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 in apatite.

Amorphous surface layer versus transient amorphous precursor phase in bone - A case study investigated by solid-state NMR spectroscopy.

PubMed

Von Euw, Stanislas; Ajili, Widad; Chan-Chang, Tsou-Hsi-Camille; Delices, Annette; Laurent, Guillaume; Babonneau, Florence; Nassif, Nadine; Azaïs, Thierry

2017-09-01

The presence of an amorphous surface layer that coats a crystalline core has been proposed for many biominerals, including bone mineral. In parallel, transient amorphous precursor phases have been proposed in various biomineralization processes, including bone biomineralization. Here we propose a methodology to investigate the origin of these amorphous environments taking the bone tissue as a key example. This study relies on the investigation of a bone tissue sample and its comparison with synthetic calcium phosphate samples, including a stoichiometric apatite, an amorphous calcium phosphate sample, and two different biomimetic apatites. To reveal if the amorphous environments in bone originate from an amorphous surface layer or a transient amorphous precursor phase, a combined solid-state nuclear magnetic resonance (NMR) experiment has been used. The latter consists of a double cross polarization 1 H→ 31 P→ 1 H pulse sequence followed by a 1 H magnetization exchange pulse sequence. The presence of an amorphous surface layer has been investigated through the study of the biomimetic apatites; while the presence of a transient amorphous precursor phase in the form of amorphous calcium phosphate particles has been mimicked with the help of a physical mixture of stoichiometric apatite and amorphous calcium phosphate. The NMR results show that the amorphous and the crystalline environments detected in our bone tissue sample belong to the same particle. The presence of an amorphous surface layer that coats the apatitic core of bone apatite particles has been unambiguously confirmed, and it is certain that this amorphous surface layer has strong implication on bone tissue biogenesis and regeneration. Questions still persist on the structural organization of bone and biomimetic apatites. The existing model proposes a core/shell structure, with an amorphous surface layer coating a crystalline bulk. The accuracy of this model is still debated because amorphous calcium phosphate (ACP) environments could also arise from a transient amorphous precursor phase of apatite. Here, we provide an NMR spectroscopy methodology to reveal the origin of these ACP environments in bone mineral or in biomimetic apatite. The 1 H magnetization exchange between protons arising from amorphous and crystalline domains shows unambiguously that an ACP layer coats the apatitic crystalline core of bone et biomimetic apatite platelets. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

[Apatite-forming ability of pure titanium implant after micro-arc oxidation treatment].

PubMed

Tian, Zhihui; Zhang, Yu; Wang, Lichao; Nan, Kaihui

2013-10-01

To investigate the apatite forming ability of pure titanium implant after micro-arc oxidation treatment in simulated body fluid (SBF) and obtain implants with calcium phosphate (Ca-P) layers. The implants were immersed in (SBF) after micro-arc oxidation treatment for different time lengths, and their apatite forming ability and the morphology and constituents of the Ca-P layers formed on the sample surface were analyzed using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive electron probe. After immersion in SBF, large quantities of Ca-P layers were induced on the surface of the samples. The Ca-P layers were composed of octacalcium phosphate and carbonated hydroxyapatite, and the crystals showed a plate-like morphology with an oriented growth. The implants with micro-arc oxidation treatment show good apatite forming ability on the surface with rich calcium and phosphorus elements. The formed layers are composed of bone-like apatite including octacalcium phosphate and carbonated hydroxyapatite.

Bioactivity of CaSiO3/poly-lactic acid (PLA) composites prepared by various surface loading methods of CaSiO3 powder.

PubMed

Okada, Kiyoshi; Hasegawa, Fumikazu; Kameshima, Yoshikazu; Nakajima, Akira

2007-05-01

Mixing bioactive ceramic powders with polymers is an effective method for generating bioactivity to the polymer-matrix composites but it is necessary to incorporate up to 40 vol% of bioactive ceramic powder. However, such a high mixing ratio offsets the advantages of the flexibility and formability of polymer matrix and it would be highly advantageous to lower the mixing ratio. Since surface loading of ceramic powders in the polymer is thought to be an effective way of reducing the mixing ratio of the ceramic powder while maintaining bioactive activity, CaSiO(3)/poly-lactic acid (PLA) composites were prepared by three methods; (1) casting, (2) spin coating and (3) hot pressing. In methods (1) and (2), a suspension was prepared by dissolving PLA in chloroform and dispersing CaSiO(3) powder in it. The suspension was cast and dried to form a film in the case of method (1) while it was spin-coated on a PLA substrate in method (2). In method (3), CaSiO(3) powder was surface loaded on to a PLA substrate by hot pressing. The bioactivity of these samples was investigated in vitro using simulated body fluid (SBF). Apatite formation was not observed in the samples prepared by method (1) but some apatite formation was achieved by mixing polyethylene glycol (PEG) with the PLA, producing a porous polymer matrix. In method (2), apatite was clearly observed after soaking for 7 days. Enhanced apatite formation was observed in method (3), the thickness of the resulting apatite layers becoming about 20 microm after soaking for 14 days. Since the amount of CaSiO(3) powder used in these samples was only

Bioactivity of CaSiO3/poly-lactic acid (PLA) composites prepared by various surface loading methods of CaSiO3 powder.

PubMed

Okada, Kiyoshi; Hasegawa, Fumikazu; Kameshima, Yoshikazu; Nakajima, Akira

2007-08-01

Mixing bioactive ceramic powders with polymers is an effective method for generating bioactivity to the polymer-matrix composites but it is necessary to incorporate up to 40 vol% of bioactive ceramic powder. However, such a high mixing ratio offsets the advantages of the flexibility and formability of polymer matrix and it would be highly advantageous to lower the mixing ratio. Since surface loading of ceramic powders in the polymer is thought to be an effective way of reducing the mixing ratio of the ceramic powder while maintaining bioactive activity, CaSiO(3)/poly-lactic acid (PLA) composites were prepared by three methods; (1) casting, (2) spin coating and (3) hot pressing. In methods (1) and (2), a suspension was prepared by dissolving PLA in chloroform and dispersing CaSiO(3) powder in it. The suspension was cast and dried to form a film in the case of method (1) while it was spin-coated on a PLA substrate in method (2). In method (3), CaSiO(3) powder was surface loaded on to a PLA substrate by hot-pressing. The bioactivity of these samples was investigated in vitro using simulated body fluid (SBF). Apatite formation was not observed in the samples prepared by method (1) but some apatite formation was achieved by mixing polyethylene glycol (PEG) with the PLA, producing a porous polymer matrix. In method (2), apatite was clearly observed after soaking for 7 days. Enhanced apatite formation was observed in method (3), the thickness of the resulting apatite layers becoming about 20 microm after soaking for 14 days. Since the amount of CaSiO(3) powder used in these samples was only < or =0.4 vol%, it is concluded that this preparation method is very effective in generating bioactivity in polymer-matrix composites by loading with only very small amounts of ceramic powder.

Effect of hot water and heat treatment on the apatite-forming ability of titania films formed on titanium metal via anodic oxidation in acetic acid solutions.

PubMed

Cui, Xinyu; Kim, Hyun-Min; Kawashita, Masakazu; Wang, Longbao; Xiong, Tianying; Kokubo, Tadashi; Nakamura, Takashi

2008-04-01

Titanium and its alloys have been widely used for orthopedic implants because of their good biocompatibility. We have previously shown that the crystalline titania layers formed on the surface of titanium metal via anodic oxidation can induce apatite formation in simulated body fluid, whereas amorphous titania layers do not possess apatite-forming ability. In this study, hot water and heat treatments were applied to transform the titania layers from an amorphous structure into a crystalline structure after titanium metal had been anodized in acetic acid solution. The apatite-forming ability of titania layers subjected to the above treatments in simulated body fluid was investigated. The XRD and SEM results indicated hot water and/or heat treatment could greatly transform the crystal structure of titania layers from an amorphous structure into anatase, or a mixture of anatase and rutile. The abundance of Ti-OH groups formed by hot water treatment could contribute to apatite formation on the surface of titanium metals, and subsequent heat treatment would enhance the bond strength between the apatite layers and the titanium substrates. Thus, bioactive titanium metals could be prepared via anodic oxidation and subsequent hot water and heat treatment that would be suitable for applications under load-bearing conditions.

[Effects of simulated body fluid flowing rate on bone-like apatite formation on porous calcium phosphate ceramics].

PubMed

Duan, You-rong; Liu, Ke-wei; Chen, Ji-yong; Zhang, Xing-dong

2002-06-01

Objective. Bone-like apatite formation on the surface of calcium phosphate ceramics was believed to be the necessary step that new bone grows on the ceramics and to be relative to the osteoinductivity of the material. This study aimed at investigating the influence of the flow rate of simulated body fluid (SBF) (2 ml/min) in skeletal muscle upon the formation of bone-like apatite on porous calcium phosphate ceramics. Method. The dynamic condition was realized by controlling the SBF flowing in/out of the sample chamber of 100 ml. The flow rate of 2 ml/min is close to that in human muscle environment. The pH and inorganic ionic composition of SBF are close to those of human body fluid. Result. Bone-like apatite formation was relatively easier to occur in static SBF than in dynamic SBF. Experiment with flowing SBF (dynamic SBF) is better in mimicking the living body fluid than static SBF. Conclusion. The results from dynamic SBF may more truly show the relation between apatite layer formation and osteoinduction in biomaterials than that from in vitro experiments before.

Experimental Constraints on the Partitioning Behavior of F, Cl, and OH Between Apatite and Basaltic Melt

NASA Technical Reports Server (NTRS)

McCubbin, Francis M.; Barnes, Jessica J.; Vander Kaaden, Kathleen E.; Boyce, Jeremy W.; Ustunisik, Gokce; Whitson, Eric S.

2017-01-01

The mineral apatite is present in a wide range of planetary materials. The presence of volatiles (F, Cl, and OH) within its crystal structure (X-site) have motivated numerous studies to investigate the partitioning behavior of F, Cl, and OH between apatite and silicate melt with the end goal of using apatite to constrain the volatile contents of planetary magmas and mantle sources. A number of recent experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in magmatic systems. Apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, the partitioning behavior is likely to change as a function of temperature, pressure, oxygen fugacity, apatite composition, and melt composition. In the present study, we have conducted experiments to assess the partitioning behavior of F, Cl, and OH between apatite and silicate melt over a pressure range of 0-6 gigapascals, a temperature range of 950-1500 degrees Centigrade, and a wide range of apatite ternary compositions. All of the experiments were conducted between iron-wustite oxidation potentials IW minus 1 and IW plus 2 in a basaltic melt composition. The experimental run products were analyzed by a combination of electron probe microanalysis and secondary ion mass spectrometry (NanoSIMS). Temperature, apatite crystal chemistry, and pressure all play important roles in the partitioning behavior of F, Cl, and OH between apatite and silicate melt. In portions of apatite ternary space that undergo ideal mixing of F, Cl, and OH, exchange coefficients remain constant at constant temperature and pressure. However, exchange coefficients vary at constant temperature (T) and pressure (P) in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. The variation in exchange coefficients exhibited by apatite that does not undergo ideal mixing far exceeds the variations induced by changes in temperature (T) or pressure (P) . In regions where apatite undergoes ideal mixing of F, Cl, and OH, temperature has a stronger effect than pressure on the partitioning behavior, but both are important. Furthermore, fluorine becomes less compatible in apatite with increasing pressure and temperature. We are still in the process of analyzing our experimental run products, but we plan to quantify the effects of P and T on apatite-melt partitioning of F, Cl, and OH.

Wet powder processing of sol-gel derived mesoporous silica-hydroxyapatite hybrid powders.

PubMed

Andersson, Jenny; Johannessen, Espen; Areva, Sami; Järn, Mikael; Lindén, Mika

2006-08-01

This paper describes a method by which a porous silica coating layer can be obtained on different apatite particles through a simple sol-gel synthesis route. Sol-gel derived powders of hydroxyapatite (HAP) and beta tricalciumphosphate (beta-TCP) were coated with a mesoporous silica using C16TAB (hexadecyltrimethylammonium bromide) as a template in order to induce mesophase formation. Further calcination of the material removes the template from the mesophase and leaves a highly ordered hexagonal arranged mesoporous silica structure with a core of HAP/beta-TCP. The phase purity of the SiO2/apatite composites has been thoroughly investigated by the means of FT-IR, XRD, and solid state 31P MAS NMR. The phase purity of these materials is shown to be dependent on the solubility properties of the used apatites. The hybrid materials are suitable as a multifunctional biomaterial where osteoconductive properties can be combined with drug delivery.

The increase of apatite layer formation by the poly(3-hydroxybutyrate) surface modification of hydroxyapatite and β-tricalcium phosphate.

PubMed

Szubert, M; Adamska, K; Szybowicz, M; Jesionowski, T; Buchwald, T; Voelkel, A

2014-01-01

The aim of this study was the surface modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) grafting and characterization of modificates. The bioactivity examination was carried out by the determination to grow an apatite layer on modified materials during incubation in simulated body fluid at 37°C. The additional issue taken up in this paper was to investigate the influence of fluid replacement. The process of the surface modification of biomaterials was evaluated by means of infrared and Raman spectroscopy. Formation of the apatite layer was assessed by means of scanning electron microscopy and confirmed by energy dispersive, Raman and Fourier transformed infrared spectroscopy. During exposure in simulated body fluid, the variation of the zeta potential, pH measurement and relative weight was monitored. Examination of scanning electron microscopy micrographs suggests that modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) significantly increases apatite layer formation. Raman spectroscopy evaluation revealed that the formation of the apatite layer was more significant in the case of hydroxyapatite modificate, when compared to the β-tricalcium phosphate modificate. Both modificates were characterized by stable pH, close to the natural pH of human body fluids. Furthermore, we have shown that a weekly changed, simulated body fluid solution increases apatite layer formation. © 2013.

Enhanced bioactive properties of BiodentineTM modified with bioactive glass nanoparticles.

PubMed

Corral Nuñez, Camila; Covarrubias, Cristian; Fernandez, Eduardo; Oliveira, Osmir Batista de

2017-01-01

To prepare nanocomposite cements based on the incorporation of bioactive glass nanoparticles (nBGs) into BiodentineTM (BD, Septodent, Saint-Maur-des-Fosses Cedex, France) and to assess their bioactive properties. nBGs were synthesised by the sol-gel method. BD nanocomposites (nBG/BD) were prepared with 1 and 2% nBGs by weight; unmodified BD and GC Fuji IX (GIC, GC Corporation, Tokyo, Japan) were used as references. The in vitro ability of the materials to induce apatite formation was assessed in SBF by X-ray diffraction (XRD), attenuated total reflectance with Fourier transform infrared spectroscopy (ATR-FTIR), and scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis. BD and nBG/BD were also applied to dentine discs for seven days; the morphology and elemental composition of the dentine-cement interface were analysed using SEM-EDX. One and two percent nBG/BD composites accelerated apatite formation on the disc surface after short-term immersion in SBF. Apatite was detected on the nBG/BD nanocomposites after three days, compared with seven days for unmodified BD. No apatite formation was detected on the GIC surface. nBG/BD formed a wider interfacial area with dentine than BD, showing blockage of dentine tubules and Si incorporation, suggesting intratubular precipitation. The incorporation of nBGs into BD improves its in vitro bioactivity, accelerating the formation of a crystalline apatite layer on its surface after immersion in SBF. Compared with unmodified BD, nBG/BD showed a wider interfacial area with greater Si incorporation and intratubular precipitation of deposits when immersed in SBF.

Adsorption and release of amino acids mixture onto apatitic calcium phosphates analogous to bone mineral

NASA Astrophysics Data System (ADS)

El Rhilassi, A.; Mourabet, M.; El Boujaady, H.; Bennani-Ziatni, M.; Hamri, R. El; Taitai, A.

2012-10-01

Study focused on the interaction of adsorbate with poorly crystalline apatitic calcium phosphates analogous to bone mineral. Calcium phosphates prepared in water-ethanol medium at physiological temperature (37 °C) and neutral pH, their Ca/P ratio was between 1.33 and 1.67. Adsorbate used in this paper takes the mixture form of two essential amino acids L-lysine and DL-leucine which have respectively a character hydrophilic and hydrophobic. Adsorption and release are investigated experimentally; they are dependent on the phosphate type and on the nature of adsorbate L-lysine, DL-leucine and their mixture. Adsorption of mixture of amino acids on the apatitic calcium phosphates is influenced by the competition between the two amino acids: L-lysine and DL-leucine which exist in the medium reaction. The adsorption kinetics is very fast while the release kinetics is slow. The chemical composition of apatite has an influence on both adsorption and release. The interactions adsorbate-adsorbent are electrostatic type. Adsorption and release reactions of the amino acid mixture are explained by the existence of the hydrated surface layer of calcium phosphate apatite. The charged sbnd COOsbnd and sbnd NH3+ of adsorbates are the strongest groups that interact with the surface of apatites, the adsorption is mainly due to the electrostatic interaction between the groups sbnd COOsbnd of amino acids and calcium Ca2+ ions of the apatite. Comparative study of interactions between adsorbates (L-lysine, DL-leucine and their mixture) and apatitic calcium phosphates is carried out in vitro by using UV-vis and infrared spectroscopy IR techniques.

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.

Developing bioactive composite scaffolds for bone tissue engineering

NASA Astrophysics Data System (ADS)

Chen, Yun

Poly(L-lactic acid) (PLLA) films were fabricated using the method of dissolving and evaporation. PLLA scaffold was prepared by solid-liquid phase separation of polymer solutions and subsequent sublimation of solvent. Bonelike apatite coating was formed on PLLA films, PLLA scaffolds and poly(glycolic acid) (PGA) scaffolds in 24 hours through an accelerated biomimetic process. The ion concentrations in the simulated body fluid (SBF) were nearly 5 times of those in human blood plasma. The apatite formed was characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The apatite formed in 5SBF was similar in morphology and composition to that formed in the classical biomimetic process employing SBF or 1.5SBF, and similar to that of natural bone. This indicated that the biomimetic apatite coating process could be accelerated by using concentrated simulated body fluid at 37°C. Besides saving time, the accelerated biomimetic process is particularly significant to biodegradable polymers. Some polymers which degrade too fast to be coated with apatite by a classical biomimetic process, for example PGA, could be coated with bone-like apatite in an accelerated biomimetic process. Collagen and apatite were co-precipitated as a composite coating on poly(L-lactic acid) (PLLA) in an accelerated biomimetic process. The incubation solution contained collagen (1g/L) and simulated body fluid (SBF) with 5 times inorganic ionic concentrations as human blood plasma. The coating formed on PLLA films and scaffolds after 24 hours incubation was characterized using EDX, XRD, FTIR, and SEM. It was shown that the coating contained carbonated bone-like apatite and collagen, the primary constituents of natural bone. SEM showed a complex composite coating of submicron bone-like apatite particulates combined with collagen fibrils. This work provided an efficient process to obtain bone-like apatite/collagen composite coating. Saos-2 osteoblast-like cells were used to evaluate the cellular behaviors on these biomimetic coatings. Cell morphologies on the surfaces of PLLA films and scaffolds, PLLA films and scaffolds with apatite coating, and PLLA films and scaffolds with apatite/collagen composite coating were studied by SEM. Cell viability was assessed by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrasodium bromide (MTT) assay. In addition, differentiated cell function was assessed by measuring alkaline phosphatase activity. These results suggested that the apatite coating and apatite/collagen composite coating fabricated through the accelerated biomimetic processes could improve the interactions between osteoblasts and PLLA. The composite coating was more effective than apatite coating in improving such interactions. PLLA scaffolds coated with submicron collagen fibrils and submicron apatite paticulates are expected to be one of the promising 3D substrates for bone tissue engineering. To facilitate coating into scaffolds, the flowing condition was introduced into the accelerated biomimetic process. The apatite formed in the different sites in the scaffold was characterized using SEM. It was found that the accelerated biomimetic process performed in the flowing condition yielded more uniform spatial distribution of apatite particles than that in the regular shaking condition. This work provides a novel condition for obtaining uniform spatial distribution of bone-like apatite within the scaffolds in a timely manner, which is expected to facilitate uniform distribution of attached cells within the scaffoldsin vitro and in vivo.

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

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 intermediate series members, as doubled peaks merged into single diffraction maxima, the latter changing position systematically with bulk composition. All of the resulting F-OH apatite series members have hexagonal symmetry. The "a" unit-cell dimension behaves linearly with composition, and "c" is nearly constant across the series. Unit-cell volume also is linear with F:OH ratio, thus behaving in a thermodynamically ideal manner. Solution calorimetric experiments have been conducted in 20.0 wt % HCl at 50 °C on all series members. Enthalpies of F-OH mixing are nonexistent at F-rich compositions but have small negative values toward the hydroxylapatite end member. There is no enthalpy barrier, therefore, to complete F-OH mixing across the series, indicated as well by the ease of chemical homogenization for intermediate F:OH series members. In addition to the synthetic specimens described above, natural samples of hydroxylapatite, fluorapatite, and chlorapatite have been obtained for study from the U.S. National Museum of Natural History, as well as the American Museum of Natural History (our sincere appreciation to both museums for providing samples). Solution calorimetric results for these samples will be compared with data for the synthetic OH, F, and Cl apatite analogs noted above.

Enhanced bioactive properties of BiodentineTM modified with bioactive glass nanoparticles

PubMed Central

CORRAL NUÑEZ, Camila; COVARRUBIAS, Cristian; FERNANDEZ, Eduardo; de OLIVEIRA, Osmir Batista

2017-01-01

Abstract Objective To prepare nanocomposite cements based on the incorporation of bioactive glass nanoparticles (nBGs) into BiodentineTM (BD, Septodent, Saint-Maur-des-Fosses Cedex, France) and to assess their bioactive properties. Material and Methods nBGs were synthesised by the sol-gel method. BD nanocomposites (nBG/BD) were prepared with 1 and 2% nBGs by weight; unmodified BD and GC Fuji IX (GIC, GC Corporation, Tokyo, Japan) were used as references. The in vitro ability of the materials to induce apatite formation was assessed in SBF by X-ray diffraction (XRD), attenuated total reflectance with Fourier transform infrared spectroscopy (ATR-FTIR), and scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis. BD and nBG/BD were also applied to dentine discs for seven days; the morphology and elemental composition of the dentine-cement interface were analysed using SEM-EDX. Results One and two percent nBG/BD composites accelerated apatite formation on the disc surface after short-term immersion in SBF. Apatite was detected on the nBG/BD nanocomposites after three days, compared with seven days for unmodified BD. No apatite formation was detected on the GIC surface. nBG/BD formed a wider interfacial area with dentine than BD, showing blockage of dentine tubules and Si incorporation, suggesting intratubular precipitation. Conclusions The incorporation of nBGs into BD improves its in vitro bioactivity, accelerating the formation of a crystalline apatite layer on its surface after immersion in SBF. Compared with unmodified BD, nBG/BD showed a wider interfacial area with greater Si incorporation and intratubular precipitation of deposits when immersed in SBF. PMID:28403358

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 with merrillite are typically Cl- and F-rich in the case of Mars but F-rich in the case of the Moon and Vesta (2-4). In a single reported example of terrestrial mantle xenoliths containing apatite and and a similar volatile-poor Ca-phosphate, whitlockite, the apatite contained significant Cl and H2O but was F-rich and similar to some lunar apatites. Our thermodynamic analysis of apatite-merrillite equilibria suggests that high phosphorous chemical potentials combined with high halogen and low water fugacities are required for the coexistence of a volatile-poor Ca-phosphate with apatite, and point out the relatively unique and typically water-rich nature of the upper mantle of the Earth compared to other differentiated planetary bodies. References 1. S. O'Reilly & W. Griffin, 2000, Lithos 53: 217. 2. A. Patiño Douce et al., 2011, Chem Geol. in press 3. F. McCubbin et al. 2009, LPSC abs 2246 4. A. Sarafian et al. 2011, Meteor. Soc. Abs 5023

In vitro bioactivity of a biocomposite fabricated from HA and Ti powders by powder metallurgy method.

PubMed

Ning, C Q; Zhou, Y

2002-07-01

Traditionally, hydroxyapatite was used as a coating material on titanium substrate by various techniques. In the present work, a biocomposite was successfully fabricated from hydroxyapatite and titanium powders by powder metallurgy method. Bioactivity of the composite in a simulated body fluid (SBF) was investigated. Main crystal phases of the as-fabricated composite are found to be Ti2O, CaTiO3, CaO, alpha-Ti and a TiP-like phase. When the composite is immersed in the simulated body fluid for a certain time, a poor-crystallized, calcium-deficient, carbonate-containing apatite film will form on the surface of the composite. The time required to induce apatite nucleation is within 2 h. In addition, the apatite is also incorporated with a little magnesium and chlorine element. It is found that Ti2O has the ability to induce the formation of bone-like apatite in the SBF. And a dissolve of the CaO phase could also provide favorable conditions for the apatite formation, by forming open pores on the surface of the composite and increasing the degree of supersaturation of the SBF with respect to the apatite.

Apatite-Melt Partitioning of Volatiles in Basaltic Systems: Implications for Determining Volatile Abundances in Planetary Bodies from Apatite

NASA Technical Reports Server (NTRS)

McCubbin, F. M.

2017-01-01

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials, and 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 [i.e., 1]. Experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in basaltic systems [e.g., 2- 3], reporting that apatite-melt partitioning of volatiles is best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, exchange coefficients may vary as a function of temperature, pressure, melt composition, and/or oxygen fugacity. Furthermore, exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite [3]. In these regions of ternary space, we anticipate that crystal chemistry could influence partitioning behavior. Consequently, we conducted experiments to investigate the effect of apatite crystal chemistry on apatite-melt partitioning of F, Cl, and OH.

Facile incorporation of hydroxyapatite onto an anodized Ti surface via a mussel inspired polydopamine coating

NASA Astrophysics Data System (ADS)

Zhe, Wang; Dong, Chaofang; Sefei, Yang; Dawei, Zhang; Kui, Xiao; Xiaogang, Li

2016-08-01

Inspired by the porous morphology of anodized Ti and the adhesive versatility of polydopamine (PDA), which can induce apatite mineralization, we fabricated a novel interface by coating a porous anodized TiO2 layer with PDA to rapidly immobilize HA on Ti-based substrates. It was found that the as-prepared PDA/anodized (HD) surface exhibited nanoscale roughness, which possessed an excellent ability to form apatite when immersed in 1.5× simulated body fluid (SBF), as observed by AFM and FE-SEM. The morphology and composition of each layer were further confirmed by XPS, XRD and FTIR. The corrosion resistance of the multilayer was investigated using potentiodynamic polarization curve and electrochemical impedance spectra (EIS) measurements in a 0.9 wt% NaCl solution, the results suggested that the HA/PDA/anodized (HDA) layer increased the corrosion resistance of pure Ti with higher corrosion potential and lower passive current, the surface wettability was also enhanced with the incorporation of HA. In vitro cellular assays showed that the HDA layer stimulated cell attachment and improved the alkaline phosphate (ALP) activity. Overall, the PDA/anodized treatment provided a viable method to quickly integrate HA, and the obtained HDA layer improved both corrosion resistance and biocompatibility of the Ti surface.

Intra-grain Common Pb Correction and Detrital Apatite U-Pb Dating via LA-ICPMS Depth Profiling

NASA Astrophysics Data System (ADS)

Boyd, P. D.; Galster, F.; Stockli, D. F.

2017-12-01

Apatite is a common accessory phase in igneous and sedimentary rocks. While apatite is widely employed as a low-temperature thermochronometric tool, it has been increasingly utilized to constrain moderate temperature cooling histories by U-Pb dating. Apatite U-Pb is characterized by a thermal sensitivity window of 375-550°C. This unique temperature window recorded by the apatite U-Pb system, and the near-ubiquitous presence of apatite in igneous and clastic sedimentary rocks makes it a powerful tool able to illuminate mid-crustal tectono-thermal processes. However, as apatite incorporates only modest amounts of U and Th (1-10s of ppm) the significant amounts of non-radiogenic "common" Pb incorporated during its formation presents a major hurdle for apatite U-Pb dating. In bedrock samples common Pb in apatite can be corrected for by the measurement of Pb in a cogenetic mineral phase, such as feldspar, that does not incorporate U or from determination of a common Pb composition from multiple analyses in Tera-Wasserburg space. While these methods for common Pb correction in apatite can work for igneous samples, they cannot be applied to detrital apatite in sedimentary rocks with variable common Pb compositions. The obstacle of common Pb in apatite has hindered the application of detrital apatite U-Pb dating in provenance studies, despite the fact that it would be a powerful tool. This study presents a new method for the in situ correction of common Pb in apatite through the utilization of novel LA-ICP-MS depth profiling, which can recover U-Pb ratios at micron-scale spatial resolution during ablation of a grain. Due to the intra-grain U variability in apatite, a mixing line for a single grain can be generated in Tera-Wasserburg Concordia space. As a case study, apatite from a Variscan alpine granite were analyzed using both the single and multi-grain method, with both methods giving identical results. As a second case study the intra-grain method was then performed on detrital apatite from the Swiss Northern Alpine Foreland Basin, where the common Pb composition and age spectra of detrital apatite grains were elucidated. The novel intra-grain apatite method enables the correction for common Pb in detrital apatite, making it feasible to incorporate detrital apatite U-Pb dating in provenance and source-to-sink studies.

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.

Thermal analysis and in vitro bioactivity of bioactive glass-alumina composites

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

Chatzistavrou, Xanthippi, E-mail: x.chatzistavrou@imperial.ac.uk; Kantiranis, Nikolaos, E-mail: kantira@geo.auth.gr; Kontonasaki, Eleana, E-mail: kont@dent.auth.gr

2011-01-15

Bioactive glass-alumina composite (BA) pellets were fabricated in the range 95/5-60/40 wt.% respectively and were heat-treated under a specific thermal treatment up to 950 {sup o}C. Control (unheated) and heat-treated pellets were immersed in Simulated Body Fluid (SBF) for bioactivity testing. All pellets before and after immersion in SBF were studied by Fourier Transform Infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM-EDS) and X-ray Diffraction (XRD) analysis. All composite pellets presented bioactive response. On the surface of the heat-treated pellets the development of a rich biological hydroxyapatite (HAp) layer was delayed for one day, compared to the respective control pellets. Independentmore » of the proportion of the two components, all composites of each group (control and heat-treated) presented the same bioactive response as a function of immersion time in SBF. It was found that by the applied methodology, Al{sub 2}O{sub 3} can be successfully applied in bioactive glass composites without obstructing their bioactive response. - Research Highlights: {yields} Isostatically pressed glass-alumina composites presented apatite-forming ability. {yields} The interaction with SBF resulted in an aluminium phosphate phase formation. {yields} The formation of an aluminium phosphate phase enhanced the in vitro apatite growth.« less

Porous SiO2 nanofiber grafted novel bioactive glass-ceramic coating: A structural scaffold for uniform apatite precipitation and oriented cell proliferation on inert implant.

PubMed

Das, Indranee; De, Goutam; Hupa, Leena; Vallittu, Pekka K

2016-05-01

A composite bioactive glass-ceramic coating grafted with porous silica nanofibers was fabricated on inert glass to provide a structural scaffold favoring uniform apatite precipitation and oriented cell proliferation. The coating surfaces were investigated thoroughly before and after immersion in simulated body fluid. In addition, the proliferation behavior of fibroblast cells on the surface was observed for several culture times. The nanofibrous exterior of this composite bioactive coating facilitated homogeneous growth of flake-like carbonated hydroxyapatite layer within a short period of immersion. Moreover, the embedded porous silica nanofibers enhanced hydrophilicity which is required for proper cell adhesion on the surface. The cells proliferated well following a particular orientation on the entire coating by the assistance of nanofibrous scaffold-like structural matrix. This newly engineered composite coating was effective in creating a biological structural matrix favorable for homogeneous precipitation of calcium phosphate, and organized cell growth on the inert glass surface. Copyright © 2016 Elsevier B.V. All rights reserved.

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 composition apatite shifts from a hexagonal unit cell with space group P63/m to a unit cell with monoclinic symmetry within space group P21/b. We anticipate that this transition occurs at >70% chlorapatite based on solution calorimetry data.

Surface modification of yttria stabilized zirconia via polydopamine inspired coating for hydroxyapatite biomineralization

NASA Astrophysics Data System (ADS)

Zain, Norhidayu Muhamad; Hussain, Rafaqat; Kadir, Mohammed Rafiq Abdul

2014-12-01

Yttria stabilized zirconia (YSZ) has been widely used as biomedical implant due to its high strength and enhanced toughening characteristics. However, YSZ is a bioinert material which constrains the formation of chemical bonds with bone tissue following implantation. Inspired by the property of mussels, the surface of YSZ ceramics was functionalized by quinone-rich polydopamine to facilitate the biomineralization of hydroxyapatite. YSZ discs were first immersed in 2 mg/mL of stirred or unstirred dopamine solution at either 25 or 37 °C. The samples were then incubated in 1.5 simulated body fluid (SBF) for 7d. The effect of coating temperature for stirred and unstirred dopamine solutions during substrate grafting was investigated on the basis of chemical compositions, wettability and biomineralization of hydroxyapatite on the YSZ functionalized surface. The results revealed that the YSZ substrate grafted at 37 °C in stirred solution of dopamine possessed significantly improved hydrophilicity (water contact angle of 44.0 ± 2.3) and apatite-mineralization ability (apatite ratio of 1.78). In summary, the coating temperature and stirring condition during grafting procedure affected the chemical compositions of the films and thus influenced the formation of apatite layer on the substrate during the biomineralization process.

Bioactive carbon-PEEK composites prepared by chemical surface treatment.

PubMed

Miyazaki, Toshiki; Matsunami, Chisato; Shirosaki, Yuki

2017-01-01

Polyetheretherketone (PEEK) has attracted much attention as an artificial intervertebral spacer for spinal reconstruction. Furthermore, PEEK plastic reinforced with carbon fiber has twice the bending strength of pure PEEK. However, the PEEK-based materials do not show ability for direct bone bonding, i.e., bioactivity. Although several trials have been conducted for enabling PEEK with bioactivity, few studies have reported on bioactive surface modification of carbon-PEEK composites. In the present study, we attempted the preparation of bioactive carbon-PEEK composites by chemical treatments with H 2 SO 4 and CaCl 2 . Bioactivity was evaluated by in vitro apatite formation in simulated body fluid (SBF). The apatite formation on the carbon-PEEK composite was compared with that of pure PEEK. Both pure PEEK and carbon-PEEK composite formed the apatite in SBF when they were treated with H 2 SO 4 and CaCl 2 ; the latter showed higher apatite-forming ability than the former. It is conjectured that many functional groups able to induce the apatite nucleation, such as sulfo and carboxyl groups, are incorporated into the dispersed carbon phase in the carbon-PEEK composites. Copyright © 2016 Elsevier B.V. All rights reserved.

Enamel-like apatite crown covering amorphous mineral in a crayfish mandible

PubMed Central

Bentov, Shmuel; Zaslansky, Paul; Al-Sawalmih, Ali; Masic, Admir; Fratzl, Peter; Sagi, Amir; Berman, Amir; Aichmayer, Barbara

2012-01-01

Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans. PMID:22588301

[Comparative studies on the material performances of natural bone-like apatite from different bone sources].

PubMed

Fan, Xiaoxia; Ren, Haohao; Chen, Shutian; Wang, Guangni; Deng, Tianyu; Chen, Xingtao; Yan, Yonggang

2014-04-01

The compressive strength of the original bone tissue was tested, based on the raw human thigh bone, bovine bone, pig bone and goat bone. The four different bone-like apatites were prepared by calcining the raw bones at 800 degrees C for 8 hours to remove organic components. The comparison of composition and structure of bone-like apatite from different bone sources was carried out with a composition and structure test. The results indicated that the compressive strength of goat bone was similar to that of human thigh bone, reached (135.00 +/- 7.84) MPa; Infrared spectrum (IR), X-ray diffraction (XRD) analysis results showed that the bone-like apatite from goat bone was much closer to the structure and phase composition of bone-like apatite of human bones. Inductively Coupled Plasma (ICP) test results showed that the content of trace elements of bone-like apatite from goat bone was closer to that of apatite of human bone. Energy Dispersive Spectrometer (EDS) results showed that the Ca/P value of bone-like apatite from goat bone was also close to that of human bone, ranged to 1.73 +/- 0.033. Scanning electron microscopy (SEM) patterns indicated that the macrographs of the apatite from human bone and that of goat bone were much similar to each other. Considering all the results above, it could be concluded that the goat bone-like apatite is much similar to that of human bone. It can be used as a potential natural bioceramic material in terms of material properties.

Inaccurate reporting of mineral composition by commercial stone analysis laboratories: implications for infection and metabolic stones.

PubMed

Krambeck, Amy E; Khan, Naseem F; Jackson, Molly E; Lingeman, James E; McAteer, James A; Williams, James C

2010-10-01

We determined the accuracy of stone composition analysis at commercial laboratories. A total of 25 human renal stones with infrared spectroscopy determined composition were fragmented into aliquots and studied with micro computerized tomography to ensure fragment similarity. Representative fragments of each stone were submitted to 5 commercial stone laboratories for blinded analysis. All laboratories agreed on the composition of 6 pure stones. Only 2 of 4 stones (50%) known to contain struvite were identified as struvite at all laboratories. Struvite was reported as a component by some laboratories for 4 stones previously determined not to contain struvite. Overall there was disagreement regarding struvite in 6 stones (24%). For 9 calcium oxalate stones all laboratories reported some mixture of calcium oxalate but the quantity of subtypes differed significantly among laboratories. In 6 apatite containing stones apatite was missed by the laboratories in 20% of samples. None of the laboratories identified atazanavir in a stone containing that antiviral drug. One laboratory reported protein in every sample while all others reported it in only 1. Nomenclature for apatite differed among laboratories with 1 reporting apatite as carbonate apatite and never hydroxyapatite, another never reporting carbonate apatite and always reporting hydroxyapatite, and a third reporting carbonate apatite as apatite with calcium carbonate. Commercial laboratories reliably recognize pure calculi. However, variability in the reporting of mixed calculi suggests a problem with the accuracy of stone analysis results. There is also a lack of standard nomenclature used by laboratories. Copyright © 2010 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

The effect of oxygen plasma pretreatment and incubation in modified simulated body fluids on the formation of bone-like apatite on poly(lactide-co-glycolide) (70/30).

PubMed

Qu, Xue; Cui, Wenjin; Yang, Fei; Min, Changchun; Shen, Hong; Bei, Jianzhong; Wang, Shenguo

2007-01-01

In this study, biodegradable poly(lactide-co-glycolide) (PLGA) (70/30) films and scaffolds were first treated with oxygen plasma and then incubated in a modified simulated body fluid 1.5SBF0 to prepare a bone-like apatite layer. The formation of the apatite and its influence on osteoblast-like cells growth were investigated. It was found that the bone-like apatite formability of PLGA(70/30) was enhanced by plasma pretreatment. The changes of surface chemistry and surface topography induced by oxygen plasma treatment were both effective for apatite formation. The apatite formability increased with increasing plasma-treating time. Under a treating condition of 20 W for 30 min, oxygen plasma treatment could penetrate into the inner scaffold. After 6 days incubation, the apatite formed in plasma-treated scaffold was better distributed than in untreated scaffold, and the weight and mechanical strength of the plasma-treated scaffold were both enhanced. Compared with PLGA(70/30), the apatite layer formed on oxygen plasma-treated PLGA(70/30) surface enhanced adhesion and proliferation of OCT-1 osteoblast-like cell, but had no significant effect on cell's ALP activity at day 7. A prolonged investigation is being in process to further verify the bone-like apatite effects on osteogenic differentiation.

Bone-like apatite layer formation on hydroxyapatite prepared by spark plasma sintering (SPS).

PubMed

Gu, Y W; Khor, K A; Cheang, P

2004-08-01

Hydroxyapatite (HA) compacts with high density and superior mechanical properties were fabricated by spark plasma sintering (SPS) using spray-dried HA powders as feedstock. The formation of bone-like apatite layer on SPS consolidated HA compacts were investigated by soaking the HA compacts in simulated body fluid (SBF) for various periods (maximum of 28 days). The structural changes in HA post-SBF were analyzed with scanning electron microscopy, grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy. It was found that a layer consisting microcrystalline carbonate-containing hydroxyapatite was formed on the surface of HA compacts after soaking for 24h. The formation mechanism of apatite on the surface of HA compacts after soaking in SBF was attributed to the ion exchange between HA compacts and the SBF solution. The increase in ionic concentration of calcium and phosphorus as well as the increase in pH after SBF immersion resulted in an increase in ionic activity product of apatite in the solution, and provided a specific surface with a low interface energy that is conducive to the nucleation of apatite on the surface of HA compacts.

Assisted deposition of nano-hydroxyapatite onto exfoliated carbon nanotube oxide scaffolds.

PubMed

Zanin, H; Rosa, C M R; Eliaz, N; May, P W; Marciano, F R; Lobo, A O

2015-06-14

Electrodeposited nano-hydroxyapatite (nHAp) is more similar to biological apatite in terms of microstructure and dimension than apatites prepared by other processes. Reinforcement with carbon nanotubes (CNTs) enhances its mechanical properties and increases adhesion of osteoblasts. Here, we carefully studied nHAp deposited onto vertically aligned multi-walled CNT (VAMWCNT) scaffolds by electrodeposition and soaking in a simulated body fluid (SBF). VAMWCNTs are porous biocompatible scaffolds with nanometric porosity and exceptional mechanical and chemical properties. The VAMWCNT films were prepared on a Ti substrate by a microwave plasma chemical vapour deposition method, and then oxidized and exfoliated by oxygen plasma etching (OPE) to produce graphene oxide (GO) at the VAMWCNT tips. The attachment of oxygen functional groups was found to be crucial for nHAp nucleation during electrodeposition. A thin layer of plate-like and needle-like nHAp with high crystallinity was formed without any need for thermal treatment. This composite (henceforth referred to as nHAp-VAMWCNT-GO) served as the scaffold for in vitro biomineralization when soaked in the SBF, resulting in the formation of both carbonate-rich and carbonate-poor globular-like nHAp. Different steps in the deposition of biological apatite onto VAMWCNT-GO and during the short-term biomineralization process were analysed. Due to their unique structure and properties, such nano-bio-composites may become useful in accelerating in vivo bone regeneration processes.

Assisted deposition of nano-hydroxyapatite onto exfoliated carbon nanotube oxide scaffolds

NASA Astrophysics Data System (ADS)

Zanin, H.; Rosa, C. M. R.; Eliaz, N.; May, P. W.; Marciano, F. R.; Lobo, A. O.

2015-05-01

Electrodeposited nano-hydroxyapatite (nHAp) is more similar to biological apatite in terms of microstructure and dimension than apatites prepared by other processes. Reinforcement with carbon nanotubes (CNTs) enhances its mechanical properties and increases adhesion of osteoblasts. Here, we carefully studied nHAp deposited onto vertically aligned multi-walled CNT (VAMWCNT) scaffolds by electrodeposition and soaking in a simulated body fluid (SBF). VAMWCNTs are porous biocompatible scaffolds with nanometric porosity and exceptional mechanical and chemical properties. The VAMWCNT films were prepared on a Ti substrate by a microwave plasma chemical vapour deposition method, and then oxidized and exfoliated by oxygen plasma etching (OPE) to produce graphene oxide (GO) at the VAMWCNT tips. The attachment of oxygen functional groups was found to be crucial for nHAp nucleation during electrodeposition. A thin layer of plate-like and needle-like nHAp with high crystallinity was formed without any need for thermal treatment. This composite (henceforth referred to as nHAp-VAMWCNT-GO) served as the scaffold for in vitro biomineralization when soaked in the SBF, resulting in the formation of both carbonate-rich and carbonate-poor globular-like nHAp. Different steps in the deposition of biological apatite onto VAMWCNT-GO and during the short-term biomineralization process were analysed. Due to their unique structure and properties, such nano-bio-composites may become useful in accelerating in vivo bone regeneration processes.

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, 875-890. Webster et al., 2014. J. Pet., 55, 2217-2248. Brenan, 1993. Chem. Geol., 110, 195-210.

Geomaterials: their application to environmental remediation

PubMed Central

Yamada, Hirohisa; Tamura, Kenji; Watanabe, Yujiro; Iyi, Nobuo; Morimoto, Kazuya

2011-01-01

Geomaterials are materials inspired by geological systems originating from the billion years long history of the Earth. This article reviews three important classes of geomaterials. The first one is smectites—layered silicates with a cation-exchange capacity. Smectites are useful for removing pollutants and as intercalation compounds, catalysts and polymer nanocomposites. The second class is layered double hydroxides (LDHs). They have an anion-exchange capacity and are used as catalysts, catalyst precursors, sorbents and scavengers for halogens. The third class of geomaterials is zeolites—microporous materials with a cation-exchange capacity which are used for removing harmful cations. Zeolite composites with LDHs can absorb ammonium and phosphate ions in rivers and lakes, whereas zeolite/apatite composites can immobilize the radioactive iodine. These geomaterials are essential for environmental remediation. PMID:27877455

Preparation and characterization of HA microflowers coating on AZ31 magnesium alloy by micro-arc oxidation and a solution treatment

NASA Astrophysics Data System (ADS)

Tang, Hui; Yu, Dezhen; Luo, Yan; Wang, Fuping

2013-01-01

Magnesium and its alloys are potential biodegradable implant materials due to their attractive biological properties. But the use of magnesium is still hampered by its poor corrosion resistance in physiological fluids. In this work, hydroxyapatite microflowers coating is fabricated by micro-arc oxidation and a solution treatment on AZ31 magnesium alloy. The microstructure and composition are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). The potentiodynamic polarization and electrochemical impedance spectroscopy are studied in simulated body fluid (SBF) solution, and the apatite-forming ability is studied also. The results show that the corrosion resistance of the magnesium alloy has been enhanced by MAO coating. And the solution treatment can improve the corrosion resistance of the MAO sample, by forming a barrier layer on the surface of the MAO coating, and by penetrating into the outer layer of the MAO film, sealing the micropores and micro-cracks existed in the MAO coating. In addition, the MAO-ST coating also exhibits a high ability to form apatite.

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.

The comparison of phosphate-titanate-silicate layers on the titanium and Ti6Al4V alloy base.

PubMed

Rokita, M

2011-08-15

The studied layers were composed of two parts: titanate-silicate underlayer for better adhesion and titanate-phosphate-silicate layers for potential bioparameters. The layers with different amounts of hydroxyapatite were deposited on titanium and Ti6Al4V alloy substrates using dipping sol-gel method and electrophoresis. The selection of sol/suspension composition, deposition time and heat treatment conditions have the decisive influence on the layers parameters. The obtained layers should be very thin and almost amorphous. The specific nature of ceramic layers on the metal substrates excludes the use of some measurements methods or makes it difficult to interpret the measurement results. All the obtained samples were compared using XRD analysis data (GID technique), SEM with EDX measurements and FTIR spectroscopy (transmission and reflection techniques) before and after soaking in simulated body fluid. FTIR spectroscopy with mathematical treatment of the spectra (BIO-RAD Win-IR program, Arithmetic-subtract function) was used to detect the increase or decrease of any phosphate phases during SBF soaking. Based on the FTIR results the processes of hydroxyapatite (HAp) growth or layer dissolution were estimated. The layers deposited on titanium substrate are more crystalline then the ones deposited on Ti6Al4V. During SBF soaking process the growth of small amount of microcrystalline carbonate hydroxyapatite was observed on titanium substrate. The layer on Ti6Al4V base contained amorphous carbonate apatite. During heating treatment above about 870-920 K this apatite transforms into carbonate hydroxyapatite. The Ti6Al4V substrate seems to be more advantageous in context of potentially bioactive materials obtaining. Copyright © 2010 Elsevier B.V. All rights reserved.

The comparison of phosphate-titanate-silicate layers on the titanium and Ti6Al4V alloy base

NASA Astrophysics Data System (ADS)

Rokita, M.

2011-08-01

The studied layers were composed of two parts: titanate-silicate underlayer for better adhesion and titanate-phosphate-silicate layers for potential bioparameters. The layers with different amounts of hydroxyapatite were deposited on titanium and Ti6Al4V alloy substrates using dipping sol-gel method and electrophoresis. The selection of sol/suspension composition, deposition time and heat treatment conditions have the decisive influence on the layers parameters. The obtained layers should be very thin and almost amorphous. The specific nature of ceramic layers on the metal substrates excludes the use of some measurements methods or makes it difficult to interpret the measurement results. All the obtained samples were compared using XRD analysis data (GID technique), SEM with EDX measurements and FTIR spectroscopy (transmission and reflection techniques) before and after soaking in simulated body fluid. FTIR spectroscopy with mathematical treatment of the spectra (BIO-RAD Win-IR program, Arithmetic-subtract function) was used to detect the increase or decrease of any phosphate phases during SBF soaking. Based on the FTIR results the processes of hydroxyapatite (HAp) growth or layer dissolution were estimated. The layers deposited on titanium substrate are more crystalline then the ones deposited on Ti6Al4V. During SBF soaking process the growth of small amount of microcrystalline carbonate hydroxyapatite was observed on titanium substrate. The layer on Ti6Al4V base contained amorphous carbonate apatite. During heating treatment above about 870-920 K this apatite transforms into carbonate hydroxyapatite. The Ti6Al4V substrate seems to be more advantageous in context of potentially bioactive materials obtaining.

Air Plasma-Sprayed La2Zr2O7-SrZrO3 Composite Thermal Barrier Coating Subjected to CaO-MgO-Al2O3-SiO2 (CMAS)

NASA Astrophysics Data System (ADS)

Cai, Lili; Ma, Wen; Ma, Bole; Guo, Feng; Chen, Weidong; Dong, Hongying; Shuang, Yingchai

2017-08-01

La2Zr2O7-SrZrO3 composite thermal barrier coatings (TBCs) were prepared by air plasma spray (APS). The La2Zr2O7-SrZrO3 composite TBCs covered with calcium-magnesium-aluminum-silicate (CMAS) powder, as well as the powder mixture of CMAS and spray-dried La2Zr2O7-SrZrO3 composite powder, were heat-treated at 1250 °C in air for 1, 4, 8, and 12 h. The phase constituents and microstructures of the reaction products were characterized by x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. Experimental results showed that the La2Zr2O7-SrZrO3 composite TBCs had higher CMAS resistance than 8YSZ coating. A dense new layer developed between CMAS and La2Zr2O7-SrZrO3 composite TBCs during interaction, and this new layer consisted mostly of apatite (Ca2La8(SiO4)6O2) and c-ZrO2. The newly developed layer effectively protected the La2Zr2O7-SrZrO3 composite TBCs from further CMAS attack.

The thickness of the crystal mush on the floor of the Bushveld magma chamber

NASA Astrophysics Data System (ADS)

Holness, Marian B.; Cawthorn, R. Grant; Roberts, James

2017-12-01

The thickness of the crystal mush on magma chamber floors can be constrained using the offset between the step-change in the median value of dihedral angles formed at the junctions between two grains of plagioclase and a grain of another phase (typically clinopyroxene, but also orthopyroxene and olivine) and the first appearance or disappearance of the liquidus phase associated with the step-change in median dihedral angle. We determined the mush thickness in the Rustenburg Layered Suite of the Bushveld Complex at clinopyroxene-in (in Lower Main Zone) and magnetite-in (in Upper Zone). We also examined an intermittent appearance of cumulus apatite in Upper Zone, using both the appearance and disappearance of cumulus apatite. In all cases, the mush thickness does not exceed 4 m. These values are consistent with field observations of a mechanically rigid mush at the bases of both magnetitite and chromitite layers overlying anorthosite. Mush thickness of the order of a few metres suggests that neither gravitationally-driven compaction nor compositional convection within the mush layer is likely to have been important processes during solidification: adcumulates in the Bushveld are most likely to have formed at the top of the mush during primary crystallisation. Similarly, it is unlikely either that migration of reactive liquids occurs through large stretches of stratigraphy, or that layering is formed by mechanisms other than primary accumulation.

Geochemistry of sapphirine-apatite-calcite-bearing gabbroic dykes from the Finero Phlogopite Peridotite (Ivrea-Verbano Zone): evidence for multistage interaction with the ambient peridotite

NASA Astrophysics Data System (ADS)

Tommaso, Giovanardi; Alberto, Zanetti; Maurizio, Mazzucchelli; Tomoaki, Morishita; Antonio, Langone

2016-04-01

The Finero Phlogopite-Peridotite (FPP) is a mantle unit outcropping in the northernmost tip of the Ivrea-Verbano Zone (IVZ, Southern Alps). It shows a virtually complete recrystallization due to pervasive to channelled melt migration. The pervasive metasomatism formed a main lithologic association constituted by phlogopite harzburgites associated to phlogopite pyroxenites (mainly olivine-websterites, websterites and orthopyroxenites). These lithologies are also rich in amphibole and do not show significant chemical gradients among them (Zanetti et al., 1999). The channelled migration stages formed dunite bodies, which sometimes contain stratiform chromitites and, more rarely, pyroxenite layers similar to those associated to phlogopite harzburgite. The FPP also shows a discrete number of other, subordinate rock-types, which are characterised by the presence of apatite usually associated to carbonates (i.e. calcite or dolomite) and exhibit marked modal and chemical gradients with respect to the host phlogopite harzburgite. Examples of these lithologies are apatite-dolomite-bearing wehrlites and harzburgites (e.g. Zanetti et al. 1999; Morishita et al., 2008), apatite-calcite zircon-syenites and hornblendites. Ar-Ar amphibole analysis and U-Pb zircon and apatite data return Triassic ages for these rocks, which have been considered to document the time of melt/fluid injection. Notwithstanding the apparent mineralogical and chemical differences with the main lithologic sequences, apatite-carbonates-bearing rocks have been frequently interpreted as cogenetic to phlogopite harzburgites. To debate the petrogenesis of these rocks, a detailed field, petrological and geochemical investigation has been carried out on a swarm of apatite-calcite-bearing gabbroic veins that randomly cut the main lithologic association. Preliminary investigation evidenced as these veins show complex metasomatic haloes and a symmetric internal layering, characterised by crystallisation of magmatic sapphirine (Giovanardi et al., 2013). The mineral assemblage of the veins is dominated by titanian pargasite towards the host peridotite and by plagioclase at the vein centre. The veins also present phlogopite and spinel. Field and petrographic evidence, major and trace element data and the O isotopic composition of such gabbroic veins indicate that they formed at shallow mantle conditions by multistage fractional crystallisation of a migrating melt unrelated to those forming phlogopite harzburgites. Besides, local strong enrichments in LILE, LREE and 18O in vein minerals confirm that such melt was deeply modified by interaction with the host phlogopite peridotite. The genetic relationships with other intrusive events recorded by the FPP and the associated crustal sequence will be addressed with the aim of placing new constraints on the petrologic and geodynamic evolution of the IVZ. Giovanardi, T., Morishita, T., Zanetti, A., Mazzucchelli, M., Vannucci, R. (2013). Igneous sapphirine as a product of melt-peridotite interactions in the Finero Phlogopite-Peridotite Massif, Western Italian Alps. European Journal of Mineralogy 25, 17-31. Morishita, T., Hattori, K.H., Terada, K., Matsumoto, T., Yamamoto, K., Takebe, M., Ishida, Y., Tamura, A., Arai, S. (2008). Geochemistry of apatite-rich layers in the Finero phlogopite-peridotite massif (Italian Western Alps) and ion microprobe dating of apatite. Chemical Geology 251, 99-111. Zanetti, A., Mazzucchelli, M., Rivalenti, G., Vannucci, R. (1999). The Finero phlogopite-peridotite massif: an example of subduction-related metasomatism. Contributions to Mineralogy and Petrology 134, 107-122.

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. J. Pet., 53, 875-890. Webster et al., 2014. J. Pet., 55, 2217-2248. Woods et al., 2000. Am. Min., 85, 480-487. Brenan, 1993. Chem. Geol., 110, 195-210.

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.

Fluids on differentiated asteroids: Evidence from phosphates in differentiated meteorites GRA 06128 and GRA 06129

NASA Astrophysics Data System (ADS)

Shearer, Charles K.; Burger, Paul V.; Papike, James J.; Sharp, Zachary D.; McKeegan, Kevin D.

2011-09-01

Abstract- Paired meteorites Graves Nunatak 06128 and 06129 (GRA) represent an ancient cumulate lithology (4565.9 Ma ± 0.3) containing high abundances of sodic plagioclase. Textures and stable isotope compositions of GRA indicate that superimposed on the igneous lithology is a complex history of subsolidus reequilibration and low-temperature alteration that may have extended over a period of 150 Myr. In GRA, apatite is halogen-rich with Cl between 4.5 and 5.5 wt% and F between 0.3 and 0.9 wt%. The Cl/(Cl+F+OH) ratio of the apatite is between 0.65 and 0.82. The Cl and F are negatively correlated and are heterogeneously distributed in the apatite. Merrillite is low in halogens with substantial Na in the 6-fold coordinated Na-site (≈2.5%) and Mg in the smaller octahedral site. The merrillite has a negative Eu anomaly, whereas the apatite has a positive Eu anomaly. The chlorine isotope composition of the bulk GRA leachate is +1.2‰ relative to standard mean ocean chloride (SMOC). Ion microprobe chlorine isotope analyses of the apatite range between -0.5 and +1.2‰. Textural relationships between the merrillite and apatite, and the high-Cl content of the apatite, suggest that the merrillite is magmatic in origin, whereas the apatite is a product of the interaction between merrillite and a Cl-rich fluid. If the replacement of merrillite by apatite occurred at approximately 800 °C, the fluid composition is f(HCl)/f(H2O) = 0.0383 and a HCl molality of 2.13 and f(HCl)/f(HF) = 50-100. It is anticipated that the calculated f(HCl)/f(H2O) and a HCl molality are minimum values due to assumptions made on the OH component in apatite and basing the calculations on the apatite with the lowest XCl. The bulk δ37Cl of GRA is a >2σ outlier from chondritic meteorites and suggests that parent body processes resulted in fractionation of the Cl isotopes.

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.

Bioactivity and structural properties of nanostructured bulk composites containing Nb2O5 and natural hydroxyapatite

NASA Astrophysics Data System (ADS)

Bonadio, T. G. M.; Sato, F.; Medina, A. N.; Weinand, W. R.; Baesso, M. L.; Lima, W. M.

2013-06-01

In this work, we investigate the bioactivity and structural properties of nanostructured bulk composites that are composed of Nb2O5 and natural hydroxyapatite (HAp) and are produced by mechanical alloying and powder metallurgy. X-ray diffraction and Raman spectroscopy data showed that the milling process followed by a heat treatment at 1000 °C induced chemical reactions along with the formation of the CaNb2O6, PNb9O25 and Ca3(PO4)2 phases. Rietveld refinement indicated significant changes in each phase weight fraction as a function of HAp concentration. These changes influenced the in vitro bioactivity of the material. XRD and FTIR analyses indicated that the composites exhibited bioactivity characteristics by forming a carbonated apatite layer when the composites were immersed in a simulated body fluid. The formed layers had a maximum thickness of 13 μm, as measured by confocal Raman spectroscopy and as confirmed by scanning electron microscopy. The results of this work suggest that the tested bulk composites are promising biomaterials for use in implants.

Nucleation of biomimetic apatite in synthetic body fluids: dense and porous scaffold development.

PubMed

Landi, Elena; Tampieri, Anna; Celotti, Giancarlo; Langenati, Ratih; Sandri, Monica; Sprio, Simone

2005-06-01

The effectiveness of synthetic body fluids (SBF) as biomimetic sources to synthesize carbonated hydroxyapatite (CHA) powder similar to the biological inorganic phase, in terms of composition and microstructure, was investigated. CHA apatite powders were prepared following two widely experimented routes: (1) calcium nitrate tetrahydrate and diammonium hydrogen phosphate and (2) calcium hydroxide and ortophosphoric acid, but using SBF as synthesis medium instead of pure water. The characteristics of the as-prepared powders were compared, also with the features of apatite powders synthesized via pure water-based classical methods. The powder thermal resistance and behaviour during densification were studied together with the mechanical properties of the dense samples. The sponge impregnation process was used to prepare porous samples having morphological and mechanical characteristics suitable for bone substitution. Using this novel synthesis was it possible to prepare nanosized (approximately equal to 20 nm), pure, carbonate apatite powder containing Mg, Na, K ions, with morphological and compositional features mimicking natural apatite and with improved thermal properties. After sintering at 1250 degrees C the carbonate-free apatite porous samples showed a surprising, high compressive strength together with a biomimetic morphology.

Bioactivity and mineralization of natural hydroxyapatite from cuttlefish bone and Bioglass® co-sintered bioceramics.

PubMed

Cozza, Natascia; Monte, Felipe; Bonani, Walter; Aswath, Pranesh; Motta, Antonella; Migliaresi, Claudio

2018-02-01

In this study, bioactive hydroxyapatite (HAP)-based bioceramics starting from cuttlefish bone powders have been prepared and characterized. In particular, fragmented cuttlefish bone was co-sintered with 30 wt% of Bioglass ® -45S5 to synthesize HAP-based powders with enhanced mechanical properties and bioactivity. Commercial synthetic HAP was treated following the same procedure and used as a reference. The structure and composition of the bioceramics formulations were characterized using Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy. After the thermal treatment of cuttlefish bone powder added with 30 wt% Bioglass, new phases with compositions of sodium calcium phosphate [Na 3 Ca 6 (PO 4 ) 5 ], β-tricalcium phosphate [Ca 3 (PO 4 )] and amorphous silica were detected. In vitro cell culture studies were performed by evaluating proliferation, metabolic activity and differentiation of human osteoblast-like cells (MG63). Scaffolds made with cuttlefish bone powder exhibited increased apatite deposition, alkaline phosphatase activity and cell proliferation compared with commercial synthetic HAP. In addition, the ceramic compositions obtained after the combination with Bioglass ® further enhanced the metabolic activity of MG63 cell and promoted the formation of a well-developed apatite layer after 7 days of incubation in Dulbecco's modified Eagle's medium. Copyright © 2017 John Wiley & Sons, Ltd.

Bone apatite composition of necrotic trabecular bone in the femoral head of immature piglets.

PubMed

Aruwajoye, Olumide O; Kim, Harry K W; Aswath, Pranesh B

2015-04-01

Ischemic osteonecrosis of the femoral head (IOFH) can lead to excessive resorption of the trabecular bone and collapse of the femoral head as a structure. A well-known mineral component to trabecular bone is hydroxyapatite, which can be present in many forms due to ionic substitution, thus altering chemical composition. Unfortunately, very little is known about the chemical changes to bone apatite following IOFH. We hypothesized that the apatite composition changes in necrotic bone possibly contribute to increased osteoclast resorption and structural collapse of the femoral head. The purpose of this study was to assess the macroscopic and local phosphate composition of actively resorbed necrotic trabecular bone to isolate differences between areas of increased osteoclast resorption and normal bone formation. A piglet model of IOFH was used. Scanning electron microscopy (SEM), histology, X-ray absorbance near edge structure (XANES), and Raman spectroscopy were performed on femoral heads to characterize normal and necrotic trabecular bone. Backscattered SEM, micro-computed tomography and histology showed deformity and active resorption of necrotic bone compared to normal. XANES and Raman spectroscopy obtained from actively resorbed necrotic bone and normal bone showed increased carbonate-to-phosphate content in the necrotic bone. The changes in the apatite composition due to carbonate substitution may play a role in the increased resorption of necrotic bone due to its increase in solubility. Indeed, a better understanding of the apatite composition of necrotic bone could shed light on osteoclast activity and potentially improve therapeutic treatments that target excessive resorption of bone.

INACCURATE REPORTING OF MINERAL COMPOSITION BY COMMERCIAL STONE ANALYSIS LABORATORIES: IMPLICATIONS FOR INFECTION AND METABOLIC STONES

PubMed Central

Krambeck, Amy E.; Khan, Naseem F.; Jackson, Molly E.; Lingeman, James E.; McAteer, James A; Williams, James C.

2011-01-01

INTRODUCTION The goal of this study was to determine the accuracy of stone composition analysis by commercial laboratories. METHODS 25 human renal stones with infrared spectroscopy (IR) determined compositions were fragmented into aliquots and studied with micro-computed tomography (CT) to ensure fragment similarity. Representative fragments of each stone were submitted to 5 commercial stone laboratories for blinded analysis. RESULTS All laboratories agreed on composition for 6 pure stones. Of 4 stones known to contain struvite, only 2(50%) were identified as struvite by all laboratories. Struvite was reported as a component by some laboratories for 4 stones previously determined not to contain struvite. Overall, there was disagreement regarding struvite in 6(24%) stones. For 9 calcium oxalate (CaOx) stones, all laboratories reported some mixture of CaOx, but the quantities of subtypes differed significantly among laboratories. In 6 apatite containing stones, apatite was missed by the laboratories in 20% of the samples. None of the laboratories identified atazanavir in a stone containing that antiviral drug. One laboratory reported protein in every sample, while all others reported it in only 1 sample. Nomenclature for apatite differed among laboratories, with one reporting apatite as carbonate apatite (CA) and never hydroxyapatite (HA), another never reporting CA and always reporting HA, and a third reporting CA as apatite with calcium carbonate. CONCLUSIONS Commercial laboratories reliably recognize pure calculi; however, variability in reporting of mixed calculi suggests a problem with accuracy of stone analysis results. Furthermore, there is a lack of standard nomenclature used by laboratories. PMID:20728108

Preparation of bioactive titania films on titanium metal via anodic oxidation.

PubMed

Cui, X; Kim, H-M; Kawashita, M; Wang, L; Xiong, T; Kokubo, T; Nakamura, T

2009-01-01

To research the crystal structure and surface morphology of anodic films on titanium metal in different electrolytes under various electrochemical conditions and investigate the effect of the crystal structure of the oxide films on apatite-forming ability in simulated body fluid (SBF). Titanium oxide films were prepared using an anodic oxidation method on the surface of titanium metal in four different electrolytes: sulfuric acid, acetic acid, phosphoric acid and sodium sulfate solutions with different voltages for 1 min at room temperature. Anodic films that consisted of rutile and/or anatase phases with porous structures were formed on titanium metal after anodizing in H(2)SO(4) and Na(2)SO(4) electrolytes, while amorphous titania films were produced after anodizing in CH(3)COOH and H(3)PO(4) electrolytes. Titanium metal with the anatase and/or rutile crystal structure films showed excellent apatite-forming ability and produced a compact apatite layer covering all the surface of titanium after soaking in SBF for 7d, but titanium metal with amorphous titania layers was not able to induce apatite formation. The resultant apatite layer formed on titanium metal in SBF could enhance the bonding strength between living tissue and the implant. Anodic oxidation is believed to be an effective method for preparing bioactive titanium metal as an artificial bone substitute even under load-bearing conditions.

Mg-Zn based composites reinforced with bioactive glass (45S5) fabricated via powder metallurgy

NASA Astrophysics Data System (ADS)

Ab llah, N.; Jamaludin, S. B.; Daud, Z. C.; Zaludin, M. A. F.

2016-07-01

Metallic implants are shifting from bio-inert to bioactive and biodegradable materials. These changes are made in order to improve the stress shielding effect and bio-compatibility and also avoid the second surgery procedure. Second surgery procedure is required if the patient experienced infection and implant loosening. An implant is predicted to be well for 15 to 20 years inside patient body. Currently, magnesium alloys are found to be the new biomaterials because of their properties close to the human bones and also able to degrade in the human body. In this work, magnesium-zinc based composites reinforced with different content (5, 15, 20 wt. %) of bioactive glass (45S5) were fabricated through powder metallurgy technique. The composites were sintered at 450˚C. Density and porosity of the composites were determined using the gas pycnometer. Microstructure of the composites was observed using an optical microscope. In-vitro bioactivity behavior was evaluated in the simulated body fluid (SBF) for 7 days. Fourier Transform Infrared (FTIR) was used to characterize the apatite forming on the samples surface. The microstructure of the composite showed that the pore segregated near the grain boundaries and bioglass clustering was observed with increasing content of bioglass. The true density of the composites increased with the increasing content of bioglass and the highest value of porosity was indicated by the Mg-Zn reinforced with 20 wt.% of bioglass. The addition of bio-glass to the Mg-Zn has also induced the formation of apatite layer after soaking in SBF solution.

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.

Preservation of rodent bones from El Harhoura 2 cave (Morocco, Neolithic - Middle Palaeolithic): Microstructure, mineralogy, crystallinity and composition

NASA Astrophysics Data System (ADS)

Farre, Bastien; Massard, Pierre; Nouet, Julius; Dauphin, Yannicke

2014-04-01

Thin sections, scanning electron microscopy (SEM), diffraction X (DRX) and infrared spectrometry (FTIR) have been used to study the structure, mineralogy, crystallinity and bulk composition of fossil rodent long bones extracted from a succession of sedimentary layers in a cave from Morocco (Neolithic - Middle Palaeolithic, El Harhoura 2). The microstructure of fossil bones is well-preserved at this scale of observation, and encrusted deposits are rare. All bones are preserved in apatite, but the crystallinity is modified, as well as the crystallite shape, the organic content and the organic-mineral ratio. No fluor enrichment has been observed. Alone or together, the studied parameters do not show a regular trend from the upper to the lower layers of the cave. The preservation of the fossil bones does not confirm the sequence of arid and humid periods inferred from taphonomic analyses.

Maruyamaite, a new K-dominant tourmaline coexisting with diamond -an important accessory mineral in UHP rocks

NASA Astrophysics Data System (ADS)

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

2014-12-01

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. J. Pet., 53, 875-890. Webster et al., 2014. J. Pet., 55, 2217-2248. Woods et al., 2000. Am. Min., 85, 480-487. Brenan, 1993. Chem. Geol., 110, 195-210.

Structural and dynamical studies of acid-mediated conversion in amorphous-calcium-phosphate based dental composites

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

Zhang, Fan; Allen, Andrew J.; Levine, Lyle E.

Our objective was to investigate the complex structural and dynamical conversion process of the amorphous-calcium-phosphate (ACP)-to-apatite transition in ACP based dental composite materials. Composite disks were prepared using zirconia hybridized ACP fillers (0.4 mass fraction) and photo-activated Bis-GMA/TEGDMA resin (0.6 mass fraction). We performed an investigation of the solution-mediated ACP-to-apatite conversion mechanism in controlled acidic aqueous environment with in situ ultra-small angle X-ray scattering based coherent X-ray photon correlation spectroscopy and ex situ X-ray diffraction, as well as other complementary techniques. We established that the ACP-to-apatite conversion in ACP composites is a two-step process, owing to the sensitivity to localmore » structural changes provided by coherent X-rays. Initially, ACP undergoes a local microstructural rearrangement without losing its amorphous character. We established the catalytic role of the acid and found the time scale of this rearrangement strongly depends on the pH of the solution, which agrees with previous findings about ACP without the polymer matrix being present. In the second step, ACP is converted to an apatitic form with the crystallinity of the formed crystallites being poor. Separately, we also confirmed that in the regular Zr-modified ACP the rate of ACP conversion to hydroxyapatite is slowed significantly compared to unmodified ACP, which is beneficial for targeted slow release of functional calcium and phosphate ions from dental composite materials. Significantly, for the first time, we were able to follow the complete solution-mediated transition process from ACP to apatite in this class of dental composites in a controlled aqueous environment. A two-step process, suggested previously, was conclusively identified.« less

Structural and dynamical studies of acid-mediated conversion in amorphous-calcium-phosphate based dental composites

DOE PAGES

Zhang, Fan; Allen, Andrew J.; Levine, Lyle E.; ...

2014-07-28

Our objective was to investigate the complex structural and dynamical conversion process of the amorphous-calcium-phosphate (ACP)-to-apatite transition in ACP based dental composite materials. Composite disks were prepared using zirconia hybridized ACP fillers (0.4 mass fraction) and photo-activated Bis-GMA/TEGDMA resin (0.6 mass fraction). We performed an investigation of the solution-mediated ACP-to-apatite conversion mechanism in controlled acidic aqueous environment with in situ ultra-small angle X-ray scattering based coherent X-ray photon correlation spectroscopy and ex situ X-ray diffraction, as well as other complementary techniques. We established that the ACP-to-apatite conversion in ACP composites is a two-step process, owing to the sensitivity to localmore » structural changes provided by coherent X-rays. Initially, ACP undergoes a local microstructural rearrangement without losing its amorphous character. We established the catalytic role of the acid and found the time scale of this rearrangement strongly depends on the pH of the solution, which agrees with previous findings about ACP without the polymer matrix being present. In the second step, ACP is converted to an apatitic form with the crystallinity of the formed crystallites being poor. Separately, we also confirmed that in the regular Zr-modified ACP the rate of ACP conversion to hydroxyapatite is slowed significantly compared to unmodified ACP, which is beneficial for targeted slow release of functional calcium and phosphate ions from dental composite materials. Significantly, for the first time, we were able to follow the complete solution-mediated transition process from ACP to apatite in this class of dental composites in a controlled aqueous environment. A two-step process, suggested previously, was conclusively identified.« less

Structural and dynamical studies of acid-mediated conversion in amorphous-calcium-phosphate based dental composites

PubMed Central

Zhang, Fan; Allen, Andrew J.; Levine, Lyle E.; Vaudin, Mark D.; Skrtic, Drago; Antonucci, Joseph M.; Hoffman, Kathleen M.; Giuseppetti, Anthony A.; Ilavsky, Jan

2014-01-01

Objective To investigate the complex structural and dynamical conversion process of the amorphous-calcium-phosphate (ACP) -to-apatite transition in ACP based dental composite materials. Methods Composite disks were prepared using zirconia hybridized ACP fillers (0.4 mass fraction) and photo-activated Bis-GMA/TEGDMA resin (0.6 mass fraction). We performed an investigation of the solution-mediated ACP-to-apatite conversion mechanism in controlled acidic aqueous environment with in situ ultra-small angle X-ray scattering based coherent X-ray photon correlation spectroscopy and ex situ X-ray diffraction, as well as other complementary techniques. Results We established that the ACP-to-apatite conversion in ACP composites is a two-step process, owing to the sensitivity to local structural changes provided by coherent X-rays. Initially, ACP undergoes a local microstructural rearrangement without losing its amorphous character. We established the catalytic role of the acid and found the time scale of this rearrangement strongly depends on the pH of the solution, which agrees with previous findings about ACP without the polymer matrix being present. In the second step, ACP is converted to an apatitic form with the crystallinity of the formed crystallites being poor. Separately, we also confirmed that in the regular Zr-modified ACP the rate of ACP conversion to hydroxyapatite is slowed significantly compared to unmodified ACP, which is beneficial for targeted slow release of functional calcium and phosphate ions from dental composite materials. Significance For the first time, we were able to follow the complete solution-mediated transition process from ACP to apatite in this class of dental composites in a controlled aqueous environment. A two-step process, suggested previously, was conclusively identified. PMID:25082155

Coating electrospun poly(epsilon-caprolactone) fibers with gelatin and calcium phosphate and their use as biomimetic scaffolds for bone tissue engineering.

PubMed

Li, Xiaoran; Xie, Jingwei; Yuan, Xiaoyan; Xia, Younan

2008-12-16

Electrospinning was employed to fabricate fibrous scaffolds of poly(epsilon-caprolactone) in the form of nonwoven mats. The surfaces of the fibers were then coated with gelatin through layer-by-layer self-assembly, followed by functionalization with a uniform coating of bonelike calcium phosphate by mineralization in the 10 times concentrated simulated body fluid for 2 h. Transmission electron microscopy, water contact angle, and scanning electron microscopy measurements confirmed the presence of gelatin and calcium phosphate coating layers, and X-ray diffraction results suggested that the deposited mineral phase was a mixture of dicalcium phosphate dehydrate (a precursor to apatite) and apatite. It was also demonstrated that the incorporation of gelatin promoted nucleation and growth of calcium phosphate. The porous scaffolds could mimic the structure, composition, and biological function of bone extracellular matrix. It was found that the preosteoblastic MC3T3-E1 cells attached, spread, and proliferated well with a flat morphology on the mineralized scaffolds. The proliferation rate of the cells on the mineralized scaffolds was significantly higher (by 1.9-fold) than that on the pristine fibrous scaffolds after culture for 7 days. These results indicated that the hybrid system containing poly(epsilon-caprolactone), gelatin, and calcium phosphate could serve as a new class of biomimetic scaffolds for bone tissue engineering.

Hydrogen Isotopic Composition of Apatite in Northwest Africa 7034: A Record of the "Intermediate" H-Isotopic Reservoir in the Martian Crust?

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 visible-infrared reflectance spectra of the martian surface measured from orbit [2]. The composition of the fine-grained matrix within NWA 7034 bears a striking resemblance to the major element composition estimated for the martian crust, with several exceptions. The NWA 7034 matrix is depleted in Fe, Ti, and Cr and enriched in Al, Na, and P [3]. The differences in Al and Fe are the most substantial, but the Fe content of NWA 7034 matrix falls within the range reported for the southern highlands crust [6]. It was previously suggested by [4] that NWA 7034 was sourced from the southern highlands based on the ancient 4.4 Ga ages recorded in NWA 7034/7533 zircons [4, 5]. In addition, the NWA 7034 matrix material is enriched in incompatible trace elements by a factor of 1.2-1.5 [7] relative to estimates of the bulk martian crust. The La/Yb ratio of the bulk martian crust is estimated to be approximately 3 [7], and the La/Yb of the NWA 7034 matrix materials ranges from approximately 3.9 to 4.4 [3, 8], indicating a higher degree of LREE enrichment in the NWA 7034 matrix materials. This elevated La/Yb ratio and enrichment in incompatible lithophile trace elements is consistent with NWA 7034 representing a more geochemically enriched crustal terrain than is represented by the bulk martian crust, which would be expected if NWA 7034 represents the bulk crust from the southern highlands. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the composition of the martian crust, particularly the ancient highlands. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034. Usui et al., [9] recently proposed that a H isotopic reservoir exists within the martian crust that has a H-isotopic composition that is intermediate (dD of 1000-2000per mille) between an isotopically light mantle (Delta D is less than 275per mille [10]) and an isotopically heavy atmosphere (dD of 2500-6100per mille [11, 12]). Apatites in NWA 7034 occur in a number of lithologic domains, however apatites across all lithologic domains have been affected by a Pb-loss event at about 1.5 Ga before present [5], so they are unlikely to have retained a primary composition and are more likely to have equilibrated with fluids within the martian crust that may or may not have exchanged with the martian atmosphere. Equilibration of apatite with crustal fluids is further supported by the chlorine-rich compositions exhibited by apatites in NWA 7034 in comparison to apatites from other martian meteorites (Figure 1; [13]). Cl is more hydrophilic than F, which promotes formation of Cl-rich apatite compositions in fluid-rich systems [e.g., 14, 15-17].

Titanium bone implants with superimposed micro/nano-scale porosity and antibacterial capability

NASA Astrophysics Data System (ADS)

Necula, B. S.; Apachitei, I.; Fratila-Apachitei, L. E.; van Langelaan, E. J.; Duszczyk, J.

2013-05-01

This study aimed at producing a multifunctional layer with micro/nano-interconnected porosity and antibacterial capability on a rough macro-porous plasma sprayed titanium surface using the plasma electrolytic oxidation process. The layers were electrochemically formed in electrolytes based on calcium acetate and calcium glycerophosphate salts bearing dispersed Ag nanoparticles. They were characterized with respect to surface morphology and chemical composition using a scanning electron microscope equipped with the energy dispersive spectroscopy and back scattering detectors. Scanning electron microscopy images showed the formation of a micro/nano-scale porous layer, comprised of TiO2 bearing Ca and P species and Ag nanoparticles, following accurately the surface topography of the plasma sprayed titanium coating. The Ca/P atomic ratio was found to be close to that of bone apatite. Ag nanoparticles were incorporated on both on top and inside the porous structure of the TiO2 layer.

Mineralization behavior and interface properties of BG-PVA/bone composite implants in simulated body fluid.

PubMed

Ma, Yanxuan; Zheng, Yudong; Huang, Xiaoshan; Xi, Tingfei; Lin, Xiaodan; Han, Dongfei; Song, Wenhui

2010-04-01

Due to the non-bioactivity and poor conjunction performance of present cartilage prostheses, the main work here is to develop the bioactive glass-polyvinyl alcohol hydrogel articular cartilage/bone (BG-PVA/bone) composite implants. The essential criterion for a biomaterial to bond with living bone is well-matched mechanical properties as well as biocompatibility and bioactivity. In vitro studies on the formation of a surface layer of carbonate hydroxyl apatite (HCA) and the corresponding variation of the properties of biomaterials are imperative for their clinical application. In this paper, the mineralization behavior and variation of the interface properties of BG-PVA/bone composites were studied in vitro by using simulated body fluid (SBF). The mineralization and HCA layer formed on the interface between the BG-PVA hydrogel and bone in SBF could provide the composites with bioactivity and firmer combination. The compression property, shear strength and interface morphology of BG-PVA/bone composite implants varying with the immersion time in SBF were characterized. Also, the influence laws of the immersion time, content of BG in the composites and aperture of bones to the mineralization behavior and interface properties were investigated. The good mineralization behavior and enhanced conjunction performance of BG-PVA/bone composites demonstrated that this kind of composite implant might be more appropriate cartilage replacements.

Understanding the evolution of S- and I-type granitic plutons through analysis of apatite.

NASA Astrophysics Data System (ADS)

Hess, B. L.; Fiege, A.; Tailby, N.

2017-12-01

The major and trace element composition of apatites from the Lachlan fold belt (LFB) S- and I-type granitoids (Australia) and the Central French Massif (CFM) S-type leucogranites (France) were analyzed to investigate their compositional and redox variation. Apatite is a common accessory mineral in magmatic systems that can incorporate a variety of trace elements, including the polyvalent elements sulfur (S), iron (Fe), and manganese (Mn). It was recently discovered that apatite can incorporate three oxidation states of S (S6+, S4+, S2-) into its structure as a function of oxygen fugacity [1]. However, the oxidation states of Mn and Fe in apatite are essentially unknown (2+ and/or 3+). In this study, we collected many electron probe line transects across apatites in several different host phases from a variety of S- and I-type plutons. The F-H-Cl contents of the S- and I-type LFB samples were similar ( 2.9 wt% F, 0.4 wt% Cl, 0.5 wt% OH). The CFM S-types contained virtually no Cl and ranged from near-endmember OH-apatite to near-endmember F-apatite. The apatites of all studied the S- and I-type plutons are characterized by similar ranges of Fe content (<1.5 wt% Fe), while Mn reaches much higher concentrations in the S-type when compared to I-type apatites (<6.5 wt% Mn). The S content of the apatites varies significantly, from <50 ppm S in the LFB S-types, up to 2,000 ppm S in the LFB I-types, and reaching 1,650 ppm S in the CFM S-types. The elevated S contents in the LFB I-type and CFM S-type apatites allowed us to measure the S oxidation states by using X-ray absorption near-edge structure (XANES) spectroscopy. The spectra show variability in S oxidation states ranging from mostly sulfate down to nearly equal S6+/S2- ratios, indicating redox variations during apatite formation. The S-type Mn + Fe content plots in a 1:1 ratio against calcium (Ca) in atoms per formula unit, while the I-type apatites have too low Mn and Fe to show a clear trend. Thus, divalent Mn and Fe probably replace Ca2+ in the S-types' apatite structure, while the incorporation of trivalent Mn or Fe in apatite is rather unlikely. We suggest that Mn and Fe contents in apatite may become a useful tracer of melt evolution once the distributions coefficients are experimentally calibrated. [1] Konecke et al. (2017), Am Mineral

High temperature annealing of fission tracks in fluorapatite, Santa Fe Springs oil field, Los Angeles Basin, California

USGS Publications Warehouse

Naeser, Nancy D.; Crowley, Kevin D.; McCulloh, Thane H.; Reaves, Chris M.; ,

1990-01-01

Annealing of fission tracks is a kinetic process dependent primarily on temperature and to a laser extent on time. Several kinetic models of apatite annealing have been proposed. The predictive capabilities of these models for long-term geologic annealing have been limited to qualitative or semiquantitative at best, because of uncertainties associated with (1) the extrapolation of laboratory observations to geologic conditions, (2) the thermal histories of field samples, and (3) to some extent, the effect of apatite composition on reported annealing temperatures. Thermal history in the Santa Fe Springs oil field, Los Angeles Basin, California, is constrained by an exceptionally well known burial history and present-day temperature gradient. Sediment burial histories are continuous and tightly constrained from about 9 Ma to present, with an important tie at 3.4 Ma. No surface erosion and virtually no uplift were recorded during or since deposition of these sediments, so the burial history is simple and uniquely defined. Temperature gradient (???40??C km-1) is well established from oil-field operations. Fission-track data from the Santa Fe Springs area should thus provide one critical field test of kinetic annealing models for apatite. Fission-track analysis has been performed on apatites from sandstones of Pliocene to Miocene age from a deep drill hole at Santa Fe Springs. Apatite composition, determined by electron microprobe, is fluorapatite [average composition (F1.78Cl0.01OH0.21)] with very low chlorine content [less than Durango apatite; sample means range from 0.0 to 0.04 Cl atoms, calculated on the basis of 26(O, F, Cl, OH)], suggesting that the apatite is not unusually resistant to annealing. Fission tracks are preserved in these apatites at exceptionally high present-day temperatures. Track loss is not complete until temperatures reach the extreme of 167-178??C (at 3795-4090 m depth). The temperature-time annealing relationships indicated by the new data from Santa Fe Springs conflict with predictions based on previously published, commonly used, kinetic annealing models for apatite. Work is proceeding on samples from another area of the basin that may resolve this discrepancy.

Surface characterization and corrosion behavior of calcium phosphate-base composite layer on titanium and its alloys via plasma electrolytic oxidation: A review paper.

PubMed

Rafieerad, A R; Ashra, M R; Mahmoodian, R; Bushroa, A R

2015-12-01

In recent years, calcium phosphate-base composites, such as hydroxyapatite (HA) and carbonate apatite (CA) have been considered desirable and biocompatible coating layers in clinical and biomedical applications such as implants because of the high resistance of the composites. This review focuses on the effects of voltage, time and electrolytes on a calcium phosphate-base composite layer in case of pure titanium and other biomedical grade titanium alloys via the plasma electrolytic oxidation (PEO) method. Remarkably, these parameters changed the structure, morphology, pH, thickness and crystallinity of the obtained coating for various engineering and biomedical applications. Hence, the structured layer caused improvement of the biocompatibility, corrosion resistance and assignment of extra benefits for Osseo integration. The fabricated layer with a thickness range of 10 to 20 μm was evaluated for physical, chemical, mechanical and tribological characteristics via XRD, FESEM, EDS, EIS and corrosion analysis respectively, to determine the effects of the applied parameters and various electrolytes on morphology and phase transition. Moreover, it was observed that during PEO, the concentration of calcium, phosphor and titanium shifts upward, which leads to an enhanced bioactivity by altering the thickness. The results confirm that the crystallinity, thickness and contents of composite layer can be changed by applying thermal treatments. The corrosion behavior was investigated via the potentiodynamic polarization test in a body-simulated environment. Here, the optimum corrosion resistance was obtained for the coating process condition at 500 V for 15 min in Ringer solution. This review has been summarized, aiming at the further development of PEO by producing more adequate titanium-base implants along with desired mechanical and biomedical features. Copyright © 2015 Elsevier B.V. All rights reserved.

Mg-Doped Hydroxyapatite/Chitosan Composite Coated 316L Stainless Steel Implants for Biomedical Applications.

PubMed

Sutha, S; Dhineshbabu, N R; Prabhu, M; Rajendran, V

2015-06-01

In this investigation, ultrasonication process was used for the synthesis of magnesium doped nano-hydroxyapatite (MH) (0, 1, 2, and 3 mol% of Mg concentration) particles with controlled size and surface morphology. The size of the prepared MH particles was in the range of 20-100 nm with narrow distribution. Increase in the concentration of Mg reduced the particle size distribution from 60 to 40 nm. On incorporation of Mg in HAp lattice, an increase of 20-66 nm in specific surface area was observed in microporous HAp particles. XRF and XRD patterns reveal that the particles possess stoichiometric composition with reduced crystallinity with respect to the Mg concentration. Surface morphology of MH/chitosan (CTS) coated implant was found to be uniform without any defects. The corrosion rate of the implant decreased with increase in Mg concentration. The in vitro formation of bonelike apatite layer on the surface of the MH/CTS coated implant was observed from simulated body fluid studies. The antimicrobial activity of the MH/CTS composites against gram-positive and gram-negative bacterial strains indicated that increasing Mg concentration enhanced antimicrobial properties. Nanoindentation analysis of apatite coated implant surface reveals that the mechanical property depends on the concentration of magnesium in HAp. From the cytotoxicity analysis against NIH 3T3 fibroblast, it was observed that the Mg incorporated HAp/CTS composite was less toxic than the MHO/CTS composite. From this result, it was concluded that the MH/CTS nanocomposites coated implant is the excellent material for implants.

In vitro remineralization of acid-etched human enamel with Ca 3SiO 5

NASA Astrophysics Data System (ADS)

Dong, Zhihong; Chang, Jiang; Deng, Yan; Joiner, Andrew

2010-02-01

Bioactive and inductive silicate-based bioceramics play an important role in hard tissue prosthetics such as bone and teeth. In the present study, a model was established to study the acid-etched enamel remineralization with tricalcium silicate (Ca 3SiO 5, C 3S) paste in vitro. After soaking in simulated oral fluid (SOF), Ca-P precipitation layer was formed on the enamel surface, with the prolonged soaking time, apatite layer turned into density and uniformity and thickness increasingly from 250 to 350 nm for 1 day to 1.7-1.9 μm for 7 days. Structure of apatite crystals was similar to that of hydroxyapatite (HAp). At the same time, surface smoothness of the remineralized layer is favorable for the oral hygiene. These results suggested that C 3S treated the acid-etched enamel can induce apatite formation, indicating the biomimic mineralization ability, and C 3S could be used as an agent of inductive biomineralization for the enamel prosthesis and protection.

Study of the interfacial reactions between a bioactive apatite-mullite glass-ceramic coating and titanium substrates using high angle annular dark field transmission electron microscopy.

PubMed

Stanton, Kenneth T; O'Flynn, Kevin P; Nakahara, Shohei; Vanhumbeeck, Jean-François; Delucca, John M; Hooghan, Bobby

2009-04-01

Glass of generic composition SiO(2) . Al(2)O(3) . P(2)O(5) . CaO . CaF(2) will crystallise predominantly to apatite and mullite upon heat-treatment. Such ceramics are bioactive, osseoconductive, and have a high resistance to fracture. As a result, they are under investigation for use as biomedical device coatings, and in particular for orthopaedic implants. Previous work has shown that the material can be successfully enamelled to titanium with an interfacial reaction zone produced during heat treatment. The present study uses high angle annular dark field transmission electron microscopy (HAADF-TEM) to conduct a detailed examination of this region. Results show evidence of complex interfacial reactions following the diffusion of titanium into an intermediate layer and the production of titanium silicides and titanium phosphides. These results confirm previously hypothesised mechanisms for the bonding of silicate bioceramics with titanium alloys.

Apatite ore mine tailings as an amendment for remediation of a lead-contaminated shooting range soil.

PubMed

Venäläinen, Salla H

2011-10-01

This study investigated the use of tailings from apatite ore beneficiation in the remediation of a heavily contaminated shooting range soil. The tailings originating in Siilinjärvi carbonatite complex, Finland, consist of apatite residues accompanied by phlogopite and calcite. In a pot experiment, organic top layer of a boreal forest soil predisposed to pellet-derived lead (Pb) was amended with tailings of various particle-sizes (Ø>0.2mm, Ø<0.2mm and unsieved material) differing in their mineralogical composition. After 9-, 10-, 14- and 21-month incubation, the samples were monitored for tailings-induced changes in the different Pb pools by means of sequential fractionation. Following the incubation, the samples were extracted with water and the extracts were analyzed for Pb species distribution by means of a cation exchange resin. The results revealed that Pb was continuously released from the shotgun pellet fragments due to weathering. However, the apatite and calcite compartments in the tailings counteracted the mobility of the released Pb through the formation of sparingly soluble fluorpyromorphite and cerussite. Furthermore, the tailings efficiently reduced the bioavailability of Pb by transferring it from the water-soluble and exchangeable pools into the organic one. The material also increased the proportion of the less toxic non-cationic Pb to the total dissolved Pb from the initial level of 5% to 9-12%. The results suggest that the tailings-induced stabilization of Pb may be an environmentally sound remediation technique at polluted sites. Copyright © 2011 Elsevier B.V. All rights reserved.

Kinetics of apatite formation on a calcium-silicate cement for root-end filling during ageing in physiological-like phosphate solutions.

PubMed

Gandolfi, Maria Giovanna; Taddei, Paola; Tinti, Anna; De Stefano Dorigo, Elettra; Rossi, Piermaria Luigi; Prati, Carlo

2010-12-01

The bioactivity of calcium silicate mineral trioxide aggregate (MTA) cements has been attributed to their ability to produce apatite in presence of phosphate-containing fluids. This study evaluated surface morphology and chemical transformations of an experimental accelerated calcium-silicate cement as a function of soaking time in different phosphate-containing solutions. Cement discs were immersed in Dulbecco's phosphate-buffered saline (DPBS) or Hank's balanced salt solution (HBSS) for different times (1-180 days) and analysed by scanning electron microscopy connected with an energy dispersive X-ray analysis (SEM-EDX) and micro-Raman spectroscopy. SEM-EDX revealed Ca and P peaks after 14 days in DPBS. A thin Ca- and P-rich crystalline coating layer was detected after 60 days. A thicker multilayered coating was observed after 180 days. Micro-Raman disclosed the 965-cm(-1) phosphate band at 7 days only on samples stored in DPBS and later the 590- and 435-cm(-1) phosphate bands. After 60-180 days, a layer approximately 200-900 μm thick formed displaying the bands of carbonated apatite (at 1,077, 965, 590, 435 cm(-1)) and calcite (at 1,088, 713, 280 cm(-1)). On HBSS-soaked, only calcite bands were observed until 90 days, and just after 180 days, a thin apatite-calcite layer appeared. Micro-Raman and SEM-EDX demonstrated the mineralization induction capacity of calcium-silicate cements (MTAs and Portland cements) with the formation of apatite after 7 days in DPBS. Longer time is necessary to observe bioactivity when cements are immersed in HBSS.

Bioactivity of fluorapatite/alumina composite coatings deposited on Ti6Al4V substrates by laser cladding

NASA Astrophysics Data System (ADS)

Chien, C. S.; Liu, C. W.; Kuo, T. Y.; Wu, C. C.; Hong, T. F.

2016-04-01

Hydroxyapatite (HA) is one of the most commonly used coating materials for metal implants. However, following high-temperature deposition, HA easily decomposes into an unstable phase or forms an amorphous phase, and hence, the long-term stability of the implant is reduced. Accordingly, the present study investigates the use of fluorapatite (FA) fortified with 20 wt% alumina (α-Al2O3) as an alternative biomedical coating material. The coatings are deposited on Ti6Al4V substrates using a Nd:YAG laser cladding process performed with laser powers and travel speeds of 400 W/200 mm/min, 800 W/400 mm/min and 1200 W/600 mm/min, respectively. The results show that for all of the specimens, a strong metallurgical bond is formed at the interface between the coating layer and the transition layer due to melting and diffusion. The XRD analysis results reveal that the cladding layers in all of the specimens consist mainly of FA, β-TCP, CaF2, Ti and θ-Al2O3 phases. In addition, the cladding layers of the specimens prepared using laser powers of 400 and 800 W also contain CaTiO3 and CaAl2O4, while that of the specimen clad using a power of 1200 W contains TTCP and CaO. Following immersion in simulated body fluid for 14 days, all of the specimens precipitate dense bone-like apatite and exhibit excellent bioactivity. However, among all of the specimens, the specimen that is prepared with a laser power of 800 W shows the best biological activity due to the presence of residual FA, apatite-generating CaTiO3 and a rough cladding layer surface.

Multi-layer porous fiber-reinforced composites for implants: in vitro calcium phosphate formation in the presence of bioactive glass.

PubMed

Nganga, Sara; Zhang, Di; Moritz, Niko; Vallittu, Pekka K; Hupa, Leena

2012-11-01

Glass-fiber-reinforced composites (FRCs), based on bifunctional methacrylate resin, have recently shown their potential for use as durable cranioplasty, orthopedic and oral implants. In this study we suggest a multi-component sandwich implant structure with (i) outer layers out of porous FRC, which interface the cortical bone, and (ii) inner layers encompassing bioactive glass granules, which interface with the cancellous bone. The capability of Bioglass(®) 45S5 granules (100-250μm) to induce calcium phosphate formation on the surface of the FRC was explored by immersing the porous FRC-Bioglass laminates in simulated body fluid (SBF) for up to 28d. In both static (agitated) and dynamic conditions, bioactive glass granules induced precipitation of calcium phosphate at the laminate surfaces as confirmed by scanning electron microscopy. The proposed dynamic flow system is useful for the in vitro simulation of bone-like apatite formation on various new porous implant designs containing bioactive glass and implant material degradation. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

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-spectroscopy proved inconclusive for apatites with small P-site deficiencies and other substituent elements in this site. Indicator REE ratios sensitive to redox conditions (δCe, δEu) and hydrothermal overprint (δY) form a fairly tight cluster of values (0.8-1.3, 0.8-1.1 and 0.6-0.9, respectively) and may be used in combination with trace-element abundances for the development of geochemical exploration tools. Hydrothermal apatite forms in carbonatites as the product of replacement of primary apatite, or is deposited in fractures and interstices as euhedral crystals and aggregates associated with typical late-stage minerals (e.g., quartz and chlorite). Hydrothermal apatite is typically depleted in Sr, REE, Mn and Th, but enriched in F (up to 4.8 wt.%) relative to its igneous precursor, and also differs from the latter in at least some of key REE ratios [e.g., shows (La/Yb)cn ≤ 25, or a negative Ce anomaly]. The only significant exception is Sr(± REE,Na)-rich replacement zones and overgrowths on igneous apatite from some dolomite(-bearing) carbonatites. Their crystallization conditions and source fluid appear to be very different from the more common Sr-REE-depleted variety. Based on the new evidence presented in this work, trace-element partitioning between apatite and carbonatitic magmas, phosphate solubility in these magmas, and compositional variation of apatite-group minerals from spatially associated carbonatitic rocks are critically re-evaluated.

Formation of apatite layers on modified canasite glass-ceramics in simulated body fluid.

PubMed

Miller, C A; Kokubo, T; Reaney, I M; Hatton, P V; James, P F

2002-03-05

Canasite glass-ceramics were modified by either increasing the concentration of calcium in the glass, or by the addition of P2O5. Samples of these novel materials were placed in simulated body fluid (SBF), along with a control material (commercial canasite), for periods ranging from 12 h to 28 days. After immersion, surface analysis was performed using thin film X-ray diffraction, Fourier transform infrared reflection spectroscopy, and scanning electron microscopy equipped with energy dispersive X-ray detectors. The concentrations of sodium, potassium, calcium, silicon, and phosphorus in the SBF solution were measured using inductively coupled plasma emission spectroscopy. No apatite was detected on the surface of commercial canasite, even after 28 days of immersion in SBF. A crystalline apatite layer was formed on the surface of a P2O5-containing canasite after 5 days, and after 3 days for calcium-enriched canasite. Ion release data suggested that the mechanism for apatite deposition was different for P2O5 and non-P2O5-containing glass-ceramics. Copyright 2001 John Wiley & Sons, Inc.

Tuning the surface microstructure of titanate coatings on titanium implants for enhancing bioactivity of implants

PubMed Central

Wang, Hui; Lai, Yue-Kun; Zheng, Ru-Yue; Bian, Ye; Zhang, Ke-Qin; Lin, Chang-Jian

2015-01-01

Biological performance of artificial implant materials is closely related to their surface characteristics, such as microtopography, and composition. Therefore, convenient fabrication of artificial implant materials with a cell-friendly surface structure and suitable composition was of great significance for current tissue engineering. In this work, titanate materials with a nanotubular structure were successfully fabricated through a simple chemical treatment. Immersion test in a simulated body fluid and in vitro cell culture were used to evaluate the biological performance of the treated samples. The results demonstrate that the titanate layer with a nanotubular structure on Ti substrates can promote the apatite-inducing ability remarkably and greatly enhance cellular responses. This highlights the potential of such titanate biomaterials with the special nanoscale structure and effective surface composition for biomedical applications such as bone implants. PMID:26089665

Apatite glass-ceramics: a review

NASA Astrophysics Data System (ADS)

Duminis, Tomas; Shahid, Saroash; Hill, Robert Graham

2016-12-01

This article is a review of the published literature on apatite glass-ceramics (GCs). Topics covered include crystallization mechanisms of the various families of the apatite GCs and an update on research and development on apatite GCs for applications in orthopedics, dentistry, optoelectronics and nuclear waste management. Most apatite GCs crystallize through a homogenous nucleation and crystallization mechanism, which is aided by a prior liquid-liquid phase separation. Careful control of the base glass composition and heat-treatment conditions, which determine the nature and morphology of the crystal phases in the GC can produce GC materials with exceptional thermal, mechanical, optical and biological properties. The GCs reviewed for orthopedic applications exhibit suitable mechanical properties and can chemically bond to bone and stimulate its regeneration. The most commercially successful apatite GCs are those developed for dental veneering. These materials exhibit excellent translucency and clinical esthetics, and mimic the natural tooth mineral. Due to the ease of solid solution of the apatite lattice, rare earth doped apatite GCs are discussed for potential applications in optoelectronics and nuclear waste management. One of the drawbacks of the commercial apatite GCs used in orthopedics is the lack of resorbability, therefore the review provides a direction for future research in the field.

Mineral chemistry of magnetite from magnetite-apatite mineralization and their host rocks: examples from Kiruna, Sweden, and El Laco, Chile

NASA Astrophysics Data System (ADS)

Broughm, Shannon G.; Hanchar, John M.; Tornos, Fernando; Westhues, Anne; Attersley, Samuel

2017-12-01

Interpretation of the mineralizing environment of magnetite-apatite deposits remains controversial with theories that include a hydrothermal or magmatic origin or a combination of those two processes. To address this controversy, we have analyzed the trace element content of magnetite from precisely known geographic locations and geologic environments from the Precambrian magnetite-apatite ore and host rocks in Kiruna, Sweden, and the Pliocene-Holocene El Laco volcano in the Atacama desert of Chile. Magnetite samples from Kiruna have low trace element concentrations with little chemical variation between the ore, host, and related intrusive rocks. Magnetite from andesite at El Laco, and dacite from the nearby Láscar volcano, has high trace element concentrations typical of magmatic magnetite. El Laco ore magnetite have low trace element concentrations and displays growth zoning in incompatible elements (Si, Ca, and Ce), compatible elements (Mg, Al, and Mn), large-ion lithophile element (Sr), and high field strength element (Y, Nb, and Th). The El Laco ore magnetite are similar in composition to magnetite that has been previously interpreted to have crystallized from hydrothermal fluids; however, there is a significant difference in the internal zoning patterns. At El Laco, each zoned element is either enriched or depleted in the same layers, suggesting the magnetite crystallized from a volatile-rich, iron-oxide melt. In general, the compositions of magnetite from these two deposits plot in very wide fields that are not restricted to the proposed fields in published discriminant diagrams. This suggests that the use of these diagrams and genetic models based on them should be used with caution.

The synergistic effects of Chinese herb and injectable calcium silicate/β-tricalcium phosphate composite on an osteogenic accelerator in vitro.

PubMed

Huang, Ming-Hsien; Kao, Chia-Tze; Chen, Yi-Wen; Hsu, Tuan-Ti; Shieh, Den-En; Huang, Tsui-Hsien; Shie, Ming-You

2015-04-01

This study investigates the physicochemical and biological effects of traditional Chinese medicines on the β-tricalcium phosphate (β-TCP)/calcium silicate (CS) composites of bone cells using human dental pulp cell. CS is an osteoconductive and bioactive material. For this research we have combined β-TCP and CS and check its effectiveness, a series of β-TCP/CS composites with different ratios of Xu Duan (XD) were prepared to make new bioactive and biodegradable biocomposites for bone repair. XD has been used in Traditional Chinese Medicine for hundreds of years as an antiosteoporosis, tonic and antiaging agent for the therapy of low back pain, traumatic hematoma, threatened abortion and bone fractures. Formation of bone-like apatite, the diametral tensile strength, and weight loss of composites were considered before and after immersion in simulated body fluid (SBF). In addition, we also examined the effects of XD released from β-TCP/CS composites and in vitro human dental pulp cell (hDPCs) and studied its behavior. The results show the XD-contained paste did not give any demixing when the weight ratio of XD increased to 5-10 % due to the filter-pressing effect during extrusion through the syringe. After immersion in SBF, the microstructure image showed a dense bone-like apatite layer covered on the β-TCP/CS/XD composites. In vitro cell experiments shows that the XD-rich composites promote human dental pulp cells (hDPCs) proliferation and differentiation. However, when the XD quantity in the composite is more than 5 %, the amount of cells and osteogenesis protein of hDPCs were stimulated by XD released from β-TCP/CS composites. The combination of XD in degradation of β-TCP and osteogenesis of CS gives strong reason to believe that these calcium-based composite cements may prove to be promising bone repair materials.

Synthesis, mechanical properties, and in vitro biocompatibility with osteoblasts of calcium silicate-reduced graphene oxide composites.

PubMed

Mehrali, Mehdi; Moghaddam, Ehsan; Shirazi, Seyed Farid Seyed; Baradaran, Saeid; Mehrali, Mohammad; Latibari, Sara Tahan; Metselaar, Hendrik Simon Cornelis; Kadri, Nahrizul Adib; Zandi, Keivan; Osman, Noor Azuan Abu

2014-03-26

Calcium silicate (CaSiO3, CS) ceramics are promising bioactive materials for bone tissue engineering, particularly for bone repair. However, the low toughness of CS limits its application in load-bearing conditions. Recent findings indicating the promising biocompatibility of graphene imply that graphene can be used as an additive to improve the mechanical properties of composites. Here, we report a simple method for the synthesis of calcium silicate/reduced graphene oxide (CS/rGO) composites using a hydrothermal approach followed by hot isostatic pressing (HIP). Adding rGO to pure CS increased the hardness of the material by ∼40%, the elastic modulus by ∼52%, and the fracture toughness by ∼123%. Different toughening mechanisms were observed including crack bridging, crack branching, crack deflection, and rGO pull-out, thus increasing the resistance to crack propagation and leading to a considerable improvement in the fracture toughness of the composites. The formation of bone-like apatite on a range of CS/rGO composites with rGO weight percentages ranging from 0 to 1.5 has been investigated in simulated body fluid (SBF). The presence of a bone-like apatite layer on the composite surface after soaking in SBF was demonstrated by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The biocompatibility of the CS/rGO composites was characterized using methyl thiazole tetrazolium (MTT) assays in vitro. The cell adhesion results showed that human osteoblast cells (hFOB) can adhere to and develop on the CS/rGO composites. In addition, the proliferation rate and alkaline phosphatase (ALP) activity of cells on the CS/rGO composites were improved compared with the pure CS ceramics. These results suggest that calcium silicate/reduced graphene oxide composites are promising materials for biomedical applications.

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 metamorphic (over)growth and fluid aided alteration/recrystallization. We seek to evaluate if apatite U-Pb thermochronology can be applied to a broad range of rock types and geological environments or if limitations must be drawn.

Apatite sulfur systematics and crystal population in the 1991 Pinatubo magmas

NASA Astrophysics Data System (ADS)

van Hoose, A. E.; Streck, M. J.; Pallister, J. S.

2010-12-01

On June 15, 1991, Mount Pinatubo, Philippines, ejected 20 mega-tonnes of sulfur dioxide into the atmosphere, significantly impacting global climate and stratospheric ozone. Recharging basaltic magma mixed into the 50 km3 dacitic magma reservoir 6 to 11 km beneath Mount Pinatubo, and triggered the 1991 eruption. The result of the magma mixing was a hybrid andesite with quenched basalt inclusions that erupted as a dome between June 7 and June 12. On June 15, approximately 5 km3 of anhydrite bearing magma was erupted from the main phenocryst-rich dacitic reservoir. We are using this extraordinary framework of the 1991 Pinatubo eruption to investigate the systematics of sulfur uptake by apatite in order to further develop apatite as a monitor for magmatic sulfur. In the dacite and hybrid andesite, apatite occurs as individual phenocrysts (up to ~200 μm diameter) or included within anhydrite, hornblende, and plagioclase phenocrysts. In the basaltic magmatic inclusions, apatite is found as acicular microphenocrysts. Electron microprobe data collected on apatite yield low- (<0.3 SO3 wt.%), medium- (0.3-0.7 SO3 wt.%), and high-sulfur (>0.7 SO3 wt.%) apatites in all juvenile products, and show that two distinct populations of apatites exist. Apatites crystallizing from silicic melt have predominantly low- to medium-sulfur contents, but high-sulfur apatites with as much as 1.2-1.6 wt.% SO3 occur sporadically and are always found in close proximity to anhydrite. Except for a few low-sulfur apatites, apatite in the basalt is always sulfur-rich with compositions forming a continuous array between 0.9 to 2.4 wt.% SO3. The population of apatite that crystallized from silicic melt has elevated cerium, fluorine, and chlorine and lower magnesium concentrations (average dacite values in wt.%: 0.22 Ce2O3; 1.4 F; 1.1 Cl, 0.14 MgO ;) relative to the population of apatite from the basalt (average basalt values in wt.%: 0.08 Ce2O3; 0.9 F; 0.9 Cl, 0.20 MgO). These compositional systematics rule out the possibility that sulfur-rich apatite from dacite are inherited from mafic magma. We will evaluate this in further detail with additional LA-ICP-MS data. These data beg the question: which condition led to the crystallization of such high-sulfur apatites in silicic Pinatubo magmas (occurring also elsewhere, e.g., Streck et al., 2007)? Equilibrium crystal-melt partitioning is unlikely the cause because these apatites appear over-enriched in SO3, as they exceed values for apatite of experimental studies with a rhyolitic melt containing 400-700 ppm sulfur at high temperature (≥900 °C) (Parat and Holtz, 2005). Close proximity of sulfur-rich apatite to anhydrite suggests that high sulfur content is a local phenomenon that occurs only where anhydrite has crystallized and may in part be diffusion and/or fluid-controlled. On the other hand, high-sulfur apatite of the basalt likely reflects the high intrinsic sulfur content of the basaltic magma. (Parat, F., Holtz, F. (2005), CMP 150: 643-651; Streck, M., Broderick, C., Halter, W. (2007) GCA 71: A979)

Fabrication of B-type carbonate apatite blocks by the phosphorization of free-molding gypsum-calcite composite.

PubMed

Zaman, Chowdury Tanira; Takeuchi, Akari; Matsuya, Shigeki; Zaman, Q H M Shawket; Ishikawa, Kunio

2008-09-01

B-type carbonate apatite (CO3Ap) block may be an ideal artificial bone substitute because it is closer in chemical composition to bone mineral. In the present study, the feasibility to fabricate CO3Ap blocks was investigated using compositional transformation, which was based on the dissolution-precipitation reaction of a gypsum-calcite composite with free-molding behavior. For the compositional change, or phosphorization, gypsum-calcite composites of varying CaCO3 contents were immersed in 1 mol/L (NH4)3PO4 aqueous solution at 100 degrees C for 24 hours. No macroscopic changes were found after the treatment, whereas microscopic change was observed at SEM level. X-ray diffraction, Fourier transform infrared spectroscopy and CHN analysis indicated that the composites were B-type CO3Ap containing approximately 6-7 wt% of CO3, a value similar to that of biological bone apatite. Diametral tensile strength of the CO3Ap block was approximately 1-3 MPa. Based on the results obtained, it was therefore concluded that gypsum-calcite was a good candidate for the fabrication of CO3Ap blocks, coupled with the advantage that the composite can be molded to any shape by virtue of the setting property of gypsum.

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.

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 increase the statistical range and make the inversion more accurate and precise. These additional non-standard apatites need only be wide-ranging in composition: They need not be homogenous nor have known H, F, or Cl concentrations. Tests utilizing synthetic data and data generated in the laboratory indicate that this method should yield satisfactory results provided apatites meet the criteria of the model. The inversion method is able to reproduce conventional calibrations to within <2.5%, a level of accuracy comparable to or even better than the uncertainty of the conventional calibration, and one that includes both error in the inversion method as well as any true error in the independently determined values of the standards. Uncertainties in the inversion calibrations range from 0.1-1.7% (2σ), typically an order of magnitude smaller than the uncertainties in conventional calibrations (~4-5% for H2O, 1-19% for F and Cl). However, potential systematic errors stem from the model assumption of 100% occupancy of this site by the measured elements. Use of this method simplifies analysis of H, F, and Cl in apatites by SIMS, and may also be amenable to other stoichiometrically limited substitution groups, including P+As+S+Si+C in apatite, and Zr+Hf+U+Th in non-metamict zircon.

Effects of phosphates on microstructure and bioactivity of micro-arc oxidized calcium phosphate coatings on Mg-Zn-Zr magnesium alloy.

PubMed

Pan, Y K; Chen, C Z; Wang, D G; Zhao, T G

2013-09-01

Calcium phosphate (CaP) coatings were prepared on Mg-Zn-Zr magnesium alloy by micro-arc oxidation (MAO) in electrolyte containing calcium acetate monohydrate (CH3COO)2Ca·H2O) and different phosphates (i.e. disodium hydrogen phosphate dodecahydrate (Na2HPO4·12H2O), sodium phosphate (Na3PO4·H2O) and sodium hexametaphosphate((NaPO3)6)). Scanning electron microscope (SEM), energy-dispersive X-ray spectrometry (EDS) and X-ray diffractometer (XRD) were employed to characterize the microstructure, elemental distribution and phase composition of the CaP coatings. Simulated body fluid (SBF) immersion test was used to evaluate the coating bioactivity and degradability. Systemic toxicity test was used to evaluate the coating biocompatibility. Fluoride ion selective electrode (ISE) was used to measure F(-) ions concentration during 30 days SBF immersion. The CaP coatings effectively reduced the corrosion rate and the surfaces of CaP coatings were covered by a new layer formed of numerous needle-like and scale-like apatites. The formation of these calcium phosphate apatites indicates that the coatings have excellent bioactivity. The coatings formed in (NaPO3)6-containging electrolyte exhibit thicker thickness, higher adhesive strength, slower degradation rate, better apatite-inducing ability and biocompatibility. Copyright © 2013 Elsevier B.V. All rights reserved.

Improving bioactivity of inert bioceramics by a novel Mg-incorporated solution treatment

NASA Astrophysics Data System (ADS)

Dehestani, Mahdi; Zemlyanov, Dmitry; Adolfsson, Erik; Stanciu, Lia A.

2017-12-01

Zirconia/alumina ceramics possess outstanding mechanical properties for dental and orthopedic applications, but due to their poor surface bioactivities they exhibit a weak bone-bonding ability. This work proposes an effective 30-min solution treatment which could successfully induce formation of bone-like apatite on the surface of 3Y-TZP and a ternary composite composed of yttria-stabilized zirconia, ceria-stabilized zirconia, and alumina (35 vol% 3Y-TZP + 35 vol% 12Ce-TZP + 30 vol% Al2O3) after 3 weeks immersion in simulated body fluid (SBF). XRD was used for phase identification in the ceramic materials. The influence of solution treatment on the surface chemistry and its role on apatite formation were investigated via SEM, EDS and XPS. In vitro apatite-forming ability for the solution-treated and untreated samples of the composite and individual substrates of 3Y-TZP, 12Ce-TZP, and Al2O3 was evaluated by immersion in SBF. Apatite crystals were formed only on 3Y-TZP and composite substrates, implying that it is mainly the 3Y-TZP constituent that contributes to the bioactivity of the composite. Further, it was found from the XPS analysis that the zirconia material with higher phase stability (12Ce-TZP) produced less Zrsbnd OH functional groups on its surface after solution treatment which accounts for its weaker bioactivity compared to 3Y-TZP.

Raman spectral, elemental, crystallinity, and oxygen-isotope variations in conodont apatite during diagenesis

NASA Astrophysics Data System (ADS)

Zhang, Lei; Cao, Ling; Zhao, Laishi; Algeo, Thomas J.; Chen, Zhong-Qiang; Li, Zhihong; Lv, Zhengyi; Wang, Xiangdong

2017-08-01

Conodont apatite has long been used in paleoenvironmental studies, often with minimal evaluation of the influence of diagenesis on measured elemental and isotopic signals. In this study, we evaluate diagenetic influences on conodonts using an integrated set of analytical techniques. A total of 92 points in 19 coniform conodonts from Ordovician marine units of South China were analyzed by micro-laser Raman spectroscopy (M-LRS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), high-resolution X-ray microdiffraction (HXRD), and secondary ion mass spectrometry (SIMS). Each conodont element was analyzed along its full length, including the albid crown, hyaline crown, and basal body, in either a whole specimen (i.e., reflecting the composition of its outer layer) or a split specimen (i.e., reflecting the composition of its interior). In the conodonts of this study, the outer surfaces consist of hydroxyfluorapatite and the interiors of strontian hydroxyfluorapatite. Ionic substitutions resulted in characteristic Raman spectral shifts in the position (SS1) and width (SS2) of the ν1-PO43- stretching band. Although multiple elements were enriched (Sr2+, Mg2+) and depleted (Fe3+, Mn2+, Ca2+) during diagenesis, geochemical modeling constraints and known Raman spectral patterns suggest that Sr uptake was the dominant influence on diagenetic redshifts of SS1. All study specimens show lower SS2 values than modern bioapatite and synthetic apatite, suggesting that band width decreases with time in ancient bioapatite, possibly through an annealing process that produces larger, more uniform crystal domains. Most specimens consist mainly of amorphous or poorly crystalline apatite, which is inferred to represent the original microstructure of conodonts. In a subset of specimens, some tissues (especially albid crown) exhibit an increased degree of crystallinity developed through aggrading neomorphism. However, no systematic relationship was observed between crystallinity and Raman spectral or elemental parameters. Oxygen isotopes show substantial variation within the conodont study specimens. Albid crown is on average 0.28-0.32‰ more depleted in 18O (equivalent to 1.2-1.4 °C higher temperatures) than hyaline crown and basal body, and the interiors of conodont elements are 1.08 ± 0.37‰ more depleted in 18O (equivalent to 3.0-6.4 °C higher temperatures) relative to their outer layers. Although albid crown is widely regarded as better preserved than other conodont tissue types, its 18O-depleted composition and greater development of secondary crystallinity suggest that, in fact, it may be the most strongly altered tissue type. We conclude that Raman spectral, LA elemental, and HXRD microstructural data can provide useful information about the extent of diagenetic alteration of conodont elements, and that such information should be taken into consideration in using conodont elemental and oxygen-isotope data in paleoenvironmental studies.

Geochemical contrasts between Late Triassic ore-bearing and barren intrusions in the Weibao Cu-Pb-Zn deposit, East Kunlun Mountains, NW China: constraints from accessory minerals (zircon and apatite)

NASA Astrophysics Data System (ADS)

Zhong, Shihua; Feng, Chengyou; Seltmann, Reimar; Li, Daxin; Dai, Zhihui

2017-12-01

The Weibao copper-lead-zinc skarn deposit is located in the northern East Kunlun terrane, NW China. Igneous intrusions in this deposit consist of barren diorite porphyry (U-Pb zircon age of 232.0 ± 2.0 Ma) and ore-bearing quartz diorite and pyroxene diorite (U-Pb zircon ages of 223.3 ± 1.5 and 224.6 ± 2.9 Ma, respectively). Whole-rock major and trace element and accessory mineral (zircon and apatite) composition from these intrusions are studied to examine the different geochemical characteristics of ore-bearing and barren intrusions. Compared to the barren diorite porphyry, the ore-bearing intrusions have higher Ce4+/Ce3+ ratios of zircon and lower Mn contents of apatite, indicating higher oxidation state. Besides, apatite from the ore-bearing intrusions shows higher Cl contents and lower F/Cl ratios. These characteristics collectively suggest the higher productivity of ore-bearing quartz diorite and pyroxene diorite. When compared with ore-bearing intrusions from global porphyry Cu deposits, those from Cu-Pb-Zn skarn deposits display lower Ce4+/Ce3+ and EuN/EuN* ratios of zircon and lower Cl and higher F/Cl ratios of apatite. We conclude that these differences reflect a general geochemical feature, and that zircon and apatite composition is a sensitive tool to infer economic potential of magmas and the resulting mineralization types in intrusion-related exploration targets.

Magnetite-apatite-dolomitic rocks of Ust-Chulman (Aldan shield, Russia): Seligdar-type carbonatites?

NASA Astrophysics Data System (ADS)

Prokopyev, Ilya R.; Doroshkevich, Anna G.; Redina, Anna A.; Obukhov, Andrey V.

2018-04-01

The Ust-Chulman apatite ore body is situated within the Nimnyrskaya apatite zone at the Aldan shield in Russia. The latest data confirm the carbonatitic origin of the Seligdar apatite deposit (Prokopyev et al. in Ore Geol Rev 81:296-308, 2017). The results of our investigations demonstrate that the magnetite-apatite-dolomitic rocks of the Ust-Chulman are highly similar to Seligdar-type dolomitic carbonatites in terms of the mineralogy and the fluid regime of formation. The ilmenite and spinel mineral phases occur as solid solutions with magnetite, and support the magmatic origin of the Ust-Chulman ores. The chemical composition of REE- and SO3-bearing apatite crystals and, specifically, monazite-(Ce) mineralisation and the formation of Nb-rutile, late hydrothermal sulphate minerals (barite, anhydrite) and haematite are typical for carbonatite complexes. The fluid inclusions study revealed similarities to the evolutionary trend of the Seligdar carbonatites that included changes of the hydrothermal solutions from highly concentrated chloride to medium-low concentrated chloride-sulphate and oxidized carbonate-ferrous.

Bioactivity and electrochemical behavior of hydroxyapatite-silicon-multi walled carbon nano-tubes composite coatings synthesized by EPD on NiTi alloys in simulated body fluid.

PubMed

Khalili, V; Khalil-Allafi, J; Frenzel, J; Eggeler, G

2017-02-01

In order to improve the surface bioactivity of NiTi bone implant and corrosion resistance, hydroxyapatite coating with addition of 20wt% silicon, 1wt% multi walled carbon nano-tubes and both of them were deposited on a NiTi substrate using a cathodic electrophoretic method. The apatite formation ability was estimated using immersion test in the simulated body fluid for 10days. The SEM images of the surface of coatings after immersion in simulated body fluid show that the presence of silicon in the hydroxyapatite coatings accelerates in vitro growth of apatite layer on the coatings. The Open-circuit potential and electrochemical impedance spectroscopy were measured to evaluate the electrochemical behavior of the coatings in the simulated body fluid at 37°C. The results indicate that the compact structure of hydroxyapatite-20wt% silicon and hydroxyapatite-20wt% silicon-1wt% multi walled carbon nano-tubes coatings could efficiently increase the corrosion resistance of NiTi substrate. Copyright © 2016 Elsevier B.V. All rights reserved.

Phosphorus K-edge XANES spectroscopy of mineral standards

PubMed Central

Ingall, Ellery D.; Brandes, Jay A.; Diaz, Julia M.; de Jonge, Martin D.; Paterson, David; McNulty, Ian; Elliott, W. Crawford; Northrup, Paul

2011-01-01

Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy was performed on phosphate mineral specimens including (a) twelve specimens from the apatite group covering a range of compositional variation and crystallinity; (b) six non-apatite calcium-rich phosphate minerals; (c) 15 aluminium-rich phosphate minerals; (d) ten phosphate minerals rich in either reduced iron or manganese; (e) four phosphate minerals rich in either oxidized iron or manganese; (f) eight phosphate minerals rich in either magnesium, copper, lead, zinc or rare-earth elements; and (g) four uranium phosphate minerals. The identity of all minerals examined in this study was independently confirmed using X-ray powder diffraction. Minerals were distinguished using XANES spectra with a combination of pre-edge features, edge position, peak shapes and post-edge features. Shared spectral features were observed in minerals with compositions dominated by the same specific cation. Analyses of apatite-group minerals indicate that XANES spectral patterns are not strongly affected by variations in composition and crystallinity typical of natural mineral specimens. PMID:21335905

Ion implantation modified stainless steel as a substrate for hydroxyapatite deposition. Part II. Biomimetic layer growth and characterization.

PubMed

Pramatarova, L; Pecheva, E; Krastev, V

2007-03-01

The interest in stainless steel as a material widely used in medicine and dentistry has stimulated extensive studies on improving its bone-bonding properties. AISI 316 stainless steel is modified by a sequential ion implantation of Ca and P ions (the basic ions of hydroxyapatite), and by Ca and P implantation and subsequent thermal treatment in air (600( composite function)C, 1 h). This paper investigates the ability of the as-modified surfaces to induce hydroxyapatite deposition by using a biomimetic approach, i.e. immersion in a supersaturated aqueous solution resembling the human blood plasma (the so-called simulated body fluid). We describe our experimental procedure and results, and discuss the physico-chemical properties of the deposed hydroxyapatite on the modified stainless steel surfaces. It is shown that the implantation of a selected combination of ions followed by the applied methodology of the sample soaking in the simulated body fluid yield the growth of hydroxyapatite layers with composition and structure resembling those of the bone apatite. The grown layers are found suitable for studying the process of mineral formation in nature (biomineralization).

Rare-earth-element minerals in martian breccia meteorites NWA 7034 and 7533: Implications for fluid-rock interaction in the martian crust

NASA Astrophysics Data System (ADS)

Liu, Yang; Ma, Chi; Beckett, John R.; Chen, Yang; Guan, Yunbin

2016-10-01

Paired martian breccia meteorites, Northwest Africa (NWA) 7034 and 7533, are the first martian rocks found to contain rare-earth-element (REE) phosphates and silicates. The most common occurrence is as clusters of anhedral monazite-(Ce) inclusions in apatite. Occasionally, zoned, irregular merrillite inclusions are also present in apatite. Monazite-bearing apatite is sometimes associated with alkali-feldspar and Fe-oxide. Apatite near merrillite and monazite generally contains more F and OH (F-rich region) than the main chlorapatite host and forms irregular boundaries with the main host. Locally, the composition of F-rich regions can reach pure fluorapatite. The chlorapatite hosts are similar in composition to isolated apatite without monazite inclusions, and to euhedral apatite in lithic clasts. The U-Th-total Pb ages of monazite in three apatite are 1.0 ± 0.4Ga (2σ), 1.1 ± 0.5Ga (2σ), and 2.8 ± 0.7Ga (2σ), confirming a martian origin. The texture and composition of monazite inclusions are mostly consistent with their formation by the dissolution of apatite and/or merrillite by fluid at elevated temperatures (>100 °C). In NWA 7034, we observed a monazite-chevkinite-perrierite-bearing benmoreite or trachyandesite clast. Anhedral monazite and chevkinite-perrierite grains occur in a matrix of sub-micrometer REE-phases and silicates inside the clast. Monazite-(Ce) and -(Nd) and chevkinite-perrierite-(Ce) and -(Nd) display unusual La and Ce depletion relative to Sm and Nd. In addition, one xenotime-(Y)-bearing pyrite-ilmenite-zircon clast with small amounts of feldspar and augite occurs in NWA 7034. One xenotime crystal was observed at the edge of an altered zircon grain, and a cluster of xenotime crystals resides in a mixture of alteration materials. Pyrite, ilmenite, and zircon in this clast are all highly altered, zircon being the most likely source of Y and HREE now present in xenotime. The association of xenotime with zircon, low U and Th contents, and the low Yb content relative to Gd and Dy in xenotime suggest the possible formation of xenotime as a byproduct of fluid-zircon reactions. On the basis of relatively fresh apatite grains and lithic clasts in the same samples, we propose that the fluid-rock/mineral reactions occurred in the source rocks before their inclusion in NWA 7034 and 7533. Additionally, monazite-bearing apatite and REE-mineral-bearing clasts are possibly derived from different crustal origins. Thus, our results imply the wide-occurrence of hydrothermal fluids in the martian crust at 1 Ga or older, which were probably induced by impacts or large igneous intrusions.

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.

Peculiar Feldspar And Quartz Inclusions Within Zircons From Anorthosites, North Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

Eliwa, H. A.; Dawoud, M. I.; Khalaf, I. M.; Negendank, J. F.; Itaya, T.

2004-12-01

Zircons from three anorthosite outcrops along Wadi Dib area, north Eastern Desert of Egypt contain abundant and conspicuous inclusions of quartz, feldspar, amphibole and apatite. These anorthosites, as (50-100m thick) layers, represent the top of mafic-ultramafic intrusions exhibiting rhythmic layering visible by reputation of melanocratic and leucocratic layers. Field and microscopic studies exhibit that these anorthosites were affected by the action of residual magmatic solutions associated with the late stage crystallization of the younger granites, which modified their mineralogical composition. They are composed totally of plagioclase with subordinate amount of clinoenstatite, augite, amphibole, biotite, K-feldspar, and quartz. Accessories are magnetite, ilmenite, apatite and zircon. The abundance and the mode of occurrence of K-feldspar, quartz, and biotite with apatite and zircon among the megacrysts suggest their formation is ascribed to the interaction with the residual solutions. The microprobe data exhibit difference between feldspar and amphiboles contained herein zircons and those as anorthosite mineral constituents. The genetic relationship between zircons and their inclusions suggests later growth of zircons than inclusions and most probably at the final stage of rock modification. Zircons are magmatic and found in the interstitial feldspar and quartz among plagioclase megacrysts in aggregates or as individual grains. The microscopic and SEM images investigation exhibit that most zircons are subhedral to euhedral equant and prismatic crystals. Most zircons have same range of crystal morphologies and internal growth structures with predominance of prism /{100/} and pyramid /{101/} and occasionally prism /{110/} and pyramid /{111/}. No evidences for poly-faceted grains, inherited cores or later overgrowths were detected. CL images distinguished zircons with visible core-rim structures and others with regular and continuous growth zones contained herein various inclusions. The dark CL cores in the core-rim structured zircons are higher in U, Y and sometimes Hf relative to the CL bright rims. Microprobe data and x-ray chemical mapping of various zoned zircons suggest that U and Y with sometimes Hf have a negative correlation to the CL brightness, while Th doesn't exhibit any significant correlation.

Comparison of an experimental bone cement with surgical Simplex P, Spineplex and Cortoss.

PubMed

Boyd, D; Towler, M R; Wren, A; Clarkin, O M

2008-04-01

Conventional polymethylmethacrylate (PMMA) cements and more recently Bisphenol-a-glycidyl dimethacrylate (BIS-GMA) composite cements are employed in procedures such as vertebroplasty. Unfortunately, such materials have inherent drawbacks including, a high curing exotherm, the incorporation of toxic components in their formulations, and critically, exhibit a modulus mismatch between cement and bone. The literature suggests that aluminium free, zinc based glass polyalkenoate cements (Zn-GPC) may be suitable alternative materials for consideration in such applications as vertebroplasty. This paper, examines one formulation of Zn-GPC and compares its strengths, modulus, and biocompatibility with three commercially available bone cements, Spineplex, Simplex P and Cortoss. The setting times indicate that the current formulation of Zn-GPC sets in a time unsuitable for clinical deployment. However during setting, the peak exotherm was recorded to be 33 degrees C, the lowest of all cements examined, and well below the threshold level for tissue necrosis to occur. The data obtained from mechanical testing shows the Zn-GPC has strengths of 63 MPa in compression and 30 MPa in biaxial flexure. Importantly these strengths remain stable with maturation; similar long term stability was exhibited by both Spineplex and Simplex P. Conversely, the strengths of Cortoss were observed to rapidly diminish with time, a cause for clinical concern. In addition to strengths, the modulus of each material was determined. Only the Zn-GPC exhibited a modulus similar to vertebral trabecular bone, with all commercial materials exhibiting excessively high moduli. Such data indicates that the use of Zn-GPC may reduce adjacent fractures. The final investigation used the well established simulated body fluid (SBF) method to examine the ability of each material to bond with bone. The results indicate that the Zn-GPC is capable of producing a bone like apatite layer at its surface within 24 h which increased in coverage and density up to 7 days. Conversely, Spineplex, and Simplex P exhibit no apatite layer formation, while Cortoss exhibits only minimal formation of an apatite layer after 7 days incubation in SBF. This paper shows that Zn-GPC, with optimised setting times, are suitable candidate materials for further development as bone cements.

The improved biological response of shark tooth bioapatites in a comparative in vitro study with synthetic and bovine bone grafts.

PubMed

López-Álvarez, M; Pérez-Davila, S; Rodríguez-Valencia, C; González, P; Serra, J

2016-06-07

Autologous bone is considered to be the gold standard for bone tissue regeneration, providing more highly efficient functional responses compared to synthetic materials, and avoiding the rejection risks of allogenic grafts. However, it presents limitations for certain types of surgery due to its high resorption levels and donor site morbidity. Different biphasic synthetic composites, based onnon-apatitic calcium phosphates enriched with apatitic phases-such as hydroxyapatite, and bioderived bone grafts of bovine and porcine origin-are proposed as lower resorption materials due to their higher crystalline structure. The present work proposes two new sources of bioapatites for bone filler applications obtained from the dentine and enameloid of shark teeth, respectively. These bioapatites each present a characteristic apatite-based composition and additional enrichments of specific trace elements, such as magnesium and fluorine, with proven roles in bone metabolism. Their processing and physicochemical characterization (SEM, FT-Raman and XRD) is presented, together with an in vitro evaluation of osteogenic activity compared to a commercial bovine mineralized matrix and synthetic HA/β TCP grafts. The results proved the globular morphology (0.5-1.5 μm) and porosity (~50 μm and ~0.5-1 μm) of shark dentine bioapatites with biphasic composition: apatitic (hydroxyapatite and apatite-(CaF)), non-apatitic (whitlockite), and an apatitic phase (fluorapatite), organized in oriented crystals in enameloid bioapatites. An evaluation of the pre-osteoblast MC3T3-E1 morphology revealed the colonization of pores in dentine bioapatites and an aligned cell growth in the oriented enameloid crystals. A higher proliferation (p  <  0.01) was detected at up to 21 d in both the shark bioapatites and synthetic biphasic graft with respect to the bovine mineralized matrix. Finally, the great potential of porous biphasic dentine bioapatites enriched with Mg and the aligned fluorapatite crystals of enameloid bioapatites in promoting greater osteogenic activity was confirmed with a significantly increased ALP synthesis (p  <  0.01) compared to the commercial grafts.

Tectono-magmatic evolution of the Chihuahua-Sinaloa border region in northern Mexico: Insights from zircon-apatite U-Pb geochronology, zircon Hf isotope composition and geochemistry of granodiorite intrusions

NASA Astrophysics Data System (ADS)

Mahar, Munazzam Ali; Goodell, Philip C.; Feinstein, Michael Nicholas

2016-11-01

We present the whole-rock geochemistry, LA-ICP-MS zircon-apatite U-Pb ages and zircon Hf isotope composition of the granodioritic plutons at the southwestern boundary of Chihuahua with the states of Sinaloa and Sonora. These granodiorites are exposed in the north and south of the Rio El Fuerte in southwest Chihuahua and northern Sinaloa. The magmatism spans over a time period of 37 Ma from 90 to 53 Ma. Zircons are exclusively magmatic with strong oscillatory zoning. No inheritance of any age has been observed. Our new U-Pb dating ( 250 analyses) does not support the involvement of older basement lithologies in the generation of the granitic magmas. The U-Pb apatite ages from granodiorites in southwest Chihuahua vary from 52 to 70 Ma. These apatite ages are 1 to 20 Ma younger than the corresponding zircon U-Pb crystallization ages, suggesting variable cooling rates from very fast to 15 °C/Ma ( 800 °C to 500 °C) and shallow to moderate emplacement depths. In contrast, U-Pb apatite ages from the Sinaloa batholith are restricted from 64 to 61 Ma and are indistinguishable from the zircon U-Pb ages range from 67 to 60 Ma within the error, indicating rapid cooling and very shallow emplacement. However, one sample from El Realito showed a larger difference of 20 Ma in zircon-apatite age pair: zircon 80 ± 0.8 Ma and apatite 60.6 ± 4 Ma, suggesting a slower cooling rate of 15 °C/Ma. The weighted mean initial εHf (t) isotope composition (2σ) of granodiorites varies from + 1.8 to + 5.2. The radiogenic Hf isotope composition coupled with previous Sr-Nd isotope data demonstrates a significant shift from multiple crustal sources in the Sonoran batholithic belt to the predominant contribution of the mantle-derived magmas in the southwest Chihuahua and northern Sinaloa. Based on U-Pb ages, the absence of inheritance, typical high Th/U ratio and radiogenic Hf isotope composition, we suggest that the Late Cretaceous-Paleogene magmatic rocks in this region are not derived from melting of a felsic older crust, neither evolved North American Proterozoic basement nor Jurassic metasedimentary rocks of the Guerrero terrane. Instead, the magma was primarily derived from partial melting of mantle related sources, possibly in the subcontinental mantle wedge above the Farallon plate. Our younger U-Pb zircon-apatite ages are well correlated with the late-stage cogenetic porphyry Cu-Au mineralization at 57 to 59 Ma. If the origin of ore mineralization is related to the magma sources of host batholiths, then a minimal input from crustal melt is suggested in the genesis of Cu-Au porphyry system.

In vivo bioactivity of titanium and fluorinated apatite coatings for orthopaedic implants: a vibrational study

NASA Astrophysics Data System (ADS)

Taddei, Paola; Tinti, Anna; Reggiani, Matteo; Monti, Patrizia; Fagnano, Concezio

2003-06-01

The bone integration of implants is a complex process which depends on chemical composition and surface morphology. To accelerate osteointegration, metal implants are coated with porous metal or apatites which have been reported to increase mineralisation, improving prosthesis fixation. To study the influence of composition and morphology on the in vivo bioactivity, titanium screws coated by Plasma Flame Spraying (PFS) with titanium or fluorinated apatite (K690) were implanted in sheep tibia and femur for 10 weeks and studied by micro-Raman and IR spectroscopy. The same techniques, together with thermogravimetry, were used for characterising the pre-coating K690 powder. Contrary to the manufacturer report, the K690 pre-coating revealed to be composed of a partially fluorinated apatite containing impurities of Ca(OH) 2 and CaCO 3. By effect of PFS, the impurities were decomposed and the crystallinity degree of the coating was found to decrease. The vibrational spectra recorded on the implanted screws revealed the presence of newly formed bone; for the K690-coated screws at least, a high level of osteointegration was evidenced.

Apatite Mineral Chemistry From IOA Deposits in Northern Chile

NASA Astrophysics Data System (ADS)

Palma, G.; Barra, F.; Reich, M.; Valencia, V.; Simon, A. C.; Vervoort, J. D.

2017-12-01

The Carmen, Fresia and Mariela iron-oxide apatite (IOA) deposits of Cretaceous age, located in the Coastal Cordillera of northern Chile, comprise massive bodies of magnetite with minor apatite and actinolite crystals spatially related to diorite intrusions. In order to provide new insights on the origin of Andean IOA deposits, we provide geochemical data of apatite grains collected from these three deposits. All studied apatite grains are zoned with respect to Cl and F, and show a decoupled behaviour between fluorapatite and chlorapatite. Carmen apatite grains are mostly F-rich, whereas in Mariela apatite grains are Cl-rich. Fresia apatite grains show a variable composition between fluorapatite and chlorapatite. Carmen apatite grains show a high REE content reaching up to 7000 ppm, and both Fresia and Mariela have lower REE content (<1400 ppm). REE patterns for all analyzed apatite grains show the typical LREE enrichment relative to the HREE and pronounced negative Eu anomaly, which indicates crystallization of plagioclase in the source magmas [1]. Chlorapatite zones are characterized by high S, Na, Sr and Fe content relative to fluorapatite zones. Notably S and Na show a coupled behaviour with Cl. Conversely LREE are depleted in chlorapatite zones, which is compatible with metasomatism through dissolution-reprecipitation mechanism and formation of monazite inclusions [2]. These results indicate a magmatic origin for fluorapatite in these Andean IOA deposits followed by variable degrees of hydrothermal overprint which resulted in the formation of Cl-rich apatites.[1] Frietsch & Perdahl (1995) Ore Geology Rev. 9 489-510. [2]Harlov et al. (2005) Contrib Mineral Petrol 150: 268-286

Stability and cellular responses to fluorapatite-collagen composites.

PubMed

Yoon, Byung-Ho; Kim, Hae-Won; Lee, Su-Hee; Bae, Chang-Jun; Koh, Young-Hag; Kong, Young-Min; Kim, Hyoun-Ee

2005-06-01

Fluorapatite (FA)-collagen composites were synthesized via a biomimetic coprecipitation method in order to improve the structural stability and cellular responses. Different amounts of ammonium fluoride (NH4F), acting as a fluorine source for FA, were added to the precipitation of the composites. The precipitated composites were freeze-dried and isostatically pressed in a dense body. The added fluorine was incorporated nearly fully into the apatite structure (fluoridation), and a near stoichiometric FA-collagen composite was obtained with complete fluoridation. The freeze-dried composites had a typical biomimetic network, consisting of collagen fibers and precipitates of nano-sized apatite crystals. The human osteoblast-like cells on the FA-collagen composites exhibited significantly higher proliferation and differentiation (according to alkaline phosphatase activity) than those on the hydroxyapatite-collagen composite. These enhanced osteoblastic cell responses were attributed to the fluorine release and the reduced dissolution rate.

The effects of injectable calcium silicate-based composites with the Chinese herb on an osteogenic accelerator in vitro.

PubMed

Chang, Nai-Jen; Chen, Yi-Wen; Shieh, Den-En; Fang, Hsin-Yuan; Shie, Ming-You

2015-09-11

We aimed to investigate the physicochemical and biological effects of calcium silicate (CS)-based cements together with the Chinese medicine Xu Duan (XD) after seeding with human adipose-derived stem cells (hADSCs). Here, we fabricated CS-based substrates with different ratios of XD (0%, 5% and 10%) as bioactive and biodegradable biocomposites, subsequent to examining their respective effectiveness for bone repair. The setting time, the injectability, the mechanical properties measured by diametral tensile strength (DTS), the in vitro degradation determined by changes in the weight loss of the composites, the characteristic formation of bone-like apatite, and cell growth as well as osteogenesis protein and bone mineralization were comprehensively evaluated before and after immersion in simulated body fluid (SBF), respectively. At the end of testing, with regard to physicochemical effects, the CS-based substrate mixed with the 10% XD group showed significantly sound mechanical properties, an applicable setting time and injectability and the formation of a dense bone-like apatite layer. In terms of biological effects, the CS-based substrate with the 10% XD group showed a significant development of osteogenic activities with sound cell proliferation and higher alkaline phosphatase (ALP) activity, as well as indicating osteogenic differentiation, greater osteocalcin (OC) protein secretion and clearly calcified tissue mineralization. The present drug-release strategy with CS-based cements may pave the way for future alternative bone repair therapy.

Improving the bioactivity of bioglass/ (PMMA-co-MPMA) organic/inorganic hybrid.

PubMed

Ravarian, R; Wei, H; Dehghani, F

2011-01-01

Binary system of CaO-SiO(2) glasses enables the apatite formation in simulated body fluid (SBF). However, the presence of phosphate content in SiO(2)-CaO-P(2)O(5) glasses leads to the formation of orthophosphate nanocrystalline nuclei, which facilitates the generation of carbonate hydroxyapatite; this compound is more compatible with natural bone. The brittle and less flexible properties of bioactive glasses are the major obstacle for their application as bone implant. The hybridization of essential constituents of bioactive glasses and glass-ceramics with polymers such as PMMA can improve their poor mechanical properties. The aim of this study was to improve the bioactivity of nanocomposites fabricated from poly(methyl metacrylate) (PMMA) and bioglass for bone implant applications. Bioglass compounds with various phosphate contents were used for the preparation of PMMA/bioglass hybrid matrices. Since the lack of adhesion between the two phases impedes the homogenous composite formation, a silane coupling agent such as 3-(trimethoxysilyl)propyl methacrylates (MPMA) was incorporated into the polymer structure. The effect of addition of MPMA on the molecular structure of composite was investigated. Furthermore, the presence of MPMA in the system improved the homogeneity of sample. Increasing phosphate content in the inorganic segment of hybrid up to 10 mol% resulted in the formation of apatite layer on the surface; hence the hybrid was bioactive and suitable candidate for bone tissue engineering.

HA/nylon 6,6 porous scaffolds fabricated by salt-leaching/solvent casting technique: effect of nano-sized filler content on scaffold properties

PubMed Central

Mehrabanian, Mehran; Nasr-Esfahani, Mojtaba

2011-01-01

Nanohydroxyapatite (n-HA)/nylon 6,6 composite scaffolds were produced by means of the salt-leaching/solvent casting technique. NaCl with a distinct range size was used with the aim of optimizing the pore network. Composite powders with different n-HA contents (40%, 60%) for scaffold fabrication were synthesized and tested. The composite scaffolds thus obtained were characterized for their microstructure, mechanical stability and strength, and bioactivity. The microstructure of the composite scaffolds possessed a well-developed interconnected porosity with approximate optimal pore size ranging from 200 to 500 μm, ideal for bone regeneration and vascularization. The mechanical properties of the composite scaffolds were evaluated by compressive strength and modulus tests, and the results confirmed their similarity to cortical bone. To characterize bioactivity, the composite scaffolds were immersed in simulated body fluid for different lengths of time and results monitored by scanning electron microscopy and energy dispersive X-ray microanalysis to determine formation of an apatite layer on the scaffold surface. PMID:21904455

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

2017-07-01

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 CaCl 2 ·2H 2 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. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1973-1983, 2017. © 2017 Wiley Periodicals, Inc.

Influence of substrate material and surface finishing on the morphology of the calcium-phosphate coating.

PubMed

Leitão, E; Barbosa, M A; de Groot, K

1997-07-01

The formation of an apatite-like layer was achieved by immersing Ti-6A1-4V, Ti-Al-2.5Fe, and 316 L stainless-steel substrata in Hank's balanced salt solution (HBSS). The layer was characterized by surface analysis techniques, namely X-ray microanalysis and X-ray diffraction, and the morphology was observed by scanning electron microscopy and atomic force microscopy. The concentrations of Ca and P were monitored as a function of time. The morphology of the precipitate layer seems to be dependent both on the type of metal substrate and its surface finish. Polished Ti-6A1-4V and Ti-Al-2.5Fe surfaces exhibit a plate precipitate morphology, whereas rougher surfaces show scattered crystal-like precipitation. The results suggest that the layer produced by immersion of polished titanium alloys in HBSS is constituted by an amorphous apatite.

Deposition of nanostructured fluorine-doped hydroxyapatite-polycaprolactone duplex coating to enhance the mechanical properties and corrosion resistance of Mg alloy for biomedical applications.

PubMed

Bakhsheshi-Rad, H R; Hamzah, E; Kasiri-Asgarani, M; Jabbarzare, S; Iqbal, N; Abdul Kadir, M R

2016-03-01

The present study addressed the synthesis of a bi-layered nanostructured fluorine-doped hydroxyapatite (nFHA)/polycaprolactone (PCL) coating on Mg-2Zn-3Ce alloy via a combination of electrodeposition (ED) and dip-coating methods. The nFHA/PCL composite coating is composed of a thick (70-80 μm) and porous layer of PCL that uniformly covered the thin nFHA film (8-10 μm) with nanoneedle-like microstructure and crystallite size of around 70-90 nm. Electrochemical measurements showed that the nFHA/PCL composite coating presented a high corrosion resistance (R(p)=2.9×10(3) kΩ cm(2)) and provided sufficient protection for a Mg substrate against galvanic corrosion. The mechanical integrity of the nFHA/PCL composite coatings immersed in SBF for 10 days showed higher compressive strength (34% higher) compared with the uncoated samples, indicating that composite coatings can delay the loss of compressive strength of the Mg alloy. The nFHA/PCL coating indicted better bonding strength (6.9 MPa) compared to PCL coating (2.2 MPa). Immersion tests showed that nFHA/PCL composite-coated alloy experienced much milder corrosion attack and more nucleation sites for apatite compared with the PCL coated and uncoated samples. The bi-layered nFHA/PCL coating can be a good alternative method for the control of corrosion degradation of biodegradable Mg alloy for implant applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Bioactive glass-coated silicone for percutaneous devices with improved tissue interaction

NASA Astrophysics Data System (ADS)

Marotta, James Scott

The discovery of bioactive glasses, in the early 1970s, has produced a material that develops a strong adherent bond with soft tissue. Many medical applications currently use silicone as an implant material, but are hindered by the formation of fibrous scar tissue surrounding the device. This fibrous scar tissue can lead to pain, infection, and/or extrusion of these devices. Bioactive ceramic materials are inherently brittle and can not be used in applications where a flexible material is needed. Therefore, the coating of existing flexible silicone medical devices, like catheters, with a bioactive glass material would give the advantages of both. The research presented here is of methods used to coat silicone with a bioactive glass powder (Bioglass°ler) and the in vitro testing of those coatings. The bioactivity of these coatings was measured using scanning electron microscopy, inductively coupled plasma spectroscopy, and Fourier transform infrared spectroscopy. It was observed that hydroxyapatite, a bonelike apatite, was formed in vitro on both the bioactive glass particles and the silicone surface between these particles. From these results a new theory was developed that related the distance between particles on a surface with the formation of an apatite layer. A critical distance between particles for the formation of an apatite layer on the substrate exists. This critical distance is a function of both the particle size and composition. In addition, a method to coat silicone catheters with bioactive glass powder is also discussed. This coated catheter could ultimately be used for improved percutaneous access in peritoneal dialysis. The one barrier to greater peritoneal dialysis use and the reason many patients switch from peritoneal to hemodialysis is recurrent exit-site infections and subsequent peritonitis. These infections are caused by the lack of a tight seal and downgrowth of epidermal tissue around the catheter at the catheter-skin interface.

Influence of cell culture medium composition on in vitro dissolution behavior of a fluoride-containing bioactive glass.

PubMed

Shah, Furqan A; Brauer, Delia S; Wilson, Rory M; Hill, Robert G; Hing, Karin A

2014-03-01

Bioactive glasses are used clinically for bone regeneration, and their bioactivity and cell compatibility are often characterized in vitro, using physiologically relevant test solutions. The aim of this study was to show the influence of varying medium characteristics (pH, composition, presence of proteins) on glass dissolution and apatite formation. The dissolution behavior of a fluoride-containing bioactive glass (BG) was investigated over a period of one week in Eagle's Minimal Essential Medium with Earle's Salts (MEM), supplemented with either, (a) acetate buffer, (b) 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer, (c) HEPES + carbonate, or (d) HEPES + carbonate + fetal bovine serum. Results show pronounced differences in pH, ion release, and apatite formation over 1 week: Despite its acidic pH (pH 5.8 after BG immersion, as compared to pH 7.4-8.3 for HEPES-containing media), apatite formation was fastest in acetate buffered (HEPES-free) MEM. Presence of carbonate resulted in formation of calcite (calcium carbonate). Presence of serum proteins, on the other hand, delayed apatite formation significantly. These results confirm that the composition and properties of a tissue culture medium are important factors during in vitro experiments and need to be taken into consideration when interpreting results from dissolution or cell culture studies. Copyright © 2013 Wiley Periodicals, Inc.

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.

Helium diffusion in apatite assessed by ERDA and implications for (U-Th)/He dating

NASA Astrophysics Data System (ADS)

Stuebner, K.; Jonckheere, R.; Ratschbacher, L.

2006-12-01

The strength of a low-temperature geochronometer, like (U-Th)/He(apatite), lies in the low activation energy of He-diffusion, which makes the system sensitive to temperatures <100°C. A thorough understanding of the diffusion kinetics of He in apatite is crucial for the interpretation of (U-Th)/He ages. Diffusion parameters derived from high temperature step heating experiments and reported in the literature span a broad range: E_a=30-40 kcal/mol (1σ-error ~2 kcal/mol); ln(D0/a2)=8-26 s^-^1 or ln(D0)=8- 130 cm2/s and with the standard experimental setup it is not possible to determine the grain size independent parameter D0. We employ a new approach using Elastic Recoil Detection Analysis (ERDA) to characterise He diffusion at low temperatures. ERDA allows to measure element-concentration profiles across the upper 2 μm of 1x1cm plane surface samples. Implantation of high-dose (5E+15 ions cm2), low- energy Helium ions (50-250 keV) in polished thin sections of a large Durango apatite crystal produces narrow, near-Gaussian distribution of Helium at a depth <1 μm beneath the crystal surface. Diffusion results in normally distributed concentration-profiles across the initial layer. The He-profile is approximated by a Gaussian curve with variance σ2 = 2 D t = D0 exp(-E_a/RT) t. Dt increases exponentially with T and linearly with t, so that knowledge of the t-T conditions of a set of samples allows to calculate the diffusion parameters from the fitted Gauss-distributions. With this approach Helium diffusion is observed on a sub-μm scale, which allows not only a precise determination of E_a and D0, but also circumvents assumptions that are necessary for the step-heating approach (spherical diffusion geometry, dimension of the diffusion domain) and is independent of grain size or shape. It facilitates investigation of the dependence of diffusion on the crystallographic direction, on the anion composition (OH, F, Cl) of apatite and on the degree of radiogenic lattice damage.

Development of Solid State Laser Materials for Application in Lasers for Atmospheric Ozone and Water Vapor Sensing

NASA Technical Reports Server (NTRS)

Noginov, Makhail A.; Loutts, G. B.

2002-01-01

We have grown neodymium doped mixed apatite crystals, (Sr(x)Ba(l-x)5(PO4)3F, Sr5(P(1-x)V(x)O4)3F, and Ba5(P(1-x)V(x)O4)3F, and spectroscopically studied them as potential gain media for a laser source for atmospheric water sensing operating at 944.11 nm0. We conclude that an appropriate apatite host material for a 944.11 nm laser should be a mixture of Sr5(PO4)3F with a small fraction of Ba5(PO4)3F. The precise wavelength tuning around 944.11 nm can be accomplished by varying the host composition, temperature, and threshold population inversion. In apatite crystals of mixed composition, the Amplified Spontaneous Emission (ASE) loss at 1.06 microns is predicted to be significantly smaller than that in the end members.

Quantitative Mineralogical Composition of Calculi and Urine Abnormalities for Calcium Oxalate Stone Formers: A Single-Center Results.

PubMed

Kustov, Andrey V; Strelnikov, Alexander I

2018-05-03

The paper focuses on the relationship of risk factors and metabolic disorders with mineralogical composition of calculi, age and gender of calcium oxalate stone formers. Stone mineralogical composition, 24 hour biochemistry and pH-profile of urine were examined for sixty four stone formers using powder X-ray diffraction, spectrophotometric and potentiometric techniques. The analysis indicated that 44 % of calculi were composed of pure calcium oxalate monohydrate, whereas other 56 % contained both monohydrate and dihydrate or usually their mixtures with hydroxyl apatite. Hypocitraturia, hypercalciuria and hyperuricosuria were identified as the most frequent disorders. Patients with pure calcium oxalate stones and calcium oxalate mixed with apatite revealed different patterns including age, acid-base balance of urine, calcium, citrate excretion etc.Conclusions: Our results demonstrate that most patients simultaneously reveal several risk factors. The special attention should be paid to normalize the daily citrate, calcium and urate excretion. High risk patients, such as postmenopausal females or stone formers with a high apatite content require a specific metabolic evaluation towards in highlighting abnormalities associated with stone formation.

A double Fe-Ti oxide and Fe-sulphide liquid immiscibility in the Itsindro Gabbro Complex, Madagascar

NASA Astrophysics Data System (ADS)

Augé, Thierry; Bailly, Laurent; Roig, Jean-Yves

2017-11-01

The petrology and mineralogy of the Itsindro complex in south-central Madagascar has been investigated through samples obtained from the 320.7 m-deep Lanjanina borehole. The section consists of a 254 m-thick pyroxenite unit with interbedded gabbro layers that overlies a gabbro unit and is itself overlain by a 19 m-thick granite unit. Most of the structures are sub-horizontal. A weak magmatic layering is locally observed but at the scale of the core, the intrusion does not appear to be a layered complex. Pyroxenite and gabbro show a systematic disseminated mineralization consisting of Fe-Ti-P oxides and Fe-(Cu-Ni) sulphides that takes the form of ilmenite-titanomagnetite ± apatite and pyrrhotite ± chalcopyrite ± pentlandite. In the upper zone, from 90 to 72 m, sub-massive centimetre-to decimetre-sized layers of oxides and sulphides comprise a total of 16 m of sub-massive sulphide (the main mineralized zone). In this mineralized zone the oxide/sulphide ratio is close to 1/1. The sulphide is strongly dominated by pyrrhotite, which may locally contain inclusions of molybdenite crystals with the Re sulphide rheniite (ReS2). Oxides are generally euhedral, included in or attached to the Fe-sulphide, and also locally form sub-massive centimetre-sized bands. Apatite as a cumulus phase is ubiquitous. Locally it may account for 30% of the ore-rich samples and some samples consist of apatite-Fe-Ti oxides-Fe-Cu-Ni sulphides with virtually no silicate. Apatite is the main REE carrier but the total REE content remains low (<90 ppm). Mineral compositions and whole rock geochemistry indicate that the rocks are highly differentiated, and in spite of a relatively limited thickness, the differentiation process is observed. Two zones can be distinguished: from the bottom to 162.8 m we see a decrease in the Mg number of olivine and pyroxene, and a drop in TiO2 and Al2O3 for the latter. A reverse trend is then observed within the pyroxenite unit from the 162.8 m level upwards. The main mineralized zone is located in the upper part of this unit, about 70 m above this discontinuity. The highly differentiated Fe-Ti-P facies of the Lanjanina series in the Itsindro Gabbro Complex have been interpreted as corresponding to the Fe-Ti-P rich, Si-poor member remaining after an immiscible segregation of an evolved mafic magma. The granite dykes and the overlying granite unit represent the second, Si-rich member of the immiscibility process. The presence of large amounts of sulphide is attributed to sulphur contamination of the Fe-Ti-rich liquid. Fe-Ti oxides will tend to crystallize on the sulphide droplets and the accumulation of dense Fe-sulphides (liquid) and associated Fe-Ti oxides (solid) will result in this complex and unusual association taking the form of a net texture.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Trace element and isotopic composition of apatite in carbonatites from the Blue River area (British Columbia, Canada) and mineralogy of associated silicate rocks

NASA Astrophysics Data System (ADS)

Mitchell, Roger; Chudy, Thomas; McFarlane, Christopher R. M.; Wu, Fu-Yuan

2017-08-01

Apatites from the Verity, Fir, Gum, Howard Creek and Felix carbonatites of the Blue River (British Columbia, Canada) area have been investigated with respect to their paragenesis, cathodoluminescence, trace element and Sr-Nd isotopic composition. Although all of the Blue River carbonatites were emplaced as sills prior to amphibolite grade metamorphism and have undergone deformation, in many instances magmatic textures and mineralogy are retained. Attempts to constrain the U-Pb age of the carbonatites by SIMS, TIMS and LA-ICP-MS studies of zircon and titanite were inconclusive as all samples investigated have experienced significant Pb loss during metamorphism. The carbonatites are associated with undersaturated calcite-titanite amphibole nepheline syenite only at Howard Creek although most contain clasts of disaggregated phoscorite-like rocks. Apatite from each intrusion is characterized by distinct, but wide ranges, in trace element composition. The Sr and Nd isotopic compositions define an array on a 87Sr/86Sr vs²Nd diagram at 350 Ma indicating derivation from depleted sub-lithospheric mantle. This array could reflect mixing of Sr and Nd derived from HIMU and EM1 mantle sources, and implies that depleted mantle underlies the Canadian Cordillera. Although individual occurrences of carbonatites in the Blue River region are mineralogically and geochemically similar they are not identical and thus cannot be considered as rocks formed from a single batch of parental magma at the same stage of magmatic evolution. However, a common origin is highly probable. The variations in the trace element content and isotopic composition of apatite from each occurrence suggest that each carbonatite represents a combination of derivation of the parental magma(s) from mineralogically and isotopically heterogeneous depleted mantle sources coupled with different stages of limited differentiation and mixing of these magmas. We do not consider these carbonatites as primary direct partial melts of the sub-lithospheric mantle which have ascended from the asthenosphere without modification of their composition.

Sub-µm structure and volatile distribution of shocked lunar apatite

NASA Astrophysics Data System (ADS)

Cernok, A.; White, L. F.; Darling, J.; Dunlop, J.; Fougerouse, D.; William, R. D. A.; Reddy, S.; Saxey, D. W.; Zhao, X.; Franchi, I.; Anand, M.

2017-12-01

Apatite is a key mineral broadly used for studying volatiles in planetary materials. Most studies in this recent frontier of planetary exploration focus on volatile content and respective isotopic composition in apatite. However, there is an imperative to contextualize geochemical data with impact-induced features, given that most planetary materials experienced at least some shock deformation. This study aims at understanding the effect of high-level shock deformation on volatile distribution in apatite from lunar highlands samples. Combining Electron Backscatter Diffraction (EBSD), NanoSIMS and Atom Probe Microscopy (APM) analyses we are gaining an insight into the µm- and nm-scale structural variation in apatite from a shocked, maskelynite- and impact-melt-bearing norite. EBSD revealed degraded crystallinity, high density of low angle grain boundaries and domains of sub-µm granular features that appear amorphous at this length scales ( 80 x 40 nm). Texture component maps show up to 25° misorientation within a single grain - evidence of severe crystal-plastic deformation, but with no obvious evidence of recrystallization. APM revealed complex microstructure of the apparently amorphous domains defined by well developed, straight to slightly curved grain boundaries meeting at 120° triple junctions. This equilibrium texture is probably accommodated by annealing and recrystallization of apatite due to the post-shock heating. Crystallites range in size from 50 to 100 nm. Grain boundaries are defined by segregation of Mg, Si and Fe impurities, which possibly originate from surrounding phases. Cl and F show homogenous distribution over the length scale of the APM analysis (1 to 500 nm). H2O content measurements of 250-600 ppm by NanoSIMS are consistent with the lower range of previously reported values for this rock, with no obvious correlation with the level of crystallinity. δD values are confirmed to be terrestrial-like and relatively constant. These preliminary data suggest that impact event(s) either did not disturb the volatile distribution and composition of homogenous magmatic apatite, or that it induced diffusion and homogenisation of primary volatile species during annealing. Apatites in a range of variably shocked lunar samples are currently being examined to further clarify this question.

Solid oxide fuel cells with apatite-type lanthanum silicate-based electrolyte films deposited by radio frequency magnetron sputtering

NASA Astrophysics Data System (ADS)

Liu, Yi-Xin; Wang, Sea-Fue; Hsu, Yung-Fu; Wang, Chi-Hua

2018-03-01

In this study, solid oxide fuel cells (SOFCs) containing high-quality apatite-type magnesium doped lanthanum silicate-based electrolyte films (LSMO) deposited by RF magnetron sputtering are successfully fabricated. The LSMO film deposited at an Ar:O2 ratio of 6:4 on an anode supported NiO/Sm0.2Ce0·8O2-δ (SDC) substrate followed by post-annealing at 1000 °C reveals a uniform and dense c-axis oriented polycrystalline structure, which is well adhered to the anode substrate. A composite SDC/La0·6Sr0·4Co0·2Fe0·8O3-δ cathode layer is subsequently screen-printed on the LSMO deposited anode substrate and fired. The SOFC fabricated with the LSMO film exhibits good mechanical integrity. The single cell with the LSMO layer of ≈2.8 μm thickness reports a total cell resistance of 1.156 and 0.163 Ωcm2, open circuit voltage of 1.051 and 0.982 V, and maximum power densities of 0.212 and 1.490 Wcm-2 at measurement temperatures of 700 and 850 °C, respectively, which are comparable or superior to those of previously reported SOFCs with yttria stabilized zirconia electrolyte films. The results of the present study demonstrate the feasibility of deposition of high-quality LSMO films by RF magnetron sputtering on NiO-SDC anode substrates for the fabrication of SOFCs with good cell performance.

In situ differentiation and evolution of potassic syenites from Svidnya, Bulgaria

NASA Astrophysics Data System (ADS)

Dyulgerov, Momchil; Platevoet, Bernard

2013-12-01

Potassic syenites from Svidnya, Bulgaria crop out as small isolated bodies as the primary for this intrusion liquid has basic to intermediate composition. The evolution in a closed magma chamber created plutonic rocks ranging from basic (melasyenite) to acid (granite) and from metaluminous to peralkaline. The most mafic varieties show cumulative textures typical for orthocumulates with cumulus phases clinopyroxene, biotite, apatite and potassium feldspar as gravitational settling is a viable process for separation of particles in the bottom parts of magma chamber. In the middle stratigraphic level of biggest body modal igneous layering with development of dark (clinopyroxene + amphibole) and light (potassium feldspar) laminas was observed. Oscillatory crystallization around eutectic point resulted in cyclic separation of mafic and felsic phases in repetitive layers. Fractionation of Ca- and Al-rich phases—clinopyroxene, biotie and potassium feldspar created peralkaline residual liquid strongly enriched in HFS elements.

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.

Sulfur concentration and isotopic variation in apatites from granitic to granodioritic plutons of a Cretaceous Cordilleran Batholith

NASA Astrophysics Data System (ADS)

Economos, R. C.

2012-12-01

Apatite is a common igneous accessory mineral with a high saturation temperature which can therefore crystallize over a significant portion of magmatic compositional space. Sulfur presents an opportunity to identify zoning in apatites. Unlike other trace elements, sulfur is relatively immobile in the apatite crystal structure and can be present in typical concentrations up to 1500 - 2000 ppm (or 0.5 to 1 wt% SO3). Sulfur concentration zoning in igneous apatites from ore producing magmatic systems has been identified (Streck and Dilles, 1998), but the interpretation of the cause of this zoning remains an open question. δ34S isotopic ratios of whole apatites have been used to track isotopic evolution associated with changes in magma fO2 and eruptive degassing (Rye, 2005). The presented work combines sulfur concentration mapping in zoned apatite crystals with in-situ SIMS 34S and 32S isotope measurements. Apatites were extracted from granite to granodiorite samples from the Cadiz Valley Batholith in the central Mojave Desert. This batholith is related to the pulse of Cretaceous Cordilleran magmatism that generated large batholiths in the Sierra Nevada and the Penninsular Ranges. The Mojave segment of the Cretaceous arc is unique in their construction into a full thickness of continental crust which exerted a strong influence on magmatic compositions. Apatite grains were mounted parallel to C axes, ground until grains were approximately bisected, and analyzed by Electron Microprobe at UCLA, for CaO, P2O5, SO3 and SiO2. Grains were surveyed and those yielding anomalous SO3 contents were investigated by micron-scale concentration mapping. Typical SO3 concentrations of apatites from all samples were ~0.2 wt%, while 8 to 10% of apatite grains from two samples contained cores with concentrations ranging up to 0.5 wt%. The sulfur zoning in these samples is oscillatory, in some grains representing 5 to 6 repetitions of high and low concentrations. Based on these textures, our initial interpretation is that this zoning is magmatic. Ratios of 32S to 34S in these grains were analyzed by Secondary Ionization Mass Spectrometry at UCLA in multi-collector mode utilizing a Cs+ primary ion beam and two electron multiplier ion counters. Although absolute δ34S values cannot be calculated without further standard, samples were analyzed relative to demonstrably isotopically homogeneous fragments of Durango apatite. Zoned apatite cores displayed δ34S variation well outside of analytical uncertainty. Analytical errors on individual isotopic measurements were ± 1.5‰ and reproducibility on standard grains through the analytical session was ± 0.5‰. Grains mounted parallel and perpendicular to the C axis displayed no discernible isotopic fractionation. Cores with high S concentrations displayed isotopic enrichment in 34S up to 11‰ relative to rims and core-free grains. Concentration variations may track trajectories of S solubility in evolving magmas (Ducea et al., 1994). Meanwhile heavier S isotopic ratios may suggest either dynamic crystallization/resorption behavior of S bearing species or an oxidizing environment for these earliest crystallizing apatites.

Electrophoretic co-deposition of PEEK-hydroxyapatite composite coatings for biomedical applications.

PubMed

Baştan, Fatih E; Atiq Ur Rehman, Muhammad; Avcu, Yasemin Yıldıran; Avcu, Egemen; Üstel, Fatih; Boccaccini, Aldo R

2018-05-03

This study focuses on the optimization of electrophoretic deposition (EPD) and suspension parameters for producing PEEK-hydroxyapatite (HA) coatings with feasible microstructure, adhesion strength, and in-vitro bioactivity. Nanostructured hydroxyapatite (HA) micro-granules were incorporated with PEEK to form PEEK-hydroxyapatite composite coatings via EPD. After EPD, a heat-treatment at 375 °C was applied for densification of the coatings and for enhancing the adhesion between the coatings and the substrates. It was found that both adhesion strength and in-vitro bioactivity of the coatings were dependent on the PEEK and HA relative contents. Thus, increasing the amount of HA improved the bioactivity while decreased the adhesion strength of the coatings. Apatite-like layer formation was observed on coatings with high HA content after incubation for three days in simulated body fluid (SBF). Finally, a deposition mechanism was proposed for the EPD of the PEEK-hydroxyapatite composite system. Copyright © 2018 Elsevier B.V. All rights reserved.

Hydroxyapatite-phosphonoformic acid hybrid compounds prepared by hydrothermal method

NASA Astrophysics Data System (ADS)

Turki, Thouraya; Othmani, Masseoud; Bantignies, Jean-Louis; Bouzouita, Khaled

2014-01-01

Hydroxyapatites were prepared in the presence of different amounts of phosphonoformic acid (PFA) via the hydrothermal method. The obtained powders were characterized through chemical analysis, XRD, IR, 31P MAS-NMR, TEM, and TG-TDA. The XRD showed that the PFA did not affect the apatite composition. Indeed, only a reduction of the crystallite size was noted. After grafting of PFA, the IR spectroscopy revealed the appearance of new bands belonging to HPO42- and carboxylate groups of the apatite and organic moiety, respectively. Moreover, the 31P MAS-NMR spectra exhibited a peak with a low intensity assigned to the terminal phosphonate group of the organic moiety in addition to that of the apatite. Based on these results, a reaction mechanism involving the surface hydroxyl groups (tbnd Casbnd OH) of the apatite and the carboxyl group of the acid was proposed.

Calcium phosphate composite cements based on simple mixture of brushite and apatite phases

NASA Astrophysics Data System (ADS)

Egorov, A. A.; Fedotov, A. Yu; Pereloma, I. S.; Teterina, A. Yu; Sergeeva, N. S.; Sviridova, I. K.; Kirsanova, V. A.; Akhmedova, S. A.; Nesterova, A. V.; Reshetov, I. V.; Barinov, S. M.; Komlev, V. S.

2018-04-01

The composite cements based on simple mixtures brishite and apatite with ratio 70/30, 50/50, 30/70 were developed. The processes of phase formation, microstructure and mechanical properties were studied. The kinetics of degradation in simulated body fluid depending on the microstructure and the materials phase composition was carried out. The biological test in vitro were performed using the MTT-test on the human fibroblast immortalized (hFB) cell line and the human osteosarcoma cell line MG-63. The materials didn’t have acute cytoxicity and possessed surface matrix properties. It was determined that the both line of cells actively proliferated, with viable cells values higher 20-60 % then control at all observation periods.

3D diffusion model within the collagen apatite porosity: An insight to the nanostructure of human trabecular bone

PubMed Central

Bini, Fabiano; Pica, Andrada; Marinozzi, Andrea; Marinozzi, Franco

2017-01-01

Bone tissue at nanoscale is a composite mainly made of apatite crystals, collagen molecules and water. This work is aimed to study the diffusion within bone nanostructure through Monte-Carlo simulations. To this purpose, an idealized geometric model of the apatite-collagen structure was developed. Gaussian probability distribution functions were employed to design the orientation of the apatite crystals with respect to the axes (length L, width W and thickness T) of a plate-like trabecula. We performed numerical simulations considering the influence of the mineral arrangement on the effective diffusion coefficient of water. To represent the hindrance of the impermeable apatite crystals on the water diffusion process, the effective diffusion coefficient was scaled with the tortuosity, the constrictivity and the porosity factors of the structure. The diffusion phenomenon was investigated in the three main directions of the single trabecula and the introduction of apatite preferential orientation allowed the creation of an anisotropic medium. Thus, different diffusivities values were observed along the axes of the single trabecula. We found good agreement with previous experimental results computed by means of a genetic algorithm. PMID:29220377

In vitro apatite formation on nano-crystalline titania layer aligned parallel to Ti6Al4V alloy substrates with sub-millimeter gap.

PubMed

Hayakawa, Satoshi; Matsumoto, Yuko; Uetsuki, Keita; Shirosaki, Yuki; Osaka, Akiyoshi

2015-06-01

Pure titanium substrates were chemically oxidized with H2O2 and subsequent thermally oxidized at 400 °C in air to form anatase-type titania layer on their surface. The chemically and thermally oxidized titanium substrate (CHT) was aligned parallel to the counter specimen such as commercially pure titanium (cpTi), titanium alloy (Ti6Al4V) popularly used as implant materials or Al substrate with 0.3-mm gap. Then, they were soaked in Kokubo's simulated body fluid (SBF, pH 7.4, 36.5 °C) for 7 days. XRD and SEM analysis showed that the in vitro apatite-forming ability of the contact surface of the CHT specimen decreased in the order: cpTi > Ti6Al4V > Al. EDX and XPS surface analysis showed that aluminum species were present on the contact surface of the CHT specimen aligned parallel to the counter specimen such as Ti6Al4V and Al. This result indicated that Ti6Al4V or Al specimens released the aluminum species into the SBF under the spatial gap. The released aluminum species might be positively or negatively charged in the SBF and thus can interact with calcium or phosphate species as well as titania layer, causing the suppression of the primary heterogeneous nucleation and growth of apatite on the contact surface of the CHT specimen under the spatial gap. The diffusion and adsorption of aluminum species derived from the half-sized counter specimen under the spatial gap resulted in two dimensionally area-selective deposition of apatite particles on the contact surfaces of the CHT specimen.

Degradation processes of reinforced concretes by combined sulfate–phosphate attack

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

Secco, Michele, E-mail: michele.secco@unipd.it; Department of Civil, Environmental and Architectural Engineering; Lampronti, Giulio Isacco, E-mail: gil21@cam.ac.uk

2015-02-15

A novel form of alteration due to the interaction between hydrated cement phases and sulfate and phosphate-based pollutants is described, through the characterization of concrete samples from an industrial reinforced concrete building. Decalcification of the cement matrices was observed, with secondary sulfate and phosphate-based mineral formation, according to a marked mineralogical and textural zoning. Five alteration layers may be detected: the two outermost layers are characterized by the presence of gypsum–brushite solid solution phases associated with anhydrous calcium sulfates and phosphates, respectively, while a progressive increase in apatite and ammonium magnesium phosphates is observable in the three innermost layers, associatedmore » with specific apatite precursors (brushite, octacalcium phosphate and amorphous calcium phosphate, respectively). The heterogeneous microstructural development of secondary phases is related to the chemical, pH and thermal gradients in the attacked cementitious systems, caused by different sources of pollutants and the exposure to the sun's radiation.« less

Tracking hydrothermal alteration and mineralization in rock-forming and accessory minerals from the Lyon Mountain Granite and related iron oxide apatite (IOA) ores from the Adirondack Mountains, New York State

NASA Astrophysics Data System (ADS)

Buchanan, A.; Hanchar, J. M.; Steele-MacInnis, M. J.; Crowley, J. L.; Valley, P. M.; Fisher, C. M.; Fedo, C.; Piccoli, P. M.; Fournelle, J.

2012-12-01

The Lyon Mountain granite (LMG) is located in the northeastern Adirondack Mountains in New York State and hosts several low-titanium iron oxide apatite (IOA) ore deposits. The ores are predominately hosted by perthite bearing granite, which has been extensively altered to albite and microcline granite by Na and K metasomatism. This alteration results in several distinct groups of rocks that are dominated by either K or Na addition and a group composed of mixed Na and K addition. The different groups of altered perthite also lie on a trend suggestive of addition of Fe to each, consistent with a secondary mineralization origin. Previous work showed that the host rocks of the IOA ores have zircon with ~1150 Ma cores and 1060-1050 Ma rims and whole grains. This study aims to further constrain the timing of LMG emplacement, subsequent hydrothermal alteration, and Fe mineralization through geochemical analysis of the major, minor, and accessory phases and geochronology of accessory phases. SIMS analyses of zircon from several of the IOA ores reveal at least two periods of growth after LMG magmatism, at 1039 +/- 4.4 Ma and 1016 +/- 7 Ma to 1000 +/- 9 Ma. In situ EMPA and LA-ICPMS trace element analyses of the zircon rims and cores reveal that in two samples the zircon rims are enriched in rare earth elements (REE) compared to their cores, potentially pointing to a hydrothermal origin. Apatite has unusually high REE and Y concentrations (some total REE2O3 > 20 wt. % oxide and up to 8 wt. % oxide Y2O3), as does titanite, which allowed for the in situ analysis of Sm-Nd in apatite and titanite by LA-MC-ICP-MS. Initial Nd isotopic composition of both ore and host rock apatite and host rock titanite are consistent with published Adirondack initial Nd whole rock data, suggesting a local source for REE in these ores. EMPA and LA-ICPMS trace-element analyses of the major rock-forming minerals indicate that the feldspar have undergone Na-metasomatism and are depleted in REEs, perhaps signifying the "local source" and the mechanism of the REE enrichment in the LMG apatite in the IOA ores and host rocks. In contrast, the minor- and trace-element compositions of the other major rock-forming minerals (e.g., clinopyroxene and fayalite) as well as the zircon, and fluorite in the LMG have average igneous granitic trace- and minor-element compositions. To better understand the timing and origin of these post ~1050 Ma events, U-Pb ID-TIMS dating of apatite and titanite, and in situ LA-MC-ICPMS Sm-Nd analysis were done on the ore and host rock samples. Apatite dates range from 1050 to 850 Ma and titanite dates range from ~1015 to 970 Ma. There is significant age variation within samples and within grains. Titanite does not have sufficient spread for accurate Sm-Nd isochron dating and two ore-apatite samples have homogenous initial Nd isotopic and Sm-Nd elemental ratios, precluding calculation of Sm-Nd dates. A third ore sample shows a large spread in Sm-Nd and yields a Sm-Nd isochron date of ~850 Ma, in close agreement with U-Pb apatite dates. The Sm-Nd isochron and U-Pb apatite dates may reflect cooling recorded in these minerals or a younger hydrothermal mineralization event.

Correlative microscopy of the constituents of a dinosaur rib fossil and hosting mudstone: Implications on diagenesis and fossil preservation.

PubMed

Kim, Jung-Kyun; Kwon, Yong-Eun; Lee, Sang-Gil; Kim, Chang-Yeon; Kim, Jin-Gyu; Huh, Min; Lee, Eunji; Kim, Youn-Joong

2017-01-01

We have applied correlative microscopy to identify the key constituents of a dorsal rib fossil from Koreanosaurus boseongensis and its hosting mudstone discovered at the rich fossil site in Boseong, South Korea, to investigate the factors that likely contributed to diagenesis and the preservation of fossil bone. Calcite and illite were the commonly occurring phases in the rib bone, hosting mudstone, and the boundary region in-between. The boundary region may have contributed to bone preservation once it fully formed by acting as a protective shell. Fluorapatite crystals in the rib bone matrix signified diagenetic alteration of the original bioapatite crystals. While calcite predominantly occupied vascular channels and cracks, platy illite crystals widely occupied miniscule pores throughout the bone matrix. Thorough transmission electron microscopy (TEM) study of illite within the bone matrix indicated the solid-state transformation of 1M to 2M without composition change, which was more evident from the lateral variation of 1M to 2M within the same layer. The high level of lattice disordering of 2M illite suggested an early stage of 1M to 2M transformation. Thus, the diagenetic alteration of both apatite and illite crystals within the bone matrix may have increased its overall density, as the preferred orientation of apatite crystals from moderate to strong degrees was evident despite the poor preservation of osteohistological features. The combined effects of rapid burial, formation of a boundary region, and diagenesis of illite and apatite within the bone matrix may have contributed to the rib bone preservation.

Highly roughened polycaprolactone surfaces using oxygen plasma-etching and in vitro mineralization for bone tissue regeneration: fabrication, characterization, and cellular activities.

PubMed

Kim, YongBok; Kim, GeunHyung

2015-01-01

Herein, poly(ɛ-caprolactone) (PCL) surfaces were treated to form various roughness values (R(a)=290-445 nm) and polar functional groups on the surfaces using a plasma-etching process, followed by immersion into simulated body fluid (SBF) for apatite formation. The surface morphology, chemical composition, and mean roughness of the plasma-etched PCL surfaces were measured, and various physical and morphological properties (water contact angles, protein absorption ability, and crystallite size of the apatite layer) of the in vitro mineralized PCL surfaces were evaluated. The roughened PCL surface P-3, which was treated with a sufficient plasma exposure time (4 h), achieved homogeneously distributed apatite formation after soaking in SBF for 7 days, as compared with other surfaces that were untreated or plasma-treated for 30 min or 2 h. Furthermore, to demonstrate their feasibility as a biomimetic surface, pre-osteoblast cells (MC3T3-E1) were cultured on the mineralized PCL surfaces, and cell viability, DAPI-phalloidin fluorescence assay, and alizarin red-staining of the P-3 surface were highly improved compared to the P-1 surface treated with a 30-min plasma exposure time; compared to untreated mineralized PCL surface (N-P), P-3 showed even greater improvements in cell viability and DAPI-phalloidin fluorescence assay. Based on these results, we found that the mineralized PCL surface supplemented with the appropriate plasma treatment can be implicitly helpful to achieve rapid hard tissue regeneration. Copyright © 2014 Elsevier B.V. All rights reserved.

Low modulus and bioactive Ti/α-TCP/Ti-mesh composite prepared by spark plasma sintering.

PubMed

Guo, Yu; Tan, Yanni; Liu, Yong; Liu, Shifeng; Zhou, Rui; Tang, Hanchun

2017-11-01

A titanium mesh scaffold composite filled with Ti/α-TCP particles was prepared by spark plasma sintering (SPS). The microstructures and interfacial reactions of the composites were investigated by scanning electron microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and X-ray diffraction (XRD) analyses. The compressive strength and elastic modulus were also measured. In vitro bioactivity and biocompatibility was evaluated by using simulated body fluid and cells culture, respectively. After high temperature sintering, Ti oxides, Ti x P y and CaTiO 3 were formed. The formation of Ti oxides and Ti x P y were resulted from the diffusion of O and P elements from α-TCP to Ti. CaTiO 3 was the reaction product of Ti and α-TCP. The composite of 70Ti/α-TCP incorporated with Ti mesh showed a high compressive strength of 589MPa and a low compressive modulus of 30GPa. The bioactivity test showed the formation of a thick apatite layer on the composite and well-spread cells attachment. A good combination of mechanical properties and bioactivity indicated a high potential application of Ti/α-TCP/Ti-mesh composite for orthopedic implants. Copyright © 2017. Published by Elsevier B.V.

FTIR absorption reflection study of biomimetic growth of phosphates on titanium implants

NASA Astrophysics Data System (ADS)

Stoch, A.; Jastrzębski, W.; Brożek, A.; Stoch, J.; Szaraniec, J.; Trybalska, B.; Kmita, G.

2000-11-01

Titanium has been used for many medical applications; however, its joining to a living bone still is not satisfactorily good, challenging appropriate investigations. The aim of this work was to generate chemical modifications at its surface such that in vivo conditions, heterogeneous nucleation, and then growth of apatite from the body fluid could be easily induced and successfully performed. For this purpose, on the titanium samples, the oxide sublayers containing titanium, calcium and silicon (TCS) were deposited from a suitable solution using the sol-gel deep-coating procedure. Dried samples were heated at 400°C then cooled and thermostatically held in synthetic body fluids (SBF, SBFIII) under physiological conditions to mimic the natural process of apatite formation. Changes in surface composition of TCS sublayers caused by the heating were studied with XPS. Infrared spectroscopy and scanning electron microscopy monitored successive steps of apatite growth. It was found that in SBF, at the precoated titanium surface, nucleation and growth of the apatite containing carbonate took place. In SBFIII, for a higher concentration of calcium ions in comparison with SBF, a much-enhanced growth of the apatite free of carbonate was observed. TCS precoatings applied on stainless steel and Cr-Co-Mo alloy (Micromed) act also as bioactive interfaces with high ability to nucleation of biologically equivalent apatite. Biomimetic formation of this apatite on biologically inactive materials can be an important step in implant surgery.

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 demonstrate that in addition to grain chemistry, He diffusivity will be strongly influenced by damage and propose a new physical model. Finally, we propose a new way of interpreting AHe datasets and practical geological examples will be given. Flowers, R., Ketcham, R.A., Shuster, D., Farley, K.A., 2009. Apatite (U-Th)/He thermochronology using a radiation damage accumulation and annealing model. Geochimica et Cosmochimica Acta 73, 2347-2365. Gautheron, C., Tassan-got, L., Barbarand, J., Pagel, M., 2009. Effect of alpha-damage annealing on apatite (U-Th)/He thermochronology. Chemical Geology 266, 166-179. Gautheron, C., Barbarand, J., Ketcham R.A., Tassan-got, L., van der Beek, P., Pagel, M., Pinna-Jamme, R., Couffignal, F., Fialin, M., 2013. Chemical influence on α-recoil damage annealing in apatite: implications for (U-Th)/He dating. Chemical Geology 351, 257-267. Mbongo-Djimbi D., Gautheron C., Roques, J., Tassan-Got, L., Gerin, C., Simoni, E.. Apatite composition effect on (U-Th)/He thermochronometer: an atomistic point of view. In review at Geochimica Cosmochimica Acta.

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. Infrared spectra show a strong band of (CO3)2- for this apatite, which indicates a possible substitution of (CO3)2-(F)- for (PO4)3-. Other techniques to mitigate temporal variation of F and Cl, including alternative metal coatings, concurrent stage movement, and cryogenic sample-cooling were attempted, but did not eliminate the disparity in measured F concentrations between the two sample orientations. Thus, we believe that F measurements on F-rich apatite samples of unknown orientation are immediately suspect and should be regarded as upper limits of true F concentration. X-ray mapping, CL imaging and subsequent quantitative analyses show compositional variations in Na, S, Si, and REE in the Durango and Wilberforce fluorapatite samples used in this study. Problems of electron beam sensitivity, X-ray intensity anisotropy due to sample orientation, and compositional heterogeneity call into question their continued use as routine microanalysis reference materials. Microanalysts are encouraged to use more robust calibration standards, such as Cl-rich or other F-poor apatites for Ca, P, O and Cl, and MgF2 for F measurements. [1] Stormer, J.C., Pierson, M.L, and Tacker, R.C. (1993) Variation of F and Cl X-ray intensity due to anisotropic diffusion in apatite during electron microprobe analysis. Am. Min., 78, 641-648.

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.

Rational Selection of Tailored Amendment Mixtures and Composites for In Situ Remediation of Contaminated Sediments

DTIC Science & Technology

2008-12-01

Certification Program GAC granular activated carbon HGR sulfur impregnated activated carbon MCA Menzie Cura and Associates MRM Minimum Required...determination of iodine number was followed. The materials tested were granular activated carbon (GAC), alumina powder, ATS, apatite, bentonite, barite...materials tested were granular activated carbon (GAC), alumina powder, ATS, apatite, bentonite, barite, ConSep 20 and 42%, and ATC. The Iodine Number

Bioactivity evaluation of titanium/hydroxyapatite composite coating on stainless steel prepared by thermal spraying

NASA Astrophysics Data System (ADS)

Azhar, Nurul Humaira; Talari, Mahesh Kumar; Koong, Chue Keen

2015-08-01

In this study, titanium powder mixed with different wt % of HA was coated on stainless steel (SS) substrate using high velocity oxy-fuel (HVOF) technique to produce composite coating for biomedical applications. As the addition of HA is expected to influence the bioactivity of the coatings, these coatings were investigated for bioactivity by immersing the samples in a simulated body fluid (SBF) solution for 14 days. The apatite growth rate was evaluated by measuring Ca and P concentration in the SBF using Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES). The concentrations of Ca and P have decreased over time in the SBF, suggesting a bone like apatite precipitation on the sample surface. It was observed that pH value increased with the increase of immersion time during initial three days and a subsequent drop after 7 days. Microstructure analysis done using FESEM technique showed nucleation and growth of bone-like apatite on the surface of the coating.

[A study of bone-like apatite formation on calcium phosphate ceramics in different kinds of animals in vivo].

PubMed

Duan, Yourong; Wu, Yao; Wang, Chaoyuan; Chen, Jiyong; Zhang, Xingdong

2003-03-01

Bone-like apatite formation on the surface of calcium phosphate ceramics has been believed to be necessary for new bone to grow on the ceramics and to be related to the osteoinductivity of the material. The research of bone-like apatite formation is a great help to understanding the mechanism of osteoinduction. Synthetic porous calcium phosphate ceramics (HA/TCP = 70/30) were implanted intramuscularly in pigs, dogs, rabbits and rats to make a comparative study of the bone-like apatite formation onto the porous HA/TCP ceramics in different animals. Specimens were harvested at 14 days after implantation. Samples were detected for the surface morphology with SEM. The chemical composition of the sample surface after implantation was analyzed with reflection infrared (R-IR). Obvious bone-like apatite formation could be detected in the sections of porous specimens harvested from all animals after 14 days intramuscular implantation. Crystal deposition could be only observed on the surface of the concave regions of the samples collected from dogs, rabbits and rat. On the contrary, evenly distributed flake-shaped crystal could be found on the pore surface and also on the outer surface of the materials implanted in pigs. The morphology of bone-like apatite in pigs was different from that in the others animals. Bone-like apatite was not observed in dense specimen implanted intramuscularly. Bone-like apatite formed faster on specimens implanted in rabbit than that in other animals. This formation sequence is different from the sequence of osteoinductivity of biphasic calcium phosphate ceramics implanted in these animals. The results demonstrated that the formation of bone-like apatite on materials is a prerequisite condition to their osteoinduction but other factors also play important roles in osteoinduction.

Nanocellulose-collagen-apatite composite associated with osteogenic growth peptide for bone regeneration.

PubMed

Saska, Sybele; Teixeira, Lucas Novaes; de Castro Raucci, Larissa Moreira Spinola; Scarel-Caminaga, Raquel Mantuaneli; Franchi, Leonardo Pereira; Dos Santos, Raquel Alves; Santagneli, Silvia Helena; Capela, Marisa Veiga; de Oliveira, Paulo Tambasco; Takahashi, Catarina Satie; Gaspar, Ana Maria Minarelli; Messaddeq, Younès; Ribeiro, Sidney José Lima; Marchetto, Reinaldo

2017-10-01

Despite advances in the field of biomaterials for bone repair/regeneration, some challenges for developing an ideal bone substitute need to be overcome. Herein, this study synthesized and evaluated in vitro a nanocomposite based on bacterial cellulose (BC), collagen (COL), apatite (Ap) and osteogenic growth peptide (OGP) or its C-terminal pentapeptide [OGP(10-14)] for bone regeneration purposes. The BC-COL nanocomposites were successfully obtained by carbodiimide-mediated coupling as demonstrated by spectroscopy analysis. SEM, FTIR and 31 P NMR analyses revealed that in situ synthesis to apatite was an effective route for obtaining of bone-like apatite. The OGP-containing (BC-COL)-Ap stimulated the early development of the osteoblastic phenotype. Additionally, the association among collagen, apatite, and OGP peptides enhanced cell growth compared with OGP-containing BC-Ap. Furthermore, none of the nanocomposites showed cytotoxic, genotoxic or mutagenic effects. These promising results suggest that the (BC-COL)-Ap associated with OGP peptides might be considered a potential candidate for bone tissue engineering applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of TiO2 addition on surface microstructure and bioactivity of fluorapatite coatings deposited using Nd:YAG laser.

PubMed

Chien, Chi-Sheng; Ko, Yu-Sheng; Kuo, Tsung-Yuan; Liao, Tze-Yuan; Lee, Tzer-Min; Hong, Ting-Fu

2014-04-01

To study the effect of titania (TiO2) addition on the surface microstructure and bioactivity of fluorapatite coatings, fluorapatite was mixed with TiO2 in 1:0.5 (FA + 0.5TiO2), 1:0.8 (FA + 0.8TiO2), and 1:1 (FA + TiO2) ratios (wt%) and clad on Ti-6Al-4V substrates using an Nd:YAG laser system. The experimental results show that the penetration depth of the weld decreases with increasing TiO2 content. Moreover, the subgrain structure of the coating layer changes from a fine cellular-like structure to a cellular-dendrite-like structure as the amount of TiO2 increases. Consequently, as the proportion of TiO2 decreases (increase in fluorapatite content), the Ca/P ratio of the coating layer also decreases. The immersion of specimens into simulated body fluid resulted in the formation of individual apatite. With a lower Ca/P ratio before immersion, the growth of the apatite was faster and then the coating layer provided a better bioactivity. X-ray diffraction analysis results show that prior to simulated body fluid immersion, the coating layer in all three specimens was composed mainly of fluorapatite, CaTiO3, and Al2O3 phases. Following simulated body fluid immersion, a peak corresponding to hydroxycarbonated apatite appeared after 2 days in the FA + 0.5TiO2 and FA + 0.8TiO2 specimens and after 7 days in the FA + TiO2 specimen. Overall, the results show that although the bioactivity of the coating layer tended to decrease with increasing TiO2 content, in accordance with the above-mentioned ratios, the bioactivity of all three specimens remained generally good.

Radiation-induced amorphization of Ce-doped Mg2Y8(SiO4)6O2 silicate apatite

NASA Astrophysics Data System (ADS)

Zhou, Jianren; Yao, Tiankai; Lian, Jie; Shen, Yiqiang; Dong, Zhili; Lu, Fengyuan

2016-07-01

Ce-doped Mg2Y8(SiO4)6O2 silicate apatite (Ce = 0.05 and 0.5) were irradiated with 1 MeV Kr2+ ion beam irradiation at different temperatures and their radiation response and the cation composition dependence of the radiation-induced amorphization were studied by in situ TEM. The two Ce-doped Mg2Y8(SiO4)6O2 silicate apatites are sensitive to ion beam induced amorphization with a low critical dose (0.096 dpa) at room temperature, and exhibits significantly different radiation tolerance at elevated temperatures. Ce concentration at the apatite AI site plays a critical role in determining the radiation response of this silicate apatite, in which the Ce3+ rich Mg2Y7.5Ce0.5(SiO4)6O2 displays lower amorphization susceptibility than Mg2Y7.95Ce0.05(SiO4)6O2 with a lower Ce3+ occupancy at the AI sites. The critical temperature (Tc) and activation energy (Ea) change from 667.5 ± 33 K and 0.162 eV of Mg2Y7.5Ce0.5(SiO4)6O2 to 963.6 ± 64 K and 0.206 eV of Mg2Y7.95Ce0.05(SiO4)6O2. We demonstrate that the radiation tolerance can be controlled by varying the chemical composition, and enhanced radiation tolerance is achieved by increasing the Ce concentration at the AI site.

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.;

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. Copyright © 2015 Elsevier B.V. All rights reserved.

Zircon (Hf, O isotopes) as melt indicator: Melt infiltration and abundant new zircon growth within melt rich layers of granulite-facies lenses versus solid-state recrystallization in hosting amphibolite-facies gneisses (central Erzgebirge, Bohemian Massif)

NASA Astrophysics Data System (ADS)

Tichomirowa, Marion; Whitehouse, Martin; Gerdes, Axel; Schulz, Bernhard

2018-03-01

In the central Erzgebirge within the Bohemian Massif, lenses of high pressure and ultrahigh pressure felsic granulites occur within meta-sedimentary and meta-igneous amphibolite-facies felsic rocks. In the felsic granulite, melt rich parts and restite form alternating layers, and were identified by petrology and bulk rock geochemistry. Mineral assemblages representing the peak P-T conditions were best preserved in melanocratic restite layers. In contrast, in the melt rich leucocratic layers, garnet and related HP minerals as kyanite are almost completely resorbed. Both layers display differences in accessory minerals: melanosomes have frequent and large monazite and Fe-Ti-minerals but lack xenotime and apatite; leucosomes have abundant apatite and xenotime while monazite is rare. Here we present a detailed petrographic study of zircon grains (abundance, size, morphology, inclusions) in granulite-facies and amphibolite-facies felsic gneisses, along with their oxygen and hafnium isotope compositions. Our data complement earlier Usbnd Pb ages and trace element data (REE, Y, Hf, U) on zircons from the same rocks (Tichomirowa et al., 2005). Our results show that the degree of melting determines the behaviour of zircon in different layers of the granulites and associated amphibolite-facies rocks. In restite layers of the granulite lenses, small, inherited, and resorbed zircon grains are preserved and new zircon formation is very limited. In contrast, new zircons abundantly grew in the melt rich leucocratic layers. In these layers, the new zircons (Usbnd Pb age, trace elements, Hf, O isotopes) best preserve the information on peak metamorphic conditions due to intense corrosion of other metamorphic minerals. The new zircons often contain inherited cores. Compared to cores, the new zircons and rims show similar or slightly lower Hf isotope values, slightly higher Hf model ages, and decreased oxygen isotope ratios. The isotope compositions (Hf, O) of new zircons indicate partial Hf isotope homogenization in the melt, and melt infiltration from an external source. New zircon was most likely formed by a peritectic reaction with melt above the wet solidus (peritectic zircon). Conversely, the amphibolite-facies host gneisses lack indications of significant melt production. Pre-metamorphic zircons experienced mainly solid-state recrystallization and variable Pb loss with only minor new zircon formation. However, subtle changes in cathodoluminescence pattern, in the Hf and O isotopes, and in the Lu/Hf, Yb/Hf ratios of zircons suggest that small volumes of melt were locally present. In difference to granulites, melt was internally produced. The detection of low degree melts (inferred from zircon geochemistry) is extremely important for the rheology because these amphibolite-facies rocks could act as large scale ductile shear zones. The new zircon data support a different P-T path for closely spaced amphibolite- and granulite-facies rocks.

Polycrystalline apatite synthesized by hydrothermal replacement of calcium carbonates

NASA Astrophysics Data System (ADS)

Kasioptas, Argyrios; Geisler, Thorsten; Perdikouri, Christina; Trepmann, Claudia; Gussone, Nikolaus; Putnis, Andrew

2011-06-01

Aragonite and calcite single crystals can be readily transformed into polycrystalline hydroxyapatite pseudomorphs by hydrothermal treatment in a (NH 4) 2HPO 4 solution. Scanning electron microscopy of the reaction products showed that the transformation of aragonite to apatite is characterised by the formation of a sharp interface between the two phases and by the development of intracrystalline porosity in the hydroxyapatite phase. In addition, electron backscattered diffraction (EBSD) imaging showed that the c-axis of apatite is predominantly oriented perpendicular to the reaction front with no crystallographic relationship to the aragonite lattice. However, the Ca isotopic composition of the parent aragonite, measured by thermal ionization mass spectrometry was inherited by the apatite product. Hydrothermal experiments conducted with use of phosphate solutions prepared with water enriched in 18O (97%) further revealed that the 18O from the solution is incorporated in the product apatite, as measured by micro-Raman spectroscopy. Monitoring the distribution of 18O with Raman spectroscopy was possible because the incorporation of 18O in the PO 4 group of apatite generates four new Raman bands at 945.8, 932, 919.7 and 908.8 cm -1, in addition to the ν1(PO 4) symmetric stretching band of apatite located at 962 cm -1, which can be assigned to four 18O-bearing PO 4 species. The relative intensities of these bands reflect the 18O content in the PO 4 group of the apatite product. By using equilibrated and non-equilibrated solutions, with respect to the 18O distribution between aqueous phosphate and water, we could show that the concentration of 18O in the apatite product is linked to the degree of 18O equilibration in the solution. The textural and chemical observations are indicative of a coupled mechanism of aragonite dissolution and apatite precipitation taking place at a moving reaction interface.

Electrophoretic deposition of double-layer HA/Al composite coating on NiTi.

PubMed

Karimi, Esmaeil; Khalil-Allafi, Jafar; Khalili, Vida

2016-01-01

In order to improve the bioactivity of NiTi alloys, which are being known as the suitable materials for biomedical applications, numerous NiTi disks were electrophoretically coated by hetero-coagulated hydroxyapatite/aluminum composite coatings in three main voltages from suspensions with different Al concentrations. In this paper, the amount of Ni ions release and bioactivity of prepared samples as well as bonding strength of the coating to substrate were investigated. The surface characterization of the coating by XRD, EDX, SEM, and FTIR showed that HA particles bonded by Al particles. It caused the formation of a free crack coating on NiTi disks. Moreover, the bonding strength of HA/Al coatings to NiTi substrate were improved by two times as compared to that of the pure HA coatings. Immersing of coated samples in SBF for 1 week showed that apatite formation ability was improved on HA/Al composite coating and Ni ions release from the surface of composite coating decreased. These results induce the appropriate bioactivity and biocompatibility of the deposited HA/Al composite coatings on NiTi disks. Copyright © 2015 Elsevier B.V. All rights reserved.

The oxidation state of sulfur in apatite: A new oxybarometer?

NASA Astrophysics Data System (ADS)

Fiege, A.; Konecke, B.; Kim, Y.; Simon, A. C.; Becker, U.; Parat, F.

2016-12-01

Oxygen fugacity (fO2) of magmatic and hydrothermal systems influences, for instance, crystallization and degassing processes as well as metal solubilities in melts and fluids. Apatite is a ubiquitous mineral in magmatic and hydrothermal environments that can record and preserve volatile zonation. It can contain several thousand μg/g of the redox sensitive element sulfur (S), making S-in-apatite a potential fO2 sensor. Despite the polyvalent properties of S (e.g., S2-, S4+, S6+), the oxidation state and incorporation mechanisms of S in the apatite structure are poorly understood. In this study, the oxidation state of S-in-apatite as a function of fO2 is investigated using X-ray absorption near-edge structures (XANES) spectroscopy at the S K-edge. Apatites crystallized from lamproitic melts at 1000°C, 300 MPa and over a broad range of fO2 and sulfur fugacities (fS2) were measured. Peaks corresponding to S6+ ( 2482 eV), S4+ ( 2478 eV) and S2- ( 2470 eV) were identified in apatite. The integrated S6+/STotal (STotal = S6+ + S4+ + S2-) peak area ratios show a distinct positive correlation with fO2, increasing from 0.17 at FMQ+0 to 0.96 at FMQ+3. Ab-initio calculations were performed to further understand the energetics and geometry of incorporation of S6+, S4+ and S2- into the apatite (F-, Cl-, OH-) end-members. The results confirm that apatite can contain three different oxidations states of S (S6+, S4+, S2-) as a function of fO2. This makes apatite probably the first geologically relevant mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions. We emphasize that the strong dependence of the S oxidation state in apatite as a function of fO2 is also coupled with changing S content of apatite and co-existing melt (i.e., with changing fS2), resulting in a complex correlation between [1] apatite-melt (or fluid) partitioning, [2] redox conditions and [3] the melt and/or fluid composition, making the application of previously determined S apatite-melt partitioning coefficient debatable. Upon calibration over a range of geologically relevant T-P-X-fO2-fS2, S-in-apatite can serve as a powerful oxybarometer to quantify fO2.

Synthesis and evaluation of bioceramics for orthopedics and tissue culture applications

NASA Astrophysics Data System (ADS)

Demirkiran, Hande

Hydroxyapatite is the most well known phosphate in the biologically active phosphate ceramic family by virtue of its similarity to natural bone mineral. Among all bioglass compositions BioglassRTM45S5 is one of the most bioactive glasses. This study initially started by adding different amounts (1, 2.5, 5, 10, and 25 wt.%) of BioglassRTM45S5 to synthetic hydroxyapatite in order to improve the bioactivity of these bioceramics. The chemistries formed by sintering and their effect on different material properties including bioactivity were identified by using various techniques, such as powder and thin film x-ray diffraction, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, X-ray absorption near edge spectroscopy, compression test, and nano indentation. All the results demonstrated that 10 and 25 wt.% BioglassRTM45S5 addition to hydroxyapatite and sintering at 1200°C for 4 hours yield new compositions with main Ca 5(PO4)2SiO4 and Na3Ca 6(PO4)5 crystalline phases dispersed in silicate glassy matrices, respectively. In addition, in vitro bioactivity tests such as bone like apatite formation in simulated body fluid and bone marrow stromal cell culture have shown that the crystalline and amorphous phases have an important role on improving bioactivity of these bioceramic compositions. Besides, compression test and nano indentation has given important information on compression strength and nano structure properties of these newly composed bioceramic materials and the bone like apatite layers formed on them, respectively. Finally, the effect of silicate addition on both formation and bioactivity of Na3Ca6(PO4)5 bioceramics were shown. These findings and different techniques used assisted to develop a phenomenological approach to demonstrate how the novel bioceramic compositions were composed and aid improving bioactivity of known bioceramic materials.

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., 2009 Earth Science J. of CUG [5] Zhao et al., 2013 GPC.

Apatitic connecting rings in moulds of Baculites sp. from the middle part of the Smoky Hill Member, Niobrara Chalk (Santonian), of western Kansas

USGS Publications Warehouse

Hasenmueller, W.A.; Hattin, D.E.

1985-01-01

Moulds of Baculites sp. are common in the Smoky Hill Member but only five known specimens contain connecting rings that have been preserved because of mineralisation by carbonate apatite. Analysis of four of these specimens suggests that the connecting rings were originally composed of organic material and were mineralised during early diagenesis. Thin sections and scanning electron microscopy demonstrate that the connecting rings had a two-layered structure consisting of a thick siphuncular wall and a thin pellicle. ?? 1985.

ID ICPMS Lu-Hf Geochronology of Apatite from Iron-Oxide Apatite (IOA) Deposits, Northern Chilean Iron Belt.

NASA Astrophysics Data System (ADS)

Zhang, C.; Vervoort, J. D.; Barra, F.; Palma, G.

2017-12-01

Determining the age of mineralization of ore deposits is important for understanding the mechanisms and timing of ore formation. In many cases, however, conventional dateable mineral phases (e.g., zircon, monazite) are lacking in the ore mineral assemblages. For example, Iron Oxide Apatite (IOA) and Iron Oxide Gold Copper Gold (IOCG) deposits have the remaining fundamental question as to whether they have formed by hydrothermal or magmatic processes, or some combination of the two. In these deposits, the mineralization of iron oxide is often accompanied by the growth of apatites, which typically have REE concentrations of tens to several thousand ppm and which makes them potentially amenable to dating by the Lu-Hf isochron method. These apatites, however, also have very low concentrations of Hf, which makes determination of precise Hf isotope compositions challenging. In this study, we attempted to date these deposits using the apatite Lu-Hf isochron method, using procedures modified from that of Münker et al., 2001 and Barfod et al., 2003 and report the first Lu-Hf ages for apatites from Carmen, Fresia, and Mariela IOA deposits in northern Chilean Iron Belt. The concentration of Hf in analyzed apatite is 0.001 ppm. To ensure at least 0.5ng of Hf is collected for MS analysis, 0.5g apatite was dissolved for each sample. A single stage of Ln-spec resin chromatographic columns was used to separate Hf from REEs as multi stages of separation columns would decrease the Hf yield considerably. Using these procedures, we determined a Lu-Hf apatite age for the Carmen deposit of 130.0±1.7 Ma, which is in accordance with a previously published U-Pb apatite age of 131.0±1.0 Ma (Gelcich et al., 2005). The apatites from Fresia and Mariela yield Lu-Hf ages of 132.8±5.3 Ma and 117.3±0.4 Ma respectively. The lower points on the isochrons are either a low Lu/Hf phase (actinolite, magnetite) or bulk earth ratios. These are some of the first Lu-Hf ages of directly dating apatite in the ore mineralization, and show the potential in apatite Lu-Hf geochronology. However, further work needs to be done on the chemical procedure to improve the Hf yield and lower the interferences in order to make this a more routine technique of dating ore deposits.

Synthesis spherical porous hydroxyapatite/graphene oxide composites by ultrasonic-assisted method for biomedical applications.

PubMed

Duan, Peizhen; Shen, Juan; Zou, Guohong; Xia, Xu; Jin, Bo; Yu, Jiaxin

2018-04-10

Spherical porous hydroxyapatite (SHA)/graphene oxide (GO) composites with different GO (w/w) content of 16%, 40%, and 71% have been fabricated through a facile and controllable ultrasonic-assisted method at room temperature. The products were characterized by x-ray diffraction, field emission scanning electron microscopy, thermogravimetric analysis, mechanical testing and biomimetic mineralization. Results showed SHA were covered by GO, and SHA/GO composites had an irregular surface with different degrees of wrinkles. The elastic modulus and hardness of SHA/GO-3 composites were up to 12.45 ± 0.33 GPa and 686.67 ± 26.95 MPa, which indicated that the contents of GO had an effect on SHA/GO composites. And the mechanical properties of SHA/GO-2 composites were similar to SHA particles. The biomimetic mineralization in SBF solution showed the bone-like apatite layer on composites surface, which demonstrated that the SHA/GO materials had osseointegration property. Moreover, in vitro cytocompatibility of SHA/GO-2 composites and pure GO were evaluated by cell adhesion and proliferation tests using MC3T3-E1 cells, which demonstrated that the SHA/GO composites can act as a good template for the cells growth and adhesion. These results suggested that the SHA/GO composites will be a promising material for biomedical application.

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 polyPs were identified at the mineralizing tessera borders using Raman spectroscopy, fluorescence microscopy and histological methods. Application of exogenous ALP to skeletal tissue cross-sections resulted in polyP disappearance, and Pi production. It is proposed that elasmobranch skeletal cells produce polyP-containing granules as a concentrated P-source, while ALP activity controls when and where Pi is cleaved from polyP, increasing the apatite supersaturation to nucleate apatite minerals in the skeleton. These data support not only interaction of polyP and ALP as a cell-mediated apatite mineralization control mechanism, but also suggest that this mechanism arose millions of years ago and is common to both bony and cartilaginous skeletal systems.

Bioactivity evolution of the surface functionalized bioactive glasses.

PubMed

Magyari, Klára; Baia, Lucian; Vulpoi, Adriana; Simon, Simion; Popescu, Octavian; Simon, Viorica

2015-02-01

The formation of a calcium phosphate layer on the surface of the SiO2 -CaO-P2 O5 glasses after immersion in simulated body fluid (SBF) generally demonstrates the bioactivity of these materials. Grafting of the surface by chemical bonding can minimize the structural changes in protein adsorbed on the surface. Therefore, in this study our interest was to evaluate the bioactivity and blood biocompatibility of the SiO2 -CaO-P2 O5 glasses after their surface modification by functionalization with aminopropyl-triethoxysilane and/or by fibrinogen. It is shown that the fibrinogen adsorbed on the glass surfaces induces a growing of the apatite-like layer. It is also evidenced that the protein content from SBF influences the growth of the apatite-like layer. Furthermore, the good blood compatibility of the materials after fibrinogen and bovine serum albumin adsorption is proved from the assessment of the β-sheet-β-turn ratio. © 2014 Wiley Periodicals, Inc.

Approach of automatic 3D geological mapping: the case of the Kovdor phoscorite-carbonatite complex, NW Russia.

PubMed

Kalashnikov, A O; Ivanyuk, G Yu; Mikhailova, J A; Sokharev, V A

2017-07-31

We have developed an approach for automatic 3D geological mapping based on conversion of chemical composition of rocks to mineral composition by logical computation. It allows to calculate mineral composition based on bulk rock chemistry, interpolate the mineral composition in the same way as chemical composition, and, finally, build a 3D geological model. The approach was developed for the Kovdor phoscorite-carbonatite complex containing the Kovdor baddeleyite-apatite-magnetite deposit. We used 4 bulk rock chemistry analyses - Fe magn , P 2 O 5 , CO 2 and SiO 2 . We used four techniques for prediction of rock types - calculation of normative mineral compositions (norms), multiple regression, artificial neural network and developed by logical evaluation. The two latter became the best. As a result, we distinguished 14 types of phoscorites (forsterite-apatite-magnetite-carbonate rock), carbonatite and host rocks. The results show good convergence with our petrographical studies of the deposit, and recent manually built maps. The proposed approach can be used as a tool of a deposit genesis reconstruction and preliminary geometallurgical modelling.

Processing and properties of ceramic matrix-polymer composites for dental applications

NASA Astrophysics Data System (ADS)

Huang, Hsuan Yao

The basic composite structure of natural hard tissue was used to guide the design and processing of dental restorative materials. The design incorporates the methodology of using inorganic minerals as the main structural phase reinforced with a more ductile but tougher organic phase. Ceramic-polymer composites were prepared by slip casting a porous ceramic structure, heating and chemical treating the porous preform, infiltrating with monomer and then curing. The three factors that determined the mechanical properties of alumina-polymer composites were the type of polymer used, the method of silane treatments, and the type of bond between particles in the porous preforms. Without the use of silane coupling agents, the composites were measured to have a lower strength. The composite with a more "flexible" porous alumina network had a greater ability to plastically dissipate the energy of propagating cracks. However, the aggressive nature of the alumina particles on opposing enamel requires that these alumina-polymer composites have a wear compatible coating for practical application. A route to dense bioactive apatite wollastonite glass ceramics (AWGC)-polymer composites was developed. The problems associated with glass dissolution into the aqueous medium for slip casting were overcome with the use of silane. The role of heating rate and development of ceramic compact microstructure on composite properties was explored. In general, if isothermal heating was not applied, decreasing heating rate increased glass crystallinity and particle-particle fusion, but decreased pore volume. Also composite strength and fracture toughness decreased while modulus and hardness increased with decreasing heating rate. If isothermal heating was applied, glass crystallinity, pore content, and composite mechanical properties showed relatively little change regardless of the initial heating rate. The potential of AWGC-polymer composites for dental and implant applications was explored. Strengths and toughnesses were not severely degraded by immersion in simulated body fluids up to 30 days. The composite elastic modulus approached that of hard tissues and its wear behavior with opposing tooth was excellent. Growth of apatite over the entire composite surface was achieved in SBF. Growth of apatite in human whole saliva was achieved on the bioactive glass surface, but not on the composite surface.

Osteoinduction on Acid and Heat Treated Porous Ti Metal Samples in Canine Muscle

PubMed Central

Kawai, Toshiyuki; Takemoto, Mitsuru; Fujibayashi, Shunsuke; Akiyama, Haruhiko; Tanaka, Masashi; Yamaguchi, Seiji; Pattanayak, Deepak K.; Doi, Kenji; Matsushita, Tomiharu; Nakamura, Takashi; Kokubo, Tadashi; Matsuda, Shuichi

2014-01-01

Samples of porous Ti metal were subjected to different acid and heat treatments. Ectopic bone formation on specimens embedded in dog muscle was compared with the surface characteristics of the specimen. Treatment of the specimens by H2SO4/HCl and heating at 600°C produced micrometer-scale roughness with surface layers composed of rutile phase of titanium dioxide. The acid- and heat-treated specimens induced ectopic bone formation within 6 months of implantation. A specimen treated using NaOH followed by HCl acid and then heat treatment produced nanometer-scale surface roughness with a surface layer composed of both rutile and anatase phases of titanium dioxide. These specimens also induced bone formation after 6 months of implantation. Both these specimens featured positive surface charge and good apatite-forming abilities in a simulated body fluid. The amount of the bone induced in the porous structure increased with apatite-forming ability and higher positive surface charge. Untreated porous Ti metal samples showed no bone formation even after 12 months. Specimens that were only heat treated featured a smooth surface composed of rutile. A mixed acid treatment produced specimens with micrometer-scale rough surfaces composed of titanium hydride. Both of them also showed no bone formation after 12 months. The specimens that showed no bone formation also featured almost zero surface charge and no apatite-forming ability. These results indicate that osteoinduction of these porous Ti metal samples is directly related to positive surface charge that facilitates formation of apatite on the metal surfaces in vitro. PMID:24520375

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 expected to be the dominant As form in hydrothermal fluids. These results show that incorporation of As in apatite is a complicated process, and sensitive to the local fluid composition during crystallization, and that some of the complexity in As zoning in partially reacted apatite may be due to local fluctuations of As(V)/As(III) ratios in the fluid and to kinetic effects during the mineral replacement reaction. Our study shows for the first time that As(III) can be incorporated into the apatite structure, although not as efficiently as As(V). Uptake of As(III) is probably highly dependent on the reaction mechanism. As(III)O33- moieties replace phosphate groups, but cause a high strain on the lattice; as a result, As(III) is easily exchanged (or oxidized) for As(V) during hydrothermal recrystallization, and the fully reacted grains only record the preferred oxidation state (i.e., As(V)) from mixed-oxidation state solutions. Overall this study shows that the observed oxidation state of As in apatite may not reflect the original As(III)/As(V) ratio of the parent fluid, due to the complex nature of As(III) uptake and possible in situ oxidation during recrystallization.

Could the eucrite Graves Nunataks 98098 be Vesta's equivalent to Lunar KREEP?

NASA Astrophysics Data System (ADS)

Sarafian, A. R.; Marschall, H.; Nielsen, S.

2013-12-01

Basaltic eucrites, members of the HED achondrite clan, are thought to derive from the asteroid 4-Vesta [1]. Most eucrites show little compositional and petrographic variability, thus anomalous eucrite could provide key insights into differentiation processes that operated on Vesta. The eucrite Graves Nunataks (GRA) 98098 is an unbrecciated eucrite with cross cutting white tabular veins consisting of mainly equigranular tridymite and euhedral plagioclase with some pyroxene [2]. In addition, GRA has the second highest modal (volume) abundance of apatite in a eucrite studied thus far. The apatite is associated with the veins [2]. The GRA bulk rock composition is enriched in incompatible elements with concentrations ca. 3-5 times higher than in most basaltic eucrites [3]. Additionally, GRA has 10-20 times more Cl than any other analyzed eucritic apatite [2]. Here we measured the trace-element concentrations of plagioclase and pyroxene by laser ablation ICP-MS and the D/H ratio of the apatites by SIMS. In the domains of GRA cut by veins, the trace elements in plagioclase and pyroxene show an up to 15x enrichment in incompatible elements compared to other basaltic eucrites [4]. Here we report the first D/H measurement of any magmatic material from Vesta. The D/H of apatite in GRA is relatively light compared to vSMOW. Based on the high abundance of incompatible elements in GRA and the high Cl content found in apatites, Sarafian et al. [2] suggested that GRA could be akin to Lunar KREEP (lunar rocks enriched in K, REEs and P). With the additional evidence of enriched incompatible elements in plagioclase and pyroxene and the similarity in D/H compared to KREEP, it is likely that GRA was infiltrated by a late-stage melt enriched in incompatible elements, similar to Lunar KREEP. Further study is needed to determine if this late-stage melt formed in a similar manner as KREEP. 1. Consolmango, G.J. and M.J. Drake, Composition and evolution of the eucrite parent body: Evidence from rare earth elements. Geochimica et Cosmochimica Acta, 1977. 41: p. 1271-1282. 2. Sarafian, A.R., M.F. Roden, and A.E. Patiño Douce, The nature of volatiles in eucrites: Clues from apatite. Meteoritics and Planetary Science, 2013. in press. 3. Mittlefehldt, D.W. and M.M. Lindstrom, Geochemistry of eucrites: genesis of basaltic eucrites, and Hf and Ta as petrogenetic indicators for altered antarctic eucrites. Geochimica et Cosmochimica Acta, 2003. 67(10): p. 1911-1934. 4. Hsu, W. and G. Crozaz, Mineral chemistry and the petrogenesis of eucrites: I. Noncumulate eucrites. Geochimica et Cosmochimica Acta, 1996. 60(22): p. 4571-4591.

The formation of phosphoran olivine and stanfieldite from the pyrometamorphic breakdown of apatite in slags from a prehistoric ritual immolation site (Goldbichl, Igls, Tyrol, Austria)

NASA Astrophysics Data System (ADS)

Schneider, Philipp; Tropper, Peter; Kaindl, Reinhard

2013-04-01

In this study we report P-rich olivine and the tric-calcium phosphate (TCP) stanfieldite in partially molten quartzphyllites from the ritual immolation site at the Goldbichl, near Innsbruck in the Tyrol, Austria. During partial melting, foamy patches of dark glassy material formed at the surface of the rocks and also as layers within the rocks. The pyrometamorphic rocks contain mostly the mineral assemblage olivine + orthopyroxene + plagioclase + spinel + glass. During the investigation of slag samples from this prehistoric ritual immolation site, extremely P-rich, apatite-bearing micro-domains were found. In these domains phosphoran olivine was found whose P contents are approaching the maximum P contents in olivine according to the experimental investigations of Boesenberg and Hewins (Geochim Cosmochim Acta 74:1923-1941, 2010). The textures within these domains indicate strongly disequilibrium conditions. The phosphoran olivines formed due to reactions involving apatite and the mineral assemblage of the quartzphyllites, and coexist with plagioclase and a tri-calcium phosphate phase (TCP) showing stanfieldite Ca4(Mg, Fe2+, Mn2+)5(PO4)6 composition. In terms of its chemical composition, olivine shows a wide range in composition with P ranging from 0.3 to 0.54 a.p.f.u, which corresponds to maximal 23 wt.% P2O5. These are the highest P-contents in olivine reported from rocks so far. The incorporation of P correlates with decreasing Si contents according to the charge balancing scheme 2{{P}^{5+ }}+□{{M}_{1,2 }}=2S{{i}^{4+ }}+{{( {Mg,Fe} )}^{2+ }}{{M}_{1,2 }} . Therefore P can only be incorporated in combination with a vacancy on the M1,2 position. Micro-Raman spectroscopy of phosphoran olivines indicates that these olivines can easily be identified with this method due to the strong signals of the SiO4 and PO4 vibrations. The external vibrations of the M1,2 sites at low wave-numbers are more complex than for P-free olivine. This might be due to the effect of P5+ on the M1 2+ and M2 2+ positions and the formation of vacancies on these sites. Since micro-Raman investigations of the TCP phase yielded no conclusive match with a known Raman spectrum of a phosphate mineral so far, therefore it is most likely that the TCP phase is stanfieldite, whose Raman spectrum has not been obtained yet. Schematical Schreinemakers analysis in the system CaO-Al2O3-FeO-SiO2-P2O5-H2O shows that P-rich olivine (fayalite-sarcopside solid solution) can form from mineral reactions involving chlorite, apatite and quartz and show that the occurrence of P-rich Fe-olivines spans a large T-range but is restricted to domains with high aSiO2. The mineral assemblage in the P-rich micro-domains shows that the formation of phosphoran olivine is not only restricted to the interaction between bone material and rocks in slags from ritual immolation sites as suggested by Tropper et al. (Eur J Mineral 16:631-640, 2004) from the immolation site in Oetz but can form locally due to the pyrometamorphic breakdown of a P-rich accessory precursor phase such as apatite.

Magnesian anorthosites and associated troctolites and dunite in Apollo 14 breccias

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

Lindstrom, M.M.; Knapp, S.A.

1984-11-15

Magnesian anorthosite, a new type of pristine lunar highlands rock, has been found in Apollo 14 breccias. It has primitive (high Ca and Mg) silicate mineral compositions, and high and variable REE concentrations. Variations in REE contents can be accounted for by variations in modal abundance of REE-rich apatite. Magnesian anorthosites are associated with troctolites and a dunite with very similar mineral compositions and it is suggested that all crystallized from a differentiated troctolitic intrusion. The origin of the REE-rich apatite is enigmatic. It is unlikely to have crystallized from an igneous liquid in equilibrium with the major minerals inmore » the anorthosite. Possible origins are assimilation of urKREEP or metasomatism by REE-rich fluids. REE-rich alkali anorthosites and gabbronorites are also found and are likely to be related to KREEP basalt magmas. Lunar compositional associations are distributed in a regional rather than global manner.« less

A Conspicuous Clay Ovoid in Nakhla: Evidence for Subsurface Hydrothermal Alteration on Mars with Implications for Astrobiology

PubMed Central

Haigh, Sarah; Lyon, Ian

2014-01-01

Abstract A conspicuous biomorphic ovoid structure has been discovered in the Nakhla martian meteorite, made of nanocrystalline iron-rich saponitic clay and amorphous material. The ovoid is indigenous to Nakhla and occurs within a late-formed amorphous mesostasis region of rhyolitic composition that is interstitial to two clinopyroxene grains with Al-rich rims, and contains acicular apatite crystals, olivine, sulfides, Ti-rich magnetite, and a new mineral of the rhoenite group. To infer the origin of the ovoid, a large set of analytical tools was employed, including scanning electron microscopy and backscattered electron imaging, wavelength-dispersive X-ray analysis, X-ray mapping, Raman spectroscopy, time-of-flight secondary ion mass spectrometry analysis, high-resolution transmission electron microscope imaging, and atomic force microscope topographic mapping. The concentric wall of the ovoid surrounds an originally hollow volume and exhibits internal layering of contrasting nanotextures but uniform chemical composition, and likely inherited its overall shape from a preexisting vesicle in the mesostasis glass. A final fibrous layer of Fe-rich phases blankets the interior surfaces of the ovoid wall structure. There is evidence that the parent rock of Nakhla has undergone a shock event from a nearby bolide impact that melted the rims of pyroxene and the interstitial matter and initiated an igneous hydrothermal system of rapidly cooling fluids, which were progressively mixed with fluids from the melted permafrost. Sharp temperature gradients were responsible for the crystallization of Al-rich clinopyroxene rims, rhoenite, acicular apatites, and the quenching of the mesostasis glass and the vesicle. During the formation of the ovoid structure, episodic fluid infiltration events resulted in the precipitation of saponite rinds around the vesicle walls, altered pyrrhotite to marcasite, and then isolated the ovoid wall structure from the rest of the system by depositing a layer of iron oxides/hydroxides. Carbonates, halite, and sulfates were deposited last within interstitial spaces and along fractures. Among three plausible competing hypotheses here, this particular abiotic scenario is considered to be the most reasonable explanation for the formation of the ovoid structure in Nakhla, and although compelling evidence for a biotic origin is lacking, it is evident that the martian subsurface contains niche environments where life could develop. Key Words: Biomorph—Clays—Search for life (biosignatures)—Martian meteorites—Hydrothermal systems. Astrobiology 14, 651–693. PMID:25046549

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

Carneiro, Karina M. M.; Zhai, Halei; Zhu, Li

We report that enamel, the outermost layer of teeth, is an acellular mineralized tissue that cannot regenerate; the mature tissue is composed of high aspect ratio apatite nanocrystals organized into rods and inter-rod regions. Amelogenin constitutes 90% of the protein matrix in developing enamel and plays a central role in guiding the hierarchical organization of apatite crystals observed in mature enamel. To date, a convincing link between amelogenin supramolecular structures and mature enamel has yet to be described, in part because the protein matrix is degraded during tissue maturation. Here we show compelling evidence that amelogenin self-assembles into an amyloid-likemore » structure in vitro and in vivo. We show that enamel matrices stain positive for amyloids and we identify a specific region within amelogenin that self-assembles into β-sheets. Lastly, we propose that amelogenin nanoribbons template the growth of apatite mineral in human enamel. This is a paradigm shift from the current model of enamel development.« less

Enhancement of biodegradation and osseointegration of poly(ε-caprolactone)/calcium phosphate ceramic composite screws for osteofixation using calcium sulfate.

PubMed

Wu, Chang-Chin; Hsu, Li-Ho; Tsai, Yuh-Feng; Sumi, Shoichiro; Yang, Kai-Chiang

2016-04-04

Internal fixation devices, which can stabilize and realign fractured bone, are widely used in fracture management. In this paper, a biodegradable composite fixator, composed of poly(ε-caprolactone), calcium phosphate ceramic and calcium sulfate (PCL/CPC/CS), is developed. The composition of CS, which has a high dissolution rate, was expected to create a porous structure to improve osteofixation to the composite fixator. PCL, PCL/CPC, and PCL/CPC/CS samples were prepared and their physical properties were characterized in vitro. In vivo performance of the composite screws was verified in the distal femurs of rabbits. Results showed that the PCL/CPC/CS composite had a higher compressive strength (28.55 ± 3.32 MPa) in comparison with that of PCL (20.64 ± 1.81 MPa) (p < 0.05). A larger amount of apatite was formed on PCL/CPC/CS than on PCL/CPC, while no apatite was found on PCL after simulated body fluid immersion. In addition, PCL/CPC/CS composites also had a faster in vitro degradation rate (13.05 ± 3.42% in weight loss) relative to PCL (1.79 ± 0.23%) and PCL/CPC (4.32 ± 2.18%) (p < 0.001). In animal studies, PCL/CPC/CS screws showed a greater volume loss than that of PCL or PCL/CPC at 24 weeks post-implantation. Under micro-computerized tomography observation, animals with PCL/CPC/CS implants had better osseointegration in terms of the structural parameters of the distal metaphysis, including trabecular number, trabecular spacing, and connectivity density, than the PCL screw. This study reveals that the addition of CS accelerates the biodegradation and enhanced apatite formation of the PCL/CPC composite screw. This osteoconductive PCL/CPC/CS is a good candidate material for internal fixation devices.

Microwave-induced production of boron-doped HAp (B-HAp) and B-HAp coated composite scaffolds.

PubMed

Tunçay, Ekin Ö; Demirtaş, T Tolga; Gümüşderelioğlu, Menemşe

2017-03-01

The aim of the present study is to produce boron (B) doped hydroxyapatite (B-HAp), which has an osteoinductive property, and investigate in-vitro osteogenesis potential of B-HAp coated chitosan (B-HAp/Ch) scaffolds. At first, B-HAp was produced by the interaction of ions within the concentrated synthetic body fluid containing boron (B-SBF) with microwave energy. Boron incorporation into HAp structure was performed by the substitution of borate ions with phosphate and hydroxyl ions. Experiments were carried out with different microwave powers and exposure times, and optimum conditions for the production of B-HAp were determined. B-HAp precipitated from B-SBF by 600W microwave power has 1.15±0.11% (w/w) B, 1.40 (w/w) Ca/P ratio, 4.30±0.07% (w/w) carbonate content, 30±4nm rod-like morphology and bone-like amorphous structure. Then, chitosan scaffolds that were prepared by freeze-drying were coated with B-HAp by performing microwave-assisted precipitation in the presence of scaffolds to improve their bioactivities and mechanical properties. The formation of apatite layer and the penetration of apatites into the pores were observed by scanning electron microscopy (SEM). Fourier Transform Infrared spectroscopy (ATR-FTIR) and X-ray diffraction (XRD) analysis also confirmed the presence of B-HAp layer. As control, hydroxyapatite coated chitosan scaffolds (HAp/Ch) produced at the same conditions were used. The results of cell culture studies indicated that B releasing from scaffolds enhances proliferation and osteoblastic differentiation of MC3T3-E1 cells. This work emphasized the importance of the use of B within the scaffolds for enhancing in-vitro bone tissue engineering applications. Copyright © 2017 Elsevier GmbH. All rights reserved.

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

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

Pramana, Stevin S.; Klooster, Wim T.; Institute of Materials Research and Engineering, 3 Research Link, Singapore 117602

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 electrolytesmore » 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.« less

Phosphorylation-dependent mineral-type specificity for apatite-binding peptide sequences.

PubMed

Addison, William N; Miller, Sharon J; Ramaswamy, Janani; Mansouri, Ahmad; Kohn, David H; McKee, Marc D

2010-12-01

Apatite-binding peptides discovered by phage display provide an alternative design method for creating functional biomaterials for bone and tooth tissue repair. A limitation of this approach is the absence of display peptide phosphorylation--a post-translational modification important to mineral-binding proteins. To refine the material specificity of a recently identified apatite-binding peptide, and to determine critical design parameters (net charge, charge distribution, amino acid sequence and composition) controlling peptide affinity for mineral, we investigated the effects of phosphorylation and sequence scrambling on peptide adsorption to four different apatites (bone-like mineral, and three types of apatite containing initially 0, 5.6 and 10.5% carbonate). Phosphorylation of the VTKHLNQISQSY peptide (VTK peptide) led to a 10-fold increase in peptide adsorption (compared to nonphosphorylated peptide) to bone-like mineral, and a 2-fold increase in adsorption to the carbonated apatite, but there was no effect of phosphorylation on peptide affinity to pure hydroxyapatite (without carbonate). Sequence scrambling of the nonphosphorylated VTK peptide enhanced its specificity for the bone-like mineral, but scrambled phosphorylated VTK peptide (pVTK) did not significantly alter mineral-binding suggesting that despite the importance of sequence order and/or charge distribution to mineral-binding, the enhanced binding after phosphorylation exceeds any further enhancement by altered sequence order. Osteoblast culture mineralization was dose-dependently inhibited by pVTK and to a significantly lesser extent by scrambled pVTK, while the nonphosphorylated and scrambled forms had no effect, indicating that inhibition of osteoblast mineralization is dependent on both peptide sequence and charge. Computational modeling of peptide-mineral interactions indicated a favorable change in binding energy upon phosphorylation that was unaffected by scrambling. In conclusion, phosphorylation of serine residues increases peptide specificity for bone-like mineral, whose adsorption is determined primarily by sequence composition and net charge as opposed to sequence order. However, sequence order in addition to net charge modulates the mineralization of osteoblast cultures. The ability of such peptides to inhibit mineralization has potential utility in the management of pathologic calcification. Copyright © 2010 Elsevier Ltd. All rights reserved.

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.

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

2016-01-01

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

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., (2009), GCA 73, 2347-2365.

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.

Effect of alkali earth oxides on hydroxy-carbonated apatite nano layer formation for SiO2-BaO-CaO-Na2O-P2O5 glass system

NASA Astrophysics Data System (ADS)

Kiran, P.; Ramakrishna, V.; Shashikala, H. D.; Udayashankar, N. K.

2017-11-01

Barium soda lime phosphosilicate [(58SiO2-(32 - x)BaO- xCao-6Na2O-4P2O5 (where x = 15, 20, 25 and 30 mol%)] samples were synthesised using conventional sol-gel method at 700 °C sintering temperature. Thermal, structural properties were studied using thermo gravimetric analysis and differential thermal analysis, X-ray diffraction, scanning electron microscopy, fourier transform infrared and Raman spectroscopy. Using Raman spectra non-bridging oxygen concentrations were estimated. The hydroxy-carbonated apatite (HCA) layer formation on samples was analysed for 7 days using simulated body fluid (SBF) soaked samples. The growth of HCA layers self-assembled on the sample surface was discussed as a function of NBO/BO ratio. Results indicated that the number of Ca2+ ions released into SBF solution in dissolution process and weight loss of SB-treated samples vary with NBO/BO ratio. The changes in NBO/BO ratios were observed to be proportional to HCA forming ability of barium soda lime phosphosilicate glasses.

Thermal properties and surface reactivity in simulated body fluid of new strontium ion-containing phosphate glasses.

PubMed

Massera, J; Petit, L; Cardinal, T; Videau, J J; Hupa, M; Hupa, L

2013-06-01

In this paper, we investigate the effect of SrO substitution for CaO in 50P₂O₅-10Na₂-(40-x)CaO-xSrO glass system (x from 0 to 40) on the thermal and structural properties and also on the glass reactivity in simulated body fluid (SBF) in order to find new glass candidates for biomedical glass fibers. The addition of SrO at the expense of CaO seems to restrain the leaching of phosphate ions in the solution limiting the reduction of the solution pH. We observed the formation of an apatite layer at the surface of the glasses when in contact with SBF. SrO and MgO were found in the apatite layer of the strontium ion-containing glasses, the concentration of which increases with an increase of SrO content. We think that it is the presence of MgO and SrO in the layer which limits the leaching of phosphate in the solution and thus the glass dissolution in SBF.

Trace element diffusion and kinetic fractionation in wet rhyolitic melt

NASA Astrophysics Data System (ADS)

Holycross, Megan E.; Watson, E. Bruce

2018-07-01

Piston-cylinder experiments were run to determine the chemical diffusivities of 21 trace elements (Sc, V, Y, Zr, Nb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Hf, Th and U) in hydrous rhyolitic melts at 1 GPa pressure and temperatures from 850 to 1250 °C. Diffusion couple glasses were doped with trace elements in low concentrations to characterize the diffusivities of all cations in a single experiment. Laser ablation ICP-MS was used to evaluate the trace element concentration gradients that developed in the silicate glasses. All calculated diffusion coefficients correspond to the temperature dependence D = D0exp(-Ea/RT). Rhyolite liquids contained either ∼4.1 wt% or ∼6.2 wt% dissolved H2O; separate Arrhenius relationships are produced for each melt composition. Trace element diffusivities in the melt with 6.2 wt% H2O are roughly two times higher than those in the less hydrous melt. Calculated trace element diffusion coefficients cover nearly two orders of magnitude at a given temperature. The high field strength elements are the slowest diffusers, followed by the transition metals and heavy rare earth elements. The light rare earth elements have the fastest diffusion rates in hydrous rhyolitic melt. The measured diffusion coefficients range down to values sufficiently low to preclude diffusive homogenization over geochemically realistic time scales in some cases. The substantial differences in the diffusivities of individual cations may result in fractionated trace element signatures in rhyolite melt pockets. A simple model is used to explore the potential for kinetic fractionation of REE during growth of an apatite crystal in a diffusive boundary layer locally saturated in P2O5. The faster-diffusing light REE are more efficiently transported away from the crystal interface than the slower-moving heavy REE. Diffusion effects will enrich the melt boundary layer in slow-moving HREE relative to the faster LREE. The kinetic fractionation of REE in the melt growth medium will result in a precipitated apatite crystal with a disequilibrium trace element composition.

Influence of carbonate ion in the crystallization medium on the formation and chemical composition of CaHA-SrHA solid solutions

NASA Astrophysics Data System (ADS)

Nikolaev, Anton; Kuz'mina, Maria; Frank-Kamenetskaya, Olga; Zorina, Maina

2015-06-01

The study of the influence of carbonate ions in a solution to Sr-distribution in system «solution-crystal» and to ion substitutions and the non-stoichiometry of formed CaHA-SrHA solid solutions was carried out. The CaHA-SrHA solid solutions were synthesized by precipitation from aqueous solutions with the atomic C/P ratio equal to 0, 0.05 and 0.1 at T = 90 °C. Resulting precipitates were studied using various methods including X-ray powder diffraction, infrared spectroscopy and different chemical analyses. The results of the study have shown that in the range of values of (Ca + Sr)/P in the water solution from 40% to 85%, the presence of carbonate ions (C/P = 0.05-0.1) promotes the incorporation of strontium in the apatite. Crystalline apatite solid solutions formed from water solutions of such composition are more defective compared to apatites that are mainly calcium or strontium. They are characterized by a smaller size coherence scattering domain length along [0 0 1] direction and a greater number of carbonate ions, water molecules and vacancies at the Ca-sites.

Mineral ecophysiological evidence for microbial activity in banded iron formation

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

Li, Dr. Yi-Liang; Konhauser, Dr, Kurt; Cole, David R

2011-01-01

The phosphorus composition of banded-iron formations (BIFs) has been used as a proxy for Precambrian seawater composition and the paleoeredox state of Earth's surface environment. However, it is unclear whether the phosphorus in BIFs originally entered the sediment as a sorbed component of the iron oxyhydroxide particles, or whether it was incorporated into the biomass of marine phytoplankton. We conducted high-resolution mineral analyses and report here the first detection of an Fe(III) acetate salt, as well as nanocrystals of apatite in association with magnetite, in the 2.48 Ga Dales Gorge Member of the Brockman Iron Formation (a BIF), Hamersley, Westernmore » Australia. The clusters of apatite are similar in size and morphology to biogenic apatite crystals resulting from biomass decay in Phanerozoic marine sediments, while the formation of an Fe(III) acetate salt and magnetite not only implies the original presence of biomass in the BIF sediments, but also that organic carbon likely served as an electron donor during bacterial Fe(III) reduction. This study is important because it suggests that phytoplankton may have played a key role in the transfer of phosphorus (and other trace elements) from the photic zone to the seafloor.« less

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.

Apatite and sodalite based glass-bonded waste forms for immobilization of 129I and mixed halide radioactive wastes

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

Goel, Ashutosh; McCloy, John S.; Riley, Brian J.

The goal of the project was to utilize the knowledge accumulated by the team, in working with minerals for chloride wastes and biological apatites, toward the development of advanced waste forms for immobilizing 129I and mixed-halide wastes. Based on our knowledge, experience, and thorough literature review, we had selected two minerals with different crystal structures and potential for high chemical durability, sodalite and CaP/PbV-apatite, to form the basis of this project. The focus of the proposed effort was towards: (i) low temperature synthesis of proposed minerals (iodine containing sodalite and apatite) leading to the development of monolithic waste forms, (ii)more » development of a fundamental understanding of the atomic-scale to meso-scale mechanisms of radionuclide incorporation in them, and (iii) understanding of the mechanism of their chemical corrosion, alteration mechanism, and rates. The proposed work was divided into four broad sections. deliverables. 1. Synthesis of materials 2. Materials structural and thermal characterization 3. Design of glass compositions and synthesis glass-bonded minerals, and 4. Chemical durability testing of materials.« less

Sr, Mg cosubstituted HA porous macro-granules: potentialities as resorbable bone filler with antiosteoporotic functions.

PubMed

Landi, Elena; Uggeri, Jacopo; Medri, Valentina; Guizzardi, Stefano

2013-09-01

Porous macro-granules of nanostructured apatite with Ca ions partially cosubstituted with Mg and Sr ions in different ratios (SrMgHAs), were synthesized at 37°C and compared with Mg and/or Sr free apatites (MgHAs and HA). Strontium improved the Mg substitution extent in the apatite and the chemical-physical and thermal stability of the resulting cosubstituted apatite. Porous macro-granules of 400-600 micron with selected composition were tested for the ionic release in synthetic body fluid and the data were related with the results of preliminary cell investigation in vitro. As compared to the corresponding Sr-free granulate, the SrMgHA could be exploited to prolong the beneficial Mg release during the bone regeneration process. In addition the contemporary in situ supply of Sr, an antiosteoporotic and anticarie ion, could influence the quality of new hard tissues. The ionic multirelease created a more favorable environment for human osteoblasts, demonstrated by a proliferative effect for each dose tested in the range 0.1-10 mg/mL. Copyright © 2013 Wiley Periodicals, Inc.

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

Ancient graphite in the Eoarchean quartz-pyroxene rocks from Akilia in southern West Greenland II: Isotopic and chemical compositions and comparison with Paleoproterozoic banded iron formations

NASA Astrophysics Data System (ADS)

Papineau, Dominic; De Gregorio, Bradley T.; Stroud, Rhonda M.; Steele, Andrew; Pecoits, Ernesto; Konhauser, Kurt; Wang, Jianhua; Fogel, Marilyn L.

2010-10-01

We present detailed petrographic surveys of apatite grains in association with carbonaceous material (CM) in two banded iron formations (BIFs) from the Paleoproterozoic of Uruguay and Michigan for comparison with similar mineral associations in the highly debated Akilia Quartz-pyroxene (Qp) rock. Petrographic and Raman spectroscopic surveys of these Paleoproterozoic BIFs show that apatite grains typically occur in bands parallel to bedding and are more often associated with CM when concentrations of organic matter are high. Carbonaceous material in the Vichadero BIF from Uruguay is generally well-crystallized graphite and occurs in concentrations around 0.01 wt% with an average δ 13C gra value of -28.6 ± 4.4‰ (1 σ). In this BIF, only about 5% of apatite grains are associated with graphite. In comparison, CM in the Bijiki BIF from Michigan is also graphitic, but occurs in concentrations around 2.4 wt% with δ 13C gra values around -24.0 ± 0.3‰ (1 σ). In the Bijiki BIF, more than 78% of apatite grains are associated with CM. Given the geologic context and high levels of CM in the Bijiki BIF, the significantly higher proportion of apatite grains associated with CM in this rock is interpreted to represent diagenetically altered biomass and shows that such diagenetic mineral associations can survive metamorphism up to the amphibolite facies. Isotope compositions of CM in muffled acidified whole-rock powders from the Akilia Qp rock have average δ 13C gra values of -17.5 ± 2.5‰ (1 σ), while δ 13C carb values in whole-rock powders average -4.0 ± 1.0‰ (1 σ). Carbon isotope compositions of graphite associated with apatite and other minerals in the Akilia Qp rock were also measured with the NanoSIMS to have similar ranges of δ 13C gra values averaging -13.8 ± 5.6‰ (1 σ). The NanoSIMS was also used to semi-quantitatively map the distributions of H, N, O, P, and S in graphite from the Akilia Qp rock, and relative abundances were found to be similar for graphite associated with apatite or with hornblende, calcite, and sulfides. These analyses revealed generally lower abundances of trace elements in the Akilia graphite compared to graphite associated with apatite from Paleoproterozoic BIFs. Graphite associated with hornblende, calcite, and sulfides in the Akilia Qp rock was fluid-deposited at high-temperature from carbon-bearing fluids, and since this graphite has similar ranges of δ 13C gra values and of trace elements compared to graphite associated with apatite, we conclude that the Akilia graphite in different mineral associations formed from the same source(s) of CM. Collectively our results do not exclude a biogenic origin of the carbon in the Akilia graphite, but because some observations can not exclude graphitization of abiogenic carbon from CO 2- and CH 4-bearing mantle fluids, there remain ambiguities with respect to the exact origin of carbon in this ancient metasedimentary rock. Accordingly, there may have been several generations of graphite formation along with possibly varying mixtures of CO 2- and CH 4-bearing fluids that may have resulted in large ranges of δ 13C gra values. The possibility of fluid-deposited graphite associated with apatite should be a focus of future investigations as this may prove to be an alternative pathway of graphitization from phosphate-bearing fluids. Correlated micro-analytical approaches tested on terrestrial rocks in this work provide insights into the origin of carbon in ancient graphite and will pave the way for the search for life on other ancient planetary surfaces.

Amphibole-bearing multiphase solid inclusions in olivine, the Murotomisaki Gabbro, Southwest Japan: An evidence of hydrous flux melting

NASA Astrophysics Data System (ADS)

Hoshide, T.; Obata, M.

2009-12-01

The Murotomisaki Gabbro is a sill-like layered intrusion of up to 220m thickness exposed near Cape Muroto, Southwest Japan. Despite the small size of the intrusion, it contains well-developed centimeter- to meter-scale layered structures of modal variation of olivine, plagioclase and augite. Hoshide et al (2006a, b) identified the ’crystal accumulation zone’ (40m from the bottom) that was formed by gravitational settling of olivine crystals and the ’crystal growth zone’ (40-100m from the bottom), in which olivine crystals grew significantly. The fine-scale compositional layering is best developed in the ’crystal growth zone’. Amphibole-bearing multiphase solid inclusions (called ‘the amphibole-clot inclusions’) are common in olivine crystals from both the crystal accumulation- and the crystal growth zones. The amphibole clot inclusions show spherical or convex-polygonal shapes and are composed of pargasitic amphibole, biotite and orthopyroxene, with minor amounts of augite, apatite and opaque minerals. Plagioclase rarely occurs in the amphibole clot inclusions. Bulk chemical compositions of the inclusions, obtained from mineral microprobe analyses and modal composition, are characteristically high in MgO content (16-23 wt %) and they roughly lie between presumable fractionated melt compositions and olivine compositions. From observations above, it is likely that amphibole clot inclusions are of melt origin, which had formed from some hydrous melts probably entrapped in growing olivine crystals. However, it may be difficult to explain both the very magnesian nature of the inclusion and absence of plagioclase in the inclusion by the crystallization of the normal hydrous basaltic melt. The difficulty may be resolved if we suppose, for a trapped melt composition, a more magnesian (i.e., picritic) composition. The highly magnesian nature of the amphibole clot inclusions may suggest that significant amount of olivine component had been added to fractionated melts that was once equilibrated with olivine. Such addition of olivine component may be realized by dissolution of olivine, which may be induced by introduction of water from the lower horizons of the crystallization boundary layer (e.g., McBirney, 1987). Amphibole clot inclusion in olivine is, therefore, considered to be a new evidence for dissolution of olivine by hydrous fluxing.

Formation conditions and REY enrichment of the 2060 Ma phosphorus mineralization at Schiel (South Africa): geochemical and geochronological constraints

NASA Astrophysics Data System (ADS)

Graupner, Torsten; Klemd, Reiner; Henjes-Kunst, Friedhelm; Goldmann, Simon; Behnsen, Helge; Gerdes, Axel; Dohrmann, Reiner; Barton, Jay M.; Opperman, Rehan

2018-02-01

Rocks of the rare-earth element (REY)-enriched apatite deposit in the eastern part of the Schiel Alkaline Complex (SAC; Southern Marginal Zone, Limpopo Belt) were studied for their whole-rock and mineral chemistry, REY mineral distribution and geochronology. Apart from phoscorite (sensu lato), pyroxenite and various syenitic rock types with quite variable apatite contents display P-REY enrichments. Field observations, mineralogical composition as well as major and trace element chemistry of soils make it possible to constrain the distribution of the hidden P-REY-rich rock types in the apatite deposit. Uranium-lead ages of zircon from phoscorite (sensu lato) and syenite are in the range of 2.06-2.05 Ga. Samarium-neodymium (ɛNd(t) -8.6 to -6.0) and in part Rb-Sr (87Sr/86Sr(t) 0.70819-0.70859) isotope data for whole-rock samples and mineral separates indicate an origin from an isotopically enriched and slightly variable source. Fluorapatite, early allanite and titanite are the main REY carriers at Schiel. Fluorapatite dominates the REY budget of pyroxenite and phoscorite, whereas early allanite hosts most of the REY in syenite. Three apatite types are distinguished based on their occurrence in the rocks, REYtotal contents and colouration in cathodoluminescence microscopy. Magmatic apatite in pyroxenite and in phoscorite (sensu lato) as well as early stage type I/II apatite in syenitic rocks have moderate to high REYtotal abundances (up to 3.2 wt%) with the mineral enriched in light REE. Early ferriallanite-(Ce) is strongly enriched in light REE and shows very high REYtotal values (13.7-26.4 wt%), while late allanite has lower REYtotal concentrations (6.9-14.9 wt%). Titanite is abundant in most syenitic rocks (REYtotal 1.7-6.4 wt%); chevkinite-(Ce) occurs locally and contributes to an REY enrichment in contact aureoles between syenite and different lithologies. Apatite-enriched rocks in the SAC in part contain significantly higher REYtotal concentrations in apatite grains compared to those in apatite-mineralized pyroxenite, phoscorite and carbonatite from Phalaborwa.

Influence of heat treatments upon the mechanical properties and in vitro bioactivity of ZrO2-toughened MgO-CaO-SiO2-P2O5-CaF2 glass-ceramics.

PubMed

Li, Huan-Cai; Wang, Dian-Gang; Meng, Xiang-Guo; Chen, Chuan-Zhong

2014-09-01

Zirconia-toughened MgO-CaO-SiO2-P2O5-CaF2 glass-ceramics are prepared using sintering techniques, and a series of heat treatment procedures are designed to obtain a glass-ceramic with improved properties. The crystallization behavior, phase composition, and morphology of the glass-ceramics are characterized. The bending strength, elastic modulus, fracture toughness, and microhardness of the glass-ceramics are investigated, and the effect mechanism of heat treatments upon the mechanical properties is discussed. The bioactivity of glass-ceramics is then evaluated using the in vitro simulated body fluid (SBF) soaking test, and the mechanism whereby apatite forms on the glass-ceramic surfaces in the SBF solution is discussed. The results indicate that the main crystal phase of the G-24 sample undergoing two heat treatment procedures is Ca5(PO4)3F (fluorapatite), and those of the G-2444 sample undergoing four heat treatment procedures are Ca5(PO4)3F and β-CaSiO3 (β-wollastonite). The heat treatment procedures are found to greatly influence the mechanical properties of the glass-ceramic, and an apatite layer is induced on the glass-ceramic surface after soaking in the SBF solution.

Biological and medical significance of calcium phosphates.

PubMed

Dorozhkin, Sergey V; Epple, Matthias

2002-09-02

The inorganic part of hard tissues (bones and teeth) of mammals consists of calcium phosphate, mainly of apatitic structure. Similarly, most undesired calcifications (i.e. those appearing as a result of various diseases) of mammals also contain calcium phosphate. For example, atherosclerosis results in blood-vessel blockage caused by a solid composite of cholesterol with calcium phosphate. Dental caries result in a replacement of less soluble and hard apatite by more soluble and softer calcium hydrogenphosphates. Osteoporosis is a demineralization of bone. Therefore, from a chemical point of view, processes of normal (bone and teeth formation and growth) and pathological (atherosclerosis and dental calculus) calcifications are just an in vivo crystallization of calcium phosphate. Similarly, dental caries and osteoporosis can be considered to be in vivo dissolution of calcium phosphates. On the other hand, because of the chemical similarity with biological calcified tissues, all calcium phosphates are remarkably biocompatible. This property is widely used in medicine for biomaterials that are either entirely made of or coated with calcium phosphate. For example, self-setting bone cements made of calcium phosphates are helpful in bone repair and titanium substitutes covered with a surface layer of calcium phosphates are used for hip-joint endoprostheses and tooth substitutes, to facilitate the growth of bone and thereby raise the mechanical stability. Calcium phosphates have a great biological and medical significance and in this review we give an overview of the current knowledge in this subject.

PET fiber fabrics modified with bioactive titanium oxide for bone substitutes.

PubMed

Kokubo, Tadashi; Ueda, Takahiro; Kawashita, Masakazu; Ikuhara, Yuichi; Takaoka, Gikan H; Nakamura, Takashi

2008-02-01

A rectangular specimen of polyethylene terephthalate (PET) was soaked in a titania solution composed of titanium isopropoxide, water, ethanol and nitric acid at 25 degrees C for 1 h. An amorphous titanium oxide was formed uniformly on the surface of PET specimen, but did not form an apatite on its surface in a simulated body fluid (SBF) within 3 d. The PET plate formed with the amorphous titanium oxide was subsequently soaked in water or HCl solutions with different concentrations at 80 degrees C for different periods of time. The titanium oxide on PET was transformed into nano-sized anatase by the water treatment and into nano-sized brookite by 0.10 M HCl treatment at 80 degrees C for 8 d. The former did not form the apatite on its surface in SBF within 3 d, whereas the latter formed the apatite uniformly on its surface. Adhesive strength of the titanium oxide and apatite layers to PET plate was increased by pre-treatment of PET with 2 wt% NaOH solution at 40 degrees C for 2 h. A two-dimensional fabric of PET fibers 24 microm in diameter was subjected to the NaOH pre-treatment at 40 degrees C, titania solution treatment at 25 degrees C and subsequent 0.10 M HCl treatment at 80 degrees C. Thus treated PET fabric formed the apatite uniformly on surfaces of individual fibers constituting the fabric in SBF within 3 d. Two or three dimensional PET fabrics modified with the nano-sized brookite on surfaces of the individual fibers constituting the fabric by the present method are believed to be useful as flexible bone substitutes, since they could be integrated with living bone through the apatite formed on their constituent fibers.

­­­Experimental Quantifications of Radiation Damage Annealing and Helium Diffusion Kinetics in Apatite

NASA Astrophysics Data System (ADS)

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

2017-12-01

(U-Th)/He thermochronology in apatite requires a quantitative description of He diffusivity as a function of temperature and through geologic time. Although variability in diffusion kinetics across a range of natural apatite samples has revealed that higher concentrations of alpha-recoil radiation damage correlates with lower He diffusivity (i.e., at a given temperature, [1]), only one published study has experimentally quantified the effects of annealing for a single apatite specimen (Durango apatite, [2]). Although these effects have been incorporated into now widely applied numerical models, underlying assumptions in these models—in particular, that He diffusivity in all apatite crystals responds with the same rate of damage annealing—have been called into question, and further evaluation is warranted (e.g., [3], [4]). Here, we will describe a suite of experiments conducted on apatite from a single hand sample of granite from Sierra Nevada, CA as well as Durango apatite, to establish whether these two apatites with different chemical compositions and thermal pasts exhibit the same response to annealing conditions. Crystals from both samples were heated under vacuum to temperatures between 220 and 500 °C for 1, 10, 100 or 1000 hours. The samples were then irradiated with 220 MeV protons to produce spallation 3He, the diffusant used in subsequent step-heating degassing experiments. Our preliminary results indicate different minima in closure temperatures of 55 oC and 65 oC for the Durango and Sierra apatite, respectively, when exposed to sufficiently high temperatures (>350 oC) for durations > 1 hour, yet similar transitions from low diffusivities at T <200 oC (and higher activation energy, Ea) to higher diffusivity (lower Ea) across a range of experimental annealing temperatures and durations. We will interpret these results with a new model framework for describing the effects of annealing on diffusivity, and will discuss potential implications of our experimental results, the required assumptions in our analyses, and potential limitations of such empirical quantifications. References: [1] Shuster, D. et al. (2006), EPSL 294, 148-161; [2] Shuster, D., Farley, K. (2009), GCA 73 (1), 6183-6196; [3] Gautheron, C. et al. (2013), Chem. Geol. 351, 257-267; [4] Fox, M., Shuster, D. (2014), EPSL 397, 174-183.

Strontium isotope systematics of scheelite and apatite from the Felbertal tungsten deposit, Austria - results of in-situ LA-MC-ICP-MS analysis

NASA Astrophysics Data System (ADS)

Kozlik, Michael; Gerdes, Axel; Raith, Johann G.

2016-02-01

The in-situ Sr isotopic systematics of scheelite and apatite from the Felbertal W deposit and a few regional Variscan orthogneisses ("Zentralgneise") have been determined by LA-MC-ICP-MS. The 87Sr/86Sr ratios of scheelite and apatite from the deposit are highly radiogenic and remarkably scattering. In the early magmatic-hydrothermal scheelite generations (Scheelite 1 and 2) the 87Sr/86Sr ratios range from 0.72078 to 0.76417 and from 0.70724 to 0.76832, respectively. Metamorphic Scheelite 3, formed by recrystallisation and local mobilisation of older scheelite, is characterised by even higher 87Sr/86Sr values between 0.74331 and 0.80689. Statistics allows discriminating the three scheelite generations although there is considerable overlap between Scheelite 1 and 2; they could be mixtures of the same isotopic reservoirs. The heterogeneous and scattering 87Sr/86Sr ratios of the two primary scheelite generations suggest modification of the Sr isotope system due to fluid-rock interaction and isotopic disequilibrium. Incongruent release of 87Sr from micas in the Early Palaeozoic host rocks of the Habach Complex contributed to the solute budget of the hydrothermal fluids and may explain the radiogenic Sr isotope signature of scheelite. Spatially resolved analyses revealed isotopic disequilibrium even on a sub-mm scale within zoned Scheelite 2 crystals indicating scheelite growth in an isotopic dynamical hydrothermal system. Zoned apatite from the W mineralised Early Carboniferous K1-K3 orthogneiss in the western ore field yielded 87Sr/86Sr of 0.72044-0.74514 for the cores and 0.74535-0.77937 for the rims. Values of magmatic apatite cores from the K1-K3 orthogneiss are comparable to those of primary Scheelite 1; they are too radiogenic to be magmatic. The Sr isotopic composition of apatite cores was therefore equally modified during the hydrothermal mineralisation processes, therefore supporting the single-stage genetic model in which W mineralisation is associated with the intrusion of the K1-K3 metagranitoid at Felbertal. The subsequent regional metamorphic overprint of the deposit caused redistribution of 87Sr as a consequence of metamorphic reactions involving Rb and Sr-bearing minerals. Metamorphic Scheelite 3 and apatite rims (e.g., in the K1-K3 orthogneiss) generally became more radiogenic during this process. However, local recrystallisation of primary scheelite under closed conditions (without addition of 87Sr by the metamorphic fluid) is also documented. The latter process resulted in a homogenisation of the isotope composition of Scheelite 3. Further increase in 87Sr/86Sr ratios in Scheelite 3 and apatite rims is attributed to Late Alpine (?) metamorphic recrystallisation and redistribution of 87Sr by metamorphic fluids.

Surface modification of bioactive glass nanoparticles and the mechanical and biological properties of poly(L-lactide) composites.

PubMed

Liu, Aixue; Hong, Zhongkui; Zhuang, Xiuli; Chen, Xuesi; Cui, Yang; Liu, Yi; Jing, Xiabin

2008-07-01

Novel bioactive glass (BG) nanoparticles/poly(L-lactide) (PLLA) composites were prepared as promising bone-repairing materials. The BG nanoparticles (Si:P:Ca=29:13:58 weight ratio) of about 40nm diameter were prepared via the sol-gel method. In order to improve the phase compatibility between the polymer and the inorganic phase, PLLA (M(n)=9700Da) was linked to the surface of the BG particles by diisocyanate. The grafting ratio of PLLA was in the vicinity of 20 wt.%. The grafting modification could improve the tensile strength, tensile modulus and impact energy of the composites by increasing the phase compatibility. When the filler loading reached around 4 wt.%, the tensile strength of the composite increased from 56.7 to 69.2MPa for the pure PLLA, and the impact strength energy increased from 15.8 to 18.0 kJ m(-2). The morphology of the tensile fracture surface of the composite showed surface-grafted bioactive glass particles (g-BG) to be dispersed homogeneously in the PLLA matrix. An in vitro bioactivity test showed that, compared to pure PLLA scaffold, the BG/PLLA nanocomposite demonstrated a greater capability to induce the formation of an apatite layer on the scaffold surface. The results of marrow stromal cell culture revealed that the composites containing either BG or g-BG particles have much better biocompatibility compared to pure PLLA material.

Slow-Release Fertilizers For Plants

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Golden, D. C.

1995-01-01

Synthetic mineral provides growing plants with nutrients, including micronutrients. Dissolves slowly in moist soil or in hydroponic solution, releasing constituents. Mineral synthetic apatite into which nutrients calcium, phosphorous, iron, manganese, copper, zinc, molybdenum, chlorine, boron, and sulfur incorporated in form of various salts. Each pellet has homogeneous inorganic composition. Composition readily adjusted to meet precise needs of plant.

Elaboration, Rietveld refinements and vibrational spectroscopic study of Na₁-xKxCaPb₃(PO₄)₃ lacunar apatites (0 ⩽ x ⩽ 1).

PubMed

Lahrich, S; Elmhammedi, M A; Manoun, B; Tamraoui, Y; Mirinioui, F; Azrour, M; Lazor, P

2015-06-15

Synthesis of apatites, Na1-xKxCaPb3(PO4)3 0 ⩽ x ⩽ 1, with anion vacancy were carried out using solid state reactions. The solid solution of apatite-type structure crystallize in the hexagonal system, space group P63/m (No. 176). Rietveld refinements showed that around 90% of Pb(2+) cations are located in the (6h) sites, the left amount of Pb(2+) cations are located in the (4f) sites; 27-31% of Ca(2+) cations are located in the (6h) sites, the left amount of Ca(2+) cations are located in the (4f) sites. The ninefold coordination sites (4f) are also occupied by the K(+) and Na(+) monovalent ions. The structure can be described as built up from [PO4](3-) tetrahedra and Pb(2+)/Ca(2+) of sixfold coordination cavities (6h positions), which delimit void hexagonal tunnels running along [001]. These tunnels are connected by cations of mixed sites (4f) which are half occupied by Pb(2+)/Ca(2+) and half by Na(+)/K(+) mixed cations. The assignment of the observed frequencies in the Raman and infrared spectra is discussed on the basis of a unit cell group analysis and by comparison with other apatites. Vibrational spectra of all the compositions are similar and show some linear shifts of the frequencies as a function of the composition toward lower values due the substitutions of Na(+) by K(+) with a larger radius. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2018-05-08

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

On the mineral characteristics and geochemistry of the Florida phosphate of Four Corners and Hardee County mines

NASA Astrophysics Data System (ADS)

Baghdady, Ashraf R.; Howari, Fares M.; Al-Wakeel, Mohamed I.

2016-08-01

The Florida phosphate deposits in Four Corners and Hardee County mines are composed mainly of phosphate minerals and quartz in addition to subordinate proportions of feldspars, dolomite, calcite, gypsum, kaolinite, attapulgite and montmorillonite. These phosphorites contain three structurally different types of mudclasts: massive mudclasts, mudclasts with concentric structure and mudclasts consisting of agglomerates of apatite microparticles. The latter are represented by particles resembling phosphatized fossil bacteria associated with microbial filaments, and hollow apatite particles having surfacial coatings and connected to microbial filaments. The Florida phosphate particles are reworked and vary in mineral composition, color and shape. They are composed of a mixture of well-crystalline species including carbonate fluorapatite (francolite), carbonate apatite and fluorapatite. The color variation of the phosphate particles is related to difference in mineral composition, extent of diagenetic effects and reworking. The light-colored mudclasts are characterized by the presence of carbonate apatite and aluminum hydroxide phosphate minerals, whereas the dark mudclasts are rich in iron aluminum hydroxide phosphate minerals. The Florida phosphorites are suggested to be formed partially by authigenetic precipitation, replacement of the sea floor carbonate and diatomite, and microbial processes. With respect to elemental geochemistry, the analyzed particles contain small percentages of sulfur and iron which are related to the occurrence of pyrite. Traces of silica and alumina are recorded which may be attributed to the diagenetic. Some of the tested particles are relatively rich in phosphorous, fluorine, calcium, and magnesium, while poor in silicon, potassium and sulfur. Whereas, the bioclasts (especially teeth) are relatively rich in calcium, phosphorous and fluorine while poor in silicon, aluminum, magnesium and potassium. Hence, the microchemical analyses revealed that differential diagenesis affected mudclasts more than bioclasts. There is a complete compositional gradation between clay and phosphate particles which reflects their interaction. This involved kaolinitization of the phosphate particles, phosphatization of the clay mineral particles and production of silica.

Effects of surface-conditioning methods on shear bond strength of brackets bonded to different all-ceramic materials.

PubMed

Saraç, Y Şinasi; Külünk, Tolga; Elekdağ-Türk, Selma; Saraç, Duygu; Türk, Tamer

2011-12-01

The aims of this study were to investigate the effects of two surface-conditioning methods on the shear bond strength (SBS) of metal brackets bonded to three different all-ceramic materials, and to evaluate the mode of failure after debonding. Twenty feldspathic, 20 fluoro-apatite, and 20 leucite-reinforced ceramic specimens were examined following two surface-conditioning methods: air-particle abrasion (APA) with 25 μm Al(2)O(3) and silica coating with 30 μm Al(2)O(3) particles modified by silica. After silane application, metal brackets were bonded with light cure composite and then stored in distilled water for 1 week and thermocycled (×1000 at 5-55°C for 30 seconds). The SBS of the brackets was measured on a universal testing machine. The ceramic surfaces were examined with a stereomicroscope to determine the amount of composite resin remaining using the adhesive remnant index. Two-way analysis of variance, Tukey's multiple comparison test, and Weibull analysis were used for evaluation of SBS. The lowest SBS was with APA for the fluoro-apatite ceramic (11.82 MPa), which was not significantly different from APA for the feldspathic ceramic (13.58 MPa). The SBS for the fluoro-apatite ceramic was significantly lower than that of leucite-reinforced ceramic with APA (14.82 MPa). The highest SBS value was obtained with silica coating of the leucite-reinforced ceramic (24.17 MPa), but this was not significantly different from the SBS for feldspathic and fluoro-apatite ceramic (23.51 and 22.18 MPa, respectively). The SBS values with silica coating showed significant differences from those of APA. For all samples, the adhesive failures were between the ceramic and composite resin. No ceramic fractures or cracks were observed. Chairside tribochemical silica coating significantly increased the mean bond strength values.

Microstructured Electrolyte Membranes to Improve Fuel Cell Performance

NASA Astrophysics Data System (ADS)

Wei, Xue

Fuel cells, with the advantages of high efficiency, low greenhouse gas emission, and long lifetime are a promising technology for both portable power and stationary power sources. The development of efficient electrolyte membranes with high ionic conductivity, good mechanical durability and dense structure at low cost remains a challenge to the commercialization of fuel cells. This thesis focuses on exploring novel composite polymer membranes and ceramic electrolytes with the microstructure engineered to improve performance in direct methanol fuel cells (DMFCs) and solid oxide fuel cells (SOFCs), respectively. Polymer/particle composite membranes hold promise to meet the demands of DMFCs at lower cost. The structure of composite membranes was controlled by aligning proton conducting particles across the membrane thickness under an applied electric field. The field-induced structural changes caused the membranes to display an enhanced water uptake, proton conductivity, and methanol permeability in comparison to membranes prepared without an applied field. Although both methanol permeability and proton conductivity are enhanced by the applied field, the permeability increase is relatively lower than the proton conductivity improvement, which results in enhanced proton/methanol selectivity and improved DMFC performance. Apatite ceramics are a new class of fast ion conductors being studied as alternative SOFC electrolytes in the intermediate temperature range. An electrochemical/hydrothermal deposition method was developed to grow fully dense apatite membranes containing well-developed crystals with c-axis alignment to promote ion conductivity. Hydroxyapatite seed crystals were first deposited onto a metal substrate electrochemically. Subsequent ion substitution during the hydrothermal growth process promoted the formation of dense, fully crystalline films with microstructure optimal for ion transport. The deposition parameters were systematically investigated, such as reactant type, reagent concentration, solution pH, and reaction time. Dense apatite films were formed on palladium substrates that can serve as intermediate temperature fuel cell anodes. The novel apatite membrane structure is promising for fuel cell applications, as well as in improving the biocompatibility of orthopedic implants when coated on stainless steel or titanium substrates.

Vibrational investigation of calcium-silicate cements for endodontics in simulated body fluids

NASA Astrophysics Data System (ADS)

Taddei, Paola; Modena, Enrico; Tinti, Anna; Siboni, Francesco; Prati, Carlo; Gandolfi, Maria Giovanna

2011-05-01

Calcium-silicate MTA (Mineral Trioxide Aggregate) cements have been recently developed for oral and endodontic surgery. This study was aimed at investigating commercial (White ProRoot MTA, White and Grey MTA-Angelus) and experimental (wTC-Bi) accelerated calcium-silicate cements with regards to composition, hydration products and bioactivity upon incubation for 1-28 days at 37 °C, in Dulbecco's Phosphate Buffered Saline (DPBS). Deposits on the surface of the cements and the composition changes during incubation were investigated by micro-Raman and ATR/FT-IR spectroscopy, and pH measurements. Vibrational techniques disclosed significant differences in composition among the unhydrated cements, which significantly affected the bioactivity as well as pH, and hydration products of the cements. After one day in DPBS, all the cements were covered by a more or less homogeneous layer of B-type carbonated apatite. The experimental cement maintained a high bioactivity, only slightly lower than the other cements and appears a valid alternative to commercial cements, in view of its adequate setting time properties. The bioactivity represents an essential property to favour bone healing and makes the calcium-silicate cements the gold standard materials for root-apical endodontic surgery.

Enhancing the mechanical and in vitro performance of robocast bioglass scaffolds by polymeric coatings: Effect of polymer composition.

PubMed

Motealleh, Azadeh; Eqtesadi, Siamak; Pajares, Antonia; Miranda, Pedro

2018-08-01

The effect of different polymeric coatings, including natural and synthetic compositions, on the mechanical performance of 45S5 bioglass robocast scaffolds is systematically analyzed in this work. Fully amorphous 45S5 bioglass robocast scaffolds sintered at 550 °C were impregnated with natural (gelatin, alginate, and chitosan) and synthetic (polycaprolactone, PCL and poly-lactic acid, PLA) polymers through a dip-coating process. Mechanical enhancement provided by these coatings in terms of both compressive strength and strain energy density was evaluated. Natural polymers, in general, and chitosan, in particular, were found to produce the greater reinforcement. The effect of these coatings on the in vitro bioactivity and degradation behavior of 45S5 bioglass robocast scaffolds was also investigated through immersion tests in simulated body fluid (SBF). Coatings from natural polymers, especially chitosan, are shown to have a positive effect on the bioactivity of 45S5 bioglass, accelerating the formation of an apatite-like layer. Besides, most coating compositions reduced the degradation (weight loss) rate of the scaffold, which has a positive impact on the evolution of their mechanical properties. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sensitivity of novel silicate and borate-based glass structures on in vitro bioactivity and degradation behaviour.

PubMed

Mancuso, Elena; Bretcanu, Oana; Marshall, Martyn; Dalgarno, Kenneth W

2017-10-15

Three novel glass compositions, identified as NCL2 (SiO 2 -based), NCL4 (B 2 O 3 -based) and NCL7 (SiO 2 -based), along with apatite-wollastonite (AW) were processed to form sintered dense pellets, and subsequently evaluated for their in vitro bioactive potential, resulting physico-chemical properties and degradation rate. Microstructural analysis showed the carbonated hydroxyapatite (HCA) precipitate morphology following SBF testing to be composition-dependent. AW and the NCL7 formulation exhibited greater HCA precursor formation than the NCL2 and NCL4-derived pellets. Moreover, the NCL4 borate-based samples showed the highest biodegradation rate; with silicate-derived structures displaying the lowest weight loss after SBF immersion. The results of this study suggested that glass composition has significant influence on apatite-forming ability and also degradation rate, indicating the possibility to customise the properties of this class of materials towards the bone repair and regeneration process.

Adsorption and conformational modification of fibronectin and fibrinogen adsorbed on hydroxyapatite. A QCM-D study.

PubMed

Fernández-Montes Moraleda, Belén; San Román, Julio; Rodríguez-Lorenzo, Luís M

2016-10-01

Hydroxyapatite is a bioactive ceramic frequently used for bone engineering/replacement. One of the parameters that influence the biological response to implanted materials is the conformation of the first adsorbed protein layer. In this work, the adsorption and conformational changes of two fibroid serum proteins; fibronectin and fibrinogen adsorbed onto four different hydroxyapatite powders are studied with a Quartz Crystal Microbalance with Dissipation (QCM-D). Each of the calcined apatites adsorbs less protein than their corresponding synthesized samples. Adsorption on synthesized samples yields always an extended conformation whereas a reorganization of the layer is observed for the calcined samples. Fg acquires a "Side on" conformation in all the samples at the beginning of the experiment except for one of the synthesized samples where an "End-on" conformation is obtained during the whole experiment. The Extended conformation is the active conformation for Fn. This conformation is favored by apatites with large specific surface area (SSA) and on highly concentrated media. Apatite surface features should be considered in the selection or design of materials for bone regeneration, since it is possible to control the conformation mode of attachment of Fn and Fg by an appropriate selection of them. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2585-2594, 2016. © 2016 Wiley Periodicals, Inc.

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 fractionation are challenges in apatite U-Pb dating by LA-ICPMS. Isochron-based approaches to common Pb correction require a significant spread in common Pb / radiogenic Pb ratios. This is not usually possible on individual detrital apatite grains and hence the 204Pb-, 207Pb- and 208Pb-correction methods are preferred. Uranium concentration measurements by ICPMS employ large peak jumps (the internal standard is a Ca isotope) which require a quadrupole or a rapid-scanning magnetic-sector LA-ICPMS system. These single-collector instruments require a prohibitively long dwell time on the low intensity 204Pb peak to measure it accurately and hence the 207Pb- and 208Pb-correction methods are preferred. Uranium-concentration measurements in fission-track dating require well-constrained ablation depths during analysis and hence spot analyses are preferred to rastering. Laser-induced U-Pb fractionation is corrected for by sample-standard bracketing using a variety of apatite standards (Durango, Emerald Lake, Fish Canyon Tuff, Kovdor, Otter Lake and McClure Mountain syenite). Of these, Emerald Lake (Chew et al., 2011) and McClure Mountain syenite apatite are recommended as primary standards with Durango apatite making a suitable secondary standard. Offline data-reduction uses custom-written software for ICPMS data processing (the UPbICP package of Ray Donelick) or the freeware IOLITE data-reduction package of Paton et al. (2010).

High-Silica Hadean Crust

NASA Astrophysics Data System (ADS)

Boehnke, P.; Bell, E. A.; Stephan, T.; Trappitsch, R.; Keller, C. B.; Pardo, O. S.; Davis, A. M.; Harrison, M.; Pellin, M. J.

2017-12-01

Understanding Hadean (>4 Ga) Earth requires knowledge of its crust. The composition of the crust and volatiles migrating through it directly influence the makeup of the atmosphere, the composition of seawater, and nutrient availability. Despite its importance, there is little known and less agreed upon regarding the nature of the Hadean crust. For example, compilations of whole-rock elemental abundances suggest to some a dominantly mafic crust, while the geochemistry and inclusions in Hadean zircons suggest the existence of felsic crust and possibly even life. We address this question by analyzing the 87Sr/86Sr ratio of apatite inclusions in Archean zircons from Nuvvuagittuq, Canada, using the Chicago Instrument for Laser Ionization (CHILI). Our results show that the protolith of the Nuvvuagittuq zircons had formed a reservoir with a high (>1) Rb/Sr ratio by 4.4 Ga. The Rb/Sr ratio of this reservoir is too high to be explained by only a mafic crust or a terrestrial "KREEP" layer. Indeed, high Rb/Sr ratios only occur in high SiO2 rocks, and our data suggests that the 4.4 Ga Nuvvuagittuq source was felsic rather than mafic. Specifically, our results suggest that the 4.4 Ga Nuvvuagittuq protolith was of rhyolitic compositions. This finding implies that the early crust had a broad range of igneous rocks, extending from mafic to highly silicic compositions.

Bioactive Glasses with Low Ca/P Ratio and Enhanced Bioactivity

PubMed Central

Araújo, Marco; Miola, Marta; Baldi, Giovanni; Perez, Javier; Verné, Enrica

2016-01-01

Three new silica-based glass formulations with low molar Ca/P ratio (2–3) have been synthesized. The thermal properties, the crystalline phases induced by thermal treatments and the sintering ability of each glass formulation have been investigated by simultaneous differential scanning calorimetry-thermogravimetric analysis (DSC-TG), X-ray diffraction (XRD) and hot stage microscopy (HSM). The glasses exhibited a good sintering behavior, with two samples achieving shrinkage of 85%–95% prior to crystallization. The bioactivity of the glasses in simulated body fluid (SBF) has been investigated by performing XRD and Fourier transform infrared spectroscopy (FTIR) on the samples prior and after immersion. The glasses with lower MgO contents were able to form a fully crystallized apatite layer after three days of immersion in simulated body fluid (SBF), while for the glass exhibiting a higher MgO content in its composition, the crystallization of the Ca–P layer was achieved after seven days. The conjugation of these properties opens new insights on the synthesis of highly bioactive and mechanically strong prosthetic materials. PMID:28773350

Citrate bridges between mineral platelets in bone

PubMed Central

Davies, Erika; Müller, Karin H.; Wong, Wai Ching; Pickard, Chris J.; Reid, David G.; Skepper, Jeremy N.; Duer, Melinda J.

2014-01-01

We provide evidence that citrate anions bridge between mineral platelets in bone and hypothesize that their presence acts to maintain separate platelets with disordered regions between them rather than gradual transformations into larger, more ordered blocks of mineral. To assess this hypothesis, we take as a model for a citrate bridging between layers of calcium phosphate mineral a double salt octacalcium phosphate citrate (OCP-citrate). We use a combination of multinuclear solid-state NMR spectroscopy, powder X-ray diffraction, and first principles electronic structure calculations to propose a quantitative structure for this material, in which citrate anions reside in a hydrated layer, bridging between apatitic layers. To assess the relevance of such a structure in native bone mineral, we present for the first time, to our knowledge, 17O NMR data on bone and compare them with 17O NMR data for OCP-citrate and other calcium phosphate minerals relevant to bone. The proposed structural model that we deduce from this work for bone mineral is a layered structure with thin apatitic platelets sandwiched between OCP-citrate–like hydrated layers. Such a structure can explain a number of known structural features of bone mineral: the thin, plate-like morphology of mature bone mineral crystals, the presence of significant quantities of strongly bound water molecules, and the relatively high concentration of hydrogen phosphate as well as the maintenance of a disordered region between mineral platelets. PMID:24706850

Amyloid-like ribbons of amelogenins in enamel mineralization

DOE PAGES

Carneiro, Karina M. M.; Zhai, Halei; Zhu, Li; ...

2016-03-24

We report that enamel, the outermost layer of teeth, is an acellular mineralized tissue that cannot regenerate; the mature tissue is composed of high aspect ratio apatite nanocrystals organized into rods and inter-rod regions. Amelogenin constitutes 90% of the protein matrix in developing enamel and plays a central role in guiding the hierarchical organization of apatite crystals observed in mature enamel. To date, a convincing link between amelogenin supramolecular structures and mature enamel has yet to be described, in part because the protein matrix is degraded during tissue maturation. Here we show compelling evidence that amelogenin self-assembles into an amyloid-likemore » structure in vitro and in vivo. We show that enamel matrices stain positive for amyloids and we identify a specific region within amelogenin that self-assembles into β-sheets. Lastly, we propose that amelogenin nanoribbons template the growth of apatite mineral in human enamel. This is a paradigm shift from the current model of enamel development.« less

Mechanical properties and in vitro bioactivity of Ca5(PO4)2SiO4 bioceramic.

PubMed

Lu, Wenhao; Duan, Wei; Guo, Yaping; Ning, Congqin

2012-02-01

Pure Ca(5)(PO(4))(2)SiO(4) bioceramic was first prepared by a sol-gel method using triethyl phosphate, tetraethoxysilane, and calcium nitrate tetrahydrate as original materials. Simulated body fluid (SBF) immersion tests revealed that Ca(5)(PO(4))(2)SiO(4) samples had a greater in vitro apatite-forming ability than hydroxyapatite (HA). After soaking Ca(5)(PO(4))(2)SiO(4) samples in the SBF for 1 day, bone-like apatite precipitated on the surfaces and the apatite layer became thicker with increasing the soaking time. However, few bone-like apatites precipitated on the HA samples even after soaking in the SBF for 7 days. The good in vitro bioactivity of Ca(5)(PO(4))(2)SiO(4) samples was attributed to the silanol (Si-OH) groups and greater solubility of Ca(5)(PO(4))(2)SiO(4). In addition, hot-pressed Ca(5)(PO(4))(2)SiO(4) ceramic exhibited lower bending strength and elastic modulus than hot-pressed HA, since the former had a lower relative density than the latter. The results have shown that Ca(5)(PO(4))(2)SiO(4) is a potential candidate material for bone repair. © The Author(s), 2010.

Influence of substituting B2O3 for CaF2 on the bonding behaviour to bone of glass-ceramics containing apatite and wollastonite.

PubMed

Kitsugi, T; Yamamuro, T; Nakamura, T; Yoshii, S; Kokubo, T; Takagi, M; Shibuya, T

1992-01-01

Glass-ceramics containing crystalline oxy-fluoroapatite (Ca10(PO4)6(O,F2)) and wollastonite (CaSiO3) (designated AWGC) are reported to have a fairly high mechanical strength as well as the capability of forming a chemical bond with bone tissue. The chemical composition is MgO 4.6, CaO 44.9, SiO2 34.2, P2O5 16.3, and CaF2 0.5 in weight ratio. In this study the influence of substituting B2O3 for CaF2 on the bonding behaviour of glass-ceramics containing apatite and wollastonite to bone tissue was investigated. Two kinds of glass-ceramics containing apatite and wollastonite were prepared. CaF2 0.5 was replaced with B2O3 at 0.5 and 2.0 in weight ratio (designated AWGC-0.5B and AWGC-2.0B). Rectangular ceramic plates (15 x 10 x 2 mm, abraded with No. 2000 alumina powder) were implanted into a rabbit tibia. The failure load, when an implant detached from the bone, or the bone itself broke, was measured. The failure load of AWGC-0.5B was 8.00 +/- 1.82 kg at 10 weeks after implantation and 8.16 +/- 1.36 kg at 25 weeks after implantation. The failure load of AWGC-2B was 8.08 +/- 1.70 kg at 10 weeks after implantation and 9.92 +/- 2.46 kg at 25 weeks after implantation. None of the loads for the two kinds of glass-ceramics decreased as time passed. Giemsa surface staining and contact microradiography revealed direct bonding between glass-ceramics and bone. SEM-EPMA showed a calcium-phosphorus rich layer (reaction zone) at the interface of ceramics and bone tissue. The thickness of the reaction zone was 10 to -15 microns and did not increase as time passed.(ABSTRACT TRUNCATED AT 250 WORDS)

Hydro-geochemical modeling of the spatial and the temporal geochemical variations of the granitic Strengbach catchment springs (Vosges massif, France)

NASA Astrophysics Data System (ADS)

Ackerer, Julien; Chabaux, François; Lucas, Yann; Pierret, Marie Claire; Viville, Daniel; Fritz, Bertrand; Clement, Alain; Beaulieu, Emilie; Negrel, Philippe

2017-04-01

Regular analysis of the major element concentrations in waters from springs emerging on the Strengbach catchment is made for more than 20 years (OHGE, Observatoire Hydro-Géochimique de l'Environnement). These data confirm the spatial variability of geochemical characteristics of the Strengbach springs linked, at least partly, to the lithological variability of the substratum (Pierret et al., 2014). The data also indicate that at the first order, the geochemical fluxes exported from each spring are mainly linked to the spring discharges, without significant variations of the relationships linking these two parameters between 1990 and 2010. There is also no observation of significant variations for the dissolved silica and for most of the cationic concentrations with time. Only a significant decrease of the Ca concentrations is observed for the Strengbach springs from 1990 to 2010. Numerical simulations, performed with the KIRMAT hydro-geochemical code, show that such a decrease can be considered as the response in the "bedrock" of the water-rock interactions to the variations of the soil solution chemical compositions recorded over the last 20 years, marked by a significant increase of pH and decrease of Ca concentrations. In particular, the modeling results show that the Ca concentration decrease is controlled by the couple apatite/clays, and that significant modifications of the apatite dissolution rate and clay compositions occurred between 1990 and 2010. This study shows that the temporal evolution of the Strengbach spring chemistry cannot be explained by the only variations of the clay mineral compositions, i.e. a modification of the chemical composition of the precipitated clays or a modification of the ionic exchange capacity of the clay minerals, but that it is definitely the interrelations between the apatite and the clay minerals that are involved.

Abnormal arrangement of a collagen/apatite extracellular matrix orthogonal to osteoblast alignment is constructed by a nanoscale periodic surface structure.

PubMed

Matsugaki, Aira; Aramoto, Gento; Ninomiya, Takafumi; Sawada, Hiroshi; Hata, Satoshi; Nakano, Takayoshi

2015-01-01

Morphological and directional alteration of cells is essential for structurally appropriate construction of tissues and organs. In particular, osteoblast alignment is crucial for the realization of anisotropic bone tissue microstructure. In this article, the orientation of a collagen/apatite extracellular matrix (ECM) was established by controlling osteoblast alignment using a surface geometry with nanometer-sized periodicity induced by laser ablation. Laser irradiation induced self-organized periodic structures (laser-induced periodic surface structures; LIPSS) with a spatial period equal to the wavelength of the incident laser on the surface of biomedical alloys of Ti-6Al-4V and Co-Cr-Mo. Osteoblast orientation was successfully induced parallel to the grating structure. Notably, both the fibrous orientation of the secreted collagen matrix and the c-axis of the produced apatite crystals were orientated orthogonal to the cell direction. To the best of our knowledge, this is the first report demonstrating that bone tissue anisotropy is controllable, including the characteristic organization of a collagen/apatite composite orthogonal to the osteoblast orientation, by controlling the cell alignment using periodic surface geometry. Copyright © 2014 Elsevier Ltd. All rights reserved.

Petrography and the REE-composition of apatite in the Paleoproterozoic Pilgujärvi Sedimentary Formation, Pechenga Greenstone Belt, Russia

NASA Astrophysics Data System (ADS)

Joosu, Lauri; Lepland, Aivo; Kreitsmann, Timmu; Üpraus, Kärt; Roberts, Nick M. W.; Paiste, Päärn; Martin, Adam P.; Kirsimäe, Kalle

2016-08-01

The first globally significant phosphorous-rich deposits appear in the Paleoproterozoic at around 2 Ga, however, the specific triggers leading to apatite precipitation are debated. We examine phosphorous-rich rocks (up to 8 wt% P2O5) in 1.98-1.92 Ga old Pilgujärvi Sedimentary Formation, Pechenga Greenstone Belt, Russia. Phosphates in these rocks occur as locally derived and resedimented sand-to-gravel/pebble sized grains consisting of apatite-cemented muddy sediments. Phosphatic grains can be subdivided into four petrographic types (A-D), each has a distinct REE signature reflecting different early-to-late diagenetic conditions and/or metamorphic overprint. Pyrite containing petrographic type D, which typically has a flat REE pattern, negative Ce anomaly and positive Eu anomaly, is the best preserved of the four types and best records conditions present during apatite precipitation. Type D phosphatic grains precipitated under (sub)oxic basinal conditions with a significant hydrothermal influence. These characteristics are similar to Zaonega Formation phosphates of NW Russia's Onega Basin, and consistent with phosphogenesis triggered by the development of anoxic(sulfidic)-(sub)oxic redoxclines at shallow sediment depth during the Paleoproterozoic.

Mineral ecophysiological evidence for biogeochemical cycles in 2461-2495 million year old banded iron formations (BIF).

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

Li, Y; Konhauser, Dr, Kurt; Cole, David

2011-01-01

The phosphorus composition of banded-iron formations (BIFs) has been used as a proxy for Precambrian seawater composition and the paleoeredox state of Earth's surface environment. However, it is unclear whether the phosphorus in BIFs originally entered the sediment as a sorbed component of the iron oxyhydroxide particles, or whether it was incorporated into the biomass of marine phytoplankton. We conducted high-resolution mineral analyses and report here the first detection of an Fe(III) acetate salt, as well as nanocrystals of apatite in association with magnetite, in the 2.48 Ga Dales Gorge Member of the Brockman Iron Formation (a BIF), Hamersley, Westernmore » Australia. The clusters of apatite are similar in size and morphology to biogenic apatite crystals resulting from biomass decay in Phanerozoic marine sediments, while the formation of an Fe(III) acetate salt and magnetite not only implies the original presence of biomass in the BIF sediments, but also that organic carbon likely served as an electron donor during bacterial Fe(III) reduction. This study is important because it suggests that phytoplankton may have played a key role in the transfer of phosphorus (and other trace elements) from the photic zone to the seafloor.« less

Crystallinity and compositional changes in carbonated apatites: Evidence from 31P solid-state NMR, Raman, and AFM analysis

NASA Astrophysics Data System (ADS)

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 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.

Tricalcium phosphate-Fluorapatite as bone tissue engineering: Evaluation of bioactivity and biocompatibility.

PubMed

Taktak, Rym; Elghazel, Achwek; Bouaziz, Jamel; Charfi, Slim; Keskes, Hassib

2018-05-01

Biocomposites consisting of β Tricalcium phosphate (β-TCP) with 26.52% Fluorapatite (Fap) were elaborated and characterized in order to evaluate it potential application in bone graft substitute. Bioactivity was determined with in vitro tests by immersion of samples in simulated fluid body for several periods of times. The SEM, EDS and Atomic Absorption Spectroscopy showed the deposition of apatite layer on the surface of samples showing a good bioactivity. However, after 6days of soaking, the dissolution rate of Ca 2+ and PO 4 3- decreased which due probably to the improvement of crystallization of the apatite layer. These findings agree with those observed after 6weeks postimplantation of prepared macroporous scaffolds in rabbits. All histological observations of the preliminary in vivo study in the tibia of rabbits proved the biocompatibility and the resorption of the investigated bioceramic. In contrast, the implantation period will have to be optimized by further extensive animal experiments. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydroxyapatite-chitosan based bioactive hybrid biomaterials with improved mechanical strength

NASA Astrophysics Data System (ADS)

Zima, A.

2018-03-01

Composites consisting of hydroxyapatite (HA) and chitosan (CTS) have recently been intensively studied. In this work, a novel inorganic-organic (I/O) HA/CTS materials in the form of granules were prepared through a simple solution-based chemical method. During the synthesis of these hybrids, the electrostatic complexes between positively charged, protonated amine groups of chitosan and the negative phosphate species (HPO42 - and H2PO4-) were formed. Our biocomposites belong to the class I of hybrids, which was confirmed by FTIR studies. XRD analysis revealed that the obtained materials consisted of hydroxyapatite as the only crystalline phase. Homogeneous dispersion of the components in HA/CTS composites was confirmed. The use of 17 wt% and 23 wt% of chitosan resulted in approximately 12-fold and 16-fold increase in the compressive strength of HA/CTS as compared to the non-modified HA material. During incubation of the studied materials in SBF, pH of the solution remained close to the physiological one. Formation of apatite layer on their surfaces indicated bioactive nature of the developed biomaterials.

A unified in vitro evaluation for apatite-forming ability of bioactive glasses and their variants.

PubMed

Maçon, Anthony L B; Kim, Taek B; Valliant, Esther M; Goetschius, Kathryn; Brow, Richard K; Day, Delbert E; Hoppe, Alexander; Boccaccini, Aldo R; Kim, Ill Yong; Ohtsuki, Chikara; Kokubo, Tadashi; Osaka, Akiyoshi; Vallet-Regí, Maria; Arcos, Daniel; Fraile, Leandro; Salinas, Antonio J; Teixeira, Alexandra V; Vueva, Yuliya; Almeida, Rui M; Miola, Marta; Vitale-Brovarone, Chiara; Verné, Enrica; Höland, Wolfram; Jones, Julian R

2015-02-01

The aim of this study was to propose and validate a new unified method for testing dissolution rates of bioactive glasses and their variants, and the formation of calcium phosphate layer formation on their surface, which is an indicator of bioactivity. At present, comparison in the literature is difficult as many groups use different testing protocols. An ISO standard covers the use of simulated body fluid on standard shape materials but it does not take into account that bioactive glasses can have very different specific surface areas, as for glass powders. Validation of the proposed modified test was through round robin testing and comparison to the ISO standard where appropriate. The proposed test uses fixed mass per solution volume ratio and agitated solution. The round robin study showed differences in hydroxyapatite nucleation on glasses of different composition and between glasses of the same composition but different particle size. The results were reproducible between research facilities. Researchers should use this method when testing new glasses, or their variants, to enable comparison between the literature in the future.

The limiting layer of fish scales: Structure and properties

DOE PAGES

Arola, D.; Murcia, S.; Stossel, M.; ...

2017-12-14

Fish scales serve as a flexible natural armor that have received increasing attention across the materials community. Most efforts in this area have focused on the composite structure of the predominately organic elasmodine, and limited work addresses the highly mineralized external portion known as the Limiting Layer (LL). This coating serves as the first barrier to external threats and plays an important role in resisting puncture. Here in this investigation the structure, composition and mechanical behavior of the LL were explored for three different fish, including the arapaima (Arapaima gigas), the tarpon (Megalops atlanticus) and the carp (Cyprinus carpio). Themore » scales of these three fish have received the most attention within the materials community. Features of the LL were evaluated with respect to anatomical position to distinguish site-specific functional differences. Results show that there are significant differences in the surface morphology of the LL from posterior and anterior regions in the scales, and between the three fish species. The calcium to phosphorus ratio and the mineral to collagen ratios of the LL are not equivalent among the three fish. Finally, results from nanoindentation showed that the LL of tarpon scales is the hardest, followed by the carp and the arapaima and the differences in hardness are related to the apatite structure, possibly induced by the growth rate and environment of each fish.« less

The limiting layer of fish scales: Structure and properties

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

Arola, D.; Murcia, S.; Stossel, M.

Fish scales serve as a flexible natural armor that have received increasing attention across the materials community. Most efforts in this area have focused on the composite structure of the predominately organic elasmodine, and limited work addresses the highly mineralized external portion known as the Limiting Layer (LL). This coating serves as the first barrier to external threats and plays an important role in resisting puncture. Here in this investigation the structure, composition and mechanical behavior of the LL were explored for three different fish, including the arapaima (Arapaima gigas), the tarpon (Megalops atlanticus) and the carp (Cyprinus carpio). Themore » scales of these three fish have received the most attention within the materials community. Features of the LL were evaluated with respect to anatomical position to distinguish site-specific functional differences. Results show that there are significant differences in the surface morphology of the LL from posterior and anterior regions in the scales, and between the three fish species. The calcium to phosphorus ratio and the mineral to collagen ratios of the LL are not equivalent among the three fish. Finally, results from nanoindentation showed that the LL of tarpon scales is the hardest, followed by the carp and the arapaima and the differences in hardness are related to the apatite structure, possibly induced by the growth rate and environment of each fish.« less

Advances in surfaces and osseointegration in implantology. Biomimetic surfaces

PubMed Central

Albertini, Matteo; Fernandez-Yague, Marc; Lázaro, Pedro; Herrero-Climent, Mariano; Bullon, Pedro; Gil, Francisco-Javier

2015-01-01

The present work is a revision of the processes occurring in osseointegration of titanium dental implants according to different types of surfaces -namely, polished surfaces, rough surfaces obtained from subtraction methods, as well as the new hydroxyapatite biomimetic surfaces obtained from thermochemical processes. Hydroxyapatite’s high plasma-projection temperatures have proven to prevent the formation of crystalline apatite on the titanium dental implant, but lead to the formation of amorphous calcium phosphate (i.e., with no crystal structure) instead. This layer produce some osseointegration yet the calcium phosphate layer will eventually dissolve and leave a gap between the bone and the dental implant, thus leading to osseointegration failure due to bacterial colonization. A new surface -recently obtained by thermochemical processes- produces, by crystallization, a layer of apatite with the same mineral content as human bone that is chemically bonded to the titanium surface. Osseointegration speed was tested by means of minipigs, showing bone formation after 3 to 4 weeks, with the security that a dental implant can be loaded. This surface can be an excellent candidate for immediate or early loading procedures. Key words:Dental implants, implants surfaces, osseointegration, biomimetics surfaces. PMID:25662555

Preliminary research on a novel bioactive silicon doped calcium phosphate coating on AZ31 magnesium alloy via electrodeposition.

PubMed

Qiu, Xun; Wan, Peng; Tan, Lili; Fan, Xinmin; Yang, Ke

2014-03-01

A silicon doped calcium phosphate coating was obtained successfully on AZ31 alloy substrate via pulse electrodeposition. A novel dual-layer structure was observed with a porous lamellar-like and outer block-like apatite layer. In vitro immersion tests were adopted in simulated body fluid within 28 days of immersion. Slow degradation rate obtained from weight loss was observed for the Si-doped Ca-P coating, which was also consistent with the results of electrochemical experiments showing an enhanced corrosion resistance for the coating. Further formation of an apatite-like layer on the surface after immersion proved better integrity and biomineralization performance of the coating. Biological characterization was carried out for viability, proliferation and differentiation of MG63 osteoblast-like cells. The coating showed a good cell growth and an enhanced cell proliferation. Moreover, an increased activity of osteogenic marker ALP was found. All the results demonstrated that the Si-doped calcium phosphate was perspective to be used as a coating for magnesium alloy implants to control the degradation rate and enhance the bioactivity, which would facilitate the rapidity of bone tissue repair. Copyright © 2013 Elsevier B.V. All rights reserved.

Parent zonation in thermochronometers - resolving complexity revealed by ID-TIMS U-Pb dates and implications for the application of decay-based thermochronometers

NASA Astrophysics Data System (ADS)

Navin Paul, Andre; Spikings, Richard; Chew, David; Daly, J. Stephen; Ulyanov, Alexey

2017-04-01

High temperature (>350℃) U-Pb thermochronometers primarily use accessory minerals such as apatite, titanite and rutile, and assume that daughter isotopes are lost by thermally activated volume diffusion while the parent remains immobile. Studies exploiting such behaviour have been successfully used to reconstruct thermal histories spanning several hundred million years (e.g. Cochrane et al., 2014). However, outliers in date (ID-TIMS) vs diffusion length space are frequently observed, and grains are frequently found to be either too young or too old for expected thermal history solutions using the diffusion data of Cherniak et al. (2010). These deviations of single grain apatite U-Pb dates from expected behaviour could be caused by a combination of i) metamorphic (over-)growth, ii) fluid-aided Pb mobilisation during alteration/recrystallization, iii) parent isotope zonation, iv) metamictisation, and v) changes in diffusion length with time (e.g. fracturing). We present a large data set from the northern Andes of South America, where we compare apatite U-Pb ID-TIMS-(TEA) data with LA-ICP-MS element maps and in-situ apatite U-Pb LA-(MC)-ICP-MS dates. These are combined with U-Pb zircon and 40Ar/39Ar (muscovite) data to attempt to distinguish between thermally activated volume diffusion and secondary overgrowth/recrystallization. We demonstrate that in young (e.g. Phanerozoic) apatites that have not recrystallized or experienced metasomatic overgrowths, U-Pb dates are dominantly controlled by volume diffusion and intra-crystal uranium zonation. This implies that ID-TIMS analyses of apatites with zoned parent isotope distributions will not usually recover accurate thermal history solutions, and an in-situ dating method is required. Recovering the uranium distribution during in-situ analysis provides a means to account for parent zonation, substantially increasing the accuracy of the modelled t-T-paths. We present in-situ data from apatites where scatter in date v diffusion length scale is observed and compare t-T-paths from single grain and in-situ modelling. Modelling of in-situ data will further show if all apatites from a single hand specimen record the same thermal history using Cherniak et al. (2010) diffusion data, or if the Pb-in-apatite diffusion parameters are a function of composition. U zonation is ubiquitous in the studied rocks (Triassic apatites extracted from peraluminous leucosomes), implying that these conclusions may also apply to lower temperature thermochronometers that are based on uranium decay, such as (U-Th)/He dating.

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 polyphosphate species were detected by Raman and IR spectroscopy. The oxygen isotope data of the reactants and products will also be presented. The possibility that carbonate acts as an intermediate reagent, transferring the oxygen from water to phosphate in biological apatite mineral formation may explain why biological apatite exhibits a significant carbonate content, and how this mineral is formed with an insignificant hydroxyl content. 1 Kohn, M.J., and Cerling, T.E. Rev Mineral Geochem 2002 (48) 455 2 Kolodny, Y., Luz, B., Navon, O. Earth Planet Sci Lett 1983 (64) 398 3 Blake, R.E., O'Neil, J.R., Garcia, G.A. Geochim et Cosmochim Acta 1997 (61) 4411 4 Blake, R.E., Alt, J.C., and Martini, A.M. PNAS 2001 (98) 2148-2153 5 Liang, Y., and Blake, R.E. Geochim Cosmochim Acta 2009 (73) 3782) 6 Pasteris, J.D. et al. Biomaterials 2004 (35) 229 7 Omelon et al., PLoS ONE 2009 4(5), e5634

Biomimetic scaffolds based on hydroxyapatite nanorod/poly(D,L) lactic acid with their corresponding apatite-forming capability and biocompatibility for bone-tissue engineering.

PubMed

Nga, Nguyen Kim; Hoai, Tran Thanh; Viet, Pham Hung

2015-04-01

This study presents a facile synthesis of biomimetic hydroxyapatite nanorod/poly(D,L) lactic acid (HAp/PDLLA) scaffolds with the use of solvent casting combined with a salt-leaching technique for bone-tissue engineering. Field emission scanning electron microscopy, Fourier transform infrared spectroscopy, and energy-dispersive X-ray spectroscopy were used to observe the morphologies, pore structures of synthesized scaffolds, interactions between hydroxyapatite nanorods and poly(D,L) lactic acid, as well as the compositions of the scaffolds, respectively. Porosity of the scaffolds was determined using the liquid substitution method. Moreover, the apatite-forming capability of the scaffolds was evaluated through simulated body fluid (SBF) incubation tests, whereas the viability, attachment, and distribution of human osteoblast cells (MG 63 cell line) on the scaffolds were determined through alamarBlue assay and confocal laser microscopy after nuclear staining with 4',6-diamidino-2-phenylindole and actin filaments of a cytoskeleton with Oregon Green 488 phalloidin. Results showed that hydroxyapatite nanorod/poly(D,L) lactic acid scaffolds that mimic the structure of natural bone were successfully produced. These scaffolds possessed macropore networks with high porosity (80-84%) and mean pore sizes ranging 117-183 μm. These scaffolds demonstrated excellent apatite-forming capabilities. The rapid formation of bone-like apatites with flower-like morphology was observed after 7 days of incubation in SBFs. The scaffolds that had a high percentage (30 wt.%) of hydroxyapatite demonstrated better cell adhesion, proliferation, and distribution than those with low percentages of hydroxyapatite as the days of culture increased. This work presented an efficient route for developing biomimetic composite scaffolds, which have potential applications in bone-tissue engineering. Copyright © 2015 Elsevier B.V. All rights reserved.

Sequestration of Sr-90 Subsurface Contamination in the Hanford 100-N Area by Surface Infiltration of a Ca-Citrate-Phosphate Solution

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

Szecsody, James E.; Rockhold, Mark L.; Oostrom, Martinus

The objective of this project is to develop a method to emplace apatite precipitate in the 100N vadose zone, which results in sorption and ultimately incorporation of Sr-90 into the apatite structure. The Ca-citrate-PO4 solution can be infiltrated into unsaturated sediments to result in apatite precipitate to provide effective treatment of Sr-90 contamination. Microbial redistribution during solution infiltration and a high rate of citrate biodegradation for river water microbes (water used for solution infiltration) results in a relatively even spatial distribution of the citrate biodegradation rate and ultimately apatite precipitate in the sediment. Manipulation of the Ca-citrate-PO4 solution infiltration strategymore » can be used to result in apatite precipitate in the lower half of the vadose zone (where most of the Sr-90 is located) and within low-K layers (which are hypothesized to have higher Sr-90 concentrations). The most effective infiltration strategy to precipitate apatite at depth (and with sufficient lateral spread) was to infiltrate a high concentration solution (6 mM Ca, 15 mM citrate, 60 mM PO4) at a rapid rate (near ponded conditions), followed by rapid, then slow water infiltration. Repeated infiltration events, with sufficient time between events to allow water drainage in the sediment profile can be used to buildup the mass of apatite precipitate at greater depth. Low-K heterogeneities were effectively treated, as the higher residual water content maintained in these zones resulted in higher apatite precipitate concentration. High-K zones did not receive sufficient treatment by infiltration, although an alternative strategy of air/surfactant (foam) was demonstrated effective for targeting high-K zones. The flow rate manipulation used in this study to treat specific depths and heterogeneities are not as easy to implement at field scale due to the lack of characterization of heterogeneities and difficulty tracking the wetting front over a large subsurface area. However, the use of real-time surface and cross-borehole geophysics can be used to track the infiltrating Ca-citrate-PO4 front so some adjustments can be made in the infiltration rate to precipitate apatite in desired zones. In addition, the reactive transport code used in this study with field scale physical parameters for sediments can be used to evaluate infiltration strategies along with preliminary water infiltration tests at field scale.« less

Experimental simulation of the alkali-carbonate metasomatism

NASA Astrophysics Data System (ADS)

Gorbachev, Nikolay; Kostyuk, Anastasia

2010-05-01

Close association of alkaline and ultrabasic rocks, carbonatites, apatitic and sulfidic mineralization, features of structure testify about mantle a source and the important role alcalic-carbonaceous fluids in genesis of these rocks. Formation alkaline silicate, carbonaceous and sulfidic melts, phase relationship, behaviour of the ti-tan, phosphorus, sulphur and zircon has been experimentally studied at pressure 3.9 GPa, temperature 1250°С in system peridotit-basalt (eclogite)-alcalic-carbonaceous fluid with additives in quality acces-sory minerals, apatite, nickel-containing pyrrhotite, ilmenite, zircon. Experiments were carried out using of apparatus high pressure (piston cilinder and anvil with hole) by a quenching technique. It was used two ampoules (platinum and peridotite, content basalt powder) method. Duration of experiments was 6-8 hours. Products of experiments were studied on electronic scanning microscope Tescan VEGA TS 5130MM with YAG detector of secondary and reflected elec-tron and energy-dispersive the x-ray microanalyzer with semi-conductor Si (Li) detector INCA Energy 350. The morphology, structure and relationship of glass, inclusions of carbonatic and sulfidic globules specify in existence in the conditions of experiment immiscibility silicate, carbonate and sulfidic melts. The composition of silicate melt answered phonolite, carbonaceous melts it is essential calciferous composition with an impurity of alkaline metals and silicate components. Solubility of zircon in silicate melts reached 0.8 wt.% ZrO2, in co-existing carbonaceous melt - 1.5 wt.%. Concentration TiO2 and Р2О5 in silicate melt reached 2 wt.%, in carbonaceous melt - 1.7 wt.% TiO2 and up to 14 wt.% Р2О5. Concentration of sulphur in these melts did not exceed 0.2 мас. %. From minerals of liqudus the main concentrators of the titan and phosphorus were the X-phase and phlogopite - up to 8 wt.% TiO2 and up to 3 wt.% Р2О5 in the X-phase, up to 6 wt. % TiO2 and to 2.5 wt. % Р2О5 in phlogopite. Absence ilmenite and apatite in experimental samples under the studied conditions is obviously caused by their high solubility in co-existing phases. The composition of X-phase is similar to composition of Cpx, but X-phase enrich in TiO2 and de-plete in SiO2 . The partition coefficient of oxides some elements between silicate and carbonaceous melts Dka/si increasing from SiO2 (D<1) to CaO (D>10). Reduction of solubility of apatite in alkaline silicate melt at pressure decline promotes silicate-phosphate stratification and formation of apatite mineralization at introduction of mantle magmas into the earth crust. Supported by grant RFBR № 09-05-01131, ONZ th. 2

Remineralization of in vitro dental caries assessed with polarization-sensitive optical coherence tomography

NASA Astrophysics Data System (ADS)

Jones, Robert S.; Darling, Cynthia L.; Featherstone, John D. B.; Fried, Daniel

2006-01-01

Polarization-sensitive optical coherence tomography (PS-OCT) is potentially useful for imaging the nonsurgical remineralization of dental enamel. This study uses an all-fiber-based PS-OCT system operating at 1310 nm to image demineralized and fluoride-enhanced remineralized artificial lesions. PS-OCT images of lesions before and after remineralization are compared with the relative mineral loss ΔZ (%vol×µm), obtained from high resolution digital microradiography (DM), and chemical composition changes by infrared spectroscopy. Severe early artificial caries show a significant increase in perpendicular-axis integrated reflectivity after remineralization. After sectioning the samples, DM demonstrates that the lesions remineralized with new mineral and the lesion surface zone show significant restoration of mineral volume. PS-OCT and DM both do not show a major change in lesion depth. For less severe artificial caries, the perpendicular-axis image resolves the scattering and depolarization of an outer growth layer after remineralization. This outer layer has a mineral volume close to that of sound enamel, and spectroscopic analysis indicates that the layer is a highly crystalline phase of apatite, without carbonate substitutions that increase the solubility of sound enamel. This study determines that PS-OCT can image the effects of fluoride-enhanced remineralization of mild and severe early artificial in vitro caries.

Distinct Chlorine Isotopic Reservoirs on Mars: Implications for Character, Extent and Relative Timing of Crustal Interaction with Mantle-Derived Magmas, Evolution of the Martian Atmosphere, and the Building Blocks of an Early Mars

NASA Technical Reports Server (NTRS)

Shearer, C. K.; Messenger, S.; Sharp, Z. D.; Burger, P. V.; Nguyen, N.; McCubbin, F. M.

2017-01-01

The style, magnitude, timing, and mixing components involved in the interaction between mantle derived Martian magmas and Martian crust have long been a point of debate. Understanding this process is fundamental to deciphering the composition of the Martian crust and its interaction with the atmosphere, the compositional diversity and oxygen fugacity variations in the Martian mantle, the bulk composition of Mars and the materials from which it accreted, and the noble gas composition of Mars and the Sun. Recent studies of the chlorine isotopic composition of Martian meteorites imply that although the variation in delta (sup 37) Cl is limited (total range of approximately14 per mille), there appears to be distinct signatures for the Martian crust and mantle. However, there are potential issues with this interpretation. New Cl isotope data from the SAM (Sample Analysis at Mars) instrument on the Mars Science Lab indicate a very wide range of Cl isotopic compositions on the Martian surface. Recent measurements by [10] duplicated the results of [7,8], but placed them within the context of SAM surface data. In addition, Martian meteorite Chassigny contains trapped noble gases with isotopic ratios similar to solar abundance, and has long been considered a pristine, mantle derived sample. However, previous studies of apatite in Chassigny indicate that crustal fluids have interacted with regions interstitial to the cumulus olivine. The initial Cl isotope measurements of apatite in Chassigny suggest an addition of crustal component to this lithology, apparently contradicting the rare gas data. Here, we examine the Cl isotopic composition of multiple generations and textures of apatite in Chassigny to extricate the crustal and mantle components in this meteorite and to reveal the style and timing of the addition of crustal components to mantle-derived magmas. These data reveal distinct Martian Cl sources whose signatures have their origins linked to both the early Solar System and the evolving Martian atmosphere.

Effects of diagenesis on strontium, carbon, nitrogen and oxygen concentration and isotopic composition of bone

NASA Astrophysics Data System (ADS)

Nelson, Bruce K.; Deniro, Michael J.; Schoeninger, Margaret J.; De Paolo, Donald J.; Hare, P. E.

1986-09-01

Paleodietary analysis based on variations in the trace element and stable isotopic composition of inorganic and organic phases in fossil bone depends on the assumption that measured values reflect in vivo values. To test for postmortem alteration, we measured 87Sr /86Sr , 13C /12C , 18O /16O and 15N /14N ratios and Sr concentrations in modern and prehistoric (610 to 5470 yr old) bones of animals with marine or terrestrial diets from Greenland. Bones from modern terrestrial feeders have substantially lower Sr concentrations and more radiogenic 87Sr /86Sr ratios than those from modern marine feeders. This contrast was not preserved in the prehistoric samples, which showed almost complete overlap for both Sr concentration and isotopic composition in bones from the two types of animals. Leaching experiments, X-ray diffraction analysis and infrared spectroscopy indicate that alteration of the Sr concentration and isotopic composition in prehistoric bone probably results from nearly complete exchange with groundwater. Oxygen isotope ratios in fossil apatite carbonate also failed to preserve the original discrimination between modern terrestrial and marine feeders. The C isotope ratio of apatite carbonate did not discriminate between animals with marine or terrestrial diets in the modern samples. Even so, the ranges of apatite δ 13C values in prehistoric bone are more scattered than in modern samples for both groups, suggesting alteration had occurred. δ 13C and δ 15N values of collagen in modern bone are distinctly different for the two feeding types, and this distinction is preserved in most of the prehistoric samples. Our results suggest that postmortem alteration of dietary tracers in the inorganic phases of bone may be a problem at all archaeological sites and must be evaluated in each case. While collagen analyzed in this study was resistant to alteration, evaluation of the possibility of diagenetic alteration of its isotopic composition in bones from other contexts is also warranted.

Chemical characterization of hydroxyapatite obtained by wet chemistry in the presence of V, Co, and Cu ions.

PubMed

Moseke, Claus; Gelinsky, Michael; Groll, Jürgen; Gbureck, Uwe

2013-04-01

A model system for the precipitation of hydroxyapatite (HA) from saturated solutions at basic pH was utilized to investigate the effects of V, Co, and Cu ions on crystallography and stoichiometry of the produced apatites. X-ray diffraction (XRD) was applied to analyze phase composition and crystallinity of powders obtained with different metal ion concentrations and annealed at different sintering temperatures. This procedure used the temperature-dependent phase transitions and decompositions of calcium phosphates to analyze the particular influences of the metal ions on apatite mineralization. Comparative XRD measurements showed that all metal ion species reduced crystallinity and crystallite size of the produced apatites. Furthermore the transformation of amorphous calcium phosphate (ACP) to HA was partially inhibited, as was deduced from the formation of α-tricalcium phosphate (α-TCP) peaks in XRD patterns of the heated powders as well as from the reduced intensity of the OH stretch vibration in FTIR spectra. The thermally induced formation of β-TCP indicated a significantly reduced Ca/P ratio as compared to stoichiometric HA. This effect was more pronounced with rising metal ion content. In addition, the appearance of metal oxides in the XRD patterns of samples heated to higher temperatures indicated the incorporation of metal ions in the precipitated apatites. Peak shifts showed that both the apatitic as well as the β-TCP phase apparently had incorporated metal ions. Copyright © 2012 Elsevier B.V. All rights reserved.

Surface characterization of colloidal-sol gel derived biphasic HA/FA coatings.

PubMed

Cheng, Kui; Zhang, Sam; Weng, Wenjian

2007-10-01

Hydroxyapatite (HA) powders are ultrasonically dispersed in the precursor of fluoridated hydroxyapatite (FHA) or fluorapatite (FA) to form a "colloidal sol". HA/FA biphasic coatings are prepared on Ti6Al4V substrate via dip coating, 150 degrees C drying and 600 degrees C firing. The coatings show homogenous distribution of HA particles in the FA matrix. The relative phase proportion can be tailored by the amount of HA in the colloidal sol. The surfaces of the coatings consist of two kinds of distinct domains: HA and FA, resulting in a compositionally heterogeneous surface. The biphasic coating surface becomes increasingly rougher with HA powders, from around 200 nm of pure FA to 400-600 nm in Ra of biphasic coatings. The rougher biphasic HA/FA surfaces with chemically controllable domains will favor cell attachment, apatite layer deposition and necessary dissolution in clinical applications.

Salivary stones: symptoms, aetiology, biochemical composition and treatment.

PubMed

Kraaij, S; Karagozoglu, K H; Forouzanfar, T; Veerman, E C I; Brand, H S

2014-12-05

Salivary stones, also known as sialoliths, are calcified concrements in the salivary glands. Sialoliths are more frequently located in the submandibular gland (84%), than in the parotid gland (13%). The majority of the submandibular stones are located in Wharton's duct (90%), whereas parotid stones are more often located in the gland itself. Salivary stones consist of an amorphous mineralised nucleus, surrounded by concentric laminated layers of organic and inorganic substances. The organic components of salivary stones include collagen, glycoproteins, amino acids and carbohydrates. The major inorganic components are hydroxyapatite, carbonate apatite, whitlockite and brushite. The management of salivary stones is focused on removing the salivary stones and preservation of salivary gland function which depends on the size and location of the stone. Conservative management of salivary stones consists of salivary gland massage and the use of sialogogues. Other therapeutic options include removal of the stone or in some cases surgical removal of the whole salivary gland.

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 silicate melt. We propose that the inclusions at Damiao record a trend of intercumulus melt evolution, which was strongly affected by separation of a hydrothermal fluid phase and the losses of alkali and Ca silicate components from the melt into the fluid.

Influences on the stable oxygen and carbon isotopes in gerbillid rodent teeth in semi-arid and arid environments: Implications for past climate and environmental reconstruction

NASA Astrophysics Data System (ADS)

Jeffrey, Amy; Denys, Christiane; Stoetzel, Emmanuelle; Lee-Thorp, Julia A.

2015-10-01

The stable isotope composition of small mammal tissues has the potential to provide detailed information about terrestrial palaeoclimate and environments, because their remains are abundant in palaeontological and archaeological sites, and they have restricted home ranges. Applications to the Quaternary record, however, have been sparse and limited by an acute lack of understanding of small mammal isotope ecology, particularly in arid and semi-arid environments. Here we document the oxygen and carbon isotope composition of Gerbillinae (gerbil) tooth apatite across a rainfall gradient in northwestern Africa, in order to test the relative influences of the 18O/16O in precipitation or moisture availability on gerbil teeth values, the sensitivity of tooth apatite 13C/12C to plant responses to moisture availability, and the influence of developmental period on the isotopic composition of gerbil molars and incisors. The results show that the isotopic composition of molars and incisors from the same individuals differs consistent with the different temporal periods reflected by the teeth; molar teeth are permanently rooted and form around the time of birth, whereas incisors grow continuously. The results indicate that tooth choice is an important consideration for applications as proxy Quaternary records, but also highlights a new potential means to distinguish seasonal contexts. The oxygen isotope composition of gerbil tooth apatite is strongly correlated with mean annual precipitation (MAP) below 600 mm, but above 600 mm the teeth reflect the oxygen isotope composition of local meteoric water instead. Predictably, the carbon isotope composition of the gerbil teeth reflected C3 and C4 dietary inputs, however arid and mesic sites could not be distinguished because of the high variability displayed in the carbon isotope composition of the teeth due to the microhabitat and short temporal period reflected by the gerbil. We show that the oxygen isotope composition of small mammal teeth strongly reflects moisture availability in semi-arid and arid environments and would provide an excellent record of palaeo-aridity in a terrestrial setting. The results illustrate that an understanding of an animal's physiology is essential for interpreting the animal's isotopic responses to external contexts, especially in arid zones.

Mechanochemical Synthesis of Hydroxyapatite and Its Modifications: Composition, Structure, and Properties

NASA Astrophysics Data System (ADS)

Chaikina, M. V.; Bulina, N. V.; Ishchenko, A. V.; Prosanov, I. Yu.

2014-02-01

The mechanochemical method is used to synthesize samples of hydroxyapatite (HA) with substitution of the phosphate ion by silicate and zirconate ions, and substitution of calcium ions by copper ions. In the process of mechanochemical synthesis, carbonate ions and water molecules are incorporated into the structure of HA due to interaction of components of the reaction mixture with air. Intrusion of carbonate into the structure of HA is a competing process with modification of apatite by silicate and zirconate anions; therefore, the composition of the product during synthesis differs from the prescribed one. After annealing of the samples, the composition of the anion-modified HA can be described by the formula Са10(РО4)6- х (АО4) х (ОН)2- х , where (АО4)4- is the modifying anion. Substitution of calcium by copper ions localized at the Са1 position has been detected. Silver ions are not incorporated into the structure of HA, but are distributed in the apatite matrix in the form of nanocrystals of metallic silver.

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. Copyright © 2011 Elsevier B.V. All rights reserved.

Control of surface topography in biomimetic calcium phosphate coatings.

PubMed

Costa, Daniel O; Allo, Bedilu A; Klassen, Robert; Hutter, Jeffrey L; Dixon, S Jeffrey; Rizkalla, Amin S

2012-02-28

The behavior of cells responsible for bone formation, osseointegration, and bone bonding in vivo are governed by both the surface chemistry and topography of scaffold matrices. Bone-like apatite coatings represent a promising method to improve the osteoconductivity and bonding of synthetic scaffold materials to mineralized tissues for regenerative procedures in orthopedics and dentistry. Polycaprolactone (PCL) films were coated with calcium phosphates (CaP) by incubation in simulated body fluid (SBF). We investigated the effect of SBF ion concentration and soaking time on the surface properties of the resulting apatite coatings. CaP coatings were examined by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR), and energy dispersive X-ray spectrometry (EDX). Young's modulus (E(s)) was determined by nanoindentation, and surface roughness was assessed by atomic force microscopy (AFM) and mechanical stylus profilometry. CaP such as carbonate-substituted apatite were deposited onto PCL films. SEM and AFM images of the apatite coatings revealed an increase in topographical complexity and surface roughness with increasing ion concentration of SBF solutions. Young's moduli (E(s)) of various CaP coatings were not significantly different, regardless of the CaP phase or surface roughness. Thus, SBF with high ion concentrations may be used to coat synthetic polymers with CaP layers of different surface topography and roughness to improve the osteoconductivity and bone-bonding ability of the scaffold. © 2012 American Chemical Society

Photoluminescence in the characterization and early detection of biomimetic bone-like apatite formation on the surface of alkaline-treated titanium implant: state of the art.

PubMed

Sepahvandi, Azadeh; Moztarzadeh, Fathollah; Mozafari, Masoud; Ghaffari, Maryam; Raee, Nahid

2011-09-01

Photoluminescence (PL) property is particularly important in the characterization of materials that contain significant proportions of noncrystalline components, multiple phases, or low concentrations of mineral phases. In this research, the ability of biomimetic bone-like apatite deposition on the surface of titanium alloy (Ti6Al4V) substrates in simulated body fluid (SBF) right after alkaline-treatment and subsequent heat-treatment was studied by the inherent luminescence properties of apatite. For this purpose, the metallic substrates were treated in 5 M NaOH solution at 60 °C. Subsequently, the substrates were heat-treated at 600 °C for 1 h for consolidation of the sodium titanate hydrogel layer. Then, they were soaked in SBF for different periods of time. Finally, the possibility to use of PL monitoring as an effective method and early detection tool is discussed. According to the obtained results, it was concluded that the PL emission peak did not have any significant shift to the shorter or higher wavelengths, and the PL intensity increased as the exposure time increased. This research proved that the observed inherent PL of the newly formed apatite coatings might be of specific interest for histological probing and bone remodelling monitoring. Copyright © 2011 Elsevier B.V. All rights reserved.

Fabrication and mechanical evaluation of hydroxyapatite/oxide nano-composite materials.

PubMed

Mohamed, Khaled R; Beherei, Hanan H; El Bassyouni, Gehan T; El Mahallawy, Nahed

2013-10-01

In the current study, the semiconducting metal oxides such as nano-ZnO and SiO2 powders were prepared via sol-gel technique and conducted on nano-hydroxyapatite (nHA) which was synthesized by chemical precipitation. The properties of fabricated nano-structured composites containing different ratios of HA, ZnO and SiO2 were examined using X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM) and transmission electron microscope (TEM) techniques. The effect of the variation of ratios between the three components on mechanical, microstructure and in-vitro properties was assessed to explore the possibility of enhancing these properties. The results proved that the mechanical properties exhibited an increment with increasing the ZnO content at the extent of HA. In-vitro study proved the formation and nucleation of apatite onto the surface of the fabricated composites after one week of immersion. It is concluded that HA composites containing SiO2 or SiO2/ZnO content had a suitable mechanical properties and ability to form apatite particles onto the composite surface. Based on bioactivity behavior, Si-HA is more bioactive than pure hydroxyapatite and nano-arrangements will provide an interface for better bone formation. Therefore, these nano-composites will be promising as bone substitutes especially in load bearing sites. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Mineralization of teeth and bones of the cave bear (Ursus spelaeus) from the Biśnik Cave, Southern Poland

NASA Astrophysics Data System (ADS)

Rogóż, Anna; Sawłowicz, Zbigniew; Socha, Paweł; Stefaniak, Krzysztof

2009-01-01

The studied bones and teeth of the cave bear (Ursus spelaeus) come from the Biśnik Cave, located in the Częstochowa Upland (Southern Poland). The specimens originate from different geological layers formed since the Odra Glaciation (250-270 thousand years BP). The fossilized bones and teeth were studied using optical microscopy, scanning electron microscopy, X-ray diffraction, FTIR spectroscopy, and INAA. They are built of recrystallized carbonate-rich apatite-(CaOH) and/or apatite-(CaOH). The teeth additionally contain some apatite-(CaF). The lack of collagen and minor REE contents suggest rapid burial and collagen decay in the early stage of diagenesis. The bones and teeth have only limited mineral infillings. In some teeth, Mn-Fe (hydroxy)oxides were found in the dentine canaliculi and in bones, some osteocyte lacunae contain Fe (hydroxy)oxides with admixture of Mn. In one bone specimen, calcite infillings are present in Haversian canals. The infillings formed during later stages of diagenesis and were succeeded by non-filled cracks.

Energetic basis for the molecular-scale organization of bone

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

Tao, Jinhui; Battle, Keith C.; Pan, Haihua

2014-12-24

The remarkable properties of bone derive from a highly organized arrangement of co-aligned nm-scale apatite platelets within a fibrillar collagen matrix. The origin of this arrangement is poorly understood and the crystal structures of hydroxyapatite (HAP) and the non-mineralized collagen fibrils alone do not provide an explanation. Moreover, little is known about collagen-apatite interaction energies, which should strongly influence both the molecular-scale organization and the resulting mechanical properties of the composite. We investigated collagen-mineral interactions by combining dynamic force spectroscopy (DFS) measurements of binding energies with molecular dynamics (MD) simulations of binding and AFM observations of collagen adsorption on singlemore » crystals of calcium phosphate for four mineral phases of potential importance in bone formation. In all cases, we observe a strong preferential orientation of collagen binding, but comparison between the observed orientations and TEM analyses native tissues shows only calcium-deficient apatite (CDAP) provides an interface with collagen that is consistent with both. MD simulations predict preferred collagen orientations that agree with observations and results from both MD and DFS reveal large values for the binding energy due to multiple binding sites. These findings reconcile apparent contradictions inherent in a hydroxyapatite or carbonated apatite (CAP) model of bone mineral and provide an energetic rationale for the molecular scale organization of bone.« less

Apatite-forming ability and mechanical properties of PTMO-modified CaO-SiO2-TiO2 hybrids derived from sol-gel processing.

PubMed

Miyata, Noboru; Fuke, Ken-ichi; Chen, Qi; Kawashita, Masakazu; Kokubo, Tadashi; Nakamura, Takashi

2004-01-01

Hydrolysis and polycondensation of triethoxysilane end-capped Poly (tetramethylene oxide) (Si-PTMO), tetraethoxysilane (TEOS), tetraisopropyltitanate (TiPT) and calcium nitrate (Ca(NO(3))(2)) gave transparent monolithics of PTMO-modified CaO-SiO(2)-TiO(2) hybrids. The samples with (TiPT)/(TEOS+TiPT) molar ratios from 0 to 0.20 under constant ratio of (Si-PTMO)/(TEOS+TiPT) of 2/3 in weight were prepared. It was found that the incorporation of TiO(2) component into a PTMO-CaO-SiO(2) hybrid results in an increase in the apatite-forming ability in a simulated body fluid: the hybrids with (TiPT)/(TEOS+TiPT) of 0.10 and 0.20 in mol formed an apatite on their surfaces within only 0.5 day. It seemed that, within the range of compositions studied, the TiO(2) content little affects the overall mechanical properties: Young's modulus were 52-55MPa, tensile strength, 7-9MPa, and strain at failure, about 30%. Thus, the organic-inorganic hybrids exhibiting both fairly high apatite-forming ability and high capability for deformation were obtained. These hybrid materials may be useful as new kind of bioactive bone-repairing materials.

Yb3+/Ho3+ Co-Doped Apatite Upconversion Nanoparticles to Distinguish Implanted Material from Bone Tissue.

PubMed

Li, Xiyu; Chen, Haifeng

2016-10-07

The exploration of bone reconstruction with time requires the combination of a biological method and a chemical technique. Lanthanide Yb 3+ and Ho 3+ co-doped fluorapatite (FA:Yb 3+ /Ho 3+ ) and hydroxyapatite (HA:Yb 3+ /Ho 3+ ) particles with varying dopant concentrations were prepared by hydrothermal synthesis and thermal activation. Controllable green and red upconversion emissions were generated under 980 nm near-infrared excitation; the FA:Yb 3+ /Ho 3+ particles resulted in superior green luminescence, while HA:Yb 3+ /Ho 3+ dominated in red emission. The difference in the green and red emission behavior was dependent on the lattice structure and composition. Two possible lattice models were proposed for Yb 3+ /Ho 3+ co-doped HA and FA along the hydroxyl channel and fluorine channel of the apatite crystal structure. We first reported the use of the upconversion apatite particles to clearly distinguish implanted material from bone tissue on stained histological sections of harvested in vivo samples. The superposition of the tissue image and material image is a creative method to show the material-tissue distribution and interrelation. The upconversion apatite particles and image superposition method provide a novel strategy for long-term discriminable fluorescence tracking of implanted material or scaffold during bone regeneration.

δ18O of apatite phosphate in small pelagic fish: insights from wild-caught and tank-grown specimens

NASA Astrophysics Data System (ADS)

Lambert, T.; Javor, B.; Paytan, A.

2011-12-01

Oxygen isotope ratios of mineralized structures in fish reflect the temperature and isotopic composition of the water in which they grow. For bulk samples (e.g., whole scales, bones, and otoliths), understanding how this signal is integrated across time and space is critical, especially for organisms exposed to high variability in growth conditions. Here, we assess the response of fish scale δ18O (from apatite phosphate) to experimentally manipulated water conditions. Wild-caught sardines were grown at controlled temperatures (13°C, 17°C, and 21°C) for 11 months. Higher growth temperatures correlated to lower δ18O values, representing a combination of scale apatite deposited before and after the temperature manipulation. Models that account for both biomineral allometry and exposure to varying water properties (e.g., by overlaying migration routes, isoscapes, and temperature maps) have the potential to quantify the varying contributions of minerals grown under different conditions. We use this method to predict δ18O of apatite phosphate for small pelagic fish found in California coastal waters, then compare expected values to those obtained from collected samples. Since phosphate oxygen is relatively resistant to diagenesis, this modern calibration establishes a framework for paleo studies.

Energetic basis for the molecular-scale organization of bone

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

Tao, Jinhui; Battle, Keith C.; Pan, Haihua

The remarkable properties of bone derive from a highly organized arrangement of co-aligned nm-scale apatite platelets within a fibrillar collagen matrix. The origin of this arrangement is poorly understood and the crystal structures of hydroxyapatite (HAP) and the non-mineralized collagen fibrils alone do not provide an explanation. Moreover, little is known about collagen-apatite interaction energies, which should strongly influence both the molecular-scale organization and the resulting mechanical properties of the composite. We investigated collagen-mineral interactions by combining dynamic force spectroscopy (DFS) measurements of binding energies with molecular dynamics (MD) simulations of binding and AFM observations of collagen adsorption on singlemore » crystals of calcium phosphate for four mineral phases of potential importance in bone formation. In all cases, we observe a strong preferential orientation of collagen binding, but comparison between the observed orientations and TEM analyses native tissues shows only calcium-deficient apatite (CDAP) provides an interface with collagen that is consistent with both. MD simulations predict preferred collagen orientations that agree with observations and results from both MD and DFS reveal large values for the binding energy due to multiple binding sites. These findings reconcile apparent contradictions inherent in a hydroxyapatite or carbonated apatite (CAP) model of bone mineral and provide an energetic rationale for the molecular scale organization of bone.« less

Ultra-structural defects cause low bone matrix stiffness despite high mineralization in osteogenesis imperfecta mice☆

PubMed Central

Vanleene, Maximilien; Porter, Alexandra; Guillot, Pascale-Valerie; Boyde, Alan; Oyen, Michelle; Shefelbine, Sandra

2012-01-01

Bone is a complex material with a hierarchical multi-scale organization from the molecule to the organ scale. The genetic bone disease, osteogenesis imperfecta, is primarily caused by mutations in the collagen type I genes, resulting in bone fragility. Because the basis of the disease is molecular with ramifications at the whole bone level, it provides a platform for investigating the relationship between structure, composition, and mechanics throughout the hierarchy. Prior studies have individually shown that OI leads to: 1. increased bone mineralization, 2. decreased elastic modulus, and 3. smaller apatite crystal size. However, these have not been studied together and the mechanism for how mineral structure influences tissue mechanics has not been identified. This lack of understanding inhibits the development of more accurate models and therapies. To address this research gap, we used a mouse model of the disease (oim) to measure these outcomes together in order to propose an underlying mechanism for the changes in properties. Our main finding was that despite increased mineralization, oim bones have lower stiffness that may result from the poorly organized mineral matrix with significantly smaller, highly packed and disoriented apatite crystals. Using a composite framework, we interpret the lower oim bone matrix elasticity observed as the result of a change in the aspect ratio of apatite crystals and a disruption of the crystal connectivity. PMID:22449447

Ultra-structural defects cause low bone matrix stiffness despite high mineralization in osteogenesis imperfecta mice.

PubMed

Vanleene, Maximilien; Porter, Alexandra; Guillot, Pascale-Valerie; Boyde, Alan; Oyen, Michelle; Shefelbine, Sandra

2012-06-01

Bone is a complex material with a hierarchical multi-scale organization from the molecule to the organ scale. The genetic bone disease, osteogenesis imperfecta, is primarily caused by mutations in the collagen type I genes, resulting in bone fragility. Because the basis of the disease is molecular with ramifications at the whole bone level, it provides a platform for investigating the relationship between structure, composition, and mechanics throughout the hierarchy. Prior studies have individually shown that OI leads to: 1. increased bone mineralization, 2. decreased elastic modulus, and 3. smaller apatite crystal size. However, these have not been studied together and the mechanism for how mineral structure influences tissue mechanics has not been identified. This lack of understanding inhibits the development of more accurate models and therapies. To address this research gap, we used a mouse model of the disease (oim) to measure these outcomes together in order to propose an underlying mechanism for the changes in properties. Our main finding was that despite increased mineralization, oim bones have lower stiffness that may result from the poorly organized mineral matrix with significantly smaller, highly packed and disoriented apatite crystals. Using a composite framework, we interpret the lower oim bone matrix elasticity observed as the result of a change in the aspect ratio of apatite crystals and a disruption of the crystal connectivity. Copyright © 2012 Elsevier Inc. All rights reserved.

Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites

NASA Technical Reports Server (NTRS)

Sarafian, Adam R.; Nielsen, Sune G.; Marschall, Horst R.; Gaetani, Glenn A.; Hauri, Erik H.; Righter, Kevin; Berger, Eve L.

2017-01-01

Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at 4563 Ma and continuing for approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.

Atomic substitutions in synthetic apatite; Insights from solid-state NMR spectroscopy

NASA Astrophysics Data System (ADS)

Vaughn, John S.

Apatite, Ca5(PO4)3X (where X = F, Cl, or OH), is a unique mineral group capable of atomic substitutions for cations and anions of varied size and charge. Accommodation of differing substituents requires some kind of structural adaptation, e.g. new atomic positions, vacancies, or coupled substitutions. These structural adaptations often give rise to important physicochemical properties relevant to a range of scientific disciplines. Examples include volatile trapping during apatite crystallization, substitution for large radionuclides for long-term storage of nuclear fission waste, substitution for fluoride to improve acid resistivity in dental enamel composed dominantly of hydroxylapatite, and the development of novel biomaterials with enhanced biocompatibility. Despite the importance and ubiquity of atomic substitutions in apatite materials, many of the mechanisms by which these reactions occur are poorly understood. Presence of substituents at dilute concentration and occupancy of disordered atomic positions hinder detection by bulk characterization methods such as X-ray diffraction (XRD) and infrared (IR) spectroscopy. Solid-state nuclear magnetic resonance (NMR) spectroscopy is an isotope-specific structural characterization technique that does not require ordered atomic arrangements, and is therefore well suited to investigate atomic substitutions and structural adaptations in apatite. In the present work, solid-state NMR is utilized to investigate structural adaptations in three different types of apatite materials; a series of near-binary F, Cl apatite, carbonate-hydroxylapatite compositions prepared under various synthesis conditions, and a heat-treated hydroxylapatite enriched in 17O. The results indicate that hydroxyl groups in low-H, near binary F,Cl apatite facilitate solid-solution between F and Cl via column reversals, which result in average hexagonal symmetry despite very dilute OH concentration ( 2 mol percent). In addition, 19F NMR spectra indicate that fluorine occupies a complex distribution of atomic positions, which give rise to complex 19F peak shapes owing to varied F-Ca distance. 13C NMR analysis of carbonate-hydroxylapatite indicates that AB-type carbonate hydroxylapatite can be prepared without the presence of sodium or heat treatment. Isotopic 17O enrichment of hydroxylapatite and 17O NMR analysis reveals distinct signals corresponding to phosphate and hydroxyl oxygens, and heat treatment under vacuum results in loss of hydroxyl signal due to decomposition to tricalcium phosphate, which was observed by powder X-Ray diffraction (PXRD).

Using the chemical analysis of magnetite to constrain various stages in the formation and genesis of the Kiruna-type chadormalu magnetite-apatite deposit, Bafq district, Central Iran

NASA Astrophysics Data System (ADS)

Heidarian, Hassan; Lentz, David; Alirezaei, Saeed; Peighambari, Sima; Hall, Douglas

2016-12-01

Textural and compositional data are presented for different types of magnetite in the Chadormalu iron deposit to discern the genesis of various styles of mineralization. Samples were chosen according to their paragenetic relations to apatite and their host setting: magnetite-apatite veins in the altered host rocks, disseminated magnetite-apatite assemblages in the marginal parts of the main ore body, and massive magnetite associated with irregular apatite veinlets from internal part of the main ore body. Scanning electron microscopy - back scatter electron (SEM-BSE) images reveal that there are three main generations of magnetite in each of the different magnetite-apatite assemblages. Primary magnetite (Mag1) features abundant porosity and a dark appearance. A second generation of magnetite (Mag2) replacing Mag1 shows a lighter appearance with both sharp and gradational contacts with the primary magnetite crystals. The two magnetite types are related to dissolution-precipitation processes due to changing physico-chemical parameters of the ore fluids. A third type of magnetite (Mag3) with a recrystallized appearance and foam-like triple junctions was mostly observed in magnetite-apatite veins in the main ore body and in veins hosted by altered rocks. Electron probe microanalyses (EPMA) were utilized to discriminate the various magnetite generations in the different magnetite-apatite assemblages. Applying published elemental discrimination diagrams shows that most primary magnetites fall into the hydrothermal- and Kiruna-type fields. Primary magnetite contains lower FeO (88.77-93.65 wt.%; average 91.5 wt.%), and higher SiO2 (0.21-2.26 wt.%; ave. 0.32 wt.%), Al2O3 (0.001-0.45 wt.%; ave. 0.053 wt.%), and CaO (0.002-0.48 wt.%; ave. 0.078 wt.%) contents, which might be related to magmatically derived fluids. Secondary magnetites have higher FeO (89.23-93.49 wt.%; ave. 92.11 wt.%), lower SiO2 (0.037-0.189 wt.%; ave. 0.072 wt.%), Al2O3 (0.004-0.072 wt.%; ave. 0.019 wt.%), and CaO (<0.034 wt.%; ave. 0.013 wt.%) possibly showing a lower contribution of magmatic fluids in the formation of Mag2. The magnetite Mag3 contains the highest FeO (91.25-93.8 wt.%; average 92.69 wt.%), low to moderate SiO2 (0.008-1.44 wt.%; ave. 0.13 wt.%), Al2O3 (<0.732 wt.%; ave. 0.059 wt.%), and CaO (<0.503 wt.%; ave. 0.072 wt.%), and appears to have formed by recrystallization of the previous two generations. The different major, minor, and trace element compositions of various magnetite generations might be due to an ore-forming fluid that was initially magmatic-hydrothermal and evolved to moderately brine-dominated meteoric fluids. The involvement of a basinal brine is supported by the occurrence of a late phase 34S-enriched pyrite in the Chadormalu deposit.

The adsorption of preferential binding peptides to apatite-based materials

PubMed Central

Segvich, Sharon J.; Smith, Hayes C.; Kohn, David H.

2009-01-01

The objective of this work was to identify peptide sequences with high affinity to bone-like mineral (BLM) to provide alternative design methods for functional bone regeneration peptides. Adsorption of preferential binding peptide sequences on four apatite-based substrates [BLM and three sintered apatite disks pressed from powders containing 0% CO32− (HA), 5.6% CO32− (CA5), 10.5% CO32− (CA10)] with varied compositions and morphologies was investigated. A combination of phage display, ELISA, and computational modeling was used to elucidate three 12-mer peptide sequences APWHLSSQYSRT (A), STLPI-PHEFSRE (S), and VTKHLNQISQSY (V), from 243 candidates with preferential adsorption on BLM and HA. Overall, peptides S and V have a significantly higher adsorption to the apatite-based materials in comparison to peptide A (for S vs. A, BLM p = 0.001, CA5 p < 0.001, CA10 p < 0.001, HA p = 0.038; for V vs. A, BLM p = 0.006, CA5 p = 0.033, CA10 p = 0.029). FT-IR analysis displayed carbonate levels in CA5 and CA10 dropped to approximately 1.1–2.2% after sintering, whereas SEM imaging displayed CA5 and CA10 possess distinct morphologies. Adsorption results normalized to surface area indicate that small changes in carbonate percentage at a similar morphological scale did not provide enough carbonate incorporation to show statistical differences in peptide adsorption. Because the identified peptides (S and V) have preferential binding to apatite, their use can now be investigated in bone and dentin tissue engineering, tendon and ligament repair, and enamel formation. PMID:19095299

The importance of particle size in porous titanium and nonporous counterparts for surface energy and its impact on apatite formation.

PubMed

Chen, Xiao-Bo; Li, Yun-Cang; Hodgson, Peter D; Wen, Cuie

2009-07-01

The importance of particle size in titanium (Ti) fabricated by powder metallurgy for the surface energy and its impact on the apatite formation was investigated. Four sorts of Ti powders of different mean particle size were realized through 20min, 2h, 5h and 8h of ball milling, respectively. Each sort of Ti powder was used to fabricate porous Ti and its nonporous counterparts sharing similar surface morphology, grain size and chemical composition, and then alkali-heat treatment was conducted on them. Surface energy was measured on the surfaces of the nonporous Ti counterparts due to the difficulty in measuring the porous surfaces directly. The surface energy increase on the alkali-heat-treated porous and nonporous Ti was observed due to the decrease in the particle size of the Ti powders and the presence of Ti-OH groups brought by the alkali-heat treatment. The apatite-inducing ability of the alkali-heat-treated porous and nonporous Ti with different surface energy values was evaluated in modified simulated body fluid and results indicated that there was a strong correlation between the apatite-inducing ability and the surface energy. The alkali-heat-treated porous and nonporous Ti discs prepared from the powders with an average particle size of 5.89+/-0.76microm possessed the highest surface energy and the best apatite-inducing ability when compared to the samples produced from the powders with the average particle size varying from 19.79+/-0.31 to 10.25+/-0.39microm.

Bi-layered zirconia/fluor-apatite bridges supported by ceramic dental implants: a prospective case series after thirty months of observation.

PubMed

Spies, Benedikt Christopher; Witkowski, Siegbert; Butz, Frank; Vach, Kirstin; Kohal, Ralf-Joachim

2016-10-01

The aim of this study was to determine the success and survival rate of all-ceramic bi-layered implant-supported three-unit fixed dental prostheses (IS-FDPs) 3 years after implant placement. Thirteen patients (seven males, six females; age: 41-78 years) received two one-piece ceramic implants (alumina-toughened zirconia) each in the region of the premolars or the first molar and were finally restored with adhesively cemented bi-layered zirconia-based IS-FDPs (3 in the maxilla, 10 in the mandible) composed of CAD/CAM-fabricated zirconia frameworks pressed-over with fluor-apatite glass-ceramic ingots. At prosthetic delivery and the follow-ups after 1, 2 and 3 years, the restorations were evaluated using modified United States Public Health Service (USPHS) criteria. Restorations with minor veneer chippings, a small-area occlusal roughness, slightly soundable restoration margins, minimal contour deficiencies and tolerable color deviations were regarded as success. In case of more distinct defects that could, however, be repaired to a clinically acceptable level, IS-FDPs were regarded as surviving. Kaplan-Meier plots were used for the success/survival analyses. To verify an impact on subjective patients' perceptions, satisfaction was evaluated by visual analog scales (VAS). All patients were seen 3 years after implant installation. No IS-FDP had to be replaced, resulting in 100% survival after a mean observation period of 29.5 months (median: 30.7). At the 3-year follow-up, 7/13 IS-FDPs showed a veneer chipping, 13/13 an occlusal roughness and 12/13 minimal deficiencies of contour/color. Since six restorations showed a major chipping and/or a major occlusal roughness, the Kaplan-Meier success rate was 53.8%. However, patients' significantly improved perceptions of function, esthetics, sense, and speech at prosthetic delivery remained stable over time. Bi-layered zirconia/fluor-apatite IS-FDPs entirely survived the observation period but showed a high frequency of technical complications. Nevertheless, the treatment highly satisfied patients' expectations. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Bioactive Titanate Layers Formed on Titanium and Its Alloys by Simple Chemical and Heat Treatments

PubMed Central

Kokubo, Tadashi; Yamaguchi, Seiji

2015-01-01

To reveal general principles for obtaining bone-bonding bioactive metallic titanium, Ti metal was heat-treated after exposure to a solution with different pH. The material formed an apatite layer at its surface in simulated body fluid when heat-treated after exposure to a strong acid or alkali solution, because it formed a positively charged titanium oxide and negatively charged sodium titanate film on its surface, respectively. Such treated these Ti metals tightly bonded to living bone. Porous Ti metal heat-treated after exposure to an acidic solution exhibited not only osteoconductive, but also osteoinductive behavior. Porous Ti metal exposed to an alkaline solution also exhibits osteoconductivity as well as osteoinductivity, if it was subsequently subjected to acid and heat treatments. These acid and heat treatments were not effective for most Ti-based alloys. However, even those alloys exhibited apatite formation when they were subjected to acid and heat treatment after a NaOH treatment, since the alloying elements were removed from the surface by the latter. The NaOH and heat treatments were also not effective for Ti-Zr-Nb-Ta alloys. These alloys displayed apatite formation when subjected to CaCl2 treatment after NaOH treatment, forming Ca-deficient calcium titanate at their surfaces after subsequent heat and hot water treatments. The bioactive Ti metal subjected to NaOH and heat treatments has been clinically used as an artificial hip joint material in Japan since 2007. A porous Ti metal subjected to NaOH, HCl and heat treatments has successfully undergone clinical trials as a spinal fusion device. PMID:25893014

Adsorption and bioactivity studies of albumin onto hydroxyapatite surface.

PubMed

Mavropoulos, Elena; Costa, Andréa M; Costa, Lilian T; Achete, Carlos A; Mello, Alexandre; Granjeiro, José M; Rossi, Alexandre M

2011-03-01

Bovine serum albumin (BSA) may have an inhibitory or promoter effect on hydroxyapatite (HA) nucleation when apatite is precipitated in a medium containing the protein. In this study we evaluated the influence of BSA on the precipitation of calcium phosphate phases (CP) from simulated body fluid (SBF) when the protein was previously bounded to HA surface. The kinetics of BSA immobilization onto hydroxyapatite surface was performed in different buffers and protein concentrations in order to adjust experimental conditions in which BSA was tightly linked to HA surface for long periods in SBF solution. It was shown that for BSA concentration higher than 0.1mg/mL the adsorption to HA surface followed Langmuir-Freundlich mechanisms, which confirmed the existence of cooperative protein-protein interactions on HA surface. Fourier Transformed Infrared Attenuated Total Reflectance Microscopy (FTIRM-ATR) evidenced changes in BSA conformational state in favor of less-ordered structure. Analyses from high resolution grazing incident X-ray diffraction using synchrotron radiation (GIXRD), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) showed that a poorly crystalline calcium phosphate was precipitated on the surface of HA discs coated with BSA, after the immersion in SBF for 4 days. The new bioactive layer had morphological characteristics similar to the one formed on the HA surface without protein. It was identified as a carbonated apatite with preferential crystal growth along apatite 002 direction. The GIXRD results also revealed that BSA layer bound to the surface inhibited the HA dissolution leading to a reduction on the formation of new calcium phosphate phase. 2010 Elsevier B.V. All rights reserved.

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 relating, for example, to apatite-based biomaterials development or in (geo)microbiology.

Water permeability, hybrid layer long-term integrity and reaction mechanism of a two-step adhesive system.

PubMed

Grégoire, Geneviève; Dabsie, Firas; Delannée, Mathieu; Akon, Bernadette; Sharrock, Patrick

2010-07-01

Our aim was to investigate the reaction mechanism of formation of the hybrid layer by a HEMA-containing self-etch adhesive and to study fluid filtration, contact angle and interfacial ultrastructure by SEM following a 1 year ageing period. Acidic behaviour and chemical interactions between Silorane System Adhesive and dentine were studied by potentiometric titrations, atomic absorption spectroscopy and infrared spectroscopy. The hydrophilicity of the adhesive was evaluated using the sessile drop method and dentine permeability by hydraulic conductance. The morphological study of the dentine/adhesive system interface was conducted using SEM. The Silorane System Adhesive behaved as a multi-acid with several different pK(a) values. When the adhesive was in contact with dentine, the acid was progressively consumed and calcium ions were released. The acrylate substituted phosphonate bound strongly to apatite crystals. The polyacrylic acid copolymer reacted with calcium ions and formed an interpenetrating polymer network (IPN). Water contact angle measurements showed rapid spreading on primer (angles reached 15 degrees at 30s) and larger contact angles when the Silorane bonding layer was added (from over 60 degrees to 44 degrees ). A thick, homogeneous hybrid layer was observed both initially and after 1 year of ageing, with a corresponding hydraulic conductance of -48.50% initially and -52.07% at 12 months. The Silorane System Adhesive is capable of both dissolving calcium ions and binding to apatite surfaces. The results showed the hydrophilicity of the adhesive, which formed an IPN-like hybrid layer that conserved adequate impermeability over a 1-year period. Copyright 2010 Elsevier Ltd. All rights reserved.

Dual-Energy Computed Tomography Gemstone Spectral Imaging: A Novel Technique to Determine Human Cardiac Calculus Composition.

PubMed

Cheng, Ching-Li; Chang, Hsiao-Huang; Ko, Shih-Chi; Huang, Pei-Jung; Lin, Shan-Yang

2016-01-01

Understanding the chemical composition of any calculus in different human organs is essential for choosing the best treatment strategy for patients. The purpose of this study was to assess the capability of determining the chemical composition of a human cardiac calculus using gemstone spectral imaging (GSI) mode on a single-source dual-energy computed tomography (DECT) in vitro. The cardiac calculus was directly scanned on the Discovery CT750 HD FREEdom Edition using GSI mode, in vitro. A portable fiber-optic Raman spectroscopy was also applied to verify the quantitative accuracy of the DECT measurements. The results of spectral DECT measurements indicate that effective Z values in 3 designated positions located in this calculus were 15.02 to 15.47, which are close to values of 15.74 to 15.86, corresponding to the effective Z values of calcium apatite and hydroxyapatite. The Raman spectral data were also reflected by the predominant Raman peak at 960 cm for hydroxyapatite and the minor peak at 875 cm for calcium apatite. A potential single-source DECT with GSI mode was first used to examine the morphological characteristics and chemical compositions of a giant human cardiac calculus, in vitro. The CT results were consistent with the Raman spectral data, suggesting that spectral CT imaging techniques could be accurately used to diagnose and characterize the compositional materials in the cardiac calculus.

Nanosized CaP-silk fibroin-PCL-PEG-PCL/PCL based bilayer membranes for guided bone regeneration.

PubMed

Türkkan, Sibel; Pazarçeviren, A Engin; Keskin, Dilek; Machin, Nesrin E; Duygulu, Özgür; Tezcaner, Ayşen

2017-11-01

Guided bone regeneration (GBR) concept has been developed to prevent the formation of non-functional scar tissue layer on defect site by undertaking barrier role. In this study, a new bilayer membrane which consisted of one layer of electrospun silk fibroin/PCL-PEG-PCL incorporating nanocalcium phosphate (SPCA) 1 and one layer of PCL membrane was developed for GBR. To improve the osteoconductivity of membranes, nanosized calcium phosphate particles synthesized by Flame Spray Pyrolysis method were incorporated into membranes at 10% (wt) (SPCA10) and 20% (wt) (SPCA20) of the polymer content. The structural and chemical analyses revealed the well-integrated two layers of membranes with a total thickness of ca 100μm. In the regenerative layer, the highly porous mesh structure had a thickness of 12.6μm with randomly oriented fibers having diameters around 760nm, and nanoparticles dispersed homogenously. The mechanical test results showed remarkable improvement on the tensile strength of membranes with incorporation of nanoparticles. Higher water affinity of nanoCaP included membranes was proved by lower contact angle values and higher percent water uptake capacity. Biomineralization assay revealed that nucleation and growth of apatites around fibers of SPCA10 and SPCA20 were apparent while on SPCA0 apatite minerals were barely detected after 10days. Human dental pulp stem cells (DPSC) were seeded on electrospun layer of the bilayer membranes for biocompatibility and osteo-compatibility study. Increasing nanoCaP amount resulted in higher cell adhesion, proliferation, ALP activity and calcium deposition on membranes. These overall results confirmed the biocompatibility and potential applicability of proposed membranes for GBR treatments. Copyright © 2017 Elsevier B.V. All rights reserved.

Ptychographic X-ray nanotomography quantifies mineral distributions in human dentine

NASA Astrophysics Data System (ADS)

Zanette, I.; Enders, B.; Dierolf, M.; Thibault, P.; Gradl, R.; Diaz, A.; Guizar-Sicairos, M.; Menzel, A.; Pfeiffer, F.; Zaslansky, P.

2015-03-01

Bones are bio-composites with biologically tunable mechanical properties, where a polymer matrix of nanofibrillar collagen is reinforced by apatite mineral crystals. Some bones, such as antler, form and change rapidly, while other bone tissues, such as human tooth dentine, develop slowly and maintain constant composition and architecture for entire lifetimes. When studying apatite mineral microarchitecture, mineral distributions or mineralization activity of bone-forming cells, representative samples of tissue are best studied at submicrometre resolution while minimizing sample-preparation damage. Here, we demonstrate the power of ptychographic X-ray tomography to map variations in the mineral content distribution in three dimensions and at the nanometre scale. Using this non-destructive method, we observe nanostructures surrounding hollow tracts that exist in human dentine forming dentinal tubules. We reveal unprecedented quantitative details of the ultrastructure clearly revealing the spatially varying mineralization density. Such information is essential for understanding a variety of natural and therapeutic effects for example in bone tissue healing and ageing.

Structural transformation of synthetic hydroxyapatite under simulated in vivo conditions studied with ATR-FTIR spectroscopic imaging

NASA Astrophysics Data System (ADS)

Sroka-Bartnicka, Anna; Borkowski, Leszek; Ginalska, Grazyna; Ślósarczyk, Anna; Kazarian, Sergei G.

2017-01-01

Hydroxyapatite and carbonate-substituted hydroxyapatite are widely used in bone tissue engineering and regenerative medicine. Both apatite materials were embedded into recently developed ceramic/polymer composites, subjected to Simulated Body Fluid (SBF) for 30 days and characterized using ATR-FTIR spectroscopic imaging to assess their behaviour and structures. The specific aim was to detect the transition phases between both types of hydroxyapatite during the test and to analyze the surface modification caused by SBF. ATR-FTIR spectroscopic imaging was successfully applied to characterise changes in the hydroxyapatite lattice due to the elastic properties of the scaffolds. It was observed that SBF treatment caused a replacement of phosphates in the lattice of non-substituted hydroxyapatite by carbonate ions. A detailed study excluded the formation of pure A type carbonate apatite. In turn, CO32- content in synthetic carbonate-substituted hydroxyapatite decreased. The usefulness of ATR-FTIR spectroscopic imaging studies in the evaluation of elastic and porous β-glucan hydroxyapatite composites has been demonstrated.

The effect of CHA-doped Sr addition to the mechanical strength of metakaolin dental implant geopolymer composite

NASA Astrophysics Data System (ADS)

Sunendar, Bambang; Fathina, Afiya; Harmaji, Andrie; Mardhian, Deby Fajar; Asri, Lia; Widodo, Haris Budi

2017-09-01

The prospective material for implant plate required sufficient mechanical properties to maintain fracture fixation and resist physiological stress until bone healing process finished. Various problem implant plate based on metal and polymer materials when used as fixation for bone defect case induced developmental of bioceramic for implant plate materials. Materials that now has been attract a lot of attention is carbonate apatite and strontium as doping which known to have good biocompability along with biointegrity and mechanical charateristics. Other materials that have been known to have good mechanical properties are metakaolin and use of chitosan as coupling agent. Metakaolin and carbonate apatite can be produced by sol-gel methode which simpler, economical and energy-saving procedure furthermore use of chitosan which is widely found in the nature of Indonesia can be used to encourage the utilization of natural resources. The aim fo this paper is to investigated effect of CHA-doped Sr 5 (%) mol addition to the mechanical strength of metakaolin dental implant geoploymer composite. In this paper metakaolin is used as geopolymerization precursors. The test results have shown that addition of filler of apatite carbonate doped 5% mol strontium can be said to increase the value of mechnical properties but high concentration of calcium in the nanocomposite also can complicate the equilibrium of the geopolymerization process and induce alkali aggregate reactivity (AAR). The sample group of nanocomposite of metakaolin and carbonate apatite-doped 5% mol strontium (2: 1% wt) with 2% chitosan as a coupling agent based on geopolymerization for implant plate application has the best mechanical properties among all sample groups but does not qualify as an implant plate on cortical bone but can be used for the application of the implant plate on the trabecular bone specifically and potentially as a bone initiator.

Sodium Is Not Essential for High Bioactivity of Glasses

PubMed Central

Chen, Xiaojing; Chen, Xiaohui; Brauer, Delia S.; Wilson, Rory M.; Law, Robert V.; Hill, Robert G.; Karpukhina, Natalia

2017-01-01

This study aims to demonstrate that excellent bioactivity of glass can be achieved without the presence of an alkali metal component in glass composition. In vitro bioactivity of two sodium-free glasses based on the quaternary system SiO2-P2O5-CaO-CaF2 with 0 and 4.5 mol% CaF2 content was investigated and compared with the sodium containing glasses with equivalent amount of CaF2. The formation of apatite after immersion in Tris buffer was followed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), 31P and 19F solid state MAS-NMR. The dissolution study was completed by ion release measurements in Tris buffer. The results show that sodium free bioactive glasses formed apatite at 3 hours of immersion in Tris buffer, which is as fast as the corresponding sodium containing composition. This signifies that sodium is not an essential component in bioactive glasses and it is possible to make equally degradable bioactive glasses with or without sodium. The results presented here also emphasize the central role of the glass compositions design which is based on understanding of structural role of components and/or predicting the network connectivity of glasses. PMID:29271977

Sodium Is Not Essential for High Bioactivity of Glasses.

PubMed

Chen, Xiaojing; Chen, Xiaohui; Brauer, Delia S; Wilson, Rory M; Law, Robert V; Hill, Robert G; Karpukhina, Natalia

2017-12-01

This study aims to demonstrate that excellent bioactivity of glass can be achieved without the presence of an alkali metal component in glass composition. In vitro bioactivity of two sodium-free glasses based on the quaternary system SiO 2 -P 2 O 5 -CaO-CaF 2 with 0 and 4.5 mol% CaF 2 content was investigated and compared with the sodium containing glasses with equivalent amount of CaF 2 . The formation of apatite after immersion in Tris buffer was followed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), 31 P and 19 F solid state MAS-NMR. The dissolution study was completed by ion release measurements in Tris buffer. The results show that sodium free bioactive glasses formed apatite at 3 hours of immersion in Tris buffer, which is as fast as the corresponding sodium containing composition. This signifies that sodium is not an essential component in bioactive glasses and it is possible to make equally degradable bioactive glasses with or without sodium. The results presented here also emphasize the central role of the glass compositions design which is based on understanding of structural role of components and/or predicting the network connectivity of glasses.

Geochemistry of cumulates from the Bjerkreim Sokndal layered intrusion (S. Norway). Part I: Constraints from major elements on the mechanism of cumulate formation and on the jotunite liquid line of descent

NASA Astrophysics Data System (ADS)

Duchesne, J. C.; Charlier, B.

2005-08-01

Whole-rock major element compositions are investigated in 99 cumulates from the Proterozoic Bjerkreim-Sokndal layered intrusion (Rogaland Anorthosite Province, SW Norway), which results from the crystallization of a jotunite (Fe-Ti-P-rich hypersthene monzodiorite) parental magma. The scattering of cumulate compositions covers three types of cumulates: (1) ilmenite-leuconorite with plagioclase, ilmenite and Ca-poor pyroxene as cumulus minerals, (2) magnetite-leuconorite with the same minerals plus magnetite, and (3) gabbronorite made up of plagioclase, Ca-poor and Ca-rich pyroxenes, ilmenite, Ti-magnetite and apatite. Each type of cumulate displays a linear trend in variation diagrams. One pole of the linear trends is represented by plagioclase, and the other by a mixture of the mafic minerals in constant proportion. The mafic minerals were not sorted during cumulate formation though they display large density differences. This suggests that crystal settling did not operate during cumulate formation, and that in situ crystallization with variable nucleation rate for plagioclase was the dominant formation mechanism. The trapped liquid fraction of the cumulate plays a negligible role for the cumulate major element composition. Each linear trend is a locus for the cotectic composition of the cumulates. This property permits reconstruction by graphical mass balance calculation of the first two stages of the liquid line of descent, starting from a primitive jotunite, the Tjörn parental magma. Another type of cumulate, called jotunite cumulate and defined by the mineral association from the Transition Zone of the intrusion, has to be subtracted to simulate the most evolved part of the liquid line of descent. The proposed model demonstrates that average cumulate compositions represent cotectic compositions when the number of samples is large (> 40). The model, however, does not account for the K 2O evolution, suggesting that the system was open to contamination by roof melts. The liquid line of descent corresponding to the Bjerkreim-Sokndal cumulates differs slightly from that obtained for jotunitic dykes in that the most Ti-, P- and Fe-rich melts (evolved jotunite) are lacking. The constant composition of the mafic poles during intervals where cryptic layering is conspicuous is explained by a compositional balance between the Fe-Ti oxide minerals, which decrease in Fe content in favour of Ti, and the pyroxenes which increase in Fe.

Ultrastructure of selected struvite-containing urinary calculi from dogs.

PubMed

Domingo-Neumann, R A; Ruby, A L; Ling, G V; Schiffman, P S; Johnson, D L

1996-09-01

To elucidate the ultrastructural details of struvite-containing urinary calculi from dogs. 38 specimens were selected from a collection of approximately 13,000 canine urinary calculi: 18 of these were composed entirely of struvite, and 20 consisted of struvite and calcium phosphate (apatite). Qualitative and quantitative analyses of specimens included use of plain and polarized light microscopy, x-ray diffractometry, scanning electron microscopy with backscattered electron imagery, x-ray fluorescence scans, and electron microprobe analysis. 4 textural types were recognized among struvite calculi, and 4 textural types of struvite-apatite calculi were described. Evidences of calculus dissolution were described from 4 calculi studied. The presence of small, well interconnected primary pores in struvite-containing urinary calculi from dogs appears to be a significant factor in determining the possible interaction of calculi with changes in the urine composition. The progress of dissolution from the calculus surface to the calculus interior appears to be largely affected by the primary porosity originally present between crystals forming the calculus framework. Apatite was observed to be more resistant to dissolution than struvite. The prevalence of fine concentric laminations having low porosity, and the common occurrence of apatite among struvite-containing urinary calculi from dogs may be 2 reasons why the efficacy of dietary and medicinal manipulations in dissolving urinary calculi is greater among cats than it is among dogs.

Energetic basis for the molecular-scale organization of bone

DOE PAGES

Tao, Jinhui; Battle, Keith C.; Pan, Haihua; ...

2014-12-24

Here, the remarkable properties of bone derive from a highly organized arrangement of co-aligned nm-scale apatite platelets within a fibrillar collagen matrix. The origin of this arrangement is poorly understood and the crystal structures of hydroxyapatite (HAP) and the non-mineralized collagen fibrils alone do not provide an explanation. Moreover, little is known about collagen-apatite interaction energies, which should strongly influence both the molecular-scale organization and the resulting mechanical properties of the composite. We investigated collagen-mineral interactions by combining dynamic force spectroscopy (DFS) measurements of binding energies with molecular dynamics (MD) simulations of binding and AFM observations of collagen adsorption onmore » single crystals of calcium phosphate for four mineral phases of potential importance in bone formation. In all cases, we observe a strong preferential orientation of collagen binding, but comparison between the observed orientations and TEM analyses native tissues shows only calcium-deficient apatite (CDAP) provides an interface with collagen that is consistent with both. MD simulations predict preferred collagen orientations that agree with observations and results from both MD and DFS reveal large values for the binding energy due to multiple binding sites. These findings reconcile apparent contradictions inherent in a hydroxyapatite or carbonated apatite (CAP) model of bone mineral and provide an energetic rationale for the molecular scale organization of bone.« less

Solid state solubility of copper oxides in hydroxyapatite

NASA Astrophysics Data System (ADS)

Zykin, Mikhail A.; Vasiliev, Alexander V.; Trusov, Lev A.; Dinnebier, Robert E.; Jansen, Martin; Kazin, Pavel E.

2018-06-01

Samples containing copper oxide doped hydroxyapatite with the composition Ca10(PO4)6(CuxOH1-x-δ)2, x = 0.054 - 0.582, in the mixture with CuO/Cu2O were prepared by a solid-state high-temperature treatment at varying annealing temperatures and at different partial water vapor and oxygen pressures. The crystal structures of the apatite compounds were refined using powder X-ray diffraction patterns and the content of copper ions x in the apatite was determined. Copper ions enter exclusively into the apatite trigonal channels formally substituting protons of OH-groups and the hexagonal cell parameters grow approximately linearly with x, the channel volume mostly expanding while the remaining volume of the crystal lattice changing only slightly. The equilibrium copper content in the apatite increases drastically, by almost a factor of 10 with the annealing temperature rising from 800° to 1200°C. The reduction of the water partial pressure leads to a further increase of x, while the dependence of x on the oxygen partial pressure exhibits a maximum. The observed relations are consistent with the proposed chemical reactions implying the copper introduction is followed by the release of a considerable quantity of gaseous products - water and oxygen. The analysis of interatomic distances suggests that the maximum content of copper ions in the channel cannot exceed 2/3.

Energetic basis for the molecular-scale organization of bone.

PubMed

Tao, Jinhui; Battle, Keith C; Pan, Haihua; Salter, E Alan; Chien, Yung-Ching; Wierzbicki, Andrzej; De Yoreo, James J

2015-01-13

The remarkable properties of bone derive from a highly organized arrangement of coaligned nanometer-scale apatite platelets within a fibrillar collagen matrix. The origin of this arrangement is poorly understood and the crystal structures of hydroxyapatite (HAP) and the nonmineralized collagen fibrils alone do not provide an explanation. Moreover, little is known about collagen-apatite interaction energies, which should strongly influence both the molecular-scale organization and the resulting mechanical properties of the composite. We investigated collagen-mineral interactions by combining dynamic force spectroscopy (DFS) measurements of binding energies with molecular dynamics (MD) simulations of binding and atomic force microscopy (AFM) observations of collagen adsorption on single crystals of calcium phosphate for four mineral phases of potential importance in bone formation. In all cases, we observe a strong preferential orientation of collagen binding, but comparison between the observed orientations and transmission electron microscopy (TEM) analyses of native tissues shows that only calcium-deficient apatite (CDAP) provides an interface with collagen that is consistent with both. MD simulations predict preferred collagen orientations that agree with observations, and results from both MD and DFS reveal large values for the binding energy due to multiple binding sites. These findings reconcile apparent contradictions inherent in a hydroxyapatite or carbonated apatite (CAP) model of bone mineral and provide an energetic rationale for the molecular-scale organization of bone.

The Abundance and Isotopic Composition of Water in Howardite-Eucrite-Diogenite Meteorites

NASA Astrophysics Data System (ADS)

Barrett, T. J.; Tartèse, R.; Anand, M.; Franchi, I. A.; Grady, M. M.; Greenwood, R. C.; Charlier, B. L. A.

2014-09-01

Using SIMs techniques we measure OH abundances and D/H ratios in apatite grains from two Eucrites (DaG 945, DaG 844).The average δD values of these two samples are also similar to carbonaceous chondrites, the Earth and the Moon.

Geochemistry of a Tertiary sedimentary phosphate deposit: Baja California Sur, Mexico

USGS Publications Warehouse

Piper, D.Z.

1991-01-01

The San Gregorio Formation in Baja California Sur, a phosphate-enriched sedimentary unit of late Oligocene to early Miocene age, has been analyzed in two areas (La Purisima and San Hilario) for its chemical composition (major oxides, Cu, Cd, Cr, Co, V, and rare-earth elements - REE) and isotopic composition (??18O and ??13C). A detrital and a marine component were determined from major oxides. The detrital component consists of an unaltered volcanic-ash fraction and a terrigenous clay-silt fraction. The marine component, which accumulated initially as biogenic and hydrogenous material, is now present as opal-A, opal-CT, CaCO3, organic matter, and an authigenic phosphate fraction, mostly pelletal and composed of the carbonate-fluorapatite mineral francolite. The minor elements have been partitioned into these components by assuming a constant composition for the two detrital fractions. The composition of the marine component of minor elements can then be interpreted by assuming that the stoichiometry of the original accumulating organic matter was equal to that of modern plankton. The Cu and Cd contents in the marine component of all rocks require that the seawater-derived fractions of these two metals were supplied to the seafloor solely by organic matter. Enrichments of Cr and V at both sites required an additional marine input. On the basis of their geochemistry in the modern ocean, Cr and V could have precipitated, or been adsorbed, onto settling particles from an O2 minimum zone in which the O2 content was low enough to promote denitrification rather than oxygen respiration. An enrichment of the REE, now within the apatite fraction, resulted from their adsorption onto particulates also in the O2 minimum zone and to the dissolution and alteration of biogenic phases (predominantly silica) within the sediment. Co and Fe2O3 show no enrichment above a detrital contribution. The ??18O-values of apatites from the La Purisima site are heavier than those of apatites from the San Hilario site, whereas the ??13C-values show the opposite trend. One possible interpretation of these variations is that ??18O reflects seawater values and ??13C sediment pore water values. This interpretation suggests that upwelling rates and primary productivity within the water column were greater at La Purisima, an interpretation that is corroborated by a greater abundance of apatite measured in outcrop at La Purisima. The Ce anomalies of the phosphate-enriched samples also differ between the two sites, indicating that they also recorded water masses, similar to the ??18O-values. ?? 1991.

Late Pliocene - Early Pleistocene paleoenvironmental reconstruction based on stable isotope compositions of Stephanorhinus sp. and Mammut sp. teeth

NASA Astrophysics Data System (ADS)

Szabó, Péter; Kovács, János; Kocsis, László; Gasparik, Mihály; Vennemann, Torsten; Demény, Attila; Virág, Attila

2014-05-01

Stable isotope measurements of skeletal apatite from herbivorous mammals are often used to provide information on the terrestrial paleoenvironment and paleoclimate. In this study fossil teeth of Stephanorhinus Kretzoi 1942 (rhinoceros) and Mammut Blumenbach 1799 (mastodon), amongst others, were investigated from the Carpathian Basin. According to the biostratigraphy, the age of the samples has a range from Late Pliocene to Early Pleistocene. Reconstructing paleoclimate and paleoenvironment of this era is important as it can be an analogue for the future climate. Oxygen and carbon isotopic compositions were measured from the tooth enamel, because it is believed to be the most resistant to diagenetic alteration (e.g., Kohn & Cerling, 2002). The carbon isotopic composition in the carbonate fraction of apatite can be related to the diet of the animal (Kohn & Cerling, 2002). Hence, it can reflect the photosynthetic pathway (C3 or C4) of the plants consumed by these herbivores. The δ18O values were determined in the phosphate fraction of apatite. In the case of large mammals that are obligate drinkers, the δ18O values closely track those of the environmental water (Bryant & Froelich, 1995). Knowing the δ18O values of environmental water and relating it to local precipitation, the mean annual temperature (MAT) of the site can be calculated (Dansgaard, 1964). The δ13C values range from -10 to -15 o (VPDB). The result clearly shows that these animals consumed C3 plants. Most of the δ13C values indicate mixed grassland-open woodland rather than a closed canopy forest. Although there is variation in the δ18O values (mean 14.2 ± 1.0 o VSMOW, n=17), most of the samples would support a MAT range of 8-12 ° C. This is in good agreement with other proxies for the localities and time period (Kovács et al., 2013). Bryant, D.J. & Froelich, P.N. (1995) A model of oxygen-isotope fractionation in bodywater of large-mammals. Geochimica et Cosmochimica Acta 59, 4523-4537. Dansgaard, W. (1964) Stable isotopes in precipitation. Tellus 16, 436-468. Kohn, M.J. & Cerling, T.E. (2002) Stable isotope compositions of biological apatite. Reviews in Mineralogy and Geochemistry 48, 455-488. Kovács, J. et al. (2013) Clay Mineralogy of Red Clay Deposits from the Central Carpathian Basin (Hungary): Implications for Plio/Pleistocene Chemical Weathering and Paleoclimate. Turkish J. Earth. Sci. 22, 414-426.

Chemical composition of phosphorites of the Phosphoria Formation

USGS Publications Warehouse

Gulbrandsen, R.A.

1966-01-01

The chemical composition, both major and minor constituents, of 60 samples of phosphorite from the Phosphoria Formation was determined. Major constituents of the average phosphorite are, by weight per cent: SiO2, 11??9; Al2O3, 1??7; Fe2O3,1??1; MgO, 0??3; CaO, 44??0; Na2O, 0??6; K2O, 0??5; total H2O, 2??2; H2O-, 0??6; TiO2, 0??1; P2O5, 30??5; CO2, 2??2; SO3, 1??8; F, 3??1; organic matter, 2??1; and oil, 0??2. Uranium averages 0??009 per cent. The phosphate mineral is basically apatite, Ca5(PO4)3F, with small but significant and variable substitutions-Na, Sr, U and Th for Ca, and CO3 and SO4 for PO4. Rare metals not associated with apatite are associated principally with the organic-matter component of the rocks. This group includes As, Ag, Cd, Cr, Cu, Mo, Ni, Sb, Se, V and Zn. Chromium is the most abundant, having a modal abundance of 0??1 per cent and a maximum concentration of 0??3 per cent. The average phosphorite is composed of approximately 80 per cent apatite, 10 per cent quartz, 5 per cent muscovite-illite, 2 per cent organic matter, 1 per cent dolomite-calcite, 1 per cent iron oxide, and 1 per cent other components. It is texturally a medium-grained pellet phosphorite. ?? 1966.

Albumin-mediated deposition of bone-like apatite onto nano-sized surfaces: Effect of surface reactivity and interfacial hydration.

PubMed

D'Elia, Noelia L; Gravina, Noel; Ruso, Juan M; Marco-Brown, Jose L; Sieben, Juan M; Messina, Paula V

2017-05-15

The bioactivity of an implant is displayed on its ability to induce heterogeneous nucleation of biogenic apatite onto its surface upon immersion in body fluids; forming, through this layer, a stable bond with the host tissue. The present article evaluates the bioactivity of different nanostructured substrates based on synthetic hydroxyapatite (HA) and titania (TiO 2 ) nanoparticles, where we extend the debate regarding the selective roles played by the presence of albumin on the biogenic apatite coating evolution. The substrates bone-bonding potential was evaluated by keeping the materials in contact with Simulated Body Fluid, while the influence of the presence of Bovine Serum Albumin in bioactivity was analyzed by a spectrophotometric technique. Our results show that materials' surface reactivity and their interfacial hydration are responsible for the bonding-site alteration and surface charge density distribution, which in turn, regulate the protein adsorption process. As a matter of fact, variations on the protein adsorbed density have a directly proportional impact on calcium binding sites, which should be responsible for the initiation of the mineralization process, disturbing the deposition of the interfacial calcium phosphate (Ca-P) mineralized coating. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Stable isotopic analysis of human diet in the Marianas Archipelago, western Pacific.

PubMed

Ambrose, S H; Butler, B M; Hanson, D B; Hunter-Anderson, R L; Krueger, H W

1997-11-01

Proportions of marine vs. terrestrial resources in prehistoric human diets in the southern Mariana Islands (Guam, Rota, Saipan), Micronesia, have been estimated by analysis of stable isotope ratios of carbon and nitrogen in bone collagen and of carbon in apatite. The isotopic composition of marine and terrestrial food resources from the Marianas have also been determined. Experimental evidence shows that collagen carbon isotopes mainly reflect those of dietary protein sources and thus overestimate the contribution of marine animal foods. Marine protein consumption apparently ranges from approximately 20% to approximately 50% on these islands. Experiments also demonstrate the carbon isotope ratio of bone apatite carbonate accurately reflects that of the whole diet. Carbonate carbon isotope data suggest some individuals consumed significant amounts of 13C-enriched (C4) plants or seaweeds. Sugar cane is an indigenous C4 crop and seaweeds are eaten throughout the Pacific, but they have not been considered by archaeologists to have been prehistoric dietary staples. Apatite carbon isotope analysis has apparently identified previously unrecognized prehistoric dietary adaptations in the Mariana Islands, but this must be confirmed by archaeobotanical evidence.

Microwave assisted synthesis and characterization of magnesium substituted calcium phosphate bioceramics.

PubMed

Khan, Nida Iqbal; Ijaz, Kashif; Zahid, Muniza; Khan, Abdul S; Abdul Kadir, Mohammed Rafiq; Hussain, Rafaqat; Anis-Ur-Rehman; Darr, Jawwad A; Ihtesham-Ur-Rehman; Chaudhry, Aqif A

2015-11-01

Hydroxyapatite is used extensively in hard tissue repair due to its biocompatibility and similarity to biological apatite, the mineral component of bone. It differs subtly in composition from biological apatite which contains other ions such as magnesium, zinc, carbonate and silicon (believed to play biological roles). Traditional methods of hydroxyapatite synthesis are time consuming and require strict reaction parameter control. This paper outlines synthesis of magnesium substituted hydroxyapatite using simple microwave irradiation of precipitated suspensions. Microwave irradiation resulted in a drastic decrease in ageing times of amorphous apatitic phases. Time taken to synthesize hydroxyapatite (which remained stable upon heat treatment at 900°C for 1h) reduced twelve folds (to 2h) as compared to traditionally required times. The effects of increasing magnesium concentration in the precursors on particle size, surface area, phase-purity, agglomeration and thermal stability, were observed using scanning electron microscopy, BET surface area analysis, X-ray diffraction and photo acoustic Fourier transform infra-red spectroscopy. Porous agglomerates were obtained after a brief heat-treatment (1h) at 900°C. Copyright © 2015 Elsevier B.V. All rights reserved.

Bioactive composites with designed interfaces

NASA Astrophysics Data System (ADS)

Orefice, Rodrigo Lambert

Bioactive glasses can bond to bone and even soft tissue. However, they are usually weak, brittle and hard to process in specific shapes. The goal of this work is to produce polymer composites having bioactive materials as a reinforcing phase that would display both bioactive behavior and mechanical properties compatible to bone. Polysulfone and bioactive glass particulate were combined in composites with different volume fractions. Composites with 40 vol.% of particulate were submitted to in vitro tests in simulated body fluids. The recorded rates of hydroxy-carbonate-apatite layer deposition were close to the ones observed for pure bioactive glasses. Mechanical properties showed values of elastic modulus, strain at failure and strength within the range of cortical bone for composites with high volume fraction of particles. Fibers can usually favor higher levels of reinforcement in composites than particles. Novel multicomponent fibers were prepared by using the sol-gel method. They were determined to be bioactive in vitro and were successfully used as a reinforcing phase in polysulfone composites. Properties of the bioactive composites were modified by altering the chemistry and structure of the interfaces. Polymers with sulfonic acid and silane groups were specially designed to interact with both the silica surface and the polymer matrix. Nano-composites with a structure and chemistry in between the macrocomponents of the composite were prepared by combining a silanated polymer and silica sol-gel. When applied as interfacial agents, these nano-composites as well as the modified polymers improved the overall properties of the bioactive system. A decay in mechanical properties was observed for composites submitted to an in vitro test. The developed interfacial agents successfully reduced the degree of degradation in properties. Interactions occurring at the interfaces of bioactive composites were studied using Atomic Force Microscopy (AFM). The effect of the structure and chemistry of interfaces was correlated to physical and chemical processes occurring at the interfaces and to the overall properties of composites.

Carbon Concentration Excursions in Apatite Phenocrysts from the Cerro Galan Ignimbrite: A SIMS View into the Transient pre-Eruptive Volatile History of a Supervolcano

NASA Astrophysics Data System (ADS)

Boyce, J. W.; Hervig, R. L.

2006-12-01

In nearly all igneous rock compositions, apatite is the most abundant mineral that regularly incorporates significant quantities of volatile elements into its structure, making it a potentially useful tool for exploring magmatic processing of volatiles (as well as REEs, Sr, Nd, and Pb isotopes, all of which are typically abundant in apatite). We have developed an analytical protocol that permits measurement of C, H, F, S, and Cl in ~8μm diameter regions of apatite using the Cameca 6f SIMS. A primary Cs+ beam (4-10 nA) is used in conjunction with electron gun charge-compensation to sputter negative ions from polished sections and unpolished crystal faces mounted in volatile-free indium mounts. We operated at mass resolving powers sufficient to separate all potential interferences (such as ^{31}PH and 16O2 from ^{32}S, and 17O from 16OH). Quantifying the SIMS data requires a set of standards that are 1) homogeneous at the few-micron scale; and 2) well-calibrated with multiple, reliable, independent volatile content measurements. Using values combed from the literature and other unpublished sources, we have assembled a set of apatite standards, none of which are proven to meet either criteria. Nevertheless, these materials allow us to create calibration curves for all of the volatile elements listed above. Traverses across polished basal sections of apatite phenocrysts from the ~1000 km3 Cerro Galan ignimbrite, Argentina (courtesy of C. Schirnick) yield the following results: Apatites are fluorine-rich, and contain significant and reproducible intracrystalline variations in C, H, S, and Cl. Positive carbon concentration excursions (up to 360 ppm) are factors of 2-7 greater than apatite baseline concentrations (40-60 ppm), the largest of which correlate with position in different grains. In the majority of the traverses, these carbon excursions also correlate spatially with 25-30% increases in sulfur concentration. We suggest that these dramatic increases in carbon and sulfur concentrations record a transient increase in magmatic SO4^{2- } and CO2 activities, perhaps the result of an underplating/recharge event, followed by a return to baseline magma chemistry. Hydrogen-poor rims are observed in all studied crystals, and are accompanied by chlorine-impoverished rims in a majority of the traverses, perhaps recording the pre- or syn-eruption exsolution of a vapor phase enriched in H and Cl.

Formation of A-type granites in the Lower Yangtze River Belt: A perspective from apatite geochemistry

NASA Astrophysics Data System (ADS)

Jiang, Xiao-Yan; Li, He; Ding, Xing; Wu, Kai; Guo, Jia; Liu, Ji-Qiang; Sun, Wei-Dong

2018-04-01

Apatite is ubiquitous in A-type granites, and can be used to elucidate the volatile contents of the silicate melt, which reflect its source characteristics. A-type granites have been recognized as a distinct group of granites. A1- and A2-type subgroups are produced under different extensional settings. However, the details of the mechanisms behind the distinctive geochemical characteristics of A1- and A2-type granites remain obscure. Belts of Cretaceous A1- and A2-type granites occur along the Lower Yangtze River Belt in eastern China. Here we investigated the major and trace element compositions of apatites from contemporary A1- and A2-type granites at different localities along the Lower Yangtze River Belt, in order to decipher their discrepant source processes. Apatites from A1- and A2-type granites show similar major and trace elements, but differ in their F and Cl concentrations. Apatites from A1-type granites in the eastern part of the Lower Yangtze River Belt have much lower F and higher Cl concentrations compared to A2-type granites in the western part. Moreover, from the east to the west, the F concentrations of apatites from A1-type granites increase, while the Cl concentrations decline. In a subducted plate, F is retained by amphibole, chlorite, serpentine and mica minerals through the amphibolite stage, and finally by phengite and lawsonite during the eclogite stage, whereas, Cl is controlled by amphibole, chlorite and serpentine. The high and varied Cl concentrations in A1 subgroup apatites, therefore, may be attributed to the breakdown of amphibole, chlorite and/or serpentine decomposition during partial melting of subducted oceanic crust releasing a large amount of Cl at shallower depth. In contrast, F is transported to deeper depths in the subducted oceanic crust, and released through breakdown of phengite and lawsonite, making an important contribution to the formation of A2-type granites. Apatites from A1- and A2-type granite samples show regular changes in LREE/HREE, LREE/MREE and MREE/HREE ratios with increasing distance from the location of the subduction zone, probably as the result of nonsynchronous dehydration of the serpentine and phengite at different stages during subduction. We propose that A1- and A2-type granites on the Lower Yangtze River Belt were derived from sources metasomatised by fluids originating from the breakdown of amphibole, chlorite and/or serpentine with higher Cl, lower F, and from phengite and/or lawsonite with relatively higher F but lower Cl, respectively.

Synergistic effect of scaffold composition and dynamic culturing environment in multilayered systems for bone tissue engineering.

PubMed

Rodrigues, Márcia T; Martins, Albino; Dias, Isabel R; Viegas, Carlos A; Neves, Nuno M; Gomes, Manuela E; Reis, Rui L

2012-11-01

Bone extracellular matrix (ECM) is composed of mineralized collagen fibrils which support biological apatite nucleation that participates in bone outstanding properties. Understanding and mimicking bone morphological and physiological parameters at a biological scale is a major challenge in tissue engineering scaffolding. Using emergent (nano)technologies scaffold designing may be critically improved, enabling highly functional tissue substitutes for bone applications. This study aims to develop novel biodegradable composite scaffolds of tricalcium phosphate (TCPs) and electrospun nanofibers of poly(ϵ-caprolactone) (PCL), combining TCPs osteoconductivity with PCL biocompatibility and elasticity, mimicking bone structure and composition. We hypothesized that scaffolds with such structure/composition would stimulate the proliferation and differentiation of bone marrow stromal cells (BMSCs) towards the osteogenic phenotype. Composite scaffolds, developed by electrospining using consecutive stacked layers of PCL and TCPs, were characterized by FTIR spectroscopy, X-Ray diffraction and scanning electronic microscopy. Cellular behavior was assessed in goat BMSCs seeded onto composite scaffolds and cultured in static or dynamic conditions, using basal or osteogenic media during 7, 14 or 21 days. Cellular proliferation was quantified and osteogenic differentiation confirmed by alkaline phosphatase activity, alizarin red staining and immunocytochemistry for osteocalcin and collagen I. Results suggest that PCL-TCP scaffolds provide a 3D support for gBMSCs proliferation and osteogenic differentiation with production of ECM. TCPs positively stimulate the osteogenic process, especially under dynamic conditions, where PCL-TCP scaffolds are sufficient to promote osteogenic differentiation even in basal medium conditions. The enhancement of the osteogenic potential in dynamic conditions evidences the synergistic effect of scaffold composition and dynamic stimulation in gBMSCs osteogenic differentiation. Copyright © 2012 John Wiley & Sons, Ltd.

One-step synthesis of bioactive glass by spray pyrolysis

NASA Astrophysics Data System (ADS)

Shih, Shao-Ju; Chou, Yu-Jen; Chien, I.-Chen

2012-12-01

Bioactive glasses (BGs) have recently received more attention from biologists and engineers because of their potential applications in bone implants. The sol-gel process is one of the most popular methods for fabricating BGs, and has been used to produce BGs for years. However, the sol-gel process has the disadvantages of discontinuous processing and a long processing time. This study presented a one-step spray pyrolysis (SP) synthesis method to overcome these disadvantages. This SP method has synthesized spherical bioactive glass (SBG) and mesoporous bioactive glass (MBG) particles using Si-, Ca- and P-based precursors. This study used transmission electron microscopy, selected area electron diffraction and X-ray dispersive spectroscopy to characterize the microstructure, crystallographic structure, and chemical composition for the BG particles. In addition, in vitro bioactive tests showed the formation of hydroxyl apatite layers on SBG and MBG particles after immersion in simulated body fluid for 5 h. Experimental results show the SP formation mechanisms of SBG and MBG particles.

Effect of magnesia on the degradability and bioactivity of sol-gel derived SiO2-CaO-MgO-P2O5 system glasses.

PubMed

Ma, J; Chen, C Z; Wang, D G; Jiao, Y; Shi, J Z

2010-11-01

Mesoporous 58SiO(2)-(38-x)CaO-xMgO-4P(2)O(5) glasses (where x=0, 5, 10 and 20 mol%) have been prepared by the sol-gel synthesis route. The effects of the substitution of MgO for CaO on glass degradation and bioactivity were studied in tris-(hydroxymethyl)-aminomethane and hydrochloric acid buffer solution (Tris-HCl) and simulated body fluid (SBF), respectively. It is observed that the synthesized glasses with various MgO contents possess the similar textural properties. The studies of in vitro degradability and bioactivity show that the rate of glass degradation gradually decreases with the increase of MgO and the formation of apatite layer on glass surface is retarded. The influences of the composition upon glass properties are explained in terms of their internal structures. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Characterization of the bioactive and mechanical behavior of dental ceramic/sol-gel derived bioactive glass mixtures.

PubMed

Abbasi, Zahra; Bahrololoum, Mohammad E; Bagheri, Rafat; Shariat, Mohammad H

2016-02-01

Dental ceramics can be modified by bioactive glasses in order to develop apatite layer on their surface. One of the benefits of such modification is to prolong the lifetime of the fixed dental prosthesis by preventing the formation of secondary caries. Dental ceramic/sol-gel derived bioactive glass mixture is one of the options for this modification. In the current study, mixtures of dental ceramic/bioactive glass with different compositions were successfully produced. To evaluate their bioactive behavior, prepared samples were immersed in a simulated body fluid at various time intervals. The prepared and soaked specimens were characterized using Fourier transform infrared spectroscopy, X-ray diffractometry and scanning electron microscopy. Since bioactive glasses have deleterious effects on the mechanical properties of dental ceramics, 3-point bending tests were used to evaluate the flexural strength, flexural strain, tangent modulus of elasticity and Weibull modulus of the specimens in order to find the optimal relationship between mechanical and bioactive properties. Copyright © 2015 Elsevier Ltd. All rights reserved.

The chemical and isotopic differentiation of an epizonal magma body: Organ Needle pluton, New Mexico

USGS Publications Warehouse

Verplanck, P.L.; Farmer, G.L.; McCurry, M.; Mertzman, S.A.

1999-01-01

Major and trace element, and Nd and Sr isotopic compositions of whole rocks and mineral separates from the Oligocene, alkaline Organ Needle pluton (ONP), southern New Mexico, constrain models for the differentiation of the magma body parental to this compositionally zoned and layered epizonal intrusive body. The data reveal that the pluton is rimmed by lower ??(Nd) (~-5) and higher 87Sr/86Sr (~0.7085) syenitic rocks than those in its interior (??(Nd) ~ 2, 87Sr/86Sr ~0.7060) and that the bulk compositions of the marginal rocks become more felsic with decreasing structural depth. At the deepest exposed levels of the pluton, the ??(Nd)~-5 lithology is a compositionally heterogeneous inequigranular syenite. Modal, compositional and isotopic data from separates of rare earth element (REE)-bearing major and accesory mineral phases (hornblende, titanite, apatite, zircon) demonstrate that this decoupling of trace and major elements in the inequigranular syenite results from accumulation of light REE (LREE)-bearing minerals that were evidently separated from silicic magmas as the latter rose along the sides of the magma chamber. Chemical and isotopic data for microgranular mafic enclaves, as well as for restite xenoliths of Precambrian granite wall rock, indicate that the isotopic distinction between the marginal and interior facies of the ONP probably reflects assimilation of the wall rock by ??(Nd) ~-2 mafic magmas near the base of the magma system. Fractional crystallization and crystal liquid separation of the crystally contaminated magma at the base and along the margins of the chamber generated the highly silicic magmas that ultimately pooled at the chamber top.

A Novel Injectable Calcium Phosphate Cement-Bioactive Glass Composite for Bone Regeneration

PubMed Central

Zhao, Kang; Tang, Yufei; Cheng, Zhe; Chen, Jun; Zang, Yuan; Wu, Jianwei; Kong, Liang; Liu, Shuai; Lei, Wei; Wu, Zixiang

2013-01-01

Background Calcium phosphate cement (CPC) can be molded or injected to form a scaffold in situ, which intimately conforms to complex bone defects. Bioactive glass (BG) is known for its unique ability to bond to living bone and promote bone growth. However, it was not until recently that literature was available regarding CPC-BG applied as an injectable graft. In this paper, we reported a novel injectable CPC-BG composite with improved properties caused by the incorporation of BG into CPC. Materials and Methods The novel injectable bioactive cement was evaluated to determine its composition, microstructure, setting time, injectability, compressive strength and behavior in a simulated body fluid (SBF). The in vitro cellular responses of osteoblasts and in vivo tissue responses after the implantation of CPC-BG in femoral condyle defects of rabbits were also investigated. Results CPC-BG possessed a retarded setting time and markedly better injectability and mechanical properties than CPC. Moreover, a new Ca-deficient apatite layer was deposited on the composite surface after immersing immersion in SBF for 7 days. CPC-BG samples showed significantly improved degradability and bioactivity compared to CPC in simulated body fluid (SBF). In addition, the degrees of cell attachment, proliferation and differentiation on CPC-BG were higher than those on CPC. Macroscopic evaluation, histological evaluation, and micro-computed tomography (micro-CT) analysis showed that CPC-BG enhanced the efficiency of new bone formation in comparison with CPC. Conclusions A novel CPC-BG composite has been synthesized with improved properties exhibiting promising prospects for bone regeneration. PMID:23638115

Employing the cyclophosphate to accelerate the degradation of nano-hydroxyapatite/poly(amino acid) (n-HA/PAA) composite materials.

PubMed

Jing, Linjing; Chen, Li; Peng, Haitao; Ji, Mizhi; Xiong, Yi; Lv, Guoyu

2017-12-01

Owing to the good degradability and biocompatibility of polyphosphoesters (PPEs), the aim of the current study was to investigate a novel degradable composite of nano-hydroxyapatite/poly(amino acid) (n-HA/PAA) with cyclophosphate (CPE) via in situ melting polymerization to improve the degradation of n-HA/PAA. The structure of each composite was characterized via Fourier transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The degradation properties were studied in terms of the weight loss and pH in a phosphate-buffered saline (PBS) solution, while the surface morphology was examined using a scanning electron microscope-energy dispersive spectrometer (SEM-EDS) after soaking the surface in simulated body fluid (SBF). The cell proliferation, cell adhesion, and alkaline phosphatase (ALP) activity were used for the analysis of cytocompatibility. The weight loss results showed that the n-HA/PAA composite was 9.98 wt%, weighed after soaking in the PBS solution for 12 weeks, whereas the nano-hydroxyapatite/polyphosphoester-amino acid (n-HA/PPE-AA) composite was 46.94 wt%. The pH of the composites was in a suitable range between 6.64 to 7.06 and finally stabilized at 7.39. The SEM and EDS results revealed the formation of an apatite-like layer on the surface of the n-HA/PPE-AA composites after soaking in SBF for one week. The cell counting Kit 8 (CCK-8) assay of the cell culture in the leaching liquid of the n-HA/PPE-AA composites exhibited non-cytotoxicity and high-proliferation, and the cell adhesion showed the well spreading and normal phenotype extension of the cells on the n-HA/PPE-AA composites surface. Concurrently, the co-culture results of the composites and cells confirmed that the n-HA/PPE-AA composites exhibited a higher ALP activity. In summary, the results demonstrated that the n-HA/PPE-AA composites had a controllable degradation property, good bioactivity, and cytocompatibility.

A new interpretation of the structure of the Sept Iles Intrusive suite, Canada

NASA Astrophysics Data System (ADS)

Higgins, Michael D.

2005-08-01

The layered mafic intrusion at Sept Iles, Canada, is one of the largest intrusions in the world. A new interpretation of its structure is proposed, based on a review of its geology and a comparison with the Skaergaard intrusion, Greenland. Several different magmatic components are recognized; hence the name Sept Iles Intrusive suite (SIIS) is proposed. Emplacement of the suite may have been preceded by eruption of flood basalts. The first magmas of the suite rose in the crust to accumulate beneath the density filter afforded by the basalts. The largest component is the Sept Iles Mafic intrusion (SIMI). The Lower series of the SIMI is dominated by leucotroctolites and leucogabbros. Above it lie the Layered series, which is largely comprised of gabbro and troctolite. Both these units are unchanged from earlier interpretations. The anorthosites (s.l.), gabbros and monzogabbros, formerly called the Transitional series, are now considered to be the Upper Border series, developed by floatation of plagioclase. Common autoliths in the Layered series are parts of the hydrothermally altered Upper Border series from towards the interior of the intrusion, which have foundered and settled through the magma. The contamination of the magma that accompanied this event oxidised iron in the magma and led to the precipitation of magnetite around the periphery of the intrusion. The subsequent depletion of Fe 3+ and/or increase in SiO 2, CaO and P 2O 5 may have induced apatite saturation and accumulation to form two layers rich in apatite, near the base and at top of the Layered series. Granitic magma was developed by fractional crystallisation and was emplaced along the roof of the chamber, where it acquired large quantities of xenoliths. These were probably derived from the flood basalts, their evolved members and fragments of mafic dykes chilled by the granitic magma. Accumulations of monzonite pillows in this unit testify to another magmatic event and a floor to the granitic magma chamber, indicating lateral transport of magma. Chemically distinct syenites in the upper part of the intrusion are part of the Point du Criade intrusion, a large, late composite sill. Diabase and leucogabbro components show a close link with the SIMI and all the acidic magmas may have originally formed by differentiation of the main magma in cupolas towards the centre of the intrusion. A series of late gabbro intrusions that cut the SIMI may represent a rejuvenation of magmatism. The Border zone is a mass of fine-grained rocks that occurs along the border of the SIMI: it may be another magmatic component, or just the lateral border series of the SIMI.

Zirconia-hydroxyapatite composite material with micro porous structure.

PubMed

Matsumoto, Takuya Junior; An, Sang-Hyun; Ishimoto, Takuya; Nakano, Takayoshi; Matsumoto, Takuya; Imazato, Satoshi

2011-11-01

Titanium plates and apatite blocks are commonly used for restoring large osseous defects in dental and orthopedic surgery. However, several cases of allergies against titanium have been recently reported. Also, sintered apatite block does not possess sufficient mechanical strength. In this study, we attempted to fabricate a composite material that has mechanical properties similar to biocortical bone and high bioaffinity by compounding hydroxyapatite (HAp) with the base material zirconia (ZrO(2)), which possesses high mechanical properties and low toxicity toward living organisms. After mixing the raw material powders at several different ZrO(2)/HAp mixing ratios, the material was compressed in a metal mold (8 mm in diameter) at 5 MPa. Subsequently, it was sintered for 5 h at 1500°C to obtain the ZrO(2)/HAp composite. The mechanical property and biocompatibility of materials were investigated. Furthermore, osteoconductivity of materials was investigated by animal studies. A composite material with a minute porous structure was successfully created using ZrO(2)/HAp powders, having different particle sizes, as the starting material. The material also showed high protein adsorption and a favorable cellular affinity. When the mixing ratio was ZrO(2)/HAp=70/30, the strength was equal to cortical bone. Furthermore, in vivo experiments confirmed its high osteoconductivity. The composite material had strength similar to biocortical bones with high cell and tissue affinities by compounding ZrO(2) and HAp. The ZrO(2)/HAp composite material having micro porous structure would be a promising bone restorative material. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Sm-Nd in marine carbonates and phosphates - Implications for Nd isotopes in seawater and crustal ages

NASA Technical Reports Server (NTRS)

Shaw, H. F.; Wasserburg, G. J.

1985-01-01

The possibility of establishing a record of variations in the isotopic composition of Nd in seawater over geologic time is explored. To construct such a record, a phase must be identified which incorporated Nd with the same isotopic composition as seawater at the time of its formation, preserves that composition, and which is relatively common in sediments. To evaluate the suitability of carbonates and phosphates, the Rb, Sr, Sm, and Nd concentrations and the Nd and Sr isotopic composition of a variety of modern and ancient marine calcite, aragonite, and apatite samples have been measured and the results are presented and discussed.

Micro-structural evolution and biomineralization behavior of carbon nanofiber/bioactive glass composites induced by precursor aging time.

PubMed

Jia, Xiaolong; Tang, Tianhong; Cheng, Dan; Zhang, Cuihua; Zhang, Ran; Cai, Qing; Yang, Xiaoping

2015-12-01

Bioactive glass (BG)-containing carbon nanofibers (CNFs) are promising orthopaedic biomaterials. Herein, CNF composites were produced from electrospinning of polyacrylonitrile (PAN)/BG sol-gel precursor solution, followed by carbonization. Choosing 58S-type BG (mol%: 58.0% SiO2-26.3% CaO-15.7% P2O5) as the model, micro-structural evolution of CNF/BG composites was systematically evaluated in relating to aging times of BG precursor solution. With aging time prolonging, BG precursors underwent morphological changes from small sol clusters with loosely and randomly branched structure to highly crosslinked Si-network structure, showing continuous increase in solution viscosity. BG precursor solution with low viscosity could mix well with PAN solution, resulting in CNF composite with homogeneously distributed BG component. Whereas, BG precursor gel with densely crosslinked Si-network structure led to uneven distribution of BG component along final CNFs due to its significant phase separation from PAN component. Meanwhile, BG nanoparticles in CNFs demonstrated micro-structural evolution that they transited from weak to strong crystal state along with longer aging time. Biomineralization in simulated body fluid and in vitro osteoblasts proliferation were then applied to determine the bioactivity of CNF/BG composites. CNF/BG composites prepared from shorter aging time could induce both faster apatite deposition and cell proliferation rate. It was suggested weakly crystallized BG nanoparticles along CNFs dissolved fast and was able to provide numerous nucleation sites for apatite deposition, which also favored the proliferation of osteoblasts cells. Aging time could thus be a useful tool to regulate the biological features of CNF/BG composites. Copyright © 2015 Elsevier B.V. All rights reserved.

Advantages of conducting in-situ U-Pb age dating of multiple U-bearing minerals from a single complex: Case in point - the Oka Carbonatite Complex

NASA Astrophysics Data System (ADS)

Chen, W.; Simonetti, A.

2012-12-01

A detailed radiometric investigation is currently underway focusing on U-bearing accessory minerals apatite, perovskite, and niocalite from the Oka Carbonatite Complex (Canada). One of the main objectives is to obtain a comparative chronology of melt crystallization for the complex. Unlike other commonly adopted U-bearing minerals (e.g., zircon, monazite) for in-situ dating investigations, apatite, perovskite, and niocalite contain relatively high contents of common Pb. Hence, careful assessment of the proportion and composition of the common Pb, and usage of appropriate matrix-matched external standards are imperative. The Madagascar apatite was utilized as the external standard for apatite dating, and the Emerald Lake and Durango apatites were adopted as secondary standards; the latter yield ages of 92.6 ±1.8 and 32.2 ±1.1 Ma, respectively, and these are identical to their accepted ages. Pb/U ages for apatite from Oka were obtained for different rock types, including 8 carbonatites, 4 okaites, 3 ijolites and 3 alnoites, and these define a range of ages between ~105 and ~135 Ma; this result suggests a protracted crystallization history. In total, 266 individual analyses define two peaks at ~115 and ~125Ma. For perovskite dating, the Ice River perovskite standard was utilized as the external standard. The perovskites from one okaite sample yield an age of 112.2 ±1.9 Ma, and is much younger than the previously reported U-Pb perovskite age of 131 ±7 Ma. Hence, the combined U-Pb perovskite ages also suggest a rather prolonged time of melt crystallization. Niocalite is a rare, accessory silicate mineral that occurs within the carbonatites at Oka. The international zircon standard BR266 was selected for use as the external standard and rastering was employed to minimize the Pb-U fractionation. Two niocalite samples give young ages at 110.6 ±1.2 and 115.0 ±1.9 Ma, and are identical to their respective apatite ages (given associated uncertainties) from the same sample. The niocalite for a carbonatite sample Oka153 defines a bimodal age distribution, with weighted average 206Pb/238U ages of 110.1 ±5.0 and 133.2 ±6.1 Ma. Apatite from the same sample also records a similar bimodal age distribution of 111.4 ±2.8 and 126.9 ±1.8 Ma. The combined in situ U-Pb dating results for apatite, pervoskite, niocalite from Oka clearly support a protracted history of magmatic activity (~30 Myr) for this carbonatite complex. Of importance, the U-Pb results from this study clearly indicate the significance of conducting a thorough geochronological investigation rather than defining the age of any one alkaline complex solely on the basis of a single radiometric age determination.

Structure, apatite inducing ability, and corrosion behavior of chitosan/halloysite nanotube coatings prepared by electrophoretic deposition on titanium substrate.

PubMed

Molaei, A; Amadeh, A; Yari, M; Reza Afshar, M

2016-02-01

In this study chitosan/halloysite nanotube composite (CS/HNT) coatings were deposited by electrophoretic deposition (EPD) on titanium substrate. Using HNT particles were investigated as new substituents for carbon nanotubes (CNTs) in chitosan matrix coatings. The ability of chitosan as a stabilizing, charging, and blending agent for HNT particles was exploited. Furthermore, the effects of pH, electrophoretic bath, and sonicating duration were studied on the deposition of suspensions containing HNT particles. Microstructure properties of coatings showed uniform distribution of HNT particles in chitosan matrix to form smooth nanocomposite coatings. The zeta potential results revealed that at pH around 3 there is an isoelectric point for HNT and it would have cathodic and anionic states at pH values less and more than 3, respectively. Therefore, CS/HNT composite deposits were produced in the pH range of 2.5 to 3. The apatite inducing ability of chitosan-HNT composite coating assigned that HNT particles were biocompatible because they formed carbonated hydroxyapatite particles on CS/HNT coating in corrected simulated body fluid (C-SBF). Finally, electrochemical corrosion characterizations determined that corrosion resistance in CS/HNT coating has been improved compared to bare titanium substrate. Copyright © 2015 Elsevier B.V. All rights reserved.

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 higher temperatures than fission-track damage and the impact on coupled apatite He and AFT dates is magnified for protracted cooling histories. Further experimental and field-based tests are important for refining radiation damage and fission-track annealing parameters for accurate interpretation of apatite He- and AFT-derived thermal histories.

Petrology of Martian meteorite Northwest Africa 998

NASA Astrophysics Data System (ADS)

Treiman, Allan H.; Irving, Anthony J.

2008-05-01

Nakhlite Northwest Africa (NWA) 998 is an augite-rich cumulate igneous rock with mineral compositions and oxygen isotopic composition consistent with an origin on Mars. This 456-gram, partially fusion-crusted meteorite consists of (by volume) ˜75% augite (core composition Wo39En39Fs22), ˜9% olivine (Fo35), ˜7% plagioclase (Ab61An35) as anhedra among augite and olivine, ˜3.5% low-calcium pyroxenes (pigeonite and orthopyroxene) replacing or forming overgrowths on olivine and augite, ˜1% titanomagnetite, and other phases including potassium feldspar, apatite, pyrrhotite, chalcopyrite, ilmenite, and fine-grained mesostasis material. Minor secondary alteration materials include "iddingsite" associated with olivine (probably Martian), calcite crack fillings, and iron oxide/hydroxide staining (both probably terrestrial). Shock effects are limited to minor cataclasis and twinning in augite. In comparison to other nakhlites, NWA 998 contains more low-calcium pyroxenes and its plagioclase crystals are blockier. The large size of the intercumulus feldspars and the chemical homogeneity of the olivine imply relatively slow cooling and chemical equilibration in the late- and post-igneous history of this specimen, and mineral thermometers give subsolidus temperatures near 730 °C. Oxidation state was near that of the QFM buffer, from about QFM-2 in earliest crystallization to near QFM in late crystallization, and to about QFM + 1.5 in some magmatic inclusions. The replacement or overgrowth of olivine by pigeonite and orthopyroxene (with or without titanomagnetite), and the marginal replacement of augite by pigeonite, are interpreted to result from late-stage reactions with residual melts (consistent with experimental phase equilibrium relationships). Apatite is concentrated in planar zones separating apatite-free domains, which suggests that residual magma (rich in P and REE) was concentrated in planar (fracture?) zones and possibly migrated through them. Loss of late magma through these zones is consistent with the low bulk REE content of NWA 998 compared with the calculated REE content of its parent magma.

Composition of bone and apatitic biomaterials as revealed by intravital Raman microspectroscopy.

PubMed

Penel, G; Delfosse, C; Descamps, M; Leroy, G

2005-05-01

Microcharacterization of biominerals allows a better understanding of the pathophysiological events that occur in calcified tissues and synthetic biomaterials. Different methods have been extensively used to conduct such investigations. A new model for the intravital study of the composition and structure of membranous bone by Raman microspectroscopy is described. Titanium bone chambers equipped with a fused-silica optical window were implanted transcutaneously in the calvaria of New Zealand rabbits. The implanted optical windows were well tolerated, and spectral acquisitions were performed without any additional invasive procedure. Bone and implanted apatitic biomaterials were analyzed at different times after surgery. All Raman bands were unambiguously identified in the bone and biomaterial spectra. The main PO4 and CO3 Raman bands in bone spectra were consistent with those found in the carbonated apatite spectrum. The major collagen bands were always observed around 1200-1300 (amide III) and 1600-1700 (amide I) delta cm(-1) and, 1400-1470 and 2800-3100 delta cm(-1) (bending and stretching modes of CH groups, respectively). The phenylalanine (Phe) band was identified in all spectra at 1003 delta cm(-1) and overlapped that of the weak HPO4(2-) ion. The CH bands frequently overlapped the lipid bands. However a distinct protein and lipid bands were detected at 2950 and 2852 delta cm(-1), respectively. In bone areas close to blood vessels, the Raman signature of hemoglobin was detected with a characteristic band at 754 delta cm(-1). The changes observed in bone varied as a function of time and location. The composition and structure of all of the biomaterials studied--including those that were resorbable--seemed to remain stable over time and location. We report for the first time the complete intravital study of Raman spectra of bone and calcium phosphate biomaterials over a period of 8 months. This new approach does not require specimen preparation and allows simultaneous observation of mineral and organic bone constituents over time, which therefore should provide insightful information about their relationship.

In vitro studies of degradation and bioactivity of aliphatic polyester composites

NASA Astrophysics Data System (ADS)

Chouzouri, Georgia

In spite of numerous publications on the potential use of combinations of aliphatic polyester composites containing bioactive fillers for bone regeneration, little information exists on the combined in vitro mechanisms involving simultaneously diffusion for polymer degradation and bioactivity through nucleation and growth of apatite in simulated body fluid (SBF) solution. The objective of this study is to contribute to the understanding of the fundamentals in designing non-porous, solid materials for bone regeneration, from experimental data along with their engineering interpretation. Bioactivity, in terms of apatite growth, was assessed through several experimental methods such as scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray-diffraction (XRD) and changes in ion concentration. In the case of the six neat fillers evaluated, the filler shape, form and chemical structure showed significant differences in bioactivity response. Bioglass and calcium silicate fillers showed faster nucleation and growth rates in the screening experiments. Composites at 30% by weight filler were prepared by solution and/or melt mixing. Polycaprolactone (PCL) composites containing five different fillers were evaluated. Solution processed PCL/calcium silicate (CS) samples showed faster bioactivity, as determined by apatite growth, compared to melt mixed samples. The onset time for bioactivity was different for all PCL composites. The limited bioactivity in the PCL composites over longer periods of time could be attributed to the PCL hydrophobicity leading to a slow polymer degradation rate, and also to the lack of SBF replenishment. For both polylactic acid (PLA) composites containing CS and bioglass, significant growth was observed after one week and in the case of CS was still evident after four weeks immersion. However, at prolonged time periods no further bioactivity was observed, although ion release results indicated a faster release rate that would eventually lead to a faster polymer degradation and possibly continuing bioactivity. The presence of silicate fillers enhanced the hydrolytic degradation rate of both PCL and PLA as shown from kinetic data calculations based on molecular weight measurements. Unfilled PLA samples showed significant embrittlement after two weeks immersion, whereas for the CS filled system more significant changes could be observed in the compressive strength and modulus after the same time period. Experimental data were also fitted into an equation proposed to calculate erosion number; in the case of unfilled PLA predictions were found to agree with literature results suggesting bulk erosion. By assuming impermeable, randomly dispersed glass flakes, water transport in a composite system, prior to significant polymer degradation could be modeled. However, modeling of transport in the case of the composite consisting of a degrading polymer and a reactive decaying filler was challenging, particularly in the case of directional bioactive reinforcements, due to the occurrence of simultaneous time dependent diffusion phenomena that altered the integrity of the sample.

Enhanced in vitro biocompatibility of ultrafine-grained biomedical NiTi alloy with microporous surface

NASA Astrophysics Data System (ADS)

Zheng, C. Y.; Nie, F. L.; Zheng, Y. F.; Cheng, Y.; Wei, S. C.; Valiev, R. Z.

2011-08-01

Bulk ultrafine-grained Ni 50.8Ti 49.2 alloy (UFG-NiTi) was successfully fabricated by equal-channel angular pressing (ECAP) technique in the present study, and to further improve its surface biocompatibility, surface modification techniques including sandblasting, acid etching and alkali treatment were employed to produce either irregularly roughened surface or microporous surface or hierarchical porous surface with bioactivity. The effect of the above surface treatments on the surface roughness, wettability, corrosion behavior, ion release, apatite forming ability and cytocompatibility of UFG-NiTi alloy were systematically investigated with the coarse-grained NiTi alloy as control. The pitting corrosion potential ( Epit) was increased from 393 mV (SCE) to 704 mV (SCE) with sandblasting and further increased to 1539 mV (SCE) with following acid etching in HF/HNO 3 solution. All the above surface treatment increased the apatite forming ability of UFG-NiTi in varying degrees when soaked them in simulated body fluid (SBF). Meanwhile, both sandblasting and acid etching could promote the cytocompatibility for osteoblasts: sandblasting enhanced cell attachment and acid etching increased cell proliferation. The different corrosion behavior, apatite forming ability and cellular response of UFG-NiTi after different surface modifications are attributed to the topography and wettability of the resulting surface oxide layer.

Bioactivity and mechanical properties of polydimethylsiloxane (PDMS)-CaO-SiO2 hybrids with different calcium contents.

PubMed

Kamitakahara, M; Kawashita, M; Miyata, N; Kokubo, T; Nakamura, T

2002-11-01

Polydimethylsiloxane (PDMS)-CaO-SiO(2) hybrids with starting compositions containing PDMS/(Si(OC(2)H(5))(4)+PDMS) weight ratio=0.30, H(2)O/Si(OC(2)H(5))(4) molar ratio=2, and Ca(NO(3))(2)/Si(OC(2)H(5))(4) molar ratios=0-0.2, were prepared by the sol-gel method. The apatite-forming ability of the hybrids increased with increasing calcium content in the Ca(NO(3))(2)/Si(OC(2)H(5))(4) molar ratio range 0-0.1. The hybrids with a Ca(NO(3))(2)/Si(OC(2)H(5))(4) molar ratio range 0.1-0.2 formed apatite on their surfaces in a simulated body fluid (SBF) within 12 h. The hybrid with a Ca(NO(3))(2)/Si(OC(2)H(5))(4) molar ratio of 0.10 showed an excellent apatite-forming ability in SBF with a low release of silicon into SBF. It also showed mechanical properties analogous to those of human cancellous bones. This hybrid is expected to be useful as a new type of bioactive material.

Materials Engineering by Ameloblasts

PubMed Central

2015-01-01

Enamel is unique. It is the only epithelial-derived mineralized tissue in mammals and has a distinct micro- and nanostructure with nanofibrous apatite crystals as building blocks. It is synthesized by a highly specialized cell, the ameloblast, which secretes matrix proteins with little homology to any other known amino acid sequence, but which is composed of a primary structure that makes it competent to self-assemble and control apatite crystal growth at the nanometer scale. The end-product of ameloblast activity is a marvel of structural engineering: a material optimized to provide the tooth with maximum biting force, withstanding millions of cycles of loads without catastrophic failure, while also protecting the dental pulp from bacterial attack. This review attempts to bring into context the mechanical behavior of enamel with the developmental process of amelogenesis and structural development, since they are linked to tissue function, and the importance of controlling calcium phosphate mineralization at the nanometer scale. The origins of apatite nanofibers, the development of a stiffness gradient, and the biological processes responsible for the synthesis of a hard and fracture-resistant dental tissue are discussed with reference to the evolution of enamel from a fibrous composite to a complex, tough, and damage-tolerant coating on dentin. PMID:25800708

Devonian climate and reef evolution: Insights from oxygen isotopes in apatite

NASA Astrophysics Data System (ADS)

Joachimski, M. M.; Breisig, S.; Buggisch, W.; Talent, J. A.; Mawson, R.; Gereke, M.; Morrow, J. R.; Day, J.; Weddige, K.

2009-07-01

Conodonts, microfossils composed of carbonate-fluor apatite, are abundant in Palaeozoic-Triassic sediments and have a high potential to preserve primary oxygen isotope signals. In order to reconstruct the palaeotemperature history of the Devonian, the oxygen isotope composition of apatite phosphate was measured on 639 conodont samples from sequences in Europe, North America and Australia. The Early Devonian (Lochkovian; 416-411 Myr) was characterized by warm tropical temperatures of around 30 °C. A cooling trend started in the Pragian (410 Myr) with intermediate temperatures around 23 to 25 °C reconstructed for the Middle Devonian (397-385 Myr). During the Frasnian (383-375 Myr), temperatures increased again with temperatures to 30 °C calculated for the Frasnian-Famennian transition (375 Myr). During the Famennian (375-359 Myr), surface water temperatures slightly decreased. Reconstructed Devonian palaeotemperatures do not support earlier views suggesting the Middle Devonian was a supergreenhouse interval, an interpretation based partly on the development of extensive tropical coral-stromatoporoid communities during the Middle Devonian. Instead, the Devonian palaeotemperature record suggests that Middle Devonian coral-stromatoporoid reefs flourished during cooler time intervals whereas microbial reefs dominated during the warm to very warm Early and Late Devonian.

A bio-recognition device developed onto nano-crystals of carbonate apatite for cell-targeted gene delivery.

PubMed

Chowdhury, E H; Akaike, Toshihiro

2005-05-20

The DNA delivery to mammalian cells is an essential tool for analyzing gene structure, regulation, and function. The approach holds great promise for the further development of gene therapy techniques and DNA vaccination strategies to treat and control diseases. Here, we report on the establishment of a cell-specific gene delivery and expression system by physical adsorption of a cell-recognition molecule on the nano-crystal surface of carbonate apatite. As a model, DNA/nano-particles were successfully coated with asialofetuin to facilitate uptake by hepatocyte-derived cell lines through the asialoglycoprotein receptor (ASGPr) and albumin to prevent non-specific interactions of the particles with cell-surface. The resulting composite particles with dual surface properties could accelerate DNA uptake and enhance expression to a notable extent. Nano-particles coated with transferrin in the same manner dramatically enhanced transgene expression in the corresponding receptor-bearing cells and thus our newly developed strategy represents a universal phenomenon for anchoring a bio-recognition macromolecule on the apatite crystal surface for targeted gene delivery, having immediate applications in basic research laboratories and great promise for gene therapy. (c) 2005 Wiley Periodicals, Inc.

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.

Flexible bipolar nanofibrous membranes for improving gradient microstructure in tendon-to-bone healing.

PubMed

Li, Xiaoxi; Cheng, Ruoyu; Sun, Zhiyong; Su, Wei; Pan, Guoqing; Zhao, Song; Zhao, Jinzhong; Cui, Wenguo

2017-10-01

Enthesis is a specialized tissue interface between the tendon and bone. Enthesis structure is very complex because of gradient changes in its composition and structure. There is currently no strategy to create a suitable environment and to regenerate the gradual-changing enthesis because of the modular complexities between two tissue types. Herein, a dual-layer organic/inorganic flexible bipolar fibrous membrane (BFM) was successfully fabricated by electrospinning to generate biomimetic non-mineralized fibrocartilage and mineralized fibrocartilage in tendon-to-bone integration of enthesis. The growth of the in situ apatite nanoparticle layer was induced on the nano hydroxyapatite-poly-l-lactic acid (nHA-PLLA) fibrous layer in simulated body solution, and the poly-l-lactic acid (PLLA) fibrous layer retained its original properties to induce tendon regeneration. The in vivo results showed that BFM significantly increased the area of glycosaminoglycan staining at the tendon-bone interface and improved collagen organization when compared to the simplex fibrous membrane (SFM) of PLLA. Implanting the bipolar membrane also induced bone formation and fibrillogenesis as assessed by micro-CT and histological analysis. Biomechanical testing showed that the BFM group had a greater ultimate load-to-failure and stiffness than the SFM group at 12weeks after surgery. Therefore, this flexible bipolar nanofibrous membrane improves the healing and regeneration process of the enthesis in rotator cuff repair. In this study, we generated a biomimetic dual-layer organic/inorganic flexible bipolar fibrous membrane by sequential electrospinning and in situ biomineralization, producing integrated bipolar fibrous membranes of PLLA fibrous membrane as the upper layer and nHA-PLLA fibrous membrane as the lower layer to mimic non-mineralized fibrocartilage and mineralized fibrocartilage in tendon-to-bone integration of enthesis. Flexible bipolar nanofibrous membranes could be easily fabricated with gradient microstructure for enthesis regeneration in rotator cuff tears. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

In Situ Immobilization of Selenium in Sediment

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

Moore, Robert C.; Stewart, Thomas Austin

2014-09-01

This project focused on the use of a sorbent, carbonated apatite, to immobilize selenium in the environment. It is know that apatite will sorb selenium and based on the mechanism of sorption it is theorized that carbonated apatite will be more effective that pure apatite. Immobilization of selenium in the environment is through the use of a sorbent in a permeable reactive barrier (PRB). A PRB can be constructed by trenching and backfill with the sorbent or in the case of apatite as the sorbent formed in situ using the apatite forming solution of Moore (2003, 2004). There is verymore » little data on selenium sorption by carbonated apatite in the literature. Therefore, in this work, the basic sorptive properties of carbonated apatite were investigated. Carbonated apatite was synthesized by a precipitation method and characterized. Batch selenium kinetic and equilibrium experiments were performed. The results indicate the carbonated apatite contained 9.4% carbonate and uptake of selenium as selenite was rapid; 5 hours for complete uptake of selenium vs. more than 100 hours for pure hydroxyapatite reported in the literature. Additionally, the carbonated apatite exhibited significantly higher distribution coefficients in equilibrium experiments than pure apatite under similar experimental conditions. The next phase of this work will be to seek additional funds to continue the research with the goal of eventually demonstrating the technology in a field application.« less

Synthesis, Characterization, In Vitro Bioactivity and Biocompatibility Evaluation of Hydroxyapatite/Bredigite (Ca7MgSi4O16) Composite Nanoparticles

NASA Astrophysics Data System (ADS)

Kouhi, Monireh; Shamanian, Morteza; Fathi, Mohammadhossein; Samadikuchaksaraei, Ali; Mehdipour, Ahmad

2016-04-01

Silicate-based bioceramics have been found to possess excellent apatite-forming ability, and they can stimulate cell proliferation and osteogenic differentiation. In this study, bredigite (Ca7MgSi4O16) nanoparticles were synthesized and incorporated into a hydroxyapatite (HA)-based matrix to produce composite nanoparticles with improved bioactivity and biocompatibility. HA/bredigite nanoparticles containing 25% and 50% bredigite were synthesized by using the sol-gel method. X-ray diffraction, transmission electron microscopy, scanning electron microscopy, energy-dispersive x-ray spectroscopy, and Fourier transform infrared techniques were used to study the phase structure, morphology, and structural properties of prepared nanoparticles. Results indicated that HA/bredigite nanoparticles with an average particle size of less than 50 nm and homogeneous distribution of bredigite were successfully synthesized. Obtained results also revealed that the presence of bredigite led to a small increase in HA lattice parameters and to a decrease in the agglomeration of composite nanoparticles. The in vitro bioactivity studies performed in the simulated body fluid showed that composite nanoparticles had higher apatite-forming ability than pure HA. The results of a cell proliferation assay revealed that the proliferation of mesenchymal stem cells in the extract of HA/bredigite was significantly higher than those in the extract of the initial HA and control group after 72 h. As the properties of HA/bredigite nanoparticles were highly improved, compared with pure HA, it is concluded that these composite nanoparticles could potentially be good candidates for use as effective bioactive materials in bone regeneration applications.

Trace Element Geochemistry of Magnetite and Accesory Phases from El Romeral Iron Oxide-Apatite Deposit, Northern Chile

NASA Astrophysics Data System (ADS)

Barra, F.; Rojas, P.; Reich, M.; Deditius, A.; Simon, A. C.

2017-12-01

Iron oxide-apatite (IOA) or "Kiruna-type" deposits are an important source of Fe, P, REE, among other essential elements for society. Three main hypotheses have been proposed to explain the genesis of these controversial deposits, which invoke liquid immiscibility, hydrothermal replacement or a magmatic-hydrothermal origin driven by flotation of magnetite-bubble pairs. Here we focus on the El Romeral, one of the largest IOA deposits located in the southernmost part of the Cretaceous Chilean Iron Belt. We combined SEM observations and EMPA analyses of magnetite, actinolite, pyrite, and apatite, with micro-Raman determinations of mineral inclusions within magnetite grains. Two textural types of magnetite were identified at El Romeral: (i) inclusion-rich magnetite (Mag I), and (ii) inclusion-poor magnetite (Mag II) that are commonly surrounding the inclusion-rich Mag I grains. Mag I is characterized by high V ( 2500-2800 ppm) and Ti (300-1000 ppm) contents with high-temperature mineral inclusions such as ilmenite, Ti-pargasite and clinochlore at depth, and quartz and phlogopite inclusions in shallower samples. These characteristics are consistent with a magmatic origin for Mag I. Inclusion-poor magnetite (Mag II) have high V (2400-2600 ppm) and lower Ti (70-200 ppm) contents than Mag I, which point to chemical changes of the mineralizing fluid(s). An increase in thermal gradient with depth is evidenced by the presence of high-temperature (low #Fe) actinolite, as well as F-rich apatite and pyrite with high Co:Ni (>1) in the deep zones. In contrast, lower Co:Ni ratios (<0.5) in pyrite and higher Cl contents in OH-rich apatite are detected in samples from shallower levels. This vertical chemical variation supports a magmatic-hydrothermal origin for the El Romeral deposit, and point to compositional changes driven by decompression of a magnetite-fluid suspension.

Preparation and bioactive properties of nano bioactive glass and segmented polyurethane composites.

PubMed

Aguilar-Pérez, Fernando J; Vargas-Coronado, Rossana F; Cervantes-Uc, Jose M; Cauich-Rodríguez, Juan V; Covarrubias, Cristian; Pedram-Yazdani, Merhdad

2016-04-01

Composites of glutamine-based segmented polyurethanes with 5 to 25 wt.% bioactive glass nanoparticles were prepared, characterized, and their mineralization potential was evaluated in simulated body fluid. Biocompatibility with dental pulp stem cells was assessed by MTS to an extended range of compositions (1 to 25 wt.% of bioactive glass nanoparticles). Physicochemical characterization showed that composites retained many of the matrix properties, i.e. those corresponding to semicrystalline elastomeric polymers as they exhibited a glass transition temperature (Tg) between -41 and -36℃ and a melting temperature (Tm) between 46 and 49℃ in agreement with X-ray reflections at 23.6° and 21.3°. However, with bioactive glass nanoparticles addition, tensile strength and strain were reduced from 22.2 to 12.2 MPa and 667.2 to 457.8%, respectively with 25 wt.% of bioactive glass nanoparticles. Although Fourier transform infrared spectroscopy did not show evidence of mineralization after conditioning of these composites in simulated body fluid, X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray microanalysis showed the formation of an apatite layer on the surface which increased with higher bioactive glass concentrations and longer conditioning time. Dental pulp stem cells proliferation at day 5 was improved in bioactive glass nanoparticles composites containing lower amounts of the filler (1-2.5 wt.%) but it was compromised at day 9 in composites containing high contents of nBG (5, 15, 25 wt.%). However, Runx2 gene expression was particularly upregulated for the dental pulp stem cells cultured with composites loaded with 15 and 25 wt.% of bioactive glass nanoparticles. In conclusion, low content bioactive glass nanoparticles and segmented polyurethanes composites deserve further investigation for applications such as guided bone regeneration membranes, where osteoconductivity is desirable but not a demanding mechanical performance. © The Author(s) 2016.

Photo-oxidation of gaseous ethanol on photocatalyst prepared by acid leaching of titanium oxide/hydroxyapatite composite

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

Ono, Y., E-mail: ono-y@kanagawa-iri.go.jp; Rachi, T.; Yokouchi, M.

2013-06-01

Highlights: ► Photocatalyst powder was prepared by acid leaching of TiO{sub 2}/apatite composite. ► The photocatalytic activity was evaluated from in situ FT-IR study using ethanol. ► Apatite in the composite had positive effect for the photo-oxidation of ethanol. ► The enhanced oxidation rate was explained by the difference in deactivation rate. - Abstract: Highly active photocatalysts were synthesized by leaching of heat-treated titanium dioxide (TiO{sub 2})/hydroxyapatite (HAp) powder with hydrochloric acid at 0.25, 0.50, 0.75 mol/l, and their photocatalytic activities were evaluated from in situ Fourier transform infrared (FT-IR) study of photo-oxidation of gaseous ethanol. By changing the acidmore » concentration, the TiO{sub 2}/HAp composite had different atomic ratios of Ca/Ti (0.0–2.8) and P/Ti (0.3–2.1). It was found that phosphate group remained on the surface of TiO{sub 2} particle even in the sample treated with concentrated acid (0.75 mol/l). These acid-treated samples showed higher rates for ethanol photo-oxidation than the commercial TiO{sub 2} powder, Degussa P25. The highest rate was obtained in the TiO{sub 2}/HAp composite treated with the dilute (0.25 mol/l) acid in spite of its low content of TiO{sub 2} photocatalyst. This enhanced photocatalytic activity was attributed to the result that the deactivation with repeated injections of ethanol gas was suppressed in the TiO{sub 2}/HAp composites compared with the TiO{sub 2} powders.« less

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

Surface modification of calcium-copper hydroxyapatites using polyaspartic acid

NASA Astrophysics Data System (ADS)

Othmani, Masseoud; Aissa, Abdallah; Bachoua, Hassen; Debbabi, Mongi

2013-01-01

Mixed calcium-copper hydroxyapatite (Ca-CuHAp), with general formula Ca(10-x)Cux(PO4)6(OH)2, where 0 ≤ x ≤ 0.75 was prepared in aqueous medium in the presence of different concentrations of poly-L-aspartic acid (PASP). XRD, IR, TG-DTA, TEM-EDX, AFM and chemical analyses were used to characterize the structure, morphology and composition of the products. All techniques show the formation of new hybrid compounds Ca-CuHAp-PASP. The presence of the grafting moiety on the apatitic material is more significant with increasing of copper amount and/or organic concentration in the starting solution. These increases lead to the affectation of apatite crystallinity. The IR spectroscopy shows the conservation of (Psbnd OH) band of (HPO4)2- groups, suggesting that PASP acid was interacted only with metallic cations of hydroxyapatite.

Biocorrosion of TiO2 nanoparticle coating of Ti-6Al-4V in DMEM under specific in vitro conditions

NASA Astrophysics Data System (ADS)

Höhn, Sarah; Virtanen, Sannakaisa

2015-02-01

A TiO2 nanoparticle coating was prepared on a biomedical Ti-6Al-4V alloy using "spin-coating" technique with a colloidal suspension of TiO2 nanopowders with the aim to optimize the surface morphology (e.g., roughness) for improved biocompatibility. The influence of a TiO2 nanoparticle (NP) coating on the corrosion behavior, metal ion release, and biomimetic apatite formation was studied in DMEM, at 37.5 °C with a continuous supply of 5% CO2. Electrochemical impedance spectroscopy measurements indicate a formation of a new layer on the surface of the NP-coated sample upon 28 days immersion in DMEM. Scanning electron microscopy (SEM) and X-ray spectroscopy confirm that the surface of the NP-coated Ti-6Al-4V shows a complete coverage by a Ca-phosphate layer in contrast to the non-coated Ti-6Al-4V alloy. Hence, the TiO2-NP coating strongly enhances biomimetic apatite formation on the alloy surface. In addition, the TiO2-NP coating can efficiently reduce Al-release from the alloy, for which the bare Ti-6Al-4V alloy is significant for at least 28 days of immersion in DMEM.

Rapidly sintering of interconnected porous Ti-HA biocomposite with high strength and enhanced bioactivity.

PubMed

Zhang, L; He, Z Y; Zhang, Y Q; Jiang, Y H; Zhou, R

2016-10-01

In this work, interconnected porous Ti-HA biocomposites with enhanced bioactivity, high porosity and compressive strength were prepared by spark plasma sintering (SPS) and space holder method. Pore characteristics, mechanical properties, corrosion behaviors and in vitro bioactivity of the porous Ti-HA were investigated. Results showed that porous Ti-HA with 5-30wt% HA contents possessed not only low elastic modulus of 8.2-15.8GPa (close to that of human bone) but also high compressive strength (86-388MPa). Although the HA partially decomposed and formed secondary phases, the sintered porous Ti-HA can still be good bioactivity. The homogeneity and the thickness of apatite layer increased significantly with the increase of HA. But with the thickness of apatite layer increased, micro-cracks appeared on the surface of porous Ti-30%HA. A model was built to discuss the current distribution and sintering mechanism of HA on Ti matrix during SPS process. It indicated that the excessive addition of HA would deteriorate the sintering quality, thus decreasing the mechanical properties and corrosion resistance. However, the combination of interconnected pore characteristics, low elastic modulus, high compressive strength and enhanced bioactivity might make porous Ti-HA biocomposites prepared by SPS a promising candidate for hard tissue implants. Copyright © 2016 Elsevier B.V. All rights reserved.

A multi-scaled hybrid orthopedic implant: bone ECM-shaped Sr-HA nanofibers on the microporous walls of a macroporous titanium scaffold.

PubMed

Han, Yong; Zhou, Jianhong; Zhang, Lan; Xu, Kewei

2011-07-08

We report here, for the first time, a novel multi-scaled hybrid orthopedic implant material consisting of a macroporous Ti scaffold, whose macropores' walls have a microporous titania layer which is fully covered with nanofibers of Sr-doped hydroxyapatite (Sr-HA). The microporous titania layer is formed on and within the Ti scaffold by micro-arc oxidation, which firmly binds to the Ti substrate and contains Ca2+, Sr2+ and PO4(3-) ions. It is then hydrothermally treated to form Sr-HA nanofibers. During the hydrothermal treatment, Sr-HA nanoprisms nucleate from Ca0.5Sr0.5TiO3 pre-formed on the TiO2 and grow in length to nanofibers at the expense of Ca2+, Sr2+ and PO4(3-) ions that migrate from the TiO2. These Sr-HA nanofibers construct a network structure similar to the hierarchical organization of bone extracellular matrix (ECM), and the resulting nanofibrous surface displays a firm adhesion to substrate, superhydrophilicity and apatite-inducing ability. The induced apatite prefers to nucleate on the basal-faceted surfaces of Sr-HA nanofibers. The nanofiber-walled scaffold has a great potential for load-bearing orthotopic use.

Preparation of laminated poly(ε-caprolactone)-gelatin-hydroxyapatite nanocomposite scaffold bioengineered via compound techniques for bone substitution

PubMed Central

Hamlekhan, Azhang; Moztarzadeh, Fathollah; Mozafari, Masoud; Azami, Mahmoud; Nezafati, Nader

2011-01-01

In this research, new bioactive nanocomposite scaffolds were successfully developed using poly(ε-caprolactone) (PCL), cross-linked gelatin and nanoparticles of hydroxyapatite (HAp) after testing different solvents and methods. First, HAp powder was synthesized via a chemical precipitation technique and characterized. Then, the nanocomposites were prepared through layer solvent casting combined with freeze-drying and lamination techniques. According to the results, the increasing of the PCL weight in the scaffolds led to the improvement of the mechanical properties. The amount of ultimate stress, stiffness and also elastic modulus increased from 8 MPa for 0% wt PCL to 23.5 MPa for 50% wt PCL. The biomineralization study revealed the formation of an apatite layer on the scaffolds after immersion in simulated body fluid (SBF). The Ca-P ratios were in accordance to nonstoichiometric biological apatite, which was approximately 1.67. The in vitro biocompatibility and cytocompatibility of the scaffolds were tested using mesenchymal stem cells (MSCs), and the results indicated no sign of toxicity, and cells were found to be attached to the scaffold walls. The in vivo biocompatibility and osteogenesis of these scaffolds in the animal experiments is also under investigation, and the result will be published at the end of the study. PMID:23507731

A multi-scaled hybrid orthopedic implant: bone ECM-shaped Sr-HA nanofibers on the microporous walls of a macroporous titanium scaffold

NASA Astrophysics Data System (ADS)

Han, Yong; Zhou, Jianhong; Zhang, Lan; Xu, Kewei

2011-07-01

We report here, for the first time, a novel multi-scaled hybrid orthopedic implant material consisting of a macroporous Ti scaffold, whose macropores' walls have a microporous titania layer which is fully covered with nanofibers of Sr-doped hydroxyapatite (Sr-HA). The microporous titania layer is formed on and within the Ti scaffold by micro-arc oxidation, which firmly binds to the Ti substrate and contains Ca2 + , Sr2 + and PO43 - ions. It is then hydrothermally treated to form Sr-HA nanofibers. During the hydrothermal treatment, Sr-HA nanoprisms nucleate from Ca0.5Sr0.5TiO3 pre-formed on the TiO2 and grow in length to nanofibers at the expense of Ca2 + , Sr2 + and PO43 - ions that migrate from the TiO2. These Sr-HA nanofibers construct a network structure similar to the hierarchical organization of bone extracellular matrix (ECM), and the resulting nanofibrous surface displays a firm adhesion to substrate, superhydrophilicity and apatite-inducing ability. The induced apatite prefers to nucleate on the basal-faceted surfaces of Sr-HA nanofibers. The nanofiber-walled scaffold has a great potential for load-bearing orthotopic use.

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

Effect of chitosan addition to characteristic and antimicrobial activity of zinc doped hydroxyapatite

NASA Astrophysics Data System (ADS)

Rasyida, A.; Wicaksono, S. T.; Pradita, N. N.; Ardhyananta, H.; Purnomo, A.

2017-07-01

Hydroxyapatite (HAp) doping with zinc was prepared using sol gel method; different chitosan content were further added to prepare the composite, namely 10, 15 and 20% wt. The samples were characterized using FTIR, XRD, SEM-EDX, and AAS. In vitro antimicrobial activities of the composite were evaluated against gram positive and negative bacteria. FTIR results revealed that there were no important changes in the structure of composite, while 10% wt of chitosan in composite shows the highest inhibition zone against Escherichia coli after 24 h incubation. In addition, after 7 days of immersion in simulated body fluid, there were apatite formations in the surface of the composite. These might indicate that this composite could be used as a material candidate for bone substitute applications.

Sequentially-crosslinked biomimetic bioactive glass/gelatin methacryloyl composites hydrogels for bone regeneration.

PubMed

Zheng, Jiafu; Zhao, Fujian; Zhang, Wen; Mo, Yunfei; Zeng, Lei; Li, Xian; Chen, Xiaofeng

2018-08-01

In recent years, gelatin-based composites hydrogels have been intensively investigated because of their inherent bioactivity, biocompatibility and biodegradability. Herein, we fabricated photocrosslinkable biomimetic composites hydrogels from bioactive glass (BG) and gelatin methacryloyl (GelMA) by a sequential physical and chemical crosslinking (gelation + UV) approach. The results showed that the compressive modulus of composites hydrogels increased significantly through the sequential crosslinking approach. The addition of BG resulted in a significant increase in physiological stability and apatite-forming ability. In vitro data indicated that BG/GelMA composites hydrogels promoted cell attachment, proliferation and differentiation. Overall, the BG/GelMA composites hydrogels combined the advantages of good biocompatibility and bioactivity, and had potential applications in bone regeneration. Copyright © 2018. Published by Elsevier B.V.

Early containment of high-alkaline solution simulating low-level radioactive waste stream in clay-bearing blended cement

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

Kruger, A.A.; Olson, R.A.; Tennis, P.D.

1995-04-01

Portland cement blended with fly ash and attapulgite clay was mixed with high-alkaline solution simulating low-level radioactive waste stream at a one-to-one weight ratio. Mixtures were adiabatically and isothermally cured at various temperatures and analyzed for phase composition, total alkalinity, pore solution chemistry, and transport properties as measured by impedance spectroscopy. Total alkalinity is characterized by two main drops. The early one corresponds to a rapid removal of phosphorous, aluminum, sodium, and to a lesser extent potassium solution. The second drop from about 10 h to 3 days is mainly associated with the removal of aluminum, silicon, and sodium. Thereafter,more » the total alkalinity continues descending, but at a lower rate. All pastes display a rapid flow loss that is attributed to an early precipitation of hydrated products. Hemicarbonate appears as early as one hour after mixing and is probably followed by apatite precipitation. However, the former is unstable and decomposes at a rate that is inversely related to the curing temperature. At high temperatures, zeolite appears at about 10 h after mixing. At 30 days, the stabilized crystalline composition Includes zeolite, apatite and other minor amounts of CaCO{sub 3}, quartz, and monosulfate Impedance spectra conform with the chemical and mineralogical data. The normalized conductivity of the pastes shows an early drop, which is followed by a main decrease from about 12 h to three days. At three days, the permeability of the cement-based waste as calculated by Katz-Thompson equation is over three orders of magnitude lower than that of ordinary portland cement paste. However, a further decrease in the calculated permeability is questionable. Chemical stabilization is favorable through incorporation of waste species into apatite and zeolite.« less

Neodymium isotopic study of rare earth element sources and mobility in hydrothermal Fe-oxide (Fe-P-REE) systems

NASA Astrophysics Data System (ADS)

Gleason, James D.; Marikos, Mark A.; Barton, Mark D.; Johnson, David A.

2000-03-01

Rare earth element (REE)-enriched, igneous-related hydrothermal Fe-oxide hosted (Fe-P-REE) systems from four areas in North America have been analyzed for their neodymium isotopic composition to constrain REE sources and mobility in these systems. The Nd isotopic results evidence a common pattern of REE concentration from igneous sources despite large differences in age (Proterozoic to Tertiary), tectonic setting (subduction vs. intraplate), and magmatic style (mafic vs. felsic). In the Middle Proterozoic St. Francois Mountains terrane of southeastern Missouri, ɛ Nd for Fe-P-REE (apatite, monazite, xenotime) deposits ranges from +3.5 to +5.1, similar to associated felsic to intermediate igneous rocks of the same age (ɛ Nd = +2.6 to +6.2). At the mid-Jurassic Humboldt mafic complex in western Nevada, ɛ Nd for Fe-P-REE (apatite) mineralization varies between +1.1 and +2.4, similar to associated mafic igneous rocks (-1.0 to +3.5). In the nearby Cortez Mountains in central Nevada, mid-Jurassic felsic volcanic and plutonic rocks (ɛ Nd = -2.0 to -4.4) are associated with Fe-P-REE (apatite-monazite) mineralization having similar ɛ Nd (-1.7 to -2.4). At Cerro de Mercado, Durango, Mexico, all assemblages analyzed in this Tertiary rhyolite-hosted Fe oxide deposit have identical isotopic compositions with ɛ Nd = -2.5. These data are consistent with coeval igneous host rocks being the primary source of REE in all four regions, and are inconsistent with a significant contribution of REE from other sources. Interpretations of the origin of these hydrothermal systems and their concomitant REE mobility must account for nonspecialized igneous sources and varied tectonic settings.

Neodymium isotopic study of rare earth element sources and mobility in hydrothermal Fe oxide (Fe-P-REE) systems

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

Gleason, J.D.; Marikos, M.A.; Barton, M.D.

2000-03-01

Rare earth element (REE)-enriched, igneous-related hydrothermal Fe-oxide hosted (Fe-P-REE) systems from four areas in North America have been analyzed for their neodymium iosotopic composition to constrain REE sources and mobility in these systems. The Nd isotopic results evidence a common pattern of REE concentration from igneous sources despite large differences in age (Proterozoic to Tertiary), tectonic setting (subduction vs. intraplate), and magmatic style (mafic vs. felsic). In the Middle Proterozoic St. Francois Mountains terrane of southeastern Missouri, {epsilon}{sub Nd} for Fe-P-REE (apatite, monazite, xenotime) deposits ranges from +3.5 to +5.1, similar to associated felsic to intermediate igneous rocks of themore » same age ({epsilon}{sub Nd} = +2.6 to +6.2). At the mid-Jurassic Humboldt mafic complex in western Nevada, {epsilon}{sub Nd} for Fe-P-REE (apatite) mineralization varies between +1.1 and +2.4, similar to associated mafic igneous rocks ({minus}1.0 to +3.5). In the nearby Cortez Mountains in central Nevada, mid-Jurassic felsic volcanic and plutonic rocks ({epsilon}{sub Nd} = {minus}2.0 to {minus}4.4) are associated with Fe-P-REE (apatite-monazite) mineralization having similar {epsilon}{sub Nd}({minus}1.7 to {minus}2.4). At Cerro de Mercado, Durango, Mexico, all assemblages analyzed in this Tertiary rhyolite-hosted Fe oxide deposit have identical isotopic compositions with {epsilon}{sub Nd} = {minus}2.5. These data are consistent with coeval igneous host rocks being the primary source of REE in all four regions, and are inconsistent with a significant contribution of REE from other sources. Interpretations of the origin of these hydrothermal systems and their concomitant REE mobility must account for nonspecialized igneous sources and varied tectonic settings.« less

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.

Slow-release fertilizer

NASA Technical Reports Server (NTRS)

Golden, Dadigamuwage C. (Inventor); Ming, Douglas W. (Inventor)

1995-01-01

A synthetic apatite containing agronutrients and a method for making the apatite are disclosed. The apatite comprises crystalline calcium phosphate having agronutrients dispersed in the crystalline structure. The agronutrients can comprise potassium, magnesium, sulfur, iron, manganese, molybdenum, chlorine, boron, copper and zinc in amounts suited for plant growth. The apatite can optionally comprise a carbonate and/or silicon solubility control agent. The agronutrients are released slowly as the apatite dissolves.

Slow-release fertilizer

NASA Technical Reports Server (NTRS)

Ming, Douglas W. (Inventor); Golden, D. C. (Inventor)

1992-01-01

A synthetic apatite containing agronutrients and a method for making the apatite are disclosed. The apatite comprises crystalline calcium phosphate having agronutrients dispersed in the crystalline structure. The agronutrients can comprise potassium, magnesium, sulfur, iron, manganese, molybdenum, chlorine, boron, copper and zinc in amounts suited for plant growth. The apatite can optionally comprise a carbonate and/or silicon solubility control agent. The agronutrients are released slowly as the apatite dissolves.

Slow-release fertilizer

NASA Astrophysics Data System (ADS)

Ming, Douglas W.; Golden, D. C.

1992-10-01

A synthetic apatite containing agronutrients and a method for making the apatite are disclosed. The apatite comprises crystalline calcium phosphate having agronutrients dispersed in the crystalline structure. The agronutrients can comprise potassium, magnesium, sulfur, iron, manganese, molybdenum, chlorine, boron, copper and zinc in amounts suited for plant growth. The apatite can optionally comprise a carbonate and/or silicon solubility control agent. The agronutrients are released slowly as the apatite dissolves.

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.

Ultrastructure of selected struvite-containing urinary calculi from cats.

PubMed

Neumann, R D; Ruby, A L; Ling, G V; Schiffman, P S; Johnson, D L

1996-01-01

To elucidate the ultrastructural details of struvite-containing urinary calculi from cats. Specimens studied were inclusive of the range of textures visible during preliminary analysis by use of a stereoscopic dissecting microscope. Textural types, which were used to infer crystal growth conditions, were differentiated with regard to crystal habit, crystal size, growth orientation, and primary porosity. Thirty specimens were selected from a collection of approximately 1,600 feline urinary calculi: 20 of these were composed entirely of struvite, and 10 consisted of struvite and calcium phosphate (apatite). Qualitative and quantitative analyses of specimens included use of plain and polarized light microscopy, x-ray diffractometry, scanning electron microscopy with backscattered electron imagery, x-ray fluorescence scans, and electron probe microanalysis. Four textural types were recognized among struvite calculi, whereas 2 textural types of struvite-apatite calculi were described. The presence of minute, well interconnected primary pores in struvite-containing urinary calculi from cats is an important feature, which may promote possible interaction of calculi with changes in urine composition. Primary porosity, which can facilitate interaction between the calculus and changing urine composition, may explain the efficacy of dietary or medicinal manipulations to promote the dissolution of struvite-containing uroliths from this species.

Synthesis of fluorine substituted hydroxyapatite nanopowders and application of the central composite design for determination of its antimicrobial effects

NASA Astrophysics Data System (ADS)

Stanić, Vojislav; Dimitrijević, Suzana; Antonović, Dušan G.; Jokić, Bojan M.; Zec, Slavica P.; Tanasković, Sladjana T.; Raičević, Slavica

2014-01-01

Synthetic biomaterials based on fluorine substituted hydroxyapatite are potentially attractive for orthopedic and dental implant applications. The new synthesis of fluorine substituted hydroxyapatite samples were done by neutralization, which consists of adding the solution of HF and H3PO4 in suspension of Ca(OH)2. Characterization studies from XRD, SEM and FTIR spectra showed that crystals are obtained with apatite structure and those particles of all samples are nano size, with an average length of 80 nm and about 15-25 nm in diameter. The central composite design was used in order to determine the optimal conditions for the antimicrobial activity of the synthesized samples. In order to evaluate the influence of operating parameters on the percent of viable cell reduction of Streptococcus mutans, three independent variables were chosen: exposure time, pH of saline and floride concentration in apatite samples. The experimental and predicted antimicrobial activities were in close agreement. Antimicrobial activity of the samples increases with the increase of fluoride concentration and the decreased pH of saline. The maximum antimicrobial activity was achieved at the initial pH of 4.

Identifying compositional and structural changes in spongy and subchondral bone from the hip joints of patients with osteoarthritis using Raman spectroscopy.

PubMed

Buchwald, Tomasz; Niciejewski, Krzysztof; Kozielski, Marek; Szybowicz, Mirosław; Siatkowski, Marcin; Krauss, Hanna

2012-01-01

Raman microspectroscopy was used to examine the biochemical composition and molecular structure of extracellular matrix in spongy and subchondral bone collected from patients with clinical and radiological evidence of idiopathic osteoarthritis of the hip and from patients who underwent a femoral neck fracture, as a result of trauma, without previous clinical and radiological evidence of osteoarthritis. The objectives of the study were to determine the levels of mineralization, carbonate accumulation and collagen quality in bone tissue. The subchondral bone from osteoarthritis patients in comparison with control subject is less mineralized due to a decrease in the hydroxyapatite concentration. However, the extent of carbonate accumulation in the apatite crystal lattice increases, most likely due to deficient mineralization. The alpha helix to random coil band area ratio reveals that collagen matrix in subchondral bone is more ordered in osteoarthritis disease. The hydroxyapatite to collagen, carbonate apatite to hydroxyapatite and alpha helix to random coil band area ratios are not significantly changed in the differently loaded sites of femoral head. The significant differences also are not visible in mineral and organic constituents' content in spongy bone beneath the subchondral bone in osteoarthritis disease.

Identifying compositional and structural changes in spongy and subchondral bone from the hip joints of patients with osteoarthritis using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Buchwald, Tomasz; Niciejewski, Krzysztof; Kozielski, Marek; Szybowicz, Mirosław; Siatkowski, Marcin; Krauss, Hanna

2012-01-01

Raman microspectroscopy was used to examine the biochemical composition and molecular structure of extracellular matrix in spongy and subchondral bone collected from patients with clinical and radiological evidence of idiopathic osteoarthritis of the hip and from patients who underwent a femoral neck fracture, as a result of trauma, without previous clinical and radiological evidence of osteoarthritis. The objectives of the study were to determine the levels of mineralization, carbonate accumulation and collagen quality in bone tissue. The subchondral bone from osteoarthritis patients in comparison with control subject is less mineralized due to a decrease in the hydroxyapatite concentration. However, the extent of carbonate accumulation in the apatite crystal lattice increases, most likely due to deficient mineralization. The alpha helix to random coil band area ratio reveals that collagen matrix in subchondral bone is more ordered in osteoarthritis disease. The hydroxyapatite to collagen, carbonate apatite to hydroxyapatite and alpha helix to random coil band area ratios are not significantly changed in the differently loaded sites of femoral head. The significant differences also are not visible in mineral and organic constituents' content in spongy bone beneath the subchondral bone in osteoarthritis disease.

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

Genesis of iron-apatite ores in Posht-e-Badam Block (Central Iran) using REE geochemistry

NASA Astrophysics Data System (ADS)

Mokhtari, Mir Ali Asghar; Zadeh, Ghader Hossein; Emami, Mohamad Hashem

2013-06-01

Rare earth elements in apatites of different ore types show characteristic patterns which are related to different modes of formation of the ores. Most of the apatite-bearing iron ores are associated with alkaline magmas with LREE/HREE fractionation varying from moderate to steep. Iron-apatite deposits in Posht-e-Badam Block (Central Iran) have a high concentration of REE (more than 1000 ppm up to 2.5%), and show a strong LREE/HREE ratio with a pronounced negative Eu anomaly. This REE pattern is typical of magmatic apatite and quiet distinct from sedimentary apatites (phosphorites) which have a low REE contents and Ce negative anomalies. On the other hand, they are comparable to the REE patterns of apatites in Kiruna-type iron ores in different parts of the world. The REE patterns of apatites, iron-apatite ores and iron ores are similar and only have different REE contents. This similarity indicates a genetic relation for these rocks. Most of the iron-apatite deposits in Central Iran have similar REE patterns too, which in turn show a genetic relation for all of these deposits. This similarity indicates a similar origin and processes in their genesis. There are some small intrusions around some of the iron-apatite deposits that are petrographically identified as syenite and gabbro. These intrusions also have REE patterns similar to that of iron-apatite ores. This demonstrates a genetic relation between these intrusions and iron-apatite ores. The REE patterns of apatites in different deposits of Posht-e-Badam Block iron-apatite ores show an affinity to alkaline to sub-alkaline magmas and rifting environment. The alkaline host rocks of Central Iran iron-apatite ores are clearly related to an extensional setting where rifting was important (SSE-NNW fault lines). A probable source for this large scale ore forming processes is relatively low partial melting of mantle rocks. The ores have originated by magmatic differentiation as a late phase in the volcanic cycle forming sub-surface injections or surface flows. These ores have formed during magmatism as immiscible liquids (silicate and Fe-P-rich magmatic liquids) which separated from strongly differentiated magmas aided by a large volatile and alkali element content. Separation of an iron oxide melt and the ensuing hydrothermal processes dominated by alkali metasomatism were both involved to different degrees in the formation of Posht-e-Badam Block iron-apatite deposits. We proposed that the separation of an iron oxide melt and the ensuing hydrothermal processes dominated by alkali metasomatism were both involved to different degrees in the formation of Posht-e-Badam Block iron-apatite deposits.

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.

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

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

PubMed

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

2014-06-01

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

Osteogenic Response to BMP-2 of hMSCs Grown on Apatite-Coated Scaffolds

PubMed Central

Davis, Hillary E.; Case, Erin M.; Miller, Stephanie L.; Genetos, Damian C.; Leach, J. Kent

2011-01-01

Osteoconductive materials play a critical role in promoting integration with surrounding bone tissue and resultant bone repair in vivo. However, the impact of 3D osteoconductive substrates coupled with soluble signals on progenitor cell differentiation is not clear. In this study, we investigated the influence of bone morphogenetic protein-2 (BMP-2) concentration on the osteogenic differentiation of human mesenchymal stem cells (hMSCs) when seeded in carbonated apatite-coated polymer scaffolds. Mineralized scaffolds were more hydrophilic and adsorbed more BMP-2 compared to nonmineralized scaffolds. Changes in alkaline phosphatase (ALP) activity within stimulated hMSCs were dependent on the dose of BMP-2 and the scaffold composition. We detected more cell-secreted calcium on mineralized scaffolds at all time points, and higher BMP-2 concentrations resulted in increased ALP and calcium levels. RUNX2 and IBSP gene expression within hMSCs was affected by both substrate and soluble signals, SP7 by soluble factors, and SPARC by substrate-mediated cues. The present data indicate that a combination of apatite and BMP-2 do not simply enhance the osteogenic response of hMSCs, but act through multiple pathways that may be both substrate- and growth factor-mediated. Thus, multiple signaling strategies will likely be necessary to achieve optimal bone regeneration. PMID:21656707

Early diagenesis and recrystallization of bone

NASA Astrophysics Data System (ADS)

Keenan, Sarah W.; Engel, Annette Summers

2017-01-01

One of the most challenging problems in paleobiology is determining how bone transforms from a living tissue into a fossil. The geologic record is replete with vertebrate fossils preserved from a range of depositional environments, including wetland systems. However, thermodynamic models suggest that bone (modeled as hydroxylapatite) is generally unstable in a range of varying geochemical conditions and should readily dissolve if it does not alter to a more thermodynamically stable phase, such as a fluorine-enriched apatite. Here, we assess diagenesis of alligator bone from fleshed, articulated skeletons buried in wetland soils and from de-fleshed bones in experimental mesocosms with and without microbial colonization. When microbial colonization of bone was inhibited, bioapatite recrystallization to a more stable apatite phase occurred after one month of burial. Ca-Fe-phosphate phases in bone developed after several months to years due to ion substitutions from the protonation of the hydroxyl ion. These rapid changes demonstrate a continuum of structural and bonding transformations to bone that have not been observed previously. When bones were directly in contact with sediment and microbial cells, rapid bioerosion and compositional alteration occurred after one week, but slowed after one month because biofilms reduced exposed surfaces and subsequent bioapatite lattice substitutions. Microbial contributions are likely essential in forming stable apatite phases during early diagenesis and for enabling bone preservation and fossilization.

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

Apatite layer growth on glassy Zr48Cu36Al8Ag8 sputtered titanium for potential biomedical applications

NASA Astrophysics Data System (ADS)

Thanka Rajan, S.; Karthika, M.; Bendavid, Avi; Subramanian, B.

2016-04-01

The bioactivity of magnetron sputtered thin film metallic glasses (TFMGs) of Zr48Cu36Al8Ag8 (at.%) on titanium substrates was tested for bio implant applications. The structural and elemental compositions of TFMGs were analyzed by XRD, XPS and EDAX. X-ray diffraction analysis displayed a broad hump around the incident angle of 30-50°, suggesting that the coatings possess a glassy structure. An in situ crystal growth of hydroxyapatite was observed by soaking the sputtered specimen in simulated body fluid (SBF). The nucleation and growth of a calcium phosphate (Ca-P) bone-like hydroxyapatite on Zr48Cu36Al8Ag8 (at.%) TFMG from SBF was investigated by using XRD, AFM and SEM. The presence of calcium and phosphorus elements was confirmed by EDAX and XPS. In vitro electrochemical corrosion studies indicated that the Zr-based TFMG coating sustain in the stimulated body-fluid (SBF), exhibiting superior corrosion resistance with a lower corrosion penetration rate and electrochemical stability than the bare crystalline titanium substrate.

Electrophoretic deposition of zinc-substituted hydroxyapatite coatings.

PubMed

Sun, Guangfei; Ma, Jun; Zhang, Shengmin

2014-06-01

Zinc-substituted hydroxyapatite nanoparticles synthesized by the co-precipitation method were used to coat stainless steel plates by electrophoretic deposition in n-butanol with triethanolamine as a dispersant. The effect of zinc concentration in the synthesis on the morphology and microstructure of coatings was investigated. It is found that the deposition current densities significantly increase with the increasing zinc concentration. The zinc-substituted hydroxyapatite coatings were analyzed by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. It is inferred that hydroxyapatite and triethanolamine predominate in the chemical composition of coatings. With the increasing Zn/Ca ratios, the contents of triethanolamine decrease in the final products. The triethanolamine can be burnt out by heat treatment. The tests of adhesive strength have confirmed good adhesion between the coatings and substrates. The formation of new apatite layer on the coatings has been observed after 7days of immersion in a simulated body fluid. In summary, the results show that dense, uniform zinc-substituted hydroxyapatite coatings are obtained by electrophoretic deposition when the Zn/Ca ratio reaches 5%. Copyright © 2014 Elsevier B.V. All rights reserved.

Surface modification of biodegradable porous Mg bone scaffold using polycaprolactone/bioactive glass composite.

PubMed

Yazdimamaghani, Mostafa; Razavi, Mehdi; Vashaee, Daryoosh; Tayebi, Lobat

2015-04-01

A reduction in the degradation rate of magnesium (Mg) and its alloys is in high demand to enable these materials to be used in orthopedic applications. For this purpose, in this paper, a biocompatible polymeric layer reinforced with a bioactive ceramic made of polycaprolactone (PCL) and bioactive glass (BG) was applied on the surface of Mg scaffolds using dip-coating technique under low vacuum. The results indicated that the PCL-BG coated Mg scaffolds exhibited noticeably enhanced bioactivity compared to the uncoated scaffold. Moreover, the mechanical integrity of the Mg scaffolds was improved using the PCL-BG coating on the surface. The stable barrier property of the coatings effectively delayed the degradation activity of Mg scaffold substrates. Moreover, the coatings induced the formation of apatite layer on their surface after immersion in the SBF, which can enhance the biological bone in-growth and block the microcracks and pore channels in the coatings, thus prolonging their protective effect. Furthermore, it was shown that a three times increase in the concentration of PCL-BG noticeably improved the characteristics of scaffolds including their degradation resistance and mechanical stability. Since bioactivity, degradation resistance and mechanical integrity of a bone substitute are the key factors for repairing and healing fractured bones, we suggest that PCL-BG is a suitable coating material for surface modification of Mg scaffolds. Published by Elsevier B.V.

Modification of electrochemically deposited apatite using supercritical water.

PubMed

Ban, S; Hasegawa, J

2001-12-01

Supercritical water was used as a modification method of electrochemically deposited apatite on pure titanium. The apatites were coated on a commercially pure titanium plate using a hydrothermal-electrochemical method. A constant direct current at 12.5 mA/cm2 was loaded for 1 hr at 25, 60, 100, 150 and 200 degrees C in an electrolyte containing calcium and phosphate ions. The deposited apatite on the titanium substrate was stored in supercritical water at 450 degrees C under 45 MPa for 8 hr. With this treatment, the crystallinity of the apatites increased, sharp edges of the deposited apatites were rounded off, and the bonding strength of the titanium substrate to the deposited apatites significantly increased. On the other hand, weight loss in 0.01 N HCl decreased and the weight gain rate in a simulated body fluid also decreased with this treatment. It is suggested that the modification using supercritical water improved the mechanical strength of the deposited apatite, but worsened its bioactivity.

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.

FT-Raman spectral analysis of human urinary stones.

PubMed

Selvaraju, R; Raja, A; Thiruppathi, G

2012-12-01

FT-Raman spectroscopy is the most useful tool for the purpose of bio-medical diagnostics. In the present study, FT-Raman spectral method is used to investigate the chemical composition of urinary calculi. Urinary calculi multi-components such as calcium oxalate, hydroxyl apatite, struvite and uric acid are studied. FT-Raman spectrum has been recorded in the range of 3500-400 cm(-1). Chemical compounds are identified by Raman spectroscopic technique. The quantitative estimations of calcium oxalate monohydrate (COM) 1463 cm(-1), calcium oxalate dehydrate (COD) 1478 cm(-1), hydroxyl apatite 959 cm(-1), struvite 575 cm(-1), uric acid 1283 cm(-1) and oxammite (ammonium oxalate monohydrate) 2129 cm(-1) are calculated using particular peaks of FT-Raman spectrum. The quantitative estimation of human urinary stones suitable for the single calibration curve was performed. Copyright © 2012 Elsevier B.V. All rights reserved.

Dark-field transmission electron microscopy of cortical bone reveals details of extrafibrillar crystals.

PubMed

Schwarcz, Henry P; McNally, Elizabeth A; Botton, Gianluigi A

2014-12-01

In a previous study we showed that most of the mineral in bone is present in the form of "mineral structures", 5-6nm-thick, elongated plates which surround and are oriented parallel to collagen fibrils. Using dark-field transmission electron microscopy, we viewed mineral structures in ion-milled sections of cortical human bone cut parallel to the collagen fibrils. Within the mineral structures we observe single crystals of apatite averaging 5.8±2.7nm in width and 28±19nm in length, their long axes oriented parallel to the fibril axis. Some appear to be composite, co-aligned crystals as thin as 2nm. From their similarity to TEM images of crystals liberated from deproteinated bone we infer that we are viewing sections through platy crystals of apatite that are assembled together to form the mineral structures. Copyright © 2014 Elsevier Inc. All rights reserved.

Oxygen isotopes suggest elevated thermometabolism within multiple Permo-Triassic therapsid clades

PubMed Central

Rey, Kévin; Amiot, Romain; Fourel, François; Abdala, Fernando; Fluteau, Frédéric; Jalil, Nour-Eddine; Liu, Jun; Rubidge, Bruce S; Smith, Roger MH; Steyer, J Sébastien; Viglietti, Pia A; Wang, Xu; Lécuyer, Christophe

2017-01-01

The only true living endothermic vertebrates are birds and mammals, which produce and regulate their internal temperature quite independently from their surroundings. For mammal ancestors, anatomical clues suggest that endothermy originated during the Permian or Triassic. Here we investigate the origin of mammalian thermoregulation by analysing apatite stable oxygen isotope compositions (δ18Op) of some of their Permo-Triassic therapsid relatives. Comparing of the δ18Op values of therapsid bone and tooth apatites to those of co-existing non-therapsid tetrapods, demonstrates different body temperatures and thermoregulatory strategies. It is proposed that cynodonts and dicynodonts independently acquired constant elevated thermometabolism, respectively within the Eucynodontia and Lystrosauridae + Kannemeyeriiformes clades. We conclude that mammalian endothermy originated in the Epicynodontia during the middle-late Permian. Major global climatic and environmental fluctuations were the most likely selective pressures on the success of such elevated thermometabolism. DOI: http://dx.doi.org/10.7554/eLife.28589.001 PMID:28716184

Co-variability of S 6+ , S 4+ , and S 2- in apatite as a function of oxidation state: Implications for a new oxybarometer

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

Konecke, Brian A.; Fiege, Adrian; Simon, Adam C.

In this study, we use micro-X-ray absorption near-edge structures (μ-XANES) spectroscopy at the S K-edge to investigate the oxidation state of S in natural magmatic-hydrothermal apatite (Durango, Mexico, and Mina Carmen, Chile) and experimental apatites crystallized from volatile-saturated lamproitic melts at 1000 °C and 300 MPa over a broad range of oxygen fugacities [( Embedded Image , FMQ+1.2, FMQ+3; FMQ = fayalite-magnetite-quartz solid buffer]. The data are used to test the hypothesis that S oxidation states other than S6+ may substitute into the apatite structure. Peak energies corresponding to sulfate S6+ (~2482 eV), sulfite S4+ (~2478 eV), and sulfide S2-more » (~2470 eV) were observed in apatite, and the integrated areas of the different sulfur peaks correspond to changes in Embedded Image and bulk S content. Here, multiple tests confirmed that the S oxidation state in apatite remains constant when exposed to the synchrotron beam, at least for up to 1 h exposure (i.e., no irradiation damages). To our knowledge, this observation makes apatite the first mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions as a function of the prevailing Embedded Image of the system. Apatites crystallized under oxidizing conditions (FMQ+1.2 and FMQ+3), where the S6+/STotal peak area ratio in the coexisting glass (i.e., quenched melt) is ~1, are dominated by S6+ with a small contribution of S4+, whereas apatites crystallizing at reduced conditions (FMQ) contain predominantly S2-, lesser amounts of S6+, and possibly traces of S4+. A sulfur oxidation state vs. S concentration analytical line transect across hydrothermally altered apatite from the Mina Carmen iron oxide-apatite (IOA) deposit (Chile) demonstrates that apatite can become enriched in S4+ relative to S6+, indicating metasomatic overprinting via a SO2-bearing fluid or vapor phase. This XANES study demonstrates that as the Embedded Image increases from FQM to FMQ+1.2 to FMQ+3 the oxidation state of S in igneous apatite changes from S2- dominant to S6+ > S4+ to S6+ >> S4+. Furthermore, these results suggest that spectroscopic studies of igneous apatite have potential to trace the oxidation state of S in magmas. The presence of three S oxidations states in apatite may in part explain the non-Henrian partitioning of S between apatite and melt. Our study reveals the potential to use the S signature of apatite to elucidate both oxygen and sulfur fugacity in magmatic and hydrothermal systems.« less

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. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy.

PubMed

Laurencin, Danielle; Wong, Alan; Chrzanowski, Wojciech; Knowles, Jonathan C; Qiu, Dong; Pickup, David M; Newport, Robert J; Gan, Zhehong; Duer, Melinda J; Smith, Mark E

2010-02-07

Despite the numerous studies of bone mineral, there are still many questions regarding the exact structure and composition of the mineral phase, and how the mineral crystals become organised with respect to each other and the collagen matrix. Bone mineral is commonly formulated as hydroxyapatite, albeit with numerous substitutions, and has previously been studied by (31)P and (1)H NMR, which has given considerable insight into the complexity of the mineral structure. However, to date, there has been no report of an NMR investigation of the other major component of bone mineral, calcium, nor of common minority cations like sodium. Here, direct analysis of the local environment of calcium in two biological apatites, equine bone (HB) and bovine tooth (CT), was carried out using both (43)Ca solid state NMR and Ca K-edge X-ray absorption spectroscopy, revealing important structural information about the calcium coordination shell. The (43)Ca delta(iso) in HB and CT is found to correlate with the average Ca-O bond distance measured by Ca K-edge EXAFS, and the (43)Ca NMR linewidths show that there is a greater distribution in chemical bonding around calcium in HB and CT, compared to synthetic apatites. In the case of sodium, (23)Na MAS NMR, high resolution 3Q-MAS NMR, as well as (23)Na{(31)P} REDOR and (1)H{(23)Na} R(3)-HMQC correlation experiments give the first direct evidence that some sodium is located inside the apatite phase in HB and CT, but with a greater distribution of environments compared to a synthetic sodium substituted apatite (Na-HA).

Experimental Study into the Partitioning Behavior of Fluorine, Chlorine, Hydroxyl, and Sulfur (S2-) Between Apatite and a Synthetic Kreep Basalt Melt

NASA Technical Reports Server (NTRS)

Turner, Amber; Vander Kaaden, Kathleen; McCubbin, Francis; Danielson, Lisa R.

2017-01-01

The mineral apatite (Ca5 (PO4)3(F, Cl, OH)) is known for its ability to constrain the petrogenesis of the rock in which it is hosted and for its ubiquity throughout the Solar System, as it is found in lunar, martian, and terrestrial rocks alike (McCubbin et. al, 2015). The abundance of volatile elements, and for this particular study, the elevated abundance of sulfur (S2-) in high-Al basalt samples bearing apatite, could provide more insight for inquiries posed about the behavior of volatiles in lunar and martian magmatic systems (Boyce et. al, 2010). Oxygen fugacity will be an important parameter for these experiments, as the Moon, Mars, and Earth have different redox states (Herd, 2008). The objective of this experimental endeavor is to determine apatite-melt partition coefficients for the volatile elements (F-, Cl-, OH-, S2-) that make up the X-site (i.e., the typically monovalent anion site) in the mineral apatite in a lunar melt composition under lunar oxygen fugacity conditions approx.1-2 log units below the iron-wüstite buffer). All experiments will be conducted at NASA, Johnson Space Center in the High Pressure Experimental Petrology Laboratory. In order to conduct apatite-melt partition experiments with oxygen fugacity as an additional parameter, we will create a synthetic mix of the lunar KREEP basalt 15386, a sample retrieved during Apollo 15 that is believed to represent an indigenous volcanic melt derived from the lunar interior (Rhodes, J.M et. al, 2006). Other geochemically significant elements including C, Co, Ni, Mo, and rare earth elements will be included in the mix at trace abundances in order to assess their partitioning behavior without effecting the overall behavior of the system. The synthetic mix will then be loaded into a piston cylinder, an apparatus used to simulate high-pressure/high-temperature conditions of planetary interiors, and exposed to 0.5 GPa of pressure, the pressure observed in the upper mantle of the Moon, and heated to the melting temperature of the materials. To make sure crystals grow large enough for the necessary analyses, the sample will be kept at the crystallization temperature for 8 hours. This extended run time should also allow the sample to achieve a steady state which is necessary to accurately assess the partitioning of these elements between apatite and melt. The results from this experimental study will allow us to determine the fate of F-, Cl-, OH-, and S2- during the magmatic evolution of the Moon.

Re-evaluation and reconstruction of water purification system using soil. I. Assessment of soil as a sorbent of humic substances and phosphate ion.

PubMed

Fujikawa, Y; Hamasaki, T; Sugahara, M; Ozaki, H; Prasai, G; Yano, T; Imada, R; Tainaka, Y; Nakamura, W; Haruki, F

2004-01-01

The purpose of our study is to develop a treatment procedure for humic substances (HS hereafter) and phosphate ion in wastewater and environmental water by percolation of the water through a constructed soil layer at the hydraulic loading of a few metres per day. In the present work, batch sorption tests were conducted for more than 80 samples of soil, sludge, mineral and organic materials in order to find good sorbents for fulvic acid (FA hereafter) and phosphate ion. The results showed that the sorption of FA was high for some charcoal, and apatite and goethite minerals. Comparatively high sorption of FA was found for some Andosols and volcanic ash soil. Significant sorption of phosphate ion, on the other hand, was found for various types of soil, sludge from water treatment plants and some waste materials. The linear isotherm was obtained for the sorption of FA to a charcoal, apatite and goethite minerals, and Andosols.

Liquid phase sintered ceramic bone scaffolds by combined laser and furnace.

PubMed

Feng, Pei; Deng, Youwen; Duan, Songlin; Gao, Chengde; Shuai, Cijun; Peng, Shuping

2014-08-21

Fabrication of mechanically competent bioactive scaffolds is a great challenge in bone tissue engineering. In this paper, β-tricalcium phosphate (β-TCP) scaffolds were successfully fabricated by selective laser sintering combined with furnace sintering. Bioglass 45S5 was introduced in the process as liquid phase in order to improve the mechanical and biological properties. The results showed that sintering of β-TCP with the bioglass revealed some features of liquid phase sintering. The optimum amount of 45S5 was 5 wt %. At this point, the scaffolds were densified without defects. The fracture toughness, compressive strength and stiffness were 1.67 MPam1/2, 21.32 MPa and 264.32 MPa, respectively. Bone like apatite layer was formed and the stimulation for apatite formation was increased with increase in 45S5 content after soaking in simulated body fluid, which indicated that 45S5 could improve the bioactivity. Furthermore, MG-63 cells adhered and spread well, and proliferated with increase in the culture time.

Multiphase inclusions in plagioclase from anorthosites in the Stillwater Complex, Montana: implications for the origin of the anorthosites

USGS Publications Warehouse

Loferski, P.J.; Arculus, R.J.

1993-01-01

Multiphase inclusions, consisting of clinopyroxene+ilmenite+apatite, occur within cumulus plagioclase grains from anorthosites in the Stillwater Complex, Montana, and in other rocks from the Middle Banded series of the intrusion. The textures and constant modal mineralogy of the inclusions indicate that they were incorporated in the plagioclase as liquid droplets that later crystallized rather than as solid aggregates. Their unusual assemblage, including a distinctive manganiferous ilmenite and the presence of baddeleyite (ZrO2), indicates formation from an unusual liquid. A process involving silicater liquid immiscibility is proposed, whereby small globules of a liquid enriched in Mg, Fe, Ca, Ti, P, REE, Zr and Mn exsolved from the main liquid that gave rise to the anorthosites, became trapped in the plagioclase, and later crystallized to form the inclusions. The immiscibility could have occurred locally within compositional boundaries around crystallizing plagioclase grains or it could have occurred pervasively throughout the liquid. It is proposed that the two immiscible liquids were analogous, n terms of their melt structures, to immiscible liquid pairs reported in the literature both in experiments and in natural basalts. For the previously reported pairs, immiscibility is between a highly polymerized liquid, typically granitic in composition, and a depolymerized liquid, typically ferrobasaltic in composition. In the case of the anorthosites, the depolymerized liquid is represented by the inclusions, and the other liquid was a highly polymerized aluminosilicate melt with a high normative plagioclase content from which the bulk of the anorthosites crystallized. Crystallization of the anorthosites from this highly polymerized liquid accounts for various distinctive textural and chemical features of the anorthosites compared to other rocks in the Stillwater Complex. A lack of correlation between P contents and chondrite-normalized rare earth element (REE) ratios of plagioclase separates indicates that the amount of apatite in the inclusions is too low to affect the REE signature of the plagioclase separates. Nevertheless, workers should use caution when attempting REE modelling studies of cumulates having low REE contents, because apatite-bearing inclusions can potentially cause problems. ?? 1993 Springer-Verlag.

Bioactivity and cell proliferation in radiopaque gel-derived CaO-P2O5-SiO2-ZrO2 glass and glass-ceramic powders.

PubMed

Montazerian, Maziar; Yekta, Bijan Eftekhari; Marghussian, Vahak Kaspari; Bellani, Caroline Faria; Siqueira, Renato Luiz; Zanotto, Edgar Dutra

2015-10-01

In this study, 10 mol% ZrO2 was added to a 27CaO-5P2O5-68SiO2 (mol%) base composition synthesized via a simple sol-gel method. This composition is similar to that of a frequently investigated bioactive gel-glass. The effects of ZrO2 on the in vitro bioactivity and MG-63 cell proliferation of the glass and its derivative polycrystalline (glass-ceramic) powder were investigated. The samples were characterized using thermo-gravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) coupled to energy dispersive X-ray spectroscopy (EDS). Release of Si, Ca, P and Zr into simulated body fluid (SBF) was determined by inductively coupled plasma (ICP). Upon heat treatment at 1000 °C, the glass powder crystallized into an apatite-wollastonite-zirconia glass-ceramic powder. Hydroxycarbonate apatite (HCA) formation on the surface of the glass and glass-ceramic particles containing ZrO2 was confirmed by FTIR and SEM. Addition of ZrO2 to the base glass composition decreased the rate of HCA formation in vitro from one day to three days, and hence, ZrO2 could be employed to control the rate of apatite formation. However, the rate of HCA formation on the glass-ceramic powder containing ZrO2 crystal was equal to that in the base glassy powder. Tests with a cultured human osteoblast-like MG-63 cells revealed that the glass and glass-ceramic materials stimulated cell proliferation, indicating that they are biocompatible and are not cytotoxic in vitro. Moreover, zirconia clearly increased osteoblast proliferation over that of the Zr-free samples. This increase is likely associated with the lower solubility of these samples and, consequently, a smaller variation in the media pH. Despite the low solubility of these materials, bioactivity was maintained, indicating that these glassy and polycrystalline powders are potential candidates for bone graft substitutes and bone cements with the special feature of radiopacity. Copyright © 2015 Elsevier B.V. All rights reserved.

Posttranslational Amelogenin Processing and Changes in Matrix Assembly during Enamel Development

PubMed Central

Pandya, Mirali; Lin, Tiffani; Li, Leo; Allen, Michael J.; Jin, Tianquan; Luan, Xianghong; Diekwisch, Thomas G. H.

2017-01-01

The extracellular tooth enamel matrix is a unique, protein-rich environment that provides the structural basis for the growth of long and parallel oriented enamel crystals. Here we have conducted a series of in vivo and in vitro studies to characterize the changes in matrix shape and organization that take place during the transition from ameloblast intravesicular matrices to extracellular subunit compartments and pericrystalline sheath proteins, and correlated these changes with stages of amelogenin matrix protein posttranslational processing. Our transmission electron microscopic studies revealed a 2.5-fold difference in matrix subunit compartment dimensions between secretory vesicle and extracellular enamel protein matrix as well as conformational changes in matrix structure between vesicles, stippled materials, and pericrystalline matrix. Enamel crystal growth in organ culture demonstrated granular mineral deposits associated with the enamel matrix framework, dot-like mineral deposits along elongating initial enamel crystallites, and dramatic changes in enamel matrix configuration following the onset of enamel crystal formation. Atomic force micrographs provided evidence for the presence of both linear and hexagonal/ring-shaped full-length recombinant amelogenin protein assemblies on mica surfaces, while nickel-staining of the N-terminal amelogenin N92 His-tag revealed 20 nm diameter oval and globular amelogenin assemblies in N92 amelogenin matrices. Western blot analysis comparing loosely bound and mineral-associated protein fractions of developing porcine enamel organs, superficial and deep enamel layers demonstrated (i) a single, full-length amelogenin band in the enamel organ followed by 3 kDa cleavage upon entry into the enamel layer, (ii) a close association of 8–16 kDa C-terminal amelogenin cleavage products with the growing enamel apatite crystal surface, and (iii) a remaining pool of N-terminal amelogenin fragments loosely retained between the crystalline phases of the deep enamel layer. Together, our data establish a temporo-spatial correlation between amelogenin protein processing and the changes in enamel matrix configuration that take place during the transition from intracellular vesicle compartments to extracellular matrix assemblies and the formation of protein coats along elongating apatite crystal surfaces. In conclusion, our study suggests that enzymatic cleavage of the amelogenin enamel matrix protein plays a key role in the patterning of the organic matrix framework as it affects enamel apatite crystal growth and habit. PMID:29089900

Posttranslational Amelogenin Processing and Changes in Matrix Assembly during Enamel Development.

PubMed

Pandya, Mirali; Lin, Tiffani; Li, Leo; Allen, Michael J; Jin, Tianquan; Luan, Xianghong; Diekwisch, Thomas G H

2017-01-01

The extracellular tooth enamel matrix is a unique, protein-rich environment that provides the structural basis for the growth of long and parallel oriented enamel crystals. Here we have conducted a series of in vivo and in vitro studies to characterize the changes in matrix shape and organization that take place during the transition from ameloblast intravesicular matrices to extracellular subunit compartments and pericrystalline sheath proteins, and correlated these changes with stages of amelogenin matrix protein posttranslational processing. Our transmission electron microscopic studies revealed a 2.5-fold difference in matrix subunit compartment dimensions between secretory vesicle and extracellular enamel protein matrix as well as conformational changes in matrix structure between vesicles, stippled materials, and pericrystalline matrix. Enamel crystal growth in organ culture demonstrated granular mineral deposits associated with the enamel matrix framework, dot-like mineral deposits along elongating initial enamel crystallites, and dramatic changes in enamel matrix configuration following the onset of enamel crystal formation. Atomic force micrographs provided evidence for the presence of both linear and hexagonal/ring-shaped full-length recombinant amelogenin protein assemblies on mica surfaces, while nickel-staining of the N-terminal amelogenin N92 His-tag revealed 20 nm diameter oval and globular amelogenin assemblies in N92 amelogenin matrices. Western blot analysis comparing loosely bound and mineral-associated protein fractions of developing porcine enamel organs, superficial and deep enamel layers demonstrated (i) a single, full-length amelogenin band in the enamel organ followed by 3 kDa cleavage upon entry into the enamel layer, (ii) a close association of 8-16 kDa C-terminal amelogenin cleavage products with the growing enamel apatite crystal surface, and (iii) a remaining pool of N-terminal amelogenin fragments loosely retained between the crystalline phases of the deep enamel layer. Together, our data establish a temporo-spatial correlation between amelogenin protein processing and the changes in enamel matrix configuration that take place during the transition from intracellular vesicle compartments to extracellular matrix assemblies and the formation of protein coats along elongating apatite crystal surfaces. In conclusion, our study suggests that enzymatic cleavage of the amelogenin enamel matrix protein plays a key role in the patterning of the organic matrix framework as it affects enamel apatite crystal growth and habit.

Absence of bacterial imprints on struvite-containing kidney stones: a structural investigation at the mesoscopic and atomic scale.

PubMed

Bazin, Dominique; André, Gilles; Weil, Raphael; Matzen, Guy; Emmanuel, Veron; Carpentier, Xavier; Daudon, M

2012-04-01

Bacterial imprints are always observed on highly carbonated apatite kidney stones but not struvite kidney stones. Struvite and carbonated apatite stones with a high CO(3)(2-)/PO(4)(3-) rate are believed to develop from infections, but their structural differences at the mesoscopic scale lack explanation. We investigated 17 urinary calculi composed mainly of struvite or carbonated apatite by Fourier transform infrared, scanning electron microscopy, and powder neutron diffraction techniques. Carbonated apatite but not struvite stones showed bacterial imprints. If the same stone contained both carbonated apatite and struvite components, bacterial imprints were observed on the carbonated apatite but not the struvite part. Moreover, neutron powder diffraction experiments revealed the crystal size of struvite stones were larger than that of carbonated apatite stones (250 ± 50 vs 50 nm). Bacterial imprints may appear more easily on kidney stones with small nanocrystals, such as carbonated apatite than with large nanocrystals, such as struvite. This approach may help identify bacteria contributing to stone formation, perhaps with negative results of urine culture. Copyright © 2012 Elsevier Inc. All rights reserved.

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.

A simple method to model the reduced environment of lake bottom sapropel formation

NASA Astrophysics Data System (ADS)

Gaskova, Olga L.; Strakhovenko, Vera D.; Ermolaeva, Nadezhda I.; Zarubina, Eugene Yu.; Ovdina, Ekaterina A.

2017-07-01

The Kambala and Barchin brackish lakes (Baraba steppe, southern West Siberia) contain an organic-rich sapropel layer that was formed in oxygen-depleted waters. We measured the bulk sediment elemental composition, the water chemistry and determined the mineralogical composition and predominant biota species (Diatoms and Cyanobacteria in phytoplankton community respectively) in the lakes. The result indicates that the first lake has a siliceous type of sapropel and the second a carbonaceous one. A computer thermodynamic model was developed for chemical interaction in water-bottom sediment systems of the Kambala and Barchin Lakes. The surface sodium bicarbonate waters are supersaturated with respect to calcite, magnesite (or low Mg-calcite), quartz and chlorite with minor strontianite, apatite and goethite (pH 8.9-9.3, Eh 0.3 V). Nevertheless, it is shown that during sapropel deposition, deep silt waters should be anoxic (Eh<0 V). The virtual component CH2O has been used to create an anoxic environment suitable for pyrite formation due to the biotic community impact and abiotic reduction. Thermodynamic calculation has shown that silt water is not necessarily euxinic (anoxic and sulfidic). Depending on Eh, sulfate sulfur can dominate in solution, causing the formation of gypsum together with pyrite. An attempt was made to find a reason for solution supersaturation with respect to Ca and Mg ions due to their complexation with humic acids.

Bioactivity of Sodium Free Fluoride Containing Glasses and Glass-Ceramics

PubMed Central

Chen, Xiaojing; Chen, Xiaohui; Brauer, Delia S.; Wilson, Rory M.; Hill, Robert G.; Karpukhina, Natalia

2014-01-01

The bioactivity of a series of fluoride-containing sodium-free calcium and strontium phosphosilicate glasses has been tested in vitro. Glasses with high fluoride content were partially crystallised to apatite and other fluoride-containing phases. The bioactivity study was carried out in Tris and SBF buffers, and apatite formation was monitored by XRD, FTIR and solid state NMR. Ion release in solutions has been measured using ICP-OES and fluoride-ion selective electrode. The results show that glasses with low amounts of fluoride that were initially amorphous degraded rapidly in Tris buffer and formed apatite as early as 3 h after immersion. The apatite was identified as fluorapatite by 19F MAS-NMR after 6 h of immersion. Glass degradation and apatite formation was significantly slower in SBF solution compared to Tris. On immersion of the partially crystallised glasses, the fraction of apatite increased at 3 h compared to the amount of apatite prior to the treatment. Thus, partial crystallisation of the glasses has not affected bioactivity significantly. Fast dissolution of the amorphous phase was also indicated. There was no difference in kinetics between Tris and SBF studies when the glass was partially crystallised to apatite before immersion. Two different mechanisms of apatite formation for amorphous or partially crystallised glasses are discussed. PMID:28788139

Magmatic apatite - a window into melt evolution of the Dalgety pluton.

NASA Astrophysics Data System (ADS)

Pope, M. D.; Tailby, N.; Webster, J. D.

2017-12-01

The Dalgety Pluton is located in the Lachlan Fold Belt in southeastern Australia, and is a coarse grained, peraluminous, S-type, biotite granodiorite. Historically, pluton emplacement has been thought of as cooling from a single, large body of magma over a geologically quick period. Current studies suggest issues with this model and propose a slower, incremental model of emplacement in some settings (Glazner et al., 2004). This work proposes that the emplacement of the Dalgety Pluton occurred in incremental phases demonstrated through halogen, minor, and trace element concentrations in apatites. Apatites from 13 samples collected along a north-south transect of the pluton were analyzed using a 5-spectrometer Cameca SX-100 calibrated for seventeen elements (F, Na, Cl, P, Mg, Al, Si, Ca, S, K, Ti, Mn, Fe, Sr, Ba, La, and Ce) at the American Museum of Natural History. The majority of apatites are fluorapatites, having >50 % F, <15 % Cl, and <25 % OH (calculated from Ketchum et al., 2015). However, the concentrations of the halogens vary throughout the pluton with the highest Cl concentrations near the southern edge. Two of the minor elements, Mn and Fe, also show distinct variation with the lowest concentrations being 0.35 wt% in Mn and 0.25 wt% in Fe and the highest being 1.10 wt% and 0.95 wt%, respectively. Trace elements Ce and La vary as well with their highest concentrations being 0.29 wt% and 0.11 wt% and their lowest for both being below the detection limit of the electron probe. Elemental variation across the pluton is seen in the concentration of minor elements and halogens with a sharp increases at 10,000 meters and again at 21,000 meters from the southern rim of the pluton. Similar shifts in concentration are also seen in the trace elements, however the concentrations decrease at these distances. These wholesale elemental fluctuations in composition are indicative of a dramatic shift in melt composition supporting the hypothesis of multiple melt injection in the Dalgety Pluton. Reference: Glazner, A.F., Bartley, J.M., Coleman, D.S., Gray, W. and Taylor, R.Z., 2004. Are plutons assembled over millions of years by amalgamation from small magma chambers?. GSA today, 14(4/5), pp.4-12.

Trace element studies of silicate-rich inclusions in the Guin (UNGR) and Kodaikanal (IIE) iron meteorites

NASA Astrophysics Data System (ADS)

Kurat, Gero; Zinner, Ernst; Varela, Maria Eugenia

2007-08-01

A devitrified glass inclusion from the Guin (UNGR) iron consists of cryptocrystalline feldspars, pyroxenes, and silica and is rich in SiO2, Al2O3, and Na2O. It contains a rutile grain and is in contact with a large Cl apatite. The latter is very rich in rare earth elements (REEs) (˜80 × CI), which display a flat abundance pattern, except for Eu and Yb, which are underabundant. The devitrified glass is very poor in REEs (<0.1 × CI), except for Eu and Yb, which have positive abundance anomalies. Devitrified glass and Cl apatite are out of chemical equilibrium and their complementary REE patterns indicate a genesis via condensation under reducing conditions. Inclusion 1 in the Kodaikanal (IIE) iron consists of glass only, whereas inclusion 2 consists of clinopyroxene, which is partly overgrown by low-Ca pyroxene, and apatite embedded in devitrified glass. All minerals are euhedral or have skeletal habits indicating crystallization from the liquid precursor of the glass. Pyroxenes and the apatite are rich in trace elements, indicating crystallization from a liquid that had 10-50 × CI abundances of REEs and refractory lithophile elements (RLEs). The co-existing glass is poor in REEs (˜0.1-1 × CI) and, consequently, a liquid of such chemical composition cannot have crystallized the phenocrysts. Glasses have variable chemical compositions but are rich in SiO2, Al2O3, Na2O, and K2O as well as in HFSEs, Be, B, and Rb. The REE abundance patterns are mostly flat, except for the glass-only inclusion, which has heavy rare earth elements (HREEs) > light rare earth elements (LREEs) and deficits in Eu and Yb—an ultrarefractory pattern. The genetic models suggested so far cannot explain what is observed and, consequently, we offer a new model for silicate inclusion formation in IIE and related irons. Nebular processes and a relationship with E meteorites (Guin) or Ca-Al-rich inclusions (CAIs) (Kodaikanal) are indicated. A sequence of condensation (CaS, TiN or refractory pyroxene-rich liquids) and vapor-solid elemental exchange can be identified that took place beginning under reducing and ending at oxidizing conditions (phosphate, rutile formation, alkali and Fe2+ metasomatism, metasomatic loss of REEs from glass).

Eruptive history, petrology, and petrogenesis of the Joe Lott Tuff Member of the Mount Belknap Volcanics, Marysvale volcanic field, west-central Utah

USGS Publications Warehouse

Budding, Karin E.

1982-01-01

The Joe Lott Tuff Member of the Mount Belknap Volcanics is the largest rhyolitic ash-flow tuff sheet in the Marysvale volcanic field. It was erupted 19 m.y. ago, shortly after the changeover from intermediate-composition calc-alkalic volcanism to bimodal basalt-rhyolite volcanism. Eruption of the tuff resulted in the formation of the Mount Belknap Caldera whose pyroclastic intracaldera stratigraphy parallels that in the outflow facies. The Joe Loft Tuff Member is a composite ash-flow sheet that changes laterally from a simple cooling unit near the source to four distinct cooling units toward the distal end. The lowest of these units is the largest and most widespread; it is 64 m thick and contains a basal vitrophyre. Eruption of the lower unit led to the initial collapse of the caldera. The lower unit is followed upward by a 43 m middle unit, a 26 m pink-colored unit which is separated by a prominent air- fall layer, and a 31 m upper unit. The Joe Loft Tuff Member is an alkali rhyolite with 75.85-77.31 wt. % silica and 8.06-9.32 wt. % K2O+Na2O; the agpaitic index (Na2O+ K2O/Al2O3) is .77-.98. The tuff contains about I% phenocrysts of quartz, sanidine, oligoclase, augite, apatite, zircon, sphene, biotite, and oxidized Fe-Ti oxides. The basal vitrophyre contains accessory allanite, chevkinite, and magnesiohastingsite. The main cooling units are chemically and mineralogically zoned indicating that the magma chamber restratified prior to each major eruption. Within each of the two thickest cooling units, the mineralogy changes systematically upwards; the Or content and relative volume of sanidine decreases and An content of plagioclase increases. The basal vitrophyre of the lower unit has a bulk composition that lies in the thermal trough near the minima of Or-Ab-Q at 1 kb PH2O. Microprobe analyses of feldspar and chemical modeling on experimental systems indicate that pre-eruption temperatures were near 750?C and that the temperature increased during the eruption of the cooling units. The chemical gradients in the apatite and whole-rock data in the Joe Loft Tuff Member and the consistent mineral assemblages throughout the ash-flow cannot be explained by crystal settling. The fractionation of the Joe Lott Tuff Member appears to closer fit the model of convection-driven thermogravitational diffusion.

Hydroxyapatite coating of titanium implants using hydroprocessing and evaluation of their osteoconductivity.

PubMed

Kuroda, Kensuke; Okido, Masazumi

2012-01-01

Many techniques for the surface modification of titanium and its alloys have been proposed from the viewpoint of improving bioactivity. This paper contains an overview of surface treatment methods, including coating with hydroxyapatite (HAp), an osteoconductive compound. There are two types of coating methods: pyroprocessing and hydroprocessing. In this paper, hydroprocessing for coating on the titanium substrate with HAp, carbonate apatite (CO(3)-Ap), a CO(3)-Ap/CaCO(3) composite, HAp/collagen, and a HAp/gelatin composite is outlined. Moreover, evaluation by implantation of surface-modified samples in rat tibiae is described.

Hydroxyapatite Coating of Titanium Implants Using Hydroprocessing and Evaluation of Their Osteoconductivity

PubMed Central

Kuroda, Kensuke; Okido, Masazumi

2012-01-01

Many techniques for the surface modification of titanium and its alloys have been proposed from the viewpoint of improving bioactivity. This paper contains an overview of surface treatment methods, including coating with hydroxyapatite (HAp), an osteoconductive compound. There are two types of coating methods: pyroprocessing and hydroprocessing. In this paper, hydroprocessing for coating on the titanium substrate with HAp, carbonate apatite (CO3–Ap), a CO3–Ap/CaCO3 composite, HAp/collagen, and a HAp/gelatin composite is outlined. Moreover, evaluation by implantation of surface-modified samples in rat tibiae is described. PMID:22400015

Mineral composition of urinary calculi from miniature schnauzer dogs.

PubMed

Klausner, J S; Osborne, C A; Clinton, C W; Stevens, J B; Griffith, D P

1981-05-15

The mineral composition of 150 calculi from the urinary tracts of Miniature Schnauzer dogs was determined by qualitative and quantitative methods. Struvite was the predominant mineral in 92% of the calculi. Other calculi contained predominantly apatite, calcium oxalate, ammonium urate, or silica. Most calculi were from the urinary bladder or urethra, or both. Four were from the renal pelves. Struvite calculi were more frequently encountered in females than males. The mean age of the dogs at the time of detection of calculi was 4.8 years. Qualitative analysis failed to detect some minerals that were identified by quantitative analysis.

Synthesis of β-tricalcium phosphate.

PubMed

Chaair, H; Labjar, H; Britel, O

2017-09-01

Ceramics play a key role in several biomedical applications. One of them is bone grafting, which is used for treating bone defects caused by injuries or osteoporosis. Calcium-phosphate based ceramic are preferred as bone graft biomaterials in hard tissue surgery because their chemical composition is close to the composition of human bone. They also have a marked bioresorbability and bioactivity. In this work, we have developed methods for synthesis of β-tricalcium phosphate apatite (β-TCP). These products were characterized by different techniques such as X-ray diffraction, infrared spectroscopy, scanning electron microscopy and chemical analysis. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Biocompatibility of composites based on chitosan, apatite, and graphene oxide for tissue applications.

PubMed

Solìs Moré, Yaimara; Panella, Gloria; Fioravanti, Giulia; Perrozzi, Francesco; Passacantando, Maurizio; Giansanti, Francesco; Ardini, Matteo; Ottaviano, Luca; Cimini, Annamaria; Peniche, Carlos; Ippoliti, Rodolfo

2018-06-01

Novel two-dimensional films and three-dimensional (3D) scaffolds based on chitosan (CHI), apatite (Ap), and graphene oxide (GO) were developed by an in situ synthesis in which self-assembly process was conducted to direct partial reduction of GO by CHI in acidic medium. Physical-chemical characterization was carried out by optical microscopy, scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. In vitro biological studies using murine fibroblast (MC3T3) and human neuroblastoma (SH-SY5Y) cell lines were also performed. Cell growth and adherence on composites was also checked using SEM. Live and death staining by confocal microscope and 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium of the samples were investigated. The results confirmed the incorporation of both Ap and GO sheets, into CHI polymeric matrix. Furthermore, it was confirmed a physical integration between inorganic Ap and organic CHI and strong chemical interaction between CHI and GO in the obtained composites. SH-SY5Y cell line showed preferential adherence on CHI/GO films surface while MC3T3 cell line displayed a good compatibility for all 3D scaffolds. This study confirms the biocompatibility of materials based on CHI, Ap, and GO for future tissues applications. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 1585-1594, 2018. © 2018 Wiley Periodicals, Inc.

Nanocomposite particles with improved microstructure for 3D culture systems and bone regeneration.

PubMed

Cecoltan, Sergiu; Stancu, Izabela-Cristina; Drăguşin, Diana Maria; Serafim, Andrada; Lungu, Adriana; Ţucureanu, Cătălin; Caraş, Iuliana; Tofan, Vlad Constantin; Sălăgeanu, Aurora; Vasile, Eugeniu; Mallet, Romain; Chappard, Daniel; Coman, Cristin; Istodorescu, Mircea; Iovu, Horia

2017-08-31

Nano-apatite and gelatin-alginate hydrogel microparticles have been prepared by a one-step synthesis combined with electrostatic bead generation, for the reconstruction of bone defects. Based on the analysis of bone composition, architecture and embryonic intramembranous ossification, a bio-inspired fabrication has been developed. Accordingly, the mineral phase has been in situ synthesized, calcifying the hydrogel matrix while the latter was crosslinked, finally generating microparticles that can assemble into a bone defect to ensure interconnected pores. Although nano-apatite-biopolymer composites have been widely investigated, microstructural optimization to provide improved distribution and stability of the mineral is rarely achieved. The optimization of the developed method progressively resulted in two types of formulations (15P and 7.5P), with 15 and 7.5 (wt%) phosphate content in the initial precursor. The osteolytic potential was investigated using differentiated macrophages. A commercially available calcium phosphate bone graft substitute (Eurocer 400) was incorporated into the hydrogel, and the obtained composites were in vitro tested for comparison. The cytocompatibility of the microparticles was studied with mouse osteoblast-like cell line MC3T3-E1. Results indicated the best in vitro performance have been obtained for the sample loaded with 7.5P. Preliminary evaluation of biocompatibility into a critical size (3 mm) defect in rabbits showed that 7.5P nanocomposite is associated with newly formed bone in the proximity of the microparticles, after 28 days.

Stable isotope chemistry of fossil bone as a new paleoclimate indicator

NASA Astrophysics Data System (ADS)

Kohn, Matthew J.; Law, J. Mclver

2006-02-01

During fossilization, bone is thought to recrystallize and alter chemically on timescales of kyr to a few tens of kyr, i.e., similar to the timescale for formation of soils. Therefore, C- and O-isotope compositions of bone apatite should correlate with trends in soil water composition and aridity, and serve as paleoclimate indicators. This hypothesis was tested by analyzing C- and O-isotope compositions of the CO 3 component of fossil bone apatite from mid-Oligocene through late Pleistocene units in Oregon and western Idaho, including the John Day (19.4-30.0 Ma), Mascall (15.2-15.8 Ma), and Rattlesnake (7.2-7.8 Ma) Formations, whose paleosol sequences have been studied in detail, and the Juntura (10-11 Ma), Hagerman (3.2 Ma), and Fossil Lake (<23-650 ka) fossil localities. Tooth enamel δ18O values provide a baseline of meteoric water compositions. Stable isotope compositions of bone CO 3 do change in response to broad climatic trends, but show poor correlation with compositions of corresponding paleosol CO 3 at specific horizons. Instead, compositional deviations between bone and paleosol CO 3 correlate with compositional deviations with the next higher paleosol; this suggests that the timescale for fossilization exceeds one paleosol cycle. Based on stratigraphic evidence and simple alteration models, fossilization timescales are estimated at 20-50 kyr, indicating that bone CO 3 will prove most useful for sequences spanning >100 kyr. C-isotopes show negative and strong positive deviations during wet and dry climates respectively, and short-term trends correspond well with changes in aridity within the Mascall and Rattlesnake Formations, as inferred from paleosols. A proposed correction to δ18O values based on δ13C anomalies implies a small, ˜1.5‰ increase in meteoric water δ18O during the late Oligocene global warming event, consistent with a minimum temperature increase of ˜4 °C. A strong inferred decrease in δ18O of 4-5‰ after 7 Ma closely parallels compositional changes in tooth enamel, and reflects a doubling in the height of the Cascade Range.

[Infrared spectrophotometry for crystalline composition of staghorn calculi].

PubMed

Ma, Kai; Huang, Xiao-bo; Xu, Qing-quan; Li, Jian-xing; Xiong, Liu-lin; Yang, Bo; Ye, Xiong-jun; Chen, Liang; Wang, Xiao-feng; Na, Yan-qun

2010-11-30

To provide theoretic rationales for treatment and prevention of staghorn calculi by analyzing stone composition and studying the relationship between stone and urinary tract infections. The clinical data of 51 staghorn calculi patients were analyzed retrospectively. The stone compositions were studied by infrared spectrophotometry. Six types of stone compositions were obtained. There were calcium oxalate monohydrate, calcium oxalate dehydrate, carbonate apatite, magnesium ammonium phosphate hexahydrate, uric acid and L-cystine. The majority of stones were of mixed compositions, pure stones were found in 15 cases (29.4%). Among all stones, calcium oxalate stones were found in 41 cases (80.4%) and uric stones in 10 cases (19.6%). Infectious stones were found in 26 cases (51.0%). Urinary tract infections were found in 40 (78.4%) patients and positive urine/stone culture was detected in 33 (64.7%) patients. With multiple crystalline compositions and etiological factors, the staghorn calculi are closely correlated with urinary tract infections.

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.

Studies on biodegradable and crosslinkable poly(castor oil fumarate)/poly(propylene fumarate) composite adhesive as a potential injectable biomaterial.

PubMed

Mitha, M K; Jayabalan, M

2009-12-01

Biodegradable hydroxyl terminated-poly(castor oil fumarate) (HT-PCF) and poly(propylene fumarate) (HT-PPF) resins were synthesized as an injectable and in situ-cross linkable polyester resins for orthopedic applications. An injectable adhesive formulation containing this resin blend, N-vinyl pyrrolidone (NVP), hydroxy apatite, free radical initiator and accelerator was developed. The Composite adhesives containing the ratio of resin blend and NVP, 2.1:1.5, 2.1:1.2 and 2.1:1.0 set fast with tolerable exothermic temperature as a three dimensionally cross linked toughened material. Crosslink density and mechanical properties of the crosslinked composite increase with increase of NVP. The present crosslinked composite has hydrophilic character and cytocompatibility with L929 fibroblast cells.

The magmatic evolution and genesis of the Quaternary basanite-trachyphonolite suite of Itasy (Madagascar) as inferred by geochemistry, Sr-Nd-Pb isotopes and trace element distribution in coexisting phases

NASA Astrophysics Data System (ADS)

Melluso, L.; Tucker, R. D.; Cucciniello, C.; le Roex, A. P.; Morra, V.; Zanetti, A.; Rakotoson, R. L.

2018-06-01

The Itasy is a Pleistocene-Holocene volcanic field in central Madagascar, located to the west of the Ankaratra volcanic complex. It comprises scoria cones and lava domes (>120), with associated pyroclastic fall and mafic lava flows, covering an area of ab. 400 km2. The last volcanic episodes probably dated ca. 6000-7100 y BP; warm springs and geysers are active. The juvenile samples comprise a peculiar, almost bimodal, rock suite ranging from potassic leucite-kaersutite-bearing basanites, tephrites and phonotephrites, to benmoreites and titanite-haüyne-bearing trachyphonolites (MgO from 9-10 wt% to 0.1 wt%). These rocks show continuous and overlapping variations in the bulk-rock and phase composition (olivine, clinopyroxene, amphibole, feldspar, leucite, haüyne, nepheline, oxides, apatite, titanite, glass and other accessories). The basanites have homogeneous isotopic composition (87Sr/86Sr = 0.70366-0.70378, 143Nd/144Nd = 0.51274-0.51277, 206Pb/204Pb = 18.7-18.9, 207Pb/204Pb = 15.53-15.56; 208Pb/204Pb = 38.89-39.01), and a marked enrichment in the most incompatible elements (LILE and HFSE reach 100-215 times primitive mantle). These features are consistent with low degrees of partial melting of a volatile-, LILE- and HFSE-rich, amphibole-bearing peridotitic mantle induced by uplift during an E-W-directed extensional regime, as is found in central Madagascar. The marked changes in the geochemical composition, and small variations of the Sr-Nd-Pb isotopes in the trachyphonolites (87Sr/86Sr = 0.70425-0.70446, 143Nd/144Nd = 0.51266-0.51269, 206Pb/204Pb = 18.18-18.39, 207Pb/204Pb = 15.49-15.51; 208Pb/204Pb = 38.38-39.57) with respect to basanites and tephrites point to a limited amount of crustal contamination by the relatively low-206Pb/204Pb, low-143Nd/144Nd, high-87Sr/86Sr Precambrian basement rocks (of Middle Archean to Late Proterozoic age), and highlight the geochemical effects of titanite and anorthoclase removal on the trace element fractionation trends, a feature also shown in the trace element composition of the phenocrysts in trachyphonolites. Supplementary Table S2: synopsis of the mineral assemblages of the main lithotypes of the Itasy complex. Supplementary Table S3: composition of olivine of the Itasy rocks. Supplementary Table S4: composition of oxides of the Itasy rocks. Supplementary Table S5: composition of pyroxene of the Itasy rocks. Supplementary Table S6: composition of amphibole, biotite and rhönite of the Itasy rocks. Supplementary Table S7: composition of feldspar and glass of the Itasy rocks. Supplementary Table S8: composition of feldspathoids of the Itasy rocks. Supplementary Table S9: composition of titanite, apatite, other accessories of the Itasy rocks. Supplementary Table S10: Recapitulation of mass balance calculations between rocks of different degree of magmatic evolution, and detailed results. The composition of the phases is reported in the supplementary tables. Supplementary Table S11: average REE mineral/bulk rock ratios for titanite, amphibole and clinopyroxene. The partition coefficients of titanite, clinopyroxene, apatite and amphibole are taken from Olin and Wolff (2012), Fedele et al. (2009, 2015) and Tiepolo et al. (2007). Note that amphibole of RT-06I-355 could not be considered in equilibrium with the host rock (cf. Supplementary Figs. S1a, S1b, S1c).

Detection of diagenetic processes in bones: the case of Arkoudospilia cave, N. Greece

NASA Astrophysics Data System (ADS)

Zisi, Nikoleta; Dotsika, Elissavet; Tsoukala, Evangelia; Psomiadis, David

2010-05-01

Diagenesis of bone material over geological time is a highly complex phenomenon involving the physical, chemical, histological and mechanical alterations that occur at different time scales from the time of death to present and depend on the local geochemical conditions. The significance of diagenesis and the information that can provide its decoding, led to its study by a variety of physicochemical techniques. Despite serious research efforts, a detailed scenario of bone diagenesis remains elusive. The δ18O of the carbonate material of hydroxyapatite of the bones is though to be a good indicator of the δ18O of the local water precipitation and therefore can be used for palaeoclimatic reconstraction, while δ13C is used for definition of palaeodiet habits. The study of isotopic composition requires the detection of the diagenetic degree, because both δ18O and δ13C can be contaminated by these processes. Stable carbon and oxygen isotope values (δ13C, δ18O) were obtained for structural carbonate in the hydroxy-apatite of bear bones from Arkoudospilia Cave, Pella, N. Greece. The age range of the fossil layers is from 32ka BP to a maximum of 38ka BP (radiocarbon dating). The findings belong to Ursus ingressus, an extinct cave bear. The difficulty in studying an extinct species lies to the fact that it cannot be easily correlated with a present one, so it is impossible to determine the diagenesis by the analytical deviation. However, in order to include the environmental and climatic differences of the past and modern bear habitats, the isotopic composition of the water should be also included in the study. Cave bears are considered to be endemic in Europe. The shortage of data in literature concerning cave bears isotopic analyses in combination with the burden of the difficulties in spotting and sampling such rare materials makes difficult to compare the results of a study. The diet and the physiology of this species are not well known. However the morphology of teeth, skull and mandible indicate a basically herbivorous regime and the metabolism of this species is usually considered similar to this of the American black bear (Ursus americanus) or of the brown bear (Ursus arctos). Structural carbonate is considered to be less resistant than phosphate to post - depositional alteration because P-O chemical bonds in apatite are stronger than the C-O bonds, however phosphate is susceptible to microbial activity. For the needs of the present study isotopic composition of fossil bones where correlated with the isotopic composition of modern bears that live in the area of the findings. Moreover both fossil and modern bones were examined with X-ray diffraction for minelalogical alterations. The comparison of the isotopic composition and mineralogical characteristics of fossil and modern bones indicated possible diagenetic effects that may lead to exclude specific samples from palaeoclimatic archives.

Fabrication of biporous low-crystalline apatite based on mannitol dissolution from apatite cement.

PubMed

Tajima, Shinya; Kishi, Yuji; Oda, Makoto; Maruta, Michito; Matsuya, Shigeki; Ishikawa, Kunio

2006-09-01

Biporous (macro- and microporous) calcium phosphate gains much attention as a bone substitute material because of its large surface area and that it improves cell penetration. In the present study, we evaluated the feasibility of biporous, low-crystalline apatite based on dissolution of mannitol from self-setting apatite cement (Biopex). Mannitol--known as a biocompatible, easily dissolved monosaccharide alcohol--was recrystallized to obtain larger crystals. It was crushed with pestle and mortar, sieved to obtain crystals which passed through a 500-microm mesh but which remained against a 300-microm mesh, and then used as porogen. Although Biopex containing 60 wt% mannitol was not able to be taken out of the mold, addition of mannitol caused no initial setting inhibition to Biopex if the amount was 40 wt% or less. Similarly, transformation to apatitic product was confirmed when the apatite cement was immersed in 0.9% saline kept at 37 degrees C for seven days. The set mass became low-crystalline, biporous apatite with approximately 60% porosity.

Development of nanosized silver-substituted apatite for biomedical applications: A review.

PubMed

Lim, Poon Nian; Chang, Lei; Thian, Eng San

2015-08-01

The favorable biocompatibility of hydroxyapatite (HA) makes it a popular bone graft material as well as a coating layer on metallic implant. To reduce implant-related infections, silver ions were either incorporated into the apatite during co-precipitation process (AgHA-CP) or underwent ion-exchange with the calcium ions in the apatite (AgHA-IE). However, the distribution of silver ions in AgHA-CP and AgHA-IE was different, thus affecting the antibacterial action. Several studies reported that nanosized AgHA-CP containing 0.5 wt.% of silver provided an optimal trade-off between antibacterial properties and cytotoxicity. Nevertheless, nanosized AgHA and AgHA nanocoatings could not function ideally due to the compromise in the bone differentiation of mesenchymal stem cells, as evidenced in the reduced alkaline phosphatase, type I collagen and osteocalcin. Preliminary studies showed that biological responses of nanosized AgHA and AgHA nanocoatings could be improved with the addition of silicon. This review will discuss on nanosized AgHA and AgHA nanocoatings. In many patients needing bone graft material, hydroxyapatite (HA) has proven to be a popular choice. Nonetheless, implant-related infections remain a major concern. Hence, effective preventive measures are needed. In this review article, the authors discussed the application of incorporating silver nanoparticles in HA and its use as bone graft biomaterials together with the addition of silica. Copyright © 2015 Elsevier Inc. All rights reserved.

Analytical approaches to the determination of phosphorus partitioning patterns in sediments.

PubMed

Pardo, P; Rauret, G; López-Sánchez, J F

2003-04-01

Three methods for phosphorus fractionation in sediments based on chemical extractions have been applied to fourteen aquatic sediment samples of different origin and characteristics. Two of the methods used different approaches to obtain the inorganic fractions. The Hieltjes and Lijklema procedure (HL) uses strong acids or bases, whereas the Golterman procedure (G) uses chelating reagents. The third one, the Standards, Measurements and Testing (SMT) protocol, was proposed in the frame of the SMT Programme (European Commission) which aimed to provide harmonisation and the validation of such methodologies. This harmonised procedure was also used for the certification of the extractable phosphorus contents in a sediment certified reference material (CRM BCR 684). Principal component analysis (PCA) was used to group sediments according to their composition and the three extraction methods were applied to the samples including CRM BCR 684. The data obtained show that there is some correlation between the results from the three methods when considering the organic and the residual fractions together. The SMT and the HL methods are the most comparable, whereas the G method, using a different type of reagent, yields different distribution patterns depending on sample composition. In relation to the inorganic phosphorus, the three methods give similar information, although the distribution between non-apatite and apatite fractions can be different.

Extraction and characterisation of apatite- and tricalcium phosphate-based materials from cod fish bones.

PubMed

Piccirillo, C; Silva, M F; Pullar, R C; Braga da Cruz, I; Jorge, R; Pintado, M M E; Castro, P M L

2013-01-01

Apatite- and tricalcium phosphate-based materials were produced from codfish bones, thus converting a waste by-product from the food industry into high added-valued compounds. The bones were annealed at temperatures between 900 and 1200 °C, giving a biphasic material of hydroxyapatite and tricalcium phosphate (Ca10(PO4)6(OH)2 and β-Ca(PO4)3) with a molar proportion of 75:25, a material widely used in biomedical implants. The treatment of the bones in solution prior to their annealing changed the composition of the material. Single phase hydroxyapatite, chlorapatite (Ca10(PO4)6Cl2) and fluorapatite (Ca10(PO4)6F2) were obtained using CaCl2 and NaF solutions, respectively. The samples were analysed by several techniques (X-ray diffraction, infrared spectroscopy, scanning electron microscopy and differential thermal/thermogravimetric analysis) and by elemental analyses, to have a more complete understanding of the conversion process. Such compositional modifications have never been performed before for these materials of natural origin to tailor the relative concentrations of elements. This paper shows the great potential for the conversion of this by-product into highly valuable compounds for biomedical applications, using a simple and effective valorisation process. Copyright © 2012 Elsevier B.V. All rights reserved.

Optimisation of the enamelling of an apatite-mullite glass-ceramic coating on Ti6Al4V.

PubMed

O'Flynn, Kevin P; Stanton, Kenneth T

2011-09-01

Apatite-mullite glass-ceramics (AMGCs) are under investigation as a potential alternative to hydroxyapatite (HA) as a coating for cementless fixation of orthopaedic implants. These materials have tailorable mechanical and chemical properties that make them attractive for use as bioactive coatings. Here, AMGC coatings on Ti(6)Al(4)V were investigated to determine an improved heat treatment regime using a systematic examination of the different inputs: composition of glass, nucleation hold and crystallisation hold. An upper limit to the heat treatment temperature was determined by the α + β --> β of Ti(6)Al(4)V at 970°C. The glass composition was modified to produce different crystallisation temperatures and sintering characteristics. A glass was found that is fully crystalline below 970°C and has good sinterability. The effects of different heat treatment time and temperature combinations on the coating and substrate morphologies were examined and the most suitable combination determined. This sample was further investigated and was found to have qualitatively good adhesion and evidence of an interfacial reaction region between the coating and substrate indicating that a chemical reaction had occurred. Oxygen infiltration into the substrate was quantified and the new route was shown to result in a 63% reduction in penetration depth.

Evaluation of low-dose dual energy computed tomography for in vivo assessment of renal/ureteric calculus composition.

PubMed

Mahalingam, Harshavardhan; Lal, Anupam; Mandal, Arup K; Singh, Shrawan Kumar; Bhattacharyya, Shalmoli; Khandelwal, Niranjan

2015-08-01

This study aimed to assess the accuracy of low-dose dual-energy computed tomography (DECT) in predicting the composition of urinary calculi. A total of 52 patients with urinary calculi were scanned with a 128-slice dual-source DECT scanner by use of a low-dose protocol. Dual-energy (DE) ratio, weighted average Hounsfield unit (HU) of calculi, radiation dose, and image noise levels were recorded. Two radiologists independently rated study quality. Stone composition was assessed after extraction by Fourier transform infrared spectroscopy (FTIRS). Analysis of variance was used to determine if the differences in HU values and DE ratios between the various calculus groups were significant. Threshold cutoff values to classify the calculi into separate groups were identified by receiver operating characteristic curve analysis. A total of 137 calculi were detected. FTIRS analysis differentiated the calculi into five groups: uric acid (n=17), struvite (n=3), calcium oxalate monohydrate and dihydrate (COM-COD, n=84), calcium oxalate monohydrate (COM, n=28), and carbonate apatite (n=5). The HU value could differentiate only uric acid calculi from calcified calculi (p<0.001). The DE ratio could confidently differentiate uric acid, struvite, calcium oxalate, and carbonate apatite calculi (p<0.001) with cutoff values of 1.12, 1.34, and 1.66, respectively, giving >80% sensitivity and specificity to differentiate them. The DE ratio could not differentiate COM from COM-COD calculi. No study was rated poor in quality by either of the observers. The mean radiation dose was 1.8 mSv. Low-dose DECT accurately predicts urinary calculus composition in vivo while simultaneously reducing radiation exposure without compromising study quality.

Evaluation of low-dose dual energy computed tomography for in vivo assessment of renal/ureteric calculus composition

PubMed Central

Mahalingam, Harshavardhan; Mandal, Arup K; Singh, Shrawan Kumar; Bhattacharyya, Shalmoli; Khandelwal, Niranjan

2015-01-01

Purpose This study aimed to assess the accuracy of low-dose dual-energy computed tomography (DECT) in predicting the composition of urinary calculi. Materials and Methods A total of 52 patients with urinary calculi were scanned with a 128-slice dual-source DECT scanner by use of a low-dose protocol. Dual-energy (DE) ratio, weighted average Hounsfield unit (HU) of calculi, radiation dose, and image noise levels were recorded. Two radiologists independently rated study quality. Stone composition was assessed after extraction by Fourier transform infrared spectroscopy (FTIRS). Analysis of variance was used to determine if the differences in HU values and DE ratios between the various calculus groups were significant. Threshold cutoff values to classify the calculi into separate groups were identified by receiver operating characteristic curve analysis. Results A total of 137 calculi were detected. FTIRS analysis differentiated the calculi into five groups: uric acid (n=17), struvite (n=3), calcium oxalate monohydrate and dihydrate (COM-COD, n=84), calcium oxalate monohydrate (COM, n=28), and carbonate apatite (n=5). The HU value could differentiate only uric acid calculi from calcified calculi (p<0.001). The DE ratio could confidently differentiate uric acid, struvite, calcium oxalate, and carbonate apatite calculi (p<0.001) with cutoff values of 1.12, 1.34, and 1.66, respectively, giving >80% sensitivity and specificity to differentiate them. The DE ratio could not differentiate COM from COM-COD calculi. No study was rated poor in quality by either of the observers. The mean radiation dose was 1.8 mSv. Conclusions Low-dose DECT accurately predicts urinary calculus composition in vivo while simultaneously reducing radiation exposure without compromising study quality. PMID:26279828

Adsorptive features of polyacrylamide-apatite composite for Pb2+, UO(2)2+ and Th4+.

PubMed

Ulusoy, Ulvi; Akkaya, Recep

2009-04-15

Micro-composite of polyacrylamide (PAA) and apatite (Apt) was prepared by direct polymerization of acrylamide in a suspension of Apt and characterized by means of FT-IR, XRD, SEM and BET analysis. The adsorptive features of PAA-Apt and Apt were then investigated for Pb(2+), UO(2)(2+) and Th(4+) in view of dependency on ion concentration, temperature, kinetics, ion selectivity and reusability. Experimentally obtained isotherms were evaluated with reference to Langmuir, Freundlich and Dubinin-Radushkevich (DR) models. Apt in PAA-Apt had higher adsorption capacity (0.81, 1.27 and 0.69 mol kg(-1)) than bare Apt (0.28, 0.41 and 1.33 mol kg(-1)) for Pb(2+) and Th(4+), but not for UO(2)(2+). The affinity to PAA-Apt increased for Pb(2+) and UO(2)(2+) but not changed for Th(4+). The values of enthalpy and entropy changed were positive for all ions for both Apt and PAA-Apt. Free enthalpy change was DeltaG<0. Well compatibility of adsorption kinetics to the pseudo-second-order model predicated that the rate-controlling step was a chemical sorption. This was consistent with the free energy values derived from DR model. The reusability tests for Pb(2+) for five uses proved that the composite was reusable to provide a mean adsorption of 53.2+/-0.7% from 4x10(-3)M Pb(2+) solution and complete recovery of the adsorbed ion was possible (98+/-1%). The results of this investigation suggested that the use of Apt in the micro-composite form with PAA significantly enhanced the adsorptive features of Apt.

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 deposition may be a novel method to effectively enhance micro-roughened titanium surfaces without altering their microscale morphology. PMID:26834469

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.

Immobilization of uranium in contaminated soil by natural apatite addition

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

Mrdakovic Popic, Jelena; Stojanovic, Mirjana; Milosevic, Sinisa

2007-07-01

Available in abstract form only. Full text of publication follows: The goal of this study was to evaluate the effectiveness of Serbian natural mineral apatite as soil additive for reducing the migration of uranium from contaminated sediments. In laboratory study we investigated the sorption properties of domestic apatite upon different experimental conditions, such as pH, adsorbent mass, reaction period, concentration of P{sub 2}O{sub 5} in apatite, solid/liquid ratio. In second part of study, we did the quantification of uranium in soil samples, taken from uranium mine site 'Kalna', by sequential extraction method. The same procedure was, also, used for uraniummore » determination in contaminated soil samples after apatite addition, in order to determine the changes in U distribution in soil fraction. The obtained results showed the significant level of immobilization (96.7%) upon certain conditions. Increase of %P{sub 2}O{sub 5} in apatite and process of mechano-chemical activation led to increase of immobilization capacity from 17.50% till 91.64%. The best results for uranium binding were obtained at pH 5.5 and reaction period 60 days (98.04%) The sequential extraction showed the presence of uranium (48.2%) in potentially available soil fractions, but with the apatite addition uranium content in these fractions decreased (30.64%), what is considering environmental aspect significant fact. In situ immobilization of radionuclide using inexpensive sequestering agents, such as apatite, is very adequate for big contaminated areas of soil with low level of contamination. This investigation study on natural apatite from deposit 'Lisina' Serbia was the first one of this type in our country. Key words: apatite, uranium, immobilization, soil, contamination. (authors)« less

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.

A review of phosphate mineral nucleation in biology and geobiology.

PubMed

Omelon, Sidney; Ariganello, Marianne; Bonucci, Ermanno; Grynpas, Marc; Nanci, Antonio

2013-10-01

Relationships between geological phosphorite deposition and biological apatite nucleation have often been overlooked. However, similarities in biological apatite and phosphorite mineralogy suggest that their chemical formation mechanisms may be similar. This review serves to draw parallels between two newly described phosphorite mineralization processes, and proposes a similar novel mechanism for biologically controlled apatite mineral nucleation. This mechanism integrates polyphosphate biochemistry with crystal nucleation theory. Recently, the roles of polyphosphates in the nucleation of marine phosphorites were discovered. Marine bacteria and diatoms have been shown to store and concentrate inorganic phosphate (Pi) as amorphous, polyphosphate granules. Subsequent release of these P reserves into the local marine environment as Pi results in biologically induced phosphorite nucleation. Pi storage and release through an intracellular polyphosphate intermediate may also occur in mineralizing oral bacteria. Polyphosphates may be associated with biologically controlled apatite nucleation within vertebrates and invertebrates. Historically, biological apatite nucleation has been attributed to either a biochemical increase in local Pi concentration or matrix-mediated apatite nucleation control. This review proposes a mechanism that integrates both theories. Intracellular and extracellular amorphous granules, rich in both calcium and phosphorus, have been observed in apatite-biomineralizing vertebrates, protists, and atremate brachiopods. These granules may represent stores of calcium-polyphosphate. Not unlike phosphorite nucleation by bacteria and diatoms, polyphosphate depolymerization to Pi would be controlled by phosphatase activity. Enzymatic polyphosphate depolymerization would increase apatite saturation to the level required for mineral nucleation, while matrix proteins would simultaneously control the progression of new biological apatite formation.

Biomimetic nanoclay scaffolds for bone tissue engineering

NASA Astrophysics Data System (ADS)

Ambre, Avinash Harishchandra

Tissue engineering offers a significant potential alternative to conventional methods for rectifying tissue defects by evoking natural regeneration process via interactions between cells and 3D porous scaffolds. Imparting adequate mechanical properties to biodegradable scaffolds for bone tissue engineering is an important challenge and extends from molecular to macroscale. This work focuses on the use of sodium montmorillonite (Na-MMT) to design polymer composite scaffolds having enhanced mechanical properties along with multiple interdependent properties. Materials design beginning at the molecular level was used in which Na-MMT clay was modified with three different unnatural amino acids and further characterized using Fourier Transform Infrared (FTIR) spectroscopy, X-ray diffraction (XRD). Based on improved bicompatibility with human osteoblasts (bone cells) and intermediate increase in d-spacing of MMT clay (shown by XRD), 5-aminovaleric acid modified clay was further used to prepare biopolymer (chitosan-polygalacturonic acid complex) scaffolds. Osteoblast proliferation in biopolymer scaffolds containing 5-aminovaleric acid modified clay was similar to biopolymer scaffolds containing hydroxyapatite (HAP). A novel process based on biomineralization in bone was designed to prepare 5-aminovaleric acid modified clay capable of imparting multiple properties to the scaffolds. Bone-like apatite was mineralized in modified clay and a novel nanoclay-HAP hybrid (in situ HAPclay) was obtained. FTIR spectroscopy indicated a molecular level organic-inorganic association between the intercalated 5-aminovaleric acid and mineralized HAP. Osteoblasts formed clusters on biopolymer composite films prepared with different weight percent compositions of in situ HAPclay. Human MSCs formed mineralized nodules on composite films and mineralized extracellular matrix (ECM) in composite scaffolds without the use of osteogenic supplements. Polycaprolactone (PCL), a synthetic polymer, was used for preparing composites (films and scaffolds) containing in situ HAPclay. Composite films showed significantly improved nanomechanical properties. Human MSCs formed mineralized ECM on films in absence of osteogenic supplements and were able to infiltrate the scaffolds. Atomic force microscopy imaging of mineralized ECM formed on composite films showed similarities in dimensions, arrangement of collagen and apatite with their natural bone counterparts. This work indicates the potential of in situ HAPclay to impart polymeric scaffolds with osteoinductive, osteoconductive abilities and improve their mechanical properties besides emphasizing nanoclays as cell-instructive materials.

Tracing Life in the Earliest Terrestrial Rock Record

NASA Astrophysics Data System (ADS)

Lepland, A.; van Zuilen, M.; Arrhenius, G.

2001-12-01

The principal method for studying the earliest traces of life in the metamorphosed, oldest (> 3.5 Ga) terrestrial rocks involves determination of isotopic composition of carbon, mainly prevailing as graphite. It is generally believed that this measure can distinguish biogenic graphite from abiogenic varieties. However, the interpretation of life from carbon isotope ratios has to be assessed within the context of specific geologic circumstances requiring (i) reliable protolith interpretation (ii) control of secondary, metasomatic processes, and (iii) understanding of different graphite producing mechanisms and related carbon isotopic systematics. We have carried out a systematic study of abundance, isotopic composition and petrographic associations of graphite in rocks from the ca. 3.8 Ga Isua Supracrustal Belt (ISB) in southern West Greenland. Our study indicates that most of the graphite in ISB occurs in carbonate-rich metasomatic rocks (metacarbonates) while sedimentary units, including banded iron formations (BIFs) and metacherts, have exceedingly low graphite concentrations. Regardless of isotopic composition of graphite in metacarbonate rocks, their secondary origin disqualifies them from providing evidence for traces of life stemming from 3.8 Ga. Recognition of the secondary origin of Isua metacarbonates thus calls for reevaluation of biologic interpretations by Schidlowski et al. (1979) and Mojzsis et al. (1996) that suggested the occurrence of 3.8 Ga biogenic graphite in these rocks. The origin of minute quantities of reduced carbon, released from sedimentary BIFs and metacherts at combustion steps > 700 C remains to be clarified. Its isotopic composition (d13C from -18 to -25%) may hint at a biogenic origin. However, such isotopically light carbon was also found in Proterozoic mafic dykes cross-cutting the metasedimentary units in the ISB. The occurrence of isotopically light, reduced carbon in biologically irrelevant dykes may indicate secondary graphite crystallization from CO2 or CH4- containing fluids that in turn may derive from bioorganic sources. If this were the case, trace amounts of isotopically light secondary graphite can also be expected in metasediments, complicating the usage of light graphite as primary biomarker. The possibility of recent organic contamination, particularly important in low graphite samples, needs also to be considered; it appears as a ubiquitous component released at combustion in the 400 to 500 deg range. - A potential use of the apatite-graphite association as a biomarker has been proposed in the study by Mojzsis et al. (1996). Close inspection of several hundred apatite crystals from Isua BIFs and metacherts did, however, not show an association between these two minerals, moreover graphite is practically absent in these metasediments. In contrast, apatite crystals in the non-sedimentary metacarbonate rocks were found commonly to have invaginations, coatings and inclusions of abundant graphite. Considering that such graphite inclusions in apatite are restricted to the secondary metasomatic carbonate rocks in the ISB this association can not be considered as a primary biomarker in the Isua Supracrustal Belt References: Mojzsis,S.J, .Arrhenius,G., McKeegan, K.D.,.Harrison, T.M.,.Nutman, A.P & C.R.L.Friend.,1996. Nature 384: 55 Schidlowski, M., Appel, P.W.U., Eichmann, R. & Junge, C.E., 1979. Geochim. Cosmochim. Acta 43: 189-190.

Interactions of bioactive glass materials in the oral environment

NASA Astrophysics Data System (ADS)

Efflandt, Sarah Elizabeth

The aim of this research was to investigate bioactive glass materials for their use in dental restorations. Mechanical properties such as strength, toughness and wear resistance were considered initially, but the focus of this thesis was the biological properties such as reactions with saliva and interactions with natural dental tissues. Bioactive composite materials were created by incorporating bioactive glass and alumina powders into an aqueous suspension, slip casting, and infiltrating with resin. Microstructure, mechanical properties and wear resistance were evaluated. Mechanically, the composites are comparable to natural dental tissues and current dental materials with a strength of 206 +/- 18.7 MPa and a toughness of 1.74 +/- 0.08 MPa(m)1/2. Interfacial reactions were examined using bulk bioactive glasses. Disks were prepared from a melt, placed in saliva and incubated at 37°C. Surfaces were analyzed at 2, 5, 10, 21, and 42 days using scanning electron microscopy (SEM) and microdiffraction. Results showed changes at 2 days with apatite crystallization by 10 days. These glass disks were then secured against extracted human dentin and incubated in saliva for 21 or 42 days. Results from SEM, electron microprobe analysis (EMPA) and microdiffraction showed that dentin and bioactive glasses adhered in this in vitro environment due to attraction of collagen to bioactive glasses and growth of an interfacial apatite. After investigating these bulk glass responses, particulate bioactive glasses were placed in in vitro and in vivo set-ups for evaluation. Particles immersed in biologically buffered saliva showed crystallization of apatite at 3 days. These bioactive glass particles were placed in the molars of mini-pigs and left in vivo. After 30 days the bioactive paste was evaluated using SEM, EMPA and microdiffraction analyses. Results showed that the paste gained structural integrity and had chemical changes in vivo. These sets of experiments show that bioactive glasses have many mechanical and biological characteristics desirable for use in dental materials. Hopefully, the conclusions presented here will lead to further investigations toward their use in dentistry.

Chlorine isotopic compositions of apatite in Apollo 14 rocks: Evidence for widespread vapor-phase metasomatism on the lunar nearside ∼4 billion years ago

NASA Astrophysics Data System (ADS)

Potts, Nicola J.; Barnes, Jessica J.; Tartèse, Romain; Franchi, Ian A.; Anand, Mahesh

2018-06-01

Compared to most other planetary materials in the Solar System, some lunar rocks display high δ37Cl signatures. Loss of Cl in a H ≪ Cl environment has been invoked to explain the heavy signatures observed in lunar samples, either during volcanic eruptions onto the lunar surface or during large scale degassing of the lunar magma ocean. To explore the conditions under which Cl isotope fractionation occurred in lunar basaltic melts, five Apollo 14 crystalline samples were selected (14053,19, 14072,13, 14073,9, 14310,171 along with basaltic clast 14321,1482) for in situ analysis of Cl isotopes using secondary ion mass spectrometry. Cl isotopes were measured within the mineral apatite, with δ37Cl values ranging from +14.6 ± 1.6‰ to +40.0 ± 2.9‰. These values expand the range previously reported for apatite in lunar rocks, and include some of the heaviest Cl isotope compositions measured in lunar samples to date. The data here do not display a trend between increasing rare earth elements contents and δ37Cl values, reported in previous studies. Other processes that can explain the wide inter- and intra-sample variability of δ37Cl values are explored. Magmatic degassing is suggested to have potentially played a role in fractionating Cl isotope in these samples. Degassing alone, however, could not create the wide variability in isotopic signatures. Our favored hypothesis, to explain small scale heterogeneity, is late-stage interaction with a volatile-rich gas phase, originating from devolatilization of lunar surface regolith rocks ∼4 billion years ago. This period coincides with vapor-induced metasomastism recorded in other lunar samples collected at the Apollo 16 and 17 landing sites, pointing to the possibility of widespread volatile-induced metasomatism on the lunar nearside at that time, potentially attributed to the Imbrium formation event.

BENTHIC COMMUNITY RESPONSE TO SEDIMENT AMENDMENTS

EPA Science Inventory

The amendments apatite, organoclay, acetate, chitin, and geotextile reactive mats containing apatite and apatite + organoclay are currently under examination for remediation of contaminated sediments. The objective of this research is to evaluate toxicity to several estuarine an...

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.

Fabrication of hydroxyapatite block from gypsum block based on (NH4)2HPO4 treatment.

PubMed

Suzuki, Yumiko; Matsuya, Shigeki; Udoh, Koh-ichi; Nakagawa, Masaharu; Tsukiyama, Yoshihiro; Koyano, Kiyoshi; Ishikawa, Kunio

2005-12-01

The aim of this study was to evaluate the feasibility of fabricating low-crystalline, porous apatite block using set gypsum as a precursor based on the fact that apatite is thermodynamically more stable than gypsum. When the set gypsum was immersed in 1 mol/L diammonium hydrogen phosphate aqueous solution at 100 degrees C, it transformed to low-crystalline porous apatite retaining its original shape. The transformation reaction caused a release of sulfate ions due to an ion exchange with phosphate ions, thus leading to a decrease in the pH of the solution. Then, due to decreased pH, dicalcium phosphate anhydrous--which has similar thermodynamic stability at lower pH--was also produced as a by-product. Apatite formed in the present method was low-crystalline, porous B-type carbonate apatite that contained approximately 0.5 wt% CO3, even though no carbonate sources--except carbon dioxide from air--were added to the reaction system. We concluded therefore that this is a useful bone filler fabrication method since B-type carbonate apatite is the biological apatite contained in bone.

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.

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

Hu, Yanyan

This thesis describes application and development of advanced solid-state nuclear magnetic resonance techniques for complex materials, in particular organic-inorganic nanocomposites and thermoelectric tellurides. The apatite-collagen interface, essential for understanding the biomineralization process in bone and engineering the interface for controlled bio-mimetic synthesis and optimized mechanical properties, is buried within the nanocomposite of bone. We used multinuclear solid-state NMR to study the composition and structure of the interface. Citrate has been identified as the main organic molecule strongly bound to the apatite surface with a density of 1/(2 nm) 2, covering 1/6 of the total surface area in bovine bone. Citratemore » provides more carboxylate groups, one of the key functional groups found to affect apatite nucleation and growth, than all the non-collagenous proteins all together in bone; thus we propose that citrate stabilizes apatite crystals at a very small thickness of ~3 nm (4 unit cells) to increase bone fracture tolerance. The hypothesis has been confirmed in vitro by adding citrate in the bio-mimetic synthesis of polymerhydroxyapatite nanocomposites. The results have shown that the size of hydroxyapatite nanocrystals decreases as increasing citrate concentration. With citrate concentrations comparable to that in body fluids, similar-sized nanocrystals as in bone have been produced. Besides the dimensions of the apatite crystals, the composition of bone also affects its biofunctional and macroscopic mechanical properties; therefore, our team also extended its effort to enhance the inorganic portion in our bio-mimetic synthesis from originally 15 wt% to current 50 wt% compared to 65 wt% in bovine bone, by using Lysine-Leucine hydroxyapatite nucleating diblock co-polypeptide, which forms a gel at very low concentration. In this thesis, various advanced solid state NMR techniques have been employed to characterize nanocomposites. Meanwhile, we have developed new methods to achieve broadband high resolution NMR and improve the accuracy of inter-nuclear distance measurements involving quadrupolar spins. Broadband high resolution NMR of spin-1/2 nuclei has been accomplished by the adaptation of the magic angle turning (MAT) method to fast magic angle spinning, termed fast MAT, by solving technical problems such as off resonance effects. Fast MAT separates chemical shift anisotropy and isotropic chemical shifts over a spectral range of ~1.8 γB 1 without significant distortions. Fast MAT 125Te NMR has been applied to study technologically important telluride materials with spectra spreading up to 190 kHz. The signal-to-noise ratio of the spectra is significantly improved by using echo-matched Gaussian filtering in offline data processing. The accuracy of the measured distances between spin-1/2 and quadrupolar nuclei with methods such as SPIDER and REAPDOR has been improved by compensating for the fast longitudinal quadrupolar relaxation on the sub-millisecond with a modified S 0 pulse sequence. Also, the T1Q effect on the spin coherence and its spinning speed dependency has been explored and documented with analytical and numerical simulations as well as experimental measurements.« less

Anthropogenic sediments and soils of tells of the Balkans and Anatolia: Composition, genesis, and relationships with the history of landscape and human occupation

NASA Astrophysics Data System (ADS)

Sedov, S. N.; Aleksandrovskii, A. L.; Benz, M.; Balabina, V. I.; Mishina, T. N.; Shishkov, V. A.; Şahin, F.; Özkaya, V.

2017-04-01

Soils and sediments composing Tell Körtik Tepe (Epipaleolithic, Turkey) and Tell Yunatsite (Chalcolithic (Eneolithic), Bulgaria) have been studied with the aim to gain a better insight into their microfabrics, determine the composition of anthropogenic artifacts, and, on this basis, to analyze similarities and distinctions between these objects and the modern soils of urban areas. The methods of micromorphology, scanning electron microscopy with an energy dispersive X-ray microanalyzer, X-ray fluorometry, and other techniques to determine the chemical and physical properties of the soils and sediments have been applied. Two paleosols have been identified in Tell Yunatsite with a total thickness of 9 m: the paleosol buried under the tell and the paleosol in its middle part. Sediments of Tell Körtik Tepe have a total thickness of up to 5 m; their accumulation began at the end of Pleistocene over the surface of buried paleosol. The cultural layer of the tells consists of construction debris mainly represented by a mixture of clay and sand and of domestic wastes with the high content of phosphorus. The major source of phosphorus is calcium phosphate (apatite) of bone tissues. The abundance of various anthropogenic materials in the sediments is clearly seen in thin sections. Even in the paleosols developed within the cultural layer (the mid-profile paleosol in Tell Yunatsite), the amount of microinclusions of bone fragments, charcoal, and burnt clay (ceramics) is very high. Micromorphological data indicate that up to 50% of the layered material filling an Epipaleolithic construction in Tell Körtik Tepe consists of the anthropogenic inclusions: bone fragments, charcoal, etc. The features of pedogenic transformation are present in the sediments. Such sediments can be classified as synlithogenic soils similar to the modern Urbic Technosols. It is shown that the formation of paleosols and sediments of Tell Körtik Tepe took place under extreme environmental conditions—arid climate of the latest Pleistocene climate cooling phase (the Younger Dryas, Tell Körtik Tepe)—and intensive anthropogenic loads (tells Körtik Tepe and Yunatsite).

Regulated fracture in tooth enamel: a nanotechnological strategy from nature.

PubMed

Ghadimi, Elnaz; Eimar, Hazem; Song, Jun; Marelli, Benedetto; Ciobanu, Ovidiu; Abdallah, Mohamed-Nur; Stähli, Christoph; Nazhat, Showan N; Vali, Hojatollah; Tamimi, Faleh

2014-07-18

Tooth enamel is a very brittle material; however it has the ability to sustain cracks without suffering catastrophic failure throughout the lifetime of mechanical function. We propose that the nanostructure of enamel can play a significant role in defining its unique mechanical properties. Accordingly we analyzed the nanostructure and chemical composition of a group of teeth, and correlated it with the crack resistance of the same teeth. Here we show how the dimensions of apatite nanocrystals in enamel can affect its resistance to crack propagation. We conclude that the aspect ratio of apatite nanocrystals in enamel determines its resistance to crack propagation. According to this finding, we proposed a new model based on the Hall-Petch theory that accurately predicts crack propagation in enamel. Our new biomechanical model of enamel is the first model that can successfully explain the observed variations in the behavior of crack propagation of tooth enamel among different humans. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rare earth patterns in shergottite phosphates and residues

NASA Technical Reports Server (NTRS)

Laul, J. C.

1987-01-01

Leaching experiments with 1M HCl on ALHA 77005 powder show that rare earth elements (REE) are concentrated in accessory phosphate phases (whitlockite, apatite) that govern the REE patterns of bulk shergottites. The REE patterns of whitlockite are typically light REE-depleted with a negative Eu anomaly and show a hump at the heavy REE side, while the REE pattern of apatite (in Shergotty) is light REE-enriched. Parent magmas are calculated from the modal compositions of residues of ALHA 77005, Shergotty, and EETA 79001. The parent magmas lack a Eu anomaly, indicating that plagioclase was a late-stage crystallizing phase and that it probably crystallized before the phosphates. The parent magmas of ALHA 77005 and Shergotty have similar REE patterns, with a subchondritic Nd/Sm ratio. However, the Sm/Nd isotopoics require a light REE-depleted source for ALHA 77005 (if the crystallization age is less than 600 Myr) and a light REE-enriched source for Shergotty. Distant Nd and Sr isotopic signatures may suggest different source regions for shergottites.

A combined qualitative and quantitative procedure for the chemical analysis of urinary calculi

PubMed Central

Hodgkinson, A.

1971-01-01

A better understanding of the physico-chemical principles underlying the formation of calculus has led to a need for more precise information on the chemical composition of stones. A combined qualitative and quantitative procedure for the chemical analysis of urinary calculi which is suitable for routine use is presented. The procedure involves five simple qualitative tests followed by the quantitative determination of calcium, magnesium, inorganic phosphate, and oxalate. These data are used to calculate the composition of the stone in terms of calcium oxalate, apatite, and magnesium ammonium phosphate. Analytical results and derived values for five representative types of calculi are presented. PMID:5551382

Structurally bound sulfide and sulfate in apatite from the Philips Mine iron oxide - apatite deposit, New York, USA: A tracer of redox changes

NASA Astrophysics Data System (ADS)

Sadove, G.; Konecke, B.; Fiege, A.; Simon, A. C.

2017-12-01

Multiple competing hypotheses attempt to explain the genesis of iron oxide-apatite (IOA) ore deposits. Many studies have investigated the chemistry of apatite because the abundances of F and Cl can distinguish magmatic vs. hydrothermal processes. Recent experiments demonstrate that apatite incorporates S6+, S4+, and S2-, and that total sulfur (∑S) as well as the S6+/∑S ratio in apatite vary systematically as a function of oxygen fugacity [1], providing information about sulfur budget and redox. Here, we present results from X-ray absorption near-edge structure (XANES) spectroscopy at the S K-edge, electron microprobe analyses, cathodoluminescence (CL) imaging, and element mapping of apatite from the Philip's Mine IOA deposit, southern Adirondack Mountains, USA. The Philip's Mine apatite contains inclusions of pyrite and pyrrhotite, where the latter includes iron oxide and Ni-rich domains. The apatite also contains inclusions of monazite, and exhibits complex CL zonation coincident with variations in the abundances of REE and S. The presence of monazite fingerprints fluid-mediated dissolution-reprecipitation of originally REE-enriched apatite [2]. The S XANES spectra reveal varying proportions of structurally bound S6+ and S2-, as the S6+/∑S ratio ranges from sulfide-only to sulfate-only. Notably, sulfide-dominated domains contain higher S contents than sulfate-dominated regions. These observations are consistent with co-crystallization of apatite and monosulfide solid solution (MSS) at reducing conditions, followed by decomposition of MSS to pyrrhotite, pyrite and intermediate solid solution (ISS, which is not preserved; [3]). Metasomatism of that assemblage by an oxidized fluid resulted in formation of monazite in apatite and iron oxide domains in pyrrhotite. We conclude that the deposit formed by a H2S-Fe-rich volatile phase, possibly evolved from a rather primitive magmatic source, which is consistent with the low Ti content of magnetite. The deposit was subsequently altered by a rather oxidized SO2-poor volatile phase more typical of evolved felsic source regions. [1] Konecke et al. (2017) American Mineralogist 102-3, 548-557; [2] Harlov (2015) Elements 11-3, 171-176; [3] Edmonds & Mather (2017) Elements 13-2, 105-110.

500 Myr of thermal history elucidated by multi-method detrital thermochronology of North Gondwana Cambrian sandstone (Eilat area, Israel)

NASA Astrophysics Data System (ADS)

Vermeesch, P.; Avigad, D.

2009-04-01

Following the Neoproterozoic Pan-African orogeny, the Arabian-Nubian Shield (ANS) of North Africa and Arabia was eroded and then covered by Cambrian sandstones that record the onset of platform sedimentation. We applied K-feldspar 40Ar/39Ar, zircon and apatite fission track and apatite (U-Th)/He thermochronology to detritus from Cambrian sandstones of southern Israel deposited at about 500 Ma. U-Pb detrital zircon ages from these sandstones predate deposition and record the earlier Neoproterozoic crustal evolution of the Pan-African orogens. 40Ar/39Ar ages from 50 single grains of K-feldspar yield a Cambrian mean of approximately 535 Ma. The 40Ar/39Ar age spectrum of a multi-grain K-feldspar aliquot displays diffusion behaviour compatible with >560 Ma cooling later affected by a heating event. Assuming that the high temperature domains of the K-feldspars have not been affected by subsequent (hydro)thermal events, and taking previously published K-Ar and Rb-Sr ages from other parts of the East African Orogen at face value, these ages apparently record Pan-African thermal resetting below a thick volcano-sedimentary pile similar to the Saramuj conglomerate in Jordan and/or the Hammamat in Egypt. Detrital zircon fission track (ZFT) ages cluster around 380 Ma, consistent with previous ZFT results from Neoproterozoic basement and sediments of the region, revealing that the Cambrian platform sequence experienced a middle Devonian thermal event and low-grade metamorphism. Regional correlation indicates that during Devonian time the sedimentary cover atop the Cambrian in Israel was never in excess of 2.5 km, requiring an abnormally steep geothermal gradient to explain the complete ZFT annealing. A basal Carboniferous unconformity can be traced from Syria to southern Saudi Arabia, suggesting that the observed Devonian ZFT ages represent a regional tectonothermal event. Similar Devonian ZFT ages were reported from ANS basement outcrops in the Eastern Desert, 500 km south of Eilat. The detrital apatites we studied all have extremely rounded cores suggestive of a distant provenance, but some grains also feature distinct euhedral U-rich apatite overgrowth rims. Authigenic apatite may have grown during the late Devonian thermal event we dated by ZFT, coinciding with existing Rb-Sr ages from authigenic clays in the same deposits and leading to the conclusion that the Devonian event was probably hydrothermal. Like the ZFT ages, the detrital apatite fission track (AFT) ages were also completely reset after deposition. Sixty single grain detrital apatite fission track (AFT) ages group at ~270 Ma with significant dispersion. Inverse modeling of the AFT data indicate extended and/or repeated residence in the AFT partial annealing zone, in turn suggesting an episodic burial-erosion history during the Mesozoic caused by low-amplitude vertical motions. Seven detrital apatite (U-Th)/He ages scatter between 33 and 77 Ma, possibly resulting from extreme compositional zonation associated with the authigenic U-rich overgrowths. The ~70 Ma (U-Th)/He ages are more likely to be accurate, setting 1-2 km as an upper limit (depending on the geothermal gradient) on the post-Cretaceous exhumation of the Cambrian sandstone and showing no evidence for substantial denudation related to Tertiary rifting of the Red Sea.

Calcium phosphate mineralization is widely applied in crustacean mandibles.

PubMed

Bentov, Shmuel; Aflalo, Eliahu D; Tynyakov, Jenny; Glazer, Lilah; Sagi, Amir

2016-02-24

Crustaceans, like most mineralized invertebrates, adopted calcium carbonate mineralization for bulk skeleton reinforcement. Here, we show that a major part of the crustacean class Malacostraca (which includes lobsters, crayfishes, prawns and shrimps) shifted toward the formation of calcium phosphate as the main mineral at specified locations of the mandibular teeth. In these structures, calcium phosphate is not merely co-precipitated with the bulk calcium carbonate but rather creates specialized structures in which a layer of calcium phosphate, frequently in the form of crystalline fluorapatite, is mounted over a calcareous "jaw". From a functional perspective, the co-existence of carbonate and phosphate mineralization demonstrates a biomineralization system that provides a versatile route to control the physico-chemical properties of skeletal elements. This system enables the deposition of amorphous calcium carbonate, amorphous calcium phosphate, calcite and apatite at various skeletal locations, as well as combinations of these minerals, to form graded composites materials. This study demonstrates the widespread occurrence of the dual mineralization strategy in the Malacostraca, suggesting that in terms of evolution, this feature of phosphatic teeth did not evolve independently in the different groups but rather represents an early common trait.

Calcium phosphate mineralization is widely applied in crustacean mandibles

PubMed Central

Bentov, Shmuel; Aflalo, Eliahu D.; Tynyakov, Jenny; Glazer, Lilah; Sagi, Amir

2016-01-01

Crustaceans, like most mineralized invertebrates, adopted calcium carbonate mineralization for bulk skeleton reinforcement. Here, we show that a major part of the crustacean class Malacostraca (which includes lobsters, crayfishes, prawns and shrimps) shifted toward the formation of calcium phosphate as the main mineral at specified locations of the mandibular teeth. In these structures, calcium phosphate is not merely co-precipitated with the bulk calcium carbonate but rather creates specialized structures in which a layer of calcium phosphate, frequently in the form of crystalline fluorapatite, is mounted over a calcareous “jaw”. From a functional perspective, the co-existence of carbonate and phosphate mineralization demonstrates a biomineralization system that provides a versatile route to control the physico-chemical properties of skeletal elements. This system enables the deposition of amorphous calcium carbonate, amorphous calcium phosphate, calcite and apatite at various skeletal locations, as well as combinations of these minerals, to form graded composites materials. This study demonstrates the widespread occurrence of the dual mineralization strategy in the Malacostraca, suggesting that in terms of evolution, this feature of phosphatic teeth did not evolve independently in the different groups but rather represents an early common trait. PMID:26906263

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. © 2014 Wiley Periodicals, Inc.

Surface functional group dependent apatite formation on bacterial cellulose microfibrils network in a simulated body fluid.

PubMed

Nge, Thi Thi; Sugiyama, Junji

2007-04-01

The apatite forming ability of biopolymer bacterial cellulose (BC) has been investigated by soaking different BC specimens in a simulated body fluid (1.5 SBF) under physiological conditions, at 37 degrees C and pH 7.4, mimicking the natural process of apatite formation. From ATR-FTIR spectra and ICP-AES analysis, the crystalline phase nucleated on the BC microfibrils surface was calcium deficient carbonated apatite through initial formation of octacalcium phosphate (OCP) or OCP like calcium phosphate phase regardless of the substrates. Morphology of the deposits from SEM, FE-SEM, and TEM observations revealed the fine structure of thin film plates uniting together to form apatite globules of various size (from <1 mum to 3 mum) with respect to the substrates. Surface modification by TEMPO (2,2,6,6-tetramethylpyperidine-1-oxyl)-mediated oxidation, which can readily form active carboxyl functional groups upon selective oxidation of primary hydroxyl groups on the surface of BC microfibrils, enhanced the rate of apatite nucleation. Ion exchanged treatment with calcium chloride solution after TEMPO-mediated oxidation was found to be remarkably different from other BC substrates with the highest deposit weight and the smallest apatite globules size. The role of BC substrates to induce mineralization rate differs according to the nature of the BC substrates, which strongly influences the growth behavior of the apatite crystals. (c) 2006 Wiley Periodicals, Inc.

Isotopic composition and identification of the origins of individuals buried in a Neolithic collective grave at Bronocice (southern Poland).

PubMed

Szostek, K; Haduch, E; Stepańczak, B; Kruk, J; Szczepanek, A; Pawlyta, J; Głąb, H; Milisauskas, S

2014-04-01

The oxygen present in a human organism comes from numerous sources, but the major factor that causes variation in the isotopic composition of this element in a tissue is available drinking water. The isotopic ratio of oxygen in an organism's tissue, including that found in bones and teeth, reflects the isotopic oxygen composition typical for the area where a given individual developed and lived. Of particular interest with regard to this issue were a series of skeletons from the multiple grave discovered at the Funnel Beaker-Baden settlement at Bronocice (southern Poland). The question therefore arose whether the specimens buried in this grave were part of the local community. The oxygen isotope level was established using apatite isolated from bones or teeth. A femur and root dentine samples taken from permanent teeth were subjected to oxygen isotope analysis. The oxygen isotope level of the site was established on the basis of local water precipitation and measurements taken from the oxygen isotope concentration in apatite samples isolated from the bones of animals co-occurring with the studied human group. It has been found that the oxygen isotope levels in the bones and dentine of almost all the analysed specimens from the excavated site at Bronocice were within the established range for the area's environment, providing evidence for their local origin. Thus, it can be assumed that the analysed group inhabiting the macrosettlement at Bronocice during the Funnel Beaker phase of the Baden culture was most probably of local origin. Copyright © 2013 Elsevier GmbH. All rights reserved.

Low temperature setting polymer-ceramic composites for bone tissue engineering

NASA Astrophysics Data System (ADS)

Sethuraman, Swaminathan

Tissue engineering is defined as "the application of biological, chemical and engineering principles towards the repair, restoration or regeneration of tissues using scaffolds, cells, factors alone or in combination". The hypothesis of this thesis is that a matrix made of a synthetic biocompatible, biodegradable composite can be designed to mimic the properties of bone, which itself is a composite. The overall goal was to design and develop biodegradable, biocompatible polymer-ceramic composites that will be a practical alternative to current bone repair materials. The first specific aim was to develop and evaluate the osteocompatibility of low temperature self setting calcium deficient apatites for bone tissue engineering. The four different calcium deficient hydroxyapatites evaluated were osteocompatible and expressed the characteristic genes for osteoblast proliferation, maturation, and differentiation. Our next objective was to develop and evaluate the osteocompatibility of biodegradable amino acid ester polyphosphazene in vitro as candidates for forming composites with low temperature apatites. We determined the structure-property relationship, the cellular adhesion, proliferation, and differentiation of primary rat osteoblast cells on two dimensional amino acid ester based polyphosphazene films. Our next goal was to evaluate the amino acid ester based polyphosphazenes in a subcutaneous rat model and our results demonstrated that the polyphosphazenes evaluated in the study were biocompatible. The physio-chemical property characterization, cellular response and gene expression on the composite surfaces were evaluated. The results demonstrated that the precursors formed calcium deficient hydroxyapatite in the presence of biodegradable polyphosphazenes. In addition, cells on the surface of the composites expressed normal phenotype and characteristic genes such as type I collagen, alkaline phosphatase, osteocalcin, osteopontin, and bone sialoprotein. The in vivo study of these novel bone cements in a 5mm unicortical defect in New Zealand white rabbits showed that the implants were osteoconductive, and osteointegrative. In conclusion, the various studies that have been carried out in this thesis to study the feasibility of a bone cement system have shown that these materials are promising candidates for various orthopaedic applications. Overall I believe that these next generation bone cements are promising bone graft substitutes in the armamentarium to treat bone defects.

Evaluation of the Ca ion release, pH and surface apatite formation of a prototype tricalcium silicate cement.

PubMed

Yamamoto, S; Han, L; Noiri, Y; Okiji, T

2017-12-01

To evaluate the Ca 2+ -releasing, alkalizing and apatite-like surface precipitate-forming abilities of a prototype tricalcium silicate cement, which was mainly composed of synthetically prepared tricalcium silicate and zirconium oxide radiopacifier. The prototype tricalcium silicate cement, white ProRoot MTA (WMTA) and TheraCal LC (a light-cured resin-modified calcium silicate-filled material) were examined. The chemical compositions were analysed with a wavelength-dispersive X-ray spectroscopy electron probe microanalyser with an image observation function (SEM-EPMA). The pH and Ca 2+ concentrations of water in which the set materials had been immersed were measured, and the latter was assessed with the EDTA titration method. The surface precipitates formed on the materials immersed in phosphate-buffered saline (PBS) were analysed with SEM-EPMA and X-ray diffraction (XRD). Kruskal-Wallis tests followed by Mann-Whitney U-test with Bonferroni correction were used for statistical analysis (α = 0.05). The prototype cement contained Ca, Si and Zr as major elemental constituents, whereas it did not contain some metal elements that were detected in the other materials. The Ca 2+ concentrations and pH of the immersion water samples exhibited the following order: WMTA = prototype cement > TheraCal LC (P < 0.05). All three materials produced Ca- and P-containing surface precipitates after PBS immersion, and the precipitates produced by TheraCal LC displayed lower Ca/P ratios than those formed by the other materials. XRD peaks corresponding to hydroxyapatite were detected in the precipitates produced by the prototype cement and WMTA. The prototype tricalcium silicate cement exhibited similar Ca 2+ -releasing, alkalizing and apatite-like precipitate-forming abilities to WMTA. The Ca 2+ -releasing, alkalizing and apatite-like precipitate-forming abilities of TheraCal LC were lower than those of the other materials. © 2016 International Endodontic Journal. Published by John Wiley & Sons Ltd.

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.

Prediction of apatite lattice constants from their constituent elemental radii and artificial intelligence methods.

PubMed

Wu, P; Zeng, Y Z; Wang, C M

2004-03-01

Lattice constants (LCs) of all possible 96 apatite compounds, A(5)(BO(4))(3)C, constituted by A[double bond]Ba(2+), Ca(2+), Cd(2+), Pb(2+), Sr(2+), Mn(2+); B[double bond]As(5+), Cr(5+), P(5+), V(5+); and C[double bond]F(1-), Cl(1-), Br(1-), OH(1-), are predicted from their elemental ionic radii, using pattern recognition (PR) and artificial neural networks (ANN) techniques. In particular, by a PR study it is demonstrated that ionic radii predominantly govern the LCs of apatites. Furthermore, by using ANN techniques, prediction models of LCs a and c are developed, which reproduce well the measured LCs (R(2)=0.98). All the literature reported on 30 pure and 22 mixed apatite compounds are collected and used in the present work. LCs of all possible 66 new apatites (assuming they exist) are estimated by the developed ANN models. These proposed new apatites may be of interest to biomedical research especially in the design of new apatite biomaterials for bone remodeling. Similarly these techniques may also be applied in the study of interface growth behaviors involving other biomaterials.

[The effects of surface morphology of calcium phosphate ceramics on apatite formation in dynamic SBF].

PubMed

Duan, Yourong; Lü, Wanxin; Wang, Chaoyuan; Chen, Jiyong; Zhang, Xingdong

2002-06-01

Bone-like apatite formation on the surface of calcium phosphate ceramics has been believed to be the prerequisite of new bone growth on ceramics and to be related to the osteoinductivity of the material. The research of the factors effecting bone-like apatite formation is a great help in understanding the mechanism of osteoinduction. This paper is aimed to a comparative study of in vitro formation of bone-like apatite on the surface of dense and rough calcium phosphate ceramics with SBF flowing at different rates. The results showed that the rough surface was beneficial to the formation of bone-like apatite, and the apatite formed faster in 1.5 SBF than in SBF. Rough surface, namely, larger surface area, increased the dissolution of Ca2+ and HPO4(2-) and higher concentration of Ca2+ and HPO4(2-) ions of SBF and was in turn advantageous to the accumulation of Ca2+, HPO4(2-), PO4(3-) near the ceramic surface. Local supersaturating concentration of Ca2+, HPO4(2-), PO4(3-) near sample surface was essential to nucleation of apatite on the surface of sample.

Stable isotopic constraints on fluid-rock interaction and Cu-PGE-S redistribution in the Sonju Lake intrusion, Minnesota

USGS Publications Warehouse

Park, Y.-R.; Ripley, E.M.; Miller, J.D.; Li, C.; Mariga, J.; Shafer, P.

2004-01-01

The Sonju Lake intrusion, part of the 1.1 Ga Midcontinent rift-related Beaver Bay Complex, is a 1,200-m-thick, strongly differentiated, layered sequence of mafic cumulates located in northeastern Minnesota. Basal melatroctolite and dunite layers are overlain by troctolite, gabbro, Fe-Ti oxide-rich gabbro, apatite diorite, and monzodiorite. Stratigraphic intervals rich in Pt + Pd, Cu, and S occur over ???500 m in the Fe-Ti oxide-rich gabbro and apatite diorite units. Peak concentrations show offsets that are similar to those found in other tholeiitic layered intrusions. Concentrations of Pd in excess of 100 ppb are confined to the lowermost 25 m of the interval. Copper shows a sharp increase to 630 ppm above the Pd-rich interval. Sulfur contents are low (<375 ppm) in the Cu-rich interval, but they increase to values as high as 3,150 ppm above in the apatite diorite. Disseminated sulfides in the intrusion have ??34S values that range from -2.2 to 3 per mil Vienna-Canyon Diablo Troilite (V-CDT) and suggest that contamination by country rock sulfur was not an important process in the formation of the metal-rich interval. ??18O values of plagioclase from the intrusion range from 5.6 to 12.0 per mil (V-SMOW) and indicate that a relatively low-18O fluid (??18O ???3-5 ???) interacted with the rocks of the intrusion at temperatures less than ???275??C. Clinopyroxene and Fe-Ti oxides (ilmenite with minor amounts of titanomagnetite) show much more restricted ranges in ??18O values (4.6-5.7 and 5.5-6.7 per mil, respectively) and attest to the kinetic control of the oxygen isotope exchange process. The externally derived fluid that interacted with rocks now enriched in platinum group elements (PGE) + Cu- and Fe-sulfide minerals locally liberated sulfur and replaced chalcopyrite and pyrite with goethite. In the Cu-rich zone, goethite that replaces chalcopyrite may contain up to 8.5 weight percent Cu. It is evident that hydrothermal alteration resulted in a decoupling of copper and sulfur, with sulfur being transferred out of the Cu-rich interval. Interaction between rocks in the PGE-Cu-S interval of the Sonju Lake intrusion and an externally derived fluid at low temperatures modified what appears to have been a primary stratigraphic metal-sulfur zonation. The effects of hydrothermal alteration on PGE and base-metal sulfide mobility and redistribution must be understood before models of primary zonation processes can be meaningfully applied. ?? 2004 by Economic Geology.

Framework Guidance Manual for In Situ Wetland Restoration Demonstration

DTIC Science & Technology

2013-08-26

within the laboratory include activated carbon, apatite, coke, organoclay, zeolites , and zero valent iron (Barth, 2008; Reible, 2004). Three of...apatite, coke, organoclay, zeolites , and zero-valent iron (Barth, 2008; Reible, 2004, Patmont et al., 2013). Activated carbon, apatite and organoclay

[Synthesis and characterization of CO-3(2-) doping nano-hydroxyapatite].

PubMed

Liao, Jian-Guo; Li, Yan-Qun; Duan, Xing-Ze; Liu, Qiong

2014-11-01

CO3(2-) doping is an effective method to increase the biological activity of nano-hydroxyapatite (n-HA). In the present study, calcium nitrate and trisodium phosphate were chosen as raw materials, with a certain amount of Na2CO3 as a source of CO-3(2-) ions, to synthesize nano-carbonate hydroxyapatite (n-CHA) slurry by solution precipitation method. The structure and micro-morphology of n-CHA were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FTIR) and Raman spectroscopy (RS). The results revealed that the synthetic n-HA crystals are acicular in nanometer scale and have a crystal size of 20-30 nm in diameter and 60-80 nm in length, which are similar to natural bone apatite. And the crystallinity of n-CHA crystals decreases to the increment of CO3(2-). Samples with more CO3(2) have composition and structure more similar to the bone apatite. The value of lattice parameters a decreases, value of c increases, and c/a value increases with the increase in the amount of CO3(2-), in accordance with crystal cell parameters change rule of type B replacement. In the AB mixed type (substitution OH- and PO4(3-)) CHA, IR characteristic peak of CO3(2-) out-of-plane bending vibration appears at 872 cm(-1), meanwhile, the asymmetry flexible vibration band is split into band at 1 454 cm(-1) and band at 1 420 cm(-1), while weak CO3(2)-peak appears at 1 540 cm(-1). CO3(2-) Raman peak of symmetric stretching vibration appears at 1 122 cm(-1). CO3(2-) B-type (substitution PO4(3-)) peak appeared at 1 071 cm(-1). Through the calculation of integral area ratio of PO4(3-)/ CO3(2-), OH-/CO3(2-), and PO4(3-)/OH-, low quantity CO3(2-) is B-type and high quantity CO3(2-) is A-type (substitution OH-). The results show that the synthesized apatite crystals are AB hybrid substitued nano-carbonate hydroxyapatite, however B-type replacement is the main substitute mode. Due to similarity inthe shape, size, crystal structure and growth mode, the synthesized apatite crystals can be called a kind of bone-like apatite.

Does a Heavy Fe-Isotope Composition of Akilia Quartz-Amphibole-Pyroxene Rocks Necessitate a BIF Origin?

PubMed

Whitehouse, M J; Schoenberg, R; Fedo, C M; Kamber, B S

2015-10-01

The age and origin of the quartz-amphibole-pyroxene (qap) gneiss from the island of Akilia, southern West Greenland, have been the subject of intense debate since the light C-isotope composition of graphite inclusions in apatite was interpreted to indicate the presence of Earth's earliest biological activity. Although this claim for biogenic relicts has been vigorously challenged, the possibility that the rocks might represent some of Earth's earliest water-lain sediments and, hence, a suitable repository for life remains an open question. While some workers have suggested that the entire sequence represents an originally mafic-ultramafic igneous precursor subsequently modified by metasomatism, quartz injection, high-grade metamorphism, and extreme ductile deformation, others maintain that at least a small part of the sequence retains geochemical characteristics indicative of a chemical sedimentary origin. Fractionated Fe isotopes with δ(56)Fe values similar to those observed in Isua BIF have been reported from high-SiO2 units of qap and used to support a chemical sedimentary protolith for the qap unit. Here, we present new Fe isotope data from all lithologic variants in the qap gneiss on Akilia, including layers of undisputed ultramafic igneous origin. Since the latter require introduction of fractionated Fe into at least part of the qap unit, we argue that Fe isotopes must therefore be treated with considerable caution when used to infer BIF for part or all of the qap protolith.

Ferromanganese crusts as indicators for paleoceanographic events in the NE Atlantic

NASA Astrophysics Data System (ADS)

Koschinsky, A.; Halbach, P.; Hein, J. R.; Mangini, A.

Hydrogenetic ferromanganese crusts reflect the chemical conditions of the seawater from which they formed. Fine-scale geochemical analysis of crust layers in combination with age determinations can therefore be used to investigate paleoceanographic changes which are recorded in geochemical gradients in the crusts. At Tropic seamount (off northwest Africa), uniform crust growth influenced by terrigenous input from the African continent occurred during approximately the past 12Ma. Phosphatization of these crusts is minor. In contrast, crusts from Lion seamount, located between Madeira and the Portuguese coast, display a much more variable growth history. A pronounced increase in Ni, Cu, and Zn is observed in some intervals of the crusts, which probably reflects increased surface productivity. A thick older phosphatized generation occurs in many samples. Hydrographic profiles indicate that Mediterranean outflow water (MOW) may play an important role in the composition of these crusts. 10Be dating of one sample confirms that the interruption of the MOW during the Messinian salinity crisis (6.2-5Ma ago) resulted in changes in element composition. Sr-isotope dating of the apatite phase of the old crust generation has been carried out to obtain a minimum age for the older generation of Atlantic crusts and to determine whether crust phosphatization in the Atlantic can be related to phosphatization episodes recorded in Pacific crusts. The preliminary data show that the old phosphatized crust generation might be as old as approximately 30-40Ma.

Ferromanganese crusts as indicators for paleoceanographic events in the NE Atlantic

USGS Publications Warehouse

Koschinsky, A.; Halbach, P.; Hein, J.R.; Mangini, A.

1996-01-01

Hydrogenetic ferromanganese crusts reflect the chemical conditions of the seawater from which they formed. Fine-scale geochemical analysis of crust layers in combination with age determinations can therefore be used to investigate paleoceanographic changes which are recorded in geochemical gradients in the crusts. At Tropic seamount (off northwest Africa), uniform crust growth influenced by terrigenous input from the African continent occurred during approximately the past 12 Ma. Phosphatization of these crusts is minor. In contrast, crusts from Lion seamount, located between Madeira and the Portuguese coast, display a much more variable growth history. A pronounced increase in Ni, Cu, and Zn is observed in some intervals of the crusts, which probably reflects increased surface productivity. A thick older phosphatized generation occurs in many samples. Hydrographic profiles indicate that Mediterranean outflow water (MOW) may play an important role in the composition of these crusts. 10Be dating of one sample confirms that the interruption of the MOW during the Messinian salinity crisis (6.2-5 Ma ago) resulted in changes in element composition. Sr-isotope dating of the apatite phase of the old crust generation has been carried out to obtain a minimum age for the older generation of Atlantic crusts and to determine whether crust phosphatization in the Atlantic can be related to phosphatization episodes recorded in Pacific crusts. The preliminary data show that the old phosphatized crust generation might be as old as approximately 30-40 Ma.

Microbial weathering of apatite and wollastonite in a forest soil: Evidence from minerals buried in a root-free zone

NASA Astrophysics Data System (ADS)

Nezat, C. A.

2011-12-01

Mineral weathering is an important process in biogeochemical cycling because it releases nutrients from less labile pools (e.g., rocks) to the food chain. A field experiment was undertaken to determine the degree to which microbes - both fungi and bacteria - are responsible for weathering of Ca-bearing minerals. The experiment was performed at the Hubbard Brook Experimental Forest (HBEF) in the northeastern USA, where acid deposition has leached plant-available calcium from soils for decades. Trees obtain soil nutrients through root uptake as well as through mycorrhizal fungi with which they are symbiotically associated. These fungi extend their hyphae from the tree roots into the soil and exude organic acids that may enhance mineral dissolution. The two most common types of symbiotic fungal-tree associations are ectomycorrhizae, which are associated with spruce (Picea), fir (Abies), and beech (Fagus); and arbuscular mycorrhizae which are commonly associated with angiosperms, such as maples (Acer). To examine the role of fungi and bacteria in weathering of Ca- and/or P-bearing minerals, mesh bags containing sand-sized grains of quartz (as a control), quartz plus 1% wollastonite (CaSiO3), or quartz plus 1% apatite (Ca5(PO4)3F) were buried ~15 cm deep in mineral soil beneath American beech, sugar maple, and mixed spruce and balsam fir stands at the HBEF. Half of the bags were constructed of 50-μm mesh to exclude roots but allow fungal hyphae and bacteria to enter the bags; the remaining bags had 1-μm mesh to exclude fungi and roots but allow bacteria to enter. The bags were retrieved ~ 1, 2 or 4 years after burial. Microbial community composition and biomass in the mesh bags and surrounding soil were characterized and quantified using phospholipid fatty acid (PLFA) analysis. Fungal biomass in the soil and control bags did not differ significantly among stand types. In contrast, the degree of fungal colonization in apatite- and wollastonite-amended bags varied significantly, suggesting that microbial response was due to tree species, type of mycorrhizal fungi, nutrient status of the soils, and mineral composition of the mesh bags. Mineral surfaces were examined using scanning electron microscopy (SEM) to investigate the degree of mineral dissolution as a function of stand type, microbial composition, and time.

Sr-containing hydroxyapatite: morphologies of HA crystals and bioactivity on osteoblast cells.

PubMed

Aina, Valentina; Bergandi, Loredana; Lusvardi, Gigliola; Malavasi, Gianluca; Imrie, Flora E; Gibson, Iain R; Cerrato, Giuseppina; Ghigo, Dario

2013-04-01

A series of Sr-substituted hydroxyapatites (HA), of general formula Ca(10-x)Srx(PO4)6(OH)2, where x=2 and 4, were synthesized by solid state methods and characterized extensively. The reactivity of these materials in cell culture medium was evaluated, and the behavior towards MG-63 osteoblast cells (in terms of cytotoxicity and proliferation assays) was studied. Future in vivo studies will give further insights into the behavior of the materials. A paper by Lagergren et al. (1975), concerning Sr-substituted HA prepared by a solid state method, reports that the presence of Sr in the apatite composition strongly influences the apatite diffraction patterns. Zeglinsky et al. (2012) investigated Sr-substituted HA by ab initio methods and Rietveld analyses and reported changes in the HA unit cell volume and shape due to the Sr addition. To further clarify the role played by the addition of Sr on the physico-chemical properties of these materials we prepared Sr-substituted HA compositions by a solid state method, using different reagents, thermal treatments and a multi-technique approach. Our results indicated that the introduction of Sr at the levels considered here does influence the structure of HA. There is also evidence of a decrease in the crystallinity degree of the materials upon Sr addition. The introduction of increasing amounts of Sr into the HA composition causes a decrease in the specific surface area and an enrichment of Sr-apatite phase at the surface of the samples. Bioactivity tests show that the presence of Sr causes changes in particle size and/or morphology during soaking in MEM solution; on the contrary the morphology of pure HA does not change after 14 days of reaction. The presence of Sr, as Sr-substituted HA and SrCl2, in cultures of human MG-63 osteoblasts did not produce any cytotoxic effect. In fact, Sr-substituted HA increased the proliferation of osteoblast cells and enhanced cell differentiation: Sr in HA has a positive effect on MG-63 cells. In contrast, Sr ions alone, at the concentrations released by Sr-HA (1.21-3.24 ppm), influenced neither cell proliferation nor differentiation. Thus the positive effects of Sr in Sr-HA materials are probably due to the co-action of other ions such as Ca and P. Copyright © 2012 Elsevier B.V. All rights reserved.

The origin of water in the primitive Moon as revealed by the lunar highlands samples

NASA Astrophysics Data System (ADS)

Barnes, Jessica J.; Tartèse, Romain; Anand, Mahesh; McCubbin, Francis M.; Franchi, Ian A.; Starkey, Natalie A.; Russell, Sara S.

2014-03-01

The recent discoveries of hydrogen (H) bearing species on the lunar surface and in samples derived from the lunar interior have necessitated a paradigm shift in our understanding of the water inventory of the Moon, which was previously considered to be a ‘bone-dry’ planetary body. Most sample-based studies have focused on assessing the water contents of the younger mare basalts and pyroclastic glasses, which are partial-melting products of the lunar mantle. In contrast, little attention has been paid to the inventory and source(s) of water in the lunar highlands rocks which are some of the oldest and most pristine materials available for laboratory investigations, and that have the potential to reveal the original history of water in the Earth-Moon system. Here, we report in-situ measurements of hydroxyl (OH) content and H isotopic composition of the mineral apatite from four lunar highlands samples (two norites, a troctolite, and a granite clast) collected during the Apollo missions. Apart from troctolite in which the measured OH contents in apatite are close to our analytical detection limit and its H isotopic composition appears to be severely compromised by secondary processes, we have measured up to ˜2200 ppm OH in the granite clast with a weighted average δD of ˜ -105±130‰, and up to ˜3400 ppm OH in the two norites (77215 and 78235) with weighted average δD values of -281±49‰ and -27±98‰, respectively. The apatites in the granite clast and the norites are characterised by higher OH contents than have been reported so far for highlands samples, and have H isotopic compositions similar to those of terrestrial materials and some carbonaceous chondrites, providing one of the strongest pieces of evidence yet for a common origin for water in the Earth-Moon system. In addition, the presence of water, of terrestrial affinity, in some samples of the earliest-formed lunar crust suggests that either primordial terrestrial water survived the aftermath of the putative impact-origin of the Moon or water was added to the Earth-Moon system by a common source immediately after the accretion of the Moon.

Biomineralized diamond-like carbon films with incorporated titanium dioxide nanoparticles improved bioactivity properties and reduced biofilm formation.

PubMed

Lopes, F S; Oliveira, J R; Milani, J; Oliveira, L D; Machado, J P B; Trava-Airoldi, V J; Lobo, A O; Marciano, F R

2017-12-01

Recently, the development of coatings to protect biomedical alloys from oxidation, passivation and to reduce the ability for a bacterial biofilm to form after implantation has emerged. Diamond-like carbon films are commonly used for implanted medical due to their physical and chemical characteristics, showing good interactions with the biological environment. However, these properties can be significantly improved when titanium dioxide nanoparticles are included, especially to enhance the bactericidal properties of the films. So far, the deposition of hydroxyapatite on the film surface has been studied in order to improve biocompatibility and bioactive behavior. Herein, we developed a new route to obtain a homogeneous and crystalline apatite coating on diamond-like carbon films grown on 304 biomedical stainless steel and evaluated its antibacterial effect. For this purpose, films containing two different concentrations of titanium dioxide (0.1 and 0.3g/L) were obtained by chemical vapor deposition. To obtain the apatite layer, the samples were soaked in simulated body fluid solution for up to 21days. The antibacterial activity of the films was evaluated by bacterial eradication tests using Staphylococcus aureus biofilm. Scanning electron microscopy, X-ray diffraction, Raman scattering spectroscopy, and goniometry showed that homogeneous, crystalline, and hydrophilic apatite films were formed independently of the titanium dioxide concentration. Interestingly, the diamond-like films containing titanium dioxide and hydroxyapatite reduced the biofilm formation compared to controls. A synergism between hydroxyapatite and titanium dioxide that provided an antimicrobial effect against opportunistic pathogens was clearly observed. Copyright © 2017 Elsevier B.V. All rights reserved.

Compressive, diametral tensile and biaxial flexural strength of cutting-edge calcium phosphate cements.

PubMed

Luo, Jun; Ajaxon, Ingrid; Ginebra, Maria Pau; Engqvist, Håkan; Persson, Cecilia

2016-07-01

Calcium phosphate cements (CPCs) are widely used in bone repair. Currently there are two main types of CPCs, brushite and apatite. The aim of this project was to evaluate the mechanical properties of particularly promising experimental brushite and apatite formulations in comparison to commercially available brushite- and apatite-based cements (chronOS(™) Inject and Norian(®) SRS(®), respectively), and in particular evaluate the diametral tensile strength and biaxial flexural strength of these cements in both wet and dry conditions for the first time. The cements׳ porosity and their compressive, diametral tensile and biaxial flexural strength were tested in wet (or moist) and dry conditions. The surface morphology was characterized by scanning electron microscopy. Phase composition was assessed with X-ray diffraction. It was found that the novel experimental cements showed better mechanical properties than the commercially available cements, in all loading scenarios. The highest compressive strength (57.2±6.5MPa before drying and 69.5±6.0MPa after drying) was found for the experimental brushite cement. This cement also showed the highest wet diametral tensile strength (10.0±0.8MPa) and wet biaxial flexural strength (30.7±1.8MPa). It was also the cement that presented the lowest porosity (approx. 12%). The influence of water content was found to depend on cement type, with some cements showing higher mechanical properties after drying and some no difference after drying. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Electrodeposition of Ca-P coatings on biodegradable Mg alloy: in vitro biomineralization behavior.

PubMed

Song, Yang; Zhang, Shaoxiang; Li, Jianan; Zhao, Changli; Zhang, Xiaonong

2010-05-01

Preparing stabilized apatite on biodegradable Mg alloy may improve biocompatibility and promote osteointegration. In the present work, three kinds of Ca-P coatings, brushite (DCPD, CaHPO(4).2H(2)O), hydroxyapatite (HA, Ca(10)(PO(4))(6)(OH)(2)) and fluoridated hydroxyapatite (FHA, Ca(5)(PO(4))(3)(OH)(1-)(x)F(x)) are fabricated by electrodeposition on a biodegradable Mg-Zn alloy. The crystalline structures, morphologies and compositions of these Ca-P coatings have been characterized by X-ray diffrection, scanning electron microscopy and energy-dispersive spectoscopy. The effects of these coatings on the degradation behavior and mineralization activity of the Mg-Zn alloy have also been investigated. The experimental results showed that these coatings decreased the degradation rate of Mg-Zn alloy, while the precipitates on the uncoated and DCPD-coated Mg-Zn alloy in modified simulated biological fluid had low Ca/P molar ratios, which delayed bone-like apatite formation. Both the HA and FHA coating could promote the nucleation of osteoconductive minerals (bone-like apatite or beta-TCP) for 1month. However, the HA coating transformed from DCPD through alkali heat treatment was fragile and less stable, and therefore its long-term corrosion resistance was not satisfactory. Instead, the FHA was more stable and had better corrosion resistance, and thus it should be better suited as a coating of Mg implants for orthopedic applications. Copyright (c) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Neutron Diffraction Studies of Carbonate Apatite

NASA Astrophysics Data System (ADS)

Moghaddam, Hadi Y.; Leventouri, Theodora; Chakoumakos, Bryan C.

1998-11-01

Moghaddam H.Y., Leventouri Th.* (Dept. of Physics & Alloy Research Center, Florida Atlantic Univ.) Chakoumakos B.C. (Solid State Division, Oak Ridge National Lab.**,kou@ornl.gov) We report Rietveld structural refinements of neutron diffraction data of a highly crystalline, single-phase natural carbonate apatite,(francolite of Epirus, Greece), in order to elucidate the details of carbonate substitution in the apatites. The composition is Ca9.56Na0.38Mg0.08(PO4)4.82(CO3)0.946(SO4)0.2F2.34, as determined by electron microprobe analysis. We report refinements of data for the native francolite as a function of temperature between 296K and 10K after the material had been heated at 750 °C to drive off adsorbed water and CO2. The neutron diffractioii@data were collected using a wavelength 1.0912 A on the HB4 high resolution powder diffractometer at the High Flux Isotope Reactor at Oak Ridge National Laboratory. Analysis of the temperature dependence of the anisotropic displacement parameters can reveal the contribution from the temperature independent static positional disorder. Difference displacement parameters evaluated along various bonding directions are being used to describe the mechanics and dynamics of the carbonate for phosphate substitution.*Supported by a SURA-ORNL Summer Cooperative Research Program 1998.**Supported by the Division of Materials Sciences,U.S. D.O.E. (contract DE-AC05-96OR22464 with Lockheed Martin Energy Research Corporation).

The effect of secondary apatite on the initial 87Sr/86Sr ratio determination in granitic rocks: a case study of the Tadamigawa pluton, northeastern Japan

NASA Astrophysics Data System (ADS)

Wakasugi, Y.; Ichino, K.; Tanioka, Y.; Wakaki, S.; Tsuboi, M.; Ishikawa, T.

2017-12-01

Apatite is a major accessory mineral in igneous rocks. Because Rb contents in apatite are very low, 87Sr/86Sr ratios of magmatic apatite are useful to estimate the initial 87Sr/86Sr ratio (SrI) of igneous rocks. Secondary post-magmatic event such as hydrothermal alteration may also crystallize secondary apatite, which may inhibit the estimation of SrI of igneous rocks. In this study, we examine the effects of secondary apatite on the initial 87Sr/86Sr ratio determination of granitic rocks by using acid leaching technique. Leached apatite samples were first separated from the whole rock powder as a heavy mineral fraction by heavy liquid technique, and the heavy mineral fraction was then leached by 3 M HNO3. The isotopic ratios of Sr and the concentrations of Rb and Sr were analyzed by TIMS and ICP-MS at Kochi Core Center, respectively. The Tadamigawa Older-stage granites, which locate in the Taishaku Mountains at the northeastern part of Japan, intrude into the Ashio Jurassic complex, and the ages of these rocks are late Cretaceous to Paleogene. The U-Pb ages of zircon and the K-Ar ages of biotite for these rocks are c. 100 Ma [1, 2]. Rb-Sr whole-rock isochron age of the pluton is 96.5 ± 1.3 Ma (SrI = 0.70534 ± 0.00003) and it is concordant with other radiometric ages. Rb-Sr mineral isochron ages range from 84.4 to 97.3 Ma and these ages are relatively younger than the Rb-Sr whole-rock isochron age. The difference among radiometric ages may reflect the difference of the closure temperature in each isotopic system. The Tadamigawa Older-stage granites have SrI for Rb-Sr mineral isochron range from 0.7053 to 0.7061 and are very similar to that (0.70534) for Rb-Sr whole-rock isochron. These may suggest that the Tadamigawa Older-stage granites are generated from same parental magma. However, 87Sr/86Sr ratios of the leached apatite samples were 0.70544-0.70856 and are relatively higher than SrI obtained from the Rb-Sr mineral isochrons (0.7053-0.7061). This result suggests that leached apatite samples contain not only magmatic apatite but also secondary apatite. A careful apatite separation is needed to obtain the magmatic initial 87Sr/86Sr ratios by the isotopic analyses of apatite. [1] Tanioka et al. (2014) Japan. Mag. Mineral. Petrol. Sci. 43, 215-227. [2] Wakasugi et al. (2014) 121st Ann. Meet. Geo. Soc. Japan, Abstr., 57.

Crystallographic nature of fluoride in enameloids of fish.

PubMed

LeGeros, R Z; Suga, S

1980-01-01

X-ray diffraction studies on calcified tissues (teeth and/or scales) of fish and of shark showed that the presence of fluoride affects the crystallite size and lattice parameters of the apatite phase. An inverse correlation between F contents (ranging from 0.2 to 3.8 wt% F) and alpha-axis dimensions (9.441 to 9.375 +/- 0.003 A) exists for both synthetic and enameloid apatites and is consistent with the F-for-OH substitution in the apatite, idealized as Ca10(PO4)6(OH)2 and Ca10(PO4)6F2, for fluoride-free and maximum fluoride-substituted apatite, respectively. In synthetic systems, the incorporation of F is found to be dependent on the F concentration of the media from which the apatite formed. This dependency is also observed between F content of the dentine apatites and the F concentration of the water from which the fish can (i.e., less than 0.08 ppmF in fresh water, about 1.3 ppm in seawater). However, no such dependency was observed between the F incorporation in fish enameloid apatite and the F concentration in the water of origin. In some cases, the F incorporated in the enameloid apatite is much in excess of what can be expected from the F concentration of water. These observations suggest that in some fish, a fluoride-concentrating mechanism is operative during the formation of the enameloid but not during the formation of the dentine, and this mechanism appears to be specie-related.

Fabrication, characterization, and in vitro study of zinc substituted hydroxyapatite/silk fibroin composite coatings on titanium for biomedical applications.

PubMed

Zhong, Zhenyu; Ma, Jun

2017-09-01

Zinc substituted hydroxyapatite/silk fibroin composite coatings were deposited on titanium substrates at room temperature by electrophoretic deposition. Microscopic characterization of the synthesized composite nanoparticles revealed that the particle size ranged 50-200 nm, which increased a little after zinc substitution. The obtained coatings maintained the phase of hydroxyapatite and they could induce fast apatite formation in simulated body fluid, indicating high bone activity. The cell culturing results showed that the biomimetic hydroxyapatite coatings could regulate adhesion, spreading, and proliferation of osteoblastic cells. Furthermore, the biological behavior of the zinc substituted hydroxyapatite coatings was found to be better than the bare titanium without coatings and hydroxyapatite coatings without zinc, increasing MC3T1-E1 cell differentiation in alkaline phosphatase expression.

Characterization and Bioactivity Evaluation of (Polyetheretherketone/Polyglycolicacid)-Hydroyapatite Scaffolds for Tissue Regeneration

PubMed Central

Shuai, Cijun; Shuai, Chenying; Wu, Ping; Yuan, Fulai; Feng, Pei; Yang, Youwen; Guo, Wang; Fan, Xiaohan; Su, Ting; Peng, Shuping; Gao, Chengde

2016-01-01

Bioactivity and biocompatibility are crucial for tissue engineering scaffolds. In this study, hydroxyapatite (HAP) was incorporated into polyetheretherketone/polyglycolicacid (PEEK/PGA) hybrid to improve its biological properties, and the composite scaffolds were developed via selective laser sintering (SLS). The effects of HAP on physical and chemical properties of the composite scaffolds were investigated. The results demonstrated that HAP particles were distributed evenly in PEEK/PGA matrix when its content was no more than 10 wt %. Furthermore, the apatite-forming ability became better with increasing HAP content after immersing in simulated body fluid (SBF). Meanwhile, the composite scaffolds presented a greater degree of cell attachment and proliferation than PEEK/PGA scaffolds. These results highlighted the potential of (PEEK/PGA)-HAP scaffolds for tissue regeneration. PMID:28774058

Synthesis, characterization and electrical properties of a lead sodium vanadate apatite

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

Chakroun-Ouadhour, E.; Ternane, R.; Hassen-Chehimi, D. Ben

2008-08-04

The lacunary lead sodium vanadate apatite Pb{sub 8}Na{sub 2}(VO{sub 4}){sub 6} was synthesized by the solid-state reaction method. The compound was characterized by X-ray powder diffraction, infrared (IR) absorption spectroscopy and Raman scattering spectroscopy. By comparing the effect of vanadate and phosphate ions on electrical properties, it was concluded that Pb{sub 8}Na{sub 2}(VO{sub 4}){sub 6} apatite is better conductor than Pb{sub 8}Na{sub 2}(PO{sub 4}){sub 6} apatite.

Laser ablation U-Th-Sm/He dating of detrital apatite

NASA Astrophysics Data System (ADS)

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

2016-12-01

Detrital apatite U-Th-Sm/He thermochronology has the potential to be a powerful tool for conducting basin thermal history analyses as well as complementing the well-established detrital zircon U-Pb approach in source to sink studies. A critical roadblock that prevents the routine application of detrital apatite U-Th-Sm/He thermochronology to solving geological problems is the costly and difficult whole grain approach that is generally used to obtain apatite U-Th-Sm/He data. We present a new analytical method for laser ablation thermochronology on apatite. Samples are ablated using a Resonetics™ 193 nm excimer laser and liberated 4He is measured using an ASI (Australian Scientific Instruments) Alphachron™ quadrupole mass spectrometer system; collectively known as the Resochron™. The ablated sites are imaged using a Zygo ZescopeTM optical profilometer and ablated pit volume measured using PitVol, a custom MatLabTM algorithm. The accuracy and precision of the method presented here was confirmed using well-characterized Durango apatite and Fish Canyon Tuff (FCT) apatite reference materials, with Durango apatite used as a primary reference and FCT apatite used as a secondary reference. The weighted average of our laser ablation Durango ages (30.5±0.35 Ma) compare well with ages obtained using conventional whole grain degassing and dissolution U-Th-Sm/He methods (32.56±0.43 Ma) (Jonckheere et.al., 1 993; Farley, 2000; McDowell et.al., 2005) for chips of the same Durango crystal. These Durango ages were used to produce a K-value to correct the secondary references and unknown samples. After correction, FCT apatite has a weighted average age of 28.37 ± 0.96 Ma, which agrees well with published ages. As a further test of this new method we have conducted a case study on a set of samples from the British Mountains of the Yukon Territory in NW Canada. Sandstone samples collected across the British Mountains were analyzed using conventional U-Th-Sm/He whole grain methods and then reanalyzed using our new Laser ablation approach. The laser ablation results are consistent with those obtained using conventional methods, confirming that apatite laser ablation U-Th-Sm/He thermochronology is a viable alternative for collecting large low temperature thermochronology data sets from detrital samples.

Sulfur-in-apatite: An indicator of the volatile evolution during lunar magmatism

NASA Astrophysics Data System (ADS)

Konecke, B.; Fiege, A.; Simon, A. C.; Holtz, F.

2017-12-01

The volatile content of lunar magmas remains controversial despite nearly five decades of interrogating samples from the NASA Apollo missions. Recently, the mineral apatite in lunar mare basalts has been investigated owing to its potential to constrain the volatile (F, Cl, H, S) budget of magmas [1-3]. The F-Cl-H signatures of lunar apatite were interpreted to record fractional crystallization, with nucleation and growth of apatite from a late-stage, interstitial, nearly anhydrous (<10 μg/g H2O), rhyolitic melt that evolved from a sulfide-undersaturated mare basalt [1]. The enigmatic S signature reported for those apatite grains was not interpreted due to the absence of published thermodynamic (partitioning) data for S. Here, we report new experimentally determined apatite/melt partition coefficients for S (DSap/m) at conditions applicable to lunar systems. The DSap/m values and thermodynamically modeled S content (XS) of lunar residual melt were used to constrain plausible S contents of lunar apatite produced by crystal fractionation (Sap = XS * DSap/m). Our results demonstrate that apatite crystallizing under lunar-like conditions from rhyolitic melt cannot obtain the reported 430 μg/g of S [2] by fractional crystallization. The results indicate that 5-35x higher S contents than feasible in sulfide-undersaturated, hydrous and dry rhyolitic melt, respectively, would be required to support crystal fractionation models [1]. Even elevated water concentrations in a sulfide-saturated rhyolitic melt cannot explain the S contents of lunar apatite rims. We propose two plausible scenarios: (A) The necessary concentration of S in rhyolitic melts may be achieved at >5 orders of magnitude higher fO2 (>ΔFMQ+1.2) than reported for lunar magmas, where S6+ is the prevalent oxidation state of S in rhyolitic melt, related to the significant degassing and preferential loss of H2 that drives oxidation of the residual melt [4]. (B) The volatile (F-Cl-H-S) signatures of lunar apatites may reflect cryptic metasomatic reactions between apatite and a S-Cl-rich, F-poor volatile phase released by underlying magma reservoirs. [1] Boyce et at., 2014, Science 344:400-402. [2] Greenwood et al., 2011, Nat. Geosci 4:79-82. [3] Webster et al., 2009, Geochim. Cosmochim. Acta 73, 559-581. [4] McCanta et al., 2017, Icarus 285, 95-102.

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 retrogression of the subducted slab. Such SiO 2-rich hydrous fluids may act as an oxidizing agent, a feasible explanation for the high oxygen fugacity in convergent margin systems.

Worldwide occurrence of silica-rich melts in sub-continental and sub-oceanic mantle minerals

NASA Astrophysics Data System (ADS)

Schiano, P.; Clocchiatti, R.

1994-04-01

ROCK samples derived from the Earth's upper mantle commonly show indirect evidence for chemical modification. Such modification, or 'metasomatism', can be recognized by the precipitation of exotic minerals such as phlogopite, amphibole or apatite1, and by the overprinting of the bulk compositions of the mantle rocks by a chemical signature involving the enrichment of potassium and other 'incompatible' elements2. Here we study the composition of the metasomatic agents more directly by examining melt and fluid inclusions trapped in mantle minerals. These inclusions are secondary, forming trails along healed fracture planes. A systematic study of the chemical compositions and entrapment temperatures and pressures of inclusions from 14 ultramaflc peridotites from both continental and oceanic intraplate regions shows that volatile- and silica-rich metasomatic melts are present throughout the litho-sphere. Their compositions, which differ dramatically from those of erupted, mantle-derived magmas, are more akin to continental than to oceanic crust.

Dense Membranes for Anode Supported all Perovskite IT-SOFCs

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

Rambabu Bobba

2006-09-14

During this first year of the project, a post doctoral fellow (Dr. Hrudananda Jena), and two graduate students (Mr. Vinay B. V. Sivareddy, Aswin Somuru), were supported through this project funds. Also, partial support was provided to three undergraduate students (Jonthan Dooley, India Snowden, Jeremy Gilmore) majoring in Chemistry, Physics, and Engineering disciplines. Various wet chemical methods of synthesis have been attempted to prepare perovskite oxide powders with a hope to improve and engineer its properties to meet the requirements of Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFCs) components. Various compounds were synthesized, characterized by XRD, TEM, SEM, XPS, electronmore » microprobe and their electrical transport properties were measured by EIS at elevated temperatures and compared. Sonochemical technique (power of ultra sonic probe 750 watt) combined with hydrothermal treatment of precursors for the preparation of calcium hydroxy apatites (Ca-HAp) was used for the first time. Ca-HAp was substituted with Sr and Mg (50% replacement of Ca in Ca-HAp) to study the effect of substitution on Ca-HAp. Calcium hydroxy apatite is a bioceramic and has potential applications as artificial bone, enamel materials. In this study we tried to investigate its use as proton conductors in PC-SOFC. The properties like electrical conductivity, crystal structure, compositions of CaHAp were studied and compared with the natural bone material. The comparison found to be excellent indicating the efficiency of the preparation techniques. The typical value of conductivity measured is 0.091 x 10{sup -6} Scm{sup -1} at 25 C and 19.26 x 10{sup -6} Scm{sup -1} at 850 C with an applied frequency of 100 kHz. The conductivity increases on increasing frequency and temperature and reaches 0.05mS/cm at 500 C. The crystal structure and phase stability of perovskites as well as apatites were investigated with respect to substitution of various iso-valent and alivalent ions to determine the % of solubility in the crystal lattice of perovskite, apatites. Various electrode and electrolyte material compositions were prepared and characterized by XRD, SEM, XPS and electron microprobe. The material compositions were selected based on their thermo-physical properties to achieve compatibility with each other in ideal fuel cell operating conditions. The series of electrode materials investigated are LaGa{sub 1-x}M{sub x}O{sub 3} (M = Mn, Mg, x = 0.1), LaCr{sub 1-x}M{sub x}O{sub 3} (M = Mn, Mg, Co, x=0.1), LaNi{sub 1-x}Fe{sub x}O{sub 3} (0 < x < 0.6) and Gd{sub 1-x}M{sub x}CoO{sub 3} (M=Ca, x=0.1). Attempts were made to prepare proton-conducting perovskites of SrCe{sub 1-x} M{sub x}O{sub 3} (M= Dy, Eu, Er, Tb, x=0.1) by using sonochemical and hydrothermal technique followed by microwave sintering processes. These compositions were prepared characterized by XRD, TEM, SEM and electrical conductivity of the pellets was measured. The interest of low temperature proton conducting electrolyte is to replace the well known oxide ion conducting solid electrolyte in SOFCs, thereby reducing the operating temperature of SOFC to lower temperature (i.e 400-600 C) and named it as PC-SOFC (proton conducting-solid oxide fuel cell).« less

Fluoride-containing nanoporous calcium-silicate MTA cements for endodontics and oral surgery: early fluorapatite formation in a phosphate-containing solution.

PubMed

Gandolfi, M G; Taddei, P; Siboni, F; Modena, E; Ginebra, M P; Prati, C

2011-10-01

To test the chemical-physical properties and apatite-forming ability of experimental fluoride-doped calcium silicate cements designed to create novel bioactive materials for use in endodontics and oral surgery. A thermally treated calcium silicate cement (wTC) containing CaCl(2) 5%wt was modified by adding NaF 1%wt (FTC) or 10%wt (F10TC). Cements were analysed by environmental scanning electron microscopy with energy-dispersive X-ray analysis, IR and micro-Raman spectroscopy in wet conditions immediately after preparation or after ageing in a phosphate-containing solution (Dulbecco's phosphate-buffered saline). Calcium and fluoride release and pH of the storage solution were measured. The results obtained were analysed statistically (Tukey's HSD test and two-way anova). The formation of calcium phosphate precipitates (spherulites) was observed on the surface of 24 h-aged cements and the formation of a thick bone-like B-type carbonated apatite layer (biocoating) on 28 day-aged cements. The rate of apatite formation was FTC>F10TC>wTC. Fluorapatite was detected on FTC and F10TC after 1 day of ageing, with a higher fluoride content on F10TC. All the cements released calcium ions. At 5 and 24 h, the wTC had the significantly highest calcium release (P<0.001) that decreased significantly over the storage time. At 3-28 days, FTC and F10TC had significantly higher calcium release than wTC (P<0.05). The F10TC had the significantly highest fluoride release at all times (P<0.01) that decreased significantly over storage time. No significant differences were observed between FTC and wTC. All the cements had a strong alkalinizing activity (OH(-) release) that remained after 28 days of storage. The addition of sodium fluoride accelerated apatite formation on calcium silicate cements. Fluoride-doped calcium silicate cements had higher bioactivity and earlier formation of fluorapatite. Sodium fluoride may be introduced in the formulation of mineral trioxide aggregate cements to enhance their biological behaviour. F-doped calcium silicate cements are promising bone cements for clinical endodontic use. © 2011 International Endodontic Journal.

High spatial resolution U-Pb geochronology and Pb isotope geochemistry of magnetite-apatite ore from the Pea Ridge iron oxide-apatite deposit, St. Francois Mountains, southeast Missouri, USA

USGS Publications Warehouse

Neymark, Leonid; Holm-Denoma, Christopher S.; Pietruszka, Aaron; Aleinikoff, John N.; Fanning, C. Mark; Pillers, Renee M.; Moscati, Richard J.

2016-01-01

The Pea Ridge iron oxide-apatite (IOA) deposit is one of the major rhyolite-hosted magnetite deposits of the St. Francois Mountains terrane, which is located within the Mesoproterozoic (1.5–1.3 Ga) Granite-Rhyolite province in the U.S. Midcontinent. Precise and accurate determination of the timing and duration of oreforming processes in this deposit is crucial for understanding its origin and placing it within a deposit-scale and regional geologic context. Apatite and monazite, well-established U-Pb mineral geochronometers, are abundant in the Pea Ridge orebody. However, the potential presence of multiple generations of dateable minerals, processes of dissolution-reprecipitation, and occurrence of micrometer-sized intergrowths and inclusions complicate measurements and interpretations of the geochronological results. Here, we employ a combination of several techniques, including ID-TIMS and high spatial resolution geochronology of apatite and monazite using LA-SC-ICPMS and SHRIMP, and Pb isotope geochemistry of pyrite and magnetite to obtain the first direct age constraints on the formation and alteration history of the Pea Ridge IOA deposit. The oldest apatite TIMS 207Pb*/206Pb* dates are 1471 ± 1 and 1468 ± 1 Ma, slightly younger than (but within error of) the ~1474 to ~1473 Ma U-Pb zircon ages of the host rhyolites. Dating of apatite and monazite inclusions within apatite provides evidence for at least one younger metasomatic event at ~1.44 Ga, and possibly multiple superimposed metasomatic events between 1.47 and 1.44 Ga. Lead isotop analyses of pyrite show extremely radiogenic 206Pb/204Pb ratios up to ~80 unsupported by in situ U decay. This excess radiogenic Pb in pyrite may have been derived from the spatially associated apatite as apatite recrystallized several tens of million years after its formation. The low initial 206Pb/204Pb ratio of ~16.5 and 207Pb/204Pb ratio of ~15.4 for individual magnetite grains indicate closed U-Pb system behavior in this mineral and are consistent with derivation of the Pb from a mantle-like source.

Project Work Plan: Sequestration of Strontium-90 Subsurface Contamination in the Hanford 100-N Area by Surface Infiltration of an Apatite Solution

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

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 yearsmore » 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.« less

Symposium KK: Structure-Property Relationships in Biomineralized and Bio-mimetic Composites

DTIC Science & Technology

2010-04-06

Preventive and Restorative Dental Sciences, UCSF, San Francisco, California. 4:45 PM KK2.8 Damage and Crack Evolution in Mammalian Enamel James Jin...Technology, Graz, Austria. 9:45AMKK6.S AFM and PFM measurements of Enamel in order to Determine the Crack Tip Toughness and Cohesive Zone of Enamel Gerold...11:00 AM KK9.7 Enamel Matrix Guided Growth of Apatite Vuk Uskokovic1. Li Zhu2, Wu Li2 and Stefan Habelitz1; ’Department of Preventive and

Trace-element and Nd-isotope systematics in detrital apatite of the Po river catchment: Implications for provenance discrimination and the lag-time approach to detrital thermochronology

NASA Astrophysics Data System (ADS)

Malusà, Marco G.; Wang, Jiangang; Garzanti, Eduardo; Liu, Zhi-Chao; Villa, Igor M.; Wittmann, Hella

2017-10-01

Detrital thermochronology is often employed to assess the evolutionary stage of an entire orogenic belt using the lag-time approach, i.e., the difference between the cooling and depositional ages of detrital mineral grains preserved in a stratigraphic succession. The impact of different eroding sources to the final sediment sink is controlled by several factors, including the short-term erosion rate and the mineral fertility of eroded bedrock. Here, we use apatite fertility data and cosmogenic-derived erosion rates in the Po river catchment (Alps-Apennines) to calculate the expected percentage of apatite grains supplied to the modern Po delta from the major Alpine and Apenninic eroding sources. We test these predictions by using a cutting-edge dataset of trace-element and Nd-isotope signatures on 871 apatite grains from 14 modern sand samples, and we use apatite fission-track data to validate our geochemical approach to provenance discrimination. We found that apatite grains shed from different sources are geochemically distinct. Apatites from the Lepontine dome in the Central Alps show relative HREE enrichment, lower concentrations in Ce and U, and higher 147Sm/144Nd ratios compared to apatites derived from the External Massifs. Derived provenance budgets point to a dominant apatite contribution to the Po delta from the high-fertility Lepontine dome, consistent with the range independently predicted from cosmonuclide and mineral-fertility data. Our results demonstrate that the single-mineral record in the final sediment sink can be largely determined by high-fertility source rocks exposed in rapidly eroding areas within the drainage. This implies that the detrital thermochronology record may reflect processes affecting relatively small parts of the orogenic system under consideration. A reliable approach to lag-time analysis would thus benefit from an independent provenance discrimination of dated mineral grains, which may allow to proficiently reconsider many previous interpretations of detrital thermochronology datasets in terms of orogenic-wide steady state.

Effect of nitrogen and fluorine on mechanical properties and bioactivity in two series of bioactive glasses.

PubMed

Bachar, Ahmed; Mercier, Cyrille; Tricoteaux, Arnaud; Hampshire, Stuart; Leriche, Anne; Follet, Claudine

2013-07-01

Bioactive glasses are able to bond to bone through formation of carbonated hydroxyapatite in body fluids, and fluoride-releasing bioactive glasses are of interest for both orthopaedic and, in particular, dental applications for caries inhibition. However, because of their poor strength their use is restricted to non-load-bearing applications. In order to increase their mechanical properties, doping with nitrogen has been performed on two series of bioactive glasses: series (I) was a "bioglass" composition (without P2O5) within the quaternary system SiO2-Na2O-CaO-Si3N4 and series (II) was a simple substitution of CaF2 for CaO in series (I) glasses keeping the Na:Ca ratio constant. The objective of this work was to evaluate the effect of the variation in nitrogen and fluorine content on the properties of these glasses. The density, glass transition temperature, hardness and elastic modulus all increased linearly with nitrogen content which indicates that the incorporation of nitrogen stiffens the glass network because N is mainly in 3-fold coordination with Si atoms. Fluorine addition significantly decreases the thermal property values but the mechanical properties of these glasses remain unchanged with fluorine. The combination of both nitrogen and fluorine in oxyfluoronitride glasses gives better mechanical properties at much lower melting temperatures since fluorine reduces the melting point, allows higher solubility of nitrogen and does not affect the higher mechanical properties arising from incorporation of nitrogen. The characterization of these N and F substituted bioactive glasses using (29)Si MAS NMR has shown that the increase in rigidity of the glass network can be explained by the formation of SiO3N, SiO2N2 tetrahedra and Q(4) units with extra bridging anions at the expense of Q(3) units. Bioactivity of the glasses was investigated in vitro by examining apatite formation on the surface of glasses treated in acellular simulated body fluid (SBF) with ion concentrations similar to those in human blood plasma. Formation of a bioactive apatite layer on the samples treated in SBF was confirmed by grazing incidence X-ray diffraction and scanning electron microscopy (SEM) combined with energy dispersive X-ray spectroscopy (EDS). The crystallinity of this layer decreases with increasing N content suggesting that N may decrease bioactivity slightly. Copyright © 2013. Published by Elsevier Ltd.

Compositional controls on early diagenetic pathways in fine-grained sedimentary rocks: Implications for predicting unconventional reservoir attributes of mudstones

USGS Publications Warehouse

Keller, Margaret A.; Macquaker, Joe H.S.; Taylor, Kevin G.; Polya, David

2014-01-01

Diagenesis significantly impacts mudstone lithofacies. Processes operating to control diagenetic pathways in mudstones are poorly known compared to analogous processes occurring in other sedimentary rocks. Selected organic-carbon-rich mudstones, from the Kimmeridge Clay and Monterey Formations, have been investigated to determine how varying starting compositions influence diagenesis.The sampled Kimmeridge Clay Formation mudstones are organized into thin homogenous beds, composed mainly of siliciclastic detritus, with some constituents derived from water-column production (e.g., coccoliths, S-depleted type-II kerogen, as much as 52.6% total organic carbon [TOC]) and others from diagenesis (e.g., pyrite, carbonate, and kaolinite). The sampled Monterey Formation mudstones are organized into thin beds that exhibit pelleted wavy lamination, and are predominantly composed of production-derived components including diatoms, coccoliths, and foraminifera, in addition to type-IIS kerogen (as much as 16.5% TOC), and apatite and silica cements.During early burial of the studied Kimmeridge Clay Formation mudstones, the availability of detrital Fe(III) and reactive clay minerals caused carbonate- and silicate-buffering reactions to operate effectively and the pore waters to be Fe(II) rich. These conditions led to pyrite, iron-poor carbonates, and kaolinite cements precipitating, preserved organic carbon being S-depleted, and sweet hydrocarbons being generated. In contrast, during the diagenesis of the sampled Monterey Formation mudstones, sulfide oxidation, coupled with opal dissolution and the reduced availability of both Fe(III) and reactive siliciclastic detritus, meant that the pore waters were poorly buffered and locally acidic. These conditions resulted in local carbonate dissolution, apatite and silica cements precipitation, natural kerogen sulfurization, and sour hydrocarbons generation.Differences in mud composition at deposition significantly influence subsequent diagenesis. These differences impact their source rock attributes and mechanical properties.

Effect of ionic activity products on the structure and composition of mineral self assembled on three-dimensional poly(lactide-co-glycolide) scaffolds

PubMed Central

Shin, Kyungsup; Jayasuriya, Ambalangodage C.; Kohn, David H.

2009-01-01

A biomimetic approach involving the self-assembly of mineral within the pores of three-dimensional porous polymer scaffolds is a promising strategy to integrate advantages of inorganic and organic phases into a single material for hard tissue engineering. Such a material enhances the ability of progenitor cells to differentiate down an osteoblast lineage in vitro and in vivo, compared with polymer scaffolds. The mechanisms regulating mineral formation in this one-step process, however, are poorly understood, especially the effects of ionic activity products (IP) of the mineralizing solution and incubation time. The aims of this study were to define the structure and composition of mineral formed within the pores of biodegradable polymer scaffolds as a function of IP and time. Three-dimensional poly(lactide-co-glycolide) scaffolds were fabricated by solvent casting/particulate leaching and incubated for 4–16 days in six variants of simulated body fluid whose IPs were varied by adjusting ionic concentrations. Scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy demonstrated the formation of carbonated apatite with sub-micrometer sized crystals that grew into spherical globules extending out of the scaffold pore surfaces. As IP increased, more mineral grew on the scaffold pore surfaces, but the apatite became less crystalline and the Ca/P molar ratio decreased from 1.63 ± 0.005 to 1.51 ± 0.002. Since morphology, composition, and structure of mineral are factors that affect cell function, this study demonstrates that the IP of the mineralizing solution is an important modulator of material properties, potentially leading to enhanced control of cell function. PMID:17584901

Dispersion fraction enhances cellular growth of carbon nanotube and aluminum oxide reinforced ultrahigh molecular weight polyethylene biocomposites.

PubMed

Patel, Anup Kumar; Balani, Kantesh

2015-01-01

Ultrahigh molecular weight polyethylene (UHMWPE) is widely used as bone-replacement material for articulating surfaces due to its excellent wear resistance and low coefficient of friction. But, the wear debris, generated during abrasion between mating surfaces, leads to aseptic loosening of implants. Thus, various reinforcing agents are generally utilized, which may alter the surface and biological properties of UHMWPE. In the current work, the cellular response of compression molded UHMWPE upon reinforcement of bioactive multiwalled carbon nanotubes (MWCNTs) and bioinert aluminum oxide (Al2O3) is investigated. The phase retention and stability were observed using X-ray diffraction, Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The reinforcement of MWCNTs and Al2O3 has shown to alter the wettability (from contact angle of ~88°±2° to ~118°±4°) and surface energy (from ~23.20 to ~17.75 mN/m) of composites with respect to UHMWPE, without eliciting any adverse effect on cytocompatibility for the L929 mouse fibroblast cell line. Interestingly, the cellular growth of the L929 mouse fibroblast cell line is observed to be dominated by the dispersion fraction of surface free energy (SFE). After 48 h of incubation period, a decrease in metabolic activity of MWCNT-Al2O3 reinforced composites is attributed to apatite formation that reduces the dispersion fraction of surface energy. The mineralized apatite during incubation was confirmed and quantified by energy dispersive spectroscopy and X-ray diffraction respectively. Thus, the dispersion fraction of surface free energy can be engineered to play an important role in achieving enhanced metabolic activity of the MWCNT-Al2O3 reinforced UHMWPE biopolymer composites. Copyright © 2014 Elsevier B.V. All rights reserved.

Study of the formation of the apatite-type phases La9.33+x(SiO4)6O2+3x/2 synthesized from a lanthanum oxycarbonate La2O2CO3

NASA Astrophysics Data System (ADS)

Pons, A.; Jouin, J.; Béchade, E.; Julien, I.; Masson, O.; Geffroy, P. M.; Mayet, R.; Thomas, P.; Fukuda, K.; Kagomiya, I.

2014-12-01

Lanthanum silicated apatites with nominal composition La9.33+x(SiO4)6O2+3x/2 (-0.2 < x < 0.27) have been successfully synthesized by solid state reaction using a new reagent La2O2CO3 and amorphous SiO2 precursors. The formation mechanism of La2O2CO3 reagent, which cannot be purchased, has been followed by in-situ temperature depend XRD of La2O3 under CO2 atmosphere. The stability of this reagent during the synthesis step allowed to limit the formation of secondary phase La2Si2O7 and made the weighting of the reagent easier. High purity powders could be synthesized at the temperature of 1400 °C. Dense pellets (more than 98.5%) were obtained by isostatic pressing of powders calcined at 1200 °C and then sintered at 1550 °C. Traces of La2SiO5 secondary phase present in synthesized powder disappeared after densification and pure oxyapatite materials were obtained for all the compositions. Electrical measurements confirmed that conductivity behaviors of the sintered pellets were dependent to the oxygen over-stoichiometry. Indeed, a relatively high conductivity of 1 × 10-2 S cm-1 was exhibited at 800 °C for the nominal composition La9.60(SiO4)6O2.405 with low activation energy around 0.79 eV. The ionic conductivity properties were comparable with that of the earlier obtained materials.

Ultrastructural properties of laser-irradiated and heat-treated dentin.

PubMed

Rohanizadeh, R; LeGeros, R Z; Fan, D; Jean, A; Daculsi, G

1999-12-01

Previous studies using scanning electron microscopy and infrared absorption spectroscopy reported that laser irradiation causes compositional changes in enamel. The purpose of this study was to evaluate the ultrastructural and compositional changes in dentin caused by irradiation with a short-pulse laser (Q-switched Nd:YAG). The irradiated and non-irradiated areas of the lased dentin samples were investigated by scanning (SEM) and transmission electron microscopy (TEM), micro-micro electron diffraction, and electron microprobe analysis of dispersive energy (EDX). Heat-treated dentin was similarly investigated. This study demonstrated that laser irradiation resulted in the recrystallization of dentin apatite and in the formation of additional calcium phosphate phases consisting of magnesium-substituted beta-tricalcium phosphate, beta-TCMP, beta-(Ca,Mg)3(PO4)2, and tetracalcium phosphate, TetCP, Ca4(PO4)O. TEM analyses of the modified and unmodified zones of the irradiated areas showed two types of crystal populations: much larger crystals from the modified zone and crystals with size and morphology similar to those of dentin apatite in the unmodified zone. The morphology of crystals in the modified zones in the irradiated dentin resembled those of dentin sintered at 800 or 950 degrees C. In the irradiated areas (modified and unmodified zones), the Ca/P ratio was lower compared with that in the non-irradiated dentin. The Mg/Ca ratio in the modified zones was higher than that in the unmodified zones and in the non-irradiated dentin. In sintered dentin, the Mg/Ca ratio increased as a function of sintering temperature. The ultrastructural and compositional changes observed in laser-irradiated dentin may be attributed to high temperature and high pressure induced by microplasma during laser irradiation. These changes may alter the solubility of the irradiated dentin, making it less susceptible to acid dissolution or to the caries process.

Solvent Extraction of Rare Earth Elements from a Nitric Acid Leach Solution of Apatite by Mixtures of Tributyl Phosphate and Di-(2-ethylhexyl) Phosphoric Acid

NASA Astrophysics Data System (ADS)

Ferdowsi, Ali; Yoozbashizadeh, Hossein

2017-12-01

Solvent extraction of rare earths from nitrate leach liquor of apatite using mixtures of tributyl phosphate (TBP) and di-(2-ethylhexyl) phosphoric acid (D2EHPA) was studied. The effects of nitrate and hydrogen ion concentration of the aqueous phase as well as the composition and concentration of extractants in the organic phase on the extraction behavior of lanthanum, cerium, neodymium, and yttrium were investigated. The distribution ratio of REEs increases by increasing the nitrate concentration in aqueous phase and concentration of extractants in organic phase, but the hydrogen ion concentration in aqueous phase has a decreasing effect. Yttrium as a heavy rare earth is more sensitive to these parameters than light rare earth elements. Although the composition of organic phase has a minor effect on the extraction of light rare earths, the percent of extraction of yttrium decreases dramatically by increasing the TBP content of organic phase. Mixtures of TBP and D2EHPA can show either synergism or antagonism extraction depending on the concentration and composition of extractants in organic phase. The best condition for separating rare earth elements in groups of heavy and light REEs can be achieved at high nitrate concentration, low H+ concentration, and high concentration of D2EHPA in organic phase. Separation of Ce and La by TBP and D2EHPA is practically impossible in the studied conditions; however, low nitrate concentration and high hydrogen ion concentration in aqueous phase and low concentration of extractants in organic phase favor the separation of Nd from other light rare earth elements.

Fast synthesis of La-substituted apatite by the dry mechanochemical method and analysis of its structure

NASA Astrophysics Data System (ADS)

Bulina, Natalia V.; Chaikina, Marina V.; Prosanov, Igor Yu.; Dudina, Dina V.; Solovyov, Leonid A.

2017-08-01

Compared to pure apatite, La-substituted apatites have improved thermal, mechanical and biological characteristics. In this article, a fast synthesis of La-substituted apatites by a dry mechanochemical method is presented. Structural studies by X-ray diffraction and Fourier transform infrared spectroscopy indicated the formation of a single-phase nanosized product after 30 min of high-energy ball milling of the reaction mixtures. The dry mechanochemical method is technologically attractive for the preparation of La-substituted apatites, as it allows reducing the processing time down to half an hour and does not require prolonged high-temperature annealing normally used in the synthesis practice of the substituted apatite. As the mechanochemically synthesized samples are nanosized, it is difficult to determine the details of their crystal structure by the Rietveld refinement method. Therefore, a series of the mechanochemically synthesized samples with different concentrations of lanthanum were annealed at 1000°C for 5 h. It was found that the annealed powders are microcrystalline La-substituted apatites Ca10-xLax(PO4)6Ox(OH)2-x, where 0 ≤ x ≤2. In their structure, the Ca2+ ions are replaced by the La3+ ions localized near the Ca2 sites, and the OH- groups are replaced by the O2- ions in the hexagonal channels.

Protein content of human apatite and brushite kidney stones: significant correlation with morphologic measures.

PubMed

Pramanik, Rocky; Asplin, John R; Jackson, Molly E; Williams, James C

2008-10-01

Apatite and brushite kidney stones share calcium and phosphate as their main inorganic components. We tested the hypothesis that these stone types differ in the amount of proteins present in the stones. Intact stones were intensively analyzed by microcomputed tomography (micro CT) for both morphology (including the volume of voids, i.e., space devoid of X-ray dense material) and mineral type. To extract all proteins present in kidney stones in soluble form we developed a three-step extraction procedure using the ground stone powder. Apatite stones had significantly higher levels of total protein content and void volume compared to brushite stones. The void volume was highly correlated with the total protein contents in all stones (r2 = 0.61, P < 0.0001), and brushite stones contained significantly fewer void regions and proteins than did apatite stones (3.2 +/- 4.5% voids for brushite vs. 10.8 +/- 11.2% for apatite, P < 0.005; 4.1 +/- 1.6% protein for brushite vs. 6.0 +/- 2.4% for apatite, P < 0.03). Morphological observations other than void volume did not correlate with protein content of stones, and neither did the presence or absence of minor mineral components. Our results show that protein content of brushite and apatite stones is higher than that was previously thought, and also suggest that micro CT-visible void regions are related to the presence of protein.

Compositional Variation of Tourmaline from the Paleoproterozoic Bhukia Gold Prospect of Aravalli Supergroup, Western India: Implications for the Provenance and Gold Metallogeny

NASA Astrophysics Data System (ADS)

Mukherjee, R.; Venkatesh, A. S.; Fareeduddin, F.

2016-12-01

Bhukia is a unique gold prospect in terms of its host lithologies such as albitite and carbonates with respect to greenstone hosted Archean gold deposits from India. Tourmaline occurs along with apatite, magnetite, graphite, chalcopyrite and gold-sulfide association in Bhukia gold prospect preserve geochemical record of changing physico-chemical conditions during its growth. Tourmalinization is one of the distinct hydrothermal alterations present in the study area. Chemical composition of two varieties of tourmalines presents as significant amounts within albitite and carbonate rocks from Bhukia gold prospect. EPMA analysis of two varieties of tourmalines viz. 1) rounded to sub-rounded, euhedral, green colored tourmalines and 2) elongated, zoned, brown colored tourmalines unlocks their chemical compositions as well as variations from core to rim. In some albitite litho-units, tourmaline occurs as major constituents (>15%), present as layers, termed as tourmalinites. Al-Fe-Mg and Na/ (Na+Ca) vs Fe/ (Fe+Mg) suggests that tourmalines from the Bhukia gold prospect are Mg-rich dravite to Fe-rich schrol in composition. Tourmalines present within the albitite rocks show variations in iron and sodium content from core to rim whereas similarity exist from core to rim in case of carbonate rocks. Presence of albite confirms the role of Na-rich fluids during the formation of tourmalines. Tourmalines present in Bhukia gold prospect is mainly influenced by boron influx and the source may be boron bearing hydrothermal fluid or boron bearing minerals. Dewatering of original un-metamorphosed rock during progressive metamorphism may remove boron from the metasedimentary rocks. Due to the mobile nature of boron, it dispersed and mixed with hydrothermal fluids and alumina that is required for the formation of the tourmaline might have been leached from metasedimentary rocks present in Bhukia gold prospect. Presence of hydrothermal alterations such as tourmalinization and albitization along with Au-Cu-graphite-magnetite association suggest this deposit to be an IOCG (Iron oxide copper gold) type.

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 fluids. The high fluorine content of the apatite at Khanlogh may testify to the presence of Ti-fluoride complex in the fluids. Formation of apatite crystals was concurrent with development of titanium lamellae in magnetite. The apatite possesses high REE content which is possibly associated with monazite inclusions. The SEM studies better show these inclusions are occasionally present at the margin of apatite crystals and veins. Based upon field relations, microscopic examinations, and the results of XRD analyses, sodic (albite), propylitic (epidote, chlorite, calcite), and argillic (montmorillonite) alterations are developed in the study area. The principal minerals in these alteration zones are albite, epidote, sericite, chlorite, quartz, calcite, and montmorllonite. Mineralogy, alteration, geochemistry, structure, and texture of the ores at Khanlogh indicate that the magnetite and apatite were chiefly formed by hydrothermal solutions which were enriched in iron mainly transported by F- and Cl- rich fluids. Reference Hou,,T., Zhaochong, Z., Timothy, K., (2011). Gushan magnetite-apatite deposit in the Ningwu basin, Lower Yangtze River Valley, SE China: Hydrothermal or Kiruna-type? Ore geology review, 43, 333-346. Purtov, V.K., Kotelnikova, A.L. (1993). Solubility of titanium in chloride and fluoride hydrothermal solution. International Geology Review 35, 274 -287.

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 and organic acids" experiment demonstrated that the apatite dissolution efficacy of organic acids was higher than for the inorganic acid and varied in function of the acids: oxalic acid > citric acid > gluconic acid > nitric acid for pH ⩽3.5. In addition, apatite dissolution increased with increasing acidity for each acid. Only oxalic acid generated non-stoichiometric release of calcium and phosphorus from apatite in the solution at pH ⩽3.5, due to the precipitation of Ca-oxalate crystals at apatite surfaces. Comparison of the experiments revealed that the apatite dissolution rate by Scots pines supplied with nutritive solution at pH 5.5 reached 2.0 × 10-13 mol cm-2 s-1 and was equivalent to rates with nitric acid at pH 3.2, gluconic acid at pH 3.5, citric acid at pH 3.7, and oxalic acid at pH 3.8. Altogether our results highlight that, through the production of weathering agents, notably protons and organic acids, tree roots and root-associated microorganisms are able to significantly increase the release of macro- and micro-nutrients from apatite, thus maintaining high-nutrient conditions to support their growth.

Effect of Alkali-Acid-Heat Chemical Surface Treatment on Electron Beam Melted Porous Titanium and Its Apatite Forming Ability

PubMed Central

Bsat, Suzan; Amin Yavari, Saber; Munsch, Maximilian; Valstar, Edward R.; Zadpoor, Amir A.

2015-01-01

Advanced additive manufacturing techniques such as electron beam melting (EBM), can produce highly porous structures that resemble the mechanical properties and structure of native bone. However, for orthopaedic applications, such as joint prostheses or bone substitution, the surface must also be bio-functionalized to promote bone growth. In the current work, EBM porous Ti6Al4V alloy was exposed to an alkali acid heat (AlAcH) treatment to bio-functionalize the surface of the porous structure. Various molar concentrations (3, 5, 10M) and immersion times (6, 24 h) of the alkali treatment were used to determine optimal parameters. The apatite forming ability of the samples was evaluated using simulated body fluid (SBF) immersion testing. The micro-topography and surface chemistry of AlAcH treated samples were evaluated before and after SBF testing using scanning electron microscopy and energy dispersive X-ray spectroscopy. The AlAcH treatment successfully modified the topographical and chemical characteristics of EBM porous titanium surface creating nano-topographical features ranging from 200–300 nm in size with a titania layer ideal for apatite formation. After 1 and 3 week immersion in SBF, there was no Ca or P present on the surface of as manufactured porous titanium while both elements were present on all AlAcH treated samples except those exposed to 3M, 6 h alkali treatment. An increase in molar concentration and/or immersion time of alkali treatment resulted in an increase in the number of nano-topographical features per unit area as well as the amount of titania on the surface. PMID:28788021

Functional biomimetic analogs help remineralize apatite-depleted demineralized resin-infiltrated dentin via a bottom-up approach

PubMed Central

Kim, Jongryul; Arola, Dwayne D.; Gu, Lisha; Kim, Young Kyung; Mai, Sui; Liu, Yan; Pashley, David H.; Tay, Franklin R.

2010-01-01

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 resin-dentin bonds. PMID:20045745

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 resin-dentin bonds. Copyright 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effect of Alkali-Acid-Heat Chemical Surface Treatment on Electron Beam Melted Porous Titanium and Its Apatite Forming Ability.

PubMed

Bsat, Suzan; Yavari, Saber Amin; Munsch, Maximilian; Valstar, Edward R; Zadpoor, Amir A

2015-04-08

Advanced additive manufacturing techniques such as electron beam melting (EBM), can produce highly porous structures that resemble the mechanical properties and structure of native bone. However, for orthopaedic applications, such as joint prostheses or bone substitution, the surface must also be bio-functionalized to promote bone growth. In the current work, EBM porous Ti6Al4V alloy was exposed to an alkali acid heat (AlAcH) treatment to bio-functionalize the surface of the porous structure. Various molar concentrations (3, 5, 10M) and immersion times (6, 24 h) of the alkali treatment were used to determine optimal parameters. The apatite forming ability of the samples was evaluated using simulated body fluid (SBF) immersion testing. The micro-topography and surface chemistry of AlAcH treated samples were evaluated before and after SBF testing using scanning electron microscopy and energy dispersive X-ray spectroscopy. The AlAcH treatment successfully modified the topographical and chemical characteristics of EBM porous titanium surface creating nano-topographical features ranging from 200-300 nm in size with a titania layer ideal for apatite formation. After 1 and 3 week immersion in SBF, there was no Ca or P present on the surface of as manufactured porous titanium while both elements were present on all AlAcH treated samples except those exposed to 3M, 6 h alkali treatment. An increase in molar concentration and/or immersion time of alkali treatment resulted in an increase in the number of nano-topographical features per unit area as well as the amount of titania on the surface.

Inhibition of precipitation of carbonate apatite by trisodium citrate analysed in base of the formation of chemical complexes in growth solution

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

Prywer, Jolanta, E-mail: jolanta.prywer@p.lodz.pl; 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 ofmore » 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.« less

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

PubMed

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

2011-01-01

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

Preparation of hydroxyapatite/poly(lactic acid) hybrid microparticles for local drug delivery

NASA Astrophysics Data System (ADS)

Loca, D.; Locs, J.; Berzina-Cimdina, L.

2013-12-01

Calcium phosphate (CaP) bioceramic is well known as bioactive and biocompatible material in bone tissue regeneration applications. Apatitic CaP, especially nano sized hydroxyapatite (NHAp), is more similar to the natural apatite presented in the bone tissue than CaP bioceramics. In the current research NHAp was modified using biodegradable polymer - poly(lactic acid) (PLA) to develop composites providing bone regeneration and local drug delivery. NHAp/PLA microcapsules were prepared using solid-in-water-in-oil-in-water (s/w1/o/w2) encapsulation technology. The impact of primary and secondary emulsion stability on the emulsion droplet and microparticle properties was evaluated. The stability of final emulsion can be increased by varying the process parameters. Stable s/w1/o/w2 emulsion using 3ml of NHAp suspension, not less than 100ml of 4% PVA water solution and 10ml of 10% PLA solution in dichloromethane can be obtained. S/w1/o/w2 microencapuslation method can be effectively used for the preparation of multi-domain microcapsules achieving high NHAp encapsulation efficacy (93%).

Fabrication of Carbonate Apatite Block through a Dissolution-Precipitation Reaction Using Calcium Hydrogen Phosphate Dihydrate Block as a Precursor.

PubMed

Tsuru, Kanji; Yoshimoto, Ayami; Kanazawa, Masayuki; Sugiura, Yuki; Nakashima, Yasuharu; Ishikawa, Kunio

2017-03-31

Carbonate apatite (CO₃Ap) block, which is a bone replacement used to repair defects, was fabricated through a dissolution-precipitation reaction using a calcium hydrogen phosphate dihydrate (DCPD) block as a precursor. When the DCPD block was immersed in NaHCO₃ or Na₂CO₃ solution at 80 °C, DCPD converted to CO₃Ap within 3 days. β-Tricalcium phosphate was formed as an intermediate phase, and it was completely converted to CO₃Ap within 2 weeks when the DCPD block was immersed in Na₂CO₃ solution. Although the crystal structures of the DCPD and CO₃Ap blocks were different, the macroscopic structure was maintained during the compositional transformation through the dissolution-precipitation reaction. CO₃Ap block fabricated in NaHCO₃ or Na₂CO₃ solution contained 12.9 and 15.8 wt % carbonate, respectively. The diametral tensile strength of the CO₃Ap block was 2 MPa, and the porosity was approximately 57% regardless of the carbonate solution. DCPD is a useful precursor for the fabrication of CO₃Ap block.

Surface modification of calcium hydroxyapatite by grafting of etidronic acid

NASA Astrophysics Data System (ADS)

Othmani, Masseoud; Aissa, Abdallah; Bac, Christophe Goze; Rachdi, Férid; Debbabi, Mongi

2013-06-01

The surface of prepared calcium hydroxyapatite CaHAp has been modified by grafting the etidronic acid (ETD). For that purpose, CaHAp powders have been suspended in an aqueous etidronate solution with different concentrations. The obtained composites CaHAp-(ETD) were characterized by TEM and AFM techniques to determinate morphological properties and were also characterized by XRD, IR, NMR and chemical and thermal analysis to determinate their physico-chemical properties and essentially the nature of the interaction between the inorganic support and the grafted organic ETD. After reaction with ETD, XRD powder analysis shows that the apatitic structure remains unchanged with slight affectation of its crystallinity. The presence of etidronate fragment bounded to hydroxyapatite was confirmed by IR and solid-state NMR spectroscopy. TEM and AFM techniques indicate that the presence of etidronate changes the morphology of the particles. Basing on the obtained results, a reactional mechanism was proposed to explain the formation of covalent Casbnd Osbnd Porg bonds on the hydroxyapatite surface between the superficial hydroxyl groups (tbnd Casbnd OH) of the apatite and phosphonate group (Psbnd OH) of etidronate.

Degradation, bioactivity, and cytocompatibility of diopside, akermanite, and bredigite ceramics.

PubMed

Wu, Chengtie; Chang, Jiang

2007-10-01

The aim of this study was to investigate the effect of three bioceramics in the CaO-SiO(2)-MgO systems with different composition on the in vitro degradation, bioactivity, and cytocompatibility. The degradation was evaluated through the activation energy of Si ion release from ceramics and the weight loss of the ceramics in Tris-HCl buffers. The in vitro bioactivity of the ceramics was investigated by analysis of apatite-formation ability in the simulated body fluid (SBF). The cytocompatibility was evaluated through osteoblast morphology and proliferation. The results showed that the activation energy of Si ion release increased and the degradation decreased from bredigite to diopside ceramics with the increase of Mg content, and the apatite-formation ability in SBF decreased. The Ca, Si, and Mg containing ionic products from three ceramics could stimulate cell proliferation at lower concentration, and inhibit cell proliferation with the increase of ion concentrations. Furthermore, osteoblasts could adhere, spread, and proliferate on three ceramic disks, and cell proliferation on diopside was more obvious than that on other two ceramic disks.

Hydrothermal synthesis and characterization of hydroxyapatite and fluorhydroxyapatite nano-size powders.

PubMed

Montazeri, Leila; Javadpour, Jafar; Shokrgozar, Mohammad Ali; Bonakdar, Shahin; Javadian, Sayfoddin

2010-08-01

Pure hydroxyapatite (HAp) and fluoride-containing apatite powders (FHAp) were synthesized using a hydrothermal method. The powders were assessed by x-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscope (SEM) and F-selective electrode. X-ray diffraction results revealed the formation of single phase apatite structure for all the compositions synthesized in this work. However, the addition of a fluoride ion led to a systematic shift in the (3 0 0) peak of the XRD pattern as well as modifications in the FTIR spectra. It was found that the efficiency of fluoride ion incorporation decreased with the increase in the fluoride ion content. Fluorine incorporation efficiency was around 60% for most of the FHAp samples prepared in the current study. Smaller and less agglomerated particles were obtained by fluorine substitution. The bioactivity of the powder samples with different fluoride contents was compared by performing cell proliferation, alkaline phosphatase (ALP) and Alizarin red staining assays. Human osteoblast cells were used to assess the cellular responses to the powder samples in this study. Results demonstrated a strong dependence of different cell activities on the level of fluoridation.

Hydrophobic agglomeration of apatite fines induced by sodium oleate in aqueous solutions

NASA Astrophysics Data System (ADS)

Yang, Bingqiao; Huang, Pengliang; Song, Shaoxian; Luo, Huihua; Zhang, Yi

2018-06-01

In this work, the hydrophobic agglomeration of apatite fines induced by sodium oleate in aqueous solutions has been investigated through the measurement of agglomeration degree and fractal dimension. The results showed that the agglomeration degree of apatite fines and agglomerates morphology was strongly depended on sodium oleate concentration, pH, stirring speed and time. Better agglomeration degree and more regular agglomerates were achieved at sodium oleate concentration of 5 × 10-5 mol/L under neutral condition. The critical stirring speed for agglomerates rupture was 1000 rev/min, above which, prolonged stirring time would cause breakage and restructure of the agglomerates after a certain stirring time, resulting in lower agglomeration degree and more regular agglomerates. The agglomeration degree of apatite fines could be greatly enhanced with the addition of emulsified kerosene, but only if the apatite surface was hydrophobic enough.

Nanoscale petrographic and geochemical insights on the origin of the Palaeoproterozoic stromatolitic phosphorites from Aravalli Supergroup, India.

PubMed

Papineau, D; De Gregorio, B; Fearn, S; Kilcoyne, D; McMahon, G; Purohit, R; Fogel, M

2016-01-01

Stromatolites composed of apatite occur in post-Lomagundi-Jatuli successions (late Palaeoproterozoic) and suggest the emergence of novel types of biomineralization at that time. The microscopic and nanoscopic petrology of organic matter in stromatolitic phosphorites might provide insights into the suite of diagenetic processes that formed these types of stromatolites. Correlated geochemical micro-analyses of the organic matter could also yield molecular, elemental and isotopic compositions and thus insights into the role of specific micro-organisms among these communities. Here, we report on the occurrence of nanoscopic disseminated organic matter in the Palaeoproterozoic stromatolitic phosphorite from the Aravalli Supergroup of north-west India. Organic petrography by micro-Raman and Transmission Electron Microscopy demonstrates syngeneity of the organic matter. Total organic carbon contents of these stromatolitic phosphorite columns are between 0.05 and 3.0 wt% and have a large range of δ(13) Corg values with an average of -18.5‰ (1σ = 4.5‰). δ(15) N values of decarbonated rock powders are between -1.2 and +2.7‰. These isotopic compositions point to the important role of biological N2 -fixation and CO2 -fixation by the pentose phosphate pathway consistent with a population of cyanobacteria. Microscopic spheroidal grains of apatite (MSGA) occur in association with calcite microspar in microbial mats from stromatolite columns and with chert in the core of diagenetic apatite rosettes. Organic matter extracted from the stromatolitic phosphorites contains a range of molecular functional group (e.g. carboxylic acid, alcohol, and aliphatic hydrocarbons) as well as nitrile and nitro groups as determined from C- and N-XANES spectra. The presence of organic nitrogen was independently confirmed by a CN(-) peak detected by ToF-SIMS. Nanoscale petrography and geochemistry allow for a refinement of the formation model for the accretion and phototrophic growth of stromatolites. The original microbial biomass is inferred to have been dominated by cyanobacteria, which might be an important contributor of organic matter in shallow-marine phosphorites. © 2015 John Wiley & Sons Ltd.

Comparative study on inorganic composition and crystallographic properties of cortical and cancellous bone.

PubMed

Wang, Xiao-Yan; Zuo, Yi; Huang, Di; Hou, Xian-Deng; Li, Yu-Bao

2010-12-01

To comparatively investigate the inorganic composition and crystallographic properties of cortical and cancellous bone via thermal treatment under 700 °C. Thermogravimetric measurement, infrared spectrometer, X-ray diffraction, chemical analysis and X-ray photo-electron spectrometer were used to test the physical and chemical properties of cortical and cancellous bone at room temperature 250 °C, 450 °C, and 650 °C, respectively. The process of heat treatment induced an extension in the a-lattice parameter and changes of the c-lattice parameter, and an increase in the crystallinity reflecting lattice rearrangement after release of lattice carbonate and possible lattice water. The mineral content in cortical and cancellous bone was 73.2wt% and 71.5wt%, respectively. For cortical bone, the weight loss was 6.7% at the temperature from 60 °C to 250 °C, 17.4% from 250 °C to 450 °C, and 2.7% from 450 °C to 700 °C. While the weight loss for the cancellous bone was 5.8%, 19.9%, and 2.8 % at each temperature range, the Ca/P ratio of cortical bone was 1.69 which is higher than the 1.67 of stoichiometric HA due to the B-type CO₃²⁻ substitution in apatite lattice. The Ca/P ratio of cancellous bone was lower than 1.67, suggesting the presence of more calcium deficient apatite. The collagen fibers of cortical bone were arrayed more orderly than those of cancellous bone, while their mineralized fibers ollkded similar. The minerals in both cortical and cancellous bone are composed of poorly crystallized nano-size apatite crystals with lattice carbonate and possible lattice water. The process of heat treatment induces a change of the lattice parameter, resulting in lattice rearrangement after the release of lattice carbonate and lattice water and causing an increase in crystal size and crystallinity. This finding is helpful for future biomaterial design, preparation and application. Copyright © 2010 The Editorial Board of Biomedical and Environmental Sciences. Published by Elsevier B.V. All rights reserved.

The effect of ZrO2 and TiO 2 on solubility and strength of apatite-mullite glass-ceramics for dental applications.

PubMed

Fathi, Hawa M; Miller, Cheryl; Stokes, Christopher; Johnson, Anthony

2014-03-01

The effect of ZrO2 and TiO2 on the chemical and mechanical properties of apatite-mullite glass-ceramics was investigated after sample preparation according to the ISO (2768:2008) recommendations for dental ceramics. All materials were characterized using differential thermal analysis, X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. X-ray fluorescence spectroscopy was used to determine the concentrations of elements present in all materials produced. The chemical solubility test and the biaxial flexural strength (BFS) test were then carried out on all the samples. The best solubility value of 242 ± 61 μg/cm(2) was obtained when HG1T was heat-treated for 1 h at the glass transition temperature plus 20 °C (Tg + 20 °C) followed by 5 h at 1200 °C. The highest BFS value of 174 ± 38 MPa was achieved when HG1Z and HG1Z+T were heat-treated for 1 h at the Tg + 20 °C followed by 7 h at 1200 °C. The present study has demonstrated that the addition of TiO2 to the reference composition showed promise in both the glass and heat-treated samples. However, ZrO2 is an effective agent for developing the solubility or the mechanical properties of an apatite-mullite glass-ceramic separately but does not improve the solubility and the BFS simultaneously.

Sm-Nd isotopic compositions of LREE minerals for use as reference materials for in situ analysis by LA-MC-ICPMS

NASA Astrophysics Data System (ADS)

Fisher, C. M.; McFarlane, C. R.; Sylvester, P.; Hanchar, J. M.; Lam, R.; Schmitz, M. D.

2009-12-01

Recent work has demonstrated the possibility of obtaining both accurate and precise in situ Sm-Nd isotopic data in light rare earth enriched (LREE) accessory minerals including apatite, titanite, and monazite, using laser ablation-multicollector-inductively coupled plasma mass spectrometry (LA-MC-ICPMS). A distinct advantage of using LA-MC-ICPMS is that Sm-Nd isotopic data from these minerals can be determined in sub-grain domains potentially avoiding problems of isotopic mixing from inherited or xenocrystic components and allowing both valuable tracer isotope and geochronologic data to be obtained. However, a number of analytical obstacles complicate accurate Sm-Nd determination by LA-MC-ICPMS including mass bias corrections, the 144Sm isobaric interference on 144Nd, and potential offset (ca. 20-40 ppm) from thermal ionization mass spectrometry (TIMS) determination of similar materials. Thus, in order to verify Sm-Nd isotopic determination from unknowns, matrix-matched quality control standards (i.e., reference materials) must be developed to test the data handling protocol. This talk will present new Sm-Nd isotopic data determined by both TIMS as well as LA-MC-ICPMS of a number of natural potential reference minerals including Durango apatite, Fish Canyon titanite, Daibosatsu allanite, Trebilcock monazite, as well as a monazite from the Doi Inthanon core complex in northern Thailand. Our preliminary LA-MC-ICPMS results demonstrate that Durango apatite, Fish Canyon titanite, and Thailand monazite show both inter- and intra-grain homogeneity at current levels of precision (ca. 0.3-0.5 ɛNd) and close agreement with our TIMS data.

Rare earth elements in apatite: Uptake from H{sub 2}O-bearing phosphate-fluoride melts and the role of volatile components

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

Fleet, M.E.; Pan, Yuanming

The partitioning of rare earth elements (REEs) between fluorapatite (FAp) and H{sub 2}O- bearing phosphate-fluoride melts has been studied at about 700 and 800{degrees}C and 0.10-0.15 GPa. REE uptake patterns, i.e., plots of D(REE:FAp/melt), are convex upwards and peak near Nd for single-REE substituted FAp at minor (0.03-0.25 wt% REE{sub 2}O{sub 3}) abundances, and binary (LREE + HREE)-substituted FAp, and hexa-REE-substituted FAp at minor to major (0.25-7.8 wt% REE{sub 2}O{sub 3}) abundances. Partition coefficients for minor abundances of REE and depolymerized phosphate melts are about 5, 8, and 1 for La, Nd, and Lu, respectively and broadly comparable to thosemore » for early fluorapatite in the fractionation of melts of basaltic composition. The Ca2 site exerts marked control on the selectivity of apatite for REE because it preferentially incorporates LREE and its effective size varies with substitution of the A-site volatile anion component (F, Cl, OH). Using simple crystal-chemical arguments, melt(or fluid)-normalized REE patterns are predicted to peak near Nd for fluorapatite and be more LREE-enriched for chlorapatite. These predictions are consistent with data from natural rocks and laboratory experiments. The wide variation in D(REE:apatite/melt) in nature (from <1 for whitlockite-bearing lunar rocks to about 100 for evolved alkalic rocks) is attributed largely to the influence of the volatile components. 49 refs., 8 figs., 3 tabs.« less

Carbonate formation on bioactive glasses.

PubMed

Cerruti, Marta; Morterra, Claudio

2004-07-20

The system termed 58S is a sol-gel-synthesized bioactive glass composed of SiO2, CaO, and P2O5, used in medicine as bone prosthetic because, when immersed in a physiological fluid, a layer of hydroxycarbonate apatite is formed on its surface. The mechanism of bioactive glass 58S carbonation was studied in the vacuum by means of in-situ FTIR spectroscopy with the use of CO2, H2O, and CD3CN as probe molecules. The study in the vacuum was necessary to identify both the molecules specifically involved in the carbonation process and the type of carbonates formed. Bioactive glass 58S was compared to a Ca-doped silica and to CaO. On CaO, ionic carbonates could form by contact with CO2 alone, whereas on 58S and on Ca-doped silica carbonation occurred only if both CO2 and an excess of H2O were present on the sample. The function of H2O was not only to block surface cationic sites, so that CO2 could not manifest its Lewis base behavior, but also to form a liquid-like (mono)layer that allowed the formation of carbonate ions. The presence of H2O is also supposed to promote Ca2+ migration from the bulk to the surface. Carbonates formed at the surface of CaO and of Ca-bearing silicas (thus including bioactive glasses) are of the same type, but are produced through two different mechanisms. The finding that a water excess is necessary to start heavy carbonation on bioactive glasses seemed to imply that the mechanism leading to in-situ carbonation simulates, in a simplified and easy-to-reproduce system, what happens both in solution, when carbonates are incorporated in the apatite layer, and during sample shelf-aging. Copyright 2004 American Chemical Society

In vitro degradation and biocompatibility of a strontium-containing micro-arc oxidation coating on the biodegradable ZK60 magnesium alloy

NASA Astrophysics Data System (ADS)

Lin, Xiao; Yang, Xiaoming; Tan, Lili; Li, Mei; Wang, Xin; Zhang, Yu; Yang, Ke; Hu, Zhuangqi; Qiu, Jianhong

2014-01-01

Magnesium alloys are promising biodegradable implant candidates for orthopedic application. In the present study, a phosphate-based micro-arc oxidation (MAO) coating was applied on the ZK60 alloy to decrease its initial degradation rate. Strontium (Sr) was incorporated into the coating in order to improve the bioactivity of the coating. The in vitro degradation studies showed that the MAO coating containing Sr owned a better initial corrosion resistance, which was mainly attributed to the superior inner barrier layer, and a better long-term protective ability, probably owning to its larger thickness, superior inner barrier layer and the superior apatite formation ability. The degradation of MAO coating was accompanied by the formation of degradation layer and Ca-P deposition layer. The in vitro cell tests demonstrated that the incorporation of Sr into the MAO coating enhanced both the proliferation of preosteoblast cells and the alkaline phosphatase activity of the murine bone marrow stromal cells. In conclusion, the MAO coating with Sr is a promising surface treatment for the biodegradable magnesium alloys.

Fabrication of hydroxyapatite and TiO 2 nanorods on microarc-oxidized titanium surface using hydrothermal treatment

NASA Astrophysics Data System (ADS)

Song, Ho-Jun; Kim, Ji-Woo; Kook, Min-Suk; Moon, Won-Jin; Park, Yeong-Joon

2010-09-01

AC-type microarc oxidation (MAO) and hydrothermal treatment techniques were used to enhance the bioactivity of commercially pure titanium (CP-Ti). The porous TiO 2 layer fabricated by the MAO treatment had a dominant anatase structure and contained Ca and P ions. The MAO-treated specimens were treated hydrothermally to form HAp crystallites on the titanium oxide layer in an alkaline aqueous solution (OH-solution) or phosphorous-containing alkaline solution (POH-solution). A small number of micro-sized hydroxyapatite (HAp) crystallites and a thin layer composed of nano-sized HAps were formed on the Ti-MAO-OH group treated hydrothermally in an OH-solution, whereas a large number of micro-sized HAp crystallites and dense anatase TiO 2 nanorods were formed on the Ti-MAO-POH group treated hydrothermally in a POH-solution. The layer of bone-like apatite that formed on the surface of the POH-treated sample after soaking in a modified simulated body fluid was thicker than that on the OH-treated samples.

Rock-eating fungi: Ectomycorrhizal fungi are picky eaters

NASA Astrophysics Data System (ADS)

Rosenstock, Nicholas; Smits, Mark; Berner, Christoffer; Kram, Pavel; Wallander, Hakan

2014-05-01

Ectomycorrhizal fungi, which form mutualistic symbiosis with the roots of most temperate and boreal forest trees, play a key role in the provision of nitrogen and phosphorus to their plant symbionts; they have also been shown to provide potassium and magnesium. Ectomycorhizal hyphae colonize and take up mineral nutrients (including P, K, and Mg) from primary mineral surfaces in the soil. It is poorly understood whether mineral colonization and uptake of nutrients from minerals can increase in accordance with host plant demand for these nutrients, and this question has been difficult to address in field settings. Ectomycorrhizal fungal communities are diverse and niche separation according to nutrient uptake and transport to the host is commonly considered one of the major factors maintaining diversity and shaping ectomycorrhizal community composition.We investigated ectomycorrhizal growth, community composition, and mineral colonization in a series of connected Norway spruce forests in the Czech republic. These forests have similar aspect, climate and stand history, but are underlain by different parent materials and are, as a result, limited by different nutrients. The productivity of forests overlying a high amount of serpentinite rock are co-limited by K and P, those growing on primarily granitic rock are limited by Mg, while those on amphibolite are N limited. We assessed the fungal community in both soil and in-growth mesh bags measuring biomarkers, using in-growth assays and performing community analysis with 454 sequencing of the ITS region. In-growth mesh bags were filled with quartz sand and incubated for two growing seasons in the soil. These mesh bags select for ectomycorrhizal hyphae and were either pure quartz sand or amended with ground apatite (Ca and P source), hornblende (Mg source) or biotite (K source). Ectomycorrhizal growth and community composition were most strongly affected by parent material. The phosphorus-limited site had the lowest tree growth but the highest ectomycorrhizal growth. Apatite amendment (a phosphorus source) increased fungal in-growth in the serpentinite sites, but had no effect on the other (not P-limited) sites, while hornblende and biotite had no effect on fungal in-growth on any sites. Mineral amendments in the mesh bags had a small but significant effect on fungal community composition; this effect was strongest in apatite-amended bags and on serpentinite sites. Fungal species-specific responses to different mineral amendments were also observed. These results indicate that the parent material from which a soil is formed has a major effect on the soil fungal community, and that ectomycorrhizal communities may respond to the phosphorus limitation of their host trees by increased colonization of phosphorus-containing minerals. In contrast, this response to nutrient limitation does not appear to exist for potassium or magnesium limitation.

Lu-Hf isotope systematics of fossil biogenic apatite and their effects on geochronology

NASA Astrophysics Data System (ADS)

Herwartz, Daniel; Münker, Carsten; Tütken, Thomas; Hoffmann, J. Elis; Wittke, Andreas; Barbier, Bruno

2013-01-01

Reliable methods for direct dating of biogenic apatite from pre-Pleistocene fossils are currently not available, and recent attempts using the Lu-Hf decay system yielded highly inaccurate ages for both bones and teeth. The geological processes accounting for this poor accuracy of Lu-Hf chronometry are not yet understood. Here we explore Lu-Hf systematics in fossil bones and teeth in detail, by applying five different sample digestion techniques that are tested on bones and composites of bone and sediment. Our current dataset implies that dissolution methods only slightly affect the resulting Lu-Hf ages, while clear differences between the individual digestion techniques became apparent for element concentrations. By analysing the insoluble leftovers from incomplete sample dissolution, four main reservoirs of Hf in fossil bones were identified: (1) a radiogenic end-member associated with apatite; (2) an unradiogenic end-member represented by the authigenic minerals or the embedding sediment; (3) a highly unradiogenic end-member that can be attributed to detrital zircon; and (4) a moderately soluble phase (probably a Zr(Hf)-phosphate) that yielded very low Lu/Hf but a highly radiogenic Hf isotope composition at the same time. This Zr(Hf)-phase must have been precipitated within the fossil bone sample at a late stage of burial history, thereby incorporating radiogenic 176Hf released from apatite surfaces over geological timescales. A second focus of our study is the effect of different sediment matrices and of crystal size on the preservation of pristine Lu-Hf isotope compositions in bioapatite. Because near-depositional Lu-Hf ages of phosphate fossils have previously been reported for the London Clay (England) and a calcareous marl from Tendaguru (Tanzania), we herein investigate specimens fossilised in carbonate matrices (calcareous marl from Oker, Germany; carbonate concretions from the Santana Formation, Brazil; carbonate from the Eifel, Germany) and argillaceous matrices with low permeability (oil shale of Messel, Germany; Posidonienschiefer of Holzmaden, Germany). Materials analysed from these localities include bones, teeth, conodonts, as well as coproliths and diagenetic minerals (siderite, montgomeryite and messelite). Near-depositional Lu-Hf ages were obtained for a bony fish sample (Notelops brama) encapsulated in an early diagenetic carbonate concretion from the Early Cretaceous Santana Formation, Brazil and for conodonts from a Middle Devonian carbonate from the Eifel, Germany. Low 176Lu/177Hf ratios in all materials from the Middle Eocene Messel oil shale (e.g., bones, fish scales, sediment, siderite) result in poor age precision and an age that is near-depositional due to this large analytical error. In agreement with previous results, all other ages determined here for both bones and teeth are by far younger than respective chronostratigraphic ages. A model illustrating the behaviour of Lu and Hf over time, with respect to the fossilisation process is presented, which accounts both for the formation of a late diagenetic radiogenic Zr(Hf) phase and long term open system behaviour. The continuous Lu-Hf element exchange between the fossils and the embedding sediment is probably related to the nm-scale crystal size of fossil bones, dentine and also of enamel that generate large surface areas facilitating sorption/desorption processes and open system behaviour.

Sr-90 Immobilization by Infiltration of a Ca-Citrate-PO4 Solution into the Hanford 100-N Area Vadose Zone

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

Szecsody, Jim E.; Fruchter, Jonathan S.; Burns, Carolyn A.

This project was initiated to develop a strategy for infiltration of a Ca-citrate-PO4 solution in order to precipitate apatite [Ca6(PO4)10(OH)2] in desired locations in the vadose zone for Sr-90 remediation. Laboratory experiments have demonstrated that infiltration of a Ca-citrate-PO4 solution into sediments at low and high water saturation results in citrate biodegradation and formation of apatite. The citrate biodegradation rate was relatively uniform, in spite of the spatial variability of sediment microbial biomass, likely because of microbial transport processes that occur during solution infiltration. The precipitate was characterized as hydroxyapatite, and the Sr-90 substitution into apatite was shown to havemore » a half-life of 5.5 to 16 months. 1-D and 2-D laboratory infiltration experiments quantified the spatial distribution of apatite that formed during solution infiltration. Slow infiltration in 2-D experiments at low water saturation show the apatite precipitate concentrated in the upper third of the infiltration zone. More rapid 1-D infiltration studies show the apatite precipitate concentrated at greater depth.« less

Nucleation and growth of apatite on NaOH-treated PEEK, HDPE and UHMWPE for artificial cornea materials.

PubMed

Pino, M; Stingelin, N; Tanner, K E

2008-11-01

The skirt of an artificial cornea must integrate the implant to the host sclera, a major failure of present devices. Thus, it is highly desirable to encourage the metabolic activity of the cornea by using more bioactive, flexible skirt materials. Here we describe attempts to increase the bioactivity of polyether ether ketone (PEEK), high-density polyethylene (HDPE) and ultra-high molecular weight polyethylene (UHMWPE) films. The effectiveness of different strength NaOH pre-treatments to initiate apatite deposition on PEEK, HDPE and UHMWPE is investigated. We find that exposure of PEEK, HDPE and UHMWPE films to NaOH solutions induces the formation of potential nuclei for apatite (calcium phosphate), from which the growth of an apatite coating is stimulated when subsequently immersing the polymer films in 1.5 strength Simulated Body Fluid (SBF). As immersion time in SBF increases, further nucleation and growth produces a thicker and more compact apatite coating that can be expected to be highly bioactive. Interestingly, the apatite growth is found to also be dependent on both the concentration of NaOH solution and the structure of the polymer surface.

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 and apatite, but preferentially to calcium carbonate. Together, these studies highlight the specific binding affinity of the augmented amelogenin polyproline repeat region to calcium phosphates versus calcium carbonate, and its unique role in the growth of thin apatite crystals as they occur in vertebrate biominerals. Our data suggest that the rise of apatite-based biominerals in vertebrates might have been facilitated by a rapid evolution of specialized polyproline repeat proteins flanked by a charged domain, resulting in apatite crystals with reduced width, increased length, and tailored biomechanical properties. PMID:25426079