction mechanisms between BPs and biomimetic apatites.

  3. Nanocrystalline carbonate-apatites: role of Ca/P ratio on the upload and release of anticancer platinum bisphosphonates.

    PubMed

    Iafisco, Michele; Palazzo, Barbara; Martra, Gianmario; Margiotta, Nicola; Piccinonna, Sara; Natile, Giovanni; Gandin, Valentina; Marzano, Cristina; Roveri, Norberto

    2012-01-07

    In the present study two nanocrystalline apatites have been investigated as bone-specific drug delivery devices to be used for treatment of bone tumors either by local implantation or by injection. In order to assess how the Ca/P ratio can influence the adsorption and release of anticancer platinum-bisphosphonate complexes, two kinds of apatite nanocrystals having different Ca/P ratios but similar morphologies, degree of crystallinity, and surface areas have been synthesized and characterized. The two platinum-bisphosphonate complexes considered were the bis-{ethylenediamineplatinum(ii)}-2-amino-1-hydroxyethane-1,1-diyl-bisphosphonate and the bis-{ethylenediamineplatinum(ii)}medronate. The Ca/P ratio plays an important role in the adsorption as well as in the release of the two drugs. In fact, the apatite with a higher Ca/P ratio showed greater affinity for both platinum complexes. Also the chemical structure of the two Pt complexes appreciably affects their affinity towards as well as their release from the two kinds of apatites. In particular, the platinum complex whose bisphosphonate contains a free aminic group showed greater upload and smaller release. The cytotoxicity of the Pt complexes released from the apatite was tested against human cervical, colon, and lung cancer cells as well as against osteosarcoma cells. In agreement with previous work, the Pt complexes released were found to be more cytotoxic than the unmodified complexes.

  4. Geology, alteration, age, and origin of iron oxide-apatite deposits in Upper Eocene quartz monzonite, Zanjan district, NW Iran

    NASA Astrophysics Data System (ADS)

    Nabatian, Ghasem; Ghaderi, Majid; Corfu, Fernando; Neubauer, Franz; Bernroider, Manfred; Prokofiev, Vsevolod; Honarmand, Maryam

    2014-02-01

    Iron oxide-apatite deposits are present in Upper Eocene pyroxene-quartz monzonitic rocks of the Zanjan district, northwestern Iran. Mineralization occurred in five stages: (1) deposition of disseminated magnetite and apatite in the host rock; (2) mineralization of massive and banded magnetite ores in veins and stockwork associated with minor brecciation and calcic alteration of host rocks; (3) deposition of sulfide ores together with potassic alteration; (4) formation of quartz and carbonate veins and sericite, chlorite, epidote, silica, carbonate, and tourmaline alteration; and (5) supergene alteration and weathering. U-Pb dating of monazite inclusions in the apatite indicates an age of 39.99 ± 0.24 Ma, which is nearly coeval with the time of emplacement of the host quartz monzonite, supporting the genetic connection. Fluid inclusions in the apatite have homogenization temperatures of about 300 °C and oxygen isotopic compositions of the magnetite support precipitation from magmatic fluids. Late-stage quartz resulted from the introduction of a cooler, less saline, and isotopically depleted fluid. The iron oxide-apatite deposits in the Tarom area of the Zanjan district are typical of a magmatic-hydrothermal origin and are similar to the Kiruna-type deposits with respect to mineral assemblages, fabric and structure of the iron ores, occurrence of the ore bodies, and wall rock alteration.

  5. Apatite 4He/3He thermochronometry evidence for an ancient Grand Canyon, Colorado Plateau, USA

    NASA Astrophysics Data System (ADS)

    Flowers, R. M.; Farley, K. A.

    2012-12-01

    The very existence of Grand Canyon inspires questions about why canyons are carved, how drainage systems and landscapes evolve, and how these processes relate to the elevation gain of plateaus. Yet when and why Grand Canyon was carved have been extraordinarily controversial for more than 150 years. Over the last several decades, the dominant view for the origin of the canyon is one of rapid incision at 5-6 Ma, when detritus derived from the upstream reaches of the Colorado River system appeared in Grand Wash Trough at the Colorado River's western exit from the Colorado Plateau. The absence of such diagnostic deposits prior to 6 Ma has been used to argue that Grand Canyon was not yet excavated (e.g., Karlstrom et al., 2008). However, a variety of data hint at a more ancient age for part or all of the canyon, and it has been proposed that a smaller drainage basin in largely carbonate lithologies could explain the absence of pre-6 Ma Colorado River clastics in Grand Wash Trough even if a significant Grand Canyon were present. Most recently, apatite (U-Th)/He (AHe) thermochronometry data from western Grand Canyon were used to infer excavation of this area to within several hundred meters of its modern depth by ca. 70 Ma (Wernicke, 2011), an interpretation in direct conflict with the young canyon model. The unexpected implications of the initial Grand Canyon AHe work motivated the apatite 4He/3He and U-Th zonation study presented here. Apatite 4He/3He thermochronometry provides information about the spatial distribution of radiogenic 4He in an apatite crystal that can better constrain a sample's cooling history. A key premise of AHe and 4He/3He spectra interpretation is that the He kinetic model used is accurate. We first investigate whether differing 4He/3He spectra for apatites of variable AHe date, radiation damage, and U-Th zonation from eastern Grand Canyon yield mutually consistent thermal history results using the RDAAM kinetic model, which must be true if the

  6. Evidence for distinct stages of magma history recorded by the compositions of accessory apatite and zircon

    NASA Astrophysics Data System (ADS)

    Miles, A. J.; Graham, C. M.; Hawkesworth, C. J.; Gillespie, M. R.; Hinton, R. W.

    2013-07-01

    Accessory minerals contain a robust and accessible record of magma evolution. However, they may reflect relatively late-stage conditions in the history of the host magmas. In the normally zoned Criffell granitic pluton (Scotland), whole-rock (WR) compositions reflect open system assimilation and fractional crystallisation at depths of >11 km, whereas amphibole barometry and the absence of inherited zircon suggest that the observed mineral assemblages crystallised following emplacement of magmas with little or no crystal cargo at depths of 4-6 km. The crystallisation history is documented by large trace-element variations amongst apatite crystals from within individual samples: decreasing LREE and Th concentrations in apatite crystals from metaluminous samples reflect broadly synchronous crystallisation of allanite, whereas lower LREE and Th, and more negative Nd anomalies in apatites from peraluminous samples reflect the effects of monazite crystallisation. WR evolution is likely to have occurred within a deep crustal hot zone where H2O-rich (~6 wt%), low-viscosity magmas segregated and ascended adiabatically in a super-liquidus state, leading to resorption of most entrained crystals. Stalling, emplacement and crystallisation resulted from intersection with the H2O-saturated liquidus at ~4 km. H2O contents are as important as temperature in the development of super-liquidus magmas during ascent, blurring distinctions between apparently `hot' and `cold' granites. The trace-element contents of most accessory minerals are controlled by competitive crystallisation of other accessory minerals in small melt batches, consistent with the incremental assembly of large granitic plutons.

  7. Early apatite deposition and osteoblast growth on plasma-sprayed dicalcium silicate coating.

    PubMed

    Liu, Xuanyong; Xie, Youtao; Ding, Chuanxian; Chu, Paul K

    2005-09-01

    Dicalcium silicate coating was deposited onto a Ti-6Al-4V substrate using plasma-spraying technology. The coating was immersed in simulated body fluid (SBF) for 1, 3, 6, 12, 24, and 48 h to investigate early apatite formation on the coating. Osteoblasts were also seeded onto the surface of the dicalcium silicate coating to evaluate its biocompatibility. Cold field-emission scanning electron microscopy and energy-dispersive X-ray spectrometry were used to evaluate the morphologies and determine the chemical composition of the coatings. The surface structural changes caused by immersion in SBF were analyzed using thin-film X-ray diffraction. After the dicalcium silicate coating was soaked in SBF solution 1-6 h, two types of particles containing calcium and phosphorus were formed on the surface. One type consisted of relatively larger particles (P1) precipitated on the surface of the coating from the precursor cluster formed in the SBF solution. The second type was composed of particles (P2) nucleated on the surface of the coating. With increasing immersion time, the particles coalesced to form a surface Ca-P layer. The Ca-P layer was composed of amorphous calcium phosphate that was not transformed to crystalline apatite until the immersion time in SBF exceeded 24 h. The formation mechanism of the Ca-P layer and apatite on the surface of the coating is believed to be involved in the formation of the Si 3-ring active surface site with negative charge. The cell-seeding test revealed that osteoblasts grew and proliferated very well on the surface of the dicalcium silicate coating.

  8. Colocation and role of polyphosphates and alkaline phosphatase in apatite biomineralization of elasmobranch tesserae.

    PubMed

    Omelon, Sidney; Georgiou, John; Variola, Fabio; Dean, Mason N

    2014-09-01

    Elasmobranchs (e.g. sharks and rays), like all fishes, grow continuously throughout life. Unlike other vertebrates, their skeletons are primarily cartilaginous, comprising a hyaline cartilage-like core, stiffened by a thin outer array of mineralized, abutting and interconnected tiles called tesserae. Tesserae bear active mineralization fronts at all margins and the tesseral layer is thin enough to section without decalcifying, making this a tractable but largely unexamined system for investigating controlled apatite mineralization, while also offering a potential analog for endochondral ossification. The chemical mechanism for tesserae mineralization has not been described, but has been previously attributed to spherical precursors, and alkaline phosphatase (ALP) activity. Here, we use a variety of techniques to elucidate the involvement of phosphorus-containing precursors in the formation of tesserae at their mineralization fronts. Using Raman spectroscopy, fluorescence microscopy and histological methods, we demonstrate that ALP activity is located with inorganic phosphate polymers (polyP) at the tessera-uncalcified cartilage interface, suggesting a potential mechanism for regulated mineralization: inorganic phosphate (Pi) can be cleaved from polyP by ALP, thus making Pi locally available for apatite biomineralization. The application of exogenous ALP to tissue cross-sections resulted in the disappearance of polyP and the appearance of Pi in uncalcified cartilage adjacent to mineralization fronts. We propose that elasmobranch skeletal cells control apatite biomineralization by biochemically controlling polyP and ALP production, placement and activity. Previous identification of polyP and ALP shown previously in mammalian calcifying cartilage supports the hypothesis that this mechanism may be a general regulating feature in the mineralization of vertebrate skeletons.

  9. A Bayesian approach to calibrating apatite fission track annealing models for laboratory and geological timescales

    NASA Astrophysics Data System (ADS)

    Stephenson, John; Gallagher, Kerry; Holmes, Chris

    2006-10-01

    We present a new approach for modelling annealing of fission tracks in apatite, aiming to address various problems with existing models. We cast the model in a fully Bayesian context, which allows us explicitly to deal with data and parameter uncertainties and correlations, and also to deal with the predictive uncertainties. We focus on a well-known annealing algorithm [Laslett, G.M., Green, P.F., Duddy, I.R., Gleadow. A.J.W., 1987. Thermal annealing of fission tracks in apatite. 2. A quantitative-analysis. Chem. Geol., 65 (1), 1-13], and build a hierachical Bayesian model to incorporate both laboratory and geological timescale data as direct constraints. Relative to the original model calibration, we find a better (in terms of likelihood) model conditioned just on the reported laboratory data. We then include the uncertainty on the temperatures recorded during the laboratory annealing experiments. We again find a better model, but the predictive uncertainty when extrapolated to geological timescales is increased due to the uncertainty on the laboratory temperatures. Finally, we explictly include a data set [Vrolijk, P., Donelick, R.A., Quenq, J., Cloos. M., 1992. Testing models of fission track annealing in apatite in a simple thermal setting: site 800, leg 129. In: Larson, R., Lancelet, Y. (Eds.), Proceedings of the Ocean Drilling Program, Scientific Results, vol. 129, pp. 169-176] which provides low-temperature geological timescale constraints for the model calibration. When combined with the laboratory data, we find a model which satisfies both the low-temperature and high-temperature geological timescale benchmarks, although the fit to the original laboratory data is degraded. However, when extrapolated to geological timescales, this combined model significantly reduces the well-known rapid recent cooling artifact found in many published thermal models for geological samples.

  10. Fungal Bioweathering of Mimetite and a General Geomycological Model for Lead Apatite Mineral Biotransformations.

    PubMed

    Ceci, Andrea; Kierans, Martin; Hillier, Stephen; Persiani, Anna Maria; Gadd, Geoffrey Michael

    2015-08-01

    Fungi play important roles in biogeochemical processes such as organic matter decomposition, bioweathering of minerals and rocks, and metal transformations and therefore influence elemental cycles for essential and potentially toxic elements, e.g., P, S, Pb, and As. Arsenic is a potentially toxic metalloid for most organisms and naturally occurs in trace quantities in soil, rocks, water, air, and living organisms. Among more than 300 arsenic minerals occurring in nature, mimetite [Pb5(AsO4)3Cl] is the most stable lead arsenate and holds considerable promise in metal stabilization for in situ and ex situ sequestration and remediation through precipitation, as do other insoluble lead apatites, such as pyromorphite [Pb5(PO4)3Cl] and vanadinite [Pb5(VO4)3Cl]. Despite the insolubility of mimetite, the organic acid-producing soil fungus Aspergillus niger was able to solubilize mimetite with simultaneous precipitation of lead oxalate as a new mycogenic biomineral. Since fungal biotransformation of both pyromorphite and vanadinite has been previously documented, a new biogeochemical model for the biogenic transformation of lead apatites (mimetite, pyromorphite, and vanadinite) by fungi is hypothesized in this study by application of geochemical modeling together with experimental data. The models closely agreed with experimental data and provided accurate simulation of As and Pb complexation and biomineral formation dependent on, e.g., pH, cation-anion composition, and concentration. A general pattern for fungal biotransformation of lead apatite minerals is proposed, proving new understanding of ecological implications of the biogeochemical cycling of component elements as well as industrial applications in metal stabilization, bioremediation, and biorecovery.

  11. The status of strontium in biological apatites: an XANES/EXAFS investigation.

    PubMed

    Bazin, Dominique; Dessombz, Arnaud; Nguyen, Christelle; Ea, Hang Korng; Lioté, Frédéric; Rehr, John; Chappard, Christine; Rouzière, Stephan; Thiaudière, Dominique; Reguer, Solen; Daudon, Michel

    2014-01-01

    Osteoporosis represents a major public health problem through its association with fragility fractures. The public health burden of osteoporotic fractures will rise in future generations, due in part to an increase in life expectancy. Strontium-based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk but the molecular mechanisms of the action of these Sr-based drugs are not totally elucidated. The local environment of Sr(2+) cations in biological apatites present in pathological and physiological calcifications in patients without such Sr-based drugs has been assessed. In this investigation, X-ray absorption spectra have been collected for 17 pathological and physiological calcifications. These experimental data have been combined with a set of numerical simulations using the ab initio FEFF9 X-ray spectroscopy program which takes into account possible distortion and Ca/Sr substitution in the environment of the Sr(2+) cations. For selected samples, Fourier transforms of the EXAFS modulations have been performed. The complete set of experimental data collected on 17 samples indicates that there is no relationship between the nature of the calcification (physiological and pathological) and the adsorption mode of Sr(2+) cations (simple adsorption or insertion). Such structural considerations have medical implications. Pathological and physiological calcifications correspond to two very different preparation procedures but are associated with the same localization of Sr(2+) versus apatite crystals. Based on this study, it seems that for supplementation of Sr at low concentration, Sr(2+) cations will be localized into the apatite network.

  12. Novel contributions on luminescent apatite-based colloids intended for medical imaging.

    PubMed

    Al-Kattan, Ahmed; Santran, Veronique; Dufour, Pascal; Dexpert-Ghys, Jeannette; Drouet, Christophe

    2014-01-01

    The setup of colloidal hybrid nanosystems based on biomimetic calcium phosphate apatites doped with europium ions has recently raised great interest in the pharmacological community, especially due to their bio-inspired character. This is especially relevant in relation with medical imaging for cancer diagnosis. Questions however remain in relation to a number of applicability aspects, some of which have been examined in this contribution. In a first part of this work, we explored further the luminescence properties of such colloidal nanoparticles. We pointed out, upon excitation of europium, the existence of some non-radiative de-excitation via the vibration of O-H oscillators located at the vicinity of the Eu(3+) luminescent centers. The replacement of Eu(3+) by Tb(3+) ions, less prone to non-radiative de-excitation, was then tested in a preliminary way and can be seen as a promising alternative. In a second part of this work, we inspected the possibility to store these colloids in a dry state while retaining a re-suspension ability preserving the nanometer size of the initial nanoparticles, and we propose a functional protocol involving the addition of glucose prior to freeze-drying. We finally showed for the first time, based on titrations of intracellular Ca(2+) and Eu(3+) ions, that folic acid-functionalized biomimetic apatite nanoparticles were able to target cancer cells that overexpress folate receptors on their membrane, which we point out here in the case of T-47-D breast carcinoma cells, as opposed to ZR-75-1 cells that do not express folate receptors. This contribution thus opens new exciting perspectives in the field of targeted cancer diagnosis, thus confirming the promise of biomimetic apatites-based colloidal formulations.

  13. RMSRo: A vitrinite reflectance model consistent with the temperature-apatite fission track system

    NASA Astrophysics Data System (ADS)

    Nielsen, Søren B.; Clausen, Ole R.; McGregor, Eoin D.

    2014-05-01

    Observed temperature, vitrinite reflectance and apatite fission tracks provide different but related information regarding temperature history. Their combined use in borehole heat flow determination as well as thermal and tectonic reconstruction requires a set of predictive models which are internally consistent. While the temperature-fission track system seems well-calibrated, several different vitrinite reflectance models exist. Although variability in vitrinite reflectance values is related to natural variations in the organic material such as; initial composition, depositional environment, degree of oxygenation etc., the most important factor affecting the construction of vitrinite reflectance models is bias in the geological temperature history of the samples used for calibration. Here we add to the vitrinite reflectance calibration data set of Suggate (1998) with more borehole data and construct a kinetic vitrinite reflectance model by minimizing the root mean square (RMS) distance between the calibration data set and model predictions. We validate this kinetic model on wells in the North Sea which have maximum temperature at the present day, and on two wells in the eastern North Sea, which have experience cooling since the early Eocene thermal maximum. The two latter wells have unusually high quality temperature, vitrinite reflectance and fission track data, and it appears that the independently derived RMSRo-model is consistent with the temperature-apatite fission track system. Keywords: vitrinite reflectance, basin analysis, thermal history, hydrocarbon exploration, apatite fission tracks Suggate, R.P., 1998. Relations between depth of burial, vitrinite reflectance and geothermal gradient. Journal of Petroleum Geology, v. 21(1), January 1998, 5-32.

  14. Fungal Bioweathering of Mimetite and a General Geomycological Model for Lead Apatite Mineral Biotransformations

    PubMed Central

    Ceci, Andrea; Kierans, Martin; Hillier, Stephen; Persiani, Anna Maria

    2015-01-01

    Fungi play important roles in biogeochemical processes such as organic matter decomposition, bioweathering of minerals and rocks, and metal transformations and therefore influence elemental cycles for essential and potentially toxic elements, e.g., P, S, Pb, and As. Arsenic is a potentially toxic metalloid for most organisms and naturally occurs in trace quantities in soil, rocks, water, air, and living organisms. Among more than 300 arsenic minerals occurring in nature, mimetite [Pb5(AsO4)3Cl] is the most stable lead arsenate and holds considerable promise in metal stabilization for in situ and ex situ sequestration and remediation through precipitation, as do other insoluble lead apatites, such as pyromorphite [Pb5(PO4)3Cl] and vanadinite [Pb5(VO4)3Cl]. Despite the insolubility of mimetite, the organic acid-producing soil fungus Aspergillus niger was able to solubilize mimetite with simultaneous precipitation of lead oxalate as a new mycogenic biomineral. Since fungal biotransformation of both pyromorphite and vanadinite has been previously documented, a new biogeochemical model for the biogenic transformation of lead apatites (mimetite, pyromorphite, and vanadinite) by fungi is hypothesized in this study by application of geochemical modeling together with experimental data. The models closely agreed with experimental data and provided accurate simulation of As and Pb complexation and biomineral formation dependent on, e.g., pH, cation-anion composition, and concentration. A general pattern for fungal biotransformation of lead apatite minerals is proposed, proving new understanding of ecological implications of the biogeochemical cycling of component elements as well as industrial applications in metal stabilization, bioremediation, and biorecovery. PMID:25979898

  15. Preparation of nanocrystalline bredigite powders with apatite-forming ability by a simple combustion method

    SciTech Connect

    Huang Xianghui; Chang Jiang

    2008-06-03

    Nanocrystalline bredigite (Ca{sub 7}MgSi{sub 4}O{sub 16}) powders were synthesized by a simple solution combustion method. Phase pure bredigite powders with particle sizes ranging from 234 to 463 nm could be obtained at a relatively low temperature of 650 deg. C. The apatite-forming ability of the bredigite powders was examined by soaking them in a stimulated body fluid. The compositional and morphological changes of the powders before and after soaking were analyzed by X-ray diffraction and scanning electron microscopy and the results showed that hydroxyapatite was formed after soaking for 4 days.

  16. Thermodynamic Properties of Sulfatian Apatite: Constraints on the Behavior of Sulfur in Calc-Alkaline Magmas

    NASA Astrophysics Data System (ADS)

    Core, D.; Essene, E. J.; Luhr, J. F.; Kesler, S. E.

    2004-12-01

    The Gibbs free energy of hydroxyellestadite [Ca10(SiO4)3(SO4)3(OH)2] was estimated using mineral equilibria applied to analyzed assemblages from the experimental charges of Luhr (1990). The apatite analyses of Peng et al. (1997) were used in conjunction with new analyses of the oxides and silicates in this study. An ideal mixing model was employed for apatite combined with mixing models from MELTS (Ghiorso & Sack, 1994) and Gibbs free energy data from Robie & Hemingway (1995) for the other crystalline phases. The resultant equation of the Gibbs free energy vs. T for hydroxyellestadite is as follows: DG°T(elem) = [2.817(T - 273) - 11831]/1000 kJ/mol, T in K. The calculated entropy for hydroxyellestadite is 1944 J/mol.K at 1073 K and 2151 J/mol.K at 1227 K. Independent estimates of the entropy of hydroxyellestadite obtained with the method of Robinson & Haas (1983) are within 5% of these values. The thermodynamic data on hydroxyellestadite were used to calculate the locus of the reactions: 2Ca10(SiO4)3(SO4)3(OH)2 + 7S2 + 21O2 = 20CaSO4 + 6SiO2 + 2H2O 6Ca10(SiO4)3(SO4)3(OH)2 + 102SiO2 + 20Fe3O4 = 60CaFeSi2O6 + 6H2O + 9S2 + 37O2 2Ca10(SiO4)3(SO4)3(OH)2 + 10Mg2Si2O6 + 14SiO2 = 20CaMgSi2O6 + 2H2O + 3S2 + 9O2 in fO2-fS2 space at fixed P-T. Application of these equilibria to apatite zoned in sulfate from oxidized granitoids reflects a drop in fS2 by more than 1 log unit during its growth. The zoning is interpreted to represent the removal of a magmatic vapor phase during crystallization of these plutons. Removal of sulfur from magmas by hydrothermal fluids is important to the ore-forming process and to the production of acid sulfate aerosols during eruption of oxidized magmas. Preservation of sulfatian apatite may yield data on the sulfidation states of ancient flood basalts such as the Deccan Traps of India and the Parana basalts of Brazil to address the environmental impact of these giant eruptions.

  17. Study on surface modification of porous apatite-wollastonite bioactive glass ceramic scaffold

    NASA Astrophysics Data System (ADS)

    Cao, Bin; Zhou, Dali; Xue, Ming; Li, Guangda; Yang, Weizhong; Long, Qin; Ji, Li

    2008-11-01

    Chitosan (CS) was used to modify the surface of apatite-wollastonite bioactive glass ceramic (AW GC) scaffold to prepare AW/CS composite scaffold. The in vitro bioactivity of the AW/CS composite scaffold was investigated by simulated body fluid (SBF) soaking experiment. Cell growth on the surface of the material was evaluated by co-culturing osteogenic marrow stromal cells (MSCs) of rabbits with the scaffold. The results showed that the compressive strength of AW GC scaffold was improved dramatically after being modified by CS, whereas the mineralization rate was delayed. MSCs can attach well on the surface of the composite scaffold.

  18. In-Situ Apatite Laser Ablation U-Th-Sm/He Dating, Methods and Challenges

    NASA Astrophysics Data System (ADS)

    Pickering, J. E.; Matthews, W.; Guest, B.; Hamilton, B.; Sykes, C.

    2015-12-01

    In-situ, laser ablation U-Th-Sm/He dating is an emerging technique in thermochronology that has been proven as a means to date zircon and monzonite1-5. In-situ U-Th-Sm/He thermochronology eliminates many of the problems and inconveniences associated with traditional, whole grain methods, including; reducing bias in grain selection based on size, shape and clarity; allowing for the use of broken grains and grains with inclusions; avoiding bad neighbour effects; and eliminating safety hazards associated with dissolution. In-situ apatite laser ablation is challenging due to low concentrations of U and Th and thus a low abundance of radiogenic He. For apatite laser ablation to be effective the ultra-high-vacuum (UHV) line must have very low and consistent background levels of He. To reduce He background, samples are mounted in a UHV stable medium. Our mounting process uses a MicroHePP (Microscope Mounted Heated Platen Press) to press samples into FEP (fluorinated ethylene propylene) bonded to an aluminum backing plate. Samples are ablated using a Resonetics 193 nm excimer laser and liberated He is measured using a quadrupole mass spectrometer on the ASI Alphachron noble gas line; collectively this system is known as the Resochron. The ablated sites are imaged using a Zygo Zescope optical profilometer and ablated pit volume measured using PitVol, a custom MatLab algorithm developed to enable precise and unbiased measurement of the ablated pit geometry. We use the well-characterized Durango apatite to demonstrate the accuracy and precision of the method. He liberated from forty-two pits, having volumes between 1700 and 9000 um3, were measured using the Resochron. The ablated sites were imaged using a Zygo Zescope optical profilometer and ablated pit volume measured using PitVol. U, Th and Sm concentrations were measured by laser ablation and the U-Th-Sm/He age calculated by standard age equation. An age of 33.8±0.31 Ma was determined and compares well with conventional

  19. SAXS study on the morphology of etched and un-etched ion tracks in apatite

    NASA Astrophysics Data System (ADS)

    Nadzri, A.; Schauries, D.; Afra, B.; Rodriguez, M. D.; Mota-Santiago, P.; Muradoglu, S.; Hawley, A.; Kluth, P.

    2015-04-01

    Natural apatite samples were irradiated with 185 MeV Au and 2.3 GeV Bi ions to simulate fission tracks. The resulting track morphology was investigated using synchrotron small angle x-ray scattering (SAXS) measurements before and after chemical etching. We present preliminary results from the SAXS measurement showing the etching process is highly anisotropic yielding faceted etch pits with a 6-fold symmetry. The measurements are a first step in gaining new insights into the correlation between etched and unetched fission tracks and the use of SAXS as a tool for studying etched tracks.

  20. Comparative study of apatite formation on CaSiO3 ceramics in simulated body fluids with different carbonate concentrations.

    PubMed

    Iimori, Yusuke; Kameshima, Yoshikazu; Okada, Kiyoshi; Hayashi, Shigeo

    2005-01-01

    Apatite formation on CaSiO3 ceramics was investigated using two different simulated body fluids (SBF) proposed by Kokubo (1990) and Tas (2000) and three sample/SBF (S/S) ratios (1.0, 2.5 and 8.3 mg/ml) at 36.5 degrees C for 1-25 days. The CaSiO3 ceramic was prepared by firing coprecipitated gel with Ca/Si = 0.91 at 1400 degrees C. The bulk density was 2.14 g/cm3 and the relative density about 76%. The two SBF solutions contain different concentrations of HCO3- and Cl- ions, the concentrations of which are closer to human blood plasma in the Tas SBF formulation than in the Kokubo formulation. The pH values in the former solution are also more realistic. The CaSiO3 ceramics show apatite formation in SBF (Kokubo) after soaking for only 1 day at all S/S ratios whereas different phases were formed at each S/S ratio in SBF (Tas). The crystalline phases formed were mainly apatite at S/S = 1.0 mg/ml, carbonate-type apatite at 2.5 mg/ml and calcite at 8.3 mg/ml. At higher S/S ratios the increase in the Ca concentration became higher while the P concentration became lower in the reacted SBF. These changes in SBF concentrations and increasing pH occurred at higher S/S ratios, producing more favorable conditions in the SBF for the formation of carbonate bearing phases, finally leading to the formation of calcite instead of apatite in the higher HCO3- ion concentration SBF (Tas). Apatite is, however, formed in the lower HCO3- ion concentration SBF (Kokubo) even though the Ca and P concentrations change in a similar manner to SBF (Tas).

  1. The evaluation of hydroxyl ions as a nucleating agent for apatite on electrospun non-woven poly( ϵ -caprolactone) fabric.

    PubMed

    Kim, Hyung-Sup; Um, Seung-Hoon; Rhee, Sang-Hoon

    2012-01-01

    The capacity of hydroxyl ions when used as a nucleating agent to form apatite in simulated body fluid (SBF) was investigated. A 25 wt% poly(ϵ-caprolactone) solution was prepared using 1,1,3,3-hexafluoro-2-propanol as a solvent and was electrospun under an electric field of 1 kV/cm. Subsequently, non-woven poly(ϵ-caprolactone) fabrics were dipped into 4 M NaOH solution and the experimental group was then directly air-dried (NaOH coated), while the control group was washed with deionized water and air-dried (NaOH treated) under ambient conditions. The non-woven poly(ϵ-caprolactone) fabrics that were coated and treated with NaOH were exposed to SBF for 1 week, which resulted in the deposition of a layer of apatite crystals on the non-woven poly(ϵ-caprolactone) fabric coated with NaOH only. On the other hand, when the non-woven poly(ϵ-caprolactone) fabrics were dipped into 0.05, 0.1, 1 and 4 M NaOH solutions, respectively, air-dried, and then soaked in SBF, the apatite forming capacity was gradually increased according to the concentration of NaOH solution. These results were explained in terms of the degree of apatite supersaturation in SBF induced by the release of hydroxyl ions from the coated NaOH because hydroxyl ions are one of the constituent elements of apatite. These results suggest that hydroxyl ions have a good potential for use as a nucleating agent for apatite on a previously non-bioactive polymer surface.

  2. Possible secondary apatite fission track age standard from altered volcanic ash beds in the middle Jurassic Carmel Formation, Southwestern Utah

    USGS Publications Warehouse

    Kowallis, B.J.; Christiansen, E.H.; Everett, B.H.; Crowley, K.D.; Naeser, C.W.; Miller, D.S.; Deino, A.L.

    1993-01-01

    Secondary age standards are valuable in intra- and interlaboratory calibration. At present very few such standards are available for fission track dating that is older than Tertiary. Several altered volcanic ash beds occur in the Middle Jurassic Carmel Formation in southwestern Utah. The formation was deposited in a shallow marine/sabhka environment. Near Gunlock, Utah, eight ash beds have been identified. Sanidines from one of the ash beds (GUN-F) give a single-crystal laser-probe 40Ar/39Ar age of 166.3??0.8 Ma (2??). Apatite and zircon fission track ages range from 152-185 Ma with typically 15-20 Ma errors (2??). Track densities in zircons are high and most grains are not countable. Apatites are fairly common in most of the ash beds and have reasonable track densities ranging between 1.2-1.5 ?? 106 tracks/cm2. Track length distributions in apatites are unimodal, have standard deviations <1??m, and mean track lengths of about 14-14.5 ??m. High Cl apatites (F:Cl:OH ratio of 39:33:28) are particularly abundant and large in ash GUN-F, and are fairly easy to concentrate, but the concentrates contain some siderite, most of which can be removed by sieving. GUN-F shows evidence of some reworking and detriaal contamination based on older single grain 40Ar/39Ar analyses and some rounding of grains, but the apatite population appears to be largely uncontaminated. At present BJK has approximately 12 of apatite separate from GUN-F. ?? 1993.

  3. Biomimetic growth and substrate dependent mechanical properties of bone like apatite nucleated on Ti and magnetron sputtered TiO2 nanostructure

    NASA Astrophysics Data System (ADS)

    Sarma, Bimal K.; Das, Apurba; Barman, Pintu; Pal, Arup R.

    2016-04-01

    This report presents findings on biomimetic growth of hydroxyapatite (HAp) nanocrystals on Ti and sputtered TiO2 substrates. The possibility of TiO2 nanostructure as candidate materials for future biomedical applications has been explored through the comparison of microstructural and mechanical properties of bone like apatite grown on Ti and nano-TiO2 surfaces. Raman spectroscopy and x-ray diffraction studies reveal formation of carbonate apatite with apparent domain size in the nanoscale range. A better interaction at the nano-TiO2/nano-HAp interface due to higher interfacial area could promote the growth of bone like apatite. The crystal phases, crystallinity, and surface morphology of nano-TiO2 are considered as parameters to understand the nucleation and growth of apatite with different mechanical properties at the nanoscale. The methodology of x-ray line profile analysis encompasses deconvolution of merged peaks by preserving broadening due to nanosized HAp aggregates. The Young’s modulus of bone like apatite exhibits crystallographic directional dependence which suggests the presence of elastic anisotropy in bone like apatite. The lattice contraction in the c-direction is associated with the degree of carbonate substitution in the apatite lattice. The role of residual stress is critical for the lattice distortion of HAp deposited at physiological conditions of temperature and pH of human blood plasma. The ion concentration is crucial for the uniformity, crystallinity, and mechanical behaviour of the apatite.

  4. Calibration of the Fluorine, Chlorine and Hydrogen Content of Apatites With the ChemCam LIBS Instrument

    NASA Technical Reports Server (NTRS)

    Meslin, P.-Y.; Cicutto, L.; Forni, O.; Drouet, C.; Rapin, W.; Nachon, M.; Cousin, A.; Blank, J. G.; McCubbin, F. M.; Gasnault, O.; Newsom, H.; Mangold, N.; Schroeder, S.; Sautter, V.; Maurice, S.; Wiens, R. C.

    2016-01-01

    Determining the composition of apatites is important to understand the behavior of volatiles during planetary differentiation. Apatite is an ubiquitous magmatic mineral in the SNC meteorites. It is a significant reservoir of halogens in these meteorites and has been used to estimate the halogen budget of Mars. Apatites have been identified in sandstones and pebbles at Gale crater by ChemCam, a Laser-Induced Breakdown Spectroscometer (LIBS) instrument onboard the Curiosity rover. Their presence was inferred from correlations between calcium, fluorine (using the CaF molecular band centered near 603 nm, whose detection limit is much lower that atomic or ionic lines and, in some cases, phosphorus (whose detection limit is much larger). An initial quantification of fluorine, based on fluorite (CaF2)/basalt mixtures and obtained at the LANL laboratory, indicated that the excess of F/Ca (compared to the stoichiometry of pure fluorapatites) found on Mars in some cases could be explained by the presence of fluorite. Chlorine was not detected in these targets, at least above a detection limit of 0.6 wt% estimated from. Fluorapatite was later also detected by X-ray diffraction (with CheMin) at a level of approx.1wt% in the Windjana drill sample (Kimberley area), and several points analyzed by ChemCam in this area also revealed a correlation between Ca and F. The in situ detection of F-rich, Cl-poor apatites contrasts with the Cl-rich, F-poor compositions of apatites found in basaltic shergottites and in gabbroic clasts from the martian meteorite NWA 7034, which were also found to be more Cl-rich than apatites from basalts on Earth, the Moon, or Vesta. The in situ observations could call into question one of the few possible explanations brought forward to explain the SNC results, namely that Mars may be highly depleted in fluorine. The purpose of the present study is to refine the calibration of the F, Cl, OH and P signals measured by the ChemCam LIBS instrument, initiated

  5. Backstacking apatite fission-track stratigraphy: A method for resolving the erosional and isostatic rebound components of tectonic uplift histories

    SciTech Connect

    Brown, R.W. )

    1991-01-01

    Measuring tectonic uplift of the mean surface of Earth using thermochronological data to document uplift histories is often plagued by confusion arising from the independent nature of the thermal and sea-level frames of reference. The technique of backstacking apatite fission-track stratigraphy differentiates between vertical movement of rocks toward Earth's surface due to erosional or tectonic denudation and tectonic uplift of Earth's surface. Apatite fission-track analysis can also be used to identify episodes of erosion where no other evidence for the erosional event exists, in addition to providing information about the timing, magnitude, and geographic distribution of erosion.

  6. Calcium and phosphate adsorption as initial steps of apatite nucleation on sol-gel-prepared titania surface.

    PubMed

    Coreño, Juan; Martínez, Antonia; Coreño, Oscar; Bolarín, Ana; Sánchez, Félix

    2003-01-01

    Titania powders have been prepared by the sol-gel route from Ti (IV) ethoxide under acidic conditions. Adsorption experiments of calcium and phosphate ions on gel-derived titania suspensions were performed to suggest a likely initial step of apatite growth on its surface. Experiments were performed as a function of time and pH at 37 degrees C with and without NaCl present in the suspensions. Also, zeta (zeta) potential experiments were performed to determine the kind of calcium adsorption. Results suggest that, apparently, calcium and phosphate adsorption can act as two different initial steps for apatite growth.

  7. Preparation and preliminary cytocompatibility of magnesium doped apatite cement with degradability for bone regeneration.

    PubMed

    Lu, Jingxiong; Wei, Jie; Yan, Yonggang; Li, Hong; Jia, Junfeng; Wei, Shicheng; Guo, Han; Xiao, Tiqiao; Liu, Changsheng

    2011-03-01

    In the present study, we fabricated magnesium doped apatite cement (md-AC) with rapid self-setting characteristic by adding the mixed powders of magnesium oxide and calcium dihydrogen phosphate (MO-CDP) into hydroxyapatite cement (HAC). The results revealed that the md-AC with 50 wt% MO-CDP could set within 6 min and the compression strength could reach 51 MPa after setting for 1 h, indicating that the md-AC had highly initial mechanical strength. The degradability of the md-AC in Tris-HCl solution increased with the increase of MO-CDP amount, and the weight loss ratio of md-AC with 50 wt% MO-CDP was 57.5 wt% after soaked for 12 weeks. Newly flake-like apatite could be deposited on the md-AC surfaces after soaked in simulated body fluid (SBF) for 7 days. Cell proliferation ratio of MG(63) cells on md-AC was obviously higher than that of HAC on days 4 and 7. The cells with normal phenotype spread well on the md-AC surfaces and attached intimately with the substrate, and alkaline phosphatase (ALP) activity of the cells on md-AC significantly improved compared with HAC on day 7. The results demonstrate that the md-AC has a good ability to support cell proliferation and differentiation, and indicate a good cytocompatibility.

  8. Halogen Variations in Apatite of the Lac Des Iles Palladium Deposit, Ontario, Canada

    NASA Astrophysics Data System (ADS)

    Boudreau, A. E.

    2014-12-01

    Analysis of apatite from the Mine Block Intrusion (MBI) of the Lac des Iles Igneous Complex show two pronounced trends in the halogens. Apatite from relatively fresh norite and melanorites from the Pd-sulfide zone contain up to 57 mole % chlorapatite endmember with significant hydroxyapatite component. In contrast, in altered rock (amphibolite and greenschist assemblages) and in the more evolved barren rocks the chlorapatite component is typically less than 10 mole % with wide variation in the F- and OH-endmember components. The latter trend is attributed to Cl loss to degassing and alteration whereas the former is attributed to Cl-enrichment in the ore-bearing rocks. It is suggested that the relatively H2O-rich and intermediate Cl content of the early igneous fluids degassed from the deeper levels of the MBI can explain the high Pd/Pt and Pd/Ir ratios of the deposit. A model is presented in which disseminated Pd-rich sulfide are initially introduced by a high temperature magmatic fluid that also influenced crystallization to produce the gross modal variations of the igneous host rock. This high temperature mineralization event was subsequently modified by the influx of late igneous and country fluids at amphibolite to greenschist conditions.

  9. The Lac Des Iles Palladium Deposit, Ontario, Canada. Part II. Halogen variations in apatite

    NASA Astrophysics Data System (ADS)

    Schisa, Paul; Boudreau, Alan; Djon, Lionnel; Tchalikian, Arnaud; Corkery, John

    2015-03-01

    Analysis of apatite from the Mine Block Intrusion (MBI) of the Lac des Iles Igneous Complex shows two pronounced trends in the halogens. Apatite from relatively fresh norite and melanorites from the Pd-sulfide zone contain up to 57 mol% chlorapatite endmember with significant hydroxyapatite component. In contrast, in altered rock (amphibolite and greenschist assemblages) the chlorapatite component is typically less than 10 mol% with wide variation in the F- and OH-endmember components. The latter trend is attributed to Cl loss to degassing and alteration, whereas the former is attributed to Cl enrichment in the ore-bearing rocks. It is suggested that the relatively H2O-rich and intermediate Cl content of the early igneous fluids degassed from the deeper levels of the MBI can explain the high Pd/Pt and Pd/Ir ratios of the deposit. A model is presented in which disseminated Pd-rich sulfides are initially introduced by a high-temperature magmatic fluid that also influenced crystallization to produce the gross modal variations of the igneous host rock. This high-temperature mineralization event was subsequently modified by the influx of late igneous and country fluids at amphibolite to greenschist conditions.

  10. Sorption behavior of Zn(II) ions on synthetic apatitic calcium phosphates

    NASA Astrophysics Data System (ADS)

    Sebei, Haroun; Pham Minh, Doan; Nzihou, Ange; Sharrock, Patrick

    2015-12-01

    The synthesis, characterization and the reactivity of apatitic calcium phosphates (Ca-HA, chemical formula Ca10(PO4)6(OH)2) is reported. Calcium carbonate (CaCO3) and potassium dihydrogen orthophosphate (KH2PO4) were selected as economical starting materials for the synthesis of Ca-HA under atmospheric conditions. Monocalcium phosphate monohydrate (MCPM), dicalcium phosphate dihydrate (DCPD), and octacalcium phosphate pentahydrate (OCP) were identified as the main intermediates of the synthesis reaction. The product obtained after 48 h of reaction contains mainly low-crystalline Ca-HA and small amounts of other calcium phosphates such as octacalcium phosphate (OCP), B-type carbonate apatite (CAP), as well as unreacted calcium carbonate. This Ca-HA was found to be active for the removal of Zn2+ from an aqueous solution. Its sorption capacity reached up to 120 mg of Zn2+ per g of Ca-HA powder after 24 h of reaction. The monitoring of soluble Zn, Ca and P during the sorption experiment allowed characterizing the mechanism of Zn uptake. Dissolution-precipitation, ionic exchange and surface complexation are the three main mechanisms involved in the sorption processes. The contribution of these mechanisms is discussed in detail.

  11. Microwave assisted apatite coating deposition on Ti6Al4V implants.

    PubMed

    Zhou, Huan; Nabiyouni, Maryam; Bhaduri, Sarit B

    2013-10-01

    In this work we report a novel microwave assisted technology to deposit a uniform, ultra-thin apatite coating without any cracks on titanium implants in minutes. This method comprises of conventional biomimetic coating in synergism with microwave irradiation to result in alkaline earth phosphate nucleation. The microwave assisted coating process mainly follows the initial stages of biomimetic coating until the step of the Ca-P nuclei formation. After that, due to microwave irradiation more Ca-P nuclei are formed to cover the whole surface of the implant instead of the growth of deposited Ca-P nuclei to Ca-P globules and coatings. It is interesting to note the doping of Mg(2+) to Ca-P apatite coating can significantly change the properties and performances of as-deposited coatings. The hydrophilicity, physical properties, bioactivity, cell adhesion, and growth capability of as-deposited microwave assisted coatings were investigated. The study shows that this coating technology has great potential in biomedical applications. Additionally, since biomimetic coating can be applied to series of implant materials such as polymer, metals and glass, it is expected this microwave assisted coating technology can also be applied to these materials if they can remains stable at 100 °C, the boiling point of water.

  12. High-relief glacial landscape evolution constrained by apatite 4He/3He thermochronometry

    NASA Astrophysics Data System (ADS)

    Shuster, D. L.; Sanders, J. W.; Cuffey, K. M.

    2009-12-01

    Apatite 4He/3He thermochronometry of bedrock samples collected from high-relief and heavily glaciated terrain near Milford Sound in Fiordland, New Zealand reveals clear differences between the cooling histories of high and low elevation samples. Across the region, the youngest apatite (U-Th)/He ages ~1 million years (Ma) generally occur at cirque floor elevations (~500-700 m elevation) rather than at sea level where (U-Th)/He ages approach ~2 Ma. Thermal histories constrained by 4He/3He thermochronometry of three vertically oriented samples collected along the headwall of a ~1100 meter deep cirque indicate that since ~1 Ma ago: (i) rocks presently located near the cirque rim (~1720 m elevation) have resided at temperatures <25 oC, while (ii) rocks at the floor of the cirque (~575 m elevation) continuously cooled from ~75-110 oC to the present surface temperature. These thermal histories indicate that most of the cirque relief developed over the last ~1 Ma and/or the sub-surface thermal field was highly perturbed during that time interval over an ~1 km horizontal scale. We will interpret sample cooling histories in conjunction with a 3-D model of subsurface temperature evolution in response to changes in topography. The goal is to constrain the rates and patterns of glacial valley development over the Quaternary.

  13. The role of intracellular calcium phosphate in osteoblast-mediated bone apatite formation

    PubMed Central

    Boonrungsiman, Suwimon; Gentleman, Eileen; Carzaniga, Raffaella; Evans, Nicholas D.; McComb, David W.; Porter, Alexandra E.; Stevens, Molly M.

    2012-01-01

    Mineralization is a ubiquitous process in the animal kingdom and is fundamental to human development and health. Dysfunctional or aberrant mineralization leads to a variety of medical problems, and so an understanding of these processes is essential to their mitigation. Osteoblasts create the nano-composite structure of bone by secreting a collagenous extracellular matrix (ECM) on which apatite crystals subsequently form. However, despite their requisite function in building bone and decades of observations describing intracellular calcium phosphate, the precise role osteoblasts play in mediating bone apatite formation remains largely unknown. To better understand the relationship between intracellular and extracellular mineralization, we combined a sample-preparation method that simultaneously preserved mineral, ions, and ECM with nano-analytical electron microscopy techniques to examine osteoblasts in an in vitro model of bone formation. We identified calcium phosphate both within osteoblast mitochondrial granules and intracellular vesicles that transported material to the ECM. Moreover, we observed calcium-containing vesicles conjoining mitochondria, which also contained calcium, suggesting a storage and transport mechanism. Our observations further highlight the important relationship between intracellular calcium phosphate in osteoblasts and their role in mineralizing the ECM. These observations may have important implications in deciphering both how normal bone forms and in understanding pathological mineralization. PMID:22879397

  14. Thermal history of Michigan Basin and southern Canadian Shield from apatite fission track analysis

    SciTech Connect

    Crowley, K.D. )

    1991-01-10

    Apatite fission track ages and confined-length distributions were collected from 38 basement outcrop and 5 basement drillcore samples in order to reconstruct the Phanerozoic thermal history of the Michigan Basin and southern Canadian Shield. The apatite data indicate two periods of thermal activity in the region: Triassic heating/cooling that affected the basin and adjacent shield and Cretaceous or post-Cretaceous heating/cooling that primarily affected the basin. The magnitude, timing, and cause of Cretaceous thermal activity cannot be identified with the present data. Model calculations suggest that some of the shield samples and probably all of the basin samples were heated to temperatures of at least 90C just prior to relatively rapid cooling in the Triassic. Available stratigraphic and geochemical constraints suggest that these elevated temperatures were the result of burial by an additional 2-5 km of late Paleozoic (probably Pennsylvanian and Permian) sediments. It is likely that the basin was buried during the Alleghenian Orogeny as observed for the adjacent Appalachian Basin.

  15. Structural, microstructural and vibrational characterization of apatite-type lanthanum silicates prepared by mechanical milling

    NASA Astrophysics Data System (ADS)

    Rodríguez-Reyna, E.; Fuentes, A. F.; Maczka, M.; Hanuza, J.; Boulahya, K.; Amador, U.

    2006-02-01

    Apatite-type lanthanum silicates have been successfully prepared at room temperature by dry milling hexagonal A-La 2O 3 and either amorphous or low cristobalite SiO 2. Milling a stochiometric mixture of these chemicals in a planetary ball mill with a moderate rotating disc speed (350 rpm), allows the formation of the target phase after only 3 h although longer milling times are needed to eliminate all SiO 2 and La 2O 3 traces. Thus, the mechanically activated chemical reaction proceeds faster when using amorphous silica instead of low cristobalite as silicon source and pure phases are obtained after only 9 and 18 h, respectively. As obtained powder phases are not amorphous and show an XRD pattern as well as IR and Raman bands characteristic of the lanthanum silicate. The domain size of the as-prepared phases varies gradually with the temperature of post-milling thermal treatment with activation energies of about 26(8) and 52(10) kJ mol -1 K -1 for the apatites obtained from amorphous silica and low-cristobalite, respectively. These values suggest crystallite growth to be favored when using amorphous silica as reactant.

  16. Micro-Raman and FTIR studies of synthetic and natural apatites.

    PubMed

    Antonakos, Anastasios; Liarokapis, Efthymios; Leventouri, Theodora

    2007-07-01

    B-type synthetic carbonate hydroxyapatite (CHAp), natural carbonate fluorapatite (CFAp) and silicon-substituted hydroxyapatite (SiHAp) have been studied by using micro-Raman and infrared (IR) spectroscopy. It was found that while B-type carbonate substitution predominates in carbonate apatites (CAps), A-type is also detected. B-type carbonate substitution causes a broadening of the v(1) P-O stretching mode that is associated with the atomic disorder and lowering of the local symmetry in CAps from C(6h)(2) to C(3h). An approximately 15 cm(-1) shift of the v(3c) PO(4) stretching IR mode was observed upon decarbonation of the CFAp. Such shift which was confirmed by lattice dynamics calculations points out that the P-O bond lengths on the mirror plane increase when carbonate leaves the apatite structure. The present results support the substitution mechanism proposed on the basis of neutron powder diffraction studies of the same samples whereby carbonate substitutes on the mirror plane of the phosphate tetrahedron. The intensity ratios of the v(2) IR CO(3) and v(1) PO(4) bands in samples of various carbonate contents provide a measure of the degree of carbonation for CAps.

  17. Analgesic properties of calcium phosphate apatite loaded with bupivacaine on postoperative pain.

    PubMed

    Verron, Elise; Gauthier, Olivier; Janvier, Pascal; Le Guen, Herve; Holopherne, Delphine; Cavagna, Remi; Bouler, Jean-Michel

    2010-07-01

    Synthetic calcium-deficient apatites (CDA) are structurally similar to biological apatites and are well known as chemical precursors of biphasic calcium phosphates (BCP). BCP are mixtures of hydroxyapatite and beta-tricalcium phosphate and are widely used as bone substitutes in human surgery. Bupivacaine, a local anesthetic, has been loaded onto CDA using isostatic compaction. The purpose of this study was to evaluate the in vivo performance of such a local release on pain after having previously defined the in vitro release profile of bupivacaine. CDA was loaded with 1%, 4%, and 16% of bupivacaine using an isostatic compaction process. In vitro release profile assays performed indicated the complete release of bupivacaine after 24 h. Wistar male rats received 50 mg implants of CDA associated, respectively, with 0, 1%, 4%, and 16% of bupivacaine into the distal femur. Analgesia was measured using the electronic version of the Von Frey monofilament test, assessing the inflammatory response and a neurological score. During the first postoperative days, a dose-dependent analgesic effect was observed with the bupivacaine adsorbed on the resorbable implant. This combined device system thus appears to release local anesthetic in a manner that prevents or limits postoperative pain following bone surgery. This innovative approach could be integrated into a global pain management program, for example, in the context of bone harvesting where bone reconstruction is required.

  18. High-resolution electron microscopy study of synthetic carbonate and aluminum containing apatites.

    PubMed

    Layani, J D; Cuisinier, F J; Steuer, P; Cohen, H; Voegel, J C; Mayer, I

    2000-05-01

    Aluminum (Al)-containing calcium-deficient carbonated hydroxyapatites were produced by a precipitation method from aqueous solution with carbonate (0-6.1%) and aluminum (0.1-0.5%) concentrations close to those found in biological materials. Two series of apatites were prepared: one at pH 7.0 and another at pH 9. 0. High-resolution electron microscopy has shown that many of them possess structural defects such as screw dislocations, grain boundaries, and central defects. Samples with high carbonate content and high water and high Al(3+) content had a high amount of structural defects. Accordingly, a sample (7Al1) with a relatively high carbonate content (6.1%) and a sample (7Al6) without carbonate but with a relatively high water (2.0 mol) and Al(3+) content (0. 39%) presented the highest amount of structural defects, 54% and 47%, respectively. A sample (7Al13) with a low level of crystalline water (1 mol) and low carbonate (2.5%) showed a small amount of defects. The presence of water associated with Al(3+) induced a high number of crystals having a central defect with a great similarity to the so-called water layer of octacalcium phosphate (OCP). Observed images of all these crystals have shown good correspondence with the computer-simulated image based on the crystal structure of hydroxyapatite, indicating that the addition of Al(3+) and carbonate does not perturb the apatitic structure.

  19. FTIR study of carbonate loss from carbonated apatites in the wide temperature range.

    PubMed

    Rau, J V; Cesaro, S Nunziante; Ferro, D; Barinov, S M; Fadeeva, I V

    2004-11-15

    The mineral constituent of bone tissue is a carbonate-substituted apatite (CHA). The thermal stability of the CHA has been revealed to depend on the substitution type and degree, although relatively little is known about this behavior. The aim of this study was to investigate the carbonate loss from synthetic CHAs in equilibrium conditions in a wide temperature range. An approach based on FTIR spectroscopy of condensed gas phase was applied to evaluate the CO and CO2 release with increasing temperature. Four different CHAs were studied, which were prepared by either precipitation from solution or the solid-state interaction. The samples differ from each other by the substitution degree. In one of the samples calcium was partially substituted by magnesium. Decomposition was shown to start at surprisingly low temperature, about 400 degrees C, and the CO content increases monotonously with the increase of temperature. The CO2 content goes through a maximum due to its decomposition into carbon monoxide and oxygen, the temperature of this maximum being strongly dependent on the chemical synthesis route. Therefore, control of the sintering atmosphere with respect to the CO2/CO ratio is needed when preparing the carbonated apatite bioceramics.

  20. Influence of anionic vacancies on the ionic conductivity of silicated rare earth apatites

    SciTech Connect

    Panteix, P.J. Bechade, E.; Julien, I.; Abelard, P.; Bernache-Assollant, D.

    2008-05-06

    Oxyapatites are very promising materials in terms of ionic conductivity. They can be considered as a potential electrolyte for Solid Oxide Fuel Cells (SOFC). Doped silicated rare earth apatites with formula La{sub 9.33-x}Ca{sub x}(SiO{sub 4}){sub 6}O{sub 2-x/2} (0 {<=} x {<=} 1) have been prepared by solid state reaction at high temperature in order to determine the influence of anionic vacancies on the electrical properties of the material. The incorporation of calcium in the structure has been checked by characterizations of the powders (X-ray diffraction, helium pycnometry). The cell parameters of the hexagonal apatite were refined. Samples were sintered at 1550 deg. C. Electrical properties of each composition have been studied between 280 and 620 deg. C by the complex impedance method. The evolution of the bulk conductivity and of the activation energy with the substituting ratio gives information on the conductivity mechanism in these materials. An improvement of ionic conductivity about one order of magnitude has been observed for low calcium substitution ratios.

  1. The mechanism of CO2- radical formation in biological and synthetic apatites.

    PubMed

    Rudko, V V; Vorona, I P; Baran, N P; Ishchenko, S S; Zatovsky, I V; Chumakova, L S

    2010-02-01

    Biological apatites (tooth enamel, bone) and their synthetic analogues were exposed to gamma rays, UV light, or thermal treatment and studied by electron paramagnetic resonance (EPR). The thermal generation of CO2- radicals in synthetic apatite was observed for the first time. It was shown that the experimental EPR spectra of all of the above-mentioned materials are caused by the contribution of two types of CO2- radicals: axial and orthorhombic. The ratio of their concentrations depends on the characteristic energy of the external influence (i.e., the energy of quantum for radiation or kT for thermal treatment) and also on the quality of the initial material (defectiveness). Based on the analysis of EPR spectra recorded immediately after gamma-irradiation, the authors conclude that the main short-lived radical in bioapatites is CO3(3)- . The unified mechanism of CO2- radical formation in hydroxyapatites at different external influences is proposed; the main stages of transformation are CO3(2)- + e --> CO3(3)- --> CO2-, where the electron (e) originates from the ionization of impurities by radiation/temperature.

  2. Sorption of selenium anionic species on apatites and iron oxides from aqueous solutions.

    PubMed

    Duc, Myriam; Lefevre, Gregory; Fedoroff, Michel; Jeanjean, Janine; Rouchaud, J C; Monteil-Rivera, Fanny; Dumonceau, Jacques; Milonjic, Slobodan

    2003-01-01

    The sorption of selenite and selenate ions from aqueous solutions was investigated on hydroxyapatite, fluorapatite, goethite and hematite, in order to simulate the behavior of radioactive selenium in natural or artificial sorbing media. Correlation studies with acido-basic properties and solubility of the solids were also performed. The sorption is pH dependant, but these solids are very efficient for retaining selenite at pH values generally encountered in natural waters, with however higher K(d) values for oxides than apatites. Selenate ions are much less sorbed than selenite. Several methods such as electron microscopy and spectroscopic techniques were used to identify the sorption mechanisms. In the case of hydroxyapatite, sorption proceeds by substitution of phosphate groups in the lattice of the apatite crystal in the superficial layers of the solid. In the case of goethite and hematite, sorption can be interpreted and modeled by a surface complexation process, but there is a discrepancy between sorption site densities for selenite and for protons.

  3. An apatite-rich, ferroan, mafic lithology from lunar meteorite ALHA81005

    NASA Technical Reports Server (NTRS)

    Goodrich, C. A.; Taylor, G. J.; Keil, K.

    1985-01-01

    Antarctic meteorite Allan Hills A81005 is a polymict, anorthositic regolith breccia of lunar origin. Most lithic clasts in the meteorite 81005 are similar to those from other lunar rocks. However, some, such as 'hyperferroan' anorthosites, have not been reported before the discovery of 81005. On the basis of the composition of some granulitic polymict breccia clasts, it appears possible that other new lithologies are present. In the present paper, a description is provided of an unusual, apatite-rich, ferroan, mafic lithology, and its origin is discussed. Three clasts which appeared to contain two minerals were separated as samples ,32 ,28 and ,27. It is found in a study that the clast in ,32 and ,28 is an apatite-rich ferroan anorthositic troctolite which is probably pristine. This rock is unique among lunar samples. On the basis of an evaluation of the significance of the results of the study, it is concluded that complex processes were apparently involved in the evolution of the primitive lunar crust.

  4. Effect of the chemical impurities on the luminescence emission of natural apatites.

    PubMed

    Roman-Lopez, J; Correcher, V; Garcia-Guinea, J; Prado-Herrero, P; Rivera, T; Lozano, I B

    2014-05-21

    This paper reports on both cathodoluminescence (CL) and blue thermoluminescence (TL) emission of well-characterized natural Spanish and Brazilian apatites [Ca5(PO4)3(OH, F, Cl)]. Chemical analyses performed by means of Electron Microprobe Analysis (EMPA) have shown the presence of trace elements that can induce CL bands. In this sense, the apatites shown emission bands peaked at 3.26, 2.86, 2.62, 2.14, 2.02 and 1.94eV are respectively linked to substitutional Ce(3+), Tb(3+), Dy(3+), Pr(3+), Sm(3+) and Mn(2+) in structural Ca(2+) positions. The 3.18eV emission band can be associated with intrinsic electron defects on oxygen of the phosphate group (PO4)(3-). The presence of (UO2)(2+) gives rise to an emission at 2.14eV. All the studied aliquots exhibit one single UV-blue TL peak that modifies the position from one sample to another (370, 256 and 268°C) probably due to (i) the variation in the crystallinity index (from 0.88 to 1.34) and (ii) successive chemical processes such as oxidation, dehydration, dehydroxylation, and fluorine ions losses due to the thermal readout.

  5. Effect of the chemical impurities on the luminescence emission of natural apatites

    NASA Astrophysics Data System (ADS)

    Roman-Lopez, J.; Correcher, V.; Garcia-Guinea, J.; Prado-Herrero, P.; Rivera, T.; Lozano, I. B.

    This paper reports on both cathodoluminescence (CL) and blue thermoluminescence (TL) emission of well-characterized natural Spanish and Brazilian apatites [Ca5(PO4)3(OH, F, Cl)]. Chemical analyses performed by means of Electron Microprobe Analysis (EMPA) have shown the presence of trace elements that can induce CL bands. In this sense, the apatites shown emission bands peaked at 3.26, 2.86, 2.62, 2.14, 2.02 and 1.94 eV are respectively linked to substitutional Ce3+, Tb3+, Dy3+, Pr3+, Sm3+ and Mn2+ in structural Ca2+ positions. The 3.18 eV emission band can be associated with intrinsic electron defects on oxygen of the phosphate group (PO4)3-. The presence of (UO2)2+ gives rise to an emission at 2.14 eV. All the studied aliquots exhibit one single UV-blue TL peak that modifies the position from one sample to another (370, 256 and 268 °C) probably due to (i) the variation in the crystallinity index (from 0.88 to 1.34) and (ii) successive chemical processes such as oxidation, dehydration, dehydroxylation, and fluorine ions losses due to the thermal readout.

  6. Histological Comparison in Rats between Carbonate Apatite Fabricated from Gypsum and Sintered Hydroxyapatite on Bone Remodeling.

    PubMed

    Ayukawa, Yasunori; Suzuki, Yumiko; Tsuru, Kanji; Koyano, Kiyoshi; Ishikawa, Kunio

    2015-01-01

    Carbonate apatite (CO3Ap), the form of apatite found in bone, has recently attracted attention. The purpose of the present study was to histologically evaluate the tissue/cellular response toward the low-crystalline CO3Ap fabricated using a dissolution-precipitation reaction with set gypsum as a precursor. When set gypsum was immersed in a 100°C 1 mol/L Na3PO4 aqueous solution for 24 h, the set gypsum transformed into CO3Ap. Both CO3Ap and sintered hydroxyapatite (s-HAp), which was used as a control, were implanted into surgically created tibial bone defects of rats for histological evaluation. Two and 4 weeks after the implantation, histological sections were created and observed using light microscopy. The CO3Ap granules revealed both direct apposition of the bone matrix by osteoblasts and osteoclastic resorption. In contrast, the s-HAp granules maintained their contour even after 4 weeks following implantation which implied that there was a lack of replacement into the bone. The s-HAp granules were sometimes encapsulated with fibrous tissue, and macrophage polykaryon was occasionally observed directly apposed to the implanted granules. From the viewpoint of bone remodeling, the CO3Ap granules mimicked the bone matrix, suggesting that CO3Ap may be an appropriate bone substitute.

  7. Involvement of 3D osteoblast migration and bone apatite during in vitro early osteocytogenesis.

    PubMed

    Robin, Marc; Almeida, Claudia; Azaïs, Thierry; Haye, Bernard; Illoul, Corinne; Lesieur, Julie; Giraud-Guille, Marie-Madeleine; Nassif, Nadine; Hélary, Christophe

    2016-07-01

    The transition from osteoblast to osteocyte is described to occur through passive entrapment mechanism (self-buried, or embedded by neighboring cells). Here, we provide evidence of a new pathway where osteoblasts are "more" active than generally assumed. We demonstrate that osteoblasts possess the ability to migrate and differentiate into early osteocytes inside dense collagen matrices. This step involves MMP-13 simultaneously with IBSP and DMP1 expression. We also show that osteoblast migration is enhanced by the presence of apatite bone mineral. To reach this conclusion, we used an in vitro hybrid model based on both the structural characteristics of the osteoid tissue (including its density, texture and three-dimensional order), and the use of bone-like apatite. This finding highlights the mutual dynamic influence of osteoblast cell and bone extra cellular matrix. Such interactivity extends the role of physicochemical effects in bone morphogenesis complementing the widely studied molecular signals. This result represents a conceptual advancement in the fundamental understanding of bone formation.

  8. Multi-scale simulations of apatite-collagen composites: from molecules to materials

    NASA Astrophysics Data System (ADS)

    Zahn, Dirk

    2017-03-01

    We review scale-bridging simulation studies for the exploration of atomicto-meso scale processes that account for the unique structure and mechanic properties of apatite-protein composites. As the atomic structure and composition of such complex biocomposites only partially is known, the first part (i) of our modelling studies is dedicated to realistic crystal nucleation scenarios of inorganic-organic composites. Starting from the association of single ions, recent insights range from the mechanisms of motif formation, ripening reactions and the self-organization of nanocrystals, including their interplay with growth-controlling molecular moieties. On this basis, (ii) reliable building rules for unprejudiced scale-up models can be derived to model bulk materials. This is exemplified for (enamel-like) apatite-protein composites, encompassing up to 106 atom models to provide a realistic account of the 10 nm length scale, whilst model coarsening is used to reach μm length scales. On this basis, a series of deformation and fracture simulation studies were performed and helped to rationalize biocomposite hardness, plasticity, toughness, self-healing and fracture mechanisms. Complementing experimental work, these modelling studies provide particularly detailed insights into the relation of hierarchical composite structure and favorable mechanical properties.

  9. Synthesis of functionally graded bioactive glass-apatite multistructures on Ti substrates by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Tanaskovic, D.; Jokic, B.; Socol, G.; Popescu, A.; Mihailescu, I. N.; Petrovic, R.; Janackovic, Dj.

    2007-12-01

    Functionally graded glass-apatite multistructures were synthesized by pulsed laser deposition on Ti substrates. We used sintered targets of hydroxyapatite Ca 10(PO 4) 6(OH) 2, or bioglasses in the system SiO 2-Na 2O-K 2O-CaO-MgO-P 2O 5 with SiO 2 content of either 57 wt.% (6P57) or 61 wt.% (6P61). A UV KrF* ( λ = 248 nm, τ > 7 ns) excimer laser source was used for the multipulse laser ablation of the targets. The hydroxyapatite thin films were obtained in H 2O vapors, while the bioglass layers were deposited in O 2. Thin films of 6P61 were deposited in direct contact with Ti, because Ti and this glass have similar thermal expansion behaviors, which ensure good bioglass adhesion to the substrate. This glass, however, is not bioactive, so yet more depositions of 6P57 bioglass and/or hydroxyapatite thin films were performed. All structures with hydroxyapatite overcoating were post-treated in a flux of water vapors. The obtained multistructures were characterized by various techniques. X-ray investigations of the coatings found small amounts of crystalline hydroxyapatite in the outer layers. The scanning electron microscopy analyses revealed homogeneous coatings with good adhesion to the Ti substrate. Our studies showed that the multistructures we had obtained were compatible with further use in biomimetic metallic implants with glass-apatite coating applications.

  10. Influence of the microstructure on the bulk and grain boundary conductivity in apatite-type electrolytes

    NASA Astrophysics Data System (ADS)

    Marrero-López, D.; dos Santos-Gómez, L.; León-Reina, L.; Canales-Vázquez, J.; Losilla, E. R.

    2014-01-01

    Silicate and germanate apatites have attracted great interest because of their high ionic conductivity for fuel cells and other electrochemical applications. The values of conductivity of these materials are comparable or even higher than those of Zr0.84Y0.16O1.92 (YSZ), but vary depending on the synthetic method used and the level of densification. In order to evaluate the influence of the microstructure on the transport properties of apatite-type electrolytes, La10Si5.5Al0.5O26.75 (LSA) and La9.6Ge5.5Al0.5O26.15 (LGA) ceramics with different porosity and average grain size were prepared by varying the sintering temperature and time. Impedance spectroscopy was used to study separately both the bulk and grain boundary contributions from the overall conductivity. The bulk and grain boundary conductivities of silicates resulted highly dependent on both the porosity and the sintering temperature, on the contrary, the conductivity in germanates is barely affected by the microstructure.

  11. New development of carbonate apatite-chitosan scaffold based on lyophilization technique for bone tissue engineering.

    PubMed

    Ariani, Maretaningtias Dwi; Matsuura, Ayumu; Hirata, Isao; Kubo, Takayasu; Kato, Koichi; Akagawa, Yasumasa

    2013-01-01

    Carbonate apatite-chitosan scaffolds (CA-ChSs) were fabricated using the lyophilization technique. It was found that ChSs prepared with 200 mg chitosan powder (ChSs200) had well-structured three-dimensional architecture with high porosity and good retentive form without brittleness. In addition, it was shown that the number of osteoblast-like cells MC3T3-E1 proliferated on desalinated ChSs200 was larger than that on the non-desalinated ChSs200. CA-ChSs were fabricated by adding 100 mg carbonate apatite (CA) to 200 mg chitosan gels followed by freeze-drying (CA100ChSs200). SEM observation revealed that CA100ChSs200 had favorable three- dimensional porous structures. The number of living cells increased more rapidly on CA100ChSs200 prepared with different amounts of CA than on ChSs. ALP activity significantly increased after day 14 and reached a plateau after day 21 in ChSs200 and CA100ChSs200. It was concluded that newly developed CA100ChSs200 may be a possible scaffold material for tissue engineering.

  12. A first report of hydroxylated apatite as structural biomineral in Loasaceae – plants’ teeth against herbivores

    NASA Astrophysics Data System (ADS)

    Ensikat, Hans-Jürgen; Geisler, Thorsten; Weigend, Maximilian

    2016-05-01

    Biomineralization provides living organisms with various materials for the formation of resilient structures. Calcium phosphate is the main component of teeth and bones in vertebrates, whereas especially silica serves for the protection against herbivores on many plant surfaces. Functional calcium phosphate structures are well-known from the animal kingdom, but had not so far been reported from higher plants. Here, we document the occurrence of calcium phosphate biomineralization in the South-American plant group Loasaceae (rock nettle family), which have stinging trichomes similar to those of the well-known stinging nettles (Urtica). Stinging hairs and the smaller, glochidiate trichomes contained nanocrystalline hydroxylated apatite, especially in their distal portions, replacing the silica found in analogous structures of other flowering plants. This could be demonstrated by chemical, spectroscopic, and diffraction analyses. Some species of Loasaceae contained both calcium phosphate and silica in addition to calcium carbonate. The intriguing discovery of structural hydroxylated apatite in plants invites further studies, e.g., on its systematic distribution across the family, the genetic and cellular control of plant biomineralization, the properties and ultrastructure of calcium phosphate. It may prove the starting point for the development of biomimetic calcium phosphate composites based on a cellulose matrix.

  13. A first report of hydroxylated apatite as structural biomineral in Loasaceae – plants’ teeth against herbivores

    PubMed Central

    Ensikat, Hans-Jürgen; Geisler, Thorsten; Weigend, Maximilian

    2016-01-01

    Biomineralization provides living organisms with various materials for the formation of resilient structures. Calcium phosphate is the main component of teeth and bones in vertebrates, whereas especially silica serves for the protection against herbivores on many plant surfaces. Functional calcium phosphate structures are well-known from the animal kingdom, but had not so far been reported from higher plants. Here, we document the occurrence of calcium phosphate biomineralization in the South-American plant group Loasaceae (rock nettle family), which have stinging trichomes similar to those of the well-known stinging nettles (Urtica). Stinging hairs and the smaller, glochidiate trichomes contained nanocrystalline hydroxylated apatite, especially in their distal portions, replacing the silica found in analogous structures of other flowering plants. This could be demonstrated by chemical, spectroscopic, and diffraction analyses. Some species of Loasaceae contained both calcium phosphate and silica in addition to calcium carbonate. The intriguing discovery of structural hydroxylated apatite in plants invites further studies, e.g., on its systematic distribution across the family, the genetic and cellular control of plant biomineralization, the properties and ultrastructure of calcium phosphate. It may prove the starting point for the development of biomimetic calcium phosphate composites based on a cellulose matrix. PMID:27194462

  14. Multi-scale simulations of apatite-collagen composites: from molecules to materials

    NASA Astrophysics Data System (ADS)

    Zahn, Dirk

    2017-01-01

    We review scale-bridging simulation studies for the exploration of atomicto-meso scale processes that account for the unique structure and mechanic properties of apatite-protein composites. As the atomic structure and composition of such complex biocomposites only partially is known, the first part (i) of our modelling studies is dedicated to realistic crystal nucleation scenarios of inorganic-organic composites. Starting from the association of single ions, recent insights range from the mechanisms of motif formation, ripening reactions and the self-organization of nanocrystals, including their interplay with growth-controlling molecular moieties. On this basis, (ii) reliable building rules for unprejudiced scale-up models can be derived to model bulk materials. This is exemplified for (enamel-like) apatite-protein composites, encompassing up to 106 atom models to provide a realistic account of the 10 nm length scale, whilst model coarsening is used to reach μm length scales. On this basis, a series of deformation and fracture simulation studies were performed and helped to rationalize biocomposite hardness, plasticity, toughness, self-healing and fracture mechanisms. Complementing experimental work, these modelling studies provide particularly detailed insights into the relation of hierarchical composite structure and favorable mechanical properties.

  15. Carbonate-containing apatite (CAP) synthesis under moderate conditions starting from calcium carbonate and orthophosphoric acid.

    PubMed

    Pham Minh, Doan; Tran, Ngoc Dung; Nzihou, Ange; Sharrock, Patrick

    2013-07-01

    The synthesis of carbonate-containing apatite (CAP) from calcium carbonate and orthophosphoric acid under moderate conditions was investigated. In all cases, complete precipitation of orthophosphate species was observed. The reaction temperature influenced strongly the decomposition of calcium carbonate and therefore the composition of formed products. The reaction temperature of 80 °C was found to be effective for the complete decomposition of calcium carbonate particles after 48 h of reaction. Infra-red spectroscopy (IR), nuclear magnetic resonance (NMR), thermogravimetry/mass spectroscopy (TG-MS) coupling, and X-ray diffraction (XRD) characterizations allowed the identification of the composition of formed products. By increasing the reaction temperature from 20 °C to 80 °C, the content of A-type CAP increased and that of B-type CAP decreased, according to the favorable effect of temperature on the formation of A-type CAP. The total amount of carbonate content incorporated in CAP's structure, which was determined by TG-MS analysis, increased with the reaction temperature and reached up to 4.1% at 80 °C. At this temperature, the solid product was mainly composed of apatitic components and showed the typical flat-needle-like structure of CAP particles obtained in hydrothermal conditions. These results show an interesting one-step synthesis of CAP from calcium carbonate and orthophosphoric acid as low cost but high purity starting materials.

  16. Synthesis and characterization of nanocrystalline apatites from solution modeling human blood

    NASA Astrophysics Data System (ADS)

    Solodyankina, Anna; Nikolaev, Anton; Frank-Kamenetskaya, Olga; Golovanova, Olga

    2016-09-01

    Present paper is devoted to the research of the calcification processes in the blood plasma of human body. Spontaneous crystallization from the solution modeling the inorganic part of the blood plasma has been carried out. Obtained precipitates were studied by the various instrumental methods (X-ray powder diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, electron probe microanalysis and gas-volumetric method). All gathered data allow to summarize that nonstoichiometric carbonated hydroxyapatite with low crystallinity (CSD lengths 18-28 nm), high water content and small amount of chlorine ion was obtained throughout the syntheses. Part of vacancies at the Ca sites varies from 0.17 to 0.87; the value of the Cat/(P + C) ratio-from 1.52 to 1.64 (where Cat = Ca2+ + Na+ + K+ + Mg2+). The poor crystallized synthetic apatites with high carbonate ion content (from 4.34 to 5.54 wt%) and c parameter (6.888-6.894 Å) are analogues of the apatites of the pathological cardiovascular deposits. They can be obtained from the solution modeling human blood plasma by the inorganic components with calcium phosphate supersaturation 25 and 50 and with 10 and 12 weeks experiment time.

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

    PubMed

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

    2015-05-01

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

  18. Adsorption of O-Phospho-L-Serine and L-Serine onto Poorly Crystalline Apatite.

    PubMed

    Benaziz, Lhaj; Barroug, Allal; Legrouri, Ahmed; Rey, Christian; Lebugle, Albert

    2001-06-01

    The adsorption of phosphoserine and serine was studied to determine the effect of amino acid functional groups on the surface reactivity of synthetic poorly crystalline apatite similar to bone mineral. The experimental results for phosphoserine and serine uptake agree respectively with the Langmuir and Freundlich models. Phosphoserine exhibits stronger adsorption capacity and a higher affinity constant for the surface crystals compared to serine molecules. The enhanced adsorption capacity noted for phosphoserine might be related to the presence of phosphate groups in the molecule, which are specific attachment sites. This observation suggests that the strength of phosphate bonds to the solid surface, especially to calcium ions, is higher than that of carboxyl and hydroxyl ones. Spectroscopic observations provide evidence of an adsorption mechanism involving the anionic species of the amino acids and the surface of the crystals. Thus, a change in the position of the band of carboxyl groups occurred for the adsorbed molecules compared to the native amino acids. This revealed that the molecular residues do interact with apatite surface calcium. The shift noted in the frequencies of the bands associated with carboxylate vibrations is more pronounced for phosphoserine, confirming the stronger interaction noted for this molecule. Based on these results, one can conclude that the sorbent and sorbate charged species play an important role in the mechanism of uptake of the amino acids onto crystal surfaces. This may contribute to a better understanding of the mechanism by which phosphoproteins could influence mineralization processes and caries. Copyright 2001 Academic Press.

  19. Seawater rare-earth element patterns preserved in apatite of Pennsylvanian conodonts?

    NASA Astrophysics Data System (ADS)

    Bright, Camomilia A.; Cruse, Anna M.; Lyons, Timothy W.; MacLeod, Kenneth G.; Glascock, Michael D.; Ethington, Raymond L.

    2009-03-01

    Past workers have used rare-earth element patterns recorded in biogenic apatite as proxies for original seawater chemistry. To explore the potency of this approach, we analyzed Pennsylvanian conodonts from limestones, gray shales, and black shales of the Fort Scott and Pawnee formations (Desmoinesian) and Swope and Dennis formations (Missourian) in Kansas, Missouri, and Iowa, U.S.A. Analysis of individual platform conodonts from seven taxa using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) revealed a consistent enrichment in the middle rare-earth elements (MREE). Analogous MREE enrichment has been observed in authigenic apatite and bulk samples of phosphate-rich black shales from the same formations. Importantly, however, phosphate-depleted shales intimately associated with the P-rich intervals are relatively depleted in MREE. These antithetic patterns argue convincingly for secondary migration from the bulk sediment into the phosphate, and the extent of MREE enrichment in the conodonts is correlated positively with the total REE content. MREE enrichment in conodonts does not vary systematically as a function of lithology, stratigraphic level, conodont genus, geographic location, or with independent estimates of paleoredox conditions in the bottom waters. Collectively, these results argue for postmortem (diagenetic) REE uptake resulting in a pronounced (and progressive) MREE enrichment. Any cerium anomalies, if initially present, were masked by diagenetic uptake of REE. Paleoenvironmental interpretations of conodont REE, particularly for samples exhibiting MREE enrichment, should therefore be viewed with caution.

  20. Apatite intergrowths in clinopyroxene megacrysts from the Ostrzyca Proboszczowicka (SW Poland) basanite

    NASA Astrophysics Data System (ADS)

    Lipa, Danuta; Puziewicz, Jacek; Ntaflos, Theodoros; Matusiak-Małek, Magdalena

    2015-04-01

    The Cenozoic basanite from the Ostrzyca Proboszczowicka in Lower Silesia (SW Poland) belongs to numerous lavas occurring in the NE part of the Central European Volcanic Province. Basanite contains clinopyroxene megacrysts up to 3 cm in size. The clinopyroxene has the composition of aluminian-sodian diopside (mg# 0.61-0.70, 0.08-0.12 atoms Na pfu and 0.88-0.93 atoms Ca pfu). Cr is absent. The REE contents are above the primitive mantle reaching up to 18 x PM at Nd. Primitive-mantle normalized REE patterns show enrichment in LREE relative to HREE (LaN/LuN=3.81-5.01). The REE patterns of all the megacrysts show deflection in La-Nd. The trace element patterns are characterized by positive Zr, Hf and in some cases also Ta anomalies, and negative U, La, Sr, Ti and Pb ones. In some samples strong depletion (down to 0.01 x PM) in Rb and Ba is observed.The Ostrzyca megacrysts formed cumulate, which crystallized from magma similar to the host basanite, but more fractionated and enriched in REE, particularly in LREE (Lipa et al., 2014). This happened at mid-crustal depths (10-15 km) and the new pulse of basanitic magma entrained the crystals forming the non-solidified cumulate and brought them to the surface (Lipa et al., 2014). Clinopyroxene megacrysts contain large, transparent, euhedral apatite crystals up to 7 mm. The major element composition indicates the fluor-apatite with F content ranging from 0.87 to 1.93 wt.%. Chlorine content is strongly variable between grains (0.05-1.75 wt.%). Apatite is strongly enriched in LREE relative to HREE (LaN/LuN=60.39-62.23, about 1000 x PM for LREE and about 10 x PM for HREE). The REE patterns are nearly linear, with slight positive Nd and Gd anomalies. The trace element patterns are characterized by very strong negative anomalies of HFSE (Nb, Ta, Zr, Hf, Ti) and Pb, and weaker negative Sr anomaly. Concentration of Yb and Lu is on the level 10 x PM, whereas Rb, Hf and Ti are depleted relative to PM. Apatite preceded clinopyroxene

  1. Apatite Weathering and Phosphorus Availability in Deep Regolith, Luquillo Mountains, Puerto Rico

    NASA Astrophysics Data System (ADS)

    Buss, H. L.; Williams, J. Z.; White, A. F.; Brantley, S. L.

    2007-05-01

    Rapid weathering and erosion rates in mountainous tropical watersheds lead to highly variable soil and saprolite thicknesses which in turn impact nutrient fluxes and biological populations. Here we investigate the weathering of primary minerals containing iron and phosphorous and the role of resident microorganisms in the cycling of these elements in the deep regolith of the Rio Icacos watershed in the Luquillo Experimental Forest, a tropical montane rainforest in northeastern Puerto Rico. In the Rio Icacos watershed, which has one of the fastest documented chemical weathering rates of granitic rocks in the world, the quartz diorite bedrock weathers spheroidally, producing a complex interface comprised of partially weathered rock layers called rindlets. This rindlet zone (about 0.2-3 m thick) is overlain by saprolite (2-8 m) topped by soil (0.5-1 m). Samples were taken from cores augered to 7.5 m on a ridgetop. The profile included about 5 m of regolith (soil \\p saprolite), and more than 2.5 m of rindlets. A 0.5 m thick rindlet zone was also sampled in a nearby roadcut. Weathering reactions of primary minerals were examined in thin sections made from rindlets. Total chemistry was measured on all solid samples and Fe, Fe(II), and P were measured in 0.1 M NaOH and 0.5 M HCl extractions performed on augered samples. NaOH-extractable P was assumed to include inorganic and organic P that is bioavailable on both short and long timescales including P associated with secondary Fe(III)- (hydro)oxides. Concentrations of NaOH-extractable P are very low throughout the regolith but increase significantly in the rindlet zone (below 5 m depth). Residual P, believed to include primary apatite and occluded, resistant organic and inorganic forms of P, generally increases with depth. Below 5 m depth, this fraction of P is near zero. Solid-state reaction rates can be calculated for minerals in a weathering profile from the elemental distribution in the profile. Here we quantify a

  2. Experimental Determination of Hydrogen Partitioning in an Apatite-Haplobasalt Andesite Melt System at 1200°C and 1 GPa

    NASA Astrophysics Data System (ADS)

    Huh, M. C.; Boyce, J.; Manning, C. E.; Medard, E.

    2011-12-01

    Igneous apatite crystals contain a record of the evolving concentrations of magmatic volatile elements such as F, H, and Cl during crystallization and degassing. In order to develop apatite as a quantitative barometer of magmatic volatile species, improved understanding of apatite-melt volatile equilibria is needed. We conducted apatite crystallization experiments using a piston cylinder apparatus at 1,200°C and 1 GPa. Apatite crystals were grown from an Fe- and Cl-free, haplobasaltic-andesite melt of constant composition. Experiments were quenched to below 700°C in 15 seconds, producing homogeneous glass plus apatite crystals ranging from 5 to 30 microns in diameter. Apatite and coexisting glass were analyzed using the Cameca ims 6f SIMS, with an O- beam and positive secondary ions, following the methods of Boyce and Hervig (2008, 2009), but using the inversion-based calibration routines of Boyce and Eiler (this meeting). These measurements provide the first direct constraint on the partitioning of hydrogen between apatite and melt. For the exchange reaction F-(melt) + OHapatite = OH-(melt) + Fapatite, the Keq was calculated from the measured data to be ~25, consistent with the results of Mathez and Webster (2004) and Webster et al. (2008), despite our experiments being nominally Cl- and Fe-free. Significant non-Henrian behavior is observed for hydrogen, but trace F behaves effectively Henrian at low concentrations, again consistent with previous work. These preliminary results reinforce the assertion that simple Henry's or Raoult's Law models of volatile partitioning between apatite and melt are rarely - if ever - appropriate, and that both F and H concentrations must be considered in order to use hydrogen concentrations in apatite to determine concentrations of hydrogen in the coexisting melt.

  3. The role of ammonium citrate washing on the characteristics of mechanochemical-hydrothermal derived magnesium-containing apatites.

    PubMed

    Chen, Chun-Wei; Suchanek, Wojciech L; Shuk, Pavel; Byrappa, Kullaiah; Oakes, Charles; Riman, Richard E; Brown, Kelly; Tenhuisen, Kevor S; Janas, Victor F

    2007-07-01

    The role of citrate washing on the physical and chemical characteristics of magnesium-substituted apatites (HAMgs) was performed. HAMgs were synthesized by a mechanochemical-hydrothermal route at room temperature in as little as 1 h, which is five times faster than our previous work. Magnesium-substituted apatites had concentrations as high as 17.6 wt% Mg with a corresponding specific surface area (SSA) of 216 m(2)/g. A systematic study was performed to examine the influence of increasing magnesium content on the physical and chemical characteristics of the reaction products. As the magnesium content increased from 0 to 17.6 wt%, magnesium-doped apatite crystallite size decreased from 12 to 8.8 nm. The Mg/(Mg + Ca) ratio in the product was enriched relative to that used for the reacting precursor solution. During mechanochemical-hydrothermal reaction, magnesium doped apatites co-crystallize with magnesium hydroxide. Citrate washing serves to remove the magnesium hydroxide phase. The concomitant increase in surface area results because of the removal of this phase. Possible mechanisms for magnesium hydroxide leaching are discussed to explain the measured trends.

  4. Comment on "Apatite: A new redox proxy for silicic magmas?" [Geochimica et Cosmochimica Acta 132 (2014) 101-119

    NASA Astrophysics Data System (ADS)

    Marks, Michael A. W.; Scharrer, Manuel; Ladenburger, Sara; Markl, Gregor

    2016-06-01

    Recently Miles et al. (2014) proposed that a negative correlation between oxygen fugacity (expressed as logfO2 and the Mn content of apatite from a range of intermediate to silicic igneous rocks could be used as an oxybarometer (Eq. (1)).

  5. Characterization of mesostasis regions in lunar basalts: Understanding late-stage melt evolution and its influence on apatite formation

    NASA Astrophysics Data System (ADS)

    Potts, Nicola J.; TartèSe, Romain; Anand, Mahesh; Westrenen, Wim; Griffiths, Alexandra A.; Barrett, Thomas J.; Franchi, Ian A.

    2016-09-01

    Recent studies geared toward understanding the volatile abundances of the lunar interior have focused on the volatile-bearing accessory mineral apatite. Translating measurements of volatile abundances in lunar apatite into the volatile inventory of the silicate melts from which they crystallized, and ultimately of the mantle source regions of lunar magmas, however, has proved more difficult than initially thought. In this contribution, we report a detailed characterization of mesostasis regions in four Apollo mare basalts (10044, 12064, 15058, and 70035) in order to ascertain the compositions of the melts from which apatite crystallized. The texture, modal mineralogy, and reconstructed bulk composition of these mesostasis regions vary greatly within and between samples. There is no clear relationship between bulk-rock basaltic composition and that of bulk-mesostasis regions, indicating that bulk-rock composition may have little influence on mesostasis compositions. The development of individual melt pockets, combined with the occurrence of silicate liquid immiscibility, exerts greater control on the composition and texture of mesostasis regions. In general, the reconstructed late-stage lunar melts have roughly andesitic to dacitic compositions with low alkali contents, displaying much higher SiO2 abundances than the bulk compositions of their host magmatic rocks. Relevant partition coefficients for apatite-melt volatile partitioning under lunar conditions should, therefore, be derived from experiments conducted using intermediate compositions instead of compositions representing mare basalts.

  6. Framework 'interstitial' oxygen in La(10)(GeO(4))(5-)(GeO(5))O(2) apatite electrolyte.

    PubMed

    Pramana, Stevin S; Klooster, Wim T; White, T J

    2007-08-01

    Oxygen conduction at low temperatures in apatites make these materials potentially useful as electrolytes in solid-oxide fuel cells, but our understanding of the defect structures enabling ion migration is incomplete. While conduction along [001] channels is dominant, considerable inter-tunnel mobility has been recognized. Using neutron powder diffraction of stoichiometric 'La(10)(GeO(4))(6)O(3)', it has been shown that this compound is more correctly described as an La(10)(GeO(4))(5-)(GeO(5))O(2) apatite, in which high concentrations of interstitial oxygen reside within the channel walls. It is suggested that these framework interstitial O atoms provide a reservoir of ions that can migrate into the conducting channels of apatite, via a mechanism of inter-tunnel oxygen diffusion that transiently converts GeO(4) tetrahedra to GeO(5) distorted trigonal bipyramids. This structural modification is consistent with known crystal chemistry and may occur generally in oxide apatites.

  7. Volatile budget of Tenerife phonolites inferred from combined haüyne-apatite mineral records

    NASA Astrophysics Data System (ADS)

    Cooper, Lauren B.; Bachmann, Olivier; Huber, Christian

    2015-04-01

    Intermediate to silicic volcanic eruptions often emit more S than predicted by petrological models -- this is called the "excess S problem." While most common minerals in these magmas are poor in volatile elements, the occurrence of large phenocrysts of S-rich haüyne (up to ~13 wt% SO3) in phonolites holds much promise for better constraining volcanic volatile budgets in differentiated alkaline magmatic systems. We have examined textural zonation patterns in haüyne separates from Tenerife (Spain), using mineral oil to enhance grain transparency. Included phases were characterized by energy dispersive spectroscopy, X-ray maps, and Raman spectroscopy. Slow growth of haüyne, inferred from zones with few inclusions, likely represents cooling-induced crystallization from S-rich melt during storage in the upper crust. By contrast, rapid growth of phenocrystic haüyne, generating "wispy" zones containing Fe-rich haüyne laths and zones rich in melt inclusions, fluid inclusions, and Fe-sulfide inclusions, may be associated with magma recharge and/or upward percolation of a low-density fluid phase (i.e., "gas sparging"). Both processes could bring new pulses of S from deep within the magmatic system. Zones containing thousands of fluid inclusions provide direct physical evidence that the melt was fluid-saturated during periods of rapid haüyne growth. Transfer of S-rich fluid should occur in all volatile-rich magmatic systems, including dacitic-rhyolitic arc systems with large S excesses, but is difficult to document in such magmas devoid of a large S-rich mineral phase like haüyne. Apatite, a mineral present in all volcanic rocks, may also contain information about S. We have observed intricate chemical zonation in backscattered electron images of apatite microphenocrysts from the same Tenerife samples. Variations in volatile and trace element concentrations between successive zones (measured via wavelength dispersive spectroscopy and laser ablation-inductively coupled

  8. Apatite triple dating of Andrill AND-2A sediments (McMurdo Sound, Antarctica)

    NASA Astrophysics Data System (ADS)

    Andreucci, B.; Zattin, M.; Reiners, P. W.; Sandroni, S.; Talarico, F.; Thomson, S. N.

    2011-12-01

    The Andrill AND-2A drill core documents the last 20 myr of the geological history of the Ross Sea region. In this work we date detrital apatites from the upper 1000 m by three different techniques on the same grain: U-Pb (UPb), fission-track (AFT) and U-Th/He (AHe) analysis. The UPb data clearly indicate that most of apatites derive from a crystalline source that cooled at about 500 Ma. Similar intrusion ages are compatible with UPb data on zircon which are widespread along the Transantarctic Mountains (TAM) and are related to Ross Orogeny that took place in the Early Paleozoic. Most of the AFT ages from the core are younger than 40 Ma, thus suggesting the presence of active tectonics (Zattin et al., Terra Nova, 2010) or re-heating events at the end of the Oligocene. Most of the AHe data on these samples are only slightly younger than AFT ages, thus documenting high rates of cooling. Furthermore, as AHe ages are nearly all older than 20 Ma, these data document very low erosion rates from Miocene onwards, confirming what observed on bedrock data (Fitzgerald et al, Chem. Geol., 2006). A significant group of apatite crystals, nearly all from a sample collected from the deepest section of the core, has been dated by the UPb method at 30 Ma. The same grains yield AFT and AHe ages some Myr younger. These data are not related to exhumation but provide the evidence for the occurrence of a magmatic event which is much older than the Miocene alkaline volcanism of the McMurdo Volcanic Group. Actually, volcanoclastic sediments and tephra found in other drill cores extend the history of alkaline volcanism back to 26 Ma (e.g. Sandroni & Talarico, Terra Antarctica, 2004) but late Eocene-Oligocene plutons and dikes occur only along the Northern Victoria Land (Rocchi et al., JGR, 2002). Therefore, these ages raise the issue of location of this magmatic source. According to petrographic and AFT data, main provenance is from the Mulock-Skelton Glacier area but the possible presence

  9. Investigation of the stability of Co-doped apatite ionic conductors in NH{sub 3}

    SciTech Connect

    Headspith, D.A.; Orera, A.; Young, N.A.; Francesconi, M.G.

    2010-12-15

    Hydrogen powered solid oxide fuel cells (SOFCs) are of enormous interest as devices for the efficient and clean production of electrical energy. However, a number of problems linked to hydrogen production, storage and transportation are slowing down the larger scale use of SOFCs. Identifying alternative fuel sources to act as intermediate during the transition to the full use of hydrogen is, therefore, of importance. One excellent alternative is ammonia, which is produced on a large scale, is relatively cheap and has the infrastructure for storage and transportation already in place. However, considering that SOFCs operate at temperatures higher than 500 {sup o}C, a potential problem is the interaction of gaseous ammonia with the materials in the cathode, anode and solid electrolyte. In this paper, we extend earlier work on high temperature reactions of apatite electrolytes with NH{sub 3} to the transition metal (Co) doped systems, La{sub 9.67}Si{sub 5}CoO{sub 26} and La{sub 10}(Si/Ge){sub 5}CoO{sub 26.5}. A combination of PXRD, TGA and XAFS spectroscopy data showed a better structural stability for the silicate systems. Apatite silicates and germanates not containing transition metals tend to substitute nitride anions for their interstitial oxide anions, when reacted with NH{sub 3} at high temperature and, consequentially, lower the interstitial oxide content. In La{sub 9.67}Si{sub 5}CoO{sub 26} and La{sub 10}(Si/Ge){sub 5}CoO{sub 26.5} reduction of Co occurs as a competing process, favouring lower levels of nitride-oxide substitution. -- Graphical Abstract: In reactions between the apatites La{sub 9.67}Si{sub 5}CoO{sub 26} and La{sub 10}(Si/Ge){sub 5}CoO{sub 26.5} and NH{sub 3} (g) at temperatures T>500 {sup o}C, the partial substitution of the Si and Ge by Co seems to discourage O{sup 2-}/N{sup 3-} substitution in favour of the reduction of the metal. Display Omitted

  10. REE Mineralization in Kiruna-type Magnetite-Apatite Ore Deposits: Magmatism and Metasomatism

    NASA Astrophysics Data System (ADS)

    Harlov, D. E.

    2015-12-01

    Magnetite-apatite ore bodies of the Kiruna type occur worldwide and are generally associated with volcanic rocks or volcanism. They also show strong evidence of extensive metasomatism over a wide P-T range. Notable examples include the Kiirunavaara ore body, northern Sweden (Harlov et al., 2002, Chem. Geol., 191, 47-72); the Grängesberg ore body, central Sweden (Jonsson et al., 2010, NGF abstracts, vol 1, 88-89); the Mineville ore body, Adirondacks, New York, USA (McKeown and Klemc, 1956, U.S. Geol Sur Bull (1956), pp. 9-23); the Pea Ridge ore body, SE Missouri, USA (Kerr, 1998, MS Thesis, Univ. Windsor, Windsor, Ontario, Canada 113 pp); the Jurassic Marcona ore body in south-central Peru (Chen et al., 2010, Econ Geol, 105, 1441-1456); and a collection of ore bodies from the Bafq Region, central Iran (Daliran et al., 2010, Geol. Assoc. Canada, Short Course Notes, v. 20, p.147-159). In these ore bodies, low Th and U monazite, xenotime, allanite, REE carbonates, and/or REE fluorides are commonly associated with the apatite as inclusions, rim grains, or as independent grains in the surrounding mineral matrix. High contrast BSE imaging, coupled with EMPA and LA-ICPMS, indicates that the apatite has experienced fluid-induced alteration in the form of (Y+REE) + Na + Si + Cl depletion implying that it served as the source for the (Y+REE) (e.g. Kiirunavaara, northern Sweden; Harlov et al., 2002). Formation of monazite and xenotime associated with fluorapatite, as inclusions or rim grains, has experimentally been demonstrated to originate from the fluorapatite as the result of fluid-aided, coupled dissolution-reprecipitation processes (Harlov et al., 2005, Contrib. Mineral. Petrol. 150, 268-286). This is explains the low Th and U content of the monazite and xenotime. Fluid sources could range from 700-900 °C, residual, acidic (HCl, H2HSO4) grain boundary fluids, remaining after the last stages of ore body crystallization, to later stage, cooler (< 600 °C) (H2O-CO2-(Na

  11. Apatite-hosted melt inclusions in Damiao massif anorthosite complex, North China

    NASA Astrophysics Data System (ADS)

    Wang, M.; Veksler, I. V.; Zhang, Z.

    2014-12-01

    Models for the nelsonite formation are currently highly contentious, with liquid immiscibility and fractional crystallization as frequently proposed formation mechanisms. The nelsonites in the Damiao massif anorthosite complex in the North China Craton and experimental evidence are revisited for the existence of silica-free CaO-FeO-Fe2O3-TiO2-P2O5 immiscible nelsonitic liquids. Our results of differential scanning calorimetry (DSC) demonstrate that nelsonite with the composition of one-third apatite and two-thirds Fe-Ti oxides by weight completely melts well above 1450 ºC, which is in good agreement with numerous experimental studies of the CaO-P2O5-FexO system in connection to metallurgy. Thus, the composition cannot be molten at temperatures relevant for crystallization of the Damiao magma. A review of experimental studies of liquid immiscibility and analyses of natural immiscible glasses show that all the liquids on the Fe- and P-rich side of the miscibility gap have at least 20 wt. % of aluminosilicate components. Main results of this study come from the analyses of apatite-hosted melt inclusions in Damiao nelsonite. The inclusions range from ~3 to 200 μm in diameter. They are ubiquitous and meet all the morphological criteria of primary melt inclusions crystallised into assemblages of daughter minerals. Almost all of them contain vermiculite and chlorite, and some contain biotite, amphibole, phlogopite and Fe-Ti oxides. Out of dozens analysed inclusions, only three have high contents of SiO2 (62.1-73.8 wt. %) and low contents of FeO (0.25-2.35 wt. %). Bulk compositions of other inclusions show large variations in SiO2 (20.79-50.16 wt. %) and FeOt (13.44-32.78 wt. %). With a few exceptions, the inclusions are very low in CaO (0.04-1.51 wt. %, and high in Al2O3 (10-21.17 wt. %). Despite the high Fe content, the compositions differ from those of the typical immiscible Fe-rich melts. It appears that the cumulus apatite crystallised from Fe-rich, hydrated

  12. Apatite U-Pb thermochronolgy applied to complex geological settings - insights from geo/thermochronology and geochemistry

    NASA Astrophysics Data System (ADS)

    Paul, Andre; Spikings, Richard; Ulyanov, Alexey; Chew, David

    2016-04-01

    Application of high temperature (>350oC) thermochronology is limited to the U-Pb system of accessory minerals, such as apatite, under the assumption that radiogenic lead is lost to thermally activated volume diffusion into an infinite reservoir. Cochrane et al. (2015) have demonstrated a working example from the northern Andes of South America. Predictions from volume diffusion theory were compared with measured single grain U-Pb date correlated to shortest diffusion radius and in-situ profiles measured by LA-ICP-MS. Results from both techniques were found to be in agreement with predictions from thermally activated, volume diffusion. However, outliers from the ID-TIMS data suggested some complexity, as grains were found to be too young relative to their diffusion radius. Interaction of multiple processes can be responsible for the alteration of apatite U-Pb dates such as: (1) metamorphic (over)growth, (2) fluid aided alteration/recrystallization and (3) metamictization and fracturing of the grain. Further, predictions from volume diffusion rely on the input parameters: (a) diffusivity, (b) activation energy and (c) shortest diffusion radius. Diffusivity and activation energy are potentially influenced by the chemical composition and subsequent changes in crystal structure. Currently there is one value for diffusion parameter and activation energy established for (Durango) apatite (Cherniak et al., 1991). Correlation between diffusivity/activation energy and composition has not been established. We investigate if correlations exist between diffusivity/activation energy and composition by obtaining single grain apatite U-Pb date and chemical compostion and correlating these to their diffusion radius. We test the consistency of apatite closure temperature, by comparing the apatite U-Pb dates with lower temperature thermochronometers such as white mica and K-feldspar Ar/Ar and by petrographic observations. We test if chemical information can be a proxy to identify

  13. Polytopic Vector Analysis (PVA) modelling of whole-rock and apatite chemistry from the Karkonosze composite pluton (Poland, Czech Republic)

    NASA Astrophysics Data System (ADS)

    Lisowiec, Katarzyna; Słaby, Ewa; Förster, Hans-Jürgen

    2015-08-01

    This study presents a novel approach for analysing the magma evolution path in composite plutons, applying the so-termed Polytopic Vector Analysis (PVA) to whole-rock and apatite chemistry. As an example of a multiphase magmatic body the Karkonosze granitoid pluton was chosen, which formed by a combination of magma mixing and fractional crystallization of two distinct melts - granitic crust-derived and lamprophyric mantle-derived. The goal was to model end-member magma compositions recorded by apatite and to estimate to what extent these end-members interacted with each other. Although using single minerals as proxies to magma compositions is tricky, the studied apatite well reflects the compositional trends within the magma (e.g., decreasing LREE/Y ratios, varying halogen content, increasing Mn and Na concentrations). The results of PVA simulations for whole-rock geochemistry demonstrate a model similar to that constrained from previous studies. Apart from the main trend of mixing between a felsic (~ 80 wt.% SiO2) and a mafic (~ 53 wt.% SiO2) end-member (EM), an additional process has been recognized, representing most probably the continuous evolution of the mafic end-member, responsible for the compositional diversity of some rocks. One felsic (REE-poor, Mn-F-rich) and one mafic (Cl-Sr-Si-REE-rich) apatite end-members were recognized, whereas the third one represents most probably a fluid component (enriched in Si, Y, Ce and Nd), present at all magmatic stages, however, most prominent during the late stage. The widest range of EM proportions and the highest contribution of the mafic EM are displayed by apatites from the early stage. During the middle and late stages, the apatites present a narrow range of EM proportions, with almost all apatites bearing a felsic signature. This pattern reflects the progressive homogenization of the system. Although the PVA method applied to mineral chemistry poses some limitations, it may provide a more detailed image of the

  14. Determination of Sr and Ba partition coefficients between apatite from fish ( Sparus aurata) and seawater: The influence of temperature

    NASA Astrophysics Data System (ADS)

    Balter, Vincent; Lécuyer, Christophe

    2010-06-01

    The Sr/Ca and Ba/Ca ratios in inorganic apatite are strongly dependent on the temperature of the aqueous medium during precipitation. If valid in biogenic apatite, these thermometers would offer the advantage of being more resistant to diagenesis than those calibrated on biogenic calcite and aragonite. We have reared seabreams ( Sparus aurata) in tanks with controlled conditions during experiments lasting for more than 2 years at 13, 17, 23 and 27 °C, in order to determine the variations in Sr and Ba partitioning relative to Ca ( DSr and DBa, respectively) between seawater and fish apatitic hard tissues (i.e. teeth and bones), as a function of temperature. The sensitivity of the Sr and Ba thermometers (i.e. ∂ DSr/∂ T and ∂ DBa/∂ T, respectively), are similar in bone ( ∂Db-wSr/∂ T = 0.0036 ± 0.0003 and ∂Db-wBa/∂ T = 0.0134 ± 0.0026, respectively) and enamel ( ∂De-wSr/∂ T = 0.0037 ± 0.0005 and ∂De-wBa/∂ T = 0.0107 ± 0.0026, respectively). The positive values of ∂ DSr/∂ T and ∂ DBa/∂ T in bone and enamel indicate that DSr and DBa increase with increasing temperature, a pattern opposite to that observed for inorganic apatite. This distinct thermodependent trace element partitioning between inorganic and organic apatite and water highlights the contradictory effects of the crystal-chemical and biological controls on the partitioning of Ca, Sr and Ba in vertebrate organisms. Taking into account the diet Sr/Ca and Ba/Ca values, it is shown that the bone Ba/Ca signature of fish can be explained by Ca-biopurification and inorganic apatite precipitation, whereas both of these processes fail to predict the bone Sr/Ca values. Therefore, the metabolism of Ca as a function of temperature still needs to be fully understood. However, the biogenic Sr thermometer is used to calculate an average seawater temperature of 30.6 °C using the Sr/Ca compositions of fossil shark teeth at the Cretaceous/Tertiary boundary, and a typical seawater Sr

  15. Genesis of rare-metal pegmatites and alkaline apatite-fluorite rocks of Burpala massi, Northern Baikal folded zone

    NASA Astrophysics Data System (ADS)

    Sotnikova, Irina; Vladykin, Nikolai

    2015-04-01

    Burpalinsky rare metal alkaline massif in the Northern Baikal folded zone in southern margin of Siberian Platform, is a of intrusion central type, created 287 Ma covering area of about 250 km2. It is composed of nepheline syenites and pulaskites grading to quartz syenites in the contacts. Veines and dykes are represented by shonkinites, sodalite syenite, leucocratic granophyres, alkali granites and numerous rare metal alkaline syenite pegmatites and two dykes of carbonatites. All rocks except for granites are cut by a large apatite-fluorite dyke rocks with mica and magnetite, which in turn is cut by alaskite granites dyke. The massif has been studied by A.M. Portnov, A.A. Ganzeev et al. (1992) Burpalinsky massif is highly enriched with trace elements, which are concentrated in pegmatite dykes. About 70 rare-metal minerals we found in massif. Zr-silicates: zircon, eudialyte, lovenite, Ti-lovenite, velerite, burpalite, seidozerite, Ca- seidozerite, Rosenbuschite, vlasovite, katapleite, Ca-katapleite, elpidite. Ti- minerals:- sphene, astrophyllite, ramsaite, Mn-neptunite bafertisite, chevkinite, Mn-ilmenite, pirofanite, Sr-perrerit, landauite, rutile, anatase, brookite; TR- minerals - loparite, metaloparite, britolite, rinkolite, melanocerite, bastnesite, parisite, ankilite, monazite, fluocerite, TR-apatite; Nb- minerals - pyrochlore, loparite. Other rare minerals leucophanite, hambergite, pyrochlore, betafite, torite, thorianite, tayniolite, brewsterite, cryolite and others. We have proposed a new scheme massif: shonkinites - nepheline syenites - alkaline syenite - quartz syenites - veined rocks: mariupolites, rare-metal pegmatites, apatite, fluorite rock alyaskite and alkaline granites and carbonatites (Sotnikova, 2009). Apatite-fluorite rocks are found in the central part of massif. This is a large vein body of 2 km length and a 20 m width cutting prevailing pulaskites. Previously, these rocks were regarded as hydrothermal low-temperature phase. New geological and

  16. An inversion-based self-calibration for SIMS measurements: Application to H, F, and Cl in apatite

    NASA Astrophysics Data System (ADS)

    Boyce, J. W.; Eiler, J. M.

    2011-12-01

    Measurements of volatile abundances in igneous apatites can provide information regarding the abundances and evolution of volatiles in magmas, with applications to terrestrial volcanism and planetary evolution. Secondary ion mass spectrometry (SIMS) measurements can produce accurate and precise measurements of H and other volatiles in many materials including apatite. SIMS standardization generally makes use of empirical linear transfer functions that relate measured ion ratios to independently known concentrations. However, this approach is often limited by the lack of compositionally diverse, well-characterized, homogeneous standards. In general, SIMS calibrations are developed for minor and trace elements, and any two are treated as independent of one another. However, in crystalline materials, additional stoichiometric constraints may apply. In the case of apatite, the sum of concentrations of abundant volatile elements (H, Cl, and F) should closely approach 100% occupancy of their collective structural site. Here we propose and document the efficacy of a method for standardizing SIMS analyses of abundant volatiles in apatites that takes advantage of this stoichiometric constraint. The principle advantage of this method is that it is effectively self-standardizing; i.e., it requires no independently known homogeneous reference standards. We define a system of independent linear equations relating measured ion ratios (H/P, Cl/P, F/P) and unknown calibration slopes. Given sufficient range in the concentrations of the different elements among apatites measured in a single analytical session, solving this system of equations allows for the calibration slope for each element to be determined without standards, using only blank-corrected ion ratios. In the case that a data set of this kind lacks sufficient range in measured compositions of one or more of the relevant ion ratios, one can employ measurements of additional apatites of a variety of compositions to

  17. Fabrication and Intracellular Delivery of Doxorubicin/Carbonate Apatite Nanocomposites: Effect on Growth Retardation of Established Colon Tumor

    PubMed Central

    Chowdhury, Ezharul Hoque; Wu, Xin; Hirose, Hajime; Haque, Amranul; Doki, Yuichiro; Mori, Masaki; Akaike, Toshihiro

    2013-01-01

    In continuing search for effective treatments of cancer, the emerging model aims at efficient intracellular delivery of therapeutics into tumor cells in order to increase the drug concentration. However, the implementation of this strategy suffers from inefficient cellular uptake and drug resistance. Therefore, pH-sensitive nanosystems have recently been developed to target slightly acidic extracellular pH environment of solid tumors. The pH targeting approach is regarded as a more general strategy than conventional specific tumor cell surface targeting approaches, because the acidic tumor microclimate is most common in solid tumors. When nanosystems are combined with triggered release mechanisms in endosomal or lysosomal acidic pH along with endosomolytic capability, the nanocarriers demonstrated to overcome multidrug resistance of various tumors. Here, novel pH sensitive carbonate apatite has been fabricated to efficiently deliver anticancer drug Doxorubicin (DOX) to cancer cells, by virtue of its pH sensitivity being quite unstable under an acidic condition in endosomes and the desirable size of the resulting apatite-DOX for efficient cellular uptake as revealed by scanning electron microscopy. Florescence microscopy and flow cytometry analyses demonstrated significant uptake of drug (92%) when complexed with apatite nanoparticles. In vitro chemosensitivity assay revealed that apatite-DOX nanoparticles executed high cytotoxicity in several human cancer cell lines compared to free drugs and consequently apatite-DOX-facilitated enhanced tumor inhibitory effect was observed in colorectal tumor model within BALB/cA nude mice, thereby shedding light on their potential applications in cancer therapy. PMID:23613726

  18. A re-evaluation of geological timescale benchmarks and temperature sensitivity of fission-track annealing in apatites

    NASA Astrophysics Data System (ADS)

    Luijendijk, Elco; Andriessen, Paul

    2016-04-01

    Current models of the temperature sensitivity of fission track annealing in apatites have been calibrated using fission track data from boreholes, with the assumption that these samples are currently at maximum burial depth and temperatures. The most detailed data-set comes from boreholes located in the Otway basin, Australia. However, several lines of evidence suggest that these samples are not at their maximum burial depth and temperature and consequently the cooling temperature of the apatite fission track thermochronometer would then be higher than previously assumed. Significant late Cenozoic exhumation in the Otway Basin was suggested by earlier studies that document a major late-Miocene erosional unconformity, folding and trusting of underlying sediments and elevated strandlines along the coast. In addition, anomalously young apatite (U-Th)/He ages in several boreholes in the basin suggest that the basin's sediments have been exhumed and cooled in the late Cenozoic. We explore the effects of late Cenozoic exhumation on fission track data in the Otway basin using a 1D model of burial and thermal history. We show that simulating several 100s of meters of exhumation in the basin results in significant misfit between current annealing models and observed fission track data. The additional exhumation reconciles the Otway basin data with a second detailed fission track dataset from boreholes in Southern Texas with a well-constrained thermal and burial history. We combine vitrinite reflectance data and U-Th/He data from the Otway basin to recalibrate the burial history of the Otway basin. Subsequently we combine the new thermal history of the Otway basin with the Southern Texas dataset to recalibrate the fission track annealing algorithm. The results suggest that fission-track annealing in apatites is underestimated by approximately 20°C by current annealing models, with significant implications for studies that use apatite fission track thermochronology to

  19. Crystallinity and compositional changes in carbonated apatites: Evidence from {sup 31}P solid-state NMR, Raman, and AFM analysis

    SciTech Connect

    McElderry, John-David P.; Zhu, Peizhi; Mroue, Kamal H.; Xu, Jiadi; Pavan, Barbara; Fang, Ming; Zhao, Guisheng; McNerny, Erin; Kohn, David H.; Franceschi, Renny T.; Holl, Mark M.Banaszak; Tecklenburg, Mary M.J.; Ramamoorthy, Ayyalusamy; Morris, Michael D.

    2013-10-15

    Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and {sup 31}P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse {sup 31}P NMR linewidth and inverse Raman PO{sub 4}{sup 3−}ν{sub 1} bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3–10.3 wt% CO{sub 3}{sup 2−} range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the {sup 31}P NMR chemical shift frequency and the Raman phosphate ν{sub 1} band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals. - Graphical abstract: Carbonated apatite shows an abrupt change in spectral (NMR, Raman) and morphological (AFM) properties at a composition of about one carbonate substitution per unit cell. Display Omitted - Highlights: • Crystallinity (XRD), particle size (AFM) of carbonated apatites and bone mineral. • Linear relationships among crystallinity, {sup 31}P NMR and Raman inverse bandwidths. • Low and high carbonated apatites use different charge-balancing ion-loss mechanism.

  20. Structural, morphological and surface characteristics of two types of octacalcium phosphate-derived fluoride-containing apatitic calcium phosphates.

    PubMed

    Shiwaku, Y; Anada, T; Yamazaki, H; Honda, Y; Morimoto, S; Sasaki, K; Suzuki, O

    2012-12-01

    Octacalcium phosphate (OCP) has been reported to stimulate bone regeneration during hydrolysis into hydroxyapatite (HA). The present study was designed to characterize structural, morphological and surface properties of fluoride-containing apatitic calcium phosphates (CaP) obtained through OCP hydrolysis or direct precipitation of OCP in the presence of 12-230ppm of fluoride (F). The products were characterized by chemical analysis, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and Fourier transform infrared spectroscopy (FTIR) as well as measurements of surface area, solubility, osteoblastic activities and bovine serum albumin (BSA) adsorption. XRD analysis re-confirmed that both preparations yielded more apatitic CaP with a higher concentration of F. However, the co-precipitated products (CF-CaP) maintained the properties of OCP, in particular the solubility, whereas the hydrolysis products (HF-CaP) had the characteristics of fluoridated apatite. The crystals of plate-like OCP were changed to the crystals of rod-like CF-CaP and small irregular HF-CaP with the advance of the hydrolysis. The SAED analysis detected both OCP and apatite crystals even in the most hydrolyzed CF-CaP. Mouse bone marrow stromal ST-2 cells grew better on CF-CaP compared with HF-CaP. BSA adsorption was inhibited on HF-CaP more than on CF-CaP. These results show that OCP produces physicochemically distinct apatitic fluoridated CaP during hydrolysis, regarding the structure, the crystal morphology and the protein adsorption, depending on the fluoride introduction route, which provides biologically interesting material.

  1. The influence of burial heating on the (U-Th)/He system in apatite: Grand Canyon case study

    NASA Astrophysics Data System (ADS)

    Fox, Matthew; Shuster, David L.

    2014-07-01

    Thermochronological data can constrain the cooling paths of rocks exhumed through the uppermost 1-2 km of earth's crust, and have thus been pivotal in illuminating topographic development over timescales >0.1 Ma. However, in some cases, different methods have led to conflicting conclusions about timing of valley-scale exhumation. Here, we investigate the case of Western Grand Canyon, USA, where different thermochronological datasets have been interpreted to record very different timings of canyon incision (∼70 Ma versus ∼5 Ma). We present a method to assess key assumptions in these constraints and demonstrate that burial heating conditions of basement rocks in the Mesozoic can result in incomplete annealing of radiation damage in apatite. In turn, this has a dramatic effect on the temperature sensitivity of the apatite (U-Th)/He system and its ability to record post-burial exhumation. The possibility of incomplete annealing resolves the apparent conflict in time-temperature paths inferred over the last 70 Ma, although it requires temperatures during burial that are lower than predicted by apatite fission track data. A refinement of parameters that prescribe the kinetics of damage annealing and related control on 4He diffusivity in apatite would account for this discrepancy, specifically if alpha recoil damage anneals at a lower rate than fission tracks at a given temperature. These effects will be important for any application of the apatite (U-Th)/He system in geologic settings that experienced prolonged residence (>10 Ma) between 50-150 °C; the approaches developed here provide means to assess these effects.

  2. Quantitative regulation of bone-mimetic, oriented collagen/apatite matrix structure depends on the degree of osteoblast alignment on oriented collagen substrates.

    PubMed

    Matsugaki, Aira; Isobe, Yoshihiro; Saku, Taro; Nakano, Takayoshi

    2015-02-01

    Bone tissue has a specific anisotropic morphology derived from collagen fiber alignment and the related apatite crystal orientation as a bone quality index. However, the precise mechanism of cellular regulation of the crystallographic orientation of apatite has not been clarified. In this study, anisotropic construction of cell-produced mineralized matrix in vitro was established by initiating organized cellular alignment and subsequent oriented bone-like matrix (collagen/apatite) production. The oriented collagen substrates with three anisotropic levels were prepared by a hydrodynamic method. Primary osteoblasts were cultured on the fabricated substrates until mineralized matrix formation is confirmed. Osteoblast alignment was successfully regulated by the level of substrate collagen orientation, with preferential alignment along the direction of the collagen fibers. Notably, both fibrous orientation of newly synthesized collagen matrix and c-axis of produced apatite crystals showed preferential orientation along the cell direction. Because the degree of anisotropy of the deposited apatite crystals showed dependency on the directional distribution of osteoblasts cultured on the oriented collagen substrates, the cell orientation determines the crystallographic anisotropy of produced apatite crystals. To the best of our knowledge, this is the first report demonstrating that bone tissue anisotropy, even the alignment of apatite crystals, is controllable by varying the degree of osteoblast alignment via regulating the level of substrate orientation.

  3. Indirect selective laser sintering of apatite-wollostonite glass-ceramic.

    PubMed

    Xiao, K; Dalgarno, K W; Wood, D J; Goodridge, R D; Ohtsuki, C

    2008-10-01

    This paper develops an indirect selective laser sintering (SLS) processing route for apatite-wollastonite (A-W) glass-ceramic, and shows that the processing route, which can create porous three-dimensional products suitable for bone implants or scaffolds, does not affect the excellent mechanical and biological properties of the glass-ceramic. 'Green parts' with fine integrity and well-defined shape have been produced from glass particles of single-size range or mixed-size ranges with acrylic binder in various ratios by weight. A subsequent heat treatment process has been developed to optimize the crystallization process, and an infiltration process has been explored to enhance mechanical strength. Three-point bending test results show flexural strengths of up to 102 MPa, dependent on porosity, and simulated body fluid (SBF) tests show that the laser sintered porous A-W has comparable biological properties to that of conventionally produced A-W.

  4. Structural and phase transformation of apatite and quartz in the indentation process single crystals

    SciTech Connect

    Chaikina, Marina

    2014-11-14

    Using the method of scanning and high-resolution electron microscopy, the zones of indentation by scratching for apatite and quartz single crystals were investigated. The textural, structural and phase transformations revealed have been conventionally ascribed to “deformation” and “diffusion” processes of plastic deformation. In zones of indentation by scratching of single crystals there have been two levels of structural transformations revealed, with a sharp boundary between them, at a stress equal to the theoretical ultimate stress limit (σ{sub TSL}). In the top zone of scratches, within the range of stress from the microhardness value H{sub s} up to the σ{sub TSL} value the substance undergoes profound structural and phase transformations. In the bed of scratches at the stress value lower than σ{sub TSL} values, single crystal fragmentation occurs with the formation of blocks and steps.

  5. Fish Canyon Tuff Apatite: A New Look At An Old Low-Temperature Thermochronology Standard

    NASA Astrophysics Data System (ADS)

    Kohn, B. P.; Gleadow, A. J.; Harrison, M.; Lugo-Zazueta, R.

    2011-12-01

    Fish Canyon Tuff (FCT) is one of the most voluminous (>5,000 km3) ignimbrite eruptions documented on Earth. It erupted over a relatively short period from the ~80 km x 30 km La Garita caldera, San Juan volcanic field, Colorado and has served as an important source for geochronology standards, particularly for K-Ar, 40Ar/39Ar and fission track dating [e.g. 1-6]. Ar and U/Pb studies over many years to determine the age of FCT have resulted in disagreement [e.g. 3-5] and this has compromised the potential use of some FCT minerals as geochronology standards. However, a recent study, reporting an improved assessment of the 40K decay constants indicates a 40Ar/39Ar sanidine age of 28.305±0.036 Ma, which can also be reconciled with U/Pb zircon data [6]. In an effort to evaluate the suitability of FCT apatite as a standard for (U-Th-Sm)/He (AHe) thermochronometry we analysed samples from the lithic-rich classic site, some 8.7 km SW of South Fork, Colorado used for early fission track and Ar studies [1-2] and also from a ~330 m vertical section of FCT above that site. Average weighted mean AHe ages (±95% confidence level) from multiple analyses at five sites range from 20.5±1.5 Ma to 23.3±2.2 Ma. Apatite fission track (AFT) ages from the same samples determined by automated image capture and counting, in combination with LA-ICP-MS for U determination, range from 28.4±1.2 Ma at the classic site to 23.3±1.6 Ma at the top of the measured profile. AFT ages can be related to kinetic parameters Dpar and Cl content which are highest (2.19±0.3 μm and 0.73-0.87 wt % respectively) at the classic site, but vary through the profile. AHe and some AFT data provide strong evidence for substantial post-eruptive Early Miocene cooling of the FCT from temperatures estimated between >~80°C to ~110°C, and attributed to km-scale erosion, possibly triggered by structural changes related to formation of the nearby Rio Grande rift. Despite evidence for some later cooling, FCT apatite at

  6. Chemical solution deposition of the highly c-axis oriented apatite type lanthanum silicate thin films.

    PubMed

    Hori, Shigeo; Takatani, Yasuhiro; Kadoura, Hiroaki; Uyama, Takeshi; Fujita, Satoru; Tani, Toshihiko

    2015-10-28

    Highly c-axis oriented apatite-type lanthanum silicate (LSO) thin films were fabricated by a simple solution coating method. In the solution coating method, LSO thin films are obtained by crystallization of initially deposited amorphous LSO precursor thin films. The degree of orientation was influenced by the precursor morphologies and a dense LSO precursor led to a high c-axis orientation perpendicular to the substrate. The oriented LSO thin films were composed of columnar grains with a single crystal orientation over the entire film thickness. In-plane orientation was not detected, which indicates that the c-axis orientation of the LSO thin films can be attributed to self-orientation.

  7. Apatite metaprism twist angle ({phi}) as a tool for crystallochemical diagnosis

    SciTech Connect

    Lim, S.C.; Baikie, Tom; Pramana, Stevin S.; Smith, Ron; White, T.J.

    2011-11-15

    [A{sup I}]{sub 4}[A{sup II}]{sub 6}(BO{sub 4}){sub 6}X{sub 2} apatites can flexibly accommodate numerous cationic, metalloid and anionic substitutions. Using a combination of new refinements and published structures, this paper reviews correlations between substituent type and framework adaptation through adjustment of the A{sup I}O{sub 6} metaprism twist angle, {phi}. These systematics are illustrated through powder neutron diffraction refinement of the crystal chemistry of A{sub 10}(PO{sub 4}){sub 6}F{sub 2} (A=Ca, Sr) fluorapatites. Variations in {phi} reflect changes in the relative size of the A{sup I}{sub 4}(BO{sub 4}){sub 6} framework and A{sup II}{sub 6}X{sub 2} tunnel content and can be used to quantitatively assess the reliability of A{sup I}/A{sup II} cation partitioning coefficients determined by Rietveld analysis. In the simplest cases of bi-ionic substitution, the metaprism twist systematics conform to three principle trends (i) For A-type divalent substitution, the larger A{sup 2+} species preferentially enters the channel before partitioning to the framework. This leads to parabolic modification in {phi} across the compositional series; (ii) For B-type pentavalent compounds, the {phi} variation will be linear in accord with the relative B{sup 5+} ionic size; and (iii) For X-type substitution of halide anions, {phi} will be reduced as the average size increases. Departures from these trends may indicate polymorphism, compositional anomalies, A{sup I}/A{sup II} order disequilibrium, or poor structure refinement, and may be extended to chemically complex apatites with simultaneous substitutions over the A, B and X sites. - Graphical abstract: [A{sup I}]{sub 4}[A{sup II}]{sub 6}(BO{sub 4}){sub 6}X{sub 2} apatites can flexibly accommodate numerous cationic, metalloid and anionic substitutions. Using a combination of new refinements and published structures, this paper reviews correlations between substituent type and framework adaptation through

  8. Strong correlation in 1D oxygen-ion conduction of apatite-type lanthanum silicate

    NASA Astrophysics Data System (ADS)

    Imaizumi, Kouta; Toyoura, Kazuaki; Nakamura, Atsutomo; Matsunaga, Katsuyuki

    2015-09-01

    Oxygen-ion conduction in apatite-type lanthanum silicate, La9.33+0.67x (SiO4)6O2+x (x = 1), has theoretically been analyzed in a first-principles manner followed by the nudged elastic band method and the kinetic Monte Carlo method. Unlike the conventional cooperative interstitialcy mechanism along the single O4 columns, diffusing interstitial oxygen ions are frequently blocked by adjacent interstitial oxygen ions (Oint ions), leading to the strongly-correlated diffusivity and conductivity of oxygen ions in the case of chemical compositions with large x values. The getting-out mechanism from the O4 column is of importance in the long-range conduction, which temporarily transfers a part of Oint ions out of the columns to relax the blocking effect. The getting-out mechanism plays a key role also in the conduction perpendicular to the c axis (in the ab plane).

  9. Analysis of monazite, zircon, and apatite from the southeastern Piedmont. National uranium resource evaluation program

    SciTech Connect

    Karfunkel, B S; Fay, W M; Price, V Jr

    1981-12-01

    Two hundred sixty-three monazite, 191 zircon, and 16 apatite grains from 52 stream-sediment locations in the Southeastern Piedmont were analyzed by electron microprobe for one of the following suites of elements: Ca, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Dy, Y, Th, U, P, and F, or Ca, La, Ce, Fe, Er, Hf, Y, Th, U, P, Zr, Mg, Al, and Si. Monazite samples that had high uranium or thorium content and zircon samples that had high hafnium or iron content from a total of six locations were reanalyzed to confirm the initial results. This report contains a description of sample collection and preparation procedures, analytical methods, tables of analyses, and a statistical summary of analyses.

  10. Possible Roles of Fluoride and Carbonate in Biochemical Carbonated Apatite Formation

    NASA Astrophysics Data System (ADS)

    Meouch, Orysia; Omelon, Sidney

    2016-04-01

    Marine phosphorites are predominantly composed of carbonated fluorapatite (CFA = Ca10-a-b-cNaaMgb(PO4)6-x(CO3)x-y-z(CO3.F)y(SO4)zF2, where x=y+a+2c, and c represents the number of Ca vacancies, with a P2O5 content that ranges from 18-40 %. Sulphur-oxidizing bacteria of the Beggiatoa genus concentration phosphorous as intracellular polyphosphate ((PO3-)n) which is depolymerized into inorganic orthophosphate (Pi). Consequently, an increase in pore water Pi concentration favours carbonated apatite precipitation. The carbonate and fluoride that is characteristic of phosphorite CFA is also located in the vertebrate skeleton. This similarity suggests a biochemical pathway for CFA precipitation. Preliminary Raman spectroscopy and powder x-ray diffraction results that suggest a role for fluoride, and possibly carbonate, in the biochemical depolymerisation of polyphosphates with alkaline phosphatase will be presented.

  11. A Sequential Leach Method and Pb Isotope Approach to Studying Apatite Weathering in Granitoid Soils at Hubbard Brook Experimental Forest, NH, USA

    NASA Astrophysics Data System (ADS)

    Nezat, C. A.; Blum, J. D.

    2005-12-01

    Easily dissolved minerals such as calcite and apatite can be important in controlling stream and ground water chemistry even though these minerals are only present in trace amounts in granitoid rocks. Because of its solubility, apatite, a calcium phosphate mineral, may be a significant source of essential nutrients (especially phosphorous) for vegetation, and has been shown to strongly influence stream and soil water composition (e.g, calcium, strontium and rare earth elements). There are additional sources of Ca (e.g., feldspars, hornblende) and P (e.g., organic matter or bound to Fe and Al oxides) in granitoid soils. In order to distinguish the chemical constituents of apatite from other pools in the bulk soil, we selectively dissolved apatite with a dilute acid leach, and measured Pb isotopic ratios of apatite, feldspar, and leachates. We tested the leaching procedure on mineral separates and verified that a dilute nitric solution primarily dissolves apatite. Silicates were dissolved in subsequent steps by successively stronger acids. We then applied this method to bulk soils collected from several soil pits across a small watershed at the Hubbard Brook Experimental Forest (HBEF), New Hampshire, USA, to determine the spatial distribution of Ca and P pools, and determine the depth of apatite depletion in the soil. We also measured Pb isotope ratios in the soil leachates to distinguish among the various sources of Pb (e.g., apatite, feldspars and anthropogenic sources). We found that Pb in the dilute nitric leach of the HBEF organic soils is dominated by anthropogenic sources and that Pb from apatite becomes increasingly important with depth.

  12. Understanding the influence of alendronate on the morphology and phase transformation of apatitic precursor nanocrystals.

    PubMed

    Zhang, Guiling; Huang, Rong; Li, Zhicheng; Yang, Xianyan; Chen, Xiaoyi; Xia, Wei; Sun, Xiaoliang; Yang, Guojing; Gao, Changyou; Gou, Zhongru

    2012-08-01

    Bisphosphonates (BPs) are a class of synthetic pyrophosphate analogs that can prevent the loss of bone mass, given orally to treat postmenopuasal osteoporosis. It is not clear yet if the benefits of BPs include the possibility of affecting bone apatitic precursors transition for bone consolidation except for encouraging osteoclasts to undergo apoptosis. Furthermore, the complexity of the in vivo system makes it difficult to isolate and study such extracellular topographical cues that trigger bone turnover response. Herein, we proposed a wet-chemical approach employing alendronate sodium (AS) as a guide of hydroxyapatite (HA) precursor growth and conversion which was initiated from the nucleantion of octacalcium phosphate (OCP) in a cell membrane-mimicking surfactant micelle aqueous system. The nanocrystal clusters of dicalcium phosphate dihydrate (DCPD) and OCP nanocryatals were readily precipitated within a relatively narrow AS concentration range (2-8 μM). However, such low concentrations of AS seemed to stabilize the more acidic phases, and to delay the transformation into HA, to an extent which increased on increasing AS concentration. In contrast, at a slight higher concentrations (16-32 μM), AS promoted HA precipitation after ageing for 1h. It was found that the effect of AS on the phase selectivity of apatitic precursors was concentration-dependent within a prolonged ageing time stage (0.5-168 h). The AS-assisted reactions in vitro offer an expedient way to understand the underlying implementarity between bone and BPs for bone consolidation, and to improve our understanding of benefit of BP dosages on bone turnover and trauma healing.

  13. Nanomedicine: Interaction of biomimetic apatite colloidal nanoparticles with human blood components.

    PubMed

    Choimet, Maëla; Hyoung-Mi, Kim; Jae-Min, Oh; Tourrette, Audrey; Drouet, Christophe

    2016-09-01

    This contribution investigates the interaction of two types of biomimetic-apatite colloidal nanoparticles (negatively-charged 47nm, and positively-charged 190nm NPs) with blood components, namely red blood cells (RBC) and plasma proteins, with the view to inspect their hemocompatibility. The NPs, preliminarily characterized by XRD, FTIR and DLS, showed low hemolysis ratio (typically lower than 5%) illustrating the high compatibility of such NPs with respect to RBC, even at high concentration (up to 10mg/ml). The presence of glucose as water-soluble matrix for freeze-dried and re-dispersed colloids led to slightly increased hemolysis as compared to glucose-free formulations. NPs/plasma protein interaction was then followed, via non-specific protein fluorescence quenching assays, by contact with whole human blood plasma. The amount of plasma proteins in interaction with the NPs was evaluated experimentally, and the data were fitted with the Hill plot and Stern-Volmer models. In all cases, binding constants of the order of 10(1)-10(2) were found. These values, significantly lower than those reported for other types of nanoparticles or molecular interactions, illustrate the fairly inert character of these colloidal NPs with respect to plasma proteins, which is desirable for circulating injectable suspensions. Results were discussed in relation with particle surface charge and mean particle hydrodynamic diameter (HD). On the basis of these hemocompatibility data, this study significantly complements previous results relative to the development and nontoxicity of biomimetic-apatite-based colloids stabilized by non-drug biocompatible organic molecules, intended for use in nanomedicine.

  14. Influence of crystallite microstrain on surface complexes governing the metastable equilibrium solubility behavior of carbonated apatites.

    PubMed

    Papangkorn, Kongnara; Yan, Guang; Heslop, Dustin D; Moribe, Kunikazu; Baig, Arif A; Otsuka, Makoto; Higuchi, William I

    2008-04-01

    This study was on the influence of the mineral phase crystallite microstrain (CM) on the nature of the surface complex (SC) governing the metastable equilibrium solubility (MES) behavior of carbonated apatites (CAPs) in aqueous acidic media (0.10 M acetate buffers, with and without fluoride, 0.50 M ionic strength maintained with NaCl). The MES behavior of a set of four CAPs (synthesized at 85 degrees C by a precipitation method) of increasing CM and therefore of increasing MES (CAP4 > CAP3 > CAP2 > CAP1) was quantified. The following were the findings. For CAP1 and CAP2, the SCs deduced were Ca10(PO4)6(OH)2 and Ca10(PO4)6F2 for the nonfluoride and the fluoride cases, respectively. For CAP3 and CAP4, the SCs deduced were Ca9.5(PO4)6OH or Ca9.5(HPO4)(PO4)5(OH)2 and NaCa9.5(PO4)6F2 for the nonfluoride and the fluoride cases, respectively. These results together with that from an earlier limited study show that the Ca/P ratio of the SC decreases from 1.67 to 1.58 to 1.50 with increasing CM of the CAPs; this relationship inversely correlates with the chemistry of maturation of aqueously precipitated defective apatites. Also the SCs do not appear to exist as a continuous series and only a few SCs may account for the MES behavior over a wide range of CAP preparations.

  15. On the annealing of fission tracks in randomly oriented grains of apatite

    NASA Astrophysics Data System (ADS)

    Guedes, Sandro; Curvo, Eduardo A. C.; Tello, Carlos A.; Hadler, Julio C.; Iunes, Pedro J.; Paulo, Sérgio R.; Palissari, Rosane

    2007-03-01

    Apatite fission-track thermochronology has been based upon measurements in prismatic sections. Until now, all annealing data sets referred to this kind of measurement. However, prismatic sections are not always available, e.g. for detrital apatite grains, making the work impossible. An alternative would be to use grains in any orientation. This requires that a suitable annealing model be employed, i.e. one obtained from measurements in grains without preferential orientation. In this work, the angular distribution of confined fission tracks parallel to the surfaces of grains randomly oriented relative to the crystallographic c-axis is obtained. This distribution shows that track at higher angles relative to c-axis, when compared with the prismatic section distribution, are found. The procedure measurements in randomly oriented sections is presented along with empirical model equations. Model parameters have been obtained for the most common empirical equations and the partial annealing zone has been calculated for these equations. Results are compared with geological benchmarks; the fanning linear Arrhenius model yields the best agreement. This empirical model and those most used in literature have been applied to samples from the São Francisco Craton, Brazil, to show an instance in which the effects of grain orientation is important. Thermal histories of geological samples have been obtained through these equations. The samples tested presented moderate annealing and experienced a relatively simple thermal history. Under these conditions, taking into account the uncertainties in the model equations and confined track measurements, and using compatible systems, the presented model equations and the most used prismatic face ones constrained the same thermal history feature.

  16. Synchrotron Microanalytical Methods in the Study of Trace and Minor Elements in Apatite

    SciTech Connect

    Rakovan,J.; Luo, Y.; Borkiewicz, O.

    2008-01-01

    Synchrotron X-ray facilities have the capability for numerous microanalytical methods with spatial resolutions in the micron to submicron range and sensitivities as low as ppm to ppb. These capabilities are the result of a high X-ray brilliance (many orders of magnitude greater than standard tube and rotating anode sources); a continuous, or white, spectrum through the hard X-ray region; high degrees of X-ray columniation and polarization; and new developments in X-ray focusing methods. The high photon flux and pulsed nature of the source also allow for rapid data collection and high temporal resolution in certain experiments. Of particular interest to geoscientists are X-ray fluorescence microprobes which allow for numerous analytical techniques including X-ray fluorescence (XRF) analysis of trace element concentrations and distributions; X-ray absorption spectroscopy (XAS) for chemical speciation, structural and oxidation state information; X-ray diffraction (XRD) for phase identification; and fluorescence microtomography (CMT) for mapping the internal structure of porous or composite materials as well as elemental distributions. We have employed several synchrotron based microanalytical methods including XRF, microEXAFS (Extended X-ray Absorption Fine Structure), microXANES (X-ray Absorption Near Edge Structure) and CMT for the study of minor and trace elements in apatite (and other minerals). We have also been conducting time resolved X-ray diffraction to study nucleation of and phase transformations among precursor phases in the formation of apatite from solution at earth surface conditions. Summaries of these studies are given to exemplify the capabilities of synchrotron microanalytical techniques.

  17. Isoexergonic Conformations of Surface-Bound Citrate Regulated Bioinspired Apatite Nanocrystal Growth.

    PubMed

    Wang, Ziqiu; Xu, Zhijun; Zhao, Weilong; Chen, Wei; Miyoshi, Toshikazu; Sahai, Nita

    2016-10-05

    The superior biomechanical properties of bone and dentin are dictated, in part, by the unique plate-like morphology of hydroxyapatite (HAP) nanocrysals within a hierarchically assembled collagen matrix. Understanding the mechanism of crystal growth and thus morphology is important to the rational design of bioinspired apatite nanocrystals for orthopedic and dental applications. Citrate has long been proposed to modulate apatite crystal growth, but major questions exist regarding the HAP-bound citrate conformations and the identities of the interacting functional groups and HAP surface sites. Here, we conducted a comprehensive investigation of the mechanism from the angstrom to submicrometer scale by detailed correlation of the results of high-level metadynamics simulations, employing force-fields benchmarked to experiment and density functional theory calculations with the results of high resolution transmission electron microscopy, nuclear magnetic resonance spectroscopy, solution analysis, and thermogravimetric analysis. Crystal morphology changed from needle- to plate-like with increasing citrate concentration. Citrate adsorbed more strongly on the HAP (100) face than on the (001) face, thus resulting in preferential growth in the [001] direction and the plate-like morphology. Two very different bound conformations were obtained, involving interactions of either one or both terminal carboxyl groups with three or five surface calcium ions, respectively, and a hydrogen bond between the citrate hydroxyl and the HAP surface. Remarkably, despite fewer interaction sites in the single bound carboxyl conformation, the structures were isoexergonic, so both exist at equilibrium. Identification of the former conformation is significant because it allows a greater adsorption density than is traditionally assumed and can help explain concentration-dependence of citrate in modulating crystal morphology. These unique results were enabled first by the application of advanced

  18. Ion microprobe U-Pb dating and REE abundance of biogenic apatite

    NASA Astrophysics Data System (ADS)

    Sano, Y.; Terada, K.; Ueki, S.

    2001-12-01

    If the direct U-Pb dating of a fossil itself is possible, the method could have great impact on stratigraphic studies in establishing the absolute chronology of sedimentary sequences. Micro fossil ?conodont? are candidates for this purpose since they consist of apatite (Ca2(PO5)3 (F,Cl,OH)), which would uptake U, Th and Pb after sedimentation no longer than a few million years and is supposed to remain closed to U and Pb under relatively low effective closure temperature. We report here results of direct ion microprobe U-Th-Pb dating of two conodonts; Trichognathus from Kinderhookian stage of Mississippian sedimentary sequence from Illinois Basin region in North America and Panderodus from a Llandoverian sedimentary sequence on Langkawi Island, northern Malaysia. Secondary purpose of the study is to indicate in situ analysis of all REE on the same spots of U-Pb measurements. Samples were cast into epoxy resin discs with a few grains of standard apatite, PRAP, derived from an alkaline rock of Prairie Lake circular complex in the Canadian Shield and polished until they were exposed through their mid-sections. U, Th and REE abundances, and Pb isotopic compositions were measured by using SHRIMP installed at Hiroshima University. Thirteen spots on Trichognathus yield a 238U/206Pb isochron age of 323+/-36 Ma, which is consistent with the depositional and early diagenetic ages. Fifteen spots on Panderodus give 232Th/208Pb isochron age of 429+/-50 Ma, which is again comparable to an early Silurian. Shale-normalized REE of Trichognathus shows a broadly flat pattern from light to middle REE and a decrease from middle to heavy REE with negative anomalies of Ce and Eu. In contrast Panderodus indicates a concave-shape pattern with middle REE enrichment. These characteristics are probably due to a different formation environment as suggested by other workers.

  19. Solubility of apatite in H2O-NaCl and silicate-bearing solutions at 0.7-3.0 GPa, 800° C

    NASA Astrophysics Data System (ADS)

    Antignano, A.; Manning, C. E.

    2004-12-01

    Apatite is a major reservoir for the rare-earth elements (REE) in the earth's crust. However, little is known about its solubility in metamorphic fluids. We measured the solubility of apatite in H2O-NaCl and silicate bearing fluids at 800° C and 1.0-2.0 GPa using a piston-cylinder apparatus with NaCl-graphite furnaces. A single Durango fluor-apatite crystal was loaded into a 1.6 mm OD Pt inner capsule, which was crimped and then placed in a 3.5 OD Pt outer capsule with ultra pure H2O and NaCl or powdered albite. Solubility was determined by the weight loss of the apatite grain after 24 hrs. In the H2O-NaCl experiments, total dissolved solids (TDS) were initially below detection (0.4 millimolal) between XNaCl= 0 and XNaCl= 0.025. At XNaCl= 0.035, solubility was 3.3(0.2) millimolal (errors are 1s), and it increased to 57.5(0.4) millimolal at XNaCl= 0.526. Our results show that there is an enhancement in apatite solubility with increasing pressure in pure H2O. Solubility is initially below detection at <1.0 GPa, but increases to 0.8(0.2) and 1.2(0.2) millimolal at 1.5 GPa and 2.0 GPa respectively. At 1.0 GPa, apatite solubility in H2O-albite (Ab) fluids increases from 0.5(0.2) millimolal at Xalbite= 0.004 to 1.4(0.2) at Xalbite= 0.007. Monazite occurs as <1 μ m subhedral grains on apatite surfaces in all runs, but its weight is insignificant and does not effect the solubility measurements. Our results demonstrate that, at a given P and T, apatite solubility rises with increasing concentrations of NaCl and albite, suggesting that the additional components promote mass transport of dissolved apatite components during metamorphism. Concentrated brines may explain the origin of apatite veins associated with in high-grade granulite terranes and ore bodies. The formation of monazite demonstrates that the REE are less soluble in H2O-NaCl and silicate bearing solutions. This probably explains textures in which monazite mantles apatite, which are common in granulite

  20. Synthesis of trace element bearing single crystals of Chlor-Apatite (Ca5(PO4)3Cl) using the flux growth method

    PubMed Central

    2013-01-01

    We present a new strategy on how to synthesize trace-element bearing (REE, Sr) chlorapatites Ca5(PO4)3Cl using the flux growth method. Synthetic apatites were up to several mm long, light blue in colour. The apatites were characterized using XRD, electron microprobe and laser ablation ICP-MS (LA-ICPMS) techniques and contained several hundred μg/g La, Ce, Pr, Sm, Gd and Lu and about 1700 μg/g Sr. The analyses indicate that apatites were homogenous (within the uncertainties) for major and trace elements. PMID:23531340

  1. Partitioning behavior of chlorine and fluorine in the system apatite melt fluid. II: Felsic silicate systems at 200 MPa

    NASA Astrophysics Data System (ADS)

    Webster, James D.; Tappen, Christine M.; Mandeville, Charles W.

    2009-02-01

    Hydrothermal experiments were conducted to determine the partitioning of Cl between rhyolitic to rhyodacitic melts, apatite, and aqueous fluid(s) and the partitioning of F between apatite and these melts at ca. 200 MPa and 900-924 °C. The number of fluid phases in our experiments is unknown; they may have involved a single fluid or vapor plus saline liquid. The partitioning behavior of Cl between apatite and melt is non-Nernstian and is a complex function of melt composition and the Cl concentration of the system. Values of DClapat/melt (wt. fraction of: Cl in apatite/Cl in melt) vary from 1 to 4.5 and are largest when the Cl concentrations of the melt are at or near the Cl-saturation value of the melt. The Cl-saturation concentrations of silicate melts are lowest in evolved, silica-rich melts, so with elevated Cl concentrations in a system and with all else equal, the maximum values of DClapat/melt occur with the most felsic melt. In contrast, values of DFapat/melt range from 11 to 40 for these felsic melts, and many of these are an order of magnitude greater than those applying to basaltic melts at 200 MPa and 1066-1150 °C. The Cl concentration of apatite is a simple and linear function of the concentration of Cl in fluid. Values of DClfluid/apat for these experiments range from 9 to 43, and some values are an order of magnitude greater than those determined in 200-MPa experiments involving basaltic melts at 1066-1150 °C. In order to determine the concentrations and interpret the behavior of volatile components in magmas, the experimental data have been applied to the halogen concentrations of apatite grains from chemically evolved rocks of Augustine volcano, Alaska; Krakatau volcano, Indonesia; Mt. Pinatubo, Philippines; Mt. St. Helens, Washington; Mt. Mazama, Oregon; Lascar volcano, Chile; Santorini volcano, Greece, and the Bishop Tuff, California. The F concentrations of these magmas estimated from apatite-melt equilibria range from 0.06 to 0.12 wt% and are

  2. Reply to comment by Marks et al. (2016) on "Apatite: A new redox proxy for silicic magmas?" [Geochimica et Cosmochimica Acta 132 (2014) 101-119

    NASA Astrophysics Data System (ADS)

    Miles, Andrew; Graham, Colin; Hawkesworth, Chris; Gillespie, Martin; Hinton, Richard; Bromiley, Geoffrey

    2016-06-01

    Marks et al. (2016) investigate the applicability of the Mn-in-apatite oxybarometer proposed by Miles et al. (2014) across a range of magma compositions using published data on well-characterised samples. The authors show that for magma compositions outside of the calc-alkaline and intermediate to silicic range used in the preliminary calibration, fO2 values calculated from Mn-in-apatite vary significantly from independently constrained estimates. These data are used to reiterate our warnings that other controls that are additional to oxygen fugacity are likely to affect Mn partitioning into apatite in some rock types, and particularly so in magmas that lie outside of the range of compositions and conditions used in the calibration. Marks et al. (2016) highlight that temperature may have an especially important effect on Mn partitioning in apatite in some rock types.

  3. Evidence for the exsolution of Cl-rich fluids in martian magmas: Apatite petrogenesis in the enriched lherzolitic shergottite Northwest Africa 7755

    NASA Astrophysics Data System (ADS)

    Howarth, G. H.; Pernet-Fisher, J. F.; Bodnar, R. J.; Taylor, L. A.

    2015-10-01

    Martian meteorite Northwest Africa 7755 is a new example of an enriched, lherzolitic shergottite, containing some of the coarsest-grained apatite yet identified in shergottite meteorites. Their size has permitted detailed observations of volatile distributions within single grains. We have demonstrated that some apatites have been invaded by shock melts, which act to devolatilize parts of grains, resulting in significant Cl-enrichment in the adjacent regions. The extent of chemical heterogeneity within single grains must be carefully considered in other shergottites, so that the effects of secondary modification of apatites are well-constrained, prior to interpreting the volatile contents and primary magmatic processes. Apatite grains unaffected by shock melts are OH-F enriched and Cl-poor (∼F50Cl14OH36), relative to interstitial apatites reported in other shergottites. The volatile compositions are similar to interstitial apatites reported in terrestrial mafic intrusions. Such apatites in terrestrial intrusions are argued to have formed after significant Cl-loss due to the exsolution and migration of Cl-rich brines. Calculated relative F2, Cl2, and H2O fugacities for NWA 7755 apatites show a trend of degassing rather than fractionation, noted in previous studies. Indeed, we interpret the volatile contents of apatites analyzed in the cumulate shergottite NWA 7755 to represent snapshots of the evolving late-stage residual liquid during exsolution of a Cl-rich brine. This fluid phase has subsequently been lost from an open magma system, migrating upward through the cumulate sequence enriching residual liquids in Cl. Alternatively, it formed a hydrothermal system in the martian crust surrounding the intrusion. Furthermore, by comparison with terrestrial examples, we suggest that the late-stage evolution of volatile-bearing phases in NWA 7755 is similar to that of comparable terrestrial mafic rocks. Primary cumulus apatites are F-rich, whereas interstitial apatites

  4. Relationship between apatite-forming ability and mechanical properties of bioactive PMMA-based bone cement modified with calcium salts and alkoxysilane.

    PubMed

    Sugino, Atsushi; Miyazaki, Toshiki; Kawachi, Giichiro; Kikuta, Koichi; Ohtsuki, Chikara

    2008-03-01

    Polymethylmethacrylate (PMMA)-based bone cement is used for the fixation of artificial joints in orthopaedics. However, the fixation is liable to loosen in the body, because the cement does not bond to living bone. So-called bioactive ceramics bond directly to living bone through the apatite layer formed on their surfaces in the body. We previously revealed that modification using gamma-methacryloxypropyltrimethoxysilane (MPS) and water-soluble calcium salts such as calcium acetate and calcium hydroxide was effective for providing the PMMA-based bone cement with apatite-forming ability in a simulated body fluid (SBF, Kokubo solution) that closely reproduces the body environment. However, the effect of the chemical reaction forming the apatite on the mechanical properties of the cements has not been clarified. The present work aimed to investigate this issue from the viewpoint of the interface structure between the apatite and the cement. The surface of the cement modified with calcium acetate and MPS was fully covered with newly formed apatite after soaking in Kokubo solution within 7 days, while half of the surface area of the cement modified with calcium hydroxide and MPS was covered with the apatite. The bending strength of the modified cements decreased after soaking in Kokubo solution. Porous structure was observed in the region about 50-100 microm in depth from the top surface because of release of the Ca2+ ions by both modified cements after soaking in Kokubo solution. The decrease in bending strength of the modified cements could be attributed to the formation of the pores. In addition, the pores on the top surfaces of the cements were filled with the newly formed apatite. The apatite formation would be effective not only for bioactivity but also for decreasing the reduction of mechanical strength.

  5. The Calcium Phosphate Matrix of FGF-2-Apatite Composite Layers Contributes to Their Biological Effects

    PubMed Central

    Mutsuzaki, Hirotaka; Ito, Atsuo; Sogo, Yu; Sakane, Masataka; Oyane, Ayako; Yamazaki, Masashi

    2014-01-01

    The purpose of the present study was to fabricate fibroblast growth factor (FGF)-2-apatite composite layers on titanium (Ti) pins in one step at 25 °C using a supersaturated calcium phosphate (CaP) solution, and to evaluate the physicochemical characteristics and biological effects of the coated Ti pins compared with coated Ti pins fabricated at 37 °C. Ti pins were immersed in a supersaturated CaP solution containing 0.5, 1.0, or 2.0 µg/mL FGF-2 at 25 °C for 24 h (25F0.5, 25F1.0, and 25F2.0) or containing 4.0 µg/mL FGF-2 at 37 °C for 48 h (37F4.0). Except for the 25F0.5, the chemical compositions and the mitogenic activity levels of FGF-2 of the composite layers formed by these two methods were similar, except for the Ca/P molar ratio, which was markedly smaller at 25 °C (1.55–1.56 ± 0.01–0.02, p = 0.0008–0.0045) than at 37 °C (1.67 ± 0.11). Thus, either the apatite was less mature or the amount of amorphous calcium phosphate was higher in the composite layer formed at 25 °C. In vivo, the pin tract infection rate by visual inspection for 37F4.0 (45%) was lower than that for 25F1.0 (80%, p = 0.0213), and the rate of osteomyelitis for 37F4.0 (35%) was lower than that for 25F0.5 (75%, p = 0.0341). The extraction torque for 37F4.0 (0.276 ± 0.117 Nm) was higher than that for 25F0.5 (0.192 ± 0.117 Nm, p = 0.0142) and that for 25F1.0 (0.176 ± 0.133 Nm, p = 0.0079). The invasion rate of S. aureus for 37F4.0 (35%) was lower than that for 25F0.5 (75%, p = 0.0110). On the whole, the FGF-2-apatite composite layer formed at 25 °C tended to be less effective at improving fixation strength in the bone-pin interface and resisting pin tract infections. These results suggest that the chemistry of the calcium phosphate matrix that embeds FGF-2, in addition to FGF-2 content and activity, has a significant impact on composite infection resistance and fixation strength. PMID:24918287

  6. Apatite/Melt Partitioning Experiments Reveal Redox Sensitivity to Cr, V, Mn, Ni, Eu, W, Th, and U

    NASA Technical Reports Server (NTRS)

    Righter, K.; Yang, S.; Humayun, M.

    2016-01-01

    Apatite is a common mineral in terrestrial, planetary, and asteroidal materials. It is commonly used for geochronology (U-Pb), sensing volatiles (H, F, Cl, S), and can concentrate rare earth elements (REE) during magmatic fractionation and in general. Some recent studies have shown that some kinds of phosphate may fractionate Hf and W and that Mn may be redox sensitive. Experimental studies have focused on REE and other lithophile elements and at simplified or not specified oxygen fugacities. There is a dearth of partitioning data for chalcophile, siderophile and other elements between apatite and melt. Here we carry out several experiments at variable fO2 to study the partitioning of a broad range of trace elements. We compare to existing data and then focus on several elements that exhibit redox dependent partitioning behavior.

  7. Pyridine and phenol removal using natural and synthetic apatites as low cost sorbents: influence of porosity and surface interactions.

    PubMed

    Bouyarmane, H; El Asri, S; Rami, A; Roux, C; Mahly, M A; Saoiabi, A; Coradin, T; Laghzizil, A

    2010-09-15

    A natural phosphate rock and two synthetic mesoporous hydroxyapatites were evaluated for the removal of pyridine and phenol from aqueous solutions. Experiments performed by the batch method showed that the sorption process occurs by a first order reaction for both pyridine and phenol. In contrast, the Freundlich model was able to describe sorption isotherms for phenol but not for pyridine. In parallel, the three apatites exhibit similar pyridine sorption capacities whereas phenol loading was in agreement with their respective specific surface area. This was attributed to the strong interaction arising between pyridine and apatite surface that hinders further inter-particular diffusion. This study suggests that, despite its low specific surface area, natural phosphate rock may be used as an efficient sorbent material for specific organic pollutants, with comparable efficiency and lower processing costs than some activated carbons.

  8. Inhibition of precipitation of carbonate apatite by trisodium citrate analysed in base of the formation of chemical complexes in growth solution

    NASA Astrophysics Data System (ADS)

    Prywer, Jolanta; Olszynski, Marcin; Mielniczek-Brzóska, Ewa

    2015-11-01

    Effect of trisodium citrate on the precipitation of carbonate apatite is studied. The experimental series are performed in the solution of artificial urine. The investigations are related to infectious urinary stones formation as carbonate apatite is one of the main components of this kind of stones. To mimic a real infection in urinary tract the aqueous ammonia solution was added to the solution of artificial urine. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to carbonate apatite formation and decreases the efficiency of carbonate apatite precipitation. The inhibitory effect of trisodium citrate on the precipitation of carbonate apatite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is mainly related with the fact that trisodium citrate binds Ca2+ ions and causes the formation of CaCit- and Ca10(PO4)6CO3 complexes. Trisodium citrate binds Ca2+ ions in the range of pH from 6 to 9.5 for which carbonate apatite is favored to be formed.

  9. On the mechanism of apatite-induced precipitation on 45S5 glass pellets coated with a natural-derived polymer

    NASA Astrophysics Data System (ADS)

    Araújo, Marco; Miola, Marta; Bertone, Elisa; Baldi, Giovanni; Perez, Javier; Verné, Enrica

    2015-10-01

    In this work, the bioactive glass 45S5 (also known by its commercial name Bioglass®) was successfully dip-coated by a natural derived biopolymer, increasing its apatite-forming ability. The biopolymer was shown to accelerate the first stages of bioactivity, inducing a fast transition to step 4 (formation of amorphous Casbnd P layer) in the apatite-forming ability mechanism. The faster precipitation of Ca/P crystals in the coated samples resulted in the formation of an intermediate amorphous octacalcium phosphate, which later transforms into an apatite layer with high thickness. The effect of the thickness of the coating was also studied on samples coated with polymer suspensions of different concentrations (0.15% and 1.5%, w/v), revealing that the kinetics of formation of the final hydroxycarbonate apatite layer increases with the thickness of the coating. The mechanism by which this apatite-forming ability is accelerated was also investigated, revealing that certain functional groups present in the structure of the polymer allow it to act as an organic matrix and preferential nucleation site for the growth of the hydroxycarbonate apatite layer.

  10. The possibility of the formation of protocells and their structural components on the basis of the apatite matrix and cocrystallizing minerals.

    PubMed

    Kostetsky, Eduard Y

    2005-12-01

    This paper presents the author's theory on the possibility of simultaneous hard-phase synthesis of various organic molecules from gas-phase elements on the basis of the apatite matrix and cocrystallizing minerals (carbonate-apatite, calcite, mica). These molecules and their ensembles gave rise to living systems and protocells of the pro- and eukaryotic types. Synthesis might have occurred through gradual substitution of the mineral matrix by crystal organic matter. The structure and size of the molecules synthesized were determined by the structure, physical parameters, and arrangement of organizing centers in the crystal lattice. Apatite phosphates were embedded in a synthesized nucleic helix and their size and purine-pyrimidine complementarity were determined. Apatite and cocrystallizing minerals were seen to be involved in the synthesis of four basic classes of cell components: apatite-DNA and nucleoproteide complexes; carbonate-apatite-enzymes, other proteins involved in DNA replication, all RNA types and their complexes with the specific proteins and enzymes of transcription and translation; calcite-cytoskeletal proteins; and mica-membrane lipids and proteins. The evidence supporting this theory is presented. A possible mechanism to account for the transition from crystal through organo-mineral crystal to liquid crystal (protocell) and a model of the occurrence of the matrix mechanism of transcription and translation are proposed. Some principal problems in the biochemistry and molecular biology of the origin of life on the Earth are discussed.

  11. Vacuum-sintered body of a novel apatite for artificial bone

    NASA Astrophysics Data System (ADS)

    Tamura, Kenichi; Fujita, Tatsushi; Morisaki, Yuriko

    2013-12-01

    We produced regenerative artificial bone material and bone parts using vacuum-sintered bodies of a novel apatite called "Titanium medical apatite (TMA®)" for biomedical applications. TMA was formed by chemically connecting a Ti oxide molecule with the reactive [Ca10(PO4)6] group of Hydroxyapatite (HAp). The TMA powders were kneaded with distilled water, and solid cylinders of compacted TMA were made by compression molding at 10 MPa using a stainless-steel vessel. The TMA compacts were dried and then sintered in vacuum (about 10-3 Pa) or in air using a resistance heating furnace in the temperature range 1073-1773 K. TMA compacts were sintered at temperatures greater than 1073 K, thus resulting in recrystallization. The TMA compact bodies sintered in the range 1273-1773 K were converted into mixtures composed of three crystalline materials: α-TCP (tricalcium phosphate), β-TCP, and Perovskite-CaTiO3. The Perovskite crystals were stable and hard. In vacuum-sintering, the Perovskite crystals were transformed into fibers (approximately 1 µm in diameter × 8 µm in length), and the fiber distribution was uniform in various directions. We refer to the TMA vacuum-sintered bodies as a "reinforced composite material with Perovskite crystal fibers." However, in atmospheric sintering, the Perovskite crystals were of various sizes and were irregularly distributed as a result of the effect of oxygen. After sintering temperature at 1573 K, the following results were obtained: the obtained TMA vacuum-sintered bodies (1) were white, (2) had a density of approximately 2300 kg/m3 (corresponding to that of a compact bone or a tooth), and had a thermal conductivity of approximately 31.3 W/(m·K) (corresponding to those of metal or ceramic implants). Further, it was possible to cut the TMA bodies into various forms with a cutting machine. An implant made of TMA and inserted into a rabbit jaw bone was covered by new bone tissues after just one month because of the high

  12. In-situ Strontium Isotopes Analysis on Single Conodont Apatite by LA-MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Zhao, L.; Zhang, L.; Chen, Z. Q.; Ma, D.; Qiu, H.; Lv, Z.; Hu, Z.; Wang, F.

    2014-12-01

    Strontium isotope played an important role in stratigraphic chronology and sedimentary geochemistry research (McArthur et al., 2001). Conodonts is a kind of extinct species of marine animals and widely distributed in marine sediments all over the world. Rich in radiogenic Sr contents and difficulty to be affected during diagenesis alteration makes conodonts a good choice in seawater Sr isotope composition studies (John et al., 2008). Conodont samples were collected from 24th to 39th layer across Permian-Triassic boundary at Meishan D section (GSSP), Zhejiang Province, South China (Yin et al., 2001). Conodonts was originated from fresh limestone and only conodont elements with CAI<2 were chosen for in-situ strontium isotope analysis using laser-ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Conodont samples are from totally 25 layers in seven conodont zones making it possible for a high resolution 87Sr/ 86Sr curve reconstruction during the Permian-Triassic transition. 87Sr/ 86Sr ratio kept a relatively high value (0.70752) in the middle part of the Clarkina yini zone and a lower value (0.70634) in the upperpart of Clarkina taylorae zone. Of which, 87Sr/ 86Sr ratio emerged a rapid decrease within the Clarkina taylorae zone. After a subsequent increase, 87Sr/ 86Sr ratio dropped to 0.70777 in the Isarcicella staeschei zone. These results helps providing reference data for the biological mass extinction events during the Permian-Triassic transition. Our study also makes is possible for high resolution 87Sr/ 86Sr ratio testing on the single conodont apatite and riched the in-situ studies on the conodont apatite, which of great significance for the future conodont Sr isotope research (Zhao et al., 2009; Zhao et al., 2013). Keywords: Conodonts, Strontium isotope, LA-MC-ICP-MS, Permian-Triassic transition, Meishan D section [1] John et al., 2008 3P[2] McArthur et al., 2001 J. of Geology [3] Yin et al., 2001 Episodes [4] Zhao et al

  13. Strontium ranelate changes the composition and crystal structure of the biological bone-like apatite produced in osteoblast cell cultures.

    PubMed

    Querido, William; Campos, Andrea P C; Martins Ferreira, Erlon H; San Gil, Rosane A S; Rossi, Alexandre M; Farina, Marcos

    2014-09-01

    We evaluate the effects of strontium ranelate on the composition and crystal structure of the biological bone-like apatite produced in osteoblast cell cultures, a system that gave us the advantage of obtaining mineral samples produced exclusively during treatment. Cells were treated with strontium ranelate at concentrations of 0.05 and 0.5 mM Sr(2+). Mineral substances were isolated and analyzed by using a combination of methods: Fourier transform infrared spectroscopy, solid-state (1)H nuclear magnetic resonance, X-ray diffraction, micro-Raman spectroscopy and energy dispersive X-ray spectroscopy. The minerals produced in all cell cultures were typical bone-like apatites. No changes occurred in the local structural order or crystal size of the minerals. However, we noticed several relevant changes in the mineral produced under 0.5 mM Sr(2+): (1) increase in type-B CO3 (2-) substitutions, which often lead to the creation of vacancies in Ca(2+) and OH(-) sites; (2) incorporation of Sr(2+) by substituting slightly less than 10 % of Ca(2+) in the apatite crystal lattice, resulting in an increase in both lattice parameters a and c; (3) change in the PO4 (3-) environments, possibly because of the expansion of the lattice; (4) the Ca/P ratio of this mineral was reduced, but its (Ca+Sr)/P ratio was the same as that of the control, indicating that its overall cation/P ratio was preserved. Thus, strontium ranelate changes the composition and crystal structure of the biological bone-like apatite produced in osteoblast cell cultures.

  14. Theoretical study of the local charge compensation and spectroscopic properties of B-type carbonate defects in apatite

    NASA Astrophysics Data System (ADS)

    Yi, Haohao; Balan, Etienne; Gervais, Christel; Ségalen, Loïc; Blanchard, Marc; Lazzeri, Michele

    2014-05-01

    The structure and spectroscopic properties of selected models of B-type carbonate defects in apatite locally compensated by fluoride or hydroxyl ions are investigated using first-principles quantum mechanical calculations. Theoretical infrared absorption spectra and 13C, and 19F nuclear magnetic resonance chemical shifts are determined. Among the investigated models, only the clumped (CO3 2-, F-) defect, with the carbonate group close to the sloping face of the tetrahedral site and the F- ion at the remaining apex, corresponds to previous experimental observations performed on carbonate-fluorapatite samples. Although the substitution of hydroxyl by fluoride ions is commonly observed in minerals, the clumped (CO3 2-, OH-) defects are unlikely to occur in apatite, considering both their theoretical spectroscopic properties and relative stability. Anionic F- for OH- exchange between channel and B sites displays a preference of ~20 kJ/mol for the local charge compensation by fluoride ions at the B-site, pointing to a significantly different behavior of F- and OH- ions in the charge compensation mechanism. This difference is ascribed to the poor H-bond acceptor character of available oxygen atoms surrounding the apex of the tetrahedral site. The explicit calculation of the infrared absorption spectra of the defect models is also used to interpret the significant difference observed in the linewidth of the ν2 and ν3 CO3 infrared powder absorption bands of carbonated apatite samples. It is shown that for a concentration of 4.4 wt% of CO2, long-range electrostatic effects already significantly contribute to the broadening of the ν3 CO3 bands in apatite.

  15. Effect of Mn-Zn ferrite on apatite-wollastonite glass-ceramic (A-W GC).

    PubMed

    Da Li, Guang; Zhou, Da Li; Pan, Tao Hua; Chen, Guo Sheng; Lin, Yun; Mao, Mao; Yan, Guo

    2009-08-01

    Magnetic bioactive glass-ceramics (M GC) were prepared by doping apatite-wollastonite glass-ceramic (A-W GC) with Mn-Zn ferrite. The effect of different contents of Mn-Zn ferrite on the phase structure, magnetic property and bioactivity of A-W GC was investigated. X-ray powder diffraction results showed that A-W GC exhibited apatite, fluorapatite and wollastonite as the main phases. The doping of Mn-Zn ferrite caused the formation of a new phase Zn(0.75)Mn(0.75)Fe(1.5)O(4) in M GC. The amount of this new phase increased with increasing content of Mn-Zn ferrite. Under a magnetic field of 7.96 x 10(5) A m(-1), the saturation magnetization of M GC increased from 4.63 to 9.7 A m(2) kg(-1), but the coercive forces of M GC decreased from 2.39 x 10(4) to 7.56 x 10(3) A m(-1) as the Mn-Zn ferrite content increased from 5% to 20% in the material. The bioactivity of samples was evaluated by soaking in simulated body fluid (SBF). The results showed that the doping of Mn-Zn ferrite decreased the bioactivity of A-W GC dramatically. It took 7 days for an apatite layer to form on the surface of A-W GC, while at least 30 days was needed for an apatite layer forming on the surface of M GC.

  16. Biomimetic apatite sintered at very low temperature by spark plasma sintering: physico-chemistry and microstructure aspects.

    PubMed

    Grossin, David; Rollin-Martinet, Sabrina; Estournès, Claude; Rossignol, Fabrice; Champion, Eric; Combes, Christèle; Rey, Christian; Geoffroy, Chevallier; Drouet, Christophe

    2010-02-01

    Nanocrystalline apatites analogous to bone mineral are very promising materials for the preparation of highly bioactive ceramics due to their unique intrinsic physico-chemical characteristics. Their surface reactivity is indeed linked to the presence of a metastable hydrated layer on the surface of the nanocrystals. Yet the sintering of such apatites by conventional techniques, at high temperature, strongly alters their physico-chemical characteristics and biological properties, which points out the need for "softer" sintering processes limiting such alterations. In the present work a non-conventional technique, spark plasma sintering, was used to consolidate such nanocrystalline apatites at non-conventional, very low temperatures (T<300 degrees C) so as to preserve the surface hydrated layer present on the nanocrystals. The bioceramics obtained were then thoroughly characterized by way of complementary techniques. In particular, microstructural, nanostructural and other major physico-chemical features were investigated and commented on. This work adds to the current international concern aiming at improving the capacities of present bioceramics, in view of elaborating a new generation of resorbable and highly bioactive ceramics for bone tissue engineering.

  17. Quinone-rich polydopamine functionalization of yttria stabilized zirconia for apatite biomineralization: The effects of coating temperature

    NASA Astrophysics Data System (ADS)

    Zain, Norhidayu Muhamad; Hussain, Rafaqat; Abdul Kadir, Mohammed Rafiq

    2015-08-01

    The use of yttria stabilized zirconia (YSZ) as biomedical implants is often offset by its bioinert nature that prevents its osseointegration to occur. Therefore, the functionalization of YSZ surface by polydopamine to facilitate the biomineralization of apatite layer on top of the coated film has incessantly been studied. In this study YSZ discs were first immersed in 2 mg/mL of stirred dopamine solution at coating temperatures between 25 and 80 °C. The specimens were then incubated for 7d in 1.5 SBF. The effect of coating temperature on the properties (chemical compositions and wettability) and the apatite mineralization on top of the generated films was investigated. It was found that at 50 °C, the specimen displayed the highest intensity of Ca 2p peak (1.55 ± 0.42 cps) with Ca/P ratio of 1.67 due to the presence of abundant quinone groups (Cdbnd O). However, the hydrophilicity (40.9 ± 01.7°) was greatly improved at 60 °C accompanied by the highest film thickness of 306 nm. Therefore, it was concluded that the presence of high intensity of quinone groups (Cdbnd O) in polydopamine film at elevated temperature affects the chelation of Ca2+ ions and thus enhance the growth of apatite layer on top of the functionalized YSZ surface.

  18. Ca L2,3-edge XANES and Sr K-edge EXAFS study of hydroxyapatite and fossil bone apatite

    NASA Astrophysics Data System (ADS)

    Zougrou, I. M.; Katsikini, M.; Brzhezinskaya, M.; Pinakidou, F.; Papadopoulou, L.; Tsoukala, E.; Paloura, E. C.

    2016-08-01

    Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

  19. Iron and oxygen isotope signatures of the Pea Ridge and Pilot Knob magnetite-apatite deposits, southeast Missouri, USA

    USGS Publications Warehouse

    Childress, Tristan; Simon, Adam C.; Day, Warren C.; Lundstrom, Craig C.; Bindeman, Ilya N.

    2016-01-01

    New O and Fe stable isotope ratios are reported for magnetite samples from high-grade massive magnetite of the Mesoproterozoic Pea Ridge and Pilot Knob magnetite-apatite ore deposits and these results are compared with data for other iron oxide-apatite deposits to shed light on the origin of the southeast Missouri deposits. The δ18O values of magnetite from Pea Ridge (n = 12) and Pilot Knob (n = 3) range from 1.0 to 7.0 and 3.3 to 6.7‰, respectively. The δ56Fe values of magnetite from Pea Ridge (n = 10) and Pilot Knob (n = 6) are 0.03 to 0.35 and 0.06 to 0.27‰, respectively. These δ18O and the δ56Fe values suggest that magnetite crystallized from a silicate melt (typical igneous δ56Fe ranges 0.06–0.49‰) and grew in equilibrium with a magmatic-hydrothermal aqueous fluid. We propose that the δ18O and δ56Fe data for the Pea Ridge and Pilot Knob magnetite-apatite deposits are consistent with the flotation model recently proposed by Knipping et al. (2015a), which invokes flotation of a magmatic magnetite-fluid suspension and offers a plausible explanation for the igneous (i.e., up to ~15.9 wt % TiO2 in magnetite) and hydrothermal features of the deposits.

  20. Ca L2,3-edge XANES and Sr K-edge EXAFS study of hydroxyapatite and fossil bone apatite.

    PubMed

    Zougrou, I M; Katsikini, M; Brzhezinskaya, M; Pinakidou, F; Papadopoulou, L; Tsoukala, E; Paloura, E C

    2016-08-01

    Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

  1. Revisiting the localization of Zn2+ cations sorbed on pathological apatite calcifications made through X-ray absorption spectroscopy

    SciTech Connect

    Bazin, D.; Carpentier, X.; Brocheriou, I.; Dorfmuller, P.; Aubert, S.; Chappard, C.; Thiaudiere, D.; Reguer, S.; Waychunas, G.; Jungers, P.; Daudon, M.

    2009-04-01

    The role of oligo-elements such as Zn in the genesis of pathological calcifications is widely debated in the literature. An essential element of discussion is given by their localization either at the surface or within the Ca apatite crystalline network. To determine the localization, X-ray absorption experiments have been performed at SOLEIL. The Exafs results suggest that Zn atoms, present in the Zn{sup 2+} form, are bound to about 4 O atoms at a distance of 2.00{angstrom}, while the interatomic distance R{sub CaO} ranges between 2.35 {angstrom} and 2.71 {angstrom}. Taking into account the content of Zn (around 1000 ppm) and the difference in ionic radius between Zn{sup 2+} (0.074 nm) and Ca{sup 2+} (0.099 nm), a significant longer interatomic distance would be expected in the case of Zn replacing Ca within the apatite crystalline network. We thus conclude that Zn atoms are localized at the surface and not in the apatite nanocrystal structure. Such structural result has essential biological implications for at least two reasons. Some oligoelements have a marked effect on the transformation of chemical phases, and may modify the morphology of crystals. These are both major issues because, in the case of kidney stones, the medical treatment depends strongly on the precise chemical phase and on the morphology of the biological entities at both macroscopic and mesoscopic scales.

  2. Effect of geometrical structure on drug release rate of a three-dimensionally perforated porous apatite/collagen composite cement.

    PubMed

    Otsuka, Makoto; Nakagawa, Hidenori; Ito, Atsuo; Higuchi, William I

    2010-01-01

    To improve the biocompatibility, inter-connective pore structure, and drug delivery ability of self-setting apatite/collagen composite cement (ACC), a three-dimensionally perforated porous apatite/collagen composite cement (TPPACC) containing 3% indomethacin (IMC) was obtained in an arranged multi-cross with 20, 40, and 60 stainless steel needlelike male dies, and stored and hardened at 37 degrees C and 100% relative humidity for 24 h. The mean radius of micro-pores of the TPPACC was evaluated to be 0.125 microm by mercury porosimetry. X-ray powder diffraction and FT-IR spectroscopy suggested that TPPACC consisted of carbonated apatite and had a structure similar to that of natural rat bone. The IMC release rates from a TPPACC block containing the drug were measured in simulated body fluid. The rate of release increased with the number of macro-pores that from planar surface matrix systems followed the Higuchi equation. The relationship between the Higuchi constant and surface area of TPPACC showed a straight line with K = 0.2123 and R(2) = 0.9892. These results indicated that the rate of drug release from TPPACC could be controlled by the number of macro-pores for bone cells.

  3. Human osteoblast behavior on as-synthesized SiO(4) and B-CO(3) co-substituted apatite.

    PubMed

    Landi, Elena; Uggeri, Jacopo; Sprio, Simone; Tampieri, Anna; Guizzardi, Stefano

    2010-07-01

    The functional behavior of synthetic apatite, commonly used as fillers or scaffolds, depends on physical and chemical parameters, which vary in response to chemical substitutions and to thermal treatments. The effect of silicon co-substituting with carbonate ions in the apatite lattice on the properties of the as-synthesized powder and finally on human osteoblast in vitro behavior was investigated. Dose-response curves of Si-free and Si-substituted carbonated apatites (namely CHA and SiCHA-1 and SiCHA-2 with 0.88 and 0.55 wt % of Si, respectively) showed that SiCHA-1 had toxic effect, whereas CHA and SiCHA-2, at worst, hindered osteoblast proliferation, but no toxicity occurred. Subsequent experiments compared the effects of CHA and SiCHA-2 used at the doses of 0.3 and 1 mg/mL. After 7 days of treatment, both the powders stimulated cell proliferation and protein content and inhibited alkaline phosphatase activity. However, SiCHA-2 slightly stimulated osteoblast differentiation, as shown by higher calcium deposition, compared with CHA. The cell behaviors were linked to the peculiar powder characteristics. The as-synthesized powder represents the most critical system in terms of reactivity toward cells and can inform on the limits for positively exploiting the characteristics of SiCHA powders in making bone fillers or scaffolds, using no thermal treatments. (c) 2010 Wiley Periodicals, Inc. J Biomed Mater Res, 2010.

  4. Apatite, SiO2, rutile and orthopyroxene precipitates in minerals of eclogite xenoliths from Yakutian kimberlites, Russia

    NASA Astrophysics Data System (ADS)

    Alifirova, T. A.; Pokhilenko, L. N.; Korsakov, A. V.

    2015-06-01

    Eclogite mantle xenoliths from the central part of Siberian craton (Udachnaya and Zarnitsa kimberlite pipes) as well as from the northeastern edge of the craton (Obnazhennaya kimberlite) were studied in detail. Garnet and clinopyroxene show evident exsolution textures. Garnet comprises rutile, ilmenite, apatite, and quartz/coesite oriented inclusions. Clinopyroxene contains rutile (± ilmenite) and apatite precipitates. Granular inclusions of quartz in kyanite and garnet usually retain features of their high-pressure origin. According to thermobarometric calculations, the studied eclogitic suite was equilibrated within lithospheric mantle at 3.2-4.9 GPa and 813-1080 °C. The precursor composition of garnets from Udachnaya and Zarnitsa eclogites suggests their stability at depths 210-260 km. Apatite precipitation in clinopyroxenes of Udachnaya and Zarnitsa allows us to declare that original pyroxenes could have been indicative of their high P-T stability. Raman spectroscopic study of quartz and coesite precipitates in garnet porphyroblasts confirms our hypothesis on the origin of the exsolution textures during pressure-temperature decrease. With respect to mineralogical data, we suppose the rocks to be subjected to stepwise decompression and cooling within mantle reservoir.

  5. Apatite-type SrPr(4)(SiO(4))(3)O.

    PubMed

    Sakakura, Terutoshi; Kamoshita, Minami; Iguchi, Hironaga; Wang, Jun; Ishizawa, Nobuo

    2010-08-25

    Single crystals of the title compound, strontium tetra-praseo-dymium tris-(silicate) oxide, SrPr(4)(SiO(4))(3)O, have been grown by the self-flux method using SrCl(2). The structure is isotypic with the apatite supergroup family having the generic formula (IX)M1(2) (VII)M2(3)((IV)TO(4))(3)X, where M = alkaline earth and rare earth metals, T = Si and X = O. The M1 site (3.. symmetry) is occupied by Pr and Sr atoms with almost even proportions and is surrounded by nine O atoms forming a tricapped trigonal prism. The M2 site (m.. symmetry) is almost exclusively occupied by Pr and surrounded by seven O atoms, forming a distorted penta-gonal bipyramid. The Si atom (m.. symmetry) is surrounded by two O (m.. symmetry) and two O atoms in general positions, forming an isolated SiO(4) tetra-hedron. Another O atom at the inversion centre (.. symmetry) is surrounded by three M2 sites, forming an equilateral triangle perpendicular to the c axis.

  6. Oxygen isotopes from biogenic apatites suggest widespread endothermy in Cretaceous dinosaurs

    NASA Astrophysics Data System (ADS)

    Amiot, Romain; Lécuyer, Christophe; Buffetaut, Eric; Escarguel, Gilles; Fluteau, Frédéric; Martineau, François

    2006-06-01

    The much debated question of dinosaur thermophysiology has not yet been conclusively solved despite numerous attempts. We used the temperature-dependent oxygen isotope fractionation between vertebrate body water (δ 18O body water) and phosphatic tissues (δ 18O p) to compare the thermophysiology of dinosaurs with that of non-dinosaurian ectothermic reptiles. Present-day δ 18O p values of vertebrate apatites show that ectotherms have higher δ 18O p values than endotherms at high latitudes due to their lower body temperature, and conversely lower δ 18O p values than endotherms at low latitudes. Using a data set of 80 new and 49 published δ 18O p values, we observed similar and systematic differences in δ 18O p values (Δ 18O) between four groups of Cretaceous dinosaurs (theropods, sauropods, ornithopods and ceratopsians) and associated fresh water crocodiles and turtles. Expressed in terms of body temperatures ( Tb), these Δ 18O values indicate that dinosaurs maintained rather constant Tb in the range of endotherms whatever ambient temperatures were. This implies that high metabolic rates were widespread among Cretaceous dinosaurs belonging to widely different taxonomic groups and suggest that endothermy may be a synapomorphy of dinosaurs, or may have been acquired convergently in the studied taxa.

  7. Effects of fluoride on the interactions between amelogenin and apatite crystals.

    PubMed

    Tanimoto, K; Le, T; Zhu, L; Chen, J; Featherstone, J D B; Li, W; DenBesten, P

    2008-01-01

    Fluorosed enamel is more porous and less mineralized, possibly related to altered amelogenin-modulated crystal growth. The purpose of this study was to examine the role of fluoride in interactions between amelogenin and apatite crystals. Recombinant human amelogenin (rh174) was bound to carbonated hydroxyapatite containing various amounts of fluoride, and analyzed by protein assay, SDS PAGE, and AFM. Interactions between rh174 and fluoride were assayed by isothermal titration calorimetry (ITC). The initial binding rate of rh174, as well as total amount of rh174 bound to fluoride-containing carbonated hydroxyapatite, was greater than that in the control carbonated hydroxyapatite. Fluoride in solution at physiologic (5.3 micromolar, or 0.1 ppm) concentrations showed no significant effect on binding, but higher fluoride levels significantly decreased protein binding. ITC showed no interactions between fluoride and rh174. These results suggest that fluoride incorporation into the crystal lattice alters the crystal surface to enhance amelogenin binding, with no direct interactions between fluoride and amelogenin.

  8. Characterizations of Bone-Like Apatite Powder Fabricated Using Modified Simulated Body Fluid.

    PubMed

    An, Ji-Hae; Han, Ok-Seong; Kohn, David H; Park, Yeong-Joon; Song, Ho-Jun

    2015-08-01

    The objective of this study is to fabricate bone-like apatite (BLAp) powder using the modified simulated body fluid (SBF). The SBF2X and SBF4X groups were prepared by increasing the concentration of inorganic ions by two and four times, respectively, to that of the standard SBF. The mSBF4X group was prepared by particularly increasing the concentrations of calcium and phosphate ions in SBF. Bovine serum albumin (BSA) was added for SBF2X-BSA, SBF4X-BSA, and mSBF4X-BSA groups. BLAp powders were precipitated in these SBFs while being kept at 60 °C. Micro-morphology of BLAp powders showed tens of micrometers-sized rounded clusters which composed with sheet-like nano crystallites. The radius of BLAp clusters were decreased by increasing the concentration of inorganic ions and by incorporating the BSA. The hydroxyapatite crystalline structure was dominant for all sample groups. Further, octacalcium phosphate structure was detected in the mSBF4X group. However, these peaks were decreased in mSBF4X-BSA. FT-IR spectra demonstrated that BSA was co-precipitated in BLAp crystallites, and the amount of BSA was higher in the mSBF4X-BSA group than in the SBF4X-BSA group.

  9. Magmatic origin of giant ‘Kiruna-type’ apatite-iron-oxide ores in Central Sweden

    PubMed Central

    Jonsson, Erik; Troll, Valentin R.; Högdahl, Karin; Harris, Chris; Weis, Franz; Nilsson, Katarina P.; Skelton, Alasdair

    2013-01-01

    Iron is the most important metal for modern industry and Sweden is by far the largest iron-producer in Europe, yet the genesis of Sweden's main iron-source, the ‘Kiruna-type’ apatite-iron-oxide ores, remains enigmatic. We show that magnetites from the largest central Swedish ‘Kiruna-type’ deposit at Grängesberg have δ18O values between −0.4 and +3.7‰, while the 1.90−1.88 Ga meta-volcanic host rocks have δ18O values between +4.9 and +9‰. Over 90% of the magnetite data are consistent with direct precipitation from intermediate to felsic magmas or magmatic fluids at high-temperature (δ18Omgt > +0.9‰, i.e. ortho-magmatic). A smaller group of magnetites (δ18Omgt ≤ +0.9‰), in turn, equilibrated with high-δ18O, likely meteoric, hydrothermal fluids at low temperatures. The central Swedish ‘Kiruna-type’ ores thus formed dominantly through magmatic iron-oxide precipitation within a larger volcanic superstructure, while local hydrothermal activity resulted from low-temperature fluid circulation in the shallower parts of this system. PMID:23571605

  10. New bismuth calcium oxysilicate with apatite structure: Synthesis and structural characterization

    SciTech Connect

    Uvarov, Vladimir; Shenawi-Khalil, Sanaa; Popov, Inna

    2010-07-15

    New bismuth calcium silicon oxide Ca{sub 4}Bi{sub 4.3}(SiO{sub 4})(HSiO{sub 4}){sub 5}O{sub 0.95}, with apatite structure has been synthesized. The structure was refined from powder X-ray diffraction data. The refinement revealed that the phase has P6{sub 3}/m (176) space group with unit cell parameters a=b=9.6090(7) A, c=7.0521(7) A, V=563.9 A{sup 3} and c/a=0.734. The R{sub wp} factor at Rietveld refinement was equal to 0.082. The synthesized phase has an unusual quantity of cation vacancies in a crystal lattice. Mechanisms of compensation of the excess charge of a lattice are considered and checked experimentally using the FT-IR spectroscopy, the thermal analysis and the XPS analysis. - Graphical abstract: The fragment Ca{sub 4}Bi{sub 4.3}(SiO{sub 4})(HSiO{sub 4}){sub 5}O{sub 0.95} structure along c-axis in polygonal mode.

  11. REE partitioning between apatite and melt in a peralkaline volcanic suite, Kenya Rift Valley

    USGS Publications Warehouse

    Macdonald, R.; Baginski, B.; Belkin, H.E.; Dzierzanowski, P.; Jezak, L.

    2009-01-01

    Electron microprobe analyses are presented for fluorapatite phenocrysts from a benmoreite-peralkaline rhyolite volcanic suite from the Kenya Rift Valley. The rocks have previously been well characterized petrographically and their crystallization conditions are reasonably well known. The REE contents in the M site increase towards the rhyolites, with a maximum britholite component of ~35 mol.%. Chondrite-normalized REE patterns are rather flat between La and Sm and then decrease towards Yb. Sodium and Fe occupy up to 1% and 4%, respectively, of the M site. The major coupled substitution is REE3+ + Si4+ ??? Ca2+ + P5+. The substitution REE3+ + Na+ ??? 2Ca2+ has been of minor importance. The relatively large Fe contents were perhaps facilitated by the low fo2 conditions of crystallization. Zoning is ubiquitous and resulted from both fractional crystallization and magma mixing. Apatites in some rhyolites are relatively Y-depleted, perhaps reflecting crystallization from melts which had precipitated zircon. Mineral/glass (melt) ratios for two rhyolites are unusually high, with maxima at Sm (762, 1123). ?? 2008 The Mineralogical Society.

  12. Proliferation and differentiation of osteoblast-like cells on apatite-wollastonite/polyethylene composites.

    PubMed

    Rea, S M; Brooks, R A; Best, S M; Kokubo, T; Bonfield, W

    2004-08-01

    Glass-ceramic apatite-wollastonite (A-W)/high-density polyethylene composite (AWPEX) materials have been designed to match the mechanical strength of human cortical bone and to provide favourable bioactivity, with potential use in many orthopaedic applications. To better understand AWPEX properties, the effects of surface finish and ceramic filler size and content on osteoblast-like cell attachment, proliferation, and differentiation were examined. Glass-ceramic content was tested at 30 and 50 vol% and median particle size at 4.5 and 7.7 microm. Samples were prepared as 1 x 10 x 10 mm(3) tiles with polished or rough surfaces, sterilized by gamma irradiation (2.5 Mrad), and characterized by scanning electron microscopy (SEM) and surface profilometry. Saos-2 human osteoblast-like cells were cultured on each surface at an initial concentration of 4500 cells/cm(2) for 1, 3, or 7 days. At each time point, adenosine triphosphate and alkaline phosphatase levels were measured to assess cell number and osteoblast differentiation. SEM imaging of cells on the composite surfaces showed preferential cell attachment to filler particles within the polymer matrix. Significant biochemical assay differences were found at 7 days, confirmed by ANOVA post-hoc testing using Bonferroni's correction. Overall, increased exposure of the glass-ceramic A-W phase in AWPEX through surface polishing, higher volume fraction and/or larger particle size was found to lead to an improved cell response.

  13. Long-term exhumation history of the Inner Mongolian Plateau constrained by apatite fission track analysis

    NASA Astrophysics Data System (ADS)

    Li, Ke; Jolivet, Marc; Zhang, Zhicheng; Li, Jianfeng; Tang, Wenhao

    2016-01-01

    The Inner Mongolian Plateau, along the southeastern flank of the wider Mongolian Plateau, is a vast undulating surface ranging in elevation between 900 and 1500 m above sea level. The peculiar topography of this area is assumed to be closely related to its complex tectono-thermal evolution since Late Paleozoic. The lithospheric structure of the Plateau includes three continental blocks: the Mandula and the Bart Obo blocks form the southern margin of the Central Asian Orogenic Belt in that area, and to the south, the Plateau includes the northern margin of the North China Craton. Apatite fission track (AFT) ages and track length distributions from 13 basement outcrops situated in the main tectonic blocks forming the Inner Mongolian Plateau were determined in order to reconstruct its denudation history. The thermal histories inferred from these data imply multi-phased, differential exhumation/burying processes from the Late Paleozoic to the Early Cretaceous. This complex thermal history is largely related to the Early/Middle Triassic closure of the Paleo-Asian Ocean, the Jurassic closure of the Mongol-Okhotsk Ocean, and the Early Cretaceous orogenic collapse of the Mongol-Okhotsk belt. Finally, since Late Cretaceous, no further major tectonic movement occurred and the Inner Mongolian Plateau has been largely peneplained.

  14. Innovative delivery of siRNA to solid tumors by super carbonate apatite.

    PubMed

    Wu, Xin; Yamamoto, Hirofumi; Nakanishi, Hiroyuki; Yamamoto, Yuki; Inoue, Akira; Tei, Mitsuyoshi; Hirose, Hajime; Uemura, Mamoru; Nishimura, Junichi; Hata, Taishi; Takemasa, Ichiro; Mizushima, Tsunekazu; Hossain, Sharif; Akaike, Toshihiro; Matsuura, Nariaki; Doki, Yuichiro; Mori, Masaki

    2015-01-01

    RNA interference (RNAi) technology is currently being tested in clinical trials for a limited number of diseases. However, systemic delivery of small interfering RNA (siRNA) to solid tumors has not yet been achieved in clinics. Here, we introduce an in vivo pH-sensitive delivery system for siRNA using super carbonate apatite (sCA) nanoparticles, which is the smallest class of nanocarrier. These carriers consist simply of inorganic ions and accumulate specifically in tumors, yet they cause no serious adverse events in mice and monkeys. Intravenously administered sCA-siRNA abundantly accumulated in the cytoplasm of tumor cells at 4 h, indicating quick achievement of endosomal escape. sCA-survivin-siRNA induced apoptosis in HT29 tumors and significantly inhibited in vivo tumor growth of HCT116, to a greater extent than two other in vivo delivery reagents. With innovative in vivo delivery efficiency, sCA could be a useful nanoparticle for the therapy of solid tumors.

  15. A glucose carbonate apatite complex exhibits in vitro and in vivo anti-tumour effects.

    PubMed

    Yamamoto, Hirofumi; Wu, Xin; Nakanishi, Hiroyuki; Yamamoto, Yuki; Uemura, Mamoru; Hata, Taishi; Nishimura, Junichi; Takemasa, Ichiro; Mizushima, Tsunekazu; Sasaki, Jun-Ichi; Imazato, Satoshi; Matsuura, Nariaki; Doki, Yuichiro; Mori, Masaki

    2015-01-13

    Tumour targeting nanotechnology has recently made therapeutic progress and several therapeutic nanoparticles have been approved for clinical application. However, an ideal nanotechnology based therapeutic for solid tumours, particularly for systemic administration, still remains a challenge in clinical cancer therapy. We previously reported a pH sensitive in vivo delivery system of doxorubicin, or microRNA, using carbonate apatite (CA) nanoparticles. To further explore utility of CA in cancer therapy, we attempted to transport excess glucose into tumour cells by conjugating glucose (Glc) to the nanoparticle. Despite the non-toxicity of CA and Glc, the complex (CA-[Glc]) exhibited an unexpected anti-cancer effect in vitro and in vivo. CA-[Glc] significantly reduced the growth of colon cancer cell lines. Intravenous injections successfully suppressed solid tumour growth. In mice and monkeys, intravenously injected CA-[Glc] complex resulted in no serious abnormalities in body weight or blood chemistry. Because cancer cells intensively metabolise glucose than normal cells, treatment of cancer using glucose seems paradoxical. However, with the aid of CA, this safe and 'sweet' complex may be a novel anti-cancer reagent.

  16. The function of Sn(II)-apatite as a Tc immobilizing agent

    SciTech Connect

    Asmussen, R. Matthew; Neeway, James J.; Lawter, Amanda R.; Levitskaia, Tatiana G.; Lukens, Wayne W.; Qafoku, Nikolla P.

    2016-11-01

    Technetium-99 is a radioactive contaminant of high concern at many nuclear waste storage sites. At the U.S. Department of Energy Hanford Site, 99Tc is a component of low-activity waste (LAW) fractions of the nuclear tank waste, which are highly caustic, high ionic strength and have high concentrations of chromate. Removal of 99Tc from LAW streams would greatly benefit the site remediation process. In this study, we investigated the removal of 99Tc(VII), as pertechnetate, from deionized water (DIW) and a LAW simulant using two solid sorbents, tin (II) apatite (Sn-A) and SnCl2 through batch sorption testing and solid phase characterization. Sn-A showed higher levels of removal of Tc from both DIW and LAW simulant compared with the SnCl2. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/XEDS) and X-ray adsorption spectroscopy (XAS) of Sn-A following batch experiments in DIW showed that TcO4- is reduced to Tc(IV) on the Sn-A surface with no incorporation into the lattice structure of Sn-A. The performance of Sn-A in the LAW simulant was lowered due to a combined effect of the high alkalinity, which lead to an increased dissolution of Sn from the Sn-A, and a preference for the reduction of Cr(VI) over Tc(VII).

  17. Effects of PLGA reinforcement methods on the mechanical property of carbonate apatite foam.

    PubMed

    Munar, Girlie M; Munar, Melvin L; Tsuru, Kanji; Ishikawa, Kunio

    2014-01-01

    The purpose of this study was to improve the mechanical property of brittle carbonate apatite (CO3Ap) foam aimed as bone substitute material by reinforcement with poly(DL-lactide-co-glycolide) (PLGA). The CO3Ap foam was reinforced with PLGA by immersion and vacuum infiltration methods. Compressive strength of CO3Ap foam (12.0±4.9 kPa) increased after PLGA reinforcement by immersion (187.6±57.6 kPa) or vacuum infiltration (407.0±111.4 kPa). Scanning electron microscopic (SEM) observation showed a gapless PLGA and CO3Ap foam interface and larger amount of PLGA inside the hollow space of the strut when vacuum infiltration method was employed. In contrast a gap was observed at the PLGA and CO3Ap foam interface and less amount of PLGA inside the hollow space of the strut when immersion method was employed. Strong PLGA-CO3Ap foam interface and larger amount of PLGA inside the hollow space of the strut is therefore the key to higher mechanical property obtained for CO3Ap foam when vacuum infiltration was employed for PLGA reinforcement.

  18. Ameloblastin-rich enamel matrix favors short and randomly oriented apatite crystals.

    PubMed

    Lu, Xuanyu; Ito, Yoshihiro; Kulkarni, Ashok; Gibson, Carolyn; Luan, Xianghong; Diekwisch, Thomas G H

    2011-12-01

    Molecular evolution studies suggest that amelogenin (AMELX), the principal component of the mammalian enamel matrix, emerged considerably later than ameloblastin (AMBN), and enamelin. Here, we created a transgenic mouse model to ask the question how a conceivable basal enamel lacking AMELX and enriched in the more basal AMBN might compare with recent mouse enamel. To answer this question we overexpressed AMBN using a keratin 14 (K14) promoter and removed AMELX from the genetic background by crossbreeding with amelx(-/-) mice. Enamel coverings of amelx(-/-) mice and of the squamate Iguana iguana were used for comparison. Scanning electron microscopic analysis documented that AMBN transgenic (TG) × amelx(-/-) mouse molars were covered by a 5 μm thin 'enameloid' layer resembling the thin enamel of the Iguana squamate. Transmission electron microscopy revealed that the enamel of developing AMBN TG × amelx(-/-) mouse molars contained short (approximately 70 nm) and randomly oriented crystals, while WT controls, AMBN overexpressors, and AMELX(-/-) mice all featured elongated and parallel oriented crystals measuring between 300 and 600 nm in average length. Together, these studies illustrate that AMBN promotes the growth of a crystalline enamel layer with short and randomly oriented crystals, but lacks the ability to facilitate the formation of long and parallel oriented apatite crystals.

  19. The function of Sn(II)-apatite as a Tc immobilizing agent

    NASA Astrophysics Data System (ADS)

    Asmussen, R. Matthew; Neeway, James J.; Lawter, Amanda R.; Levitskaia, Tatiana G.; Lukens, Wayne W.; Qafoku, Nikolla P.

    2016-11-01

    At the U.S. Department of Energy Hanford Site, Tc-99 is a component of low-activity waste (LAW) fractions of the nuclear tank waste and removal of Tc from LAW streams would greatly benefit the site remediation process. In this study, we investigated the removal of Tc(VII), as pertechnetate, from deionized water (DIW) and a LAW simulant through batch sorption testing and solid phase characterization using tin (II) apatite (Sn-A) and SnCl2. Sn-A showed higher levels of Tc removal from both DIW and LAW simulant. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/XEDS) and X-ray absorption spectroscopy (XAS) of reacted Sn-A in DIW showed that TcO4- is reduced to Tc(IV) on the Sn-A surface. The performance of Sn-A in the LAW simulant was lowered due to a combined effect of the high alkalinity, which lead to an increased dissolution of Sn from the Sn-A, and a preference for the reduction of Cr(VI).

  20. Magmatic origin of giant 'Kiruna-type' apatite-iron-oxide ores in central Sweden.

    PubMed

    Jonsson, Erik; Troll, Valentin R; Högdahl, Karin; Harris, Chris; Weis, Franz; Nilsson, Katarina P; Skelton, Alasdair

    2013-01-01

    Iron is the most important metal for modern industry and Sweden is by far the largest iron-producer in Europe, yet the genesis of Sweden's main iron-source, the 'Kiruna-type' apatite-iron-oxide ores, remains enigmatic. We show that magnetites from the largest central Swedish 'Kiruna-type' deposit at Grängesberg have δ(18)O values between -0.4 and +3.7‰, while the 1.90-1.88 Ga meta-volcanic host rocks have δ(18)O values between +4.9 and +9‰. Over 90% of the magnetite data are consistent with direct precipitation from intermediate to felsic magmas or magmatic fluids at high-temperature (δ(18)Omgt > +0.9‰, i.e. ortho-magmatic). A smaller group of magnetites (δ(18)Omgt ≤ +0.9‰), in turn, equilibrated with high-δ(18)O, likely meteoric, hydrothermal fluids at low temperatures. The central Swedish 'Kiruna-type' ores thus formed dominantly through magmatic iron-oxide precipitation within a larger volcanic superstructure, while local hydrothermal activity resulted from low-temperature fluid circulation in the shallower parts of this system.

  1. Bisphosphonate binding affinity as assessed by inhibition of carbonated apatite dissolution in vitro

    PubMed Central

    Henneman, Zachary J.; Nancollas, George H.; Ebetino, F. Hal; Russell, R. Graham G.; Phipps, Roger J.

    2009-01-01

    Bisphosphonates (BPs), which display a high affinity for calcium phosphate surfaces, are able to selectively target bone mineral, where they are potent inhibitors of osteoclast-mediated bone resorption. The dissolution of synthetic hydroxyapatite (HAP) has been used previously as a model for BP effects on natural bone mineral. The present work examines the influence of BPs on carbonated apatite (CAP), which mimics natural bone more closely than does HAP. Constant composition dissolution experiments were performed at pH 5.50, physiological ionic strength (0.15M) and temperature (37°C). Selected BPs were added at (0.5 × 10−6) to (50.0 × 10−6)M, and adsorption affinity constants, KL, were calculated from the kinetics data. The BPs showed concentration-dependent inhibition of CAP dissolution, with significant differences in rank order zoledronate > alendronate > risedronate. In contrast, for HAP dissolution at pH 5.50, the differences between the individual BPs were considerably smaller. The extent of CAP dissolution was also dependent on the relative undersaturation, σ, and CAP dissolution rates increased with increasing carbonate content. These results demonstrate the importance of the presence of carbonate in mediating the dissolution of CAP, and the possible involvement of bone mineral carbonate in observed differences in bone affinities of BPs in clinical use. PMID:17907244

  2. In vivo biocompatibility of custom-fabricated apatite-wollastonite-mesenchymal stromal cell constructs.

    PubMed

    Lee, Jennifer A; Knight, Charlotte A; Kun, Xiao; Yang, Xuebin B; Wood, David J; Dalgarno, Kenneth W; Genever, Paul G

    2015-10-01

    We have used the additive manufacturing technology of selective laser sintering (SLS), together with post SLS heat treatment, to produce porous three dimensional scaffolds from the glass-ceramic apatite-wollastonite (A-W). The A-W scaffolds were custom-designed to incorporate a cylindrical central channel to increase cell penetration and medium flow to the center of the scaffolds under dynamic culture conditions during in vitro testing and subsequent in vivo implantation. The scaffolds were seeded with human bone marrow mesenchymal stromal cells (MSCs) and cultured in spinner flasks. Using confocal and scanning electron microscopy, we demonstrated that MSCs formed and maintained a confluent layer of viable cells on all surfaces of the A-W scaffolds during dynamic culture. MSC-seeded, with and without osteogenic pre-differentiation, and unseeded A-W scaffolds were implanted subcutaneously in MF1 nude mice where osteoid formation and tissue in-growth were observed following histological assessment. The results demonstrate that the in vivo biocompatibility and osteo-supportive capacity of A-W scaffolds can be enhanced by SLS-custom design, without the requirement for osteogenic pre-induction, to advance their potential as patient-specific bone replacement materials.

  3. Biomimetic formation of apatite on the surface of porous gelatin/bioactive glass nanocomposite scaffolds

    NASA Astrophysics Data System (ADS)

    Mozafari, Masoud; Rabiee, Mohammad; Azami, Mahmoud; Maleknia, Saied

    2010-12-01

    There have been several attempts to combine bioactive glasses (BaGs) with biodegradable polymers to create a scaffold material with excellent biocompatibility, bioactivity, biodegradability and toughness. In the present study, the nanocomposite scaffolds with compositions based on gelatin (Gel) and BaG nanoparticles in the ternary SiO 2-CaO-P 2O 5 system were prepared. In vitro evaluations of the nanocomposite scaffolds were performed, and for investigating their bioactive capacity these scaffolds were soaked in a simulated body fluid (SBF) at different time intervals. The scaffolds showed significant enhancement in bioactivity within few days of immersion in SBF solution. The apatite formation at the surface of the nanocomposite samples confirmed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray powder diffraction (XRD) analyses. In vitro experiments with osteoblast cells indicated an appropriate penetration of the cells into the scaffold's pores, and also the continuous increase in cell aggregation on the bioactive scaffolds with increase in the incubation time demonstrated the ability of the scaffolds to support cell growth. The SEM observations revealed that the prepared scaffolds were porous with three dimensional (3D) and interconnected microstructure, pore size was 200-500 μm and the porosity was 72-86%. The nanocomposite scaffold made from Gel and BaG nanoparticles could be considered as a highly bioactive and potential bone tissue engineering implant.

  4. Intense turquoise colors of apatite-type compounds with Mn5+ in tetrahedral coordination

    NASA Astrophysics Data System (ADS)

    Medina, Elena A.; Li, Jun; Stalick, Judith K.; Subramanian, M. A.

    2016-02-01

    The solid solutions of chlorapatite compounds Ba5Mn3-xVxO12Cl (x = 0-3.0) and Ba5Mn3-xPxO12Cl (x = 0-3.0) have been synthesized through solid state reactions and Pechini or sol-gel method using citric acid. The colors of the samples change from white (x = 3.0) through turquoise (x = 1.5) to dark green (x = 0) with increasing amount of manganese. Optical measurements reveal that the origin of the color is presumably a combination of d-d transitions of Mn5+ and cation-anion charge transfer from transition metals to oxygens. Near IR reflectance measurements indicate that synthesized compounds are promising materials for "cool pigments" applications. Magnetic measurements verify that manganese has two unpaired electrons and exhibits 5 + oxidation state. The IR spectra change systematically with sample compositions and the fingerprint region (700 cm-1 to 1100 cm-1) indicates characteristic bands belonging to (MnO4)3-, (VO4)3- and (PO4)3- functional groups. Structure refinements using neutron data confirm that Mn5+, V5+ and P5+ cations occupy the tetrahedral sites in the apatite structure.

  5. Bioactive glasses with improved processing. Part 1. Thermal properties, ion release and apatite formation.

    PubMed

    Groh, Daniel; Döhler, Franziska; Brauer, Delia S

    2014-10-01

    Bioactive glasses, particularly Bioglass® 45S5, have been used to clinically regenerate human bone since the mid-1980s; however, they show a strong tendency to undergo crystallization upon heat treatment, which limits their range of applications. Attempts at improving their processing (by reducing their tendency to crystallize) have included increasing their silica content (and thus their network connectivity), incorporating intermediate oxides or reducing their phosphate content, all of which reduce glass bioactivity. Therefore, bioactive glasses known for their good processing (e.g. 13-93) are considerably less bioactive. Here, we investigated if the processing of 45S5 bioactive glass can be improved while maintaining its network connectivity and phosphate content. The results show that, by increasing the calcium:alkali cation ratio, partially substituting potassium for sodium (thereby making use of the mixed alkali effect) and adding small amounts of fluoride, bioactive glasses can be obtained which have a larger processing window (suggesting that they can be processed more easily, allowing for sintering of scaffolds or drawing into fibres) while degrading readily and forming apatite in aqueous solution within a few hours.

  6. Nanostructured materials based on mesoporous silica and mesoporous silica/apatite as osteogenic growth peptide carriers.

    PubMed

    Mendes, L S; Saska, S; Martines, M A U; Marchetto, R

    2013-10-01

    The aim of this work was the preparation of inorganic mesoporous materials from silica, calcium phosphate and a nonionic surfactant and to evaluate the incorporation and release of different concentrations of osteogenic growth peptide (OGP) for application in bone regeneration. The adsorption and release of the labeled peptide with 5,6-carboxyfluorescein (OGP-CF) from the mesoporous matrix was monitored by fluorescence spectroscopy. The specific surface area was 880 and 484 m(2) g(-1) for pure silica (SiO) and silica/apatite (SiCaP), respectively; the area influenced the percentage of incorporation of the peptide. The release of OGP-CF from the materials in simulated body fluid (SBF) was dependent on the composition of the particles, the amount of incorporated peptide and the degradation of the material. The release of 50% of the peptide content occurred at around 4 and 30 h for SiCaP and SiO, respectively. In conclusion, the materials based on SiO and SiCaP showed in vitro bioactivity and degradation; thus, these materials should be considered as alternative biomaterials for bone regeneration.

  7. Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration.

    PubMed

    Fuller, C C; Bargar, J R; Davis, J A

    2003-10-15

    Uranium binding to bone charcoal and bone meal apatite materials was investigated using U L(III)-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 < or = 5500 microg 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 > or = 5500 microg 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 microg 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

  8. 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

  9. Growth and dissolution of apatite precipitates formed in vivo on the surface of a bioactive glass coating film and its relevance to bioactivity

    NASA Astrophysics Data System (ADS)

    Jallot, E.; Benhayoune, H.; Kilian, L.; Irigaray, J. L.; Balossier, G.; Bonhomme, P.

    2000-11-01

    Development of bioactive glasses for use as a coating on Ti6Al4V prostheses requires a better understanding of reactions at the bone/bioactive glass interface. Indeed, the bioactive glasses bond to bone through physico-chemical reactions. In vivo, an apatite rich layer is built up on top of a pure silica rich layer at the bioactive glass periphery. In this paper, we have studied Ti6Al4V cylinders coated with a bioactive glass and implanted in sheep femora for two, three and six months. At each time period, the samples were analysed with scanning transmission electron microscopy coupled with energy dispersive x-ray spectroscopy. In vivo, the bioactive glass dissolution led to the formation on its surface of spherical particles with different sizes. The distributions of Si, Al, Ca, P and Mg concentrations across the particles reveal precipitation of apatite with the incorporation of magnesium. Apatite precipitation is governed by diffusion through an Si layer and occurs under specific supersaturation conditions. Measurements of supersaturation for Ca and P demonstrate that the largest precipitates grow and the smallest dissolve. These results allow us to study the growth and dissolution rate of the apatite precipitates and their relevance to bioactivity. Particles with a radius twice the average radius () grow the fastest and, if the radius increases, the rate of growth decreases. Before three months, the growth of apatite precipitates (≈1 µm) leads to the growth of a Ca-P interfacial layer. After three months, is of the order of 0.5 µm, and the majority of the apatite layer dissolves. The effects of aluminium and magnesium on apatite generation are also studied.

  10. Insight into He diffusion in apatite by ion beam experiments and quantum calculations: implication for the (U-Th)/He thermochronometer

    NASA Astrophysics Data System (ADS)

    Gautheron, C.; Mbongo-Djimbi, D.; Gerin, C.; Roques, J.; Bachelet, C.; Oliviero, E.; Tassan-Got, L.

    2015-12-01

    The apatite (U-Th)/He (AHe) system has rapidly become a very popular thermochronometer, however, interpretation of AHe age depends on a precise knowledge of He diffusion. Several studies suggest that He retention is function of the amount of damage that is controlled by U-Th concentration, grain chemistry and thermal history. Still, the models are not well constrained and do not fully explain the mechanism of He retention. In order to have a deeper insight into this issue, a multidisciplinary study on apatite combining physical methods such as multi-scale theoretical diffusion calculations based on Density Functional Theory (DFT) with diffusion experiments by ion beam Elastic Recoil Diffusion Analysis (ERDA) were performed. Quantum calculations permit to quantify He diffusivity base level for damage-free crystal and to estimate the additional energy cost to extract He atoms trapped in point defects (i.e. vacancies). On the other hand ion beam ERDA experiments allow to measure He diffusivity in artificially damaged crystals. We show that damage-free apatite crystals are characterized by low retention behavior and closure temperature of ~35°C for pure F-apatite to higher value for Cl rich apatite (up to 12°C higher), for typical grain size and cooling rate (Mbongo-Djimbi et al., 2015). Our computed closure temperature is slightly lower than previously reported experimental values (~50°C). Using ERDA and DFT modeling of damage, we show how He diffusivity is influenced by damage. Finally, we are able to propose a new modeling of He diffusion incorporating mechanisms not included in classical damage models, and taking into account the level of damage and apatite chemistry. We show that it could affect significantly AHe age interpretation. Mbongo-Djimbi D. et al. 2015. Apatite composition effect on (U-Th)/He thermochronometer: an atomistic point of view. Geohimica Cosmochim. Acta.

  11. Inhibition of precipitation of carbonate apatite by trisodium citrate analysed in base of the formation of chemical complexes in growth solution

    SciTech Connect

    Prywer, Jolanta; Olszynski, Marcin; Mielniczek-Brzóska, Ewa

    2015-11-15

    Effect of trisodium citrate on the precipitation of carbonate apatite is studied. The experimental series are performed in the solution of artificial urine. The investigations are related to infectious urinary stones formation as carbonate apatite is one of the main components of this kind of stones. To mimic a real infection in urinary tract the aqueous ammonia solution was added to the solution of artificial urine. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to carbonate apatite formation and decreases the efficiency of carbonate apatite precipitation. The inhibitory effect of trisodium citrate on the precipitation of carbonate apatite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is mainly related with the fact that trisodium citrate binds Ca{sup 2+} ions and causes the formation of CaCit{sup −} and Ca{sub 10}(PO{sub 4}){sub 6}CO{sub 3} complexes. Trisodium citrate binds Ca{sup 2+} ions in the range of pH from 6 to 9.5 for which carbonate apatite is favored to be formed. - Highlights: • Trisodium citrate (TC) increases induction time of carbonate apatite (CA) formation. • TC decreases the efficiency of CA precipitation. • The inhibitory effect of TC is explained in base of chemical speciation analysis. • The inhibitory effect is mainly related with the fact that TC binds Ca{sup 2+} ions. • TC binds Ca{sup 2+} ions in the range of pH from 6 to 9.5 for which CA is formed.

  12. Premixed, injectable PLA-modified calcium deficient apatite biocement (cd-AB) with washout resistance.

    PubMed

    Wu, Fan; Ngothai, Yung; Wei, Jie; Liu, Changsheng; O'Neill, Brian; Wu, Yuequn

    2012-04-01

    By using a non-aqueous solution as the mixing liquid, the washout resistance of the calcium deficient apatite biocement (cd-AB) was significantly improved, over that of the conventional method of using cd-AB with water as the liquid phase. In this study, premixed and injectable cd-AB was prepared, which had the advantage of being stable in the syringe and hardens only after being delivered to the defect area. The cd-AB powder with a Ca/P ratio of 1.5 consists of a mixture of tetracalcium phosphate (TTCP) and dicalcium phosphate anhydrous (DCPA). A solution of polylactide (PLA) in N-methyl-2-pyrrolidone (NMP) was used as the liquid phase of the premixed cd-AB. The premixed cd-AB paste injected into an aqueous environment exhibited excellent washout resistance. The premixed cd-AB had longer setting time and lower compressive strength than conventional cd-AB. The hydration products of premixed cd-AB were a mixture of calcium deficient hydroxyapatite (cd-HA) and PLA. In vitro Tris-HCl immersion tests demonstrated that the premixed cd-AB could be degradable. The results revealed that the premixed cd-AB was cytocompatible and had no adverse effects on the attachment and proliferation of MG-63 osteoblast-like cells in vitro. The most distinct advantages of premixed and injectable PLA-modified cd-AB were its excellent washout resistance and in vitro degradability, suggesting that it may be a promising candidate for bone repair.

  13. Metastable equilibrium solubility behavior of carbonated apatite in the presence of solution strontium.

    PubMed

    Heslop, D D; Bi, Y; Baig, A A; Higuchi, W I

    2004-01-01

    The purpose of this study was to use the concept of metastable equilibrium solubility (MES) to describe the anomalous solubility behavior of carbonated apatite (CAP) in the presence of solution strontium. A CAP sample (4.8 wt% CO(3), synthesized at 70 degrees C) was prepared by precipitation. Baseline MES distributions were determined in a series of 0.1 M acetate buffers containing only calcium and phosphate (no strontium) over a broad range of solution conditions. In order to assess the influence of strontium, MES profiles were then determined in a similar fashion with 20, 30, 40, 50, 60, 70, and 80% of the solution calcium being replaced on an equal molar basis by solution strontium. From the compositions of the equilibrating buffer solutions, ion activity products (IAPs) of the form Ca(10-n)Sr(n)(PO(4))(6)(OH)(2) (n = 0-10) were calculated in an attempt to determine the correct function governing the dissolution of the CAP preparation. The results demonstrate the following important findings: (a) at high solution strontium/calcium ratios (i.e., when 60% or more of the solution calcium was replaced by strontium), the MES profiles in all the experiments were found to be essentially superimposable when the solution IAPs were calculated using the stoichiometry of Ca(6)Sr(4)(PO(4))(6)(OH)(2), and (b), at low solution strontium/calcium ratios (i.e., when 40% or less of the solution calcium was replaced by strontium), the stoichiometry yielding MES data superpositioning was found to be that of hydroxyapatite. When other stoichiometries were assumed, good superpositioning of the data was not possible.

  14. Relationships involving metastable equilibrium solubility, surface complexes, and crystallite disorder with carbonated apatites.

    PubMed

    Zhuang, H; Baig, A A; Zhang, N; Chhettry, A; Higuchi, W I

    2001-12-01

    Previous studies have shown that the metastable equilibrium solubility (MES) behavior of carbonated apatites (CAPs) may be described by a surface complex with the hydroxyapatite (HAP) stoichiometry in the absence of solution fluoride and by that with the fluorapatite (FAP) stoichiometry when appreciable solution fluoride is present. Studies have also shown that the magnitude of the MES is directly related to the crystallinity of the CAP. The aim of the present investigation was to examine the relationship between the CAP MES determined in the presence of solution fluoride and CAP crystallinity and to examine the effect of the change in the stoichiometry of the surface complex (from that of HAP to that of FAP) upon the relationship of the CAP MES to crystallinity. CAP samples were prepared by methods based on the precipitation of CAP from calcium phosphate solutions and the hydrolysis of dicalcium phosphate dihydrate in bicarbonate solutions. From X-ray diffraction experiments, the crystallite microstrain, and the full width at half maximum (FWHM) of the 002 reflection were determined for the CAPs. From CAP MES experiments conducted in the presence of solu tion fluoride, linear plots of the mean MES (i.e., mean pK(FAP)) values vs the crystallinity parameter (i.e., microstrain and FWHM) were obtained that yielded slopes that were essentially the same as those obtained in the absence of solution fluoride (i.e., mean pK(HAP) values vs crystallinity). This parallel finding suggests that the CAP crystallite disorder affects the energetics of the two surface complexes essentially to the same extent and provides new insight into the nature of CAP surface complexes.

  15. pH-sensitive carbonate apatite nanoparticles as DNA vaccine carriers enhance humoral and cellular immunity.

    PubMed

    He, Pan; Takeshima, Shin-nosuke; Tada, Seiichi; Akaike, Toshihiro; Ito, Yoshihiro; Aida, Yoko

    2014-10-29

    To demonstrate the potential of pH-sensitive carbonate apatite (CO₃Ap) nanoparticles as DNA vaccine carriers to enhance vaccination efficacy, we examined the humoral and cellular immune responses of C57BL/6 mice immunized with the plasmid expression vector pCI-neo encoding the full-length soluble ovalbumin (OVA) (pCI-neo-sOVA), pCI-neo-sOVA/CO₃Ap complexes, or pCI-neo/CO₃Ap complexes as a control. Mice immunized with a low dose of pCI-neo-sOVA-loaded CO₃Ap (10 μg) produced ex vivo splenocyte proliferation after stimulation with CD8 T-cell but not CD4 T-cell epitopes and a delayed-type-hypersensitivity reaction more efficiently than mice in the other groups. Furthermore, mice receiving this immunization generated the same levels of OVA-specific antibodies and interferon (IFN)-γ secretion after CD8 T-cell and CD4 T-cell epitope challenges as those in mice treated with 100 μg of free pCI-neo-sOVA, whereas mice injected with a high dose of pCI-neo-sOVA-loaded CO₃Ap (100 μg) or with control plasmids produced negligible levels of OVA-specific antibodies or IFN-γ. Therefore, our results showed that 10 μg of pCI-neo-sOVA delivered by CO₃Ap strongly elicited humoral and cellular immune responses. This study is the first to demonstrate the promising potential of CO₃Ap nanoparticles for DNA vaccine delivery.

  16. Crystallisation in apatite-mullite glass-ceramics as a function of fluorine content

    NASA Astrophysics Data System (ADS)

    Stanton, Kenneth T.; Hill, Robert G.

    2005-02-01

    Apatite-mullite glass-ceramics are materials prepared by the controlled heat-induced devitrification of glasses of suitable composition and are under investigation for applications in dentistry and orthopaedics. The glasses used here are based on a system with the composition 1.5(5- x)SiO 2·(5- x)Al 2O 3·1.5P 2O 5·(5- x)CaO· xCaF 2. The amount of fluorine in the glasses was varied to investigate the crystallisation behaviour as a function of both fluorine content and temperature. The resultant crystalline phases are fluorapatite [Ca 10(PO 4) 6F 2], mullite [Al 6Si 2O 13] and in some cases, anorthite [CaAl 2Si 2O 8]. Crystal phases were identified using X-ray diffraction (XRD) from both the surface and the bulk of heat-treated monolithic samples and scanning electron microscopy (SEM) was used to image the crystal phase morphologies. Crystallisation characteristics varied widely in terms of apparent nucleation mechanism, crystal phases formed and microstructure. In general, glasses with higher fluorine content devitrified more readily to fluorapatite (FAp) with a higher nucleation density and for glasses with an intermediate to low fluorine content there tended to be an interdependence between FAp and mullite crystallisation. A greater tendency towards anorthite formation, especially at surfaces, was observed for glasses with lower fluorine contents. Furthermore, on decreasing the fluorine content, glasses tended to crystallise by formation of FAp spherulites with increasing diameter and with greater crystal aspect ratio.

  17. The effects of silver, silicon-containing apatite towards bacteria and cell responses.

    PubMed

    Lim, Poon Nian; Shi, Zhilong; Neoh, Koon Gee; Ho, Bow; Tay, Bee Yen; Thian, Eng San

    2014-02-01

    An integrated approach is proposed to incorporate silicon and silver into hydroxyapatite (HA) to enhance the biological response and reduce implant-related infection in bone substitutes. This study examined the responses of Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacteria to silver, silicon-containing apatite (Ag,Si-HA). Scanning electron microscopy images revealed significant reduction in adherence of S. aureus and E. coli bacteria on Ag,Si-HA as compared to HA. The antibacterial property of Ag,Si-HA was shown from a 7-log reduction of S. aureus population in the test solution and on the sample's surface as compared to HA at day 7. Rapid inhibition of the adherent bacteria suggested that the antibacterial action of Ag incorporated in Ag,Si-HA could be attributed to the Ag(+) ions on the crystal surface rather than the released Ag(+) ions. Presence of Ag may influence the biological response of HA and as such, the long-term interaction between human adipose-derived mesenchymal stem cells and Ag,Si-HA was evaluated in-vitro. An alamarBlue™ assay showed higher cell proliferation for Ag,Si-HA as compared to HA from day 3 onwards. Immunofluorescence staining revealed well-spread actin cytoskeletons on Ag,Si-HA. In addition, signs of extracellular matrix secretion and biomineralization were observed on Ag,Si-HA at day 14 onwards. Results demonstrated enhanced bone differentiation on Ag,Si-HA, as indicated by a higher level of protein expressions (type 1 collagen and osteocalcin) from day 14 to 21. Therefore, the incorporation of Ag and Si complement each other by endowing HA with antibacterial property, and concurrently promoting biological performance of the cells.

  18. Enhancing Osteoconductivity of Fibrin Gels with Apatite-Coated Polymer Microspheres

    PubMed Central

    Davis, Hillary E.; Binder, Bernard Y.K.; Schaecher, Phillip; Yakoobinsky, Dana D.; Bhat, Archana

    2013-01-01

    Fibrin gels are a promising material for use in promoting bone repair and regeneration due to their ease of implant formation, tailorability, biocompatibility, and degradation by natural processes. However, these materials lack necessary osteoconductivity to nucleate calcium, integrate with surrounding bone, and promote bone formation. Polymeric substrata formed from poly(lactide-co-glycolide) (PLG) are widely used in bone tissue engineering. A carbonated apatite layer of bone-like mineral can be successfully grown on the surface of PLG microspheres after a multiday incubation process in modified simulated body fluid. Such coatings improve the osteoconductivity of the polymer, provide nucleation sites for cell-secreted calcium, and enhance the potential osseointegration with host tissue. We examined the capacity of mineralized polymeric microspheres suspended within fibrin hydrogels to enhance the osteoconductivity of fibrin gels and increase the osteogenic potential of these materials. The inclusion of microparticles, both nonmineralized and mineralized, reduced the capacity of mesenchymal stem cells (MSCs) to contract the gel. When cultured in osteogenic media, we detected a near linear increase in both calcium and phosphate incorporation in gels containing mineralized microspheres and entrapped MSCs. The osteoconductivity of acellular fibrin gels with mineralized and nonmineralized microspheres was assessed in a rodent calvarial bone defect over 12 weeks. Compared to untreated rodent calvarial bone defects, we detected significant increases in early vascularization when treated with fibrin gels, with greater vascularization, on average, occurring with gels containing microspheres. We detected a trend for increased bone mineral density in gels containing mineralized microspheres after 12 weeks. These findings demonstrate that the osteoconductivity of fibrin gels can be increased by inclusion of mineralized microspheres, but additional signals may be required to

  19. Stability and heavy metal distribution of soil aggregates affected by application of apatite, lime, and charcoal.

    PubMed

    Cui, Hongbiao; Ma, Kaiqiang; Fan, Yuchao; Peng, Xinhua; Mao, Jingdong; Zhou, Dongmei; Zhang, Zhongbin; Zhou, Jing

    2016-06-01

    Only a few studies have been reported on the stability and heavy metal distribution of soil aggregates after soil treatments to reduce the availability of heavy metals. In this study, apatite (22.3 t ha(-1)), lime (4.45 t ha(-1)), and charcoal (66.8 t ha(-1)) were applied to a heavy metal-contaminated soil for 4 years. The stability and heavy metal distribution of soil aggregates were investigated by dry and wet sieving. No significant change in the dry mean weight diameter was observed in any treatments. Compared with the control, three-amendment treatments significantly increased the wet mean weight diameter, but only charcoal treatment significantly increased the wet aggregate stability. The soil treatments increased the content of soil organic carbon, and the fraction 0.25-2 mm contained the highest content of soil organic carbon. Amendments' application slightly increased soil total Cu and Cd, but decreased the concentrations of CaCl2 -extractable Cu and Cd except for the fraction <0.053 mm. The fractions >2 and 0.25-2 mm contained the highest concentrations of CaCl2-extractable Cu and Cd, accounted for about 74.5-86.8 % of CaCl2-extractable Cu and Cd in soil. The results indicated that amendments' application increased the wet soil aggregate stability and decreased the available Cu and Cd. The distribution of available heavy metals in wet soil aggregates was not controlled by soil aggregate stability, but possibly by soil organic carbon.

  20. Biological Behavior of Osteoblast Cell and Apatite Forming Ability of the Surface Modified Ti Alloys.

    PubMed

    Zhao, Jingming; Hwang, K H; Choi, W S; Shin, S J; Lee, J K

    2016-02-01

    Titanium as one kind of biomaterials comes in direct contact with the body, making evaluation of biocompatibility an important aspect to biomaterials development. Surface chemistry of titanium plays an important role in osseointegration. Different surface modification alters the surface chemistry and result in different biological response. In this study, three kinds of mixed acid solutions were used to treat Ti specimens to induce Ca-P formation. Following a strong mixed acid activation process, Ca-P coating successfully formed on the Ti surfaces in simulated body fluid. Strong mixed acid increased the roughness of the metal surface, because the porous and rough surface allows better adhesion between Ca-P coatings and substrates. After modification of titanium surface by mixed acidic solution and subsequently H2O2/HCL treatment evaluation of biocompatibility was conducted from hydroxyapatite formation by biomimetic process and cell viability on modified titanium surface. Nano-scale modification of titanium surfaces can alter cellular and tissue responses, which may benefit osseointegration and dental implant therapy. Results from this study indicated that surface treatment methods affect the surface morphology, type of TiO2 layer formed and subsequent apatite deposition and biological responses. The thermo scientific alamarblue cell viability assay reagent is used to quantitatively measure the viability of mammalian cell lines, bacteria and fungi by incorporating a rapid, sensitive and reliable fluorometric/colorimetric growth indicator, without any toxic and side effect to cell line. In addition, mixed acid treatment uses a lower temperature and shorter time period than widely used alkali treatment.

  1. Synthesis of sodium caseinate-calcium carbonate microspheres and their mineralization to bone-like apatite

    NASA Astrophysics Data System (ADS)

    Xu, Zhewu; Liang, Guobin; Jin, Lin; Wang, Zhenling; Xing, Chao; Jiange, Qing; Zhang, Zhiguang

    2014-06-01

    Phosphoproteins can induce and stabilize calcium carbonate (CaCO3) vaterite, which has desirable features for high reactivity. The purpose of this study was to synthesize bioactive CaCO3 microspheres for bone regeneration. Sodium caseinate (NaCas)-containing CaCO3 microspheres, with the crystal phase of vaterite, were synthesized by fast precipitation in an aqueous solution of CaCl2, Na2CO3, and 2 mg/mL of NaCas. The uniform microspheres exhibited rougher surfaces and lower negative charges than CaCO3 particles without NaCas addition. Fourier-transform infrared spectroscopy (FT-IR) of the microspheres showed characteristic peaks or bands corresponding to phosphate and hydroxyl groups. Thermogravimetric analysis (TGA) curves exhibited approximately 5% weight loss below 600 °C due to the decomposition of NaCas. Scanning electron microscope (SEM) images showed lath-like hydroxyapatite (HAp) on the surface after soaking in simulated body fluid (SBF) at 37 °C for 5 and 10 days. Energy dispersive X-ray spectrometry (EDS) revealed that the agglomerates were composed of Ca, C, O, P, Na, and Mg elements, and the Ca/P ratios ranged from 1.53 to 1.56. X-ray diffraction (XRD) patterns exhibited peaks characteristic of hydroxyapatite. The results of this study demonstrated that the addition of NaCas induced the formation of vaterite microspheres which possesses an enhanced apatite formation after soaking in SBF at 37 °C for 5 and 10 days. These NaCas-CaCO3 microspheres may be a potential biomaterial for bone regeneration.

  2. Increase of apatite dissolution rate by Scots pine roots associated or not with Burkholderia glathei PML1(12)Rp in open-system flow microcosms

    NASA Astrophysics Data System (ADS)

    Calvaruso, Christophe; Turpault, Marie-Pierre; Frey-Klett, Pascale; Uroz, Stéphane; Pierret, Marie-Claire; Tosheva, Zornitza; Kies, Antoine

    2013-04-01

    The release of nutritive elements through apatite dissolution represents the main source of phosphorus, calcium, and several micronutrients (e.g., Zn, Cu) for organisms in non-fertilized forest ecosystems. The aim of this study was to quantify, for the first time, the dissolution rate of apatite grains by tree roots that were or were not associated with a mineral weathering bacterial strain, and by various acids known to be produced by tree roots and soil bacterial strains in open-system flow microcosms. In addition, we explored whether the mobilization of trace elements (including rare earth elements) upon apatite dissolution was affected by the presence of trees and associated microorganisms. The dissolution rate of apatite by Scots pine plants that were or were not inoculated with the strain Burkholderia glathei PML1(12)Rp, and by inorganic (nitric) and organic (citric, oxalic and gluconic) acids at pH 5.5, 4.8, 3.8, 3.5, 3.0, and 2.0 was monitored in two controlled experiments: "plant-bacteria interaction" and "inorganic and organic acids". Analyses of the outlet solutions in the "plant-bacteria interaction" experiment showed that Scots pine roots and B. glathei PML1(12)Rp produced protons and organic acids such as gluconate, oxalate, acetate, and lactate. The weathering budget calculation revealed that Scots pines (with or without PML1(12)Rp) significantly increased (factor > 10) the release of Ca, P, As, Sr, Zn, U, Y, and rare earth elements such as Ce, La, Nd from apatite, compared to control abiotic treatment. Scanning electron microscopy observation confirmed traces of apatite dissolution in contact of roots. Most dissolved elements were taken up by Scots pine roots, i.e., approximately 50% of Ca, 70% of P, 30% of As, 70% of Sr, 90% of Zn, and 100% of U, Y, and rare earth elements. Interestingly, no significant additional effect due to the bacterial strain PML1(12)Rp on apatite dissolution and Scots pine nutrition and growth was observed. The "inorganic

  3. Apatite trace element and halogen compositions as petrogenetic-metallogenic indicators: Examples from four granite plutons in the Sanjiang region, SW China

    NASA Astrophysics Data System (ADS)

    Pan, Li-Chuan; Hu, Rui-Zhong; Wang, Xin-Song; Bi, Xian-Wu; Zhu, Jing-Jing; Li, Chusi

    2016-06-01

    The abundances of trace elements including Sr, Ga and rare earth elements (REE) and halogens in apatite crystals from four intermediate-felsic plutons in the Zhongdian terrane in the Sanjiang region have been determined using electron microprobe and laser ablation inductively coupled plasma mass spectrometry to evaluate the potential of apatite as a petrogenic-metallogenic indicator. The selected plutons include one that is not mineralized (the Triassic Xiuwacu pluton, or the TXWC pluton), one that hosts a porphyry-type Cu deposit (the Pulang pluton, or the PL pluton), one that hosts a porphyry-type Mo deposit (the Tongchanggou pluton, or the TCG pluton), and one that hosts a vein-type Mo deposit (the Cretaceous Xiuwacu pluton, or the CXWC pluton). Except for the CXWC pluton, the other three plutons have adakite-like trace element signatures in whole rocks. The results from this study show that REE, Sr and halogens in apatite can be used to track magma compositions, oxidation states and crystallization history. Apatite crystals from the adakite-like plutons are characterized by much higher Sr/Y and δEu than the non-adakite-type pluton. This means that apatite, which is not susceptible to alteration, is a useful tool for identifying the adakite-like plutons that no longer preserve the initial Sr/Y ratios in whole rocks due to weathering and hydrothermal alteration. Based on apatite Ga contents and δEu values, it is inferred that the parental magmas for the two adakite-like plutons containing porphyry-type Cu and Mo mineralization are more oxidized than that for the non-adakite-type pluton containing vein-type Mo mineralization. Apatite crystals from the vein-type Mo deposit have much lower Cl/F ratios than those from the porphyry-type Cu and Mo deposits. Apatite crystals from the adakite-like pluton without Cu or Mo mineralization is characterized by much lower Cl/F ratios than those from the adakite-like plutons that host the porphyry-type Cu and Mo deposits. The

  4. Solid-state MAS NMR, TEM, and TGA studies of structural hydroxyl groups and water in nanocrystalline apatites prepared by dry milling.

    PubMed

    Pajchel, Lukasz; Kolodziejski, Waclaw

    2013-01-01

    A series of nanocrystalline calcium hydroxyapatites was prepared by dry milling and characterized using proton and (31)P MAS NMR, TEM, and TGA methods. The samples contained stubby rod-shaped crystals, which length and width varied in the 130-30 and 95-20 nm ranges, respectively. It was confirmed that concentration of structural hydroxyl groups in nanocrystalline apatites decreases with the decreasing crystal size. In the series of the studied apatites, the decrease was from 86 to ca. 50 % in reference to stoichiometric apatite. Water was found in the surface hydrated layer and in the c-axis channels, in which compartments existed as adsorbed and structural, respectively. Molecules of the adsorbed water were capable of moving from the crystal surface into the lattice c-axis channels of apatite. This process introduced considerable structural disorder within and around those channels and reduced the content of the structural hydroxyl groups, particularly in the region underneath the apatite crystal surface.

  5. Project Work Plan: Sequestration of Strontium-90 Subsurface Contamination in the Hanford 100-N Area by Surface Infiltration of an Apatite Solution

    SciTech Connect

    Szecsody, Jim E.

    2006-04-30

    We propose to develop an infiltration strategy that defines the precipitation rate of an apatite-forming solution and Sr-90 sequestration processes under variably saturated (low water content) conditions. We will develop this understanding through small-scale column studies, intermediate-scale two-dimensional (2-D) experiments, and numerical modeling to quantify individual and coupled processes associated with apatite formation and Sr-90 transport during and after infiltration of the Ca-citrate-PO4 solution. Development of capabilities to simulate these coupled biogeochemical processes during both injection and infiltration will be used to determine the most cost-effective means to emplace an in situ apatite barrier with a longevity of 300 years to permanently sequester Sr-90 until it decays. Biogeochemical processes that will be investigated are citrate biodegradation and apatite precipitation rates at varying water contents as a function of water content. Coupled processes that will be investigated include the influence of apatite precipitation (which occupies pore space) on the hydraulic and transport properties of the porous media during infiltration.

  6. Refinement of collagen-mineral interaction: a possible role for osteocalcin in apatite crystal nucleation, growth and development.

    PubMed

    Chen, Ling; Jacquet, Robin; Lowder, Elizabeth; Landis, William J

    2015-02-01

    Mineralization of vertebrate tissues such as bone, dentin, cementum, and calcifying tendon involves type I collagen, which has been proposed as a template for calcium and phosphate ion binding and subsequent nucleation of apatite crystals. Type I collagen thereby has been suggested to be responsible for the deposition of apatite mineral without the need for non-collagenous proteins or other extracellular matrix molecules. Based on studies in vitro, non-collagenous proteins, including osteocalcin and bone sialoprotein, are thought to mediate vertebrate mineralization associated with type I collagen. These proteins, as possibly related to mineral deposition, have not been definitively localized in vivo. The present study has reexamined their localization in the leg tendons of avian turkeys, a representative model of vertebrate mineralization. Immunocytochemistry of osteocalcin demonstrates its presence at the surface of, outside and within type I collagen while that of bone sialoprotein appears to be localized at the surface of or outside type I collagen. The association between osteocalcin and type I collagen structure is revealed optimally when calcium ions are added to the antibody solution in the methodology. In this manner, osteocalcin is found specifically located along the a4-1, b1, c2 and d bands defining in part the hole and overlap zones within type I collagen. From these data, while type I collagen itself may be considered a stereochemical guide for intrafibrillar mineral nucleation and subsequent deposition, osteocalcin bound to type I collagen may also possibly mediate nucleation, growth and development of platelet-shaped apatite crystals. Bone sialoprotein and osteocalcin as well, each immunolocalized at the surface of or outside type I collagen, may affect mineral deposition in these portions of the avian tendon.

  7. Understanding Landscape Exhumation from Apatite He Age Data Dispersion: An Example from the Ethiopian Plateau, East Africa

    NASA Astrophysics Data System (ADS)

    Gani, N. D.; Blackburn, N. C.; Van Soest, M. C.

    2014-12-01

    The Blue Nile, a major tributary of the Nile River, extensively incised the long-wavelength Ethiopian Plateau developed within the East African Rift System, exposing various rock formations ranging in age from Neoproterozoic to Recent. The 1.6 km deep Blue Nile Canyon, the only deep and extensive canyon in the greater Nile drainage basin, characterizes the plateau, which has an average elevation of 2.5 km. The time line of the plateau uplift is still not well understood, and has been highly contested, with some suggesting early (before 20 Ma) and others arguing late (after 10 Ma) rise of the plateau. A recent modeling of deep-mantle convection beneath the African continent showed that the Ethiopian Plateau started to rise rapidly around 10 Ma. Quantifying the incision history of the Ethiopian Plateau is critical in unraveling the causes and timing of plateau's elevation gain. Low temperature thermochronology provides a rigorous analytical tool in determining the cooling history to reconstruct canyon incision. From apatite (U-Th)/He ages measured from Neoproterozoic basement rocks and Mesozoic sedimentary strata exposed along the valley wall of the Blue Nile canyon, we investigate rock cooling history of the Ethiopian Plateau induced by this canyon incision. Although our apatite He dates show strong data dispersion, both within and among samples and ranging from 58 to 460 Ma, these ages positively correlate with apatite effective uranium concentrations. Hence, this age dispersion is likely linked to changes in helium retention and diffusivity related to differential accumulation of radiation damage. Our inverse thermal model simulations determine the best-fit cooling history that shows the onset of major canyon incision after 30 Ma with regional exhumation accelerated after 15 Ma. These observations are also supported by our quantitative geomorphic data extracted from the Blue Nile tributaries that correlates with mantle tomography data.

  8. In vitro response of osteoblast-like and odontoblast-like cells to unsubstituted and substituted apatites.

    PubMed

    Inoue, Miho; LeGeros, Racquel Z; Inoue, Masahisa; Tsujigiwa, Hidetsugu; Nagatsuka, Hitoshi; Yamamoto, Toshio; Nagai, Noriyuki

    2004-09-15

    Different types of calcium phosphate compounds [calcium-deficient apatite (CDA); beta-tricalcium phosphate (beta-TCP); biphasic calcium phosphate (BCP)] are commercially available for medical and dental applications as bone substitute materials. Most of the reported in vitro studies on cell-material interactions have used osteoblast-like cells. The purpose of this study was to investigate the in vitro response of osteoblast-like (MC3T3-E1) and odontoblast-like (MDPC23) cells on unsubstituted (HA) and substituted (F-substituted) apatites. MC3T3-E1 and MDPC23 were cultured in alpha-modified medium containing 10% fetal bovine serum, ascorbic acid (50 microg/mL) and beta-glycerophosphate (2 mM). The cells were seeded on pellets made from HA, and FAp (with low, medium, and high F concentrations). Cell morphology was observed after 7 and 14 days using scanning electron microscopy (SEM). Cell attachment and differentiation were determined from the DNA content, alkaline phosphatase (ALP) activity, and total collagen content. Pellet surface composition was characterized by using Fourier Transform infrared spectroscopy. MC3T3-E1 and MDPC23 cells on HA were normal in shape and in fusion but not on FAp. Results of this study showed that the pattern of cell proliferation of osteoblast-like cells was different from that of the odontoblast-like cells. This study suggests that cell morphology, fusion, and proliferation on biomaterial surfaces depend on cell type (osteoblast-like vs odontoblast-like cell) and biomaterial composition (unsubstituted vs substituted F-apatites).

  9. Dynamic Recovery in Silicate-Apatite Structures Under Irradiation and Implications for Long-Term Immobilization of Actinides

    SciTech Connect

    Weber, William J.; Zhang, Yanwen; Xiao, Haiyan Y.; Wang, Lumin M.

    2011-11-14

    The irradiation responses of Ca{sub 2}La{sub 8}(SiO{sub 4}){sub 6}O{sub 2} and Sr{sub 2}Nd{sub 8}(SiO{sub 4}){sub 6}O{sub 2} with the apatite structure are investigated to predict their long-term behaviour as host phases for immobilization of actinide elements from the nuclear fuel cycle. Different ions and energies are used to study the effects of dose, temperature, atomic displacement rate and ionization rate on irradiation-induced amorphization and recrystallization. The dose for amorphization increases with temperature in two stages, below and above 150 K. In the high temperature stage relevant to actinide immobilization, the increase of amorphization dose with temperature exhibits a strong dependence on the ratio of ionization rate to displacement rate for the different ions. Data analysis using a dynamic model for amorphization reveals that ionization-induced processes, with activation energy of 0.15 {+-} 0.02 eV, dominate dynamic recovery for ions from Ne through Xe. For heavier Au ions or for alpha-recoil nuclei emitted in alpha decay of actinides, ionization becomes less dominant and dynamic recovery is controlled primarily by thermally-driven processes. In post-irradiation annealing studies of amorphous samples, epitaxial thermal recrystallization is observed at 1123 K, and irradiation-enhanced nucleation of nanocrystallites is observed under irradiation with heavier ions. The recrystallization temperature under irradiation decreases with increasing ion mass to a value of {approx} 823 K, which also defines the thermally-driven critical temperature for amorphization under irradiation with heavy ions. Some partial recovery due to alpha particle irradiation at 300 K is observed that suggests a self-healing mechanism in apatite phases containing actinides. Based on the results and dynamic model, the temperature and time dependences of amorphization in silicate-apatite host phases for actinide immobilization are predicted.

  10. Dynamic recovery in silicate-apatite structures under irradiation and implications for long-term immobilization of actinides

    SciTech Connect

    Weber, William J; Zhang, Yanwen; Xiao, Haiyan; Wang, Prof. Lumin

    2012-01-01

    The irradiation responses of Ca2La8(SiO4)6O2 and Sr2Nd8(SiO4)6O2 with the apatite structure are investigated to predict their long-term behaviour as host phases for immobilization of actinide elements from the nuclear fuel cycle. Different ions and energies are used to study the effects of dose, temperature, atomic displacement rate and ionization rate on irradiation-induced amorphization and recrystallization. The dose for amorphization increases with temperature in two stages, below and above 150 K. In the high temperature stage relevant to actinide immobilization, the increase of amorphization dose with temperature exhibits a strong dependence on the ratio of ionization rate to displacement rate for the different ions. Data analysis using a dynamic model for amorphization reveals that ionization-induced processes, with activation energy of 0.15 0.02 eV, dominate dynamic recovery for ions from Ne through Xe. For heavier Au ions or for alpha-recoil nuclei emitted in alpha decay of actinides, ionization becomes less dominant and dynamic recovery is controlled primarily by thermally-driven processes. In post-irradiation annealing studies of amorphous samples, epitaxial thermal recrystallization is observed at 1123 K, and irradiation-enhanced nucleation of nanocrystallites is observed under irradiation with heavier ions. The recrystallization temperature under irradiation decreases with increasing ion mass to a value of ~ 823 K, which also defines the thermally-driven critical temperature for amorphization under irradiation with heavy ions. Some partial recovery due to alpha particle irradiation at 300 K is observed that suggests a self-healing mechanism in apatite phases containing actinides. Based on the results and dynamic model, the temperature and time dependences of amorphization in silicate-apatite host phases for actinide immobilization are predicted.

  11. Enhanced ionic conductivity of apatite-type lanthanum silicate electrolyte for IT-SOFCs through copper doping

    NASA Astrophysics Data System (ADS)

    Ding, Xifeng; Hua, Guixiang; Ding, Dong; Zhu, Wenliang; Wang, Hongjin

    2016-02-01

    Apatite-type Lanthanum silicate (LSO) is among the most promising electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs) owing to the high conductivity and low activation energy at lower temperature than traditional doped-zirconia electrolyte. The ionic conductivity as well as the sintering density of lanthanum silicate oxy-apatite, La10Si6-xCuxO27-δ (LSCO, 0 ≤ x ≤ 2), was effectively enhanced through a small amount of doped copper. The phase composition, relative density, ionic conductivity and thermal expansion behavior of La10Si6-xCuxO27-δ was systematically investigated by X-ray diffraction (XRD), Archimedes' drainage method, scanning electron microscope (SEM), electrochemical impedance spectra (EIS) and thermal dilatometer techniques. With increasing copper doping content, the ionic conductivity of La10Si6-xCuxO27-δincreased, reaching a maximum of 4.8 × 10-2 S cm-1 at 800 °C for x = 1.5. The improved ionic conductivity could be primarily associated with the enhanced grain conductivity. The power output performance of NiO-LSCO/LSCO/LSCF single cell was superior to that obtained on NiO-LSO/LSO/LSCF at different temperatures using hydrogen as fuel and oxygen as oxidant, which could be attributed to the enhanced oxygen ionic conductivity as well as the sintering density for the copped doped lanthanum silicate. In conclusion, the apatite La10Si4.5Cu1.5O25.5 is a promising candidate electrolyte for IT-SOFCs.

  12. Fingerprinting young ignimbrites in Dominica (Lesser Antilles): Constraints from bulk REEs, apatite chemistry, and U-Th zircon chronology

    NASA Astrophysics Data System (ADS)

    Frey, H. M.; Manon, M. R.; Brehm, S.

    2015-12-01

    Multiple methods of fingerprinting tephra deposits enable distinction of separate magma batches beneath the island of Dominica. Previous studies have invoked a single large batholith but apatite REE chemistry is inconsistent with generation of multiple ignimbrites by fractional crystallization. The crystal-rich, andesite-dacite (58-66 wt% SiO2) ignimbrites comprise the largest explosive eruption in the Caribbean in the last 200 kyr, erupting a magma volume >58 km3 (Carey and Sigurdsson, 1980). Although the ignimbrites appear to emanate from several vents, their broad similarity in bulk chemistry, phase assemblage (pl + opx + cpx + hbl + ilm + mag + zrn + ap), and mineral composition, has led previous workers to suggest that Dominica is underlain by a single large batholith eruptions younging from north to south. However, bulk REE chemistry, solution ICP-MS chemistry of individual apatite grains, and ion microprobe U-Th dating of zircon rims from pumice clasts suggest a more complex plumbing system. More than 150 pumice clasts from northernmost (Morne aux Diables), northern (Wesley, Pointe Ronde, Grand Savanne), central (Layou, Roseau, Rosalie), and southern (Grand Bay, Grand Fonde) ignimbrites were analyzed for bulk chemistry. Geographically controlled differences exist in the concavity of the middle-heavy REE (Dy*). In central Dominica, apatites from the more evolved Layou Ignimbrite are depleted in middle REE compared to the nearby Roseau Ignimbrite, belying a genetic relationship via fractional crystallization. U-Th zircon rim ages in the northernmost and northern deposits were in secular equilibrium (>350 ka), whereas the central and southern ignimbrites yielded several populations of crystallization ages: Layou (99±12 ka), Roseau (139±12 ka; 65±17 ka), and Grand Bay (107±15 ka; 211±61 ka). Collectively, these observations are consistent with partial melting of magma batches prior to eruption rather than fractional crystallization of a single magma chamber.

  13. Probing the limit of magnesium uptake by β-tricalcium phosphate in biphasic mixtures formed from calcium deficient apatites

    SciTech Connect

    Kumar, P. Nandha; Mishra, Sandeep K.; Kannan, S.

    2015-11-15

    A series of magnesium doped non-stoichiometric calcium deficient apatites were synthesized through an aqueous precipitation route. The resultant structural changes during heat treatment were investigated by X-ray diffraction, Raman and FT-IR spectroscopy and Rietveld refinement. The results confirmed the formation of biphasic mixtures comprising Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} and β-Ca{sub 3}(PO{sub 4}){sub 2} after heat treatment at 1000 °C with the preferential occupancy of Mg{sup 2+} at the crystal lattice of β-Ca{sub 3}(PO{sub 4}){sub 2}. The concentration of Mg{sup 2+} uptake in β-Ca{sub 3}(PO{sub 4}){sub 2} is limited till reaching the stoichiometric ratio of (Ca+Mg)/P=1.67 and beyond this stoichiometric value [(Ca+Mg)/P>1.67], Mg{sup 2+} precipitates as Mg(OH){sub 2} and thereafter gets converted to MgO during heat treatment. Any kind of Mg{sup 2+} uptake in the crystal lattice of Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} is discarded from the investigation. - Highlights: • Aqueous co-precipitation of calcium deficient apatites with excess magnesium (Mg{sup 2+}) additions. • Heat treatments beyond 800 °C results in the formation of biphasic apatite mixtures. • Mg{sup 2+} gets accommodated at the β-Ca{sub 3}(PO{sub 4}){sub 2} lattice of biphasic mixtures. • Mg{sup 2+} additions exceeding stoichiometric value (Ca/P>1.67) results in its formation as MgO. • Mg{sup 2+} occupancy at β-Ca{sub 3}(PO{sub 4}){sub 2} lattice delays its allotropic conversion α-Ca{sub 3}(PO{sub 4}){sub 2} till 1350 °C.

  14. Isomorphous Substitution of Rare-Earth Elements in Lacunary Apatite Pb8Na2(PO4)6.

    PubMed

    Get'man, Evgeni I; Loboda, Stanislav N; Ignatov, Alexey V; Prisedsky, Vadim V; Abdul Jabar, Mohammed A B; Ardanova, Lyudmyla I

    2016-03-07

    The substitution of rare-earth elements (REEs) for Pb in the lacunary apatite Pb8Na2(PO4)6 with void structural channels was studied by means of powder X-ray diffraction (including the Rietveld refinement), scanning electron microscopy, energy-dispersive X-ray microanalysis, and IR spectroscopy and also measurements of the electrical conductivity. The substitution limits (xmax in Pb8-xLnxNa2(PO4)6Ox/2) at 800 °C were found to decrease with the atomic number of the REE from 1.40 for La to 0.12 for Yb with a rapid drop from light to heavy lanthanides (between Gd and Tb). The REE atoms substitute for Pb predominantly at Pb2 sites of the apatite structure according to the scheme 2Pb(2+) + □ → 2Ln(3+) + O(2-), where □ is a vacancy in the structural channel. The substitution in lacunary apatite produces quite different changes in the structural parameters compared with broadly studied alkaline-earth hydroxyapatites. In spite of the much lower ionic radii of REE than that of Pb(2+), the mean distances ⟨Pb1-O⟩ somewhat increase, whereas the distances ⟨Pb2-Pb2⟩ and ⟨Pb2-O4⟩ do not change considerably with the degree of substitution. This implies control of the substitution by not only spatial and charge accommodation of REE ions but also the availability of a stereochemically active 6s(2) electron pair on Pb(2+). The high-temperature electrical conductivity shows dependence on the degree of substitution with a minimum at x = 0.2 indicative of a possible change of the type of conductivity.

  15. Preparation of a non-woven poly(ε-caprolactone) fabric with partially embedded apatite surface for bone tissue engineering applications by partial surface melting of poly(ε-caprolactone) fibers.

    PubMed

    Kim, In Ae; Rhee, Sang-Hoon

    2017-03-21

    This article describes a novel method for the preparation of a biodegradable non-woven poly(ε-caprolactone) fabric with a partially embedded apatite surface designed for application as a scaffold material for bone tissue engineering. The non-woven poly(ε-caprolactone) fabric was generated by the electro-spinning technique and then apatite was coated in simulated body fluid after coating the PVA solution containing CaCl2 ·2H2 O. The apatite crystals were partially embedded or fully embedded into the thermoplastic poly(ε-caprolactone) fibers by controlling the degree of poly(ε-caprolactone) fiber surface melting in a convection oven. Identical apatite-coated poly(ε-caprolactone) fabric that did not undergo heat-treatment was used as a control. The features of the embedded apatite crystals were evaluated by FE-SEM, AFM, EDS, and XRD. The adhesion strengths of the coated apatite layers and the tensile strengths of the apatite coated fabrics with and without heat-treatment were assessed by the tape-test and a universal testing machine, respectively. The degree of water absorbance was assessed by adding a DMEM droplet onto the fabrics. Moreover, cell penetrability was assessed by seeding preosteoblastic MC3T3-E1 cells onto the fabrics and observing the degrees of cell penetration after 1 and 4 weeks by staining nuclei with DAPI. The non-woven poly(ε-caprolactone) fabric with a partially embedded apatite surface showed good water absorbance, cell penetrability, higher apatite adhesion strength, and higher tensile strength compared with the control fabric. These results show that the non-woven poly(ε-caprolactone) fabric with a partially embedded apatite surface is a potential candidate scaffold for bone tissue engineering due to its strong apatite adhesion strength and excellent cell penetrability. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2017.

  16. The predominant role of collagen in the nucleation, growth, structure and orientation of bone apatite.

    PubMed

    Wang, Yan; Azaïs, Thierry; Robin, Marc; Vallée, Anne; Catania, Chelsea; Legriel, Patrick; Pehau-Arnaudet, Gérard; Babonneau, Florence; Giraud-Guille, Marie-Madeleine; Nassif, Nadine

    2012-07-01

    The involvement of collagen in bone biomineralization is commonly admitted, yet its role remains unclear. Here we show that type I collagen in vitro can initiate and orientate the growth of carbonated apatite mineral in the absence of any other vertebrate extracellular matrix molecules of calcifying tissues. We also show that the collagen matrix influences the structural characteristics on the atomic scale, and controls the size and the three-dimensional distribution of apatite at larger length scales. These results call into question recent consensus in the literature on the need for Ca-rich non-collagenous proteins for collagen mineralization to occur in vivo. Our model is based on a collagen/apatite self-assembly process that combines the ability to mimic the in vivo extracellular fluid with three major features inherent to living bone tissue, that is, high fibrillar density, monodispersed fibrils and long-range hierarchical organization.

  17. Stable carbon isotopic evidence for differences in the dietary origin of bone cholesterol, collagen and apatite: implications for their use in palaeodietary reconstruction

    NASA Astrophysics Data System (ADS)

    Jim, Susan; Ambrose, Stanley H.; Evershed, Richard P.

    2004-01-01

    Rats were raised on a variety of isotopically controlled diets comprising 20% C 3, C 4 or marine protein and C 3 and/or C 4 non-protein or energy (i.e. sucrose, starch and oil) macronutrients. Compound specific stable carbon isotope (δ 13C) analysis was performed on the cholesterol isolated from the diet ( n=7 ) and bone ( n=15 ) of these animals and the values compared with bulk δ 13C measurements of bone collagen and apatite. The dietary signals reflected by these three bone biochemical components were investigated using linear regression analysis. δ 13C values of bone cholesterol were shown to reflect whole diet δ 13C values, collagen to reflect mainly dietary protein values and apatite to reflect whole diet values. Further correlations between dietary protein-to-energy spacings (Δ 13C prot-engy = δ 13C protein - δ 13C energy) and whole diet-to-bone component fractionations (Δ 13C bcomp- wdiet = δ 13C bone component - δ 13C whole diet) indicates that for hypothetical diets where protein δ 13C values are equal to energy values, fractionations between whole diet and bone biochemical fractions are -3.3‰ for cholesterol, +5.4‰ for collagen and +9.5‰ for apatite. Moreover, the narrow range of variation observed in apatite-to-cholesterol spacings (Δ 13C apat- bchol ) suggests that cholesterol δ 13C values can potentially also be used as an independent test for the isotopic integrity of apatite δ 13C values. These insights into bone cholesterol, collagen and apatite dietary signals, diet-to-bone fractionations and bone component-to-bone component spacings provide the basis for more accurate interpretations of the dietary behaviour of archaeological populations and food webs when the δ 13C analysis of bone is employed.

  18. 100-NR-2 Apatite Treatability Test: Fall 2010 Tracer Infiltration Test (White Paper)

    SciTech Connect

    Vermeul, Vincent R.; Fritz, Brad G.; Fruchter, Jonathan S.; Greenwood, William J.; Johnson, Timothy C.; Horner, Jacob A.; Strickland, Christopher E.; Szecsody, James E.; Williams, Mark D.

    2011-04-14

    change and the associated change in moisture content so that 4D images of moisture content change can be generated. Results from this field test will be available for any future Ca-citrate-PO4 amendment infiltration tests, which would be designed to evaluate the efficacy of using near surface application of amendments to form apatite mineral phases in the upper portion of the zone of water table fluctuation.

  19. The crystal chemistry of the alkaline-earth apatites A(10)(PO(4))(6)Cu(x)O(y)(H)(z) (A = Ca, Sr and Ba).

    PubMed

    Baikie, Tom; Ng, George M H; Madhavi, S; Pramana, Stevin S; Blake, Kevin; Elcombe, Margaret; White, T J

    2009-09-14

    The crystal chemistry of the cuprate apatites A(I)(4)A(II)(6)(PO(4))(6)Cu(x)O(y)(H)(z) (A = Ca, Sr and Ba) was investigated by powder X-ray (PXRD) and neutron diffraction (PND) and X-ray photoelectron spectroscopy (XPS). The refined crystal structures confirmed earlier X-ray diffraction studies that showed copper resides in the apatite channels and additionally, located hydrogen. For all materials copper is primarily divalent (Cu(2+)) but in the calcium and strontium analogues co-exists with minor Cu(3+). This is in contrast with a previous work where Cu(1+) and Cu(2+) were reported.

  20. Fabrication of macroporous carbonate apatite foam by hydrothermal conversion of alpha-tricalcium phosphate in carbonate solutions.

    PubMed

    Wakae, H; Takeuchi, A; Udoh, K; Matsuya, S; Munar, M L; LeGeros, R Z; Nakasima, A; Ishikawa, K

    2008-12-15

    Bone consists of a mineral phase (carbonate apatite) and an organic phase (principally collagen). Cancellous bone is characterized by interconnecting porosity necessary for tissue ingrowth and nourishment of bone cells. The purpose of the present study was to fabricate macroporous carbonate apatite (CAP) blocks with interconnecting porosity as potential bone substitute biomaterials by hydrothermal conversion of alpha-TCP foam in carbonate solution. The fabrication of the macroporous CAP was accomplished in two steps: (1) preparation of alpha-TCP foams using polyurethane foams as templates, and (2) hydrothermal conversion at 200 degrees C of alpha-TCP foam in the presence of ammonium carbonate solutions of different concentrations. The maximum carbonate content of the resultant CAP foam was approximately 7.4 wt %. The mean porosity of the CAP foam was as high as 93 vol %. The macroporous CAP blocks or granules prepared in this manner has properties similar to that of bone in mineral composition and in having interconnecting macroporosity necessary for osteoconductivity and tissue ingrowth. On the basis of composition and interconnecting macroporosity, the CAP foam materials could be ideal biomaterials for bone repair and as scaffolds for tissue engineering.

  1. In-Situ U-Pb Dating of Apatite by Hiroshima-SHRIMP: Contributions to Earth and Planetary Science.

    PubMed

    Terada, Kentaro; Sano, Yuji

    2012-01-01

    The Sensitive High Resolution Ion MicroProbe (SHRIMP) is the first ion microprobe dedicated to geological isotopic analyses, especially in-situ analyses related to the geochronology of zircon. Such a sophisticated ion probe, which can attain a high sensitivity at a high mass resolution, based on a double focusing high mass-resolution spectrometer, designed by Matsuda (1974), was constructed at the Australian National University. In 1996, such an instrument was installed at Hiroshima University and was the first SHRIMP to be installed in Japan. Since its installation, our focus has been on the in-situ U-Pb dating of the mineral apatite, as well as zircon, which is a more common U-bearing mineral. This provides the possibility for extending the use of in-situ U-Pb dating from determining the age of formation of volcanic, granitic, sedimentary and metamorphic minerals to the direct determination of the diagenetic age of fossils and/or the crystallization age of various meteorites, which can provide new insights into the thermal history on the Earth and/or the Solar System. In this paper, we review the methodology associated with in-situ apatite dating and our contribution to Earth and Planetary Science over the past 16 years.

  2. Formation of apatitic calcium phosphates in a Na-K-phosphate solution of pH 7.4.

    PubMed

    Tas, A C; Aldinger, F

    2005-02-01

    Poorly crystalline, apatitic calcium phosphate powders have been synthesized by slowly adding a Na- and K-containing reference phosphate solution with a pH value of 7.4 to an aqueous calcium nitrate solution at 37 degrees C. Nano-particulated apatitic powders obtained were shown to contain small amounts of Na and K, which render them more similar in chemical composition to that of the bone mineral. Precipitated and dried powders were found to exhibit self-hardening cement properties when kneaded in a mortar with a sodium citrate- and sodium phosphate-containing starter solution. The same phosphate solution used in powder synthesis was found to be able to partially convert natural, white and translucent marble pieces of calcite (CaCO3) into calcium-deficient hydroxyapatite upon aging the samples in that solution for 3 days at 60 degrees C. Sample characterization was performed by using scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, inductively-coupled plasma atomic emission spectroscopy, and simultaneous thermogravimetry and differential thermal analysis.

  3. A Biomimetic Collagen-Apatite Scaffold with a Multi-Level Lamellar Structure for Bone Tissue Engineering

    PubMed Central

    Xia, Z.; Villa, M. M.; Wei, M.

    2014-01-01

    Collagen-apatite (Col-Ap) scaffolds have been widely employed for bone tissue engineering. We fabricated a Col-Ap scaffold with a unique multi-level lamellar structure consisting of co-aligned micro and macro pores. The basic building blocks of this scaffold are bone-like mineralized collagen fibers developed via a biomimetic self-assembly process in a collagen-containing modified simulated body fluid (m-SBF). This biomimetic method preserves the structural integrity and great tensile strength of collagen by reinforcing the collagen hydrogel with apatite nano-particles. Unidirectional aligned macro pores with a size of 63.8 to 344 μm are created by controlling the freezing rate and direction. The thickness of Col-Ap lamellae can be adjusted in the range 3.6 to 23 μm depending on the self-compression time. Furthermore, the multi-level lamellar structure has led to a twelve-fold increase in Young's modulus and a two-fold increase in the compression modulus along the aligned direction compared to a scaffold of the same composition with an isotropic equiaxed pore structure. Moreover, this novel lamellar scaffold supports the attachment and spreading of MC3T3-E1osteoblasts. Therefore, owing to the biomimetic composition, tunable structure, improved mechanical strength, and good biocompatibility of this novel scaffold, it has great potential to be used in bone tissue engineering applications. PMID:24999428

  4. Crystallinity and compositional changes in carbonated apatites: Evidence from 31P solid-state NMR, Raman, and AFM analysis

    PubMed Central

    McElderry, John-David P.; Zhu, Peizhi; Mroue, Kamal H.; Xu, Jiadi; Pavan, Barbara; Fang, Ming; Zhao, Guisheng; McNerny, Erin; Kohn, David H.; Franceschi, Renny T.; Holl, Mark M. Banaszak; Tecklenburg, Mary M.J.; Ramamoorthy, Ayyalusamy; Morris, Michael D.

    2013-01-01

    Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and 31P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse 31P NMR linewidth and inverse Raman PO43− ν1 bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3–10.3 wt% CO32− range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the 31P NMR chemical shift frequency and the Raman phosphate ν1 band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals. PMID:24273344

  5. In-Situ U–Pb Dating of Apatite by Hiroshima-SHRIMP: Contributions to Earth and Planetary Science

    PubMed Central

    Terada, Kentaro; Sano, Yuji

    2012-01-01

    The Sensitive High Resolution Ion MicroProbe (SHRIMP) is the first ion microprobe dedicated to geological isotopic analyses, especially in-situ analyses related to the geochronology of zircon. Such a sophisticated ion probe, which can attain a high sensitivity at a high mass resolution, based on a double focusing high mass-resolution spectrometer, designed by Matsuda (1974), was constructed at the Australian National University. In 1996, such an instrument was installed at Hiroshima University and was the first SHRIMP to be installed in Japan. Since its installation, our focus has been on the in-situ U–Pb dating of the mineral apatite, as well as zircon, which is a more common U-bearing mineral. This provides the possibility for extending the use of in-situ U–Pb dating from determining the age of formation of volcanic, granitic, sedimentary and metamorphic minerals to the direct determination of the diagenetic age of fossils and/or the crystallization age of various meteorites, which can provide new insights into the thermal history on the Earth and/or the Solar System. In this paper, we review the methodology associated with in-situ apatite dating and our contribution to Earth and Planetary Science over the past 16 years. PMID:24349912

  6. Crystallinity and compositional changes in carbonated apatites: Evidence from (31)P solid-state NMR, Raman, and AFM analysis.

    PubMed

    McElderry, John-David P; Zhu, Peizhi; Mroue, Kamal H; Xu, Jiadi; Pavan, Barbara; Fang, Ming; Zhao, Guisheng; McNerny, Erin; Kohn, David H; Franceschi, Renny T; Holl, Mark M Banaszak; Tecklenburg, Mary M J; Ramamoorthy, Ayyalusamy; Morris, Michael D

    2013-10-01

    Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and (31)P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse (31)P NMR linewidth and inverse Raman PO4(3-) ν1 bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3-10.3 wt% CO3(2-) range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the (31)P NMR chemical shift frequency and the Raman phosphate ν1 band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals.

  7. Preferential occupancy of strontium in the hydroxyapatite lattice in biphasic mixtures formed from non-stoichiometric calcium apatites.

    PubMed

    Nandha Kumar, P; Mishra, Sandeep K; Udhay Kiran, R; Kannan, S

    2015-05-07

    The present study reports the variations in phase content of biphasic mixtures and structural changes induced by different levels of strontium addition in calcium-deficient apatite (Ca/P = 1.60) powders during heat treatment. The synthesis was attempted by an in situ aqueous precipitation technique and X-ray diffraction, Raman spectroscopy and Rietveld refinement of the powder X-ray diffraction data were employed for comprehensive analysis. The results confirm the preferential occupancy of Sr(2+) at two different Ca(2+) sites of the hydroxyapatite [Ca10(PO4)6(OH)2, HAP] lattice, with the Ca(2+) (2) site accommodating more Sr(2+) than the Ca(2+) (1) site. Increasing Sr(2+) addition in calcium-deficient apatite has led to a decline in the phase content of β-tricalcium phosphate [β-Ca3(PO4)2, β-TCP] in biphasic mixtures of HAP and β-TCP. Sr(2+) addition exceeding the critical limit of a (Ca + Sr)/P > 1.75 molar ratio has resulted in the formation of CaO as an additional phase, and this justifies the lack of enough PO4(3-) ions to promote any kind of calcium phosphate precipitation. Sr(2+) accommodation in the lattice sites of HAP has induced an increase in the lattice parameters and has also led to the significant distortion of the PO4 tetrahedron and OH groups, confirmed by Raman and FT-IR spectroscopic techniques.

  8. Surface characteristics of nanocrystalline apatites: effect of mg surface enrichment on morphology, surface hydration species, and cationic environments.

    PubMed

    Bertinetti, Luca; Drouet, Christophe; Combes, Christele; Rey, Christian; Tampieri, Anna; Coluccia, Salvatore; Martra, Gianmario

    2009-05-19

    The incorporation of foreign ions, such as Mg2+, exhibiting a biological activity for bone regeneration is presently considered as a promising route for increasing the bioactivity of bone-engineering scaffolds. In this work, the morphology, structure, and surface hydration of biomimetic nanocrystalline apatites were investigated before and after surface exchange with such Mg2+ ions, by combining chemical alterations (ion exchange, H2O-D2O exchanges) and physical examinations (Fourier transform infrared spectroscopy (FTIR) and high-resolution transmission electron microscopy (HRTEM)). HRTEM data suggested that the Mg2+/Ca2+ exchange process did not affect the morphology and surface topology of the apatite nanocrystals significantly, while a new phase, likely a hydrated calcium and/or magnesium phosphate, was formed in small amount for high Mg concentrations. Near-infrared (NIR) and medium-infrared (MIR) spectroscopies indicated that the samples enriched with Mg2+ were found to retain more water at their surface than the Mg-free sample, both at the level of H2O coordinated to cations and adsorbed in the form of multilayers. Additionally, the H-bonding network in defective subsurface layers was also noticeably modified, indicating that the Mg2+/Ca2+ exchange involved was not limited to the surface. This work is intended to widen the present knowledge on Mg-enriched calcium phosphate-based bioactive materials intended for bone repair applications.

  9. Fourier transform infrared microspectroscopic investigation of the maturation of nonstoichiometric apatites in mineralized tissues: a horse dentin study.

    PubMed

    Magne, D; Pilet, P; Weiss, P; Daculsi, G

    2001-12-01

    Fourier transform infrared microspectroscopy (FTIRM) was used to study carbonated apatite/collagen interactions and maturation in horse secondary dentin. Unlike human dentin, this model contains no peritubular material around the odontoblastic processes and is thus quite similar to bone in composition, but not subject to tissue turnover. Crystals close to the mineralization front were very immature, showing high HPO(4) and very low CO(3) levels. Carbonate ions were located essentially in very labile, reactive environments, probably on the crystal surface. Removal of some of the HPO(4) ions from crystals during maturation was linked to an increase in total carbonate content. The CO(3) ions in labile environments decreased, probably after incorporation into more organized regions of the lattice. However, this increase of total carbonate content was associated with greater mineral crystallinity, confirming findings in other studies of synthetic apatite maturation in vitro. The good correlation between these results and those of in vitro experiments suggests that crystal maturation is essentially due to physicochemical processes and that the organic matrix controls only crystal size, multiplication, and/or organization.

  10. Composites of Eu(3+)-doped calcium apatite nanoparticles and silica particles: comparative study of two preparation methods.

    PubMed

    Isobe, Ayumu; Takeshita, Satoru; Isobe, Tetsuhiko

    2015-02-10

    We synthesized composites of Eu(3+)-doped calcium apatite (CaAp:Eu(3+)) nanoparticles and silica particles via two methods: (i) in situ synthesis of CaAp:Eu(3+) in the presence of silica particles and (ii) electrostatic adsorption of CaAp:Eu(3+) nanoparticles on silica particle surfaces. In both methods, submicrometer spherical silica particles were covered with CaAp:Eu(3+) nanoparticles without forming any impurity phases, as confirmed by X-ray diffractometry, Fourier-transform infrared spectroscopy, and scanning electron microscopy. In method i, part of the silica surface acted as a nucleation site for apatite crystals and silica particles were inhomogeneously covered with CaAp:Eu(3+) nanoparticles. In method ii, positively charged CaAp:Eu(3+) nanoparticles were homogeneously adsorbed on the negatively charged silica surface through electrostatic interactions. The bonds between the silica surface and CaAp:Eu(3+) nanoparticles are strong enough not to break under ultrasonic irradiation, irrespective of the synthetic method used. The composite particles showed red photoluminescence corresponding to 4f → 4f transitions of Eu(3+) under near-UV irradiation. Although the absorption coefficient of the forbidden 4f → 4f transitions of Eu(3+) was small, the red emission was detectable with a commercial fluorescence microscope because the CaAp:Eu(3+) nanoparticles accumulated on the silica particle surfaces.

  11. Multiple cooling episodes in the Central Tarim (Northwest China) revealed by apatite fission track analysis and vitrinite reflectance data

    NASA Astrophysics Data System (ADS)

    Chang, Jian; Qiu, Nansheng; Song, Xinying; Li, Huili

    2016-06-01

    Apatite fission track and vitrinite reflectance are integrated for the first time to study the cooling history in the Central Tarim, northwest China. The paleo-temperature profiles from vitrinite reflectance data of the Z1 and Z11 wells showed a linear relationship with depth, suggesting an approximately 24.8 °C/km paleo-geothermal gradient and 2700-3900 m of erosion during the Early Mesozoic. The measured apatite fission track ages from well Z2 in the Central Tarim range from 39 to 159 Ma and effectively record the Meso-Cenozoic cooling events that occurred in Central Tarim. Moreover, two cooling events at 190-140 Ma in the Early Jurassic-Early Cretaceous and 80-45 Ma in the Late Cretaceous-Paleocene revealed by measured AFT data and thermal modeling results are related to the collisions of the Qiangtang-Lhasa terranes and the Greater India Plate with the southern margin of the Eurasian Plate, respectively. This study provides new insights into the tectonic evolution of the Tarim Basin (and more broadly Central Asia) and for hydrocarbon generation and exploration in the Central Tarim.

  12. Hydrothermal calcium modification of 316L stainless steel and its apatite forming ability in simulated body fluid.

    PubMed

    Valanezahad, Alireza; Ishikawa, Kunio; Tsuru, Kanji; Maruta, Michito; Matsuya, Shigeki

    2011-01-01

    To understand the feasibility of calcium (Ca) modification of type 316L stainless steel (316L SS) surface using hydrothermal treatment, 316L SS plates were treated hydrothermally in calcium chloride (CaCl(2)) solution. X-ray photoelectron spectroscopic analysis revealed that the surface of 316L SS plate was modified with Ca after hydrothermal treatment at 200°C. And the immobilized Ca increased with CaCl(2) concentration. However no Ca-modification was occurred for 316L SS plates treated at 100°C. When Ca-modified 316L SS plate was immersed in simulated body fluid (SBF) with ion concentrations nearly equal to those of human blood plasma, low crystalline apatite was precipitated on its surface whereas no precipitate was observed on non Ca-modified 316L SS. The results obtained in the present study indicated that hydrothermal treatment at 200°C in CaCl(2) solution is useful for Ca-modification of 316L SS, and Ca-modification plays important role for apatite precipitation in SBF.

  13. In vitro evaluation for apatite-forming ability of cellulose-based nanocomposite scaffolds for bone tissue engineering.

    PubMed

    Saber-Samandari, Samaneh; Saber-Samandari, Saeed; Kiyazar, Shiva; Aghazadeh, Jamshid; Sadeghi, Ali

    2016-05-01

    Research on synthetic bioactive bone graft materials has significantly expanded in the past decade. In this study, the nanocomposite scaffold of semi-interpenetrating networks (semi-IPN) cellulose-graft-polyacrylamide/nano-hydroxyapatite was synthesized through free radical polymerization. The scaffolds were fabricated by the freeze-drying technique. The prepared semi-IPN nanocomposite scaffolds were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD) analysis. In addition, the mechanical properties (i.e., elastic modulus and compressive strength) of the scaffolds were investigated. The SEM images showed that the pores of the scaffolds were interconnected, and their sizes ranged from 120 μm to 190 μm. Under optimum conditions, the prepared scaffolds had a compressive strength of 4.80 MPa, an elastic modulus of 0.29 GPa and a value of 47.37% porosity. Furthermore, the apatite-forming ability of the scaffolds was determined using simulated body fluid (SBF) for 28 days. The results revealed that the new apatite particles could grow on the surface of the scaffolds after a 14-day immersion in SBF. Finally, this study suggests that the prepared semi-IPN nanocomposites that closely mimic the properties of bone tissue could be a promising scaffold for bone tissue engineering.

  14. Determination of light rare earth elements in apatite by x-ray fluorescence spectrometry after anion exchange extraction

    SciTech Connect

    Roelandts, I.

    1981-04-01

    The results of an investigation, the purpose of which was to study the feasibility of analysis of La, Ce, Pr, and Nd in apatite minerals, utilizing x-ray fluorescence spectrometry (XRF), are discussed. After sample dissolution in HNO/sub 3/, rare-earth elements (REEs) are separated by a mixed solvent anion exchange using the batch extraction technique. The anion exchanger employed is the strongly basic resin Dowex 1X8, 100 to 200 mesh (nitrate form). REEs are fixed on the resin from a medium consisting of 95% CH/sub 3/OH-5% 7 M HNO/sub 3/ (v/v). The dried resin is uniformly spread over a disk of self-adhesive foil backed with a cellulose support. The thin resin film formed is then used for XRF analysis. Synthetic standards prepared following the same procedure are employed for calibration. Analytical results of two apatite samples are presented. Good correlation is obtained between XRF and neutron activation analysis data. Limits of detection, precision, and accuracy of the results are discussed.

  15. Resolving Histories of Magmatic Volatiles in Fluids and Silicate Melts as a Function of Pressure, Temperature, and Melt Composition through Apatite Geochemistry

    NASA Astrophysics Data System (ADS)

    Webster, J. D.; Piccoli, P. M.; Goldoff, B. A.

    2012-12-01

    Fluids including aqueous or aqueous-carbonic vapor, aqueous liquid, and hydrosaline liquid, if present in magma, influence magmatic and volcanic processes, and the exsolution of fluids from magma sequesters and buffers volatile components from melt thus impacting the textural and chemical evolution of melts and phenocrysts. Establishing the timing of initial magmatic fluid saturation and monitoring changes in fluid chemistry through textural interpretations are often challenging because primary magmatic fluid inclusions are uncommon to most plutonic systems and are extremely rare in phenocrysts of eruptive magmas. Moreover, miarolitic cavities, often interpreted to be a priori evidence of fluid exsolution, are rarely observed in igneous systems. Geochemical tools used to resolve magmatic volatile histories include the analysis and interpretation of melt inclusion compositions and those of hydrous minerals including micas, amphiboles, and apatite. We have conducted more than 50 new hydrothermal experiments involving apatite+rhyodacite melt±fluids at 28, 50, 100, 200, and 400 MPa, and have combined these new data with published results for apatite-saturated melts at 200 MPa. This integrated body of data supports determination of a broadly applicable geochemical relationship that correlates the mole fractions of H2O and Cl in apatite with mole fractions of H2O and Cl in coexisting silicate melt as a function of pressure, temperature, and melt composition (for felsic to basaltic melts). The mathematical expression of this relationship is useful for a wide variety of applications: constraining H2O, Cl, and F concentrations in silicate melts and hence verifying concentrations of magmatic volatiles determined from silicate melt inclusions; establishing pressures or temperatures of apatite crystallization or last equilibration with melt ± fluids (if temperature and pressure, respectively, are constrained from other geothermobarometers); determining concentrations of

  16. Quantifying glacial erosion in the European Alps using apatite fission track dating

    NASA Astrophysics Data System (ADS)

    Wangenheim, Cornelia; Glotzbach, Christoph

    2015-04-01

    To investigate the impact of glacial erosion on landscape evolution during the Quaternary, problems may occur in choosing the best method, because many methods only reflect parts of the era. Erosion rate calculations based on cosmogenic nuclides only cover the Holocene and erosion rate calculations based on river load gauging reflect even shorter timescales (e.g. von Blanckenburg 2005). In this study we investigate the potential of thermochronological methods, especially apatite fission track dating (AFT) to quantify glacial erosion in the European Alps. The topography of the European Alps is strongly influenced by Quaternary glaciations, as it formed characteristic features like overdeepened and hanging valleys. The study area is located in the Central Alps of Switzerland, which is a high mountain area. At ~0.9 Ma glacial erosion has led to a considerable increase in valley incision rates in this area (Haeuselmann et al. 2007) and therefore it is ideally suited to study the glacial impact on landscape evolution. The advantage of using AFT dating, while studying changes in erosional processes, is that possibly arising nonsteady-state erosion will be recorded within the spatial distribution of thermochronological ages. In this study we applied AFT dating on both bedrock and sediments. The bedrock samples derive from different elevations to figure out whether or not spatial differences and elevation dependencies exist. Combined with already published data we have a relatively high sample density distributed throughout the whole study area. The detrital samples originate from stream sediments and from glacial deposits in the form of late glacial moraines and cave sediments from the last ~0.5 Ma in order to obtain possible lateral variations in erosion. The AFT ages of the bedrocks vary between ~4 Ma and ~9 Ma, resulting in an average long-term exhumation rate of ~0.5 km/Ma. Most of the ages range between 7 and 9 Ma, confirmed by prevailing ages of stream sediment

  17. Interim Report: 100-NR-2 Apatite Treatability Test: Low Concentration Calcium Citrate-Phosphate Solution Injection for In Situ Strontium-90 Immobilization

    SciTech Connect

    Williams, Mark D.; Fritz, Brad G.; Mendoza, Donaldo P.; Rockhold, Mark L.; Thorne, Paul D.; Xie, YuLong; Bjornstad, Bruce N.; Mackley, Rob D.; Newcomer, Darrell R.; Szecsody, James E.; Vermeul, Vincent R.

    2008-07-11

    Following an evaluation of potential Sr-90 treatment technologies and their applicability under 100-NR-2 hydrogeologic conditions, U.S. Department of Energy, Fluor Hanford, Inc., Pacific Northwest National Laboratory, and the Washington Department of Ecology agreed that the long-term strategy for groundwater remediation at 100-N Area will include apatite sequestration as the primary treatment, followed by a secondary treatment if necessary (most likely phytoremediation). Since then, the agencies have worked together to agree on which apatite sequestration technology has the greatest chance of reducing Sr-90 flux to the river at a reasonable cost. In July 2005, aqueous injection, (i.e., the introduction of apatite-forming chemicals into the subsurface) was endorsed as the interim remedy and selected for field testing. Studies are in progress to assess the efficacy of in situ apatite formation by aqueous solution injection to address both the vadose zone and the shallow aquifer along the 300 ft of shoreline where Sr-90 concentrations are highest. This report describes the field testing of the shallow aquifer treatment.

  18. A simple and general route for the preparation of pure and high crystalline nanosized lanthanide silicates with the structure of apatite at low temperature

    SciTech Connect

    Ferdov, Stanislav; Rauwel, Protima; Lin, Zhi; Ferreira, Rute A. Sa; Lopes, Augusto

    2010-11-15

    Rare earth silicates with the structure of apatite are attracting considerable interest since they show oxygen ion conductivities higher than that of yttria-stabilized zirconia (YSZ) at moderate temperature. Based on the hydrothermal synthesis we presented a simple one step process for the direct preparation of the pure and the high crystalline nanosized rare earth silicates with the structure of apatite under a mild condition (230 {sup o}C). Since the preparation of the high crystalline silicon based rare earth apatites is performed at high temperature previously and accompanied by subsequent process of grinding, results of this work provide a promising alternative of the existing methodology. Furthermore, due to the relatively low temperature of the preparation of these materials, high doping of monovalent cation can be done, which was not achieved before. -- Graphical abstract: A simple one step process for the preparation of the rare earth silicates with the structure of apatite under a mild condition (230 {sup o}C) is presented. The process is based on the hydrothermal synthesis and the obtained powder materials are pure, high crystalline and with nanosize. Display Omitted

  19. A Holistic Model That Physicochemically Links Iron Oxide - Apatite and Iron Oxide - Copper - Gold Deposits to Magmas

    NASA Astrophysics Data System (ADS)

    Simon, A. C.; Reich, M.; Knipping, J.; Bilenker, L.; Barra, F.; Deditius, A.; Lundstrom, C.; Bindeman, I. N.

    2015-12-01

    Iron oxide-apatite (IOA) and iron oxide-copper-gold deposits (IOCG) are important sources of their namesake metals and increasingly for rare earth metals in apatite. Studies of natural systems document that IOA and IOCG deposits are often spatially and temporally related with one another and coeval magmatism. However, a genetic model that accounts for observations of natural systems remains elusive, with few observational data able to distinguish among working hypotheses that invoke meteoric fluid, magmatic-hydrothermal fluid, and immiscible melts. Here, we use Fe and O isotope data and high-resolution trace element (e.g., Ti, V, Mn, Al) data of individual magnetite grains from the world-class Los Colorados (LC) IOA deposit in the Chilean Iron Belt to elucidate the origin of IOA and IOCG deposits. Values of d56Fe range from 0.08‰ to 0.26‰, which are within the global range of ~0.06‰ to 0.5‰ for magnetite formed at magmatic conditions. Values of δ18O for magnetite and actinolite are 2.04‰ and 6.08‰, respectively, consistent with magmatic values. Ti, V, Al, and Mn are enriched in magnetite cores and decrease systematically from core to rim. Plotting [Al + Mn] vs. [Ti + V] indicates that magnetite cores are consistent with magmatic and/or magmatic-hydrothermal (i.e., porphyry) magnetites. Decreasing Al, Mn, Ti, V is consistent with a cooling trend from porphyry to Kiruna to IOCG systems. The data from LC are consistent with the following new genetic model for IOA and IOCG systems: 1) magnetite cores crystallize from silicate melt; 2) these magnetite crystals are nucleation sites for aqueous fluid that exsolves and scavenges inter alia Fe, P, S, Cu, Au from silicate melt; 3) the magnetite-fluid suspension is less dense that the surrounding magma, allowing ascent; 4) as the suspension ascends, magnetite grows in equilibrium with the fluid and takes on a magmatic-hydrothermal character (i.e., lower Al, Mn, Ti, V); 5) during ascent, magnetite, apatite and

  20. Mineralogy, 40Ar/ 39Ar dating and apatite fission track dating of rocks along the Castle Mountain fault, Alaska

    NASA Astrophysics Data System (ADS)

    Parry, W. T.; Bunds, M. P.; Bruhn, R. L.; Hall, C. M.; Murphy, J. M.

    2001-07-01

    The Castle Mountain fault is a 200-km-long, right-lateral fault that forms the northern boundary of the Cook Inlet basin and Matanuska Valley, Alaska. Fault gouge and fault rock at six localities contain the clay minerals illite, smectite, chlorite, and interstratified illite/smectite. At one locality, gouge contains deformed illite/smectite with very little wall rock chlorite contamination. Fine (<0.03 μm), medium (0.03-0.2 μm), and coarse (0.2-2.0 μm) illite/smectite from this site were dated using 40Ar/ 39Ar micro-encapsulation and laser microprobe methods. Total gas ages for the three size fractions are 28.21±0.12, 32.42±0.11 and 36.24±0.08 Ma for fine to coarse sizes respectively. Argon retention ages obtained from 40Ar and 39Ar retained in the three size fractions of illite at room temperature during neutron irradiation are 37.36±0.15, 42.11±0.14 and 47.20±0.10 respectively. Apatite fission track ages were measured in arkose at a locality on the fault 60 km west of the gouge locality. Three samples of arkose were dated: one within 10 m of the fault core, one 170 m from the fault, and one 335 m from the fault. The sample nearest to the fault yielded an age of 29.3±2.8 Ma, but it only had four track lengths at 10-13 μm. Two apatite grains from the intermediate sample yielded a pooled age of 34.3±6.1 Ma. The distant sample (25 grains counted, 101 track lengths) yielded an age of 32.0±2.9 Ma. This sample has a broad distribution of track lengths and a broad distribution of individual grain ages ranging from 14.8±5.1 to 67.8±8.8 Ma. Monte Carlo modeling of the apatite age and track length data is consistent with hydrothermal mineralization at 37-39 Ma followed by rapid uplift and cooling after 10 Ma. The 40Ar/ 39Ar total gas ages (K-Ar) are minimum ages, and the argon retention ages are maximum ages. The thermal model derived from the fission track data, and the argon retention age for the finest illite fraction of ˜37 Ma date a hydrothermal

  1. Evidence for Rapid Post-Pliocene Exhumation of the Santa Monica Mountains, California, from Apatite (U-Th)/He Thermochronometry

    NASA Astrophysics Data System (ADS)

    Niemi, N. A.; Clark, M. K.; Yakovlev, P. V.

    2015-12-01

    Potential losses related to large earthquakes on blind or previously unrecognized thrust faults is of significant concern to southern California, where numerous individual mountain ranges are underlain by active faults. Some of the most hazardous thrust fault systems in Southern California are associated with high-slip-rate faults in the northern portion of the western Transverse Ranges, while the southern region is generally considered to be less seismically active. Determining slip rates on faults bounding the Santa Monica Mountains has been challenging, in part because many of the faults that underlie the range have submarine surface traces. Existing geologic studies predict that these faults slip relatively slowly; however, recent GPS models predict a band of relatively fast contraction on faults that lie beneath the Santa Monica Mountains (Marshall et al., 2013). These geodetic models suggest unrecognized hazard associated with shortening and vertical uplift of this range. Late Cenozoic strata in the central Santa Monica Mountains are of sufficient thickness to bury Cretaceous and Paleocene strata above the closure temperature for apatite (U-Th)/He thermochronometry (~70°C). As a result, these older rocks, now exposed in the southern Santa Monica Mountains, may record exhumation associated with fault slip and associated structural deformation of the range. Preliminary apatite (U-Th)/He ages near Las Flores Canyon span from 3.5 to 6.5 Ma, and are the youngest apatite (U-Th)/He ages we are aware of in southern California outside of the transpressional San Andreas system. When plotted as depth beneath the base of the marine Modelo Formation, an inflection in age/depth gradient at 4 Ma is inferred to reflect the onset of fault motion and is consistent with the late Miocene age of the Modelo Formation. Based on average geothermal gradients for the Ventura and Los Angeles basins and an assumed thrust fault dip of 20°, observed apparent exhumation rates are

  2. Apatite formation on bioactive calcium-silicate cements for dentistry affects surface topography and human marrow stromal cells proliferation.

    PubMed

    Gandolfi, Maria Giovanna; Ciapetti, Gabriela; Taddei, Paola; Perut, Francesca; Tinti, Anna; Cardoso, Marcio Vivan; Van Meerbeek, Bart; Prati, Carlo

    2010-10-01

    The effect of ageing in phosphate-containing solution of bioactive calcium-silicate cements on the chemistry, morphology and topography of the surface, as well as on in vitro human marrow stromal cells viability and proliferation was investigated. A calcium-silicate cement (wTC) mainly based on dicalcium-silicate and tricalcium-silicate was prepared. Alpha-TCP was added to wTC to obtain wTC-TCP. Bismuth oxide was inserted in wTC to prepare a radiopaque cement (wTC-Bi). A commercial calcium-silicate cement (ProRoot MTA) was tested as control. Cement disks were aged in DPBS for 5 h ('fresh samples'), 14 and 28 days, and analyzed by ESEM/EDX, SEM/EDX, ATR-FTIR, micro-Raman techniques and scanning white-light interferometry. Proliferation, LDH release, ALP activity and collagen production of human marrow stromal cells (MSC) seeded for 1-28 days on the cements were evaluated. Fresh samples exposed a surface mainly composed of calcium-silicate hydrates CSH (from the hydration of belite and alite), calcium hydroxide, calcium carbonate, and ettringite. Apatite nano-spherulites rapidly precipitated on cement surfaces within 5 h. On wTC-TCP the Ca-P deposits appeared thicker than on the other cements. Aged cements showed an irregular porous calcium-phosphate (Ca-P) coating, formed by aggregated apatite spherulites with interspersed calcite crystals. All the experimental cements exerted no acute toxicity in the cell assay system and allowed cell growth. Using biochemical results, the scores were: fresh cements>aged cements for cell proliferation and ALP activity (except for wTC-Bi), whereas fresh cementsapatite nano-spherulites; (2) the alpha-TCP doped cement aged for 28 days displayed the highest bioactivity and cell proliferation; (3) the deleterious effect of bismuth on cell

  3. Microchemical and structural regular variability of apatites in “overbuilt” enamel and dentin of human molar teeth

    NASA Astrophysics Data System (ADS)

    Kuczumow, A.; Nowak, J.; ChaŁas, R.

    2011-10-01

    The aim of a recent paper was to recognize the chemical and structural changes in apatites, which form both the enamel and the dentin of the human tooth. The aim was achieved by scrutinizing the linear elemental profiles along the cross-sections of human molar teeth. Essentially, the task was accomplished with the application of the Electron Probe Microanalysis method and with some additional studies by Micro-Raman spectrometry. All the trends in linear profiles were strictly determined. In the enamel zone they were either increasing or decreasing curves of exponential character. The direction of the investigations was to start with the tooth surface and move towards the dentin-enamel junction (DEJ). The results of the elemental studies were more visible when the detected material was divided, in an arbitrary way, into the prevailing "core" enamel (˜93.5% of the total mass) and the remaining "overbuilt" enamel. The material in the "core" enamel was fully stable, with clearly determined chemical and mechanical features. However, the case was totally different in the "overbuilt enamel", with dynamic changes in the composition. In the "overbuilt" layer Ca, P, Cl and F profiles present the decaying distribution curves, whereas Mg, Na, K and CO 32- present the growing ones. Close to the surface of the tooth the mixture of hydroxy-, chlor- and fluor-apatite is formed, which is much more resistant than the rest of the enamel. On passing towards the DEJ, the apatite is enriched with Na, Mg and CO 32-. In this location, three of six phosphate groups were substituted with carbonate groups. Simultaneously, Mg is associated with the hydroxyl groups around the hexad axis. In this way, the mechanisms of exchange reactions were established. The crystallographic structures were proposed for new phases located close to DEJ. In the dentin zone, the variability of elemental profiles looks different, with the most characteristic changes occurring in Mg and Na concentrations. Mg

  4. The Volatile Element Evolution of Intra-plate Alkaline Rocks as Recorded by Apatite: An Example from the Hegau Volcanic Field (Southwest Germany)

    NASA Astrophysics Data System (ADS)

    Von Der Handt, A.; Rahn, M. K. W.; Wang, L. X.; Marks, M. A. W.

    2014-12-01

    The role of volatiles in the petrogenesis of alkaline intra-plate magmas has been the subject of an increasing number of experimental studies. The study of naturally occurring rocks and their volatile contents is often complicated by syn- and post-eruptive degassing and alteration processes. Minerals that incorporate volatiles into their structure such as apatites are often more faithful recorders of the pre-eruptive volatile budget. The Hegau volcanic field in Southwest Germany is part of the Central European Volcanic Province, lies around 60-70 km to the east of the Upper Rhine graben and of Miocene age. Three main lithological units can be distinguished (1) olivine melilites (2) phonolites and (3) the "Deckentuff" series referring to a series of diatreme-filling pipe breccias and lapilli tuff layers. Carbonatites occur subordinately in the Hegau province. Earlier radiometric age dating suggested distinct phases of volcanic activity of Deckentuffs, melilites and phonolites with little overlap, but new apatite fission-track and (U-Th)/He age data suggest a synchronous activity. Apatite is an abundant accessory phase in the Deckentuff and phonolite series and we investigated its major, trace and volatile element composition by EPMA, SIMS and cathodoluminescence imaging. Pronounced core-rim zoning of apatite in places attests that diffusional equilibration was very limited and they likely retained their primary compositions. This allows us to trace the entire magmatic evolution of the Hegau province from its most primitive to most evolved products as well as resolve it in time by combining age dating with compositional analysis. Apatite compositions fall along the OH-F join with low Cl-contents (<0.5 wt%). Volatile contents (Cl, OH, S) are highest in most primitive compositions and decrease with further evolution while F increases. Multiple magmatic cycles can be discerned with a general trend to the more evolved phonolite compositions toward the end of volcanic

  5. Calcium-deficient apatite: influence of granule size and consolidation mode on release and in vitro activity of vancomycin.

    PubMed

    Obadia, L; Amador, G; Daculsi, G; Bouler, J-M

    2003-03-01

    The use of dynamic compaction and isostatic compression to consolidate calcium phosphate powder loaded with a therapeutic agent avoids a sintering step that could destroy the drug. The present study applied these consolidation methods to vancomycin-loaded calcium-deficient apatite powder, using three granulometric fractions (40-80, 80-200 and 200-500 micrometer). In vitro release profiles were determined via an original system derived from low-pressure liquid chromatography. The biological activity of vancomycin was measured by an in vitro standardized bacteriologic assay, which showed that the drug is completely active after association with calcium phosphate. Regardless of the consolidation method and granulometric fraction used, release profiles were not significantly different and therefore adaptable to injectable suspensions.

  6. In vitro apatite forming ability of type I collagen hydrogels containing bioactive glass and silica sol-gel particles.

    PubMed

    Eglin, David; Maalheem, Sonia; Livage, Jacques; Coradin, Thibaud

    2006-02-01

    Type I collagen hydrogel containing bioactive glass (CaO-P2O5-SiO2) and silica sol-gel micrometric particles were prepared and their in vitroapatite-forming ability in simulated body fluid assessed. X-ray diffraction and scanning electron microscopy analysis showed that bioactive glass particles entrapment in collagen matrix did not inhibit calcium phosphate formation and induced morphology variations on the crystalline phase precipitated on the hydrogel surface. The silica--collagen hydrogel composite precipitated calcium phosphate whereas silica particles and collagen hydrogel alone did not, indicating a possible synergetic effect between collagen and silica on the apatite-forming ability. Mechanisms of calcium phosphate precipitation and its relevance to biomaterial development are discussed.

  7. Evidence of octacalcium phosphate and Type-B carbonated apatites deposited on the surface of explanted acrylic hydrogel intraocular lens.

    PubMed

    Lin, Shan-Yang; Chen, Ko-Hua; Li, May-Jane; Cheng, Wen-Ting; Wang, Shun-Li

    2004-08-15

    Fourier-transform infrared (FTIR) microspectroscopy combining with attenuated total reflection (ATR) microsampling technique and micro-Raman spectrophotometer were used to detect the deposited materials on the surface of acrylic hydrogel intraocular lens (IOL) with or without ocular implantation. Surface morphology and the interface of this IOL were further examined by a confocal laser scanning microscope. The brand-new IOL exhibited a very smooth, transparent and featureless surface, but the explanted IOL had an irregular cerebriform-like opaque appearance. Both FTIR/ATR and Raman microspectroscopic analyses showed the deposits on the surface of acrylic hydrogel IOL after ocular implantation to consist of octacalcium phosphate (OCP) and Type B carbonated apatites, leading to the opalescence of acrylic hydrogel IOL. Both vibrational microspectroscopic examinations also confirmed the mineralization still in progress on the surface of acrylic hydrogel IOL after ocular implantation for 2 years.

  8. In Vitro Corrosion Behavior and Apatite Growth of Oxygen Plasma Ion Implanted Titanium Alloy β-21S

    NASA Astrophysics Data System (ADS)

    Anandan, C.; Mohan, L.

    2013-11-01

    Titanium alloy beta 21S was implanted with oxygen ions by plasma immersion ion implantation. The implanted surface was characterized by micro-Raman, XPS and FESEM before and after potentiodynamic polarization and electrochemical impedance studies in Hanks' solution and after incubation in Hanks' solution for 1 and 7 days. The investigations show that the native oxide on the sample is replaced by a compact oxide by implantation and the new oxide layer behaves in a different way in that a two layer model is required to explain the observed electrochemical impedance data. The analysis of layers formed in the electrochemical studies and after incubation in Hanks' solution by XPS and FESEM shows that the new oxide surface is capable of inducing apatite growth on it.

  9. Superplastic deformation in carbonate apatite ceramics under constant compressive loading for near-net-shape production of bioresorbable bone substitutes.

    PubMed

    Adachi, Masanori; Wakamatsu, Nobukazu; Doi, Yutaka

    2008-01-01

    To produce carbonate apatite (CAP) ceramics with the desired complex shapes using superplastic deformation, deformation behavior of CAP ceramics under constant loading as well as physical properties after deformation were evaluated. Sintered CAP ceramics were plastically deformed in an electric furnace attached to a universal hydraulic testing machine under a constant load. CAP ceramics subjected to an initial compressive pressure of 10 MPa showed an appreciable amount of plastic deformation at temperatures ranging from 720 to 800 degrees C. Plastic deformation increased with increasing temperature from about 10% to 70% after two hours of loading. X-ray diffraction analysis and SEM observation further revealed that some CAP crystals were elongated and aligned with the c-axis normal to the loading direction during superplastic deformation. It was thus concluded that a marked plastic deformation of about 70% at 800 degrees C would be sufficient for near-net-shape production of bioresorbable CAP bone substitutes with complex shapes.

  10. Apatite fission track dating by LA-ICP-MS and External Detector Method: How do they stack up?

    NASA Astrophysics Data System (ADS)

    Seiler, C.; Gleadow, A. J.; Kohn, B. P.

    2013-12-01

    Analysis of trace element compositions by laser ablation ICP-MS has become a widely used tool to determine in-situ ages in geochronology. Although used primarily for U-Pb dating, LA-ICP-MS has been successfully adapted to other dating techniques such as apatite fission track (Hasebe et al., 2004) or (U-Th)/He (Boyce et al., 2006), making it an ideal tool for multi-system thermochronological studies. LA-ICP-MS fission track dating has several important advantages over the traditional external detector method (EDM), particularly in terms of sample turn-around time and the fact that neutron irradiations (and the handling of radioactive materials) are no longer necessary, while providing a similar level of in-situ information. Perhaps the most important benefits of LA-ICP-MS fission track dating is that it could potentially be used as an absolute dating technique with no Zeta-calibration necessary. However, beyond the initial study of Hasebe et al. (2004), little work has been done to compare results obtained by LA-ICP-MS with those from EDM analysis, and it remains unclear whether the two methods yield equivalent results. We present an extensive dataset of fission track results that were analysed using both LA-ICP-MS and EDM dating. The samples were selected to represent a variety of compositions, with single grain ages ranging from a few million to over a billion years. Both techniques were applied on identical grains, thereby eliminating uncertainties associated with natural variability. The comparison shows that, with a few exceptions, single grain fission track ages from LA-ICP-MS and EDM are concordant within analytical uncertainties and scatter symmetrically around the 1:1 correlation line. Although the relative difference in single grain ages varies significantly in either direction (up to 70%), there are no systematic variations between the two methods suggesting that this variation is simply due to random sampling effects. However, we did find systematic

  11. Partitioning in REE-saturating minerals - Theory, experiment, and modelling of whitlockite, apatite, and evolution of lunar residual magmas

    NASA Technical Reports Server (NTRS)

    Jolliff, Bradley L.; Haskin, Larry A.; Colson, Russell O.; Wadhwa, Meenakshi

    1993-01-01

    Compositions, including REEs determined by ion microprobe, of apatite and whitlockite in lunar rock assemblages rich in incompatible trace elements, are presented. Concentrations of REEs in lunar whitlockites are high, ranging from about 1.2 to 2.1 REEs (lanthanides + Y) per 56 oxygens. This slightly exceeds the level of two REE atoms per 56 oxygens at which the dominant substitution theoretically becomes saturated. This saturation effect leads to whitlockite REE(3+) D values at typical lunar whitlockite REE concentrations which are 30-40 percent lower than the D values at low concentrations. The halogen-to-phosphorous ratio in lunar melts is a key factor determining the REE distribution with crystalline assemblages. As long as P and REE concentrations of melts are in KREEP-like proportions, one or both of the phosphates will saturate in melts at similar REE concentrations.

  12. Partial melting of apatite-bearing charnockite, granulite, and diorite: Melt compositions, restite mineralogy, and petrologic implications

    NASA Technical Reports Server (NTRS)

    Beard, James S.; Lofgren, Gary E.; Sinha, A. Krishna; Tollo, Richard P.

    1994-01-01

    Melting experiments (P = 6.9 kbar, T = 850-950 deg C, NNO is less than fO2 is less than HM) were done on mafic to felsic charnockites, a dioritic gneiss, and a felsic garnet granulite, all common rock types in the Grenville basement of eastern North America. A graphite-bearing granulite gneiss did not melt. Water (H2O(+) = 0.60 to 2.0 wt %) is bound in low-grade, retrograde metamorphic minerals and is consumed during the earliest stages of melting. Most melts are water-undersaturated. Melt compositions range from metaluminous, silicic granodiorite (diorite starting composition) to peraluminous or weakly metaluminous granites (all others). In general, liquids become more feldspathic, less silicic, and less peraluminous and are enriched in FeO, MgO, and TiO2 with increasing temperature. Residual feldspar mineralogy controls the CaO, K2O, and Na2O contents of the partial melts and the behavior of these elements can be used, particularly if the degree of source melting can be ascertained, to infer some aspects of the feldspar mineralogy of the source. K-feldspar, a common restite phase in the charnockite and granulite (but not the diorite) should control the behavior of Ba and, possibly, Eu in these systems and yield signatures of these elements that can distinguish source regions and, in some cases, bulk versus melt assimilation. Apatite, a common restite phase, is enriched in rare earth elements (REE), especially middle REE. Retention of apatite in the restite will result in steep, light REE-enriched patterns for melts derived from the diorite and charnockites.

  13. Combining apatite fission track results and geomorphic indicators in the Western Moroccan Meseta (coastal Variscan Paleozoic basement)

    NASA Astrophysics Data System (ADS)

    Barbero, Luis

    2010-05-01

    In a section of the Western Moroccan Meseta different tools are combined in order to link the evolution of the topography to the general tectonic framework of western Morocco. Apatite fission track (AFT) data of granitic rocks of the Rabat - Khenifra area give ages around 200 Ma with track length distributions which are compatible with the thermal models already established for the area. A long post-Variscan thermal history is preserved in the apatite fission track thermal signal, showing several periods of cooling and heating that can be related to Jurassic to Early Creataceous rifting which seems to be widespread along the southernmost Variscan chain and also to the subsidence in relation to shortening which originated the Atlas and Rif belts. An inverse correlation between AFT ages and elevation is observed which is compatible with previous models indicating northward tilting of the whole Western Moroccan Meseta which is younger than 20-25 Ma. In order to test this possibility a detailed analysis of the topography at different scales in the Western Moroccan Meseta has been performed. Results indicate that two open folds with different amplitudes are recognised and that the one with wider wavelength could correspond to a lithospheric fold as previously stated by other authors on the basis of independent geological arguments. The northward tilting proposed based on the AFT data agrees with the results obtained in the analysis of the topography which reinforces the presence of a very open fold with a wavelength of 200-300 km in the north-western limb of the Western Moroccan Meseta.

  14. Evidence of post-Gondwana breakup in Southern Brazilian Shield: Insights from apatite and zircon fission track thermochronology

    NASA Astrophysics Data System (ADS)

    Oliveira, Christie Helouise Engelmann de; Jelinek, Andréa Ritter; Chemale, Farid; Bernet, Matthias

    2016-01-01

    Apatite and zircon fission track thermochronology studies are applied to basement and sedimentary rocks from the Sul-Rio-Grandense Shield to unravel the tectonic history of the onshore southernmost Brazilian margin. The Sul-Rio-Grandense Shield is a major geotectonic feature of southernmost Brazil that includes Paleoproterozoic basement areas and Neoproterozoic fold belts linked to the Brasiliano/Pan-African orogeny. Crustal reworking and juvenile accretion events related to this cycle were dated in the region between 900 and 500 Ma and were responsible for the assembly of southwestern Gondwana in southeastern South America. Apatite fission track (AFT) ages range from 340 ± 33 to 77 ± 6 Ma and zircon fission track (ZFT) ages range from ca. 386 to 210 Ma. Based on thermal history modeling, the most part of the samples record an early cooling event during the Carboniferous, which reflect the main tectonic activity of the final stages of the Gondwanides at the Pacific margin of West Gondwana. Subsequently, the Permo-Triassic cooling event is related to the last stages of the Gondwanides, with convergence along the southern border of Western Gondwana and consequent reactivation of N-S and NE-SW trending basement structures. The onset of initial breakup of southwestern Gondwana with opening of the South Atlantic Ocean is mostly recorded in the eastern terrain and ZFT ages show that the temperature during this period was high enough for total or at least partial resetting of fission tracks in zircon. The last cooling event of the Sul-Rio-Grandense Shield records the final breakup between South America and Africa, which began during the Late Cretaceous. However, the Cenozoic rapid cooling episode probably is a result of plate adjustment after breakup and neotectonic reactivation of faults associated with South Atlantic rift evolution.

  15. Biointeractivity-related versus chemi/physisorption-related apatite precursor-forming ability of current root end filling materials.

    PubMed

    Gandolfi, Maria Giovanna; Taddei, Paola; Modena, Enrico; Siboni, Francesco; Prati, Carlo

    2013-10-01

    Commercial root end filling materials, namely two zinc oxide eugenol-based cements [intermediate restorative material (IRM), Superseal], a glass ionomer cement (Vitrebond) and three calcium-silicate mineral trioxide aggregate (MTA)-based cements (ProRoot MTA, MTA Angelus, and Tech Biosealer root end), were examined for their ability to: (a) release calcium (Ca(2+) ) and hydroxyl (OH(-) ) ions (biointeractivity) and (b) form apatite (Ap) and/or calcium phosphate (CaP) precursors. Materials were immersed in Hank's balanced salt solution (HBSS) for 1-28 days. Ca(2+) and OH(-) release were measured by ion selective probes, surface analysis was performed by environmental scanning electron microscopy/energy dispersive X-ray analysis, micro-Raman, and Fourier transform infrared spectroscopy. IRM and Superseal released small quantities of Ca(2+) and no OH(-) ions. Uneven sparse nonapatitic Ca-poor amorphous CaP (ACP) deposits were observed after 24 h soaking. Vitrebond did not release either Ca(2+) or OH(-) ions, but uneven nonapatitic Ca-poor CaP deposits were detected after 7 days soaking. ProRoot MTA, MTA Angelus, and Tech Biosealer root end released significant amounts of Ca(2+) and OH(-) ions throughout the experiment. After 1 day soaking, nanospherulites of CaP deposits formed by amorphous calcium/magnesium phosphate (ACP) Ap precursors were detected. A more mature ACP phase was present on ProRoot MTA and on Tech Biosealer root end at all times. In conclusion, zinc oxide and glass ionomer cements had little or no ability to release mineralizing ions: they simply act as substrates for the possible chemical bonding/adsorption of environmental ions and precipitation of nonapatitic Ca-poor ACP deposits. On the contrary, calcium-silicate cements showed a high calcium release and basifying effect and generally a pronounced formation of more mature ACP apatitic precursors correlated with their higher ion-releasing ability.

  16. Thermotectonic history of the Chiplakot Crystalline Belt in the Lesser Himalaya, Kumaon, India: Constraints from apatite fission-track thermochronology

    NASA Astrophysics Data System (ADS)

    Patel, R. C.; Kumar, Yogesh; Lal, Nand; Kumar, Ashok

    2007-02-01

    Fission-track ages and confined track length distribution of apatite samples separated from the Chiplakot Crystalline Belt (CCB) of the Lesser Himalayan Crystalline (LHC) zone, located to the south of the Main Central Thrust (MCT)/Munsiari Thrust (MT) in Kumaon, India, have been determined. Ages from the CCB along the Kali and Darma valleys fall in two distinct groups. In the northern part of the CCB, the ages range from 9.8 ± 0.6 to 7.6 ± 0.6 Ma with a weighted mean of 9.6 ± 0.1 Ma, while in the southern part the ages vary from 17.9 ± 0.9 to 12.9 ± 1.1 Ma with a weighted mean of 14.1 ± 0.1 Ma. The bimodal distribution of track lengths indicates that the ages are mixed ages, rather than simple cooling ages. The apatite fission-track (AFT) ages and already published structural data of the CCB suggest a complex erosional, denudation history within the upper 3-4 km of the crust of the CCB. The ages further indicate that the CCB was thrust into place earlier than the Middle Miocene i.e. at the time of development of the MCT. Since, then these rocks have remained within the upper 3 km of crust and were affected by only moderate to slow erosion and exhumation. These results have important implications for the tectonic evolution of the LHC zone to the south of the MCT/MT. The exhumation of the LHC zone in different parts of the Himalaya was not uniform. In the Kumaon Himalaya, it was not controlled, as in the Himachal Himalaya, by any major tectonic event, since it was thrust over the Lesser Himalayan Meta-sedimentary (LHMS) zone, and underwent moderate to slow erosion and exhumation.

  17. Stable isotope (C, O) and monovalent cation fractionation upon synthesis of carbonate-bearing hydroxyl apatite (CHAP) via calcite transformation

    NASA Astrophysics Data System (ADS)

    Böttcher, Michael E.; Schmiedinger, Iris; Wacker, Ulrike; Conrad, Anika C.; Grathoff, Georg; Schmidt, Burkhard; Bahlo, Rainer; Gehlken, Peer-L.; Fiebig, Jens

    2016-04-01

    Carbonate-bearing hydroxyl-apatite (CHAP) is of fundamental and applied interest to the (bio)geochemical, paleontological, medical and material science communities, since it forms the basic mineral phase in human and animal teeth and bones. In addition, it is found in non-biogenic phosphate deposits. The stable isotope and foreign element composition of biogenic CHAP is widely used to estimate the formation conditions. This requires careful experimental calibration under well-defined boundary conditions. Within the DFG project EXCALIBOR, synthesis of carbonate-bearing hydroxyapatite was conducted via the transformation of synthetic calcite powder in aqueous solution as a function of time, pH, and temperature using batch-type experiments. The aqueous solution was analyzed for the carbon isotope composition of dissolved inorganic carbonate (gas irmMS), the oxygen isotope composition of water (LCRDS), and the cationic composition. The solid was characterized by powder X-ray diffraction, micro Raman and FTIR spectroscopy, SEM-EDX, elemental analysis (EA, ICP-OES) and gas irmMS. Temperature was found to significantly impact the transformation rate of calcite to CHAP. Upon complete transformation, CHAP was found to contain up to 5% dwt carbonate, depending on the solution composition (e.g., pH), both incorporated on the A and B type position of the crystal lattice. The oxygen isotope fractionation between water and CHAP decreased with increasing temperature with a tentative slope shallower than those reported in the literature for apatite, calcite or aragonite. In addition, the presence of dissolved NH4+, K+ or Na+ in aqueous solution led to partial incorporation into the CHAP lattice. How these distortions of the crystal lattice may impact stable isotope discrimination is subject of future investigations.

  18. Functional biomimetic analogs help remineralize apatite-depleted demineralized resin-infiltrated dentin via a bottom-up approach.

    PubMed

    Kim, Jongryul; Arola, Dwayne D; Gu, Lisha; Kim, Young Kyung; Mai, Sui; Liu, Yan; Pashley, David H; Tay, Franklin R

    2010-07-01

    Natural biominerals are formed through metastable amorphous precursor phases via a bottom-up, nanoparticle-mediated mineralization mechanism. Using an acid-etched human dentin model to create a layer of completely demineralized collagen matrix, a bio-inspired mineralization scheme has been developed based on the use of dual biomimetic analogs. These analogs help to sequester fluidic amorphous calcium phosphate nanoprecursors and function as templates for guiding homogeneous apatite nucleation within the collagen fibrils. By adopting this scheme for remineralizing adhesive resin-bonded, completely demineralized dentin, we have been able to redeposit intrafibrillar and extrafibrillar apatites in completely demineralized collagen matrices that are imperfectly infiltrated by resins. This study utilizes a spectrum of completely and partially demineralized dentin collagen matrices to further validate the necessity for using a biomimetic analog-containing medium for remineralizing resin-infiltrated partially demineralized collagen matrices in which remnant seed crystallites are present. In control specimens in which biomimetic analogs are absent from the remineralization medium, remineralization could only be seen in partially demineralized collagen matrices, probably by epitaxial growth via a top-down crystallization approach. Conversely, in the presence of biomimetic analogs in the remineralization medium, intrafibrillar remineralization of completely demineralized collagen matrices via a bottom-up crystallization mechanism can additionally be identified. The latter is characterized by the transition of intrafibrillar minerals from an inchoate state of continuously braided microfibrillar electron-dense amorphous strands to discrete nanocrystals, and ultimately into larger crystalline platelets within the collagen fibrils. Biomimetic remineralization via dual biomimetic analogs has the potential to be translated into a functional delivery system for salvaging failing

  19. Phanerozoic polycyclic evolution of the southwestern Angola margin: New insights for apatite fission track and (U-Th)/He methodologies

    NASA Astrophysics Data System (ADS)

    Venancio da Silva, Bruno; Hackspacher, Peter; Carina Siqueira Ribeiro, Marli; Glasmacher, Ulrich Anton

    2016-04-01

    The low-temperature thermochronology has been an important tool to quantify geological process in passive continental margins. In this context, the Angolan margin shows evidence of a polycyclic post-rift evolution marked by different events of uplift, basin inversion and changes in sedimentation rates to the marginal basins, which have controlled the salt tectonics and the hydrocarbon deposits (1,2,3,4). To understand the post break-up evolution of the southwestern Angola margin, it were collected outcrop samples for apatite fission track (AFT) and (U-Th)/He analysis ranging in elevation from 79 m to 1675 m from the coast toward the interior plateau in a profile between Namibe and Lubango cities. The area lies on the edge of Central and Southern Atlantic segments a few kilometers northward the Walvis ridge and encompasses the Archean and Proterozoic basement rocks of the Congo craton. The AFT ages ranging from 120.6 ± 8.9 Ma to 328.8 ± 28.5 Ma and they show a trend of increasing age toward the Great Escarpment with some exceptions. The partial mean track lengths (MTLs) vary between 11.77 ± 1.82 μm to 12.34 ± 1.13 μm with unimodal track length distributions (TDLs). The partial (U-Th)/He ages ranging from 104.85 ± 3.15 Ma to 146.95 ± 4.41 Ma and show the same trend of increasing ages landward, little younger than the AFT ages, which could be interpreted as a fast exhumation episode in Late Jurassic - Early Cretaceous times. The thermal histories modelling has been constrained with the kinetic parameters Dpar (5) and c-axis angle (6) by the software Hefty (7). Both AFT and (U-Th)/He thermal histories modelling indicate three episodes of denudation/uplift driven cooling: (a) from Late Jurassic to Early Cretaceous, (b) a smallest one in the Late Cretaceous and (c) from Oligocene-Miocene to recent, which are compatible with geophysical data of the offshore Namibe basin that estimate the greater thickness of sediments formed in the first and third episodes

  20. Apatite and clinopyroxene as tracers for metasomatic processes in nepheline clinopyroxenites of Uralian-Alaskan-type complexes in the Ural Mountains, Russian Federation

    NASA Astrophysics Data System (ADS)

    Krause, Joachim; Harlov, Daniel E.; Pushkarev, Evgeny V.; Brügmann, Gerhard E.

    2013-11-01

    Clinopyroxene and apatite are found to trace metasomatic processes in nepheline-bearing clinopyroxenites (tilaites) from the igneous, mafic-ultramafic Uralian-Alaskan-type complexes of Kytlym and Nizhny Tagil, Ural Mountains, Russian Federation. The clinopyroxenites consist predominantly of coarse-grained, partially to totally altered clinopyroxene phenocrysts in a matrix of fine-grained olivine, clinopyroxene, plagioclase, K-feldspar, and nepheline. Apatite occurs as idiomorphic inclusions (<25 μm) in the clinopyroxene and as xenomorphic grains in the matrix. In the matrix, plagioclase is partially to totally replaced by a fine-grained symplectitic intergrowth of K-feldspar and nepheline most likely due to the influx of an K2O-, Na2O-, and Al2O3-bearing fluid. During conversion of the plagioclase, CaO and SiO2 were partitioned into the fluid. Altered areas in the clinopyroxene phenocrysts are characterize