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)

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.

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.

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

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

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.

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

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.

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.

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.

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.

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.

[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.

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.

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.

Chitosan reinforced apatite-wollastonite coating by electrophoretic deposition on titanium implants.

PubMed

Sharma, Smriti; Soni, Vivek P; Bellare, Jayesh R

2009-07-01

A novel bioactive porous apatite-wollastonite/chitosan composite coating was prepared by electrophoretic deposition. The influence of synthesis parameters like pH of suspension and current density was studied and optimized. X-ray diffraction confirmed crystalline phase of apatite-wollastonite in powder as well as composite coating with coat crystallinity of 65%. Scanning electron microscope showed that the porosity had interconnections with good homogeneity between the phases. The addition of chitosan increased the adhesive strength of the composite coating. Young's modulus of the coating was found to be 9.23 GPa. One of our key findings was sheet-like apatite growth unlike ball-like growth found in bioceramics. Role of chitosan was studied in apatite growth mechanism in simulated body fluid. In presence of chitosan, dense negatively charged surface with homogenous nucleation was the primary factor for sheet-like evolution of apatite layer. The results suggest that incorporation of chitosan with apatite-wollastonite in composite coating could provide excellent in vitro bioactivity with enhanced mechanical properties.

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.

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.

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.

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.

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.

Preparation of a bonelike apatite-polymer fiber composite using a simple biomimetic process.

PubMed

Yokoyama, Yoshiro; Oyane, Ayako; Ito, Atsuo

2008-08-01

A bonelike apatite-polymer fiber composite may be useful as an implant material to replace bone, the enthesis of a tendon, and the joint part of a ligament. We treated an ethylene-vinyl alcohol copolymer (EVOH) plate and knitted EVOH fibers with an oxygen plasma to produce oxygen-containing functional groups on their surfaces. The plasma-treated samples were alternately dipped in alcoholic calcium and phosphate ion solutions three times to deposit apatite precursors onto their surfaces. The surface-modified samples formed a dense and uniform bonelike surface apatite layer after immersion for 24 h in a simulated body fluid with ion concentrations approximately equal to those of human blood plasma. The adhesive strength between the apatite layer and the sample's surface increased with increasing power density of the oxygen plasma. The apatite-EVOH fiber composite obtained by our process has similarities to natural bone in that apatite crystals are deposited on organic polymer fibers. The resulting composite would possess osteoconductivity due to the apatite phase. With proper polymer selection and optimized synthesis techniques, a composite could be made that would have bonelike mechanical properties. Hence, the present surface modification and coating process would be a promising route to obtain new implant materials with bonelike mechanical properties and osteoconductivity. (c) 2007 Wiley Periodicals, Inc.

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.

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.

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.

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.

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).

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.

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.

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

[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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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

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

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.

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.

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.

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.

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

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 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.

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.

­­­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.

Igneous layering in the peralkaline intrusions ,Kola Peninsula :leading role of gravitational differentiation

NASA Astrophysics Data System (ADS)

Kogarko, L. N..

2012-04-01

In the center of Kola Peninsula there are two large layered intrusions of agpaitic nepheline syenites - Khibina and Lovozero. . The Khibina alkaline massif (Kola Peninsula,Russia) hosts the world's largest and economically most important apatite deposit. The Khibina massif is a complex multiphase body built up from a number of ring-like and conical intrusions. The apatite bearing intrusion is ring-like and is represented by a layered body of ijolitic composition with a thickness of about 1 - 2 km. The upper zone is represented by different types of apatite ores. These rocks consist of 60-90% euhedral very small (tenths of mm)apatite crystals. The lower zone has mostly ijolitic composition. The lower zone grades into underlying massive urtite consisting of 75-90% large (several mm) euhedral nepheline. Our experimental studies of systems with apatite demonstrated the near-eutectic nature of the apatite-bearing intrusion, resulting in practically simultaneous crystallization of nepheline, apatite and pyroxene. The mathematical model of the formation of the layered apatite-bearing intrusion based on the processes of sedimentation under the conditions of steady state convection taking account of crystal sizes is proposed. Under the conditions of steady-state convection large crystals of nepheline continuously had been settling forming massive underlying urtite whereas smaller crystals of pyroxenes, nepheline and apatite had been stirred in the convecting melt. During the cooling the intensity of convection decreased causing a settling of smaller crystals of nepheline and pyroxene and later very small crystalls of apatite in the upper part of alkaline magma chamber. The Lovozero massif, the largest of the Globe layered peralkaline intrusion, comprises super-large rare-metal (Nb, Ta, REE) deposit. The main ore mineral is loparite (Na, Ce, Ca)2 (Ti, Nb)2O6 which was mined during many years. The composition of cumulus loparite changed systematically upward through the intrusion with an increase in Na, Sr, Nb, Th, Nb/Ta, U/Th and decrease in REE, Zr, V, Zn, Ba and Ti. Our investigation indicates that the formation of loparite ore was the result of several factors including the chemical evolution of highly alkaline magmatic system and mechanical accumulation of loparite at the base of convecting unit.

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

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.

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.

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.

Calibration for Infrared Measurements of OH in Apatite

NASA Astrophysics Data System (ADS)

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

2010-12-01

Apatite is a common accessory mineral, and OH in apatite can indicate the fluid conditions of crystal formation. Previously, water (OH) concentration in apatite has often been estimated through electron microprobe analyses combined with mineral stoichiometry. However, the detection limit, precision, and accuracy of this method are not high. In this work, we calibrated the infrared spectroscopy (IR) method for measurement of OH concentration in apatite by using elastic recoil detection (ERD) analysis to obtain the absolute OH concentration. Large apatite wafers were cut perpendicular to the c-axis of each crystal and doubly polished. ERD measurements were carried out in the Michigan Ion Beam Laboratory at the University of Michigan to determine the hydrogen concentration in each sample. Each ERD spectrum was fitted and a hydrogen standard was used to quantify the hydrogen concentrations. Polarized transmission IR was used on apatite sections that were cut parallel to the c-axis, and doubly polished. IR measurements were made for E-vector parallel to the c-axis. Because the OH peak is intense, very thin samples must be used to avoid absorbance saturation; the thinnest sample (corresponding to the highest OH content) used was 17 µm thick. Four different apatite crystals were successfully analyzed using both the IR and ERD methods. Two were from Durango, Mexico; one from Imilchil, High Atlas Mountains, Morocco; and one from an unknown locality, purchased online from gem dealers. The OH peak near 3550 cm-1 was a relatively simple peak in all four samples. Therefore peak height was used for the absorbance value, A. Using the Beer-Lambert Law, a calibration line was established (R2= 0.95, for IR aperture of 50 µm x 50 µm) where the weight % of H2O is 0.013 times A/d, where d is the thickness in mm. The detection limit of H2O concentration in apatite by IR approaches ppm level for 0.1 mm wafers, the precision is better than 1% relative (depending on H2O content), and the accuracy based on our calibration is 7% relative (2σ).

An ab-initio study of the energetics and geometry of sulfide, sulfite and sulfate incorporation into apatite: The thermodynamic basis for using this system as an oxybarometer

NASA Astrophysics Data System (ADS)

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

2017-12-01

We use ab-initio calculations to investigate the energetics and geometry of incorporation of S with its oxidation states S6+, S4+, and S2- into the apatite end-members fluor-, chlor-, and hydroxylapatite, [Ca10(PO4)6(F,Cl,OH)2]. The reaction energy of the balanced equation indicates the stability of the modeled S-incorporated apatite relative to the host apatite, the source, and sink phases. One possible coupled substitution mechanism involves the replacement of La3+ + PO43- ↔ Ca2+ + SO42-. Our results show that the incorporation of SO42- into La- and Na-bearing apatite, Ca8NaLa(PO4)6(F,Cl,OH)2, is energetically favored over the incorporation into La- and Si-bearing apatite, Ca9La(PO4)5(SiO4)(F,Cl,OH)2. Co-incorporation of SO42- and SO32- is energetically favored when the lone pair electrons of SO32- face towards the anion column site, compared to facing away from it. Full or partial incorporation of S2- is favored on the column anion site in the form of [Ca10(PO4)6S] and [Ca20(PO4)12SX2)], where X = F, Cl, or OH. Upon full incorporation (i.e., replacing all column ions by sulfide ions), S2- is positioned in the anion column at z = 0.5 (half way between the mirror planes at z = 1/4 and z = 3/4) in the energy-optimized structure. The calculated energies for partial incorporation of S2- demonstrate that in an energy-optimized structure, S2- is displaced from the mirror plane at z = 1/4 or 3/4, by 1.0 to 1.6 Å, depending on the surrounding species (F-, Cl- or OH-); however, the probability for S2- to be incorporated into the apatite structure is highest for chlorapatite end-members. Our results describe energetically feasible incorporation mechanisms for all three oxidations states of S (S6+, S4+, S2-) in apatite, along with structural distortion and concurring electronic structure changes. These observations are consistent with recently published experimental results (Konecke et al. 2017) that demonstrate S6+, S4+ and S2- incorporation into apatite, where the ratio of S6+/∑S in apatite is controlled by oxygen fugacity (fO2). The new computational results coupled with published experimental data provide the basis for using S in apatite as a geochemical proxy to trace variations in oxygen fugacity of magmatic and magmatic-hydrothermal systems.

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.

Framework 'interstitial' oxygen in La(10)(GeO(4))(5-)(GeO(5))O(2) apatite electrolyte.

PubMed

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

2007-08-01

Oxygen conduction at low temperatures in apatites make these materials potentially useful as electrolytes in solid-oxide fuel cells, but our understanding of the defect structures enabling ion migration is incomplete. While conduction along [001] channels is dominant, considerable inter-tunnel mobility has been recognized. Using neutron powder diffraction of stoichiometric 'La(10)(GeO(4))(6)O(3)', it has been shown that this compound is more correctly described as an La(10)(GeO(4))(5-)(GeO(5))O(2) apatite, in which high concentrations of interstitial oxygen reside within the channel walls. It is suggested that these framework interstitial O atoms provide a reservoir of ions that can migrate into the conducting channels of apatite, via a mechanism of inter-tunnel oxygen diffusion that transiently converts GeO(4) tetrahedra to GeO(5) distorted trigonal bipyramids. This structural modification is consistent with known crystal chemistry and may occur generally in oxide apatites.

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

PubMed Central

Dorozhkin, Sergey V

2012-01-01

Eight dissolution models of calcium apatites (both fluorapatite and hydroxyapatite) in acids were drawn from the published literature, analyzed and discussed. Major limitations and drawbacks of the models were conversed in details. The models were shown to deal with different aspects of apatite dissolution phenomenon and none of them was able to describe the dissolution process in general. Therefore, an attempt to combine the findings obtained by different researchers was performed which resulted in creation of the general description of apatite dissolution in acids. For this purpose, eight dissolution models were assumed to complement each other and provide the correct description of the specific aspects of apatite dissolution. The general description considers all possible dissolution stages involved and points out to some missing and unclear phenomena to be experimentally studied and verified in future. This creates a new methodological approach to investigate reaction mechanisms based on sets of affine data, obtained by various research groups under dissimilar experimental conditions. PMID:25237611

[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.

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

PubMed

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

2012-01-01

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

Active synthetic soil

NASA Technical Reports Server (NTRS)

Ming, Douglas W. (Inventor); Henninger, Donald L. (Inventor); Allen, Earl R. (Inventor); Golden, Dadigamuwage C. (Inventor)

1995-01-01

A synthetic soil/fertilizer for horticultural application having all the agronutrients essential for plant growth is disclosed. The soil comprises a synthetic apatite fertilizer having sulfur, magnesium, and micronutrients dispersed in a calcium phosphate matrix, a zeolite cation exchange medium saturated with a charge of potassium and nitrogen cations, and an optional pH buffer. Moisture dissolves the apatite and mobilizes the nutrient elements from the apatite matrix and the zeolite charge sites.

Active synthetic soil

NASA Technical Reports Server (NTRS)

Ming, Douglas W. (Inventor); Henninger, Donald L. (Inventor); Golden, Dadigamuwage C. (Inventor); Allen, Earl R. (Inventor)

1995-01-01

A synthetic soil/fertilizer for horticultural application having all the agronutrients essential for plant growth is disclosed. The soil comprises a synthetic apatite fertilizer having sulfur, magnesium and micronutrients dispersed in a calcium phosphate matrix, a zeolite cation exchange medium saturated with a charge of potassium and nitrogen cations, and an optional pH buffer. Moisture dissolves the apatite and mobilizes the nutrient elements from the apatite matrix and the zeolite charge sites.

Sr-90 Immobilization by Infiltration of a Ca-Citrate-PO{sub 4} Solution into the Hanford 100-N Area Vadose Zone

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

Szecsody, J.E.; Fruchter, J.S.; Burns, C.A.

This project was initiated to develop a strategy for infiltration of a Ca-citrate-PO{sub 4} solution in order to precipitate apatite [Ca{sub 6}(PO{sub 4}){sub 10}(OH){sub 2}] in desired locations in the vadose zone for Sr-90 remediation. Laboratory experiments have demonstrated that infiltration of a Ca-citrate-PO{sub 4} 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 substitutionmore » into apatite was shown to have an incorporation half-life of 5.5 to 16 months. One and two dimensional (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. (authors)« less

Prospects for Practical Laser Ablation U/Pb and (U-Th)/He Double-Dating (LADD) of Detrital Apatite

NASA Astrophysics Data System (ADS)

Horne, A.; Hodges, K. V.; Van Soest, M. C.

2017-12-01

A laser ablation micro-analytical technique for (U-Th)/He dating has been shown to be an effective approach to the thermochronologic study of detrital zircons (Tripathy-Lang et al., J. Geophys. Res., 2013), while Evans et al. (J. Anal. At. Spectrom., 2015) and Horne et al. (Geochim. Cosmochim. Acta, 2016) demonstrated how the technique could be modified to enable laser ablation U/Pb and (U-Th)/He double-dating (LADD) of detrital zircon and titanite. These successes beg the question of whether or not LADD is viable for another commonly encountered detrital mineral: apatite. Exploratory LADD studies in Arizona State University's Group 18 Laboratories - using Durango fluorapatite, apatite from the Fish Canyon tuff, and detrital apatite from modern fluvial sediments in the eastern Sierra Nevada of California - illustrate that the method is indeed viable for detrital apatite. However, the method may not be appropriate for all detrital samples. For example, many apatite grains encountered in detrital samples from young orogenic settings have low concentrations of U and Th and small crystal sizes. This can lead to imprecise laser ablation (U-Th)/He dates, especially for very young grains potentially obscuring or inhibiting relevant interpretations of the data set.

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.

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

USGS Publications Warehouse

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

1993-01-01

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

Stone formation and calcification by nanobacteria in the human body

NASA Astrophysics Data System (ADS)

Ciftcioglu, Neva; Bjorklund, Michael; Kajander, E. Olavi

1998-07-01

The formation of discrete and organized inorganic crystalline structures within macromolecular extracellular matrices is a widespread biological phenomenon generally referred to as biomineralization. Recently, bacteria have been implicated as factors in biogeochemical cycles for formation of many minerals in aqueous sediments. We have found nanobacterial culture systems that allow for reproducible production of apatite calcification in vitro. Depending on the culture conditions, tiny nanocolloid-sized particles covered with apatite, forming various size of aggregates and stones were observed. In this study, we detected the presence of nanobacteria in demineralized trilobit fossil, geode, apatite, and calcite stones by immunofluorescence staining. Amethyst and other quartz stones, and chalk gave negative results. Microorganisms are capable of depositing apatite outside the thermodynamic equilibrium in sea water. We bring now evidence that this occurs in the human body as well. Previously, only struvite kidney stones composed of magnesium ammonium phosphate and small amounts of apatite have been regarded as bacteria related. 90 percent of demineralized human kidney stones now screened, contained nanobacteria. At least three different distribution patterns of nanobacteria were conditions, and human kidney stones that are formed from small apatite units. Prerequisites for the formation of kidney stones are the supersaturation of urine and presence of nidi for crystallization. Nanobacteria are important nidi and their presence might be of special interest in space flights where supersaturation of urine is present due to the loss of bone. Furthermore, we bring evidence that nanobacteria may act as crystallization nidi for the formation of biogenic apatite structures in tissue calcification found in e.g., atherosclerotic plaques, extensive metastatic and tumoral calcification, acute periarthritis, malacoplakia, and malignant diseases. In nanaobacteria-infected fibroblasts, electron microscopy revealed intra- and extra-cellular needle-like crystal deposits, which were stainable with von Kossa stain and resemble calcospherules found in pathological calcification. Thus bacteria-mediated apatite formation takes place in aqueous environments, in humans and in geological sediments.

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

PubMed

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

2012-09-01

Ectomycorrhizal (EcM) fungi are increasingly recognized as important agents of mineral weathering and soil development, with far-reaching impacts on biogeochemical cycles. Because EcM fungi live in a symbiotic relationship with trees and in close contact with bacteria and archaea, it is difficult to distinguish between the weathering effects of the fungus, host tree and other micro-organisms. Here, we quantified mineral weathering by the fungus Paxillus involutus, growing in symbiosis with Pinus sylvestris under sterile conditions. The mycorrhizal trees were grown in specially designed sterile microcosms in which the supply of soluble phosphorus (P) in the bulk media was varied and grains of the calcium phosphate mineral apatite mixed with quartz, or quartz alone, were provided in plastic wells that were only accessed by their fungal partner. Under P limitation, pulse labelling of plants with (14)CO(2) revealed plant-to-fungus allocation of photosynthates, with 17 times more (14)C transferred into the apatite wells compared with wells with only quartz. Fungal colonization increased the release of P from apatite by almost a factor of three, from 7.5 (±1.1) × 10(-10) mol m(-2) s(-1) to 2.2 (±0.52) × 10(-9) mol m(-2) s(-1). On increasing the P supply in the microcosms from no added P, through apatite alone, to both apatite and orthophosphate, the proportion of biomass in roots progressively increased at the expense of the fungus. These three observations, (i) proportionately more plant energy investment in the fungal partner under P limitation, (ii) preferential fungal transport of photosynthate-derived carbon towards patches of apatite grains and (iii) fungal enhancement of weathering rate, reveal the tightly coupled plant-fungal interactions underpinning enhanced EcM weathering of apatite and its utilization as P source. © 2012 Blackwell Publishing Ltd.

LA-ICP-MS depth profile analysis of apatite: Protocol and implications for (U-Th)/He thermochronometry

NASA Astrophysics Data System (ADS)

Johnstone, Samuel; Hourigan, Jeremy; Gallagher, Christopher

2013-05-01

Heterogeneous concentrations of α-producing nuclides in apatite have been recognized through a variety of methods. The presence of zonation in apatite complicates both traditional α-ejection corrections and diffusive models, both of which operate under the assumption of homogeneous concentrations. In this work we develop a method for measuring radial concentration profiles of 238U and 232Th in apatite by laser ablation ICP-MS depth profiling. We then focus on one application of this method, removing bias introduced by applying inappropriate α-ejection corrections. Formal treatment of laser ablation ICP-MS depth profile calibration for apatite includes construction and calibration of matrix-matched standards and quantification of rates of elemental fractionation. From this we conclude that matrix-matched standards provide more robust monitors of fractionation rate and concentrations than doped silicate glass standards. We apply laser ablation ICP-MS depth profiling to apatites from three unknown populations and small, intact crystals of Durango fluorapatite. Accurate and reproducible Durango apatite dates suggest that prolonged exposure to laser drilling does not impact cooling ages. Intracrystalline concentrations vary by at least a factor of 2 in the majority of the samples analyzed, but concentration variation only exceeds 5x in 5 grains and 10x in 1 out of the 63 grains analyzed. Modeling of synthetic concentration profiles suggests that for concentration variations of 2x and 10x individual homogeneous versus zonation dependent α-ejection corrections could lead to age bias of >5% and >20%, respectively. However, models based on measured concentration profiles only generated biases exceeding 5% in 13 of the 63 cases modeled. Application of zonation dependent α-ejection corrections did not significantly reduce the age dispersion present in any of the populations studied. This suggests that factors beyond homogeneous α-ejection corrections are the dominant source of overdispersion in apatite (U-Th)/He cooling ages.

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.

He, U, and Th Depth Profiling of Apatite and Zircon Using Laser Ablation Noble Gas Mass Spectrometry and SIMS

NASA Astrophysics Data System (ADS)

Monteleone, B. D.; van Soest, M. C.; Hodges, K. V.; Hervig, R.; Boyce, J. W.

2008-12-01

Conventional (U-Th)/He thermochronology utilizes single or multiple grain analyses of U- and Th-bearing minerals such as apatite and zircon and does not allow for assessment of spatial variation in concentration of He, U, or Th within individual crystals. As such, age calculation and interpretation require assumptions regarding 4He loss through alpha ejection, diffusive redistribution of 4He, and U and Th distribution as an initial condition for these processes. Although models have been developed to predict 4He diffusion parameters, correct for the effect of alpha ejection on calculated cooling ages, and account for the effect of U and Th zonation within apatite and zircon, measurements of 4He, U, and Th distribution have not been combined within a single crystal. We apply ArF excimer laser ablation, combined with noble gas mass spectrometry, to obtain depth profiles within apatite and zircon crystals in order to assess variations in 4He concentration with depth. Our initial results from pre-cut, pre-heated slabs of Durango apatite, each subjected to different T-t schedules, suggest a general agreement of 4He profiles with those predicted by theoretical diffusion models (Farley, 2000). Depth profiles through unpolished grains give reproducible alpha ejection profiles in Durango apatite that deviate from alpha ejection profiles predicted for ideal, homogenous crystals. SIMS depth profiling utilizes an O2 primary beam capable of sputtering tens of microns and measuring sub-micron resolution variation in [U], [Th], and [Sm]. Preliminary results suggest that sufficient [U] and [Th] zonation is present in Durango apatite to influence the form of the 4He alpha ejection profile. Future work will assess the influence of measured [U] and [Th] zonation on previously measured 4He depth profiles. Farley, K.A., 2000. Helium diffusion from apatite; general behavior as illustrated by Durango fluorapatite. J. Geophys. Res., B Solid Earth Planets 105 (2), 2903-2914.

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.

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.

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

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

Fix, N. J.

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

Laser depth profiling of diffusion and alpha ejection profiles in Durango apatite: testing the fundamental parameters of apatite (U-Th)/He dating

NASA Astrophysics Data System (ADS)

van Soest, M. C.; Monteleone, B. D.; Boyce, J. W.; Hodges, K.

2009-12-01

Since its development (e.g. Zeitler et al., 1987, Lippolt et al., 1994, Farley et al., 1996, Wolf et al., 1996) as a viable low temperature thermochronological method (U-Th)/He dating of apatite has become a popular and widely applied low temperature thermochronometer. The method has been applied with success to a great variety of geological problems, and the fundamental parameters of the method: the bulk diffusion parameters of helium in apatite, and the calculated theoretical helium stopping distance in apatite used to correct the ages for the effects of alpha ejection appear sound. However, the development of the UV laser microprobe technique for the (U-Th)/He method (Boyce et al., 2006) allows for in-situ testing of the helium bulk diffusion parameters (Farley, 2000) and can provide a direct measurement of the alpha ejection distance in apatite. So, with the ultimate goal of further developing the in-situ (U-Th)/He dating method and micro-analytical depth profiling techniques to constrain cooling histories in natural grains, we conducted a helium depth profiling study of induced diffusion and natural alpha ejection profiles in Durango apatite. For the diffusion depth profiling, a Durango crystal was cut in slabs oriented parallel and perpendicular to the crystal c-axis. The slabs were polished and heated using different temperature and time schedules to induce predictable diffusion profiles based on the bulk helium diffusion parameters in apatite. Depth profiling of the 4He diffusion profiles was done using an ArF excimer laser. The measured diffusion depth profiles at 350°, 400°, and 450° C coincide well with the predicted bulk diffusion curves, independent of slab orientation, but the 300° C profiles consistently deviate significantly. The possible cause for this deviation is currently being investigated. Alpha ejection profiling was carried out on crystal margins from two different Durango apatite crystals, several faces from each crystal were analyzed to evaluate the potential effects of crystallographic orientation on alpha ejection. The results from both crystals were very reproducible irrespective of crystal surface used and confirm the findings of Monteleone et al. (2008) that the measured alpha ejection profiles deviate significantly from and are shorter than the calculated theoretical average value. Efforts are currently underway to better constrain the measured alpha ejection distance and measure alpha ejection profiles in apatite crystals other than Durango apatite. References: Boyce, J. et al. (2006) GCA 70, pp. 3031-3039. Farley, K. et al. (1996) GCA 60, pp. 4223-4229. Farley, K. (2006) JGR SE 105, p. 2903-2914. Lippolt, H. et al. (1994) Chem Geol 112, pp. 179-191. Monteleone, B. et al. (2008) Eos Trans AGU, 89 Fall Meeting V53B-2162. Wolf, R. et al. (1996) GCA 60, pp. 4231-4240. Zeitler, P. et al. (1987) GCA 51, pp. 2865-2868.

The thermal history of the Miocene Ibar Basin (Southern Serbia): new constraints from apatite and zircon fission track and vitrinite reflectance data

NASA Astrophysics Data System (ADS)

Andrić, Nevena; Fügenschuh, Bernhard; Životić, Dragana; Cvetković, Vladica

2015-02-01

The Ibar Basin was formed during Miocene large scale extension in the NE Dinaride segment of the Alpine- Carpathian-Dinaride system. The Miocene extension led to exhumation of deep seated core-complexes (e.g. Studenica and Kopaonik core-complex) as well as to the formation of extensional basins in the hanging wall (Ibar Basin). Sediments of the Ibar Basin were studied by apatite and zircon fission track and vitrinite reflectance in order to define thermal events during basin evolution. Vitrinite reflectance (VR) data (0.63-0.90 %Rr) indicate a bituminous stage for the organic matter that experienced maximal temperatures of around 120-130 °C. Zircon fission track (ZFT) ages indicate provenance ages. The apatite fission track (AFT) single grain ages (45-6.7 Ma) and bimodal track lengths distribution indicate partial annealing of the detrital apatites. Both vitrinite reflectance and apatite fission track data of the studied sediments imply post-depositional thermal overprint in the Ibar Basin. Thermal history models of the detritial apatites reveal a heating episode prior to cooling that began at around 10 Ma. The heating episode started around 17 Ma and lasted 10-8 Ma reaching the maximum temperatures between 100-130 °C. We correlate this event with the domal uplift of the Studenica and Kopaonik cores where heat was transferred from the rising warm footwall to the adjacent colder hanging wall. The cooling episode is related to basin inversion and erosion. The apatite fission track data indicate local thermal perturbations, detected in the SE part of the Ibar basin (Piskanja deposit) with the time frame ~7.1 Ma, which may correspond to the youngest volcanic phase in the region.

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

Carbonate substitution in the mineral component of bone: Discriminating the structural changes, simultaneously imposed by carbonate in A and B sites of apatite

NASA Astrophysics Data System (ADS)

Madupalli, Honey; Pavan, Barbara; Tecklenburg, Mary M. J.

2017-11-01

The mineral component of bone and other biological calcifications is primarily a carbonate substituted calcium apatite. Integration of carbonate into two sites, substitution for phosphate (B-type carbonate) and substitution for hydroxide (A-type carbonate), influences the crystal properties which relate to the functional properties of bone. In the present work, a series of AB-type carbonated apatites (AB-CAp) having varying A-type and B-type carbonate weight fractions were prepared and analyzed by Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), and carbonate analysis. A detailed characterization of A-site and B-site carbonate assignment in the FTIR ν3 region is proposed. The mass fractions of carbonate in A-site and B-site of AB-CAp correlate differently with crystal axis length and crystallite domain size. In this series of samples reduction in crystal domain size correlates only with A-type carbonate which indicates that carbonate in the A-site is more disruptive to the apatite structure than carbonate in the B-site. High temperature methods were required to produce significant A-type carbonation of apatite, indicating a higher energy barrier for the formation of A-type carbonate than for B-type carbonate. This is consistent with the dominance of B-type carbonate substitution in low temperature synthetic and biological apatites.

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.

Microbial Mineral Weathering for Nutrient Acquisition Releases Arsenic

NASA Astrophysics Data System (ADS)

Mailloux, B. J.; Alexandrova, E.; Keimowitz, A.; Wovkulich, K.; Freyer, G.; Stolz, J.; Kenna, T.; Pichler, T.; Polizzotto, M.; Dong, H.; Radloff, K. A.; van Geen, A.

2008-12-01

Tens of millions of people in Southeast Asia drink groundwater contaminated with naturally occurring arsenic. The process of arsenic release from the sediment to the groundwater remains poorly understood. Experiments were performed to determine if microbial mineral weathering for nutrient acquisition can serve as a potential mechanism for arsenic mobilization. We performed microcosm experiments with Burkholderia fungorum, phosphate free artificial groundwater, and natural apatite. Controls included incubations with no cells and with killed cells. Additionally, samples were treated with two spikes - an arsenic spike, to show that arsenic release is independent of the initial arsenic concentration, and a phosphate spike to determine whether release occurs at field relevant phosphate conditions. We show in laboratory experiments that phosphate-limited cells of Burkholderia fungorum mobilize ancillary arsenic from apatite as a by-product of mineral weathering for nutrient acquisition. The released arsenic does not undergo a redox transformation but appears to be solubilized from the apatite mineral lattice as arsenate during weathering. Apatite has been shown to be commonly present in sediment samples from Bangladesh aquifers. Analysis of apatite purified from the Ganges, Brahamputra, Meghna drainage basin shows 210 mg/kg of arsenic, which is higher than the average crustal level. Finally, we demonstrate the presence of the microbial phenotype that releases arsenic from apatite in Bangladesh sediments. These results suggest that microbial weathering for nutrient acquisition could be an important mechanism for arsenic mobilization.

Bioactive bredigite coating with improved bonding strength, rapid apatite mineralization and excellent cytocompatibility.

PubMed

Yi, Deliang; Wu, Chengtie; Ma, Bing; Ji, Heng; Zheng, Xuebin; Chang, Jiang

2014-05-01

Previous studies have shown that bredigite (Ca7MgSi4O16) bioceramics possessed excellent biocompatibility, apatite-mineralization ability and mechanical properties. In this paper, the bredigite coating on Ti-6Al-4 V substrate was prepared by plasma spraying technique. The main compositions of the coating were bredigite crystal phase with small parts of amorphous phases. The bonding strength of the coating to Ti-6Al-4 V substrate reached 49.8 MPa, which was significantly higher than that of hydroxyapatite coating and other silicate-based bioceramic coatings prepared by same method. After immersed in simulated body fluid for 2 days, a distinct apatite layer was deposited on the surface of bredigite coating, indicating that the prepared bredigite coating has excellent apatite-mineralization ability. The prepared bredigite coating supported the attachment and proliferation of rabbit bone marrow stem cells. The proliferation level of bone marrow stem cells was significantly higher than that on the hydroxyapatite coating. Our further study showed that the released SiO4 (4-) and Mg(2+) ions from bredigite coating as well as the formed nano-apatite layer on the coating surface might mainly contribute to the improvement of cell proliferation. The results indicated that the bredigite coating may be applied on orthopedic implants due to its excellent bonding strength, apatite mineralization and cytocompatibility.

Effect of white mineral trioxide aggregate compared with biomimetic carbonated apatite on dentine bridge formation and inflammatory response in a dental pulp model.

PubMed

Danesh, F; Vahid, A; Jahanbani, J; Mashhadiabbas, F; Arman, E

2012-01-01

  To evaluate the effects of apatite precipitation on the biocompatibility and hard tissue induction properties of white mineral trioxide aggregate (WMTA) in a dental pulp model.   Pulp exposures were created on the axial walls of 32 sound canine teeth of eight dogs. Four additional sound teeth served as controls. The pulps were capped either with WMTA or apatite derivatives [biomimetic carbonated apatite (BCAp)] in the interaction of WMTA with a synthetic tissue fluid and restored with zinc oxide-eugenol cement. After 7 and 70 days, the animals were killed, and the histological specimens taken from the teeth were stained with haematoxylin and eosin for histomorphological evaluation. The Brown and Brenn technique was employed to stain bacteria. The data were subjected to nonparametric Kruskall-Wallis analysis and Mann-Whitney U_tests.   Biomimetic carbonated apatite did not induce hard tissue bridge formation. WMTA performed significantly better than BCAp in this respect at both periods (P < 0.05). BCAp was associated with a significantly greater inflammatory response as compared with WMTA after 7 days (P < 0.05). Both materials were associated with similar reactions after 70 days (P >0.05).   White mineral trioxide aggregate induced hard tissue formation via a mechanism other than that postulated via apatite formation. © 2011 International Endodontic Journal.

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

PubMed

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

2012-02-14

Nanocrystalline calcium phosphate apatites constitute the mineral part of hard tissues, and the synthesis of biomimetic analogs is now well-mastered at the lab-scale. Recent advances in the fine physico-chemical characterization of these phases enable one to envision original applications in the medical field along with a better understanding of the underlying chemistry and related pharmacological features. In this contribution, we specifically focused on applications of biomimetic apatites in the field of cancer diagnosis or treatment. We first report on the production and first biological evaluations (cytotoxicity, pro-inflammatory potential, internalization by ZR-75-1 breast cancer cells) of individualized luminescent nanoparticles based on Eu-doped apatites, eventually associated with folic acid, for medical imaging purposes. We then detail, in a first approach, the preparation of tridimensional constructs associating nanocrystalline apatite aqueous gels and drug-loaded pectin microspheres. Sustained releases of a fluorescein analog (erythrosin) used as model molecule were obtained over 7 days, in comparison with the ceramic or microsphere reference compounds. Such systems could constitute original bone-filling materials for in situ delivery of anticancer drugs. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

Formation of an ascorbate-apatite composite layer on titanium.

PubMed

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

2007-09-01

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

The influence of artificial radiation damage and thermal annealing on helium diffusion kinetics in apatite

NASA Astrophysics Data System (ADS)

Shuster, David L.; Farley, Kenneth A.

2009-01-01

Recent work [Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249(3-4), 148-161] revealing a correlation between radiogenic 4He concentration and He diffusivity in natural apatites suggests that helium migration is retarded by radiation-induced damage to the crystal structure. If so, the He diffusion kinetics of an apatite is an evolving function of time and the effective uranium concentration in a cooling sample, a fact which must be considered when interpreting apatite (U-Th)/He ages. Here we report the results of experiments designed to investigate and quantify this phenomenon by determining He diffusivities in apatites after systematically adding or removing radiation damage. Radiation damage was added to a suite of synthetic and natural apatites by exposure to between 1 and 100 h of neutron irradiation in a nuclear reactor. The samples were then irradiated with a 220 MeV proton beam and the resulting spallogenic 3He used as a diffusant in step-heating diffusion experiments. In every sample, irradiation increased the activation energy ( E a) and the frequency factor ( D o/ a2) of diffusion and yielded a higher He closure temperature ( T c) than the starting material. For example, 100 h in the reactor caused the He closure temperature to increase by as much as 36 °C. For a given neutron fluence the magnitude of increase in closure temperature scales negatively with the initial closure temperature. This is consistent with a logarithmic response in which the neutron damage is additive to the initial damage present. In detail, the irradiations introduce correlated increases in E a and ln( D o/a 2) that lie on the same array as found in natural apatites. This strongly suggests that neutron-induced damage mimics the damage produced by U and Th decay in natural apatites. To investigate the potential consequences of annealing of radiation damage, samples of Durango apatite were heated in vacuum to temperatures up to 550 °C for between 1 and 350 h. After this treatment the samples were step-heated using the remaining natural 4He as the diffusant. At temperatures above 290 °C a systematic change in T c was observed, with values becoming lower with increasing temperature and time. For example, reduction of T c from the starting value of 71 to ˜52 °C occurred in 1 h at 375 °C or 10 h at 330 °C. The observed variations in T c are strongly correlated with the fission track length reduction predicted from the initial holding time and temperature. Furthermore, like the neutron irradiated apatites, these samples plot on the same E a - ln( D o/ a2) array as natural samples, suggesting that damage annealing is simply undoing the consequences of damage accumulation in terms of He diffusivity. Taken together these data provide unequivocal evidence that at these levels, radiation damage acts to retard He diffusion in apatite, and that thermal annealing reverses the process. The data provide support for the previously described radiation damage trapping kinetic model of Shuster et al. (2006) and can be used to define a model which fully accommodates damage production and annealing.

Apatite (U-Th)/He thermochronometry using a radiation damage accumulation and annealing model

NASA Astrophysics Data System (ADS)

Flowers, Rebecca M.; Ketcham, Richard A.; Shuster, David L.; Farley, Kenneth A.

2009-04-01

Helium diffusion from apatite is a sensitive function of the volume fraction of radiation damage to the crystal, a quantity that varies over the lifetime of the apatite. Using recently published laboratory data we develop and investigate a new kinetic model, the radiation damage accumulation and annealing model (RDAAM), that adopts the effective fission-track density as a proxy for accumulated radiation damage. This proxy incorporates creation of crystal damage proportional to α-production from U and Th decay, and the elimination of that damage governed by the kinetics of fission-track annealing. The RDAAM is a version of the helium trapping model (HeTM; Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249, 148-161), calibrated by helium diffusion data in natural and partially annealed apatites. The chief limitation of the HeTM, now addressed by RDAAM, is its use of He concentration as the radiation damage proxy for circumstances in which radiation damage and He are not accumulated and lost proportionately from the crystal. By incorporating the RDAAM into the HeFTy computer program, we explore its implications for apatite (U-Th)/He thermochronometry. We show how (U-Th)/He dates predicted from the model are sensitive to both effective U concentration (eU) and details of the temperature history. The RDAAM predicts an effective He closure temperature of 62 °C for a 28 ppm eU apatite of 60 μm radius that experienced a 10 °C/Ma monotonic cooling rate; this is 8 °C lower than the 70 °C effective closure temperature predicted using commonly assumed Durango diffusion kinetics. Use of the RDAAM is most important for accurate interpretation of (U-Th)/He data for apatite suites that experienced moderate to slow monotonic cooling (1-0.1 °C/Ma), prolonged residence in the helium partial retention zone, or a duration at temperatures appropriate for radiation damage accumulation followed by reheating and partial helium loss. Under common circumstances the RDAAM predicts (U-Th)/He dates that are older, sometimes much older, than corresponding fission-track dates. Nonlinear positive correlations between apatite (U-Th)/He date and eU in apatites subjected to the same temperature history are a diagnostic signature of the RDAAM for many but not all thermal histories. Observed date-eU correlations in four different localities can be explained with the RDAAM using geologically reasonable thermal histories consistent with independent fission-track datasets. The existence of date-eU correlations not only supports a radiation damage based kinetic model, but can significantly limit the range of acceptable time-temperature paths that account for the data. In contrast, these datasets are inexplicable using the Durango diffusion model. The RDAAM helps reconcile enigmatic data in which apatite (U-Th)/He dates are older than expected using the Durango model when compared with thermal histories based on apatite fission-track data or other geological constraints. It also has the potential to explain at least some cases in which (U-Th)/He dates are actually older than the corresponding fission-track dates.

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.

Crystal growth of carbonate apatite using a CaCO3 flux.

PubMed

Suetsugu, Y; Tanaka, J

1999-09-01

Single crystals of carbonate apatite were grown using a CaCO3 flux under an Ar gas pressure of 55 MPa. The crystals obtained were observed by scanning electron microscopy, optical microscopy and X-ray diffraction. Electron probe microanalyses and thermal analyses were performed. CO3 ions in planar triangle form replaced both OH sites and PO4 tetrahedral sites in the apatite structure: in particular, the OH sites were perfectly substituted by CO3 ions using this method.

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.

Modeling and Measuring 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.

2016-12-01

Understanding helium diffusion kinetics in apatite is critical for the accurate interpretation of (U-Th)/He thermochronometric data. This problem is complicated by the observation that helium diffusivity is not a simple function of temperature, but may evolve as a function of damage to the apatite crystal lattice resulting from alpha recoil. This `radiation damage' increases as a function of the amount of radiometric parent products, or effective uranium concentration, and time, but decreases due to thermal annealing of damage, necessitating a detailed understanding of radiation damage production and annealing in cases of burial heating over geologic timescales. Published observations [1,2] suggest that annealing rates of damage caused by alpha recoil and fission tracks in apatite differ. Existing models, however, assume the diffusion kinetics resulting from the two sources of damage are identical [3], demonstrating the need for further investigation of these damage sources. We present modeling and experimental work designed to interrogate the effects of radiation damage and its annealing on helium diffusion kinetics in apatite. Using previously published results [4] that investigated the effects of annealing temperature and duration on measured helium diffusivity, we fit a set of functions that are then integrated into a numerical model that tracks the evolution of radiation damage and apparent (U-Th)/He age. We compare the results of this model calibration to existing models [3]. In addition, we present data from two suites of diffusion experiments. The first suite, intended to test the published methodology and results, uses Durango apatite, while the second uses Sierran (CA) granite as a first test to determine if apatite of varying chemistry and age responds differently to the thermal annealing of radiation damage. Ultimately, the updated model and experimental results will benefit the interpretation of the effects of radiation damage accumulation and annealing in apatite and expand the range of geologic settings that can be studied using low-temperature thermochronology. References: [1] Fox, M., Shuster, D. (2014), EPSL 397, 174-183; [2] Gautheron, C. et al. (2013), Chem. Geol. 351, 257-267; [3] Flowers, R. et al. (2009), GCA 73, 2347-2365; [4] Shuster, D., Farley, K. (2009), GCA 73, 6183-6196.

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.

Amphibole and apatite insights into the evolution and mass balance of Cl and S in magmas associated with porphyry copper deposits

NASA Astrophysics Data System (ADS)

Chelle-Michou, Cyril; Chiaradia, Massimo

2017-12-01

Chlorine and sulfur are of paramount importance for supporting the transport and deposition of ore metals at magmatic-hydrothermal systems such as the Coroccohuayco Fe-Cu-Au porphyry-skarn deposit, Peru. Here, we used recent partitioning models to determine the Cl and S concentration of the melts from the Coroccohuayco magmatic suite using apatite and amphibole chemical analyses. The pre-mineralization gabbrodiorite complex hosts S-poor apatite, while the syn- and post-ore dacitic porphyries host S-rich apatite. Our apatite data on the Coroccohuayco magmatic suite are consistent with an increasing oxygen fugacity (from the gabbrodiorite complex to the porphyries) causing the dominant sulfur species to shift from S2- to S6+ at upper crustal pressure where the magmas were emplaced. We suggest that this change in sulfur speciation could have favored S degassing, rather than its sequestration in magmatic sulfides. Using available partitioning models for apatite from the porphyries, pre-degassing S melt concentration was 20-200 ppm. Estimates of absolute magmatic Cl concentrations using amphibole and apatite gave highly contrasting results. Cl melt concentrations obtained from apatite (0.60 wt% for the gabbrodiorite complex; 0.2-0.3 wt% for the porphyries) seems much more reasonable than those obtained from amphibole which are very low (0.37 wt% for the gabbrodiorite complex; 0.10 wt% for the porphyries). In turn, relative variations of the Cl melt concentrations obtained from amphibole during magma cooling are compatible with previous petrological constraints on the Coroccohuayco magmatic suite. This confirms that the gabbrodioritic magma was initially fluid undersaturated upon emplacement, and that magmatic fluid exsolution of the gabbrodiorite and the pluton rooting the porphyry stocks and dikes were emplaced and degassed at 100-200 MPa. Finally, mass balance constraints on S, Cu and Cl were used to estimate the minimum volume of magma required to form the Coroccohuayco deposit. These three estimates are remarkably consistent among each other (ca. 100 km3) and suggest that the Cl melt concentration is at least as critical as that of Cu and S to form an economic mineralization.

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.

Can Polyphosphate Biochemistry Affect Biological Apatite Saturation?

NASA Astrophysics Data System (ADS)

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

2010-12-01

Phosphorus (P) is an important and limiting element for life. One strategy for storing ortho phosphates (Pi) is polymerization. Polymerized Pi's (polyphosphates: (PO3-)n: polyPs) serve as a Pi bank, as well as a catiion chelator, energy source, & regulator of responses to stresses in the stationary phase of culture growth and development1. PolyP biochemistry has been investigated in yeasts, bacteria & plants2. Bigeochemical cycling of P includes the condensation of Pi into pyro (P2O7-4), & polyPs, & the release of Pi from these compounds by the hydrolytic degradation of Pi from phosphomonoester bonds. Alkaline phosphatase (ALP) is one of the predominate enzymes for regenerating Pi in aquatic systems3, & it cleaves Pi from polyPs. ALP is also the enzyme associated with apatite biomineralization in vertebrates4. PolyP was proposed to be the ALP substrate in bone mineralization5. Where calcium ions are plentiful in many aquatic environments, there is no requirement for aquatic life to generate Ca-stores. However, terrestrial vertebrates benefit from a bioavailable Ca-store such as apatite. The Pi storage strategy of polymerizing PO4-3 into polyPs dovetails well with Ca-banking, as polyPs sequester Ca, forming a neutral calcium polyphosphate (Ca-polyP: (Ca(PO3)2)n) complex. This neutral complex represents a high total [Ca+2] & [PO4-3], without the threat of inadvertent apatite precipitation, as the free [Ca+2] & [PO4-3], and therefore apatite saturation, are zero. Recent identification of polyP in regions of bone resorption & calcifying cartilage5 suggests that vertebrates may use polyP chemistry to bank Ca+2 and PO4-3. In vitro experiments with nanoparticulate Ca-polyP & ALP were undertaken to determine if carbonated apatite could precipitate from 1M Ca-polyP in Pi-free “physiological fluid” (0.1 M NaCl, 2 mM Ca+2, 0.8 mM Mg+2, pH ~8.0 ±0.5, 37 °C), as this is estimated to generate the [Ca+2] & [PO4-3] required to form the apatite content of bone tissue (estimated to be 1 g apatite/mL). Carbonates (as NaHCO3 or CaCO3) were used to buffer the protons produced upon polyP hydrolytic degradation to Pi, releasing Ca+2, increasing apatite saturation for precipitation. Initial Ca:P ratios (by EDS) was <1, indicative of Ca-polyP. After incubation, Ca:P ratios were >1, suggesting the formation of Ca-PO4 minerals. XRD results identified Na-Ca- carbonate phases, & hydroxyapatite & carbonated apatite, & residual carbonate reagent. Further optimization of this biological apatite precipitation system will be presented. 1 Kornberg, A., Ann Rev Biochem 1999 (68) 89 2 Kulaev IS, Vagabov VM, Kulakovskaya TV (2004) The Biochemistry of Inorganic Polyphosphates. Chichester, England, John Wiley & Sons, Ltd. 3 Blake, R. E., O’Neil, J.R., and Surov, A. Am J Sci 2005 (305) 596 4 Heersche, J. N. M. et al. (1990) Bone Regulatory Factors; Plenum Press: New York 5 Omelon et al., PLoS ONE 2009 4(5), e5634

Genesis of rare-metal pegmatites and alkaline apatite-fluorite rocks of Burpala massi, Northern Baikal folded zone

NASA Astrophysics Data System (ADS)

Sotnikova, Irina; Vladykin, Nikolai

2015-04-01

Burpalinsky rare metal alkaline massif in the Northern Baikal folded zone in southern margin of Siberian Platform, is a of intrusion central type, created 287 Ma covering area of about 250 km2. It is composed of nepheline syenites and pulaskites grading to quartz syenites in the contacts. Veines and dykes are represented by shonkinites, sodalite syenite, leucocratic granophyres, alkali granites and numerous rare metal alkaline syenite pegmatites and two dykes of carbonatites. All rocks except for granites are cut by a large apatite-fluorite dyke rocks with mica and magnetite, which in turn is cut by alaskite granites dyke. The massif has been studied by A.M. Portnov, A.A. Ganzeev et al. (1992) Burpalinsky massif is highly enriched with trace elements, which are concentrated in pegmatite dykes. About 70 rare-metal minerals we found in massif. Zr-silicates: zircon, eudialyte, lovenite, Ti-lovenite, velerite, burpalite, seidozerite, Ca- seidozerite, Rosenbuschite, vlasovite, katapleite, Ca-katapleite, elpidite. Ti- minerals:- sphene, astrophyllite, ramsaite, Mn-neptunite bafertisite, chevkinite, Mn-ilmenite, pirofanite, Sr-perrerit, landauite, rutile, anatase, brookite; TR- minerals - loparite, metaloparite, britolite, rinkolite, melanocerite, bastnesite, parisite, ankilite, monazite, fluocerite, TR-apatite; Nb- minerals - pyrochlore, loparite. Other rare minerals leucophanite, hambergite, pyrochlore, betafite, torite, thorianite, tayniolite, brewsterite, cryolite and others. We have proposed a new scheme massif: shonkinites - nepheline syenites - alkaline syenite - quartz syenites - veined rocks: mariupolites, rare-metal pegmatites, apatite, fluorite rock alyaskite and alkaline granites and carbonatites (Sotnikova, 2009). Apatite-fluorite rocks are found in the central part of massif. This is a large vein body of 2 km length and a 20 m width cutting prevailing pulaskites. Previously, these rocks were regarded as hydrothermal low-temperature phase. New geological and thermobarometric evidence suggests that apatite-fluorite rocks were formed from the residual fluid-melt, separated after crystallization of rare-metal pegmatites. Petrochemical and geochemical data Burpalinsky are in accord of general trend of crystal differentiation of alkaline magma containing small concentrations of CO2 and higher P2O5 and F, which accumulated significantly separated from the pegmatite melts. In some pegmatites fluorite with rare-metal minerals (flyuocerit etc) are separating in schlieren. Apatite-fluorite rocks are cut by leucogranite dyke, having genetic connection with rare-metal pegmatites. Late granitic phases has its own association of rare-metal minerals described by A.A. Ganzeev (1972). Thermobarometric geochemical study of apatite-fluorite rocks Burpala massif found a large number of primary fluid inclusions (15-50 micrometers). Thermal and cryometric research of 60 individual fluid inclusions in fluorite showed the domination of Na, Ca, Mg chlorides and high temperatures salt inclusions in fluorites (above 550C) and melt inclusions in apatites (800C). Apatite-fluorite rocks in massif are similar to foskorites in carbonatite complexes, with similar high Ca content, but instead fluorite, together with other "foskoritovymi" minerals - apatite, magnetite, mica, and pyroxene were formed instead for calcite. Isotopic studies (Sr-Nd) indicate the mantle source of primary magma Burpala massif close to EM-2, which is characteristic of alkaline intrusions in the folded belts (Vladykin 2009). RBRF grant 14-45-04057

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.

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.

Publications - GMC 422 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 422 Publication Details Title: Apatite fission track, magnetic susceptibility, and vitrinite Bibliographic Reference Dixit, N., and Tomsich, C.S., 2014, Apatite fission track, magnetic susceptibility, and

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.

Xe- and U-tracks in apatite and muscovite near the etching threshold

NASA Astrophysics Data System (ADS)

Wauschkuhn, Bastian; Jonckheere, Raymond; Ratschbacher, Lothar

2015-01-01

Ion irradiation of a wedge-shaped Durango apatite backed by a mica detector allows investigating ion track ranges and etching properties at different points along the tracks. Transmission profiles obtained by irradiation with 2 × 106 cm-2 11.1 MeV/amu 132Xe and 2 × 106 cm-2 11.1 MeV/amu 238U parallel to the apatite c-axis correspond to ranges calculated with SRIM (Xe: 76.3 μm; U: 81.1 μm). However, the measured profiles show much greater etchable track-length variations than the calculated longitudinal straggles. The probable cause is that the length deficit exhibits significant variation from track to track. The measured length deficit in muscovite is in agreement with most existing data. In contrast, the length deficit in apatite appears to be close to zero, which is in conflict with all earlier estimates. This probably results from the etching properties of the apatite basal face, which permit surface-assisted sub-threshold etching of track sections in the nuclear stopping regime. These sections are not accessible from the opposite direction, i.e. by etching towards the endpoint of the tracks or in the direction of the ion beam. This conclusion is supported by the fact that linear dislocations are revealed in apatite basal faces and by the observation of imperfect etch pits that are separated from the etched ion track channel by a section that appears unetched under the microscope.

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.

Beneficial use of meat and bone meal combustion residue: "an efficient low cost material to remove lead from aqueous effluent".

PubMed

Deydier, Eric; Guilet, Richard; Sharrock, Patrick

2003-07-04

Meat and bone meal (MBM) combustion residues, a natural apatite-rich substance, was evaluated as a low cost substitute for hydroxyapatite in lead sequestration from water effluents. The thermal behaviour of crude meat and bone meal was followed by TGA and 24% inorganic residue was collected. The resulting ashes were characterised by powder X-ray diffraction (XRD), particle size distribution, specific surface area (BET), and elemental analysis confirming apatite contents, with high level of phosphate (56.3%) and calcium (36.8%). Mechanism and kinetics of lead removal by this bioinorganic material were investigated and compared to mechanisms and kinetics involved with synthetic apatite. Batch metal removal experiments were carried out with 500 and 1500ppm (mg/kg) Pb(2+) solutions. Lead concentration, calcium and pH were monitored. We observed that the mechanism is similar to that occurring for pure apatite, and involved both surface complexation and calcium hydroyapatite (CaHA), Ca(10)(PO(4))(6)(OH)(2), dissolution followed by less soluble Pb(10)(PO(4))(6)(OH)(2) precipitation, as confirmed by XRD analysis of ashes after incubation with lead solution. Our results show that this natural apatite-rich material removes in a few minutes a large quantity of lead (275mg/g capacity) which remains however lower than the theoretical maximum capacity (if calcium were totally substituted by lead). Meat and bone meal combustion residues represent a valuable alternative apatite source for environmental application.

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

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.;

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.

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.

[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.

Interim Report: 100-NR-2 Apatite Treatability Test: Low Concentration Calcium Citrate-Phosphate Solution Injection for In Situ Strontium-90 Immobilization

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

Williams, Mark D.; Fritz, Brad G.; Mendoza, Donaldo P.

2008-07-11

Following an evaluation of potential Sr-90 treatment technologies and their applicability under 100-NR-2 hydrogeologic conditions, U.S. Department of Energy, Fluor Hanford, Inc., Pacific Northwest National Laboratory, and the Washington Department of Ecology agreed that the long-term strategy for groundwater remediation at 100-N Area will include apatite sequestration as the primary treatment, followed by a secondary treatment if necessary (most likely phytoremediation). Since then, the agencies have worked together to agree on which apatite sequestration technology has the greatest chance of reducing Sr-90 flux to the river at a reasonable cost. In July 2005, aqueous injection, (i.e., the introduction of apatite-formingmore » chemicals into the subsurface) was endorsed as the interim remedy and selected for field testing. Studies are in progress to assess the efficacy of in situ apatite formation by aqueous solution injection to address both the vadose zone and the shallow aquifer along the 300 ft of shoreline where Sr-90 concentrations are highest. This report describes the field testing of the shallow aquifer treatment.« less

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

ScienceCinema

Moore, Robert; Szecsody, Jim; Thompson, Mike

2018-01-16

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

Publications - GMC 220 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 220 Publication Details Title: Apatite fission track data derived from the following Barrow . Bibliographic Reference Murphy, J.M., 1994, Apatite fission track data derived from the following Barrow Arch

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

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

Moore, Robert; Szecsody, Jim; Thompson, Mike

2015-10-20

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

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.

Bone regeneration performance of surface-treated porous titanium.

PubMed

Amin Yavari, Saber; van der Stok, Johan; Chai, Yoke Chin; Wauthle, Ruben; Tahmasebi Birgani, Zeinab; Habibovic, Pamela; Mulier, Michiel; Schrooten, Jan; Weinans, Harrie; Zadpoor, Amir Abbas

2014-08-01

The large surface area of highly porous titanium structures produced by additive manufacturing can be modified using biofunctionalizing surface treatments to improve the bone regeneration performance of these otherwise bioinert biomaterials. In this longitudinal study, we applied and compared three types of biofunctionalizing surface treatments, namely acid-alkali (AcAl), alkali-acid-heat treatment (AlAcH), and anodizing-heat treatment (AnH). The effects of treatments on apatite forming ability, cell attachment, cell proliferation, osteogenic gene expression, bone regeneration, biomechanical stability, and bone-biomaterial contact were evaluated using apatite forming ability test, cell culture assays, and animal experiments. It was found that AcAl and AnH work through completely different routes. While AcAl improved the apatite forming ability of as-manufactured (AsM) specimens, it did not have any positive effect on cell attachment, cell proliferation, and osteogenic gene expression. In contrast, AnH did not improve the apatite forming ability of AsM specimens but showed significantly better cell attachment, cell proliferation, and expression of osteogenic markers. The performance of AlAcH in terms of apatite forming ability and cell response was in between both extremes of AnH and AsM. AcAl resulted in significantly larger volumes of newly formed bone within the pores of the scaffold as compared to AnH. Interestingly, larger volumes of regenerated bone did not translate into improved biomechanical stability as AnH exhibited significantly better biomechanical stability as compared to AcAl suggesting that the beneficial effects of cell-nanotopography modulations somehow surpassed the benefits of improved apatite forming ability. In conclusion, the applied surface treatments have considerable effects on apatite forming ability, cell attachment, cell proliferation, and bone ingrowth of the studied biomaterials. The relationship between these properties and the bone-implant biomechanics is, however, not trivial. Copyright © 2014 Elsevier Ltd. All rights reserved.

Biogenic hydroxyapatite (Apatite II™) dissolution kinetics and metal removal from acid mine drainage.

PubMed

Oliva, J; Cama, J; Cortina, J L; Ayora, C; De Pablo, J

2012-04-30

Apatite II™ is a biogenic hydroxyapatite (expressed as Ca(5)(PO(4))OH) derived from fish bone. Using grains of Apatite II™ with a fraction size between 250 and 500 μm, batch and flow-through experiments were carried out to (1) determine the solubility constant for the dissolution reaction Ca(5)(PO(4))(3)(OH) ⇔ 5Ca(2+) + 3PO(4)(3-) + OH(-), (2) obtain steady-state dissolution rates over the pH range between 2.22 and 7.14, and (3) study the Apatite II™'s mechanisms to remove Pb(2+), Zn(2+), Mn(2+), and Cu(2+) from metal polluted water as it dissolves. The logK(S) value obtained was -50.8±0.82 at 25 °C. Far-from-equilibrium fish-bone hydroxyapatite dissolution rates decrease by increasing pH. Assuming that the dissolution reaction is controlled by fast adsorption of a proton on a specific surface site that dominates through the pH range studied, probably ≡PO(-), followed by a slow hydrolysis step, the dissolution rate dependence is expressed in mol m(-2) s(-1) as where Rate(25 °C) = -8.9 × 10(-10) × [9.96 × 10(5) × a(H+)]/[1 + 9.96 × 10(5) × a(H+)] where a(H+) is the proton activity in solution. Removal of Pb(2+), Zn(2+), Mn(2+) and Cu(2+) was by formation of phosphate-metal compounds on the Apatite II™ substrate, whereas removal of Cd(2+) was by surface adsorption. Increase in pH enhanced the removal of aqueous heavy metals. Using the kinetic parameters obtained (e.g., dissolution rate and pH-rate dependence law), reactive transport simulations reproduced the experimental variation of pH and concentrations of Ca, P and toxic divalent metal in a column experiment filled with Apatite II™ that was designed to simulate the Apatite II™-metal polluted water interaction. Copyright © 2012 Elsevier B.V. All rights reserved.

Publications - GMC 180 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 180 Publication Details Title: Basic data for Apatite Fission Track analysis of cuttings (413 Reference Unknown, 1991, Basic data for Apatite Fission Track analysis of cuttings (413'-12375') from the

Publications - GMC 149 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 149 Publication Details Title: Apatite fission track analysis of cuttings from the following 3 Unknown, 1990, Apatite fission track analysis of cuttings from the following 3 wells: Texaco Inc. Tulugak

Bioactivity of gelatin coated magnetic iron oxide nanoparticles: in vitro evaluation.

PubMed

Gaihre, Babita; Khil, Myung Seob; Kang, Hyo Kyoung; Kim, Hak Yong

2009-02-01

Current research explores formation of bone like apatite on gelatin coated magnetic iron oxide nanoparticles (GIOPs) to evaluate the bioactivity of the material. The GIOPs were soaked in simulated body fluid (SBF) and the apatite formation on the surface was investigated in regular interval of time. Fourier transform-infrared (FT-IR) and x-ray diffraction spectroscopic (XRD) analyses were done to investigate the chemical changes and field emission-scanning electron microscopic (FE-SEM) analysis was done to investigate the morphological changes occurring on the surface of the GIOPs after soaking in different time intervals. The kinetic studies of the apatite growth in SBF suggest that initially calcium and phosphorous ions were deposited to the surface of the GIOPs from the SBF leading to formation of amorphous Ca/P particles. Later, after 9 days of the incubation the amorphous particles were fused to form needle and blade like crystalline structures of bone like apatite.

The predominant role of collagen in the nucleation, growth, structure and orientation of bone apatite

NASA Astrophysics Data System (ADS)

Wang, Yan; Azaïs, Thierry; Robin, Marc; Vallée, Anne; Catania, Chelsea; Legriel, Patrick; Pehau-Arnaudet, Gérard; Babonneau, Florence; Giraud-Guille, Marie-Madeleine; Nassif, Nadine

2012-08-01

The involvement of collagen in bone biomineralization is commonly admitted, yet its role remains unclear. Here we show that type I collagen in vitro can initiate and orientate the growth of carbonated apatite mineral in the absence of any other vertebrate extracellular matrix molecules of calcifying tissues. We also show that the collagen matrix influences the structural characteristics on the atomic scale, and controls the size and the three-dimensional distribution of apatite at larger length scales. These results call into question recent consensus in the literature on the need for Ca-rich non-collagenous proteins for collagen mineralization to occur in vivo. Our model is based on a collagen/apatite self-assembly process that combines the ability to mimic the in vivo extracellular fluid with three major features inherent to living bone tissue, that is, high fibrillar density, monodispersed fibrils and long-range hierarchical organization.

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

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

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

Somrani, Saida; Banu, Mihai; Jemal, Mohamed

2005-05-15

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

Artefactual nanoparticle activation of the inflammasome platform: in vitro evidence with a nano-formed calcium phosphate

PubMed Central

Pele, Laetitia; Haas, Carolin T; Hewitt, Rachel; Faria, Nuno; Brown, Andy; Powell, Jonathan

2015-01-01

Aim To determine whether in vitro experimental conditions dictate cellular activation of the inflammasome by apatitic calcium phosphate nanoparticles. Material & methods The responses of blood-derived primary human cells to in situ-formed apatite were investigated under different experimental conditions to assess the effect of aseptic culture, cell rest and duration of particle exposure. Cell death and particle uptake were assessed, while IL-1β and caspase 1 responses, with and without lipopolysaccharide prestimulation, were evaluated as markers of inflammasome activation. Results Under carefully addressed experimental conditions, apatitic nanoparticles did not induce cell death or engage the inflammasome platform, although both could be triggered through artefacts of experimentation. Conclusion In vitro studies often predict that engineered nanoparticles, such as synthetic apatite, are candidates for inflammasome activation and, hence, are toxic. However, the experimental setting must be very carefully considered as it may promote false-positive outcomes. PMID:24991724

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.

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

Visualization of structural organization of ventral membranes of sheared-open resorbing osteoclasts attached to apatite pellets.

PubMed

Akisaka, Toshitaka; Yoshida, Atsushi

2015-05-01

Osteoclasts are highly polarized cells from both morphological and functional points of view. Using quick-freeze, rotary-replication methods combined with cell-shearing, we clarified the variability of cytoplasmic surface of the polarized membranes of osteoclasts seeded on apatite. As to the organization of actin filaments and clathrin sheets, we confirmed almost the same ventral membrane specializations of osteoclasts on apatite as seen on glass plates. The organized actin filaments and membrane-associated particles supported the ruffled border membranes. Inside the actin sealing zone, membrane specializations were not always occupied with the ruffled border but also with other types of membranes. Some osteoclasts formed an actin ring but lacked the ruffled border projections. We report a unique and distinctive membrane modification of apatite-attached osteoclasts, i.e., the presence of dense aggregates of membrane-associated particles and related structures not found in the osteoclasts seeded on glass plates. Actin filament polarity in the podosomes was determined by decoration with myosin S1. The actin filament polarity within podosome appears to be oriented predominantly with its barbed ends toward the core, whereas the interconnecting F-actin appears to be mixed oriented. Two different types of clathrin plaques displayed different distributions: clathrin-dependent endocytosis was observed in the ruffled border regions, whereas flat clathrin sheets were found in the leading edge of lamellipodia and near podosomes. The clathrin sheets adhered to the apatite surface tightly on the ventral membranes overlaying the resorption lacunae. All these membrane specializations as mentioned above may indicate the functional variability of osteoclasts seeded on apatite.

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).

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

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

Fix, N. J.

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

Re-collection of Fish Canyon Tuff for fission-track standardization

USGS Publications Warehouse

Naeser, C.W.; Cebula, G.T.

1984-01-01

The PURPOSE of this note is to announce the availability of apatite and zircon from a third collection of the Oligocene Fish Canyon Tuff (FC-3). Apatite and zircon separated from the Fish Canyon Tuff have prove to be a useful standard for fission-track dating, both for interlaboratory comparisons and for checking procedures within a laboratory. In May 1981, about 540 kg of Fish Canyon Tuff were collected for mineral separation. Approximately 7. 5 g of apatite, 6. 5 g of zircon, and 89 g of sphene were recovered from this collection. This new material is now ready for distribution.

Fabrication of mineralized electrospun PLGA and PLGA/gelatin nanofibers and their potential in bone tissue engineering.

PubMed

Meng, Z X; Li, H F; Sun, Z Z; Zheng, W; Zheng, Y F

2013-03-01

Surface mineralization is an effective method to produce calcium phosphate apatite coating on the surface of bone tissue scaffold which could create an osteophilic environment similar to the natural extracellular matrix for bone cells. In this study, we prepared mineralized poly(D,L-lactide-co-glycolide) (PLGA) and PLGA/gelatin electrospun nanofibers via depositing calcium phosphate apatite coating on the surface of these nanofibers to fabricate bone tissue engineering scaffolds by concentrated simulated body fluid method, supersaturated calcification solution method and alternate soaking method. The apatite products were characterized by the scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR), and X-ray diffractometry (XRD) methods. A large amount of calcium phosphate apatite composed of dicalcium phosphate dihydrate (DCPD), hydroxyapatite (HA) and octacalcium phosphate (OCP) was deposited on the surface of resulting nanofibers in short times via three mineralizing methods. A larger amount of calcium phosphate was deposited on the surface of PLGA/gelatin nanofibers rather than PLGA nanofibers because gelatin acted as nucleation center for the formation of calcium phosphate. The cell culture experiments revealed that the difference of morphology and components of calcium phosphate apatite did not show much influence on the cell adhesion, proliferation and activity. Copyright © 2012 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2011-06-01

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

Supplemental Groundwater Remediation Technologies to Protect the Columbia River at Hanford, WA

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

Thompson, K. M.; Petersen, Scott W.; Fruchter, Jonathan S.

2007-12-15

Nine projects have been recently selected by the US Department of Energy (EM-22) to address groundwater contaminant migration at the Hanford Site. This paper summarizes the background and objectives of these projects. Five of the selected projects are targeted at hexavalent chromium contamination in Hanford 100 Area groundwater. These projects represent an integrated approach towards identifying the source of hexavalent chromium contamination in the Hanford 100-D Area and treating the groundwater contamination. Currently, there is no effective method to stop strontium-90 associated with the riparian zone sediments from leaching into the river. Phytoremediation may be a possible way to treatmore » this contamination. Its use at the 100-N Area will be investigated. Another technology currently being tested for strontium-90 contamination at the 100-N Area involves injection (through wells) of a calcium-citrate-phosphate solution, which will precipitate apatite, a natural calcium-phosphate mineral. Apatite will adsorb the strontium-90, and then incorporate it as part of the apatite structure, isolating the strontium-90 contamination from entering the river. This EM-22 funded apatite project will develop a strategy for infiltrating the apatite solution from ground surface or a shallow trench to provide treatment over the upper portion of the contaminated zone, which is unsaturated during low river stage.« less

Apatite nanoparticles strongly improve red blood cell cryopreservation by mediating trehalose delivery via enhanced membrane permeation.

PubMed

Stefanic, Martin; Ward, Kevin; Tawfik, Harvey; Seemann, Ralf; Baulin, Vladimir; Guo, Yachong; Fleury, Jean-Baptiste; Drouet, Christophe

2017-09-01

Cryopreservation of red blood cells (RBC) is an important method for maintaining an inventory of rare RBC units and managing special transfusion circumstances. Currently, in a clinical setting, glycerol is used as cryoprotectant against freezing damage. After thawing and before transfusion, glycerol must however be removed to avoid intravascular hemolysis, via a complex and time-consuming deglycerolization process which requires specialized equipment. Improved cryopreservation methods using non-toxic agents are required to increase biocompatibility and decrease processing time. Biocompatible cryoprotectants (e.g. trehalose) were proposed, but their low permeation through RBC membranes limits their cryoprotection efficacy. Herein, we report for the first time a glycerol-free cryopreservation approach, using colloidal bioinspired apatite nanoparticles (NP) as bioactive promoters of RBC cryopreservation mediated by trehalose. Addition of apatite NP in the medium tremendously increases RBC cryosurvival, up to 91% (42% improvement compared to a control without NP) which is comparable to FDA-approved cryoprotection protocol employing glycerol. NP concentration and incubation conditions strongly modulate the NP bioactivity. Complementary experimental and computational analyses of the interaction between apatite NP and model lipid bilayers revealed complex events occurring at the NP-bilayer interface. Apatite NP do not cross the bilayer but momentarily modulate its physical status. These changes affect the membrane behavior, and promote the permeation of trehalose and a model fluorescent molecule (FITC). This approach is a new alternative to using toxic glycerol for cells cryopreservation, and the identification of this enhancing no-pore permeation mechanism of apatite NP appears as an original delivery pathway for cryoprotectant agents and beyond. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Using apatite to discriminate synchronous ore-associated and barren granitoid rocks: A case study from the Edong metallogenic district, South China

NASA Astrophysics Data System (ADS)

Duan, Deng-Fei; Jiang, Shao-Yong

2018-06-01

In order to find criteria to discriminate the synchronous ore-associated and barren granitoid rocks, we have determined apatite chemistry associated with ore-associated (Cu-Au) and barren granitoid rocks in the Edong district of the Middle and Lower Yangtze River metallogenic belt, South China. Both rock types give zircon U-Pb ages between 135.0 and 138.7 Ma. Apatite has a higher volatile and Li content (Cl: 0.19-0.57 wt%, average 0.35 wt%, SO3: 0.08-0.71 wt%, average 0.32 wt%, Li: 0.49-7.99 ppm, average 3.23 ppm) in ore-associated rocks than those in barren rocks (Cl: 0.09-0.31 wt%, average 0.16 wt%, SO3: 0.06-0.28 wt%, average 0.16 wt%, Li: 0.15-0.89 ppm, average 0.36 ppm). Apatite (La/Yb)N ratios and Eu/Eu* values are relatively high and show wider variation in ore-associated rocks than those in barren rocks. Apatite (La/Sm)N and (Yb/Sm)N show positive correlation in ore-associated rocks but negative in barren rocks. The higher volatile content occurs in ore-associated magma, favoring Cu-Au transportation and deposition. Furthermore, amphibole fractional crystallization in ore-associated magma further enriched the ore elements in the residual melt. Barren rocks may have undergone fluid exsolution before emplacement, which makes it barren in Cl, S and ore elements (Cu, S). These signatures emphases the significance of volatile and magma evolution in mineralization and indicate that analyses of magmatic apatite can serve to distinguish ore-associated from barren intrusions.

Rare earth elements in the phosphatic-enriched sediment of the Peru shelf

USGS Publications Warehouse

Piper, D.Z.; Baedecker, P.A.; Crock, J.G.; Burnett, W.C.; Loebner, B.J.

1988-01-01

Apatite-enriched materials from the Peru shelf have been analyzed for their major oxide and rare earth element (REE) concentrations. The samples consist of (1) the fine fraction of sediment, mostly clay material, (2) phosphatic pellets and fish debris, which are dispersed throughout the fine-grained sediment, (3) tabular-shaped phosphatic crusts, which occur within the uppermost few centimeters of sediment, and (4) phosphatic nodules, which occur on the seafloor. The bulk REE concentrations of the concretions suggest that these elements are partitioned between the enclosed detrital material and the apatite fraction. Analysis of the fine-grained sediment with which the samples are associated suggested that this detrital fraction in the concretions should have shale REE values; the analysis of the fish debris suggested that the apatite fraction might have seawater values. The seawater contribution of REE's is negligible in the nodules and crust, in which the apatite occurs as a fine-grained interstitial cement. That is, the concentration of REE's and the REE patterns are predominantly a function of the amount of enclosed fine-grained sediment. By contrast, the REE pattern of the pelletal apatite suggests a seawater source and the absolute REE concentrations are relatively high. The REE P2O5 ratios of the apatite fraction of these samples thus vary from approximately zero (in the case of the crust and nodules) to as much as approximately 1.2 ?? 10-3 (in the case of the pellets). The range of this ratio suggests that rather subtle variations in the depositional environment might cause a significant variation in the REE content of this authigenic fraction of the sediment. Pelletal glauconite was also recovered from one sediment core. Its REE concentrations closely resemble those of the fish debris. ?? 1988.

Assessment of copper removal from highway stormwater runoff using Apatite II(TM) and compost : laboratory and field testing.

DOT National Transportation Integrated Search

2015-03-01

-Stormwater runoff introduces heavy metals to surface waters that are harmful to aquatic organisms, : including endangered salmon. This work evaluates Apatite II, a biogenic fish bone based adsorbent, for removing metal : from stormwater. The meta...

Crystallization, fluoridation and some properties of apatite thin films prepared through rf-sputtering from CaO-P2O5 glasses.

PubMed

Yamashita, K; Matsuda, M; Arashi, T; Umegaki, T

1998-07-01

Using calcium phosphate glass targets with the CaO/P2O5 molar ratios of 1.50-0.50, much lower than the stoichiometric value of 3.3 for hydroxyapatite, thin films of stoichiometric hydroxy-, nonstoichiometric oxyhydroxy- and Ca-deficient oxyhydroxy-apatites were prepared on alumina ceramic substrates by rf-sputtering followed by post-annealing. Based on the present results, a phase diagram for CaO-P2O5 at low temperatures in the ambience of air was depicted for thin films. The ambient H2O vapor had an influence on the phase diagram: Tricalcium phosphate was changed to apatite in the presence of H2O vapor. Dense fluorohydroxyapatite thin films were prepared by fluoridation of those apatite thin films at a low temperature such as 200 degrees C. In the present report, some functional properties of thin films thus prepared were also shown.

Pressures of skarn formation at Casting Copper NV, USA, based on Raman spectroscopy and elastic modeling of apatite inclusions in garnet

NASA Astrophysics Data System (ADS)

Steele-MacInnis, M.; Barkoff, D. W.; Ashley, K.

2017-12-01

Thermobarometry of metasomatic rocks is commonly challenging, owing to the high variance of hydrothermal mineral assemblages, thermodynamic disequilibrium and overprinting by subsequent hydrothermal episodes. Here, we estimate formation pressures of a Cu-Fe-sulfide-bearing andradite-diopside skarn deposit at Casting Copper (Yerington district, NV) using Raman spectroscopy and elastic modeling of apatite inclusions in garnet. Andradite garnet from the Casting Copper skarn contains inclusions of hydroxyl-fluorapatite, calcite, hematite, magnetite, and ilmenite. Raman spectroscopy reveals that the apatite inclusions are predominantly under tension of -23 to -123 MPa at ambient conditions. Elastic modeling of apatite-in-garnet suggest entrapment occurred at 10 to 115 MPa, assuming a trapping temperature of 400 °C, which is consistent with paleodepth estimates of 2-3 km. These results provide independent constraints on the conditions of hydrothermal skarn formation at Casting Copper, and suggest that this approach may be applied to other, less-constrained skarn systems.

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

USGS Publications Warehouse

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

1951-01-01

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

In vitro bioactivity of akermanite ceramics.

PubMed

Wu, Chengtie; Chang, Jiang; Ni, Siyu; Wang, Junying

2006-01-01

In this study, the bone-like apatite-formation ability of akermanite ceramics (Ca2MgSi2O7) in simulated body fluid (SBF) and the effects of ionic products from akermanite dissolution on osteoblasts and mouse fibroblasts (cell line L929) were investigated. In addition, osteoblast morphology and proliferation on the ceramics were evaluated. The results showed that akermanite ceramics possessed bone-like apatite-formation ability comparable with bioactive wollastonite ceramics (CaSiO3) after 20 days of soaking in SBF and the mechanism of bone-like apatite formation on akermanite ceramics is similar to that of wollastonite ceramics. The Ca, Si, and Mg ions from akermanite dissolution at certain ranges of concentration significantly stimulated osteoblast and L929 cell proliferation. Furthermore, osteoblasts spread well on the surface of akermanite ceramics, and proliferated with increasing the culture time. The results showed that akermanite ceramics possess bone-like apatite-formation ability and can release soluble ionic products to stimulate cell proliferation, which indicated good bioactivity. (c) 2005 Wiley Periodicals, Inc

High resolution rare-earth elements analyses of natural apatite and its application in geo-sciences: Combined micro-PIXE, quantitative CL spectroscopy and electron spin resonance analyses

NASA Astrophysics Data System (ADS)

Habermann, D.; Götte, T.; Meijer, J.; Stephan, A.; Richter, D. K.; Niklas, J. R.

2000-03-01

The rare-earth element (REE) distribution in natural apatite is analysed by micro-PIXE, cathodoluminescence (CL) microscopy and spectroscopy and electron spin resonance (ESR) spectroscopy. The micro-PIXE analyses of an apatite crystal from Cerro de Mercado (Mexico) and the summary of 20 analyses of six francolite (conodonts of Triassic age) samples indicate that most of the REEs are enriched in apatite and francolite comparative to average shale standard (NASC). The analyses of fossil francolite revealing the REE-distribution not to be in balance with the REE-distribution of seawater and fish bone debris. Strong inhomogenous lateral REE-distribution in fossil conodont material is shown by CL-mapping and most probably not being a vital effect. Therefore, the resulting REE-signal from fossil francolite is the sum of vital and post-mortem incorporation. The necessary charge compensation for the substitution of divalent Ca by trivalent REE being done by different kind of electron defects and defect ions.

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.

In-situ measurement of sulfur isotopic ratios in zoned apatite crystals via SIMS: a new tool for interpreting dynamic sulfur behavior in magmas

NASA Astrophysics Data System (ADS)

Economos, R. C.; Boehnke, P.; Burgisser, A.

2017-12-01

Sulfur is an important element in igneous systems due to its impact on magma redox, its role in the formation of economically valuable ore deposits, and the influence of catastrophic volcanogenic sulfur degassing on global climate. The mobility and geochemical behavior of sulfur in magmas is complex due to its multi-valent (from S2- to S6+) and multi-phase (solid, immiscible liquid, gaseous, dissolved ions) nature. Sulfur behavior is closely linked with the evolution of oxygen fugacity (fO2) in magmas; the record of fO2 evolution is often difficult to extract from rock records, particularly for intrusive systems that undergo cyclical magmatic processes and crystallize to the solidus. We apply a novel method of measuring S isotopic ratios via secondary ion mass spectrometry (SIMS) in zoned apatite crystals that we interpret as a record of open-system magmatic processes. We analyzed the S concentration and isotopic variations preserved in multiple apatite crystals from single hand specimens from the Cadiz Valley Batholith, CA via electron microprobe and ion microprobe at UCLA. A single, isotopically homogeneous crystal of Durango apatite was characterized for absolute isotopic ratio for this study (UCLA-D1). Isotopic variations in single apatite crystals ranged from 0 to 3.8‰ δ34S and total variation within a single hand sample was 6.1‰ δ34S. High S concentration cores yielded high isotopic ratios while low S concentration rims yielded low isotopic ratios. We favor an explanation of a combination of magma mixing and open-system, ascent-driven degassing under moderately reduced conditions: fO2 at or below NNO +1, although the synchronous crystallization of apatite and anhydrite is also a viable scenario. These findings have implications for the coupled S and fO2 evolution of granitic plutons and suggest that in-situ apatite S isotopic measurements could be a powerful new tool for evaluating redox and S systematics in magmatic systems.

Characterization of helium diffusion behavior from continuous heating experiments: Sample screening and identification of multiple 4He components

NASA Astrophysics Data System (ADS)

McDannell, K. T.; Idleman, B. D.; Zeitler, P. K.

2015-12-01

Old, slowly cooled apatites often yield overdispersed helium ages due to factors such as parent zonation, He implantation, radiation damage, crystal defects, and fluid inclusions. Careful mineral selection and many replicate analyses can mitigate the impact of some of these effects. However, this approach adds unnecessary costs in time and resources when dating well-behaved apatites and is generally ineffective at identifying the root cause of age dispersion and providing suitable age corrections for poorly behaved samples. We assess a new technique utilizing static-gas measurement during continuous heating as a means to rapidly screen apatite samples. In about the time required for a conventional total-gas analysis, this method can discriminate between samples showing the volume-diffusion behavior expected for apatite and those showing anomalous release patterns, inconsistent with their use in thermochronologic applications. This method may also have the potential to quantify and discriminate between the radiogenic and extraneous 4He fractions released by a sample. Continuously heated samples that outgas by volume diffusion during a linear heating schedule should produce a characteristic sigmoidal 4He fractional loss profile, with the exact shape and position of these profiles (in loss vs. heating time space) controlled by sample kinetics, grain size, and heating rate. Secondary factors such as sample zoning and alpha-loss distribution have a relatively minor impact on such profiles. Well-behaved examples such as the Durango standard and other apatites with good age reproducibility show the expected smooth, sigmoidal gas release with complete exhaustion by temperatures predicted for volume diffusion using typical apatite kinetics (e.g., by ~900˚C for linear heating at 20˚C/minute). In contrast, "bad actor" samples that do not replicate well show significant degrees of helium release deferred to higher temperatures. We report on screening results for a range of samples including a suite of slowly cooled Cretaceous apatites from the Hangay Dome in central Mongolia, assessing the degree to which screening using cumulative heating can reliably identify bad-actor grains, and possibly, correct their ages.

Dual-functioning peptides discovered by phage display increase the magnitude and specificity of BMSC attachment to mineralized biomaterials.

PubMed

Ramaraju, Harsha; Miller, Sharon J; Kohn, David H

2017-07-01

Design of biomaterials for cell-based therapies requires presentation of specific physical and chemical cues to cells, analogous to cues provided by native extracellular matrices (ECM). We previously identified a peptide sequence with high affinity towards apatite (VTKHLNQISQSY, VTK) using phage display. The aims of this study were to identify a human MSC-specific peptide sequence through phage display, combine it with the apatite-specific sequence, and verify the specificity of the combined dual-functioning peptide to both apatite and human bone marrow stromal cells. In this study, a combinatorial phage display identified the cell binding sequence (DPIYALSWSGMA, DPI) which was combined with the mineral binding sequence to generate the dual peptide DPI-VTK. DPI-VTK demonstrated significantly greater binding affinity (1/K D ) to apatite surfaces compared to VTK, phosphorylated VTK (VTK phos ), DPI-VTK phos , RGD-VTK, and peptide-free apatite surfaces (p < 0.01), while significantly increasing hBMSC adhesion strength (τ 50 , p < 0.01). MSCs demonstrated significantly greater adhesion strength to DPI-VTK compared to other cell types, while attachment of MC3T3 pre-osteoblasts and murine fibroblasts was limited (p < 0.01). MSCs on DPI-VTK coated surfaces also demonstrated increased spreading compared to pre-osteoblasts and fibroblasts. MSCs cultured on DPI-VTK coated apatite films exhibited significantly greater proliferation compared to controls (p < 0.001). Moreover, early and late stage osteogenic differentiation markers were elevated on DPI-VTK coated apatite films compared to controls. Taken together, phage display can identify non-obvious cell and material specific peptides to increase human MSC adhesion strength to specific biomaterial surfaces and subsequently increase cell proliferation and differentiation. These new peptides expand biomaterial design methodology for cell-based regeneration of bone defects. This strategy of combining cell and material binding phage display derived peptides is broadly applicable to a variety of systems requiring targeted adhesion of specific cell populations, and may be generalized to the engineering of any adhesion surface. Copyright © 2017 Elsevier Ltd. All rights reserved.

Geodynamic risk magnitude as an objective indicator of rockburst prevention effectiveness (in terms of apatite mines in Khibiny)

NASA Astrophysics Data System (ADS)

Fedotova Panin, YuV, VI

2018-03-01

The results of the statistical retrospective analysis of the officially recorded geodynamic events in mines of Apatit Company within the Khibiny Massif are presented. The risks and aftereffects of geodynamic events have been calculated. Under discussion are the results of three calculation variants taking into account the scale of human impact on rock mass. The analysis shows that the main damage due to geodynamic events is different-degree destruction of mine workings while the remaining aftereffects account for less than ten percent. That is, the geodynamic risk in apatite mines can be identified as technological.

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.

New constraints on the thermochronologic evolution at the boundary between the Eastern and Western Alps - Vorarlberg, Austria

NASA Astrophysics Data System (ADS)

Bertrand, Audrey; Pomella, Hannah; Fügenschuh, Bernhard; Zerlauth, Michael; Ortner, Hugo

2013-04-01

The study area in the westernmost part of Austria is marked by the limit between the Western and the Eastern Alps that takes place along the Rhine Valley, south of the Lake Constance. The area is composed, form the north to the south and from lowermost to uppermost structural position, by the European basement together with its autochthonous Mesozoic cover, autochthonous Molasse, subalpine Molasse, the Helvetic and Ultra-Helvetic, the Penninic and the Austroalpine nappes. These units are stacked in a succession of nappes separated by large south-trending overthrusts. This study presenting new apatite and zircon fission track ages, together with a crustal-scale cross-section (Pomella et al., this session) addresses the thermotectonic evolution of this nappe stack. In comparison with similar studies from eastern Switzerland the boundary between Western and Eastern Alps should be enlightened. Zircon fissions track ages from the lower freshwater Molasse reveal different age populations. Since all zircon fission track ages are older than the stratigraphic age this clearly indicates that post-depositional temperatures were well below the zircon partial annealing zone (i.e. below 200 °C) and the different age populations can be attributed to different source areas derived from the coevally forming and eroding alpine chain. Preliminary fission track results on apatite from the lower freshwater Molasse indicate a strong dependence of apatite fission track single-grain ages on their annealing kinetics as inferred from Dpar analyses (Gleadow and Duddy, 1981). F-rich apatites systematically yielded younger ages compared to the Cl-rich grains. The younger ages derived from the F-rich apatites are consistently younger than the stratigraphic age and thus fully annealed while Cl-rich apatites display older ages than the stratigraphic one. The difference in annealing temperatures between Cl- and F-rich apatites (Ravenhurst and Donelick, 1992) thus constrains the maximum temperature to < 100 °C, most likely reached between 20 Ma and 14 Ma by combined sediment and tectonic overburden. References Gleadow, A.J.W., and Duddy, I.R., 1981, A natural long-term annealing experiment for apatite. Nuclear Tracks Radiation Experiments, 5, 169-174. Pomella et al., this session. Alpine nappe stack in western Austria: A crustal-scale cross-section. Ravenhurst, C.E., and Donelick, R.A., 1992. Fission track thermochronology. In Short Course. Handbook on Low Temperature Thermochronology, ed. M. Zentilli & P.H. Reynolds. pp.21-42.

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.

The influence of channel anion identity on the high-pressure crystal structure, compressibility, and stability of apatite

NASA Astrophysics Data System (ADS)

Skelton, Richard; Walker, Andrew M.

2018-03-01

The material properties of the common phosphate mineral apatite are influenced by the identity of the channel anion, which is usually F-, Cl-, or (OH)-. Density functional theory calculations have been used to determine the effect of channel anion identity on the compressibility and structure of apatite. Hydroxyapatite and fluorapatite are found to have similar zero pressure bulk moduli, of 79.2 and 82.1 GPa, respectively, while chlorapatite is considerably more compressible, with K 0 = 55.0 GPa. While the space groups of hydroxyapatite and fluorapatite do not change between 0 and 25 GPa, symmetrization of the Cl- site in chlorapatite at 7.5 GPa causes the space group to change from P2 1 /b to P6 3 /m. Examination of the valence electron density distribution in chlorapatite reveals that this symmetry change is associated with a change in the coordination of the Cl- anion from threefold to sixfold coordinated by Ca. We also calculate the pressure at which apatite decomposes to form tuite, a calcium orthophosphate mineral, and find that the transition pressure is sensitive to the identity of the channel anion, being lowest for fluorapatite (13.8 GPa) and highest for chlorapatite (26.9 GPa). Calculations are also performed within the DFT-D2 framework to investigate the influence of dispersion forces on the compressibility of apatite minerals.

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.

Modeling active capping efficacy. 1. Metal and organometal contaminated sediment remediation.

PubMed

Viana, Priscilla Z; Yin, Ke; Rockne, Karl J

2008-12-01

Cd, Cr, Pb, Ag, As, Ba, Hg, CH3Hg, and CN transport through sand, granular activated carbon (GAC), organoclay, shredded tires, and apatite caps was modeled by deterministic and Monte Carlo methods. Time to 10% breakthrough, 30 and 100 yr cumulative release were metrics of effectiveness. Effective caps prevented above-cap concentrations from exceeding USEPA acute criteria at 100 yr assuming below-cap concentrations at solubility. Sand caps performed best under diffusion due to the greater diffusive path length. Apatite had the best advective performance for Cd, Cr, and Pb. Organoclay performed best for Ag, As, Ba, CH3Hg, and CN. Organoclay and apatite were equally effective for Hg. Monte Carlo analysis was used to determine output sensitivity. Sand was effective under diffusion for Cr within the 50% confidence interval (CI), for Cd and Pb (75% CI), and for As, Hg, and CH3Hg (95% CI). Under diffusion and advection, apatite was effective for Cd, Pb, and Hg (75% CI) and organoclay was effective for Hg and CH3Hg (50% CI). GAC and shredded tires performed relatively poorly. Although no single cap is a panacea, apatite and organoclay have the broadest range of effectiveness. Cap performance is most sensitive to the partitioning coefficient and hydraulic conductivity, indicating the importance of accurate site-specific measurement for these parameters.

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.

IN SITU LEAD IMMOBILIZATION BY APATITE

EPA Science Inventory

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

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

EPA Science Inventory

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

The comparison study of bioactivity between composites containing synthetic non-substituted and carbonate-substituted hydroxyapatite.

PubMed

Borkowski, Leszek; Sroka-Bartnicka, Anna; Drączkowski, Piotr; Ptak, Agnieszka; Zięba, Emil; Ślósarczyk, Anna; Ginalska, Grażyna

2016-05-01

Apatite forming ability of hydroxyapatite (HAP) and carbonate hydroxyapatite (CHAP) containing composites was compared. Two composite materials, intended for filling bone defects, were made of polysaccharide polymer and one of two types of hydroxyapatite. The bioactivity of the composites was evaluated in vitro by soaking in a simulated body fluid (SBF), and the formation of the apatite layer was determined by scanning electron microscopy with energy-dispersive spectrometer and Raman spectroscopy. The results showed that both the composites induced the formation of apatite layer on their surface after soaking in SBF. In addition, the sample weight changes and the ion concentration of the SBF were scrutinized. The results showed the weight increase for both materials after SBF treatment, higher weight gain and higher uptake of calcium ions by HAP containing scaffolds. SBF solution analysis indicated loss of calcium and phosphorus ions during experiment. All these results indicate apatite forming ability of both biomaterials and suggest comparable bioactive properties of composite containing pure hydroxyapatite and carbonate-substituted one. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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.

Europium concentration effect on characteristics and luminescent properties of hydroxyapatite nanocrystalline powders

NASA Astrophysics Data System (ADS)

Nikolaev, Anton; Kolesnikov, Ilya; Frank-Kamenetskaya, Olga; Kuz'mina, Maria

2017-12-01

Series of Eu-apatites were synthesized by precipitation from aqueous solutions with the Eu/Ca atomic ratio from 0.5% to 5% at T = 90 °C. Resulting precipitates were studied using different experimental techniques including X-ray powder diffraction, infrared and raman spectroscopy, scanning elecrton microscopy, EDX and photoluminescent spectroscopy. Eu-doped Ca-deficit nanosized non-stoichiometric hydroxyapatite with high water content has been obtained throughout the experiment. Europium content in the synthesized apatites reaches 0.24 apfu (Eu/Ca = 2.5%). Relations between Eu content is the solution and precipitate have been established. It was shown that Eu-monacite starts to precipitate as secondary phase at Eu/Ca ratio in starting solution 1% or higher. Maximum luminescence is observed in apatite with ∼2% Eu/Ca ratio (which equals to ∼0.2 apfu and corresponds to 3% Eu/Ca ratio in the starting solution). As an important and brand-new result, apatite with 2% Eu/Ca ratio can be considered as the most appropriate material for the producing biolabels for luminescent research in medicine and biology.

Altered self-assembly and apatite binding of amelogenin induced by N-terminal proline mutation

PubMed Central

Zhu, Li; Uskoković, Vuk; Le, Thuan; DenBesten, Pamela; Huang, Yulei; Habelitz, Stefan; Li, Wu

2012-01-01

Objective A single Pro-70 to Thr (p.P70T) mutation of amelogenin is known to result in hypomineralized amelogenesis imperfecta (AI). This study aims to test the hypothesis that the given mutation affects the self-assembly of amelogenin molecules and impairs their ability to conduct the growth of apatite crystals. Design Recombinant human full-length wild-type (rh174) and p.P70T mutated amelogenins were analyzed using dynamic light scattering (DLS), protein quantification assay and atomic force microscopy (AFM) before and after the binding of amelogenins to hydroxyapatite crystals. The crystal growth modulated by both amelogenins in a dynamic titration system was observed using AFM. Results As compared to rh174 amelogenin, p.P70T mutant displayed significantly increased sizes of the assemblies, higher binding affinity to apatite, and decreased crystal height. Conclusions Pro-70 plays an important structural role in the biologically relevant amelogenin self-assembly. The disturbed regularity of amelogenin nanospheres by this single mutation resulted in an increased binding to apatite and inhibited crystal growth. PMID:21081224

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

PubMed

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

2015-12-01

The recovery of phosphorus from incinerated sewage sludge ash (SSA) is assumed to be economical. Transformation from non-apatite inorganic phosphorus (NAIP) to apatite phosphorus (AP), which has a higher bioavailability and more extensive industrial applications, was studied at 750-950°C by sewage sludge incineration and model compound incineration with a calcium oxide (CaO) additive. Thermogravimetric differential scanning calorimetry analysis and X-ray diffraction measurements were used to analyze the reactions between NAIP with CaO and crystallized phases in SSA. High temperatures stimulated the volatilization of NAIP instead of AP. Sewage sludge incineration with CaO transformed NAIP into AP, and the percentage of AP from the total phosphorus reached 99% at 950°C. Aluminum phosphate reacted with CaO, forming Ca2P2O7 and Ca3(PO4)2 at 750-950°C. Reactions between iron phosphate and CaO occurred at lower temperatures, forming Ca(PO3)2 before reaching 850°C. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Annealing behaviour of ion tracks in olivine, apatite and britholite

NASA Astrophysics Data System (ADS)

Afra, B.; Lang, M.; Bierschenk, T.; Rodriguez, M. D.; Weber, W. J.; Trautmann, C.; Ewing, R. C.; Kirby, N.; Kluth, P.

2014-05-01

Ion tracks were created in olivine from San Carlos, Arizona (95% Mg2SiO4), apatite (Ca5(PO4)3(F,Cl,O)) from Durango, Mexico, and synthetic silicates with the apatite structure: Nd8Sr2(SiO4)6O2 and Nd8Ca2(SiO4)6O2 using 1.6 and 2.2 GeV Au ions. The morphology and annealing behaviour of the tracks were investigated by means of synchrotron based small angle X-ray scattering in combination with ex situ annealing. Tracks in olivine annealed above ∼400 °C undergo a significant change in track radius due to recrystallisation of the damage tracks. At temperatures higher than 620 °C, the scattering images indicate fragmentation of the track cylinders into smaller subsections. Ion tracks were annealed at elevated temperatures up to 400 °C in the Durango and Ca-britholite, and up to 560 °C in Sr-britholite. While there was a significant change in the track radii in the Durango apatite, tracks in the two synthetic samples remained almost unchanged.

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.

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

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.

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.

2003-01-01

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

Process and kinetics of bonelike apatite formation on sintered hydroxyapatite in a simulated body fluid.

PubMed

Kim, Hyun-Min; Himeno, Teruyuki; Kokubo, Tadashi; Nakamura, Takashi

2005-07-01

The surfaces of two hydroxyapatites (HA), which have been sintered at different temperatures of 800 and 1200 degrees C, was investigated as a function of soaking time in simulated body fluid (SBF) using transmission electron microscopy (TEM) attached with energy-dispersive spectrometry (EDX) and laser electrophoresis spectroscopy. The TEM-EDX indicated that after soaking in SBF, both the HAs form bonelike apatite by undergoing the same surface structural change, i.e., formations of a Ca-rich amorphous or nano-crystalline calcium phosphate (ACP) and a Ca-poor ACP, which eventually crystallized into bonelike apatite. Zeta potential characterized by the electrophoresis indicated that during exposure to SBF, the HA surfaces reveal negative surface charge, thereby interacting with the positive calcium ions in the fluid to form the Ca-rich ACP, which gains positive surface charge. The Ca-rich ACP on the HAs then interacts with the negative phosphate ions in the fluid to form the Ca-poor ACP, which stabilizes by being crystallized into bonelike apatite with a low solubility in the SBF. The exposure times for formations of these phases of the Ca-rich ACP, the Ca-poor ACP as well as the apatite were, however, all late on HA sintered at 1200 degrees C, compared with the HA sintered at 800 degrees C. This phenomenon was attributed to a lower initial negative surface charge of the HA sintered at 800 degrees C than of that one sintered at 1200 degrees C, owing to poverty in surface hydroxyl and phosphate groups which are responsible for the surface negativity of the HA. These indicate that sintered temperature of HA might influence not in terms of the process but in terms of the rate of formation of biologically active bonelike apatite on its surface, through which the HA integrates with living bone.

Influence of Common Bean (Phaseolus vulgaris) Grown in Elevated CO2 on Apatite Dissolution

NASA Astrophysics Data System (ADS)

Olsen, A. A.; Morra, B.

2016-12-01

We ran a series of experiments to test the hypothesis that release of plant nutrients contained in apatite will be accelerated by the growth of Langstrath Stringless green bean in the presence of atmospheric CO2 meant to simulate possible future atmospheric conditions due a higher demand of nutrients and growth rate caused by elevated CO2. We hypothesize that elevated atmospheric CO2 will lead to both increased root growth and organic acid exudation. These two traits will lead to improved acquisition of P derived from apatite. Experiments were designed to investigate the effect of these changes on soil mineral weathering using plants grown under two conditions, ambient CO2 (400ppm) and elevated CO2 (1000ppm). Plants were grown in flow-through microcosms consisting of a mixture of quartz and apatite sands. Mini-greenhouses were utilized to control CO2 levels. Plant growth was sustained by a nutrient solution lacking in Ca and P. Calcium and P content of the leachate and plant tissue served as a proxy for apatite dissolution. Plants were harvested biweekly during the eight-week experiment and analyzed for Ca and P to calculate apatite dissolution kinetics. Preliminary results suggest that approximately four times more P and Ca are present in the leachate from experiments containing plants under both ambient and elevated CO2 levels than in abiotic experiments; however, the amounts of both P and Ca released in experiments conducted under both ambient and elevated CO2 levels are similar. Additionally, the amount of P in plant tissue grown under ambient and elevated CO2 conditions is similar. Plants grown in elevated CO2 had a greater root to shoot ratio. The planted microcosms were found to have a lower pH than abiotic controls most likely due to root respiration and exudation of organic acids.

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.

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.

Ion microprobe U-Pb dating and strontium isotope analysis of biogenic apatite

NASA Astrophysics Data System (ADS)

Sano, Y.; Toyoshima, K.; Takahata, N.; Shirai, K.

2012-12-01

Conodonts are micro-fossils chemically composed of apatite which occurred in the body of one animal. They are guide fossils to show formation ages of sedimentary sequences with the highest resolution [1] and good samples to verify the dating method. We developed the ion microprobe U-Pb dating of apatite [2] and applied the method to a Carboniferous conodont [3] by using a SHRIMP II installed at Department of Earth and Planetary Sciences, Hiroshima University. Recently we have developed the NanoSIMS U-Pb dating method and successfully measured the formation ages of monazite [4] and zircon [5] at Atmosphere and Ocean Research Institute, University of Tokyo. In this work we carried out the NanoSIMS U-Pb dating of biogenic apatite such as conodont. Since the spot size of NanoSIMS is smaller than SHRIMP II, it is easier to have multi-spots on the single fragment of biogenic apatite. Based on the isochron method of U-Pb system, we have calculated the formation ages. They are consistent with those in literature. In order to study the chemical evolution of ocean during the past 600 Million years, strontium isotopes (87Sr/86Sr) of fossil marine carbonate such as coral skeletons and foraminifera tests were measured and compiled [6]. However they are not robust when the age is older than 500Ma, partly due to post-depositional histories. Apatite is more stable and more resistant to the alteration than carbonate [7]. Recently we have developed the method of NanoSIMS strontium isotopic analysis of a fish otolith, which composed of aragonite [8]. In this work we carried out the strontium isotopic analysis of biogenic apatite. The advantage of the ion microprobe technique over the TIMS (thermal ionization mass spectrometer) and MC-ICP-MS (multi-collector inductively coupled argon plasma mass spectrometer) method is preservation of the important textural context and to provide an opportunity for other simultaneous analytical work with high spatial resolution. This is the case for the combination of U-Pb dating and strontium isotope analysis of biogenic apatite. This method may be useful to extract the information of the chemistry of Past ocean in future. [1] Sweet and Donoghue (2001) J. Paleont. 75, 1174-1184. [3] Sano et al., (1999) Chem. Geol. 153, 249-258. [3] Sano and Terada (2001) Geophys. Res. Lett. 28, 831-834. [4] Sano et al. (2006) Geochem. J. 40, 597-608. [5] Takahata et al. (2008) Gondwana Res. 14, 587-596. [6] Prokoph et al. (2008) Earth Sci. Rev. 87, 113-133. [7] Karhu and Epstein (1986) Geochim. Cosmochim. Acta 50, 1745-1756. [8] Sano et al. (2008) App. Geochem. 23, 2406-2413.

Water in the Lunar Interior and the Apparent KREEP-Mare Dichotomy

NASA Astrophysics Data System (ADS)

McCubbin, F. M.; Nekvasil, H.

2010-12-01

Recent SIMS analysis of lunar apatite has shown that hydroxyl is structurally bound within lunar apatite from a number of different lunar lithologic types (McCubbin et al., 2010a, 2010b; Boyce et al., 2010; Greenwood et al., 2010). These studies along with previous SIMS analyses of lunar fire fountain glasses (Saal et al., 2008) confirm that there is at least some water in the lunar interior, with abundance estimates in magmatic source regions ranging from 64 ppb to 5 ppm water (McCubbin et al., 2010a). Surprisingly, apatite from rocks with KREEP-rich incompatible trace element signatures are depleted in hydroxyl in comparison to apatite from typical mare basalts. This result is counter-intuitive to the lunar magma ocean model, which predicts that incompatible constituents (e.g., water) would have been concentrated in the last dregs of liquid referred to as “urKREEP”. The mare basalts, which formed by partial melting of earlier LMO cumulates, are typically depleted in these incompatible constituents. Complicating the issue further, chlorine, another incompatible magmatic volatile element in apatite, follows the predicted trend with apatite from KREEP-rich rocks containing significant chlorine concentrations in comparison to apatite from mare basalts (McCubbin et al., 2009). The preceding results imply one of two scenarios 1) Water did not behave incompatibly during LMO crystallization and was preferentially stored within the LMO cumulate minerals 2) A secondary process such as degassing has perturbed the initial volatile contents of the urKREEP liquid or of the secondary magmas that have KREEP-rich incompatible trace element signatures. In regards to the first scenario, the mineral melt partition coefficients for water would need to have exceeded unity at the very low water concentrations of the LMO liquid. This scenario is consistent with the behavior of chlorine, as chlorine is not typically stored in nominally anhydrous phases like pyroxene or olivine, likely due to its large ionic radius. However, there is no empirical or experimental evidence to support the elevated D values for water. Regarding the second scenario, if significant degassing of the urKREEP liquid or KREEP-rich secondary magmas occurred, water would have certainly been lost preferentially to the other volatile constituents in apatite (fluorine and chlorine); however chlorine isotopes analyzed in lunar apatites are highly fractionated (Sharp et al., 2010), indicating degassing of chlorine in the absence of water. Therefore, this scenario only works if degassing on the Moon was a multi-stage and complex process where water and chlorine degassing are decoupled, which is not typically the case for terrestrial systems (Aiuppa et al., 2009, Webster and De Vivo, 2002; Webster et al., 1999). Solving this apparent KREEP-mare dichotomy regarding magmatic volatiles in the lunar interior is the next important step in figuring out the importance, relevance, and implications of water in the lunar interior. Moreover, it will lend insight into the roles of the other magmatic volatiles during the thermal and magmatic evolution of the Moon.

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.

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

NASA Astrophysics Data System (ADS)

Prywer, Jolanta; Olszynski, Marcin

2013-07-01

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

The determination of uranium (IV) in apatite

USGS Publications Warehouse

Clarke, Roy S.; Altschuler, Zalman S.

1956-01-01

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

SAXS study of ion tracks in San Carlos olivine and Durango apatite

NASA Astrophysics Data System (ADS)

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

2012-09-01

Ion tracks were generated in crystalline San Carlos olivine (Mg,Fe)2SiO4 and Durango apatite Ca10(PO4)6F2 using different heavy ions (58Ni, 101Ru, 129Xe, 197Au, and 238U) with energies ranging between 185 MeV and 2.6 GeV. The tracks and their annealing behavior were studied by means of synchrotron based small angle X-ray scattering in combination with in situ annealing. Track radii vary as a function of electronic energy loss but are very similar in both minerals. Furthermore, the annealing behavior of the track radii has been investigated and preliminary results reveal a lower recovery rate of the damaged area in olivine compared with apatite.

Synthesis of bioactive organic-inorganic nanohybrid for bone repair through sol-gel processing.

PubMed

Miyazaki, Toshiki; Ohtsuki, Chikara; Tanihara, Masao

2003-12-01

So-called bioactive ceramics have been attractive because they form bone-like apatite on their surfaces to bond directly to living bone when implanted in bony defects. However, they are much more brittle and much less flexible than natural bone. Organic-inorganic hybrids consisting of flexible organic polymers and the essential constituents of the bioactive ceramics (i.e., Si-OH groups and Ca2+ ions) are useful as novel bone substitutes, because of their bioactivity and mechanical properties analogous to those of natural bone. In the present study, organic-inorganic nanohybrids were synthesized from hydroxyethylmethacrylate (HEMA) and methacryloxypropyltrimethoxysilane (MPS), as well as various calcium salts. Bioactivity of the synthesized hybrids was assessed in vitro by examining their acceptance of apatite deposition in simulated body fluid (Kokubo solution). The prepared hybrids formed apatite in Kokubo solution when they were modified with calcium chloride (CaCl2) at 5 or 10 mol% of the total of MPS and HEMA. Deposition of a kind of calcium phosphate was observed for the hybrids modified with calcium acetate (Ca(CH3COO)2), although it could not be identified with apatite. The addition of glycerol up to 10 mol% of the total of MPS and HEMA or water up to 20 mol% as plasticizers did not appreciably decrease the acceptance of apatite formation of the hybrids. These findings allow wide selectivity in the design of bioactive nanohybrids developed by organic modification of the Si-OH group and calcium ion through sol-gel processing. Such nanohybrids have potential as novel bone substitutes with both high bioactivity and high flexibility.

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

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.

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.

Experimental evidence regarding the pressure dependence of fission track annealing in apatite

NASA Astrophysics Data System (ADS)

Schmidt, J. S.; Lelarge, M. L. M. V.; Conceicao, R. V.; Balzaretti, N. M.

2014-03-01

The main purposes of fission track thermochronology are unravelling the thermal histories of sedimentary basins, determining uplift and denudation rates, identifying the structural evolution of orogenic belts, determining sedimentary provenance, and dating volcanic rocks. The effect of temperature on fission tracks is well known and is used to determine the thermal history; however, the effect of pressure on the stability of tracks is still under debate. The present work aims to understand the role of pressure on the annealing kinetics of apatite fission tracks. The samples of Durango apatite used in our experiments were chosen for their international recognition as a calibration standard for geological dating. Neutron irradiation of the samples, after total annealing of their spontaneous tracks, produced induced tracks with homogeneous densities and lengths. The effect of pressure associated with temperature on fission track annealing was verified by experimental procedures using a hydraulic press of 1000 t with a toroidal chamber profile. The experiments consisted of a combination of applying 2 and 4 GPa with 20,150,190,235, and 290 °C for 1 and 10 h. The annealing rate was analysed by measuring the lengths of the fission tracks after each experiment using optical microscopy. The results demonstrate that the annealing of apatite fission tracks has a pressure dependence for samples subjected to 2 and 4 GPa. However, when extrapolated to pressures of ⩽150 MPa, compatible with the normal geological context in which apatite fission track methodology is broadly used, this dependence becomes insignificant compared to the temperature effect.

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.

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.

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.

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.

Fabrication and Characterization of Biomimetic Collagen-Apatite Scaffolds with Tunable Structures for Bone Tissue Engineering

PubMed Central

Xia, Zengmin; Yu, Xiaohua; Jiang, Xi; Brody, Harold D; Rowe, David W; Wei, Mei

2013-01-01

The objective of the current study is to prepare a biomimetic collagen-apatite (Col-Ap) scaffold for improved bone repair and regeneration. A novel bottom-up approach has been developed, which combines a biomimetic self-assembly method with a controllable freeze casting technology. In this study, the mineralized collagen fibers were generated using a simple one-step co-precipitation method which involved collagen self-assembly and in situ apatite precipitation in a collagen-containing modified simulated body fluid (m-SBF). The precipitates were subjected to controllable freeze casting, forming scaffolds with either an isotropic equiaxed structure or a unidirectional lamellar structure. These scaffolds were comprised of collagen fibers and poorly crystalline bone-like carbonated apatite nanoparticles. The mineral content in the scaffold could be tailored in a range 0–54 wt% by simply adjusting the collagen content in the m-SBF. Further, the mechanisms of the formation of both the equiaxed and the lamellar scaffolds were investigated, and freezing regimes for equiaxed and lamellar solidification were established. Finally, bone forming capability of such prepared scaffolds was evaluated in vivo in a mouse calvarial defect model. It was confirmed that the scaffolds well support new bone formation. PMID:23567944

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.

Infrared spectroscopy of the mineralogy of coprolites from Brean Down: evidence of past human activities and animal husbandry

NASA Astrophysics Data System (ADS)

Allen, Samantha D. M.; Almond, Matthew J.; Bell, Martin G.; Hollins, Peter; Marks, Sonja; Mortimore, Joanne L.

2002-03-01

The mineralogy of 11 concretions from the Bronze Age settlement horizons at Brean Down near Weston-super-Mare, Somerset, UK, has been examined by infrared spectroscopy. The concretions are found to contain calcite and apatite and, in some cases, quartz. Four further concretions from the later Iron Age Meare Village, soil samples from Brean Down and mineralised samples of known faecal origin from a cesspit within the Tudor Merchant's house in Tenby have been similarly examined. It is found that all samples contain calcite, but only the concretions and the Tenby cesspit samples contain apatite. None of the soil samples contain apatite, although these are relatively high in quartz. This suggests that the concretions are coprolites and that the apatite has a biological origin in small bone fragments. The infrared study is backed up by scanning electron microscopy which confirms the presence of phosphorus in the coprolite samples and shows a morphology suggestive of the presence of bone fragments; it is likely, therefore, that the coprolites result from a carnivore—most probably from dogs. The findings show the usefulness of infrared spectroscopy for the rapid identification of mineralised coprolitic material from archaeological sites.

Selenite sorption by carbonate substituted apatite

DOE PAGES

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

2016-08-31

The sorption of selenite, SeO 3 2–, by carbonate substituted hydroxylapatite was investigated using batch kinetic and equilibrium experiments. The carbonate substituted hydroxylapatite was prepared by a precipitation method and characterized by SEM, XRD, FT-IR, TGA, BET and solubility measurements. The material is poorly crystalline, contains approximately 9.4% carbonate by weight and has a surface area of 210.2 m 2/g. Uptake of selenite by the carbonated hydroxylapatite was approximately an order of magnitude higher than the uptake by uncarbonated hydroxylapatite reported in the literature. Distribution coefficients, K d, determined for the carbonated apatite in this work ranged from approximately 4200more » to over 14,000 L/kg. A comparison of the results from kinetic experiments performed in this work and literature kinetic data indicates the carbonated apatite synthesized in this study sorbed selenite 23 times faster than uncarbonated hydroxylapatite based on values normalized to the surface area of each material. Furthermore, the results indicate carbonated apatite is a potential candidate for use as a sorbent for pump-and-treat technologies, soil amendments or for use in permeable reactive barriers for the remediation of selenium contaminated sediments and groundwaters.« less

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.

The structure, bond strength and apatite-inducing ability of micro-arc oxidized tantalum and their response to annealing

NASA Astrophysics Data System (ADS)

Wang, Cuicui; Wang, Feng; Han, Yong

2016-01-01

In this study, the tantalum oxide coatings were formed on pure tantalum (Ta) by micro-arc oxidation (MAO) in electrolytic solutions of calcium acetate and β-glycerophosphate disodium, and the effect of the applied voltage on the microstructure and bond strength of the MAO coatings was systematically investigated. The effect of annealing treatment on the microstructure, bond strength and apatite-inducing ability of the MAO coatings formed at 350 and 450 V was also studied. The study revealed that during the preparation of tantalum oxide coatings on Ta substrate by MAO, the applied voltage considerably affected the phase components, morphologies and bond strength of the coatings, but had little effect on surface chemical species. After annealing treatment, newly formed CaTa4O11 phase mainly contributed to the much more stronger apatite-inducing ability of the annealed tantalum oxide coatings than those that were not annealed. The better apatite-inducing ability of the MAO coatings formed at 450 V compared to those formed at 350 V was attributed to the less amorphous phase and more crystalline phase as well as more Ca and P contained in the MAO coatings with increasing the applied voltage.

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.

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.

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.

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

Oxygen isotope analysis of phosphate: improved precision using TC/EA CF-IRMS.

PubMed

LaPorte, D F; Holmden, C; Patterson, W P; Prokopiuk, T; Eglington, B M

2009-06-01

Oxygen isotope values of biogenic apatite have long demonstrated considerable promise for paleothermometry potential because of the abundance of material in the fossil record and greater resistance of apatite to diagenesis compared to carbonate. Unfortunately, this promise has not been fully realized because of relatively poor precision of isotopic measurements, and exceedingly small size of some substrates for analysis. Building on previous work, we demonstrate that it is possible to improve precision of delta18O(PO4) measurements using a 'reverse-plumbed' thermal conversion elemental analyzer (TC/EA) coupled to a continuous flow isotope ratio mass spectrometer (CF-IRMS) via a helium stream [Correction made here after initial online publication]. This modification to the flow of helium through the TC/EA, and careful location of the packing of glassy carbon fragments relative to the hot spot in the reactor, leads to narrower, more symmetrically distributed CO elution peaks with diminished tailing. In addition, we describe our apatite purification chemistry that uses nitric acid and cation exchange resin. Purification chemistry is optimized for processing small samples, minimizing isotopic fractionation of PO4(-3) and permitting Ca, Sr and Nd to be eluted and purified further for the measurement of delta44Ca and 87Sr/86Sr in modern biogenic apatite and 143Nd/144Nd in fossil apatite. Our methodology yields an external precision of +/- 0.15 per thousand (1sigma) for delta18O(PO4). The uncertainty is related to the preparation of the Ag3PO4 salt, conversion to CO gas in a reversed-plumbed TC/EA, analysis of oxygen isotopes using a CF-IRMS, and uncertainty in constructing calibration lines that convert raw delta18O data to the VSMOW scale. Matrix matching of samples and standards for the purpose of calibration to the VSMOW scale was determined to be unnecessary. Our method requires only slightly modified equipment that is widely available. This fact, and the demonstrated improvement in precision, should help to make apatite paleothermometry far more accessible to paleoclimate researchers. Copyright 2009 John Wiley & Sons, Ltd.

Bioactive glass for dentin remineralization: A systematic review.

PubMed

Fernando, Delihta; Attik, Nina; Pradelle-Plasse, Nelly; Jackson, Phil; Grosgogeat, Brigitte; Colon, Pierre

2017-07-01

Strategies to achieve dentin remineralization is at present an important target of restorative dentistry. Remineralization of dentin by a bioactive material is complete only when the tissue regains its functionality. This is achieved when there is adequate apatite formation which most importantly translates into improved mechanical properties of dentin as a result of intrafibrillar mineralization. Bioactive glass (BAG) is a well-known implant material for bone regeneration and is proven to have excellent ability of apatite formation. Hence, recent studies have proposed BAGs as one of the most desired materials for remineralization of dentin. Therefore the aim of this systematic review was to scope the evidence of bioactive glass to remineralize dentin. The following research question was formulated: "Is there strong evidence for bioactive glass to remineralize dentin?" Three databases (Web of science, PubMed and Science direct) were scanned independently following PRISMA guidelines. Inclusion and exclusion criteria were set to identify relevant articles based on title and abstract screening. Finally, potentially relevant articles were downloaded and the full text was scrutinized to select the articles included in this review. The first phase of search returned 303 articles. A total of 19 papers with full text were scrutinized for inclusion, of which 3 papers were chosen for the final synthesis. All three studies confirm that BAG treatment leads to enhanced apatite formation in dentin. Only 1 of the 3 studies has reported the mechanical properties of dentin after BAG treatment and it revealed that the Young's modulus and flexural bend strength of BAG treated dentin were much lower than natural dentin even though they had similar apatite content. This review highlights the importance of assessing the mechanical properties of dentin alongside to the newly formed apatite content in order to prove BAGs efficiency to remineralize this tissue. Though studies have confirmed that BAGs stimulate excellent apatite formation in dentin, it should be concluded that there isn't sufficient evidence for bioactive glass to effectively remineralize this tissue as the mechanical properties of the BAG treated dentin haven't been well explored. Copyright © 2017 Elsevier B.V. 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

Development of the foremost light-curable calcium-silicate MTA cement as root-end in oral surgery. Chemical-physical properties, bioactivity and biological behavior.

PubMed

Gandolfi, Maria Giovanna; Taddei, Paola; Siboni, Francesco; Modena, Enrico; Ciapetti, Gabriela; Prati, Carlo

2011-07-01

An innovative light-curable calcium-silicate cement containing a HEMA-TEGDMA-based resin (lc-MTA) was designed to obtain a bioactive fast setting root-end filling and root repair material. lc-MTA was tested for setting time, solubility, water absorption, calcium release, alkalinizing activity (pH of soaking water), bioactivity (apatite-forming ability) and cell growth-proliferation. The apatite-forming ability was investigated by micro-Raman, ATR-FTIR and ESEM/EDX after immersion at 37°C for 1-28 days in DPBS or DMEM+FBS. The marginal adaptation of cement in root-end cavities of extracted teeth was assessed by ESEM/EDX, and the viability of Saos-2 cell on cements was evaluated. lc-MTA demonstrated a rapid setting time (2min), low solubility, high calcium release (150-200ppm) and alkalinizing power (pH 10-12). lc-MTA proved the formation of bone-like apatite spherulites just after 1 day. Apatite precipitates completely filled the interface porosities and created a perfect marginal adaptation. lc-MTA allowed Saos-2 cell viability and growth and no compromising toxicity was exerted. HEMA-TEGDMA creates a polymeric network able to stabilize the outer surface of the cement and a hydrophilic matrix permeable enough to allow water absorption. SiO(-)/Si-OH groups from the mineral particles induce heterogeneous nucleation of apatite by sorption of calcium and phosphate ions. Oxygen-containing groups from poly-HEMA-TEGDMA provide additional apatite nucleating sites through the formation of calcium chelates. The strong novelty was that the combination of a hydraulic calcium-silicate powder and a poly-HEMA-TEGDMA hydrophilic resin creates the conditions (calcium release and functional groups able to chelate Ca ions) for a bioactive fast setting light-curable material for clinical applications in dental and maxillofacial surgery. The first and unique/exclusive light-curable calcium-silicate MTA cement for endodontics and root-end application was created, with a potential strong impact on surgical procedures. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

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.

Screening apatites for (U-Th)/He thermochronometry via continuous ramped heating: He age components and implications for age dispersion

NASA Astrophysics Data System (ADS)

McDannell, Kalin T.; Zeitler, Peter K.; Janes, Darwin G.; Idleman, Bruce D.; Fayon, Annia K.

2018-02-01

Old slowly-cooled apatites often yield dispersed (U-Th)/He ages for a variety of reasons, some well understood and some not. Analytical protocols like careful grain selection can reduce the impact of this dispersion but add costs in time and resources and too often have proven insufficient. We assess a new analytical protocol that utilizes static-gas measurement during continuous ramped heating (CRH) as a means to rapidly screen apatite samples. In about the time required for a conventional total-gas analysis, this method can discriminate between samples showing expected volume-diffusion behavior and those showing anomalous release patterns inconsistent with their direct use in thermochronologic applications. This method also appears able to discriminate between the radiogenic and extraneous 4He fractions released by a sample, potentially allowing ages to be corrected. Well-behaved examples such as the Durango standard and other apatites with good age reproducibility show the expected smooth, sigmoidal gas-release curves predicted for volume diffusion using typical apatite kinetics, with complete exhaustion by ∼900 °C for linear heating at 20 °C/min. Secondary factors such as U and Th zoning and alpha-loss distribution have a relatively minor impact on such profiles. In contrast, samples having greater age dispersion show significant He release in the form of outgassing spikes and He release deferred to higher temperatures. Screening results for a range of samples permit us to assess the degree to which CRH screening can identify misbehaving grains, give insight into the source of extraneous He, and suggest that in some cases it may be possible to correct ages for the presence of such components.

U-Pb Data On Apatites With Common Lead Correction : Exemples From The Scottish Caledonides

NASA Astrophysics Data System (ADS)

Jewison, E.; Deloule, E.; Villeneuve, J.; Bellahsen, N.; Labrousse, L.; Rosenberg, C.; Pik, R.; Chew, D.

2017-12-01

Apatite is a widely used mineral in low-temperature thermochronology (U-Th/He and AFT). The use of apatite in U-Pb geochronology has a great potential, given its closure temperature around 450°C, for orogen thermostructural evolution studies. However, since apatite can accumulate significant amount of initial Pb in its structure, its use can be hindered by the lack of 204 Pb estimations. To work around this, two options are commonly used : either use a ploting sytem that does not require corrected ratios, or use a proxy to estimate 204Pb and use it to correct the ratios. In this study we use a SIMS to mesure 204Pb in order to compare Tera-Wasserburg diagram and corrected ages to examine the cooling pattern in the northern Highlands of Scotland. The Highlands is an extensively studied caledonian collision wedge which results from the closure of the Iapétus Ocean during the Orodivician-Silurian. Two orogenic events are related to this closing, the grampian event (480-460Ma) and the scandian event (435-415 Ma) that culminated in the stacking of major ductile thrusts. The thermal history of thoses nappes are hence complex and the cooling pattern poorly constrained. Corrected apatite U-Pb ages provide new constrains on ductile wedge building and improve our understanding of mid to lower-crustal deformation and orogenic exhumation. Thoses corrected ages yield equivalent errors and mean ages from the classic method. Those data suggest a global cooling younger than previously thought and a sequence departing from a simple forward sequence. We thus present a refined thermal evolution and conceptualize a model of ductile wedge evolution.

Bacterial dissolution of fluorapatite as a possible source of elevated dissolved phosphate in the environment

NASA Astrophysics Data System (ADS)

Feng, Mu-hua; Ngwenya, Bryne T.; Wang, Lin; Li, Wenchao; Olive, Valerie; Ellam, Robert M.

2011-10-01

In order to understand the contribution of geogenic phosphorus to lake eutrophication, we have investigated the rate and extent of fluorapatite dissolution in the presence of two common soil bacteria ( Pantoea agglomerans and Bacillus megaterium) at T = 25 °C for 26 days. The release of calcium (Ca), phosphorus (P), and rare earth elements (REE) under biotic and abiotic conditions was compared to investigate the effect of microorganism on apatite dissolution. The release of Ca and P was enhanced under the influence of bacteria. Apatite dissolution rates obtained from solution Ca concentration in the biotic reactors increased above error compared with abiotic controls. Chemical analysis of biomass showed that bacteria scavenged Ca, P, and REE during their growth, which lowered their fluid concentrations, leading to apparent lower release rates. The temporal evolution of pH in the reactors reflected the balance of apatite weathering, solution reactions, bacterial metabolism, and potentially secondary precipitation, which was implied in the variety of REE patterns in the biotic and abiotic reactors. Light rare earth elements (LREE) were preferentially adsorbed to cell surfaces, whereas heavy rare earth elements (HREE) were retained in the fluid phase. Decoupling of LREE and HREE could possibly be due to preferential release of HREE from apatite or selective secondary precipitation of LREE enriched phosphates, especially in the presence of bacteria. When corrected for intracellular concentrations, both biotic reactors showed high P and REE release compared with the abiotic control. We speculate that lack of this correction explains the conflicting findings about the role of bacteria in mineral weathering rates. The observation that bacteria enhance the release rates of P and REE from apatite could account for some of the phosphorus burden and metal pollution in aquatic environments.

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

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

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.

Reproducibility of apatite fission-track length data and thermal history reconstruction

NASA Astrophysics Data System (ADS)

Ketcham, Richard A.; Donelick, Raymond A.; Balestrieri, Maria Laura; Zattin, Massimiliano

2009-07-01

The ability to derive detailed thermal history information from apatite fission-track analysis is predicated on the reliability of track length measurements. However, insufficient attention has been given to whether and how these measurements should be standardized. In conjunction with a fission-track workshop we conducted an experiment in which 11 volunteers measured ~ 50 track lengths on one or two samples. One mount contained Durango apatite with unannealed induced tracks, and one contained apatite from a crystalline rock containing spontaneous tracks with a broad length distribution caused by partial resetting. Results for both mounts showed scatter indicative of differences in measurement technique among the individual analysts. The effects of this variability on thermal history inversion were tested using the HeFTy computer program to model the spontaneous track measurements. A cooling-only scenario and a reheating scenario more consistent with the sample's geological history were posed. When a uniform initial length value from the literature was used, results among analysts were very inconsistent in both scenarios, although normalizing for track angle by projecting all lengths to a c-axis parallel crystallographic orientation improved some aspects of congruency. When the induced track measurement was used as the basis for thermal history inversion congruency among analysts, and agreement with inversions based on data previously collected, was significantly improved. Further improvement was obtained by using c-axis projection. Differences among inversions that persisted could be traced to differential sampling of long- and short-track populations among analysts. The results of this study, while demonstrating the robustness of apatite fission-track thermal history inversion, nevertheless point to the necessity for a standardized length calibration schema that accounts for analyst variation.

High temperature (>350 °C) thermal histories of the long lived (>500 Ma) active margin of Ecuador and Colombia: Apatite, titanite and rutile U-Pb thermochronology

NASA Astrophysics Data System (ADS)

Paul, Andre N.; Spikings, Richard A.; Ulianov, Alexey; Ovtcharova, Maria

2018-05-01

Quantitative reconstruction of thermal histories can be a powerful tool to study numerous natural processes such as tectonic plate interaction, cratonic stability and extra-terrestrial phenomena such as asteroid ejection. A majority of thermochronological studies have focused on temperatures lower than 300 °C. Few previous studies have demonstrated that U-Pb data from apatite and other accessory phases can be used to recover thermal history information at T > 350 °C. We present U-Pb data from apatite, to constrain the thermal histories of Triassic peralluminous anatectites from the Northern Andes between the temperatures of ∼350-550 °C. The accuracy of the thermal history models is assessed by comparisons with previous geological models, and comparisons with pre-existing and newly acquired U/Pb (titanite and rutile), 40Ar/39Ar (muscovite) and low temperature thermochronological data. This study also examines the feasibility of using a large, regionally dispersed apatite U-Pb data set to obtain continuous thermal history paths along a long-lived (>500 Ma) active margin. A second aim of this study is to further test the hypothesis that the dominant mechanism for Pb displacement through apatite is volume diffusion, as opposed to aqueous fluid interaction. The thermal history models derived from the Triassic anatectites exposed in the Andes of Colombia and Ecuador are entirely consistent with lower temperature thermochronological constraints, and previously established geochronological and geochemical constraints. They reveal and quantify trench parallel changes in the amount of Jurassic - Early Cretaceous extension, significantly bolstering and adding to previous tectonic interpretations. Confirmation of the utility of U-Pb thermochronology provides geologists with a powerful tool for investigating the high-temperature thermal evolution of accessory minerals.

A prolonged Cenozoic erosional period in East Kunlun (Western China): Constraints of detrital apatite (U-Th)/He ages on the onset of mountain building along the northern margin of the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Shi, Wenbei; Wang, Fei; Wu, Lin; Yang, Liekun; Zhang, Weibin; Wang, Yinzhi

2018-01-01

The timing of the development of the highland topography along the northern margin of the Tibetan Plateau is the key to understanding the manner of Tibetan growth and the far-field effects of the collision between India and Eurasia. Although various studies have investigated the exhumation and uplift of the basement rocks, thermochronological studies on the detritus from a continuous depositional sequence inan intermontane basin are lacking but might shed light on this issue. In this study, a set of detrital apatites from an upper Eocene to Pliocene depositional sequence in the Kumukol Basin, the largest intermontane basin in the East Kunlun, were dated by using the (U-Th)/He technique. The detrital apatites had consistent ages of ∼40 Ma for all deposit formations from bottom to top, which were older than the depositional ages. The ages and their consistency suggested that these detrital apatites were not reset and that the ages represented the original ages in the provenance region. These detrital apatite ages from the upper Eocene to Pliocene formations strongly suggested that the high mountains surrounding the Kumukol Basin formed at or before ∼40 Ma and have remained high since then. The process of mountain building resulted in a prolonged period of erosion from ∼40 to 2.6 Ma. The coupling of mountain and basin at ∼40 Ma was widespread along the East Kunlun. Our present results constrain the time of onset of the mountain building along the northern margin of the Tibetan Plateau, which may represent a rapid response to the India-Eurasian collision.

Using Oxygen Isotopic Values in Order to Infer Palaeoclimatic Differences between Northern and Central-Southern Greece

NASA Astrophysics Data System (ADS)

Michael, Dimitra-Ermioni; Dotsika, Elissavet

2017-12-01

Even though isotopic analyses have been extensively implemented on human skeletal remains for the purpose of dietary reconstruction, less attention has been given to the ingested water and thus to the investigation of palaeoclimatic conditions. In particular, oxygen isotopic fingerprinting has never been applied on human skeletal remains from Greece for the abovementioned purpose before. The basic aim of the present study is to compare climatic conditions from two ancient populations, deriving from two different ecological locations; Edessa (Greek Macedonia; 2nd-4th c. AD) and Thebes (Sterea Hellas, 13th-14th c. AD). Oxygen values in Edessa are at -7.69 ±1.13 ‰ and -9.18 ±1.88 ‰ for tooth enamel and bone apatite respectively. On the other hand, oxygen signals in Thebes are at -5.8 ±2.16 ‰ and -9.23 ±1.3 % for the enamel and bone apatite respectively. The utility of oxygen isotopic signatures for the purpose of palaeoclimatic investigation lies on the fact that the ratio of 18 to 16O of meteoric precipitation, expressed as δ18O per mill (‰), relative to the international standard (vSMOW) varies geographically by temperature, humidity, evaporation, distance to the sea, altitude and latitude. Therefore, results as expected, point out that Edessa do presents more negative enamel isotopic values in relation to Thebes, however the noted difference is not observed for the bone apatite samples. The lack of bone apatite differentiation between sites could be attributed to cultural diversity (particularly in Thebes), shift in dietary habits due to migration or social status, climatic fluctuations within each site or to possible diagenetic alteration of bone apatite samples.

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

Situ formation of apatite for sequestering radionuclides and heavy metals

DOEpatents

Moore, Robert C.

2003-07-15

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

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

USGS Publications Warehouse

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

1958-01-01

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

Apatite/Melt Partitioning Experiments Reveal Redox Sensitivity to Cr, V, Mn, Ni, Eu, W, Th, and U

NASA Technical Reports Server (NTRS)

Righter, K.; Yang, S.; Humayun, M.

2016-01-01

Apatite is a common mineral in terrestrial, planetary, and asteroidal materials. It is commonly used for geochronology (U-Pb), sensing volatiles (H, F, Cl, S), and can concentrate rare earth elements (REE) during magmatic fractionation and in general. Some recent studies have shown that some kinds of phosphate may fractionate Hf and W and that Mn may be redox sensitive. Experimental studies have focused on REE and other lithophile elements and at simplified or not specified oxygen fugacities. There is a dearth of partitioning data for chalcophile, siderophile and other elements between apatite and melt. Here we carry out several experiments at variable fO2 to study the partitioning of a broad range of trace elements. We compare to existing data and then focus on several elements that exhibit redox dependent partitioning behavior.

Bonelike apatite formation on ethylene-vinyl alcohol copolymer modified with silane coupling agent and calcium silicate solutions.

PubMed

Oyane, Ayako; Kawashita, Masakazu; Nakanishi, Kazuki; Kokubo, Tadashi; Minoda, Masahiko; Miyamoto, Takeaki; Nakamura, Takashi

2003-05-01

An ethylene-vinyl alcohol copolymer (EVOH) was treated with a silane coupling agent and calcium silicate solutions, and then soaked in a simulated body fluid (SBF) with ion concentrations approximately equal to those of human blood plasma. A smooth and uniform bonelike apatite layer was successfully formed on both the EVOH plate and the EVOH-knitted fibers in SBF within 2 days. Part of the structure of the resulting apatite-EVOH fiber composite was similar to that of natural bone. If this kind of composite can be fabricated into a three-dimensional structure similar to natural bone, the resultant composite is expected to exhibit both mechanical properties analogous to those of natural bone and bone-bonding ability. Hence, it has great potential as a bone substitute. Copyright 2003 Elsevier Science Ltd.

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

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.

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.

Impact of Surface Potential on Apatite Formation in Ti Alloys Subjected to Acid and Heat Treatments

PubMed Central

Yamaguchi, Seiji; Hashimoto, Hideki; Nakai, Ryusuke; Takadama, Hiroaki

2017-01-01

Titanium metal (Ti) and its alloys are widely used in orthopedic and dental fields. We have previously shown that acid and heat treatment was effective to introduce bone bonding, osteoconduction and osteoinduction on pure Ti. In the present study, acid and heat treatment with or without initial NaOH treatment was performed on typical Ti-based alloys used in orthopedic and dental fields. Dynamic movements of alloying elements were developed, which depended on the kind of treatment and type of alloy. It was found that the simple acid and heat treatment enriched/remained the alloying elements on Ti–6Al–4V, Ti–15Mo–5Zr–3Al and Ti–15Zr–4Nb–4Ta, resulting in neutral surface charges. Thus, the treated alloys did not form apatite in a simulated body fluid (SBF) within 3 days. In contrast, when the alloys were subjected to a NaOH treatment prior to an acid and heat treatment, alloying elements were selectively removed from the alloy surfaces. As a result, the treated alloys became positively charged, and formed apatite in SBF within 3 days. Thus, the treated alloys would be useful in orthopedic and dental fields since they form apatite even in a living body and bond to bone. PMID:28946646

Fabrication and characterization of biomimetic collagen-apatite scaffolds with tunable structures for bone tissue engineering.

PubMed

Xia, Zengmin; Yu, Xiaohua; Jiang, Xi; Brody, Harold D; Rowe, David W; Wei, Mei

2013-07-01

The objective of the current study is to prepare a biomimetic collagen-apatite scaffold for improved bone repair and regeneration. A novel bottom-up approach has been developed, which combines a biomimetic self-assembly method with a controllable freeze-casting technology. In this study, the mineralized collagen fibers were generated using a simple one-step co-precipitation method which involved collagen self-assembly and in situ apatite precipitation in a collagen-containing modified simulated body fluid (m-SBF). The precipitates were then subjected to controllable freeze casting, forming scaffolds with either an isotropic equiaxed structure or a unidirectional lamellar structure. These scaffolds were comprised of collagen fibers and poorly crystalline bone-like carbonated apatite nanoparticles. The mineral content in the scaffold could be tailored in the range 0-54wt.% by simply adjusting the collagen content in the m-SBF. Further, the mechanisms of the formation of both the equiaxed and the lamellar scaffolds were investigated, and freezing regimes for equiaxed and lamellar solidification were established. Finally, the bone-forming capability of such prepared scaffolds was evaluated in vivo in a mouse calvarial defect model. It was confirmed that the scaffolds well support new bone formation. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Quantitative Identification of the Annealing Degree of Apatite Fission Tracks Using Terahertz Time Domain Spectroscopy (THz-TDS).

PubMed

Wu, Hang; Wu, Shixiang; Qiu, Nansheng; Chang, Jian; Bao, Rima; Zhang, Xin; Liu, Nian; Liu, Shuai

2018-01-01

Apatite fission-track (AFT) analysis, a widely used low-temperature thermochronology method, can provide details of the hydrocarbon generation history of source rocks for use in hydrocarbon exploration. The AFT method is based on the annealing behavior of fission tracks generated by 238 U fission in apatite particles during geological history. Due to the cumbersome experimental steps and high expense, it is imperative to find an efficient and inexpensive technique to determinate the annealing degree of AFT. In this study, on the basis of the ellipsoid configuration of tracks, the track volume fraction model (TVFM) is established and the fission-track volume index is proposed. Furthermore, terahertz time domain spectroscopy (THz-TDS) is used for the first time to identify the variation of the AFT annealing degree of Durango apatite particles heated at 20, 275, 300, 325, 450, and 500 ℃ for 10 h. The THz absorbance of the sample increases with the degree of annealing. In addition, the THz absorption index is exponentially related to annealing temperature and can be used to characterize the fission-track volume index. Terahertz time domain spectroscopy can be an ancillary technique for AFT thermochronological research. More work is urgently needed to extrapolate experimental data to geological conditions.

Synthetic hydroxyapatites doped with Zn(II) studied by X-ray diffraction, infrared, Raman and thermal analysis

NASA Astrophysics Data System (ADS)

Guerra-López, José R.; Echeverría, Gustavo A.; Güida, Jorge A.; Viña, Raúl; Punte, Graciela

2015-06-01

Calcium hydroxyapatite (CaHap) formation when different amounts of Zn(II) are present in the mother solution has been investigated by atomic absorption, infrared and Raman spectroscopies, X-ray diffraction and thermal analysis (DTA and TG). The studied samples have been synthesized at T=95 °C and pH 9 in air. The analysis of the results have shown that the pure CaHap sample crystallizes in the monoclinic form P21/b. Concentrations up to 20% of Zn(II) in the mother solution, equivalent to smaller concentrations in solid (up to 9.1% in wt), favor the formation of the hexagonal apatite, P63/m, while Zn(II) concentrations higher than 20% in solution help an amorphous phase development where vibrational spectra indicated coexistence of two phases: an apatite and ZnNH4PO4·H2O. Infrared data of thermal treated samples endorse that HPO42- ion had not been incorporated in Zn(II) doped samples during the synthesis process. Present results also allow to conclude that Zn(II) cation exhibits a preference to occupy the Ca2 site of the apatite structure and induces water adsorption and a small quantity of CO32- cation incorporation, leading to formation of a less crystalline Ca deficient apatite.

Raman spectroscopy imaging reveals interplay between atherosclerosis and medial calcification in the human aorta

PubMed Central

You, Amanda Y. F.; Bergholt, Mads S.; St-Pierre, Jean-Philippe; Kit-Anan, Worrapong; Pence, Isaac J.; Chester, Adrian H.; Yacoub, Magdi H.; Bertazzo, Sergio; Stevens, Molly M.

2017-01-01

Medial calcification in the human aorta accumulates during aging and is known to be aggravated in several diseases. Atherosclerosis, another major cause of cardiovascular calcification, shares some common aggravators. However, the mechanisms of cardiovascular calcification remain poorly understood. To elucidate the relationship between medial aortic calcification and atherosclerosis, we characterized the cross-sectional distributions of the predominant minerals in aortic tissue, apatite and whitlockite, and the associated extracellular matrix. We also compared the cellular changes between atherosclerotic and nonatherosclerotic human aortic tissues. This was achieved through the development of Raman spectroscopy imaging methods that adapted algorithms to distinguish between the major biomolecules present within these tissues. We present a relationship between apatite, cholesterol, and triglyceride in atherosclerosis, with the relative amount of all molecules concurrently increased in the atherosclerotic plaque. Further, the increase in apatite was disproportionately large in relation to whitlockite in the aortic media directly underlying a plaque, indicating that apatite is more pathologically significant in atherosclerosis-aggravated medial calcification. We also discovered a reduction of β-carotene in the whole aortic intima, including a plaque in atherosclerotic aortic tissues compared to nonatherosclerotic tissues. This unprecedented biomolecular characterization of the aortic tissue furthers our understanding of pathological and physiological cardiovascular calcification events in humans. PMID:29226241

First principles NMR study of fluorapatite under pressure.

PubMed

Pavan, Barbara; Ceresoli, Davide; Tecklenburg, Mary M J; Fornari, Marco

2012-01-01

NMR is the technique of election to probe the local properties of materials. Herein we present the results of density functional theory (DFT) ab initio calculations of the NMR parameters for fluorapatite (FAp), a calcium orthophosphate mineral belonging to the apatite family, by using the GIPAW method (Pickard and Mauri, 2001). Understanding the local effects of pressure on apatites is particularly relevant because of their important role in many solid state and biomedical applications. Apatites are open structures, which can undergo complex anisotropic deformations, and the response of NMR can elucidate the microscopic changes induced by an applied pressure. The computed NMR parameters proved to be in good agreement with the available experimental data. The structural evaluation of the material behavior under hydrostatic pressure (from -5 to +100 kbar) indicated a shrinkage of the diameter of the apatitic channel, and a strong correlation between NMR shielding and pressure, proving the sensitivity of this technique to even small changes in the chemical environment around the nuclei. This theoretical approach allows the exploration of all the different nuclei composing the material, thus providing a very useful guidance in the interpretation of experimental results, particularly valuable for the more challenging nuclei such as (43)Ca and (17)O. Copyright © 2012 Elsevier Inc. All rights reserved.

First Principles NMR Study of Fluorapatite under Pressure

PubMed Central

Pavan, Barbara; Ceresoli, Davide; Tecklenburg, Mary M. J.; Fornari, Marco

2012-01-01

NMR is the technique of election to probe the local properties of materials. Herein we present the results of density functional theory (DFT) ab initio calculations of the NMR parameters for fluorapatite (FAp), a calcium orthophosphate mineral belonging to the apatite family, by using the GIPAW method [Pickard and Mauri, 2001]. Understanding the local effects of pressure on apatites is particularly relevant because of their important role in many solid state and biomedical applications. Apatites are open structures, which can undergo complex anisotropic deformations, and the response of NMR can elucidate the microscopic changes induced by an applied pressure. The computed NMR parameters proved to be in good agreement with the available experimental data. The structural evaluation of the material behavior under hydrostatic pressure (from −5 to +100 kbar) indicated a shrinkage of the diameter of the apatitic channel, and a strong correlation between NMR shielding and pressure, proving the sensitivity of this technique to even small changes in the chemical environment around the nuclei. This theoretical approach allows the exploration of all the different nuclei composing the material, thus providing a very useful guidance in the interpretation of experimental results, particularly valuable for the more challenging nuclei such as 43Ca and 17O. PMID:22770669

Ca L2,3-edge XANES and Sr K-edge EXAFS study of hydroxyapatite and fossil bone apatite.

PubMed

Zougrou, I M; Katsikini, M; Brzhezinskaya, M; Pinakidou, F; Papadopoulou, L; Tsoukala, E; Paloura, E C

2016-08-01

Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

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

Ca L2,3-edge XANES and Sr K-edge EXAFS study of hydroxyapatite and fossil bone apatite

NASA Astrophysics Data System (ADS)

Zougrou, I. M.; Katsikini, M.; Brzhezinskaya, M.; Pinakidou, F.; Papadopoulou, L.; Tsoukala, E.; Paloura, E. C.

2016-08-01

Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

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].

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.

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.

Bone mineral as an electrical energy reservoir.

PubMed

Nakamura, Miho; Hiratai, Rumi; Yamashita, Kimihiro

2012-05-01

Mechanical stress in bone induces an electrical potential generated by piezoelectricity arising from displacement of collagen fibrils. Where and for how long the potential is stored in bone; however, are still poorly understood. We investigated the electrical properties of collagen fibrils and apatite minerals and found that bone, when polarized electrically by applying an external voltage, depolarizes by two mechanisms. Plots of thermally stimulated depolarization current show two significant peaks: one at 100°C, attributed to collagen fibrils because decalcified bone exhibits depolarization peak at 100°C, and the other at 500°C, attributed to apatite minerals because calcined bone exhibits depolarization peak at 500°C and has activation energy similar to that for synthesized apatite. The crystallographic c-axis orientation of calcined bone depends on the direction in which the bone is cut, either transverse or longitudinal, and strongly affects the polarization efficacy. Copyright © 2012 Wiley Periodicals, Inc.

100-NR-2 Apatite Treatability Test: High-Concentration Calcium-Citrate-Phosphate Solution Injection for In Situ Strontium-90 Immobilization

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

Vermeul, Vincent R.; Fritz, Brad G.; Fruchter, Jonathan S.

2010-09-01

Following an evaluation of potential strontium-90 (90Sr) treatment technologies and their applicability under 100-NR-2 hydrogeologic conditions, the U.S. Department of Energy (DOE), Fluor Hanford, Inc. (now CH2M Hill Plateau Remediation Company [CHPRC]), Pacific Northwest National Laboratory, and the Washington State Department of Ecology agreed that the long-term strategy for groundwater remediation at the 100-N Area should include apatite as the primary treatment technology. This agreement was based on results from an evaluation of remedial alternatives that identified the apatite permeable reactive barrier (PRB) technology as the approach showing the greatest promise for reducing 90Sr flux to the Columbia River atmore » a reasonable cost. This letter report documents work completed to date on development of a high-concentration amendment formulation and initial field-scale testing of this amendment solution.« less

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

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.

Hierarchical and non-hierarchical mineralisation of collagen

PubMed Central

Liu, Yan; Kim, Young-Kyung; Dai, Lin; Li, Nan; Khan, Sara; Pashley, David H.; Tay, Franklin R.

2010-01-01

Biomineralisation of collagen involves functional motifs incorporated in extracellular matrix protein molecules to accomplish the objectives of stabilising amorphous calcium phosphate into nanoprecursors and directing the nucleation and growth of apatite within collagen fibrils. Here we report the use of small inorganic polyphosphate molecules to template hierarchical intrafibrillar apatite assembly in reconstituted collagen in the presence of polyacrylic acid to sequester calcium and phosphate into transient amorphous nanophases. The use of polyphosphate without a sequestration analogue resulted only in randomly-oriented extrafibrillar precipitations along the fibrillar surface. Conversely, the use of polyacrylic acid without a templating analogue resulted only in non-hierarchical intrafibrillar mineralisation with continuous apatite strands instead of discrete crystallites. The ability of using simple non-protein molecules to recapitulate different levels of structural hierarchy in mineralised collagen signifies the ultimate simplicity in Nature’s biomineralisation design principles and challenges the need for using more complex recombinant matrix proteins in bioengineering applications. PMID:21040969

Calcium Apatite Deposition Disease: Diagnosis and Treatment

PubMed Central

2016-01-01

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

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.

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.

Vanishing Act: Experiments on Fission Track Annealing in Monazite

NASA Astrophysics Data System (ADS)

Shipley, N. K.; Fayon, A. K.

2006-12-01

To determine the viability of monazite as a low temperature thermochronometer, we conducted fission track annealing experiments under isothermal conditions. These experiments evaluated the effects of uranium concentration and zoning on annealing rates. Fission track annealing rates in monazite were also compared to those in Durango apatite. Preliminary results indicate that monazite grains with higher initial track densities anneal at faster rates than those with low initial densities and that fission tracks in monazite anneal at a faster rate than those in apatite. Monazite sand grains were selected from a placer sand deposit, mounted in teflon, and polished. Grains were imaged with electron backscattering to characterize zoning patterns and variations in uranium concentration. Monazite grain mounts were etched in boiling 37% HCl for 50 minutes and fission track densities were determined using standard fission track counting techniques. Durango apatite was etched in 5N HNO3 at room temperature for 20 seconds. After the initial track densities were determined, mounts in one group were annealed at 150 ° C for 1to 6 h. The mounts in a second group were annealed at 200 ° C for 2 hour periods along with mounts of Durango apatite grains. All grains were re-polished prior to each anneal. Upon completion of the experiment, backscatter images were taken of grains from which fission track counts were obtained to verify continuance of concentric zoning. Results of these experiments indicate that annealing rates of fission tracks in monazite vary as a function of uranium concentration. Uranium concentration was constrained on the basis of zoning patterns obtained from electron backscatter images. Fission track densities in grains with initial track densities of approximately 2.4 × 106 tracks/cm2 were reduced at average rate of 16% every two hours. In contrast, track densities in grains with initial track densities of approximately 1.6 × 106 tracks/cm2 average 4.6% density reduction every two hours. In both cases, track density reduction in monazite was faster than the rate of 0.1 % every two hours obtained for apatite. This would indicate that fission track annealing occurs at a lower temperature in monazite than in apatite. Thus monazite would be useful as a low temperature chronometer for determining cooling histories in recently exhumed rocks.

Reconciling Conflicting Geologic and Thermochronologic Interpretations Via Multiple Apatite Thermochronometers (AHe, AFT, and 4He/3He): 6 Ma Incision of the Westernmost Grand Canyon

NASA Astrophysics Data System (ADS)

Winn, C.; Karlstrom, K. E.; Shuster, D. L.; Kelley, S.; Fox, M.

2017-12-01

The application of low-temperature apatite thermochronology to the incision history of the Grand Canyon has led to conflicting hypotheses of either a 70 Ma ("old") or <6 Ma ("young") Grand Canyon. This controversy is best captured in the westernmost segment of the Grand Canyon, where several lines of evidence favor a "young" Canyon: 1) North-derived Paleocene Hindu Fanglomerate was deposited across the present track of the Canyon; 2) The Separation Point basalt (19 Ma) is stranded between high relief tributaries and the main stem of the Colorado River; 3) Relief generation in tributaries and on plateaus adjacent to the Canyon took place after 17 Ma; and 4) The late Miocene-Pliocene Muddy Creek Formation shows that no far-traveled materials entered the Grand Wash Trough until after 6 Ma. Some interpretations of apatite thermochronology data conflict with these lines of evidence and indicate a much older ( 70 Ma) westernmost Grand Canyon. We reconcile this conflict by applying apatite (U-Th)/He ages (AHe), 4He/3He thermochronometry, and apatite fission track ages and lengths (AFT) to the same sample at a key location. Using HeFTy, t-T paths that predict these data show cooling from ˜100 °C to 40-60 °C at 70-50 Ma, long-term residence at 40-60 °C from 50-10 Ma, and cooling to surface temperatures after 10 Ma, indicating young incision. New AFT (5) and AHe (3) datasets are also presented here. When datasets are examined separately, AHe data show t-T paths that cool to surface temperatures during the Laramide, consistent with an "old" Canyon. When multiple methods are applied, t-T paths instead show young incision. This inconsistency demonstrates the age of the Grand Canyon controversy. Here we reconcile the difference in t-T paths by adjusting model parameters to account for uncertainty in the rate of radiation damage annealing in apatite during burial heating and the resulting variations in He retentivity. In this area, peak burial conditions during the Laramide were likely insufficient to fully anneal radiation damage that accumulated during prolonged near-surface residence prior to burial. We conclude that application of multiple thermochronometers from common rocks reconciles conflicting thermochronologic interpretations and these data are best explained by a "young" westernmost Grand Canyon.

Phanerozoic burial and unroofing history of the western Slave craton and Wopmay orogen from apatite (U-Th)/He thermochronometry

NASA Astrophysics Data System (ADS)

Ault, Alexis K.; Flowers, Rebecca M.; Bowring, Samuel A.

2009-06-01

Low temperature thermochronometry of cratonic regions can illuminate relationships among burial and unroofing patterns, surface subsidence and uplift, and lithosphere-asthenosphere interactions. The Slave craton, initially stabilized by the development of a thick lithospheric mantle root in late Archean time, is an excellent location in which to examine these connections. Although the Slave craton currently lacks Phanerozoic cover, Phanerozoic sedimentary xenoliths entrained in ca. 610 to 45 Ma kimberlites indicate that the region underwent a more dynamic history of burial and unroofing than widely recognized. We report new apatite (U-Th)/He thermochronometry data along a southeast to northwest transect from the interior of the Slave craton into the adjacent Paleoproterozoic Wopmay orogen to resolve the region's depositional and denudational history. Six samples from the western Slave craton and three samples from Wopmay orogen yield mean dates from 296 ± 41 Ma to 212 ± 39 Ma. Individual apatite dates are broadly uniform over a wide span of apatite [eU], and this pattern can be used to more tightly restrict the spectrum of viable temperature-time paths that can explain the dataset. When coupled with geologic and stratigraphic information, temperature-time simulations of the thermochronometry results suggest complete He loss from the apatites at minimum peak temperatures of ~ 88 °C in Devonian-Pennsylvanian time, cooling to near-surface conditions by the Early Cretaceous, followed by reheating to ≤ 72 °C during Cretaceous-Early Tertiary time. Consideration of modern and ancient geotherm constraints implies ≥ 3.3 km of burial during the first Phanerozoic heating phase, with an ancillary phase of reburial in late Mesozoic-Cenozoic time. The uniformity of the apatite (U-Th)/He dates indicates that the rocks encompassed by our > 250 km-long sample transect experienced similar Phanerozoic thermal histories. Despite the distinctly different lithospheric architecture on either side of the Paleoproterozoic suture between the Slave craton and Wopmay orogen, the region behaved as a single, broadly coherent cratonic unit since at least ca. 250 Ma. The Phanerozoic burial and unroofing patterns across the craton may be a response to far-field convergent activity at the northern and western margins of North America and processes associated with episodic kimberlite emplacement.

Iron and oxygen isotope signatures of the Pea Ridge and Pilot Knob magnetite-apatite deposits, southeast Missouri, USA

USGS Publications Warehouse

Childress, Tristan; Simon, Adam C.; Day, Warren C.; Lundstrom, Craig C.; Bindeman, Ilya N.

2016-01-01

New O and Fe stable isotope ratios are reported for magnetite samples from high-grade massive magnetite of the Mesoproterozoic Pea Ridge and Pilot Knob magnetite-apatite ore deposits and these results are compared with data for other iron oxide-apatite deposits to shed light on the origin of the southeast Missouri deposits. The δ18O values of magnetite from Pea Ridge (n = 12) and Pilot Knob (n = 3) range from 1.0 to 7.0 and 3.3 to 6.7‰, respectively. The δ56Fe values of magnetite from Pea Ridge (n = 10) and Pilot Knob (n = 6) are 0.03 to 0.35 and 0.06 to 0.27‰, respectively. These δ18O and the δ56Fe values suggest that magnetite crystallized from a silicate melt (typical igneous δ56Fe ranges 0.06–0.49‰) and grew in equilibrium with a magmatic-hydrothermal aqueous fluid. We propose that the δ18O and δ56Fe data for the Pea Ridge and Pilot Knob magnetite-apatite deposits are consistent with the flotation model recently proposed by Knipping et al. (2015a), which invokes flotation of a magmatic magnetite-fluid suspension and offers a plausible explanation for the igneous (i.e., up to ~15.9 wt % TiO2 in magnetite) and hydrothermal features of the deposits.

Citrate- and Succinate-Modified Carbonate Apatite Nanoparticles with Loaded Doxorubicin Exhibit Potent Anticancer Activity against Breast Cancer Cells

PubMed Central

Mehbuba Hossain, Sultana; Chowdhury, Ezharul Hoque

2018-01-01

Biodegradable inorganic apatite-based particle complex is popular for its pH-sensitivity at the endosomal acidic environment to facilitate drug release following cellular uptake. Despite being a powerful anticancer drug, doxorubicin shows severe off-target effects and therefore would need a carrier for the highest effectiveness. We aimed to chemically modify carbonate apatite (CA) with Krebs cycle intermediates, such as citrate and succinate in order to control the growth of the resultant particles to more efficiently carry and transport the anticancer drug into the cancer cells. Citrate- or succinate-modified CA particles were synthesized with different concentrations of sodium citrate or sodium succinate, respectively, in the absence or presence of doxorubicin. The drug loading efficiency of the particles and their cellular uptake were observed by quantifying fluorescence intensity. The average diameter and surface charge of the particles were determined using Zetasizer. Cell viability was assessed by MTT assay. Citrate-modified carbonate apatite (CMCA) exhibited the highest (31.38%) binding affinity for doxorubicin and promoted rapid cellular uptake of the drug, leading to the half-maximal inhibitory concentration 1000 times less than that of the free drug in MCF-7 cells. Hence, CMCA nanoparticles with greater surface area enhance cytotoxicity in different breast cancer cells by enabling higher loading and more efficient cellular uptake of the drug. PMID:29534497

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.

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

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.

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.

Nominally hydrous magmatism on the Moon

PubMed Central

McCubbin, Francis M.; Steele, Andrew; Hauri, Erik H.; Nekvasil, Hanna; Yamashita, Shigeru; Hemley, Russell J.

2010-01-01

For the past 40 years, the Moon has been described as nearly devoid of indigenous water; however, evidence for water both on the lunar surface and within the lunar interior have recently emerged, calling into question this long-standing lunar dogma. In the present study, hydroxyl (as well as fluoride and chloride) was analyzed by secondary ion mass spectrometry in apatite [Ca5(PO4)3(F,Cl,OH)] from three different lunar samples in order to obtain quantitative constraints on the abundance of water in the lunar interior. This work confirms that hundreds to thousands of ppm water (of the structural form hydroxyl) is present in apatite from the Moon. Moreover, two of the studied samples likely had water preserved from magmatic processes, which would qualify the water as being indigenous to the Moon. The presence of hydroxyl in apatite from a number of different types of lunar rocks indicates that water may be ubiquitous within the lunar interior, potentially as early as the time of lunar formation. The water contents analyzed for the lunar apatite indicate minimum water contents of their lunar source region to range from 64 ppb to 5 ppm H2O. This lower limit range of water contents is at least two orders of magnitude greater than the previously reported value for the bulk Moon, and the actual source region water contents could be significantly higher. PMID:20547878

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

NASA Astrophysics Data System (ADS)

Ibsen, Casper Jon Steenberg; Birkedal, Henrik

2010-11-01

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

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.

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.

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.

Nominally hydrous magmatism on the Moon.

PubMed

McCubbin, Francis M; Steele, Andrew; Hauri, Erik H; Nekvasil, Hanna; Yamashita, Shigeru; Hemley, Russell J

2010-06-22

For the past 40 years, the Moon has been described as nearly devoid of indigenous water; however, evidence for water both on the lunar surface and within the lunar interior have recently emerged, calling into question this long-standing lunar dogma. In the present study, hydroxyl (as well as fluoride and chloride) was analyzed by secondary ion mass spectrometry in apatite [Ca(5)(PO(4))(3)(F,Cl,OH)] from three different lunar samples in order to obtain quantitative constraints on the abundance of water in the lunar interior. This work confirms that hundreds to thousands of ppm water (of the structural form hydroxyl) is present in apatite from the Moon. Moreover, two of the studied samples likely had water preserved from magmatic processes, which would qualify the water as being indigenous to the Moon. The presence of hydroxyl in apatite from a number of different types of lunar rocks indicates that water may be ubiquitous within the lunar interior, potentially as early as the time of lunar formation. The water contents analyzed for the lunar apatite indicate minimum water contents of their lunar source region to range from 64 ppb to 5 ppm H(2)O. This lower limit range of water contents is at least two orders of magnitude greater than the previously reported value for the bulk Moon, and the actual source region water contents could be significantly higher.

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.

A multidisciplinary analysis to constrain exhumation and recent erosion history of the Tethyan Himalaya, based on apatite (U-Th-Sm)/He and cosmogenic nuclides dates from Central Nepal (Takkhola graben and the Mustang granite)

NASA Astrophysics Data System (ADS)

Rosenkranz, Ruben; Sahragard Sohi, Mohammad; Spiegel, Cornelia

2015-04-01

The exhumation of the Himalayan arc has been studied intensively throughout the last decades. For the Tethyan Himalaya, however, the youngest exhumation history is still unclear, mostly because of the lack of a significant apatite content in most Tethyan sediments (Crouzet et al. 2007). For this study we are using apatite (U-Th-Sm)/He thermochronology and cosmogenic nuclides for investigating exhumation and denudation of the Tethyan Himalaya back through time. Apatite (U-Th-Sm)/He thermochronology is sensitive to temperatures of ~40 to 85°C and thus to movements within the upper ~1.5 to 3 km of the earth's crust. During a recent field campaign, we sampled the Mustang granite, that intrudes the Tethyan marine sediments and the Takkhola-Graben. The graben can be seen as an inusual southern part of the normal faulting system affecting the whole Tibetan Plateau (Colchen, 1999). The timing of the activation of these faulting is still highly debated. The syntectonics filling of the Takkhola-Mustag graben consists of Mio-Pliocene fluvio-lacustrine deposits (Garzione et al. 2003). These were described as containing significant amounts of apatite, derived from the past erosion of the Mustang granitic body (Adhikari and Wagreich, 2011). Being only up to 1km thick, a post depositional thermal resetting of the apatite (U-Th-Sm)/He system is unlikely, so that the (U-Th-Sm)/He dates of the sediments are expected to have retained their information regarding source area exhumation. We took several sand samples from the Kali Gandaki River draining the present-day exposure of the Mustang granite. Furthermore, we sampled different stratigraphic levels of the Mio-Pliocene sedimentary rocks, i.e., from the Tetang and Takkahola formation deposited between 11 and 7 Ma. This sampling approach will not only provide information about the youngest denudation history of the Mustang granite /Tethyan Himalaya, but will also reveal insights into its past denudation and changes of denudation rates through time for the region north to the South Tibetan Detachment. It is our expectation to link the results to the tectonic behavior of the South Tibetan Detachment or to the newly recognized Western Nepal Fault System. Corroborating our results with other ages and diverse methods will provide a robust constraint on the exhumation and erosion history of the Tethyan Himalaya, as well as insights on the U-Th/He dating technique. References Adhikari, B.R. and Wagreich, M., 2011. Provenance evolution of collapse graben fill in the Himalaya-The Miocene to Quaternary Thakkhola-Mustang graben (Nepal). Sedimentary Geology, 233(1), pp.1-14. Blythe, A.E., Burbank, D.W., Carter, A., Schmidt, K., Putkonen, J., 2007. Plio-Quaternary exhumation history of the central Nepalese Himalaya: 1. Apatite and zircon fission track and apatite [U-Th]/He analyses. Tectonics, 26(3). Crouzet, C. et al., 2007. Temperature and age constraints on the metamorphism of the Tethyan Himalaya in Central Nepal: A multidisciplinary approach. Journal of Asian Earth Sciences, 30(1), pp.113-130. Garzione, C.N, DeCelles, P.G., Hokinson, D.G., Ojha, T.P., Upreti, B.N., 2003. East-west extension and Miocene environmental change in the southern Tibetan plateau: Thakkhola graben, central Nepal. Geological Society of America Bulletin, 115(1), pp.3-20. Colchen, M., 1999. The Takkhola-Mustang graben in Nepal and the latee Cenozoic extension in the Higher Himalayas. Journal of Asian Earth Sciences, 17, pp. 683-702.

Apatite Formation and Biocompatibility of a Low Young’s Modulus Ti-Nb-Sn Alloy Treated with Anodic Oxidation and Hot Water

PubMed Central

Tanaka, Hidetatsu; Mori, Yu; Noro, Atsushi; Kogure, Atsushi; Kamimura, Masayuki; Yamada, Norikazu; Hanada, Shuji; Masahashi, Naoya; Itoi, Eiji

2016-01-01

Ti-6Al-4V alloy is widely prevalent as a material for orthopaedic implants because of its good corrosion resistance and biocompatibility. However, the discrepancy in Young’s modulus between metal prosthesis and human cortical bone sometimes induces clinical problems, thigh pain and bone atrophy due to stress shielding. We designed a Ti-Nb-Sn alloy with a low Young’s modulus to address problems of stress disproportion. In this study, we assessed effects of anodic oxidation with or without hot water treatment on the bone-bonding characteristics of a Ti-Nb-Sn alloy. We examined surface analyses and apatite formation by SEM micrographs, XPS and XRD analyses. We also evaluated biocompatibility in experimental animal models by measuring failure loads with a pull-out test and by quantitative histomorphometric analyses. By SEM, abundant apatite formation was observed on the surface of Ti-Nb-Sn alloy discs treated with anodic oxidation and hot water after incubation in Hank’s solution. A strong peak of apatite formation was detected on the surface using XRD analyses. XPS analysis revealed an increase of the H2O fraction in O 1s XPS. Results of the pull-out test showed that the failure loads of Ti-Nb-Sn alloy rods treated with anodic oxidation and hot water was greater than those of untreated rods. Quantitative histomorphometric analyses indicated that anodic oxidation and hot water treatment induced higher new bone formation around the rods. Our findings indicate that Ti-Nb-Sn alloy treated with anodic oxidation and hot water showed greater capacity for apatite formation, stronger bone bonding and higher biocompatibility for osteosynthesis. Ti-Nb-Sn alloy treated with anodic oxidation and hot water treatment is a promising material for orthopaedic implants enabling higher osteosynthesis and lower stress disproportion. PMID:26914329

Developing biogeochemical tracers of apatite weathering by ectomycorrhizal fungi

NASA Astrophysics Data System (ADS)

Vadeboncoeur, M. A.; Bryce, J. G.; Hobbie, E. A.; Meana-Prado, M. F.; Blichert-Toft, J.

2012-12-01

Chronic acid deposition has depleted calcium (Ca) from many New England forest soils, and intensive harvesting may reduce phosphorus (P) available to future rotations. Thin glacial till soils contain trace amounts of apatite, a primary calcium phosphate mineral, which may be an important long-term source of both P and Ca to ecosystems. The extent to which ECM fungi enhance the weathering rate of primary minerals in soil which contain growth-limiting nutrients remains poorly quantified, in part due to biogeochemical tracers which are subsequently masked by within-plant fractionation. Rare earth elements (REEs) and Pb isotope ratios show some potential for revealing differences in soil apatite weathering rates across forest stands and silvicultural treatments. To test the utility of these tracers, we grew birch seedlings semi-hydroponically under controlled P-limited conditions, supplemented with mesh bags containing granite chips. Our experimental design included nonmycorrhizal (NM) as well as ectomycorrhizal cultures (Cortinarius or Leccinum). Resulting mycorrhizal roots and leachates of granite chips were analyzed for these tracers. REE concentrations in roots were greatly elevated in treatments with granite relative to those without granite, demonstrating uptake of apatite weathering products. Roots with different mycorrhizal fungi accumulated similar concentrations of REEs and were generally elevated compared to the NM cultures. Ammonium chloride leaches of granite chips grown in contact with mycorrhizal hyphae show elevated REE concentrations and significantly radiogenic Pb isotope signatures relative to bulk rock, also supporting enhanced apatite dissolution. Our results in culture are consistent with data from field-collected sporocarps from hardwood stands in the Bartlett Experimental Forest in New Hampshire, in which Cortinarius sporocarp Pb isotope ratios were more radiogenic than those of other ectomycorrhizal sporocarps. Taken together, the experimental and field results imply that the coupled approach of REE and Pb isotopic values afford a means to quantify the degree to which primary mineral weathering inputs are contributing to ecosystem nutrient budgets and potentially the role of different types of ECM fungi in the weathering process.

Dental Composites with Calcium / Strontium Phosphates and Polylysine.

PubMed

Panpisut, Piyaphong; Liaqat, Saad; Zacharaki, Eleni; Xia, Wendy; Petridis, Haralampos; Young, Anne Margaret

2016-01-01

This study developed light cured dental composites with added monocalcium phosphate monohydrate (MCPM), tristrontium phosphate (TSrP) and antimicrobial polylysine (PLS). The aim was to produce composites that have enhanced water sorption induced expansion, can promote apatite precipitation and release polylysine. Experimental composite formulations consisted of light activated dimethacrylate monomers combined with 80 wt% powder. The powder phase contained a dental glass with and without PLS (2.5 wt%) and/or reactive phosphate fillers (15 wt% TSrP and 10 wt% MCPM). The commercial composite, Z250, was used as a control. Monomer conversion and calculated polymerization shrinkage were assessed using FTIR. Subsequent mass or volume changes in water versus simulated body fluid (SBF) were quantified using gravimetric studies. These were used, along with Raman and SEM, to assess apatite precipitation on the composite surface. PLS release was determined using UV spectroscopy. Furthermore, biaxial flexural strengths after 24 hours of SBF immersion were obtained. Monomer conversion of the composites decreased upon the addition of phosphate fillers (from 76 to 64%) but was always higher than that of Z250 (54%). Phosphate addition increased water sorption induced expansion from 2 to 4% helping to balance the calculated polymerization shrinkage of ~ 3.4%. Phosphate addition promoted apatite precipitation from SBF. Polylysine increased the apatite layer thickness from ~ 10 to 20 μm after 4 weeks. The novel composites showed a burst release of PLS (3.7%) followed by diffusion-controlled release irrespective of phosphate addition. PLS and phosphates decreased strength from 154 MPa on average by 17% and 18%, respectively. All formulations, however, had greater strength than the ISO 4049 requirement of > 80 MPa. The addition of MCPM with TSrP promoted hygroscopic expansion, and apatite formation. These properties are expected to help compensate polymerization shrinkage and help remineralize demineralized dentin. Polylysine can be released from the composites at early time. This may kill residual bacteria.

Hematite (U-Th)/He thermochronometry constrains intraplate strike-slip faulting on the Kuh-e-Faghan Fault, central Iran

NASA Astrophysics Data System (ADS)

Calzolari, Gabriele; Rossetti, Federico; Ault, Alexis K.; Lucci, Federico; Olivetti, Valerio; Nozaem, Reza

2018-03-01

The Kuh-e-Faghan strike-slip fault system (KFF), located to the northern edge of the Lut Block in central Iran, developed through a Neogene-Quaternary pulsed history of eastward fault propagation and fault-related exhumation. This system is a consequence of the residual stresses transmitted from the Arabia-Eurasia convergent plate boundary. Here we integrate structural and textural analysis with new and previously published apatite fission-track (AFT) and apatite (U-Th)/He (apatite He) results, chlorite thermomentry, and hematite (U-Th)/He data from hematite-coated brittle fault surfaces to constrain the timing of tectonic activity and refine patterns of late Miocene-Pliocene burial and exhumation associated with the propagation of the KFF. Twenty-nine hematite (U-Th)/He (hematite He) dates from three striated hematite coated slip surfaces from the KFF fault core and damage zone yield individual dates from 12-2 Ma. Petrographic analysis and chlorite thermometry of a polyphase, fossil fluid system in the KFF fault core document that fluid circulation and mineralization transitioned from a closed system characterized by pressure solution and calcite growth to an open system characterized by hot hydrothermal (T = 239 ± 10 °C) fluids and hematite formation. Hematite microtextures and grain size analysis reveal primary and secondary syntectonic hematite fabrics, no evidence of hematite comminution and similar hematite He closure temperatures ( 60-85 °C) in each sample. Integration of these results with thermal history modeling of AFT and apatite He data shows that KFF activity in the late Miocene is characterized by an early stage of fault nucleation, fluid circulation, hematite mineralization, and eastward propagation not associated with vertical movement that lasted from 12 to 7 Ma. Hematite He, AFT, and apatite He data track a second phase of fault system activity involving fault-related exhumation initiating at 7 Ma and continuing until present time. Our new data constrain the onset of the recognized Late Miocene-Pliocene tectonic reorganization in north-central Iran.

Tectono-thermal evolution of the southwestern Alxa Tectonic Belt, NW China: Constrained by apatite U-Pb and fission track thermochronology

NASA Astrophysics Data System (ADS)

Song, Dongfang; Glorie, Stijn; Xiao, Wenjiao; Collins, Alan S.; Gillespie, Jack; Jepson, Gilby; Li, Yongchen

2018-01-01

The Central Asian Orogenic Belt (CAOB) is regarded to have undergone multiple phases of intracontinental deformation during the Meso-Cenozoic. Located in a key position along the southern CAOB, the Alxa Tectonic Belt (ATB) connects the northernmost Tibetan Plateau with the Mongolian Plateau. In this paper we apply apatite U-Pb and fission track thermochronological studies on varieties of samples from the southwestern ATB, in order to constrain its thermal evolution. Precambrian bedrock samples yield late Ordovician-early Silurian ( 430-450 Ma) and late Permian ( 257 Ma) apatite U-Pb ages; the late Paleozoic magmatic-sedimentary samples yield relatively consistent early Permian ages from 276 to 290 Ma. These data reveal that the ATB experienced multiple Paleozoic tectono-thermal events, as the samples passed through the apatite U-Pb closure temperature ( 350-550 °C). We interpret these tectonic events to record the long-lived subduction-accretion processes of the Paleo-Asian Ocean during the formation of the southern CAOB, with possible thermal influence of the Permian Tarim mantle plume. Apatite fission track (AFT) data and thermal history modelling reveal discrete low-temperature thermal events for the ATB, inducing cooling/reheating through the AFT partial annealing zone ( 120-60 °C). During the Permian, the samples underwent rapid cooling via exhumation or denudation from deep crustal levels to temperatures < 200 °C. Subsequent thermal events in the Triassic were thought to be associated with the final amalgamation of the CAOB or the closure of the Paleotethys. During the Jurassic-Cretaceous the study area experienced heating by burial, followed by renewed cooling, which may be related with the construction and subsequent collapse of the Mongol-Okhotsk Orogeny, or the Lhasa-Eurasia collision and subsequent slab break-off. These results indicate that the ATB may have been stable after late Cretaceous in contrast to the Qilian Shan and Tianshan. Finally, our results indicate differential exhumation scenario occurred across the southwestern ATB during the Cretaceous.

A helium-based model for the effects of radiation damage annealing on helium diffusion kinetics in apatite

NASA Astrophysics Data System (ADS)

Willett, Chelsea D.; Fox, Matthew; Shuster, David L.

2017-11-01

Widely used to study surface processes and the development of topography through geologic time, (U-Th)/He thermochronometry in apatite depends on a quantitative description of the kinetics of 4He diffusion across a range of temperatures, timescales, and geologic scenarios. Empirical observations demonstrate that He diffusivity in apatite is not solely a function of temperature, but also depends on damage to the crystal structure from radioactive decay processes. Commonly-used models accounting for the influence of thermal annealing of radiation damage on He diffusivity assume the net effects evolve in proportion to the rate of fission track annealing, although the majority of radiation damage results from α-recoil. While existing models adequately quantify the net effects of damage annealing in many geologic scenarios, experimental work suggests different annealing rates for the two damage types. Here, we introduce an alpha-damage annealing model (ADAM) that is independent of fission track annealing kinetics, and directly quantifies the influence of thermal annealing on He diffusivity in apatite. We present an empirical fit to diffusion kinetics data and incorporate this fit into a model that tracks the competing effects of radiation damage accumulation and annealing on He diffusivity in apatite through geologic time. Using time-temperature paths to illustrate differences between models, we highlight the influence of damage annealing on data interpretation. In certain, but not all, geologic scenarios, the interpretation of low-temperature thermochronometric data can be strongly influenced by which model of radiation damage annealing is assumed. In particular, geologic scenarios involving 1-2 km of sedimentary burial are especially sensitive to the assumed rate of annealing and its influence on He diffusivity. In cases such as basement rocks in Grand Canyon and the Canadian Shield, (U-Th)/He ages predicted from the ADAM can differ by hundreds of Ma from those predicted by other models for a given thermal path involving extended residence between ∼40-80 °C.

Advantages and challenges in automated apatite fission track counting

NASA Astrophysics Data System (ADS)

Enkelmann, E.; Ehlers, T. A.

2012-04-01

Fission track thermochronometer data are often a core element of modern tectonic and denudation studies. Soon after the development of the fission track methods interest emerged for the developed an automated counting procedure to replace the time consuming labor of counting fission tracks under the microscope. Automated track counting became feasible in recent years with increasing improvements in computer software and hardware. One such example used in this study is the commercial automated fission track counting procedure from Autoscan Systems Pty that has been highlighted through several venues. We conducted experiments that are designed to reliably and consistently test the ability of this fully automated counting system to recognize fission tracks in apatite and a muscovite external detector. Fission tracks were analyzed in samples with a step-wise increase in sample complexity. The first set of experiments used a large (mm-size) slice of Durango apatite cut parallel to the prism plane. Second, samples with 80-200 μm large apatite grains of Fish Canyon Tuff were analyzed. This second sample set is characterized by complexities often found in apatites in different rock types. In addition to the automated counting procedure, the same samples were also analyzed using conventional counting procedures. We found for all samples that the fully automated fission track counting procedure using the Autoscan System yields a larger scatter in the fission track densities measured compared to conventional (manual) track counting. This scatter typically resulted from the false identification of tracks due surface and mineralogical defects, regardless of the image filtering procedure used. Large differences between track densities analyzed with the automated counting persisted between different grains analyzed in one sample as well as between different samples. As a result of these differences a manual correction of the fully automated fission track counts is necessary for each individual surface area and grain counted. This manual correction procedure significantly increases (up to four times) the time required to analyze a sample with the automated counting procedure compared to the conventional approach.

Plant Growth Experiments in Zeoponic Substrates: Applications for Advanced Life Support Systems

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Gruener, J. E.; Henderson, K. E.; Steinberg, S. L.; Barta, D. J.; Galindo, C.; Henninger, D. L.

2001-01-01

A zeoponic plant-growth system is defined as the cultivation of plants in artificial soils, which have zeolites as a major component (Allen and Ming, 1995). Zeolites are crystalline, hydrated aluminosilicate minerals that have the ability to exchange constituent cations without major change of the mineral structure. Recently, zeoponic systems developed at the National Aeronautics and Space Administration (NASA) slowly release some (Allen et at., 1995) or all of the essential plant-growth nutrients (Ming et at., 1995). These systems have NH4- and K-exchanged clinoptilolite (a natural zeolite) and either natural or synthetic apatite (a calcium phosphate mineral). For the natural apatite system, Ca and P were made available to the plant by the dissolution of apatite. Potassium and NH4-N were made available by ion-exchange reactions involving Ca(2+) from apatite dissolution and K(+) and NH4(+) on zeolitic exchange sites. In addition to NH4-N, K, Ca, and P, the synthetic apatite system also supplied Mg, S, and other micronutrients during dissolution (Figure 1). The overall objective of this research task is to develop zeoponic substrates wherein all plant growth nutrients are supplied by the plant growth medium for several growth seasons with only the addition of water. The substrate is being developed for plant growth in Advanced Life Support (ALS) testbeds (i.e., BioPLEX) and microgravity plant growth experiments. Zeoponic substrates have been used for plant growth experiments on two Space Shuttle flight experiments (STS-60; STS-63; Morrow et aI., 1995). These substrates may be ideally suited for plant growth experiments on the International Space Station and applications in ALS testbeds. However, there are several issues that need to be resolved before zeoponics will be the choice substrate for plant growth experiments in space. The objective of this paper is to provide an overview on recent research directed toward the refinement of zeoponic plant growth substrates.

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.

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.

(U-Th-Sm)/He thermochronological age distribution in a slowly cooled plutonic complex (Ploumanac'h intrusion, France): insights into helium diffusion processes.

NASA Astrophysics Data System (ADS)

Recanati, A. C.; Gautheron, C.; Barbarand, J.; Tassan-Got, L.; Missenard, Y.; Pinna-Jamme, R.

2015-12-01

(U-Th-Sm)/He thermochronology is widely used to determine the thermal histories of mountain ranges and sedimentary basins. Apatite crystals retain helium at low temperatures, thus giving an insight into upper crustal evolution (e.g. exhumation, subsidence, erosion). Advanced models predict He production and diffusion rates in apatite crystals, thereby allowing determination of helium dates by integration over time/temperature paths (e.g. Gautheron et al., 2009). However, scattered dates and discordance between predicted and measured dates suggest that other parameters than time or temperature may also influence helium contents in apatite. The present study determines the variables that affect He diffusion in apatite over long timescales. We report the (U-Th-Sm)/He date distribution within a slowly cooled intrusion, along with AFT data, as well as extensive petrological and chemical characterization. The Ploumanac'h site (Brittany, France) was chosen because it includes small-scale spatial variations in petrology and chemistry (6-9106 tracks/cm2). GAUTHERON C., TASSAN-GOT L., BARBARAND J., PAGEL M., 2009. Effect of alpha-damage annealing on apatite (U-Th)/He thermochronology. Chem. Geol. 266, 166-179.

Helium diffusion experiments on synthetic apatite crystals and single-grain fragments: can we retrieve the He diffusion profiles?

NASA Astrophysics Data System (ADS)

Kasanzu, C.; Beucher, R.; Brown, R. W.; Persano, C.; Stuart, F.

2011-12-01

Apatite (U-Th)/he thermochronometry is one of the most widely used methods of quantifying thermal histories of rocks within the vicinity of the surface. Theoretical and practical development carried out during the last decade, among which was the release of affordable LASERs, have led to standard practice of analyzing single grain rather than multigrain aliquots. The standard theoretical basis for interpreting these ages assumes that the technique is used on full grains. However, the natural weak cleavage of apatite leads to fragmentation of these individual prismatic crystals during the rock crushing and mineral separation process. Apatites are most often broken along a weak cleavage perpendicular to the c-axis. It is therefore common practice to analyze fragments of whole grains, not complete crystals. It is also well known that dating often leads to single ages being more dispersed than expected whatever the efforts to avoid perturbations on the He system. Using a theoretical numerical model and considering both axial and radial diffusion, we demonstrate thata largepart (most?) of the dispersion is due to analyses of single apatite fragments. This effect is larger for older grains which have exprienced a slow cooling history and have well rounded diffusive profiles. Ages are a strongfunction of the fragment size (length specifically), we show that ages from apatite fragments with 1 prismatic termination (1T) can be used to retrieve the helium diffusion profile, provided a sufficient number of single fragment analyses are carried out. The shape of the helium diffusion profile provides a strong constraint on the style of the thermal history and so we propose to use single crystal fragment analyses to extract a mean diffusion profile, and deduce the thermal history of the sample. In order to test these ideas, we performed a set of experiments with natural samples and semi-synthetic grains of apatite. Synthetic grains are obtained by drilling cores of various length/width ratios within standard Durango crystals while natural grains are separated from a deep borehole in south-Africa (BK1) and from the Australian craton. Several experiences are presented: 1) (U-Th)/He dating of about 100 1T single-fragment aliquots of different shape ratio from the BK1 borehole; 2) (U-Th)/He dating of 20 2T single-fragment aliquot from an Australian sample previously dated following standard procedure. 3) (U-Th)/He dating of synthetic fragmentsfrom synthetic grains previously degassed by a known percentageusing a thermo-regulated furnace. The results of the experiments lead to important new insight into the natural dispersion of (U-Th)/He single-grain ages. They show that far from being problematic, highly dispersed data may indeed contain first-order information on the thermal history of rocks. We discuss all the details of the standard (U-Th)/He approach such as the effects of temporally variable diffusivity (e.g. radiation damage models), zonation of U and Th and arbitrary grain size variations.

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

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.

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

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.

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.

Raman spectroscopy of apatite irradiated with swift heavy ions with and without simultaneous exertion of high pressure

NASA Astrophysics Data System (ADS)

Liu, J.; Glasmacher, U. A.; Lang, M.; Trautmann, C.; Voss, K.-O.; Neumann, R.; Wagner, G. A.; Miletich, R.

2008-04-01

Durango apatite was irradiated with energetic U ions of 2.64 GeV and Kr ions of 2.1 GeV, with and without simultaneous exposure to a pressure of 10.5 GPa. Analysis by confocal Raman spectroscopy gives evidence of vibrational changes being marginal for fluences below 5×1011 ions/cm2 but becoming dominant when increasing the fluence to 8×1012 ions/cm2. Samples irradiated with U ions experience severe strain resulting in crystal cracking and finally breakage at high fluences. These radiation effects are directly linked to the formation of amorphous tracks and the fraction of amorphized material increasing with fluence. Raman spectroscopy of pressurized irradiated samples shows small shifts of the band positions with decreasing pressure but without a significant change of the Grüneisen parameter. Compared to irradiations at ambient conditions, the Raman spectra of apatite irradiated at 10.5 GPa exhibit fewer modifications, suggesting a higher radiation stability of the lattice by the pressure applied.

Ionic Substitutions in Non-Apatitic Calcium Phosphates

PubMed Central

Laskus, Aleksandra; Kolmas, Joanna

2017-01-01

Calcium phosphate materials (CaPs) are similar to inorganic part of human mineralized tissues (i.e., bone, enamel, and dentin). Owing to their high biocompatibility, CaPs, mainly hydroxyapatite (HA), have been investigated for their use in various medical applications. One of the most widely used ways to improve the biological and physicochemical properties of HA is ionic substitution with trace ions. Recent developments in bioceramics have already demonstrated that introducing foreign ions is also possible in other CaPs, such as tricalcium phosphates (amorphous as well as α and β crystalline forms) and brushite. The purpose of this paper is to review recent achievements in the field of non-apatitic CaPs substituted with various ions. Particular attention will be focused on tricalcium phosphates (TCP) and “additives” such as magnesium, zinc, strontium, and silicate ions, all of which have been widely investigated thanks to their important biological role. This review also highlights some of the potential biomedical applications of non-apatitic substituted CaPs. PMID:29186932

Diet and mobility in a late Neolithic population of coastal Oman inferred from radiocarbon dating and stable isotope analysis.

PubMed

Zazzo, Antoine; Munoz, Olivia; Saliège, Jean-François

2014-03-01

In Oman, the presence of highly productive marine environments, coupled with relatively limited land resources, have led to intense exploitation of coastal resources, but the question of the seasonality of occupation of coastal sites remains open. Our aim is to evaluate the contribution of marine resources to the diet of the Neolithic population of Ra's al-Hamra 5 (RH-5) to shed new light on its mobility, using stable isotopes and radiocarbon ((14)C) dating as dietary tracers. Charcoal, shell, human bone and enamel apatite from eight contemporary graves were sampled. Graves are thought to provide the best chance to obtain marine and terrestrial remains that were contemporary with the human remains in order to calculate the marine reservoir effect (MRE) for this period. Inter-individual variation in human bone apatite δ(13)C value is small, suggesting a homogenous diet. Bone apatite (14)C ages are very close to the shell ages while enamel is significantly younger and plots near the charcoal ages. Older enamel ages were obtained when a stronger acetic treatment was used, demonstrating that the young ages are due to diagenetic alteration rather than a diachronic change in diet and that only bone apatite retained in vivo dietary signals. Bone ages indicate a heavy reliance on marine resources and it is therefore unlikely that the individuals analyzed here were leaving the coast seasonally, although mobility along the coast cannot be excluded. Copyright © 2013 Wiley Periodicals, Inc.

Spatial variations in focused exhumation along a continental-scale strike-slip fault: The Denali fault of the eastern Alaska Range

USGS Publications Warehouse

Benowitz, J.A.; Layer, P.W.; Armstrong, P.; Perry, S.E.; Haeussler, Peter J.; Fitzgerald, P.G.; VanLaningham, S.

2011-01-01

40Ar/39Ar, apatite fission-track, and apatite (U-Th)/He thermochronological techniques were used to determine the Neogene exhumation history of the topographically asymmetric eastern Alaska Range. Exhumation cooling ages range from ~33 Ma to ~18 Ma for 40Ar/39Ar biotite, ~18 Ma to ~6 Ma for K-feldspar minimum closure ages, and ~15 Ma to ~1 Ma for apatite fission-track ages, and apatite (U-Th)/He cooling ages range from ~4 Ma to ~1 Ma. There has been at least ~11 km of exhumation adjacent to the north side of Denali fault during the Neogene inferred from biotite 40Ar/39Ar thermochronology. Variations in exhumation history along and across the strike of the fault are influenced by both far-field effects and local structural irregularities. We infer deformation and rapid exhumation have been occurring in the eastern Alaska Range since at least ~22 Ma most likely related to the continued collision of the Yakutat microplate with the North American plate. The Nenana Mountain region is the late Pleistocene to Holocene (~past 1 Ma) primary locus of tectonically driven exhumation in the eastern Alaska Range, possibly related to variations in fault geometry. During the Pliocene, a marked increase in climatic instability and related global cooling is temporally correlated with an increase in exhumation rates in the eastern Alaska Range north of the Denali fault system.

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.

Combinatorial MAPLE deposition of antimicrobial orthopedic maps fabricated from chitosan and biomimetic apatite powders.

PubMed

Visan, A; Stan, G E; Ristoscu, C; Popescu-Pelin, G; Sopronyi, M; Besleaga, C; Luculescu, C; Chifiriuc, M C; Hussien, M D; Marsan, O; Kergourlay, E; Grossin, D; Brouillet, F; Mihailescu, I N

2016-09-10

Chitosan/biomimetic apatite thin films were grown in mild conditions of temperature and pressure by Combinatorial Matrix-Assisted Pulsed Laser Evaporation on Ti, Si or glass substrates. Compositional gradients were obtained by simultaneous laser vaporization of the two distinct material targets. A KrF* excimer (λ=248nm, τFWHM=25ns) laser source was used in all experiments. The nature and surface composition of deposited materials and the spatial distribution of constituents were studied by SEM, EDS, AFM, GIXRD, FTIR, micro-Raman, and XPS. The antimicrobial efficiency of the chitosan/biomimetic apatite layers against Staphylococcus aureus and Escherichia coli strains was interrogated by viable cell count assay. The obtained thin films were XRD amorphous and exhibited a morphology characteristic to the laser deposited structures composed of nanometric round shaped grains. The surface roughness has progressively increased with chitosan concentration. FTIR, EDS and XPS analyses indicated that the composition of the BmAp-CHT C-MAPLE composite films gradually modified from pure apatite to chitosan. The bioevaluation tests indicated that S. aureus biofilm is more susceptible to the action of chitosan-rich areas of the films, whilst the E. coli biofilm proved more sensible to areas containing less chitosan. The best compromise should therefore go, in our opinion, to zones with intermediate-to-high chitosan concentration which can assure a large spectrum of antimicrobial protection concomitantly with a significant enhancement of osseointegration, favored by the presence of biomimetic hydroxyapatite. Copyright © 2016 Elsevier B.V. All rights reserved.

Bioactivity and cytocompatibility of zirconia (ZrO(2)) films fabricated by cathodic arc deposition.

PubMed

Liu, Xuanyong; Huang, Anping; Ding, Chuanxian; Chu, Paul K

2006-07-01

Zirconium oxide thin films were fabricated on silicon wafers using a filtered cathodic arc system in concert with oxygen plasma. The structure and phase composition of the zirconium oxide thin films were characterized by atomic force microscopy (AFM), X-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS), and transmission electron microscopy (TEM). The bioactivity was assessed by investigating the formation of apatite on the film surface after soaking in simulated body fluids. Bone marrow mesenchymal stem cells (BMMSC) were used to further evaluate the cytocompatibility of the materials. The results indicate that the films are composed of stoichiometric ZrO(2) and the composition is quite uniform throughout the thickness. Bone-like apatite can be formed on the surface of the ZrO(2) thin film in our SBF immersion experiments, suggesting that the surface is bioactive. The outermost layer of the ZrO(2) thin film comprises nano-sized particles that can be identified by AFM images taken on the thin film surface and TEM micrographs obtained from the interface between the ZrO(2) thin film and apatite layer. The nanostructured surface is believed to be the key factor that apatite is induced to precipitate on the surface. Bone marrow mesenchymal stem cells are observed to grow and proliferate in good states on the film surface. Our results show that ZrO(2) thin films fabricated by cathodic arc deposition exhibit favorable bioactivity and cytocompatibility.

300 million years of basin evolution - the thermotectonic history of the Ukrainian Donbas Foldbelt

NASA Astrophysics Data System (ADS)

Spiegel, C.; Danisik, M.; Sachsenhofer, R.; Frisch, W.; Privalov, V.

2009-04-01

The Ukrainian-Russian Pripyat-Dniepr-Donets Basin is a large intracratonic rift structure formed during the Late Devonian. It is situated at the southern margin of the Precambrian East European Craton, adjacent to the Hercynian Tethyan belt in the Black Sea area and the Alpine Caucasus orogen. With a sediment thickness of more than 20 km, it is one of the deepest sedimentary basins on earth. The eastern part of the Pripyat-Dniepr-Donets Basin - called Donbas foldbelt - is strongly folded and inverted. Proposed models of basin evolution are often controversial and numerous issues are still a matter of speculation, particularly the erosion history and the timing of basin inversion. Basin inversion may have taken place during the Permian related to the Uralian orogeny, or in response to Alpine tectonics during the Late Cretaceous to Early Tertiary. We investigated the low-temperature thermal history of the Donbas Foldbelt and the adjacent Ukrainian shield by a combination of zircon fission track, apatite fission track and apatite (U-Th)/He thermochronology. Although apatite fission track ages of all sedimentary samples were reset shortly after deposition during the Carboniferous, we took advantage of the fact that samples contained kinetically variable apatites, which are sensitive to different temperatures. By using statistic-based component analysis incorporating physical properties of individual grains we identified several distinct age population, ranging from late Permian (~265 Ma) to the Late Cretaceous (70 Ma). We could thus constrain the thermal history of the Donbas Foldbelt and the adjacent basement during a ~300 Myr long time period. The Precambrian crystalline basement of the Ukrainian shield was affected by a Permo-Triassic thermal event associated with magmatic activity, which also strongly heated the sediments of the Donbas Foldbelt. The basement rocks cooled to near-surface conditions during the Early to Middle Triassic and since then was thermally stable. The basin margins started to cool during the Permo-Triassic whereas the central parts were residing or slowly cooling through the apatite partial annealing zone during the Jurassic and most of the Cretaceous and eventually cooled to near-surface conditions around the Cretaceous-Paleogene boundary. Our data show that Permian erosion was lower and Mesozoic erosion larger than generally assumed. Inversion and pop-up of the Donbas Foldbelt occurred in the Cretaceous and not in the Permian as previously thought. This is indicated by overall Cretaceous apatite fission track ages in the central parts of the basin.

Calcium-Citrate-Phosphate Solution Injection for In Situ Strontium-90 Immobilization

NASA Astrophysics Data System (ADS)

Fruchter, J. S.; Vermeul, V.; Szecsody, J.; Williams, M. D.; Fritz, B. G.

2010-12-01

Sr-90 present in groundwater and the vadose zone at the Hanford 100N area due to past waste disposal practices has reached the nearby Columbia River, as evidenced by Sr-90 concentrations in near river wells and aquifer tubes and near shore sediments. Sr-90 is currently being remediated by adsorption onto apatite (55 times stronger than Sr-90 adsorption to sediment), followed by incorporation of the Sr-90 into the apatite structure. If the Sr-90 can remain immobilized for 300 years (~ten 29.1-yr half-lives of Sr-90 decay), it will have decayed below regulatory limits to Y-90 and to stable Zr-90. Apatite [Ca10(PO4)6(OH)2] is being precipitated in situ by injection of an aqueous solution of Ca-citrate and Na-phosphate through a series of injection wells spaced 30 ft on center, forming a 300-ft-long permeable reactive barrier. Design criteria for the injection operations were based on 1) amendment volume and mass injected, 2) amendment arrival at adjacent wells, 3) water-level elevation during treatment, and 4) injection rate limitations associated with well plugging. An evaluation of compliance with these injection design criteria was used to assess operational performance and identify candidate wells for supplemental treatment. Injection design criteria were not fully met at 8 of the 16 injection well locations, with the primary deficiency at 4 of 8 locations being the limited vertical extent of Hanford formation treatment due to low-river-stage conditions during the injection. Wells whose extent of treatment did not meet design criteria were recommended for retreatment. Although injection design criteria were not fully met at a significant number of well locations, aqueous performance assessment monitoring data collected to date indicate good barrier performance. Aqueous Sr-90 monitoring in four compliance monitoring wells over a year following the high concentration injections indicates 84% to 95% decrease in Sr-90 concentrations (relative to the low and high end of the baseline range, respectively). In addition, post treatment sediment cores were collected to quantify the amount of apatite that was formed from the barrier-emplacement operations. Results indicate that the processes that account for the observed reduction in aqueous Sr-90 concentrations include: a) incorporation of Sr-90 into apatite (about 39.4% of the total Sr-90 mass in the core), b) ion exchange flushing due to the Ca-citrate-PO4 solution injection (about 47% of the mass), and c) a small increase in Sr-90 adsorbed to sediment and apatite precipitate.

Tectono-thermal evolution of north Kuqa Depression and South Tian Shan: constraints from apatite (U-Th)/He thermochronology

NASA Astrophysics Data System (ADS)

Xiao, Y.; Qiu, N.; Chang, J.

2017-12-01

The Kuqa Depression, located between Tarim Basin and South Tian Shan Orogen, is considered the most promising site for study the tectono-thermal evolution of the Central Asia Orogenic Belt (CAOB). (U-Th)/He is a new dating method and apatite He ages can record the cooling histories at low temperature between 40 ° 75°1. At present, the low temperature thermochronological data, especially the (U-Th)/He, from north Kuqa Depression are scarce, resulting in controversial issues regarding the cooling history of the upper crust and the latest uplift of South Tian Shan. We present new apatite (U-Th)/He (AHe) thermochronologic data from kuqa depression, aiming to provide insights into exhumation and thermal history of the north kuqa depression. In this study, we firstly present 43 apatite (U-Th)/He ages of 9 samples in north rim of Kuqa Depression. The (U-Th)/He ages range from 1.4±1.0Ma to 17.9±1.2Ma, which are obviously both younger than both the depositional ages and the corresponding AFT ages. To better understand the deformation evolution and thermal history of north Tarim Basin, we use these thermochronological data as inputs for HeFTy software implemented with radiation damage accumulation and annealing model (RDAAM) for time-temperature reconstruction1,2. The relationship between AHe or AFT ages and the relative stratigraphic ages shows that the AHe ages are young and almost about 10 Ma.Thermal modeling using apatite (U-Th)/He ages and geological background information in the same area allow us to obtain a cooling history. The sample T-03 suffered a cooling between 170 and 130Ma, they were re-heated at around 100° between 100 and 40Ma then rapidly cooled and exhumed to reach the surface temperature at around 5Ma. The thermal modeling results indicated the north Kuqa Depression experienced a Miocene rapid cooling event initialed at 12Ma and continued to 5Ma, resulting from far field effect of India-Asia collision. References1. Ketcham, R.A. Forward and reverse Modeling of Low-Temperature Thermochronometry Data. Reviews in Mineralogy and Geochemistry. 58, 275-314(2005). 2. Flowers, R.M. Ketcham, R.A., Shuster, D.l. & Farley, K.A. Apatite (U-Th)/He thermochronometry using a radiation damage accumulation and annealing model. Geochimica et Cosmochimica Acta. 73, 2347-2365 (2009).

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.

Annealing kinetics of latent particle tracks in Durango apatite

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

Afra, B.; Rodriguez, M. D.; Giulian, R.

2011-02-01

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

Annealing kinetics of latent particle tracks in Durango apatite

NASA Astrophysics Data System (ADS)

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

2011-02-01

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

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.

Mesozoic fault reactivation along the St. Lawrence Rift System as constrained by (U-Th/He) thermochronology

NASA Astrophysics Data System (ADS)

Bouvier, L.; Pinti, D. L.; Tremblay, A.; Minarik, W. G.; Roden-Tice, M. K.; Pik, R.

2011-12-01

The Saint Lawrence Rift System (SLRS) is a half-graben, extending for 1000 km along St. Lawrence River valley. Late Proterozoic-Early Paleozoic faults of the graben form the contact with the metamorphic Grenvillian basement to the northwest and extend under the Paleozoic sedimentary sequences of the St. Lawrence Lowlands to the southeast. The SLRS is the second most seismically active area in Canada, but the causes of this activity remain unclear. Reactivation of the SLRS is believed to have occurred along Late Proterozoic to Early Paleozoic normal faults related to the opening of the Iapetus Ocean. The absence of strata younger than the Ordovician makes difficult to determine when the faults reactivated after the Ordovician. Field relations between the normal faults bordering the SLRS and those produced by the Charlevoix impact crater suggest a reactivation of the rift younger than the Devonian, the estimated age of the impact. Apatite (U-Th)/He thermochronology is an adequate tool to recognize thermal events related to fault movements. A thermochronology study was then started along three transects across the SLRS, from Québec up to Charlevoix. Apatites were extracted and separated from five granitic to charnockitic gneisses and an amphibolite of Grenvillian age. The samples were exposed on hanging wall and footwall of the Montmorency and Saint-Laurent faults at three different locations along the SLRS. For precision and accuracy, each of the six samples was analyzed for radiogenic 4He and U-Th contents at least twice. Apatite grains were isolated by heavy liquids and magnetic separation. For each sample, ten apatite grains were selected under optical microscope and inserted into Pt capsules. Particular care was taken to isolate apatite free of mineral and fluid inclusions. Indeed, SEM investigations showed that some inclusions are U-rich monazite, which is a supplementary source of 4He to be avoided. The 4He content was determined by using a static noble gas mass spectrometer in CRPG-Nancy and duplicates using a quadrupole mass spectrometer at GEOTOP-UQAM. 4He was measured against internal He gas standards and Durango apatite, with the reference U-Th/He age of 31.13 ± 1.01 Ma. U and Th contents were determined at CRPG-Nancy and duplicated at McGill University by ICP-MS. Preliminary results of U-Th/He on St.-Laurent fault yield an age of 137±12 Ma for the hanging wall, at Sault-au-Cochon and 118±10 Ma for a sample from the footwall, at Cap-aux-oies. Previous Apatite Fission Track (AFT) performed for the two locations gave expected older ages at 149±16 Ma and 196±19 Ma for the hanging wall and the footwall, respectively. These preliminary U-Th/He results are consistent with AFT ages of the area (i.e. as expected, U-Th/He ages are younger than AFT ages) but do not yet provide new constraints for the structural evolution of the St. Lawrence rift system. We are determining further U-Th/He ages and these ages will constrain an exhumation model of the region.

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).

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.

Phosphorus geochemistry of recent sediments in the South Basin of Lake Winnipeg

USGS Publications Warehouse

Mayer, T.; Simpson, S.L.; Thorleifson, L.H.; Lockhart, W.L.; Wilkinson, Philip M.

2006-01-01

Lake Winnipeg supports the largest commercial fishery on Canadian Prairies. It has been influenced by a variety of environmental forces and anthropogenic activities. To gain a better understanding of recent changes in nutrient status of the lake, it is important to reconstruct its previous history from sedimentary records. Lacustrine sediments are known to be an important sink of many dissolved and suspended substances, including phosphorus, hence, they provide a permanent historical record of changes occurring in the lake. These changes may be induced by natural factors or by anthropogenic activities in the watershed. Phosphorus profiles from dated sediment cores collected in 1999 and 1994 from the South Basin of Lake Winnipeg were investigated to determine phosphorus enrichment in recent sediments. To interpret the nutrient status and depositional conditions responsible for the trends in total phosphorus, three operationally defined forms of phosphorus (P) were determined: non-apatite inorganic P, apatite P, and organic P. Significant increases in sediment phosphorus concentrations were observed in the uppermost 20 cm of the cores and several anomalies were observed at depth. A doubling in total phosphorus relative to aluminum over the last fifty years is largely due to increases in the non-apatite inorganic fraction, suggesting that much of sedimentary phosphorus increase is attributable to changes in the nutrient status of the water column related to anthropogenic inputs. Organic phosphorus exhibits a subtle increase in the upper 20 cm of the gravity cores, likely due to increases in the primary productivity of the lake. Except for the slight increase in deeper sediments, apatite phosphorus, which is thought to be of detrital origin, remained fairly constant over the length of the cores. Anomalous spikes in phosphorus concentrations deeper in the cores, comprised mainly of the non-apatite inorganic phosphorus fraction, likely resulted from natural variation in local oxidizing conditions, possibly induced by changes in water circulation and/or changes in sediment deposition rates due to climatic variation. The results of this investigation contribute to increased understanding of the depositional history of phosphorus in the lake over the last millennium.

A mechanistic study of the interaction of water-soluble borate glass with apatite-bound heterocyclic nitrogen-containing bisphosphonates.

PubMed

Pramanik, Chandrani; Sood, Parveen; Niu, Li-Na; Yuan, He; Ghoshal, Sushanta; Henderson, Walter; Liu, Yaodong; Jang, Seung Soon; Kumar, Satish; Pashley, David H; Tay, Franklin R

2016-02-01

Long-term oral and intravenous use of nitrogen-containing bisphosphonates (N-BPs) is associated with osteonecrosis of the jaw. Although N-BPs bind strongly to bone surfaces via non-covalent bonds, it is possible for extrinsic ions to dissociate bound N-BPs from mineralized bone by competitive desorption. Here, we investigate the effects and mechanism of using an ionic cocktail derived from borate bioactive glass for sequestration of heterocyclic N-BPs bound to apatite. By employing solid-state and solution-state analytical techniques, we confirmed that sequestration of N-BPs from bisphosphonate-bound apatite occurs in the presence of the borate-containing ionic cocktail. Simulations by density functional theory computations indicate that magnesium cation and borate anion are well within the extent of the risedronate or zoledronate anion to form precipitate complexes. The sequestration mechanism is due to the borate anion competing with bisphosphonates for similar electron-deficient sites on the apatite surface for binding. Thus, application of the borate-containing ionic cocktail represents a new topical lavage approach for removing apatite-bound heterocyclic N-BPs from exposed necrotic bone in bisphosphonate-related osteonecrosis of the jaw. Long-term oral consumption and injections of nitrogen-containing bisphosphonates (N-BPs) may result in death of the jaw bone when there is traumatic injury to the bone tissues. To date, there is no effective treatment for such a condition. This work reported the use of an ionic cocktail derived from water-soluble borate glass microfibers to displace the most potent type of N-BPs that are bound strongly to the mineral component on bone surfaces. The mechanism responsible for such an effect has been identified to be cation-mediated complexation of borate anions with negatively-charged N-BPs, allowing them to be released from the mineral surface. This borate-containing cocktail may be developed into a novel topical rinse for removing mineral-bound N-BPs from exposed dead bone. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Thermochronologic constraints on post-Paleozoic tectonic evolution of the central Transantarctic Mountains, Antarctica

NASA Astrophysics Data System (ADS)

Fitzgerald, Paul G.

1994-08-01

Built upon the roots of a compressive orogenic belt of late Proterozoic-early Paleozoic age and once adjacent to North America, the present-day Transantarctic Mountains (TAM) represent a rift flank, resulting from episodic uplift in the Cretaceous and Cenozoic. Fault blocks are discernible in present-day topography and subglacial morphology. Fission track results give information on differential block movement (uplift and denudation) and are important in constraining models for the uplift of the range. Apatite fission track thermochronology on samples collected from the central TAM record a complex thermotectonic history for this region over the past 350 m.y. Apatite ages in the Miller Range vary from ˜250 to ˜350 Ma and are from an exhumed apatite partial annealing zone formed following cooling of Cambro-Ordovician granitoids. A period of Cretaceous denudation (≲2 km), beginning at ˜115 Ma, is recorded at Moody Nunatak on the inland side of the TAM. Near the coast, samples along the Beardmore Glacier record rapid cooling indicative of denudation initiated in the early Cenozoic (˜50 Ma). The amount of uplift ˜70 km inland of the coast in the Queen Alexandra Range since the early Cenozoic is ˜7 km, with the likelihood of an additional ˜3 km at the coast. Eastward facing topographic escarpments in the Queen Alexandra Range mark the likely position of steeply dipping normal faults, which offset the apatite ages. Apatite ages on the east side of the Beardmore Glacier mouth are generally younger (average 27 Ma) than on the west side (average 33 Ma), reflecting greater denudation. Assumptions made regarding the use of an assumed paleogeothermal gradient are tested with available geologic evidence. The fission track data neither conflict with nor confirm paleobotanical evidence from the Sirius Group in the central TAM which suggests significant surface uplift (2-3 km) of the TAM since the Pliocene. Results build upon the available fission track database along the TAM and emphasize the subtle variability of uplift along the TAM due to episodic uplift involving differential block movements.

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.

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

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.

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

Fluoride and apatite formation in vivo and in vitro.

PubMed

Aoba, Takaaki; Shimazu, Yoshihito; Taya, Yuji; Soeno, Yuuichi; Sato, Kaori; Miake, Yasuo

2003-01-01

In recent years, the biomineralization process has attracted much interest from academics and industries for potential technological application. The rule in biomineralization is to have a variety of interfaces and surfaces which can act as nucleators. The ultimate step in any biomineralization process, i.e. the deposition of mineral, must conform to the driving forces operating on the system. A new paradigm in the assessment of the driving force for biomineralization is that a variety of ions existing in the mineralizing milieu are not a bystander, but are instead an active player that directly regulates the precipitation process and nature of biogenic apatites. Thus, the most putative stoichiometric model of a biomineral is (Ca)(5-x)(Mg)q(Na)u(HPO4)v(CO3)w(PO4)(3-y)(OH,F)(1-z). Fluoride participates in many aspects of calcium phosphate formation in vivo and has enormous effects on its process and on the nature and properties of the final products. In the development of biogenic apatites, fluoride ion in the mineralizing media is supposed to accelerate the hydrolysis of acidic precursor(s) and increase the growth rates by augmenting the driving force for precipitation. Inhibitory activities of ions and molecules are related to their adsorption onto the apatite surfaces. From theoretical and practical points of view, it is of paramount importance to elucidate and predict the effect and outcome of fluoride (accelerator) and inhibitors of biological relevance, because of their use in combination for healthcare in dentistry and medicine, e.g. prevention of dental caries and calculus deposition and in the formulation of antiosteoporosis treatments.

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.

Comparative in vitro studies on disodium EDTA effect with and without Proteus mirabilis on the crystallization of carbonate apatite and struvite

NASA Astrophysics Data System (ADS)

Prywer, Jolanta; Olszynski, Marcin; Torzewska, Agnieszka; Mielniczek-Brzóska, Ewa

2014-06-01

Effect of disodium EDTA (salt of ethylenediamine tetraacetic acid) on the crystallization of struvite and carbonate apatite was studied. To evaluate such an effect we performed an experiment of struvite and carbonate apatite growth from artificial urine. The crystallization process was induced by Proteus mirabilis to mimic the real urinary tract infection, which usually leads to urinary stone formation. The results demonstrate that disodium EDTA exhibits the effect against P. mirabilis retarding the activity of urease - an enzyme produced by these microorganisms. The spectrophotometric results demonstrate that, with and without P. mirabilis, the addition of disodium EDTA increases the induction time and decreases the growth efficiency compared to the baseline (without disodium EDTA). These results are discussed from the standpoint of speciation of complexes formed in the solution of artificial urine in the presence of disodium EDTA. The size of struvite crystals was found to decrease in the presence of disodium EDTA. However, struvite crystals are larger in the presence of bacteria while the crystal morphology and habit remain unchanged.

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.

What can the microstructure of stones tell us?

PubMed Central

Williams, James C.; Worcester, Elaine; Lingeman, James E.

2016-01-01

How stones are retained within the kidney while small in size is still not fully understood. In this paper we show two examples of how stones are retained during early growth: One is growth on Randall’s (interstitial) plaque, and the other is growth on mineral that has formed as a luminal plug in a terminal collecting duct. These two mechanisms of stone retention during early growth have distinctive morphologic features that can be seen by methods that show the microscopic structure of the stones. Stones growing on Randall’s plaque display an apatite region that is typically not large in size (less than 0.5 mm across) but which usually shows luminal spaces, which are signs of its origin in the connective tissue of the papilla. Stones growing on ductal plugs also show attachment to a piece of apatite, but the apatite regions are typically larger (often >1 mm long and >0.5 mm wide), and they are solid, without spaces running through them. We propose that knowing the mechanisms of stone retention during early stone formation could allow for better treatment of stone diseases. PMID:27913855

κ-Carrageenan Enhances the Biomineralization and Osteogenic Differentiation of Electrospun Polyhydroxybutyrate and Polyhydroxybutyrate Valerate Fibers.

PubMed

Goonoo, Nowsheen; Khanbabaee, Behnam; Steuber, Marc; Bhaw-Luximon, Archana; Jonas, Ulrich; Pietsch, Ullrich; Jhurry, Dhanjay; Schönherr, Holger

2017-05-08

Novel electrospun materials for bone tissue engineering were obtained by blending biodegradable polyhydroxybutyrate (PHB) or polyhydroxybutyrate valerate (PHBV) with the anionic sulfated polysaccharide κ-carrageenan (κ-CG) in varying ratios. In both systems, the two components phase separated as shown by FTIR, DSC and TGA. According to the contact angle data, κ-CG was localized preferentially at the fiber surface in PHBV/κ-CG blends in contrast to PHB/κ-CG, where the biopolymer was mostly found within the fiber. In contrast to the neat polyester fibers, the blends led to the formation of much smaller apatite crystals (800 nm vs 7 μm). According to the MTT assay, NIH3T3 cells grew in higher density on the blend mats in comparison to neat polyester mats. The osteogenic differentiation potential of the fibers was determined by SaOS-2 cell culture for 2 weeks. Alizarin red-S staining suggested an improved mineralization on the blend fibers. Thus, PHBV/κ-CG fibers resulted in more pronounced bioactive and osteogenic properties, including fast apatite-forming ability and deposition of nanosized apatite crystals.

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.

Hydrothermal calcium modification of 316L stainless steel and its apatite forming ability in simulated body fluid.

PubMed

Valanezahad, Alireza; Ishikawa, Kunio; Tsuru, Kanji; Maruta, Michito; Matsuya, Shigeki

2011-01-01

To understand the feasibility of calcium (Ca) modification of type 316L stainless steel (316L SS) surface using hydrothermal treatment, 316L SS plates were treated hydrothermally in calcium chloride (CaCl(2)) solution. X-ray photoelectron spectroscopic analysis revealed that the surface of 316L SS plate was modified with Ca after hydrothermal treatment at 200°C. And the immobilized Ca increased with CaCl(2) concentration. However no Ca-modification was occurred for 316L SS plates treated at 100°C. When Ca-modified 316L SS plate was immersed in simulated body fluid (SBF) with ion concentrations nearly equal to those of human blood plasma, low crystalline apatite was precipitated on its surface whereas no precipitate was observed on non Ca-modified 316L SS. The results obtained in the present study indicated that hydrothermal treatment at 200°C in CaCl(2) solution is useful for Ca-modification of 316L SS, and Ca-modification plays important role for apatite precipitation in SBF.

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.

A review of bioactive silicate ceramics.

PubMed

Wu, Chengtie; Chang, Jiang

2013-06-01

Silicate bioceramics, as a new family of biomaterials, have received significant attention in their application to hard tissue regeneration. Some silicate bioceramics have shown excellent apatite mineralization in simulated body fluids and their ionic products have been shown to enhance the proliferation, osteogenic differentiation and gene expression of stem cells. In this paper, we review the advances in the research of silicate system bioceramics, including preparation methods, mechanical strength, apatite mineralization, dissolution and in vitro and in vivo biological properties. The biological properties and the corresponding mechanism have been highlighted. A look forward to the application of silicate bioceramics to bone regeneration is further suggested.

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.

Probing the limit of magnesium uptake by β-tricalcium phosphate in biphasic mixtures formed from calcium deficient apatites

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

Kumar, P. Nandha; Mishra, Sandeep K.; Kannan, S., E-mail: para_kanna@yahoo.com

2015-11-15

A series of magnesium doped non-stoichiometric calcium deficient apatites were synthesized through an aqueous precipitation route. The resultant structural changes during heat treatment were investigated by X-ray diffraction, Raman and FT-IR spectroscopy and Rietveld refinement. The results confirmed the formation of biphasic mixtures comprising Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} and β-Ca{sub 3}(PO{sub 4}){sub 2} after heat treatment at 1000 °C with the preferential occupancy of Mg{sup 2+} at the crystal lattice of β-Ca{sub 3}(PO{sub 4}){sub 2}. The concentration of Mg{sup 2+} uptake in β-Ca{sub 3}(PO{sub 4}){sub 2} is limited till reaching the stoichiometric ratio of (Ca+Mg)/P=1.67 and beyond this stoichiometricmore » value [(Ca+Mg)/P>1.67], Mg{sup 2+} precipitates as Mg(OH){sub 2} and thereafter gets converted to MgO during heat treatment. Any kind of Mg{sup 2+} uptake in the crystal lattice of Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} is discarded from the investigation. - Highlights: • Aqueous co-precipitation of calcium deficient apatites with excess magnesium (Mg{sup 2+}) additions. • Heat treatments beyond 800 °C results in the formation of biphasic apatite mixtures. • Mg{sup 2+} gets accommodated at the β-Ca{sub 3}(PO{sub 4}){sub 2} lattice of biphasic mixtures. • Mg{sup 2+} additions exceeding stoichiometric value (Ca/P>1.67) results in its formation as MgO. • Mg{sup 2+} occupancy at β-Ca{sub 3}(PO{sub 4}){sub 2} lattice delays its allotropic conversion α-Ca{sub 3}(PO{sub 4}){sub 2} till 1350 °C.« less

Surface-Modification of Carbonate Apatite Nanoparticles Enhances Delivery and Cytotoxicity of Gemcitabine and Anastrozole in Breast Cancer Cells

PubMed Central

Mozar, Fitya Syarifa; Chowdhury, Ezharul Hoque

2017-01-01

pH sensitive nanoparticles of carbonate apatite (CA) have been proven to be effective delivery vehicles for DNA, siRNAs and proteins. More recently, conventional anti-cancer drugs, such as doxorubicin, methotrexate and cyclophosphamide have been successfully incorporated into CA for intracellular delivery to breast cancer cells. However, physical and chemical properties of drug molecules appeared to affect their interactions with CA, with hydrophillic drug so far exhibiting better binding affinity and cellular uptakes compared to hydrophobic drugs. In this study, anastrozole, a non-steroidal aromatase inhibitor which is largely hydrophobic, and gemcitabine, a hydrophilic nucleoside inhibitor were used as solubility models of chemotherapy drug. Aggregation tendency of poorly soluble drugs resulting in larger particle-drug complex size might be the main factor hindering their delivery effectiveness. For the first time, surface modification of CA with poly(ethylene glycol) (PEG) has shown promising result to drastically reduce anastrozole- loaded CA particle size, from approximately 1000 to 500 nm based on zeta sizer analysis. Besides PEG, a cell specific ligand, in this case fibronectin, was attached to the particles in order to facilitate receptor mediated endocytosis based on fibronectin–integrin interaction. High-performance liquid chromatography (HPLC) was performed to measure uptake of the drugs by breast cancer cells, revealing that surface modification increased the drug uptake, especially for the hydrophobic drug, compared to the uncoated particles and the free drug. In vitro chemosensitivity assay and in vivo tumor regression study also showed that coated apatite/drug nanoparticle complexes presented higher cytotoxicity and tumor regression effects than uncoated apatite/drug nanoparticles and free drugs, indicating that surface modification successfully created optimum particles size with the consequence of more effective uptake along with favorable pharmacokinetics of the particles. PMID:28590445

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.

Evaluation of the 3D spatial distribution of the Calcium/Phosphorus ratio in bone using computed-tomography dual-energy analysis.

PubMed

Hadjipanteli, A; Kourkoumelis, N; Fromme, P; Huang, J; Speller, R D

2016-01-01

The Calcium/Phosphorus (Ca/P) ratio was shown to vary between healthy bones and bones with osteoporotic symptoms. The relation of the Ca/P ratio to bone quality remains under investigation. To study this relation and determine if the ratio can be used to predict bone fractures, a non-invasive 3D imaging technique is required. The first aim of this study was to test the effectiveness of a computed-tomography dual-energy analysis (CT-DEA) technique developed to assess the Ca/P ratio in bone apatite (collagen-free bone) in identifying differences between healthy and inflammation-mediated osteoporotic (IMO) bones. The second aim was to extend the above technique for its application to a more complex structure, intact bone, that could potentially lead to clinical use. For the first aim, healthy and IMO rabbit cortical bone apatite samples were assessed. For the second aim, some changes were made to the technique, which was applied to healthy and IMO intact bone samples. Statistically significant differences between healthy and IMO bone apatite were found for the bulk Ca/P ratio, low Ca/P ratio proportion and interconnected low Ca/P ratio proportion. For the intact bone samples, the bulk Ca/P ratio was found to be significantly different between healthy and IMO. Results show that the CT-DEA technique can be used to identify differences in the Ca/P ratio between healthy and osteoporotic, in both bone apatite and intact bone. With quantitative imaging becoming an increasingly important advancement in medical imaging, CT-DEA for bone decomposition could potentially have several applications. Copyright © 2015. Published by Elsevier Ltd.

Advancements in cosmogenic 38Ar exposure dating of terrestrial rocks

NASA Astrophysics Data System (ADS)

Oostingh, K. F.; Jourdan, F.; Danišík, M.; Evans, N. J.

2017-11-01

Cosmogenic exposure dating of Ca-rich minerals using 38Ar on terrestrial rocks could be a valuable new dating tool to determine timescales of geological surface processes on Earth. Here, we show that advancement in analytical precision, using the new generation multi-collector ARGUSVI mass spectrometer on irradiated pyroxene and apatite samples, allows determination of cosmogenic 38Ar abundances above background values, as well as discrimination of 38Ar/36Ar ratios (1σ absolute precision of ±0.3%) from the non-cosmogenic background value. Four statistically significant cosmochron (38Ar/36Ar vs37Ar/36Ar) diagrams could be constructed for southeast Australian pyroxene samples from the Mt Elephant scoria cone for which a combined apparent exposure age of 313 ± 179 ka (2σ) was obtained when using a 38Ar production rate (Ca) of 250 atoms /g Ca/ yr. This exposure age overlaps within error with the known 40Ar/39Ar eruption age of 184 ± 15 ka (2σ). Although apatite shows much larger 38Ar abundances than pyroxene, our modelling and analyses of unirradiated apatite suggest that apatite suffers from both natural and reactor-derived chlorogenic as well as natural nucleogenic contributions of 38Ar. Hence, we suggest that cosmogenic 38Ar exposure dating on irradiated Ca-rich (and eventually K-rich), but Cl-free, terrestrial minerals is a potential valuable and accessible tool to determine geological surface processes on timescales of a few Ma. Calculations show that with the new generation multi-collector mass spectrometers an analytical uncertainty better than 5% (2σ) can be achieved on samples with expected exposure ages of >4 Ma.

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.

Isomorphous Substitution of Rare-Earth Elements in Lacunary Apatite Pb8Na2(PO4)6.

PubMed

Get'man, Evgeni I; Loboda, Stanislav N; Ignatov, Alexey V; Prisedsky, Vadim V; Abdul Jabar, Mohammed A B; Ardanova, Lyudmyla I

2016-03-07

The substitution of rare-earth elements (REEs) for Pb in the lacunary apatite Pb8Na2(PO4)6 with void structural channels was studied by means of powder X-ray diffraction (including the Rietveld refinement), scanning electron microscopy, energy-dispersive X-ray microanalysis, and IR spectroscopy and also measurements of the electrical conductivity. The substitution limits (xmax in Pb8-xLnxNa2(PO4)6Ox/2) at 800 °C were found to decrease with the atomic number of the REE from 1.40 for La to 0.12 for Yb with a rapid drop from light to heavy lanthanides (between Gd and Tb). The REE atoms substitute for Pb predominantly at Pb2 sites of the apatite structure according to the scheme 2Pb(2+) + □ → 2Ln(3+) + O(2-), where □ is a vacancy in the structural channel. The substitution in lacunary apatite produces quite different changes in the structural parameters compared with broadly studied alkaline-earth hydroxyapatites. In spite of the much lower ionic radii of REE than that of Pb(2+), the mean distances ⟨Pb1-O⟩ somewhat increase, whereas the distances ⟨Pb2-Pb2⟩ and ⟨Pb2-O4⟩ do not change considerably with the degree of substitution. This implies control of the substitution by not only spatial and charge accommodation of REE ions but also the availability of a stereochemically active 6s(2) electron pair on Pb(2+). The high-temperature electrical conductivity shows dependence on the degree of substitution with a minimum at x = 0.2 indicative of a possible change of the type of conductivity.

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).

Thermochronology of the Sulu ultrahigh-pressure metamorphic terrane: Implications for continental collision and lithospheric thinning

NASA Astrophysics Data System (ADS)

Liu, Li-Ping; Li, Zheng-Xiang; Danišík, Martin; Li, Sanzhong; Evans, Noreen; Jourdan, Fred; Tao, Ni

2017-08-01

The thermal history of the Dabie-Sulu orogenic belt provides important constraints on the collision process between the South China and North China blocks during the Mesozoic, and possible lithospheric thinning event(s) in the eastern North China Block. This study reports on the thermal evolution of the Sulu ultrahigh-pressure metamorphic (UHP) terrane using zircon U-Pb geochronology and multiple thermochronology methods such as mica and hornblende 40Ar/39Ar, zircon and apatite fission track, and zircon and apatite (U-Th)/He dating. 40Ar/39Ar and zircon (U-Th)/He data show that the UHP terrane experienced accelerated cooling during 180-160 Ma. This cooling event could be interpreted to have resulted from extensional unroofing of an earlier southward thrusting nappe, or, more likely, an episode of northward thrusting of the UHP rocks as a hanging wall. A subsequent episode of exhumation took place between ca. 125 Ma and 90 Ma as recorded by zircon (U-Th)/He data. This event was more pronounced in the northwest section of the UHP terrane, whereas in the southeast section, the zircon (U-Th)/He system retained Jurassic cooling ages of ca. 180-160 Ma. The mid-Cretaceous episode of exhumation is interpreted to have resulted from crustal extension due to the removal of thickened, enriched mantle. A younger episode of exhumation was recorded by apatite fission track and apatite (U-Th)/He ages at ca. 65-40 Ma. Both latter events were linked to episodic thinning of lithosphere along the Sulu UHP terrane in an extensional environment, likely caused by the roll-back of the Western Pacific subduction system.

Enhanced apatite-forming ability and antibacterial activity of porous anodic alumina embedded with CaO-SiO2-Ag2O bioactive materials.

PubMed

Ni, Siyu; Li, Xiaohong; Yang, Pengan; Ni, Shirong; Hong, Feng; Webster, Thomas J

2016-01-01

In this study, to provide porous anodic alumina (PAA) with bioactivity and anti-bacterial properties, sol-gel derived bioactive CaO-SiO2-Ag2O materials were loaded onto and into PAA nano-pores (termed CaO-SiO2-Ag2O/PAA) by a sol-dipping method and subsequent calcination of the gel-glasses. The in vitro apatite-forming ability of the CaO-SiO2-Ag2O/PAA specimens was evaluated by soaking them in simulated body fluid (SBF). The surface microstructure and chemical property before and after soaking in SBF were characterized. Release of ions into the SBF was also measured. In addition, the antibacterial properties of the samples were tested against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The results showed that CaO-SiO2-Ag2O bioactive materials were successfully decorated onto and into PAA nano-pores. In vitro SBF experiments revealed that the CaO-SiO2-Ag2O/PAA specimens dramatically enhanced the apatite-forming ability of PAA in SBF and Ca, Si and Ag ions were released from the samples in a sustained and slow manner. Importantly, E. coli and S. aureus were both killed on the CaO-SiO2-Ag2O/PAA (by 100%) samples compared to PAA controls after 3 days of culture. In summary, this study demonstrated that the CaO-SiO2-Ag2O/PAA samples possess good apatite-forming ability and high antibacterial activity causing it to be a promising bioactive coating candidate for implant materials for orthopedic applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Correlations between the in vitro and in vivo bioactivity of the Ti/HA composites fabricated by a powder metallurgy method.

PubMed

Ning, Congqin; Zhou, Yu

2008-11-01

Ti/HA composites were successfully prepared by a powder metallurgy method and the effect of phase composition on the in vitro and in vivo bioactivity of the Ti/HA composites was investigated in the present study. The correlations between the in vitro and in vivo biological behaviors were highlighted. The results showed that the in vitro and in vivo bioactivity of the Ti/HA composites was dependent on their phase composition. The in vitro bioactivity of the Ti/HA composites was evaluated in simulated body fluid with ion concentrations similar to those of human plasma. After immersion in the simulated body fluid for a certain time, apatite precipitations formed on the surface of the composites with an initial titanium content of 50 and 70 wt.%, and no apatite was found on the surface of the composite with 30% titanium. Ti(2)O was responsible for the apatite formation on the surfaces of the composites. For in vivo analysis, Ti/HA cylinders were implanted in the metaphases of the rabbit femur. At the early stage of implantation, the new bone formed on the surface of the composite with 30% titanium was much less than that on the surfaces of the composites with 50% and 70% titanium. All the Ti/HA composites formed a chemical bone-bonding interface with the host bone by 6 months after implantation. The Ti/HA composites formed the bone-bonding interface with the surrounding bone through an apatite layer. The results in the present study suggested that the in vivo results agreed well with the in vitro results.

In vitro evaluation of the sealing ability of three newly developed root canal sealers: A bacterial microleakage study

PubMed Central

Sobhani, Ehsan; Samadi-Kafil, Hossein; Pirzadeh, Ahmad; Jafari, Sanaz

2016-01-01

Background The purpose of this study was to compare the sealing ability of MTA Fillapex, Apatite Root Canal Sealer and AH26 sealers. Material and Methods The present in vitro study was carried out on 142 extracted single-rooted human mature teeth. The teeth were randomly divided into three experimental groups (n=44) and two control groups (n=5). Three root canal sealers were MTA Fillapex, Apatite Root Canal Sealer and AH26. The teeth in the control groups were either filled with no sealer or made completely impermeable. The root canals were prepared and obturated with gutta-percha and one of the sealers. The teeth were sterilized with ethylene oxide gas prior to the bacterial leakage assessment using Enterococcus faecalis. Leakage was evaluated every 24 hours for 90 days. Data were analyzed with descriptive statistical methods and chi-squared test. If the data were significant, a proper post hoc test was used. Statistical significance was set at P<0.05. Results The positive control specimens exhibited total bacterial penetration whilst the negative control specimens showed no evidence of bacterial penetration. At the end of the study, the analysis of microleakage with chi-squared test showed no significant differences between the experimental groups (P<0.05). The results of chi-squared test analyzing the pair-wise differences between the groups considering the numerical values for leakage day indicated the lowest leakage with AH26 and the highest with Apatite root sealer. Conclusions According to the results of the present study, sealing ability of AH26 was significantly higher than that of MTA Fillapex and Apatite Root Canal Sealer. Key words:Mineral Trioxide aggregate, root canal obturation, dental seal. PMID:27957271

Apatite grown in niobium by two-step plasma electrolytic oxidation.

PubMed

Pereira, Bruno Leandro; Lepienski, Carlos Maurício; Mazzaro, Irineu; Kuromoto, Neide Kazue

2017-08-01

Plasma electrolytic oxidation (PEO) of niobium plates were done electrochemically in two steps with electrolytes containing phosphorous and calcium being observed the formation of crystalline apatite. All samples were submitted to a first step of PEO using an electrolyte containing phosphate ions. The second oxidization step was made using three different electrolytes. Some samples were oxidized by PEO in electrolyte containing calcium, while in other samples it was used two mixtures of phosphoric acid and calcium acetate monohydrate solutions. Three different surface layers were obtained. The morphology and chemical composition of the films were analyzed by scanning electronic microscopy (SEM), and energy dispersive spectroscopy (EDS) respectively. It was observed that all samples submitted to two-step oxidation shown porous surface and a calcium and phosphorus rich layer. Average surface roughness (Ra) was measured by a profilometer remaining in the sub-micrometric range. The contact angle by sessile drop technique, using 1μL of distilled water was performed with an optical goniometer. It was verified a higher hydrophilicity in all surfaces compared to the polished niobium. Orthorhombic Nb 2 O 5 was identified by XRD in the oxide layer. Crystalline apatite was identified by XRD in surfaces after the second oxidation made with the Ca-rich electrolyte and a mixture of an electrolyte richer in Ca compared to P. These results indicate that a two-step oxidized niobium surface present great features for applications in the osseointegration processes: favorable chemical composition that increase the biocompatibility, the formation of crystalline niobium pentoxide (orthorhombic), high hydrophilicity and formation of crystalline calcium phosphate (apatite) under adequate electrolyte composition. Copyright © 2016 Elsevier B.V. All rights reserved.

Transformation of Pb(II) from Cerrusite to Chloropyromorphite in the Presence of Hydroxyapatite under Varying Conditions of pH

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

Ryan, J.A.; Zhang, P.

1998-10-14

Cerrusite (PbC03) is soluble under acidic conditions and considered to be a highly bioavailable soil Pb species. In this study, synthetic cerrusite and hydroxyapatite [Ca5(P04)30H] were reacted under constant and dynamic pH conditions with various P/Pb molar ratios in an attempt to evaluate the effect of reaction kinetics on the formation of chloropyromorphite (Pb5(P04)3Cl) and solubilization of Pb. Under constant pH conditions, dissolution rates of both cerrusite and apatite were rapid when pH was low. Complete conversion of Pb from cerrusite to chloropyromorphite occurred within 60 tin at pH 4 and below when the amount of phosphate in the addedmore » apatite was stoichoimetrically equal to that needed to transform all added Pb into chloropyromorphite. The concentration of soluble Pb depended upon the volubility of chloropyromorphite. The dissolution rates of apatite and cerrusite decreased with increasing pH, and the transformation was incomplete at pH 5 and above in the 60 rnin reaction period. The soluble Pb level, therefore, was determined by the volubility of cerrusite. In the dynamic pH system which simulated the gastrointestinal tract (GI tract) system, a complete transformation of Pb from cerrusite to chloropyromorphite was achieved due to the complete dissolution of apatite and cerrusite at the initial low pHs. Chloropyromorphite was the exclusive reaction product in both constant and dynamic pH systems as indicated by XRD analysis. The differences in transformation rate and the control of Pb volubility between the reactions occurring in constant and dynamic pH systems indicate the significance of kinetics in controlling the bioavailability of Pb and the potential for the reaction to occur during ingestion.« less

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

NASA Astrophysics Data System (ADS)

Oxmann, J. F.; Schwendenmann, L.

2014-06-01

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

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

NASA Astrophysics Data System (ADS)

Oxmann, J. F.; Schwendenmann, L.

2014-01-01

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

Morphology and electronic structure of nanoscale powders of calcium hydroxyapatite

NASA Astrophysics Data System (ADS)

Kurgan, Nataly; Karbivskyy, Volodymyr; Kasyanenko, Vasyl

2015-02-01

Atomic force microscopy, infrared spectroscopy and NMR studied morphological and physicochemical properties of calcium hydroxyapatite powders produced by changing the temperature parameters of synthesis. Features of morphology formation of calcium hydroxyapatite nanoparticles with an annealing temperature within 200°C to 1,100°C were determined. It is shown that the particle size of the apatite obtained that annealed 700°C is 40 nm corresponding to the particle size of apatite in native bone. The effect of dimension factor on structural parameters of calcium hydroxyapatite is manifested in a more local symmetry of the PO4 3- tetrahedra at nanodispersed calcium hydroxyapatite.

Structure of Biocompatible Coatings Produced from Hydroxyapatite Nanoparticles by Detonation Spraying

NASA Astrophysics Data System (ADS)

Nosenko, Valentyna; Strutynska, Nataliia; Vorona, Igor; Zatovsky, Igor; Dzhagan, Volodymyr; Lemishko, Sergiy; Epple, Matthias; Prymak, Oleg; Baran, Nikolai; Ishchenko, Stanislav; Slobodyanik, Nikolai; Prylutskyy, Yuriy; Klyui, Nickolai; Temchenko, Volodymyr

2015-12-01

Detonation-produced hydroxyapatite coatings were studied by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Raman spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy. The source material for detonation spraying was a B-type carbonated hydroxyapatite powder. The coatings consisted of tetracalcium phosphate and apatite. The ratio depended slightly on the degree of crystallinity of the initial powder and processing parameters of the coating preparation. The tetracalcium phosphate phase was homogeneous; the apatite phase contained defects localized on the sixfold axis and consisted of hydroxyapatite and oxyapatite. Technological factors contributing to the transformation of hydroxyapatite powder structure during coating formation by detonation spraying are discussed.

Heating, cooling, and uplift during Tertiary time, northern Sangre de Cristo Range, Colorado ( USA).

USGS Publications Warehouse

Lindsay, D.A.; Andriessen, P.A.M.; Wardlaw, B.R.

1986-01-01

Paleozoic sedimentary rocks in a wide area of the northern Sangre de Cristo Range show effects of heating during Tertiary time. Heating is tentatively interpreted as a response to burial during Laramide folding and thrusting and also to high heat flow during Rio Grande rifting. Fission-track ages of apatite across a section of the range show that rocks cooled abruptly below 120oC, the blocking temperature for apatite, approx 19 Ma ago. Cooling was probably in response to rapid uplift and erosion of the northern Sangre de Cristo Range during early Rio Grande rifting.-from Authors

Neck fracture of a cementless forged titanium alloy femoral stem following total hip arthroplasty: a case report and review of the literature

PubMed Central

Grivas, Theodoros B; Savvidou, Olga D; Psarakis, Spyridon A; Bernard, Pierre-Francois; Triantafyllopoulos, George; Kovanis, Ioannis; Alexandropoulos, Panagiotis

2007-01-01

Introduction Fractures of the neck of the femoral component have been reported in uncemented total hip replacements, however, to our knowledge, no fractures of the neck of a cementless forged titanium alloy femoral stem coated in the proximal third with hydroxy-apatite have been reported in the medical literature. Case presentation This case report describes a fracture of the neck of a cementless forged titanium alloy stem coated in the proximal third with hydroxy-apatite. Conclusion The neck of the femoral stem failed from fatigue probably because of a combination of factors described analytically below. PMID:18062807

Structure of Biocompatible Coatings Produced from Hydroxyapatite Nanoparticles by Detonation Spraying.

PubMed

Nosenko, Valentyna; Strutynska, Nataliia; Vorona, Igor; Zatovsky, Igor; Dzhagan, Volodymyr; Lemishko, Sergiy; Epple, Matthias; Prymak, Oleg; Baran, Nikolai; Ishchenko, Stanislav; Slobodyanik, Nikolai; Prylutskyy, Yuriy; Klyui, Nickolai; Temchenko, Volodymyr

2015-12-01

Detonation-produced hydroxyapatite coatings were studied by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Raman spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy. The source material for detonation spraying was a B-type carbonated hydroxyapatite powder. The coatings consisted of tetracalcium phosphate and apatite. The ratio depended slightly on the degree of crystallinity of the initial powder and processing parameters of the coating preparation. The tetracalcium phosphate phase was homogeneous; the apatite phase contained defects localized on the sixfold axis and consisted of hydroxyapatite and oxyapatite. Technological factors contributing to the transformation of hydroxyapatite powder structure during coating formation by detonation spraying are discussed.

Near-Infrared (NIR) Spectroscopy of Synthetic Hydroxyapatites and Human Dental Tissues.

PubMed

Kolmas, Joanna; Marek, Dariusz; Kolodziejski, Waclaw

2015-08-01

Near-infrared spectroscopy (NIR) was used to analyze synthetic hydroxyapatite calcined at various temperatures, synthetic carbonated hydroxyapatite, and human hard dental tissues (enamel and dentin). The NIR bands of those materials in the combination, first-overtone, and second-overtone spectral regions were assigned and evaluated for structural characterization. They were attributed to adsorbed and structural water, structural hydroxyl (OH) groups and surface P-OH groups. The NIR spectral features were quantitatively discussed in view of proton solid-state magic-angle spinning nuclear magnetic resonance ((1)H MAS NMR) results. We conclude that the NIR spectra of apatites are useful in the structural characterization of synthetic and biogenic apatites.

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.

Synthesis and characterization of nanocrystalline apatites from solution modeling human blood

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Formation and bioactivity of HA nanorods on micro-arc oxidized zirconium.

PubMed

Zhang, Lan; Zhu, Shaoyu; Han, Yong; Xiao, Chengzhang; Tang, Wu

2014-10-01

A microporous and CaO partially stabilized zirconia (Ca-PSZ) coating covered with hydroxyapatite (HA) nanorods is fabricated on Zr substrate by a hybrid approach of micro-arc oxidation (MAO) and hydrothermal treatment (HT). The effect of P ions in HT solution on the density and morphology of HA was investigated; the hydrophilicity and apatite-forming ability of the Ca-PSZ coating with HA nanorods were also examined. High-density HA nanorods (with a mean diameter of 50 nm and length of 450 nm) grow on the Ca-PSZ coating after HT in a solution containing 0.002 M β-glycerophosphate disodium (β-GP). However, only a few of coarse-grained HA crystallites grow in the MAOed pores after HT in distilled water or in an ammonia aqueous solution with an initial pH value equal to the solution containing 0.002 M β-GP. P ions in the HT solution are thought to significantly promote the formation of HA nanorods. The Ca-PSZ coating covered with HA nanorods displays good hydrophilicity and excellent apatite-inducing ability, and the induced apatite prefers to nucleate on the basal-faceted surfaces of HA nanorods. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Electron microscopy of octacalcium phosphate in the dental calculus.

PubMed

Kakei, Mitsuo; Sakae, Toshiro; Yoshikawa, Masayoshi

2009-12-01

The purpose of this study was to morphologically demonstrate the presence of octacalcium phosphate in the dental calculus by judging from the crystal lattice image and its rapid transformation into apatite crystal, as part of our serial studies on biomineral products. We also aimed to confirm whether the physical properties of octacalcium phosphate are identical with those of the central dark lines observed in crystals of ordinary calcifying hard tissues. Electron micrographs showed that crystals of various sizes form in the dental calculus. The formation of each crystal seemed to be closely associated with the organic substance, possibly originating from degenerated microorganisms at the calcification front. Many crystals had an 8.2-A lattice interval, similar to that of an apatite crystal. Furthermore, some crystals clearly revealed an 18.7-A lattice interval and were vulnerable to electron bombardment. After electron beam exposure, this lattice interval was quickly altered to about half (i.e. 8.2 A), indicating structural conversion. Consequently, a number of apatite crystals in the dental calculus are possibly created by a conversion mechanism involving an octacalcium phosphate intermediate. However, we also concluded that the calcification process in the dental calculus is not similar to that of ordinary calcifying hard tissues.

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.

Multiple cooling episodes in the Central Tarim (Northwest China) revealed by apatite fission track analysis and vitrinite reflectance data

NASA Astrophysics Data System (ADS)

Chang, Jian; Qiu, Nansheng; Song, Xinying; Li, Huili

2016-06-01

Apatite fission track and vitrinite reflectance are integrated for the first time to study the cooling history in the Central Tarim, northwest China. The paleo-temperature profiles from vitrinite reflectance data of the Z1 and Z11 wells showed a linear relationship with depth, suggesting an approximately 24.8 °C/km paleo-geothermal gradient and 2700-3900 m of erosion during the Early Mesozoic. The measured apatite fission track ages from well Z2 in the Central Tarim range from 39 to 159 Ma and effectively record the Meso-Cenozoic cooling events that occurred in Central Tarim. Moreover, two cooling events at 190-140 Ma in the Early Jurassic-Early Cretaceous and 80-45 Ma in the Late Cretaceous-Paleocene revealed by measured AFT data and thermal modeling results are related to the collisions of the Qiangtang-Lhasa terranes and the Greater India Plate with the southern margin of the Eurasian Plate, respectively. This study provides new insights into the tectonic evolution of the Tarim Basin (and more broadly Central Asia) and for hydrocarbon generation and exploration in the Central Tarim.

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.

Domestic phosphate deposits

USGS Publications Warehouse

McKelvey, V.E.; Cathcart, J.B.; Altschuler, Z.S.; Swanson, R.W.; Lutz, Katherine

1953-01-01

Most of the worlds phosphate deposits can be grouped into six types: 1) igneous apatite deposits; 2) marine phosphorites; 3) residual phosphorites; 4) river pebble deposits; 5) phosphatized rock; and 6) guano. The igneous apatites and marine phosphorites form deposits measurable in millions or billions of tons; the residual deposits are measurable in thousands or millions; and the other types generally only in thousands of tons. Igneous apatite deposits have been mined on a small scale in New York, New Jersey, and Virginia. Marine phosphorites have been mined in Montana, Idaho, Utah, Wyoming, Arkansas, Tennessee, North Carolina, South Carolina, Georgia, and Florida. Residual phosphorites have been mined in Tennessee, Pennsylvania, and Florida. River pebble has been produced in South Carolina and Florida; phosphatized rock in Tennessee and Florida; and guano in New Mexico and Texas. Present production is limited almost entirely to Florida, Tennessee, Montana, Idaho, and Wyoming. Incomplete but recently partly revised estimates indicate the presence of about 5 billion tons of phosphate deposits in the United States that is minable under present economic conditions. Deposits too lean in quality or thickness to compete with those in the western and southeastern fields probably contain tens of billions of tons.

Appearance of cell-adhesion factor in osteoblast proliferation and differentiation of apatite coating titanium by blast coating method.

PubMed

Umeda, Hirotsugu; Mano, Takamitsu; Harada, Koji; Tarannum, Ferdous; Ueyama, Yoshiya

2017-08-01

We have already reported that the apatite coating of titanium by the blast coating (BC) method could show a higher rate of bone contact from the early stages in vivo, when compared to the pure titanium (Ti) and the apatite coating of titanium by the flame spraying (FS) method. However, the detailed mechanism by which BC resulted in satisfactory bone contact is still unknown. In the present study, we investigated the importance of various factors including cell adhesion factor in osteoblast proliferation and differentiation that could affect the osteoconductivity of the BC disks. Cell proliferation assay revealed that Saos-2 could grow fastest on BC disks, and that a spectrophotometric method using a LabAssay TM ALP kit showed that ALP activity was increased in cells on BC disks compared to Ti disks and FS disks. In addition, higher expression of E-cadherin and Fibronectin was observed in cells on BC disks than Ti disks and FS disks by relative qPCR as well as Western blotting. These results suggested that the expression of cell-adhesion factors, proliferation and differentiation of osteoblast might be enhanced on BC disks, which might result higher osteoconductivity.

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

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.

Formation mechanism and adhesive strength of a hydroxyapatite/TiO2 composite coating on a titanium surface prepared by micro-arc oxidation

NASA Astrophysics Data System (ADS)

Liu, Shimin; Li, Baoe; Liang, Chunyong; Wang, Hongshui; Qiao, Zhixia

2016-01-01

A hydroxyapatite (HA)/TiO2 composite coating was prepared on a titanium surface by one-step micro-arc oxidation (MAO). The formation mechanism of the composite coating was investigated and the adhesion of the coating to the substrate was also measured. The results showed that flocculent structures could be obtained during the early stages of treatment. As the treatment period extended, increasing amounts of Ca-P precipitate appeared on the surface, and the flocculent morphology transformed into a plate-like morphology. Then the plate-like calcium and phosphate salt self-assembled to form flower-like apatite. The Ca/P atomic ratio gradually decreased, indicating that the amounts of Ca2+ ions which diffused into the coating decreased more rapidly than that of PO43- or HPO42-. The adhesive strength between the apatite and TiO2 coating was improved. This improvement is attributed to the interlocking effect between the apatite and TiO2 layer which formed simultaneously during the early stages of the one-step MAO. This study shows that it is a promising method to prepare bioactive coating on a titanium surface.

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.

Structural change in lead fluorapatite at high pressure

NASA Astrophysics Data System (ADS)

Fleet, Michael E.; Liu, Xi; Shieh, Sean R.

2010-01-01

The structure of lead fluorapatite [PbFAP; Pb10(PO4)6F2], crystallized from the melt in a platinum capsule at 1,000°C and 1 atm, has been investigated by single-crystal X-ray diffraction. Crystal data are a = 9.7638 (6), c = 7.2866 (4) Å, space group P63/ m, R = 0.043, R w = 0.034. We have also studied the compressional behaviour of the c-axis channel of PbFAP up to 9 GPa at 25°C, using a diamond-anvil cell, synchrotron X-radiation, and Rietveld powder structure refinement. Pressure-volume data for the channel polyhedron of PbFAP fitted to the third-order Birch-Murnaghan equation resulted in K T = 33.2 ± 1.2 GPa when K T ' is fixed at 4. The c-axis channel of PbFAP is about twice as compressible as the unit-cell volume of PbFAP and the channel of calcium apatites. This is attributed to the anomalous narrowing of the channel of PbFAP with increase in confining pressure. Flexibility of the apatite channel is a key factor in the scavenging of toxic heavy metals by calcium apatites.

Protein-free formation of bone-like apatite: New insights into the key role of carbonation

PubMed Central

Deymier, Alix C.; Nair, Arun K.; Depalle, Baptiste; Qin, Zhao; Arcot, Kashyap; Drouet, Christophe; Yoder, Claude H.; Buehler, Markus J.; Thomopoulos, Stavros; Genin, Guy M.; Pasteris, Jill D.

2017-01-01

The nanometer-sized plate-like morphology of bone mineral is necessary for proper bone mechanics and physiology. However, mechanisms regulating the morphology of these mineral nanocrystals remain unclear. The dominant hypothesis attributes the size and shape regulation to organic-mineral interactions. Here, we present data supporting the hypothesis that physicochemical effects of carbonate integration within the apatite lattice control the morphology, size, and mechanics of bioapatite mineral crystals. Carbonated apatites synthesized in the absence of organic molecules presented plate-like morphologies and nanoscale crystallite dimensions. Experimentally-determined crystallite size, lattice spacing, solubility and atomic order were modified by carbonate concentration. Molecular dynamics (MD) simulations and density functional theory (DFT) calculations predicted changes in surface energy and elastic moduli with carbonate concentration. Combining these results with a scaling law predicted the experimentally observed scaling of size and energetics with carbonate concentration. The experiments and models describe a clear mechanism by which crystal dimensions are controlled by carbonate substitution. Furthermore, the results demonstrate that carbonate substitution is sufficient to drive the formation of bone-like crystallites. This new understanding points to pathways for biomimetic synthesis of novel, nanostructured biomaterials. PMID:28279923

[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.

Sequence stratigraphy, geodynamics, and detrital geothermochronology of Cretaceous foreland basin deposits, western interior U.S.A

NASA Astrophysics Data System (ADS)

Painter, Clayton S.

Three studies on Cordilleran foreland basin deposits in the western U.S.A. constitute this dissertation. These studies differ in scale, time and discipline. The first two studies include basin analysis, flexural modeling and detailed stratigraphic analysis of Upper Cretaceous depocenters and strata in the western U.S.A. The third study consists of detrital zircon U-Pb analysis (DZ U-Pb) and thermochronology, both zircon (U-Th)/He and apatite fission track (AFT), of Upper Jurassic to Upper Cretaceous foreland-basin conglomerates and sandstones. Five electronic supplementary files are a part of this dissertation and are available online; these include 3 raw data files (Appendix_A_raw_isopach_data.txt, Appendix_C_DZ_Data.xls, Appendix_C_U-Pb_apatite.xls), 1 oversized stratigraphic cross section (Appendix_B_figure_5.pdf), and 1 figure containing apatite U-Pb concordia plots (Appendix_C_Concordia.pdf). Appendix A is a combination of detailed isopach maps of the Upper Cretaceous Western Interior, flexural modeling and a comparison to dynamic subsidence models as applied to the region. Using these new isopach maps and modeling, I place the previously recognized but poorly constrained shift from flexural to non-flexural subsidence at 81 Ma. Appendix B is a detailed stratigraphic study of the Upper Cretaceous, (Campanian, ~76 Ma) Sego Sandstone Member of the Mesaverde Group in northwestern Colorado, an area where little research has been done on this formation. Appendix C is a geo-thermochronologic study to measure the lag time of Upper Jurassic to Upper Cretaceous conglomerates and sandstones in the Cordilleran foreland basin. The maximum depositional ages using DZ U-Pb match existing biostratigraphic age controls. AFT is an effective thermochronometer for Lower to Upper Cretaceous foreland stratigraphy and indicates that source material was exhumed from >4--5 km depth in the Cordilleran orogenic belt between 118 and 66 Ma, and zircon (U-Th)/He suggests that it was exhumed from <8--9 km depth. Apatite U-Pb analyses indicate that volcanic contamination is a significant issue, without which, one cannot exclude the possibility that the youngest detrital AFT population is contaminated with significant amounts of volcanogenic apatite and does not represent source exhumation. AFT lag times are <5 Myr with relatively steady-state to slightly increasing exhumation rates. Lag time measurements indicate exhumation rates of ~0.9->>1 km/Myr.

Effects of Microbial and Phosphate Amendments on the Bioavailability of Lead (Pb) in Shooting Range Soil

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

Brigmon, Robin; Wilson, Christina; Knox, Anna

Heavy metals including lead (Pb) are released continually into the environment as a result of industrial, recreational, and military activities. Lead ranked number two on the CERCLA Priority List of Hazardous Substances and was identified as a major hazardous chemical found on 47% of USEPA's National Priorities List sites (Hettiarachchi and Pierzynski 2004). In-situ remediation of lead (Pb) contaminated soils may be accomplished by changing the soil chemistry and structure with the application of microbial and phosphate amendments. Soil contaminated with lead bullets was collected from the surface of the berm at Savannah River Site (SRS) Small Arms Training Academymore » (SATA) in Aiken, SC. While uncontaminated soils typically have Pb levels ranging from 2 to 200 mg/kg (Berti et al. 1998), previous analysis show Pb levels of the SATA berm to reach 8,673 mg/kg. Biosurfactants are surface-active compounds naturally produced by soil bacteria that can bind metals. Biosurfactants have a wide variety of chemical structures that reduce interfacial surface tensions (Jennings and Tanner 2000) and have demonstrated efficient metal complexion (Lin 1996). Biosurfactants also have the potential to change the availability of natural organic matter (Strong-Gunderson 1995). Two types of bacteria, Alcaligenes piechaudii and Pseudomonas putida, were employed as amendments based on their ability to produce biosurfactants and survive in metal-contaminated soils. Apatites (calcium phosphate compounds) are important in the formation of Pb phosphates. Pb phosphates form rapidly when phosphate is available and are the most stable environmental form of lead in soil (Ruby et al.1998). Pyromorphites in particular remain insoluble under a wide range of environmental conditions (Zhang et al. 1998). The three apatites evaluated in the current study were North Carolina apatite (NCA), Florida apatite (FA), and biological apatite (BA). BA is ground fish bone that has few impurities such as As, Cr, or U and contains about 27% total phosphate, most of which is available. FA and NCA are two types of rock phosphates that release small amounts of phosphate over time. Total phosphate is around 30% with only 1-2% phosphate available (Knox et al. 2005). In this study, we describe the influence of combining the two microbial and three phosphate amendments on reducing lead bioavailability in shooting range soil.« less

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

In-situ, laser ablation U-Th-Sm/He dating is an emerging technique in thermochronology that has been proven as a means to date zircon and monzonite1-5. In-situ U-Th-Sm/He thermochronology eliminates many of the problems and inconveniences associated with traditional, whole grain methods, including; reducing bias in grain selection based on size, shape and clarity; allowing for the use of broken grains and grains with inclusions; avoiding bad neighbour effects; and eliminating safety hazards associated with dissolution. In-situ apatite laser ablation is challenging due to low concentrations of U and Th and thus a low abundance of radiogenic He. For apatite laser ablation to be effective the ultra-high-vacuum (UHV) line must have very low and consistent background levels of He. To reduce He background, samples are mounted in a UHV stable medium. Our mounting process uses a MicroHePP (Microscope Mounted Heated Platen Press) to press samples into FEP (fluorinated ethylene propylene) bonded to an aluminum backing plate. Samples are ablated using a Resonetics 193 nm excimer laser and liberated He is measured using a quadrupole mass spectrometer on the ASI Alphachron noble gas line; collectively this system is known as the Resochron. The ablated sites are imaged using a Zygo Zescope optical profilometer and ablated pit volume measured using PitVol, a custom MatLab algorithm developed to enable precise and unbiased measurement of the ablated pit geometry. We use the well-characterized Durango apatite to demonstrate the accuracy and precision of the method. He liberated from forty-two pits, having volumes between 1700 and 9000 um3, were measured using the Resochron. The ablated sites were imaged using a Zygo Zescope optical profilometer and ablated pit volume measured using PitVol. U, Th and Sm concentrations were measured by laser ablation and the U-Th-Sm/He age calculated by standard age equation. An age of 33.8±0.31 Ma was determined and compares well with conventional U-Th/He methods, whole grain degassing and dissolution, that produced an age of 32.73±0.47 Ma for chips of the same Durango crystal. Further dating of other well characterized apatite crystals will be used to test the robustness of the method.

Resolving the chronology of the South African landscape through joint inverse modelling of AFT and apatite (U-Th)/He data

NASA Astrophysics Data System (ADS)

Wildman, Mark; Brown, Roderick; Beucher, Romain; Persano, Cristina; Stuart, Finlay

2013-04-01

Application of Low temperature thermochronometry (LTT) is a powerful method of constraining thermal history information on samples as they pass through isotherms in the upper crust. Inverse modelling of LTT data generates thermal history information which can then be correlated with independent datasets to infer geological processes that are responsible for producing the observed thermal history held in the thermochronometry record. A critical consideration when choosing which LTT method to use are the closure temperatures associated with each system. In order to generate more complete and robust thermal histories a single sample can be analysed using multiple low temperature thermochronometers that are sensitive over different but complimentary temperature ranges. The main focus of LTT work in South Africa has been on apatite fission track (AFT) analysis which is a world renowned method of constraining thermal history information between c. 60 and 110±10°C. The general conclusions that have been drawn from the South African AFT dataset is that the present day regional topography represents an eroded remnant of an elevated interior that experienced a significant uplift event with km-scale erosion in the Cretaceous following the break-up of Gondwana [1]. The exact nature of Cretaceous uplift and erosion varies both spatially and temporally, especially in south western Africa where at least two distinct denudation events are recorded at c. 130Ma and 90 Ma [2]. There are, however, alternative views suggesting significant epeirogenic-style uplift and subsequent erosion throughout the Cenozoic [3]. A key aspect of this debate which is yet to be fully resolved is the influence of mantle dynamics on the evolution of the overlying topography. To further investigate the timing and amount of Cenozoic uplift and erosion and to what degree this can be ascribed to dynamic topography, efforts have been made to complement the existing AFT record with Apatite (U-Th)/He analysis (AHe) (e.g. [4]). AHe is ideally suited to this task as it is sensitive over a lower temperature range (c. 40-75±5°C) and can therefore provide insights into erosion on the scale of 1-3 km. Correlating AFT and AHe datasets can be difficult due to variations in U and Th zonation, crystal geometry and structural defects (e.g. radiation damage) altering the closure temperature of the AHe system and resulting in significant dispersion of ages. It is therefore essential to fully understand the major cause of age dispersion and use thermal history modelling techniques that take these factors into account. Here we present a new suite of apatite (U-Th)/He data from samples along the Orange River alongside complimentary apatite fission track data from the same samples. Two samples with a large number of analysed grains, JN2 and GGO2 (23 and 21 grains, respectively) were modelled using HelFrag [5] which takes into account dispersion in AHe ages produced through analysis fragments of larger apatite grains. These modelled histories where compared with inverse modelling using QTQt [6] to extract thermal history information for each of the samples and provide new insights into the post-Cretaceous evolution of the SW African landscape and the behaviour of complex dispersion patterns commonly observed in AHe data sets. [1] Brown, R.W., Summerfield, M.A., and Gleadow, A.J.W., 2002, Denudational history along a transect across the Drakensberg Escarpment of southern Africa derived from apatite fission track thermochronology: Journal of Geophysical Research, v. 107, p. B12, 2350. [2] Kounov, A., Viola, G., de Wit, M., and Andreoli, M.A.G., 2009, Denudation along the Atlantic passive margin: new insights from apatite fission-track analysis on the western coast of South Africa: Geological Society, London, Special Publications, v. 324, p. 287-306. [3] Partridge, T.C., and Maud, R.R., 1987, Geomorphic evolution of southern Africa since the Mesozoic: South African Journal of Geology, v. 90, p. 179-208 [4] Flowers, R.M., and Schoene, B., 2010, (U-Th)/He thermochronometry constraints on unroofing of the eastern Kaapvaal craton and significance for uplift of the southern Africa Plateau: Geology, v. 38, p. 827-830. [5] Gallagher, K., 2012, Transdimensional inverse thermal history modeling for quantitative thermochronology: Journal of Geophysical Research, v. 117, p. 16. [6] Brown, R.W., Beucher, R., Roper, S., Gallagher, K., Persano, C. and Stuart, F., 2012, How to derive robust thermal histories from 'over-dispersed' single crystal apatite (U-Th)/He ages, Geophysical Research Abstracts, Vol. 14, EGU2012-11828, 2012, EGU General Assembly 2012

Determining the origin of enigmatic bedrock structures using apatite (U-Th)/He thermochronology: Alabama and Poverty Hills, Owens Valley, California

NASA Astrophysics Data System (ADS)

Ali, G. A.; Reiners, P. W.; Ducea, M.

2008-12-01

The Alabama and Poverty Hills are enigmatic, topographic highs of crystalline basement surrounded by Neogene sediments in Owens Valley, California. The 150-km long Owens Valley, the westernmost graben of the Basin and Range Province, initiated at about 3 Ma, creating ~2-4 km of vertical relief from the Sierra Nevada and White/Inyos crests to the valley floor. Along the valley, the active right-lateral Owens Valley Fault Zone (OVFZ) accommodates a significant portion of Pacific-North American plate motion, creating an oblique dextral fault zone, with localized transpression along minor left-stepovers. The dominantly granitic Mesozoic rocks of the Alabama Hills are bounded by the OVFZ to the east, and the granitic and metavolcanic Mesozoic rocks of the Poverty Hills are located along an apparent 3-km left stepover of the OVFZ. The tectonic origin and geodynamic significance of both these structures are not known, but previously published hypotheses include: 1) transpressional uplifts as OVFZ-related flower structures; 2) down-dropped normal fault blocks; and 3) giant landslides from adjacent ranges. We measured apatite (U-Th)/He ages on 15 samples from the Alabama and Poverty Hills to understand the history of shallow crustal exhumation of these structures, and to potentially correlate them to rocks from adjacent ranges. Apatite He dating typically yields cooling ages corresponding to closure temperatures of ~55-65 °C, corresponding roughly to depths of ~2-3 km in the crust. The majority of apatite He ages from the Alabama Hills ranged from 58-70 Ma, but the far eastern, and lowest elevation sample showed ages of 51-55 Ma. The Poverty Hills shows younger ages of 40-65 Ma and no recognizable spatial pattern. Although the data do not conclusively rule out a transpressional uplift origin of the Poverty Hills, the rocks within them could not have been exhumed from depths greater than ~2-3 km in Owens Valley. Data from both structures are most consistent with down-dropping from adjacent ranges. Apatite He ages in the Alabama Hills correlate with He ages of rocks about 2.5-3 km higher, near Mt. Whitney in the adjacent Sierra Nevada. This, coupled with the spatial pattern of ages, strongly suggests that the Alabama Hills are a down-dropped normal fault block along the Sierra Nevada frontal fault zone or a related fault. A structural reconstruction using tilt-corrected Sierran apatite He age-elevation correlations requires 2.6 km of vertical, and 1.5 km of eastward motion for the Alabama Hills. The proximity of this extensive down- dropped basement block, directly east of the highest topography in the Sierra Nevada, suggests the possibility of localized isostatic response as a cause for locally high elevation in the Mt. Whitney area.

Synchrotron-based P K-edge XANES spectroscopy reveals rapid changes of phosphorus speciation in the topsoil of two glacier foreland chronosequences

NASA Astrophysics Data System (ADS)

Prietzel, Jörg; Dümig, Alexander; Wu, Yanhong; Zhou, Jun; Klysubun, Wantana

2013-05-01

Phosphorus (P) is a crucial element for life on Earth, and the bioavailability of P in terrestrial ecosystems, which is dependent on the soil P stock and its speciation, may limit ecosystem productivity and succession. In our study, for the first time a direct speciation of soil P in two glacier foreland chronosequences has been conducted using synchrotron-based X-ray Absorption Near-Edge Structure (XANES) spectroscopy. The chronosequences are located in the forefields of Hailuogou Glacier (Gongga Shan, China) and Damma Glacier (Swiss Alps). The age since deglaciation of the investigated soils ranges from 0 to 120 years at Hailuogou, and from 15 to >700 years at Damma. Differences in climate conditions (cooler at Damma, in contrast to Hailuogou precluding the establishment of forest in advanced ecosystem succession stages) and in the chemical composition of the parent material result in different soil contents of total P and Fe/Al oxyhydroxides, which are much smaller at Damma than at Hailuogou. Nevertheless, both chronosequences show similar trends of their topsoil P status with increasing soil age. Our study reveals a rapid change of topsoil P speciation in glacier retreat areas already during initial stages of pedogenesis: Initially dominating bedrock-derived apatite-P and Al-bound P is depleted; Fe-bound P and particularly organically-bound P is accumulated. Organic P strongly dominates in the topsoil of the mature soils outside the proglacial area of Damma Glacier (age 700-3000 years), and already 50 years after deglacation in the topsoil of the retreat area of Hailuogou Glacier. A key factor for the change in topsoil P speciation is the establishment of vegetation, resulting in soil organic matter (SOM) accumulation as well as accelerated soil acidification and apatite dissolution by organic acids, which are produced by SOM-degrading micro-organisms, mykorrhiza fungi, and plant roots. Particularly the succession of grassland to forest seems to accelerate the transformation of topsoil P from apatite-P into organic P. The conceptual model developed by Walker and Syers (1976) to explain long-term (millennial) changes of P speciation, availability, and turnover in soils and terrestrial ecosystems seems to be valid to describe short-term changes of P speciation and P availability in proglacial topsoils already within a century of initial soil formation. Because the apatite-depleted topsoil horizons in the young proglacial soils are shallow, the change of topsoil P speciation should not seriously affect P availability and the P acquisition strategy of adult trees, whose roots can easily access apatite-containing C horizons. In contrast, P acquisition strategies of fungi, micro-organisms and plants confined to the topsoil probably change from apatite dissolution to mineralization of organic P already within <3000 years in a proglacial ecosystem succession from bare soil to grassland (Damma Glacier Chronosequence) or even within <100 years in a proglacial ecosystem succession to forest (Hailuogou Glacier Chronosequence).

The shape of ion tracks in natural apatite

NASA Astrophysics Data System (ADS)

Schauries, D.; Afra, B.; Bierschenk, T.; Lang, M.; Rodriguez, M. D.; Trautmann, C.; Li, W.; Ewing, R. C.; Kluth, P.

2014-05-01

Small angle X-ray scattering measurements were performed on natural apatite of different thickness irradiated with 2.2 GeV Au swift heavy ions. The evolution of the track radius along the full ion track length was estimated by considering the electronic energy loss and the velocity of the ions. The shape of the track is nearly cylindrical, slightly widening with a maximum diameter approximately 30 μm before the ions come to rest, followed by a rapid narrowing towards the end within a cigar-like contour. Measurements of average ion track radii in samples of different thicknesses, i.e. containing different sections of the tracks are in good agreement with the shape estimate.

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.

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

In-Situ U-Pb Dating of Apatite by Hiroshima-SHRIMP: Contributions to Earth and Planetary Science.

PubMed

Terada, Kentaro; Sano, Yuji

2012-01-01

The Sensitive High Resolution Ion MicroProbe (SHRIMP) is the first ion microprobe dedicated to geological isotopic analyses, especially in-situ analyses related to the geochronology of zircon. Such a sophisticated ion probe, which can attain a high sensitivity at a high mass resolution, based on a double focusing high mass-resolution spectrometer, designed by Matsuda (1974), was constructed at the Australian National University. In 1996, such an instrument was installed at Hiroshima University and was the first SHRIMP to be installed in Japan. Since its installation, our focus has been on the in-situ U-Pb dating of the mineral apatite, as well as zircon, which is a more common U-bearing mineral. This provides the possibility for extending the use of in-situ U-Pb dating from determining the age of formation of volcanic, granitic, sedimentary and metamorphic minerals to the direct determination of the diagenetic age of fossils and/or the crystallization age of various meteorites, which can provide new insights into the thermal history on the Earth and/or the Solar System. In this paper, we review the methodology associated with in-situ apatite dating and our contribution to Earth and Planetary Science over the past 16 years.

Nanodimensional and Nanocrystalline Apatites and Other Calcium Orthophosphates in Biomedical Engineering, Biology and Medicine

PubMed Central

Dorozhkin, Sergey V.

2009-01-01

Recent developments in biomineralization have already demonstrated that nanosized particles play an important role in the formation of hard tissues of animals. Namely, the basic inorganic building blocks of bones and teeth of mammals are nanodimensional and nanocrystalline calcium orthophosphates (in the form of apatites) of a biological origin. In mammals, tens to hundreds nanocrystals of a biological apatite were found to be combined into self-assembled structures under the control of various bioorganic matrixes. In addition, the structures of both dental enamel and bones could be mimicked by an oriented aggregation of nanosized calcium orthophosphates, determined by the biomolecules. The application and prospective use of nanodimensional and nanocrystalline calcium orthophosphates for a clinical repair of damaged bones and teeth are also known. For example, a greater viability and a better proliferation of various types of cells were detected on smaller crystals of calcium orthophosphates. Thus, the nanodimensional and nanocrystalline forms of calcium orthophosphates have a great potential to revolutionize the field of hard tissue engineering starting from bone repair and augmentation to the controlled drug delivery devices. This paper reviews current state of knowledge and recent developments of this subject starting from the synthesis and characterization to biomedical and clinical applications. More to the point, this review provides possible directions of future research and development.

In-Situ U–Pb Dating of Apatite by Hiroshima-SHRIMP: Contributions to Earth and Planetary Science

PubMed Central

Terada, Kentaro; Sano, Yuji

2012-01-01

The Sensitive High Resolution Ion MicroProbe (SHRIMP) is the first ion microprobe dedicated to geological isotopic analyses, especially in-situ analyses related to the geochronology of zircon. Such a sophisticated ion probe, which can attain a high sensitivity at a high mass resolution, based on a double focusing high mass-resolution spectrometer, designed by Matsuda (1974), was constructed at the Australian National University. In 1996, such an instrument was installed at Hiroshima University and was the first SHRIMP to be installed in Japan. Since its installation, our focus has been on the in-situ U–Pb dating of the mineral apatite, as well as zircon, which is a more common U-bearing mineral. This provides the possibility for extending the use of in-situ U–Pb dating from determining the age of formation of volcanic, granitic, sedimentary and metamorphic minerals to the direct determination of the diagenetic age of fossils and/or the crystallization age of various meteorites, which can provide new insights into the thermal history on the Earth and/or the Solar System. In this paper, we review the methodology associated with in-situ apatite dating and our contribution to Earth and Planetary Science over the past 16 years. PMID:24349912

Synthesis, bioactivity and zeta potential investigations of chlorine and fluorine substituted hydroxyapatite.

PubMed

Fahami, Abbas; Beall, Gary W; Betancourt, Tania

2016-02-01

Chlorine and fluorine substituted hydroxyapatites (HA-Cl-F) with different degrees of ion replacement were successfully prepared by the one step mechanochemical activation method. X-ray diffraction (XRD) and FT-IR spectra indicated that substitution of these anions in milled powders resulted in the formation of pure hydroxyapatite phase except for the small observed change in the lattice parameters and unit cell volumes of the resultant hydroxyapatite. Microscopic observations showed that the milled product had a cluster-like structure made up of polygonal and spherical particles with an average particle size of approximately ranged from 20±5 to 70±5nm. The zeta potential of milled samples was performed at three different pH (5, 7.4, and 9). The obtained zeta potential values were negative for all three pH values. Negative zeta potential was described to favor osseointegration, apatite nucleation, and bone regeneration. The bioactivity of samples was investigated on sintered pellets soaked in simulated body fluid (SBF) solution and apatite crystals formed on the surface of the pellets after being incubated for 14days. Zeta potential analysis and bioactivity experiment suggested that HA-Cl-F will lead to the formation of new apatite particles and therefore be a potential implant material. Copyright © 2015 Elsevier B.V. All rights reserved.

Influences of Sr dose on the crystal structure parameters and Sr distributions of Sr-incorporated hydroxyapatite.

PubMed

Guo, D G; Hao, Y Z; Li, H Y; Fang, C Q; Sun, L J; Zhu, H; Wang, J; Huang, X F; Ni, P F; Xu, K W

2013-10-01

Stoichiometric strontium-incorporated hydroxyapatite (Sr-HA) with different Sr concentrations [Sr/(Sr+Ca)] were synthesized using a wet chemical approach and characterized by X-ray diffraction, Fourier-transformed infrared absorption, X-ray photoelectron spectroscopy, and Rietveld Structure Refinement. The crystal lattice parameter, Sr distribution, chemical state of Sr, and also the relationships between their variations and the Sr concentrations have been intensively studied. The results show that both the crystal lattice parameters and crystal plane space of Sr-HA remarkably increase with the Sr concentration increasing. Whether Sr preferably occupies the Ca(I) site or Ca(II) site after incorporated into apatite lattice depends on the Sr number incorporated into apatite. All the Sr ions completely occupy the Ca(II) sites when the Sr concentration is below 5%. With the exception of partial Sr ions occupying the Ca(II) sites, the other Sr ions start to occupy the Ca(I) sites when the Sr concentration doped in HA is beyond 10%. The ratio of Sr ions occupying the Ca(I) sites increases with the further raising Sr concentration up to 20%. The Sr ions inherit the chemical state and environment of the original Ca(I) or Ca(II) site after incorporated into apatite. Copyright © 2013 Wiley Periodicals, Inc.

Remineralization of artificial dentinal caries lesions by biomimetically modified Mineral Trioxide Aggregate

PubMed Central

Qi, Yi-pin; Li, Nan; Niu, Li-na; Primus, Carolyn M.; Ling, Jun-Qi; Pashley, David H.; Tay, Franklin R.

2011-01-01

Fluoride-releasing restorative materials are available for remineralization of enamel and root caries. However, dentin remineralization is more difficult than enamel remineralization due to the paucity of apatite seed crystallites along the lesion surface for heterogeneous crystal growth. Extracellular matrix proteins play critical roles in controlling apatite nucleation/growth in collagenous tissues. This study examined the remineralization efficacy of mineral trioxide aggregate (MTA) in phosphate-containing simulated body fluid (SBF) by incorporating polyacrylic acid and sodium tripolyphosphate as biomimetic analogs of matrix proteins for remineralizing caries-like dentin. Artificial caries-like dentin lesions incubated in SBF were remineralized over a 6-week period using MTA or MTA containing biomimetic analogs in the absence or presence of dentin adhesive application. Lesion depths and integrated mineral loss were monitored with micro-computed tomography. Ultrastructure of baseline and remineralized lesions were examined by transmission electron microscopy. Dentin remineralization was best achieved using MTA containing biomimetic analogs regardless of whether an adhesive was applied; dentinal tubules within the remineralized dentin were occluded by apatite. It is concluded that the MTA version employed in the study may be doped with biomimetic analogs for remineralization of unbonded and bonded artificial caries-like lesions in the presence of SBF. PMID:22085925

Remineralization of artificial dentinal caries lesions by biomimetically modified mineral trioxide aggregate.

PubMed

Qi, Yi-pin; Li, Nan; Niu, Li-na; Primus, Carolyn M; Ling, Jun-Qi; Pashley, David H; Tay, Franklin R

2012-02-01

Fluoride-releasing restorative materials are available for remineralization of enamel and root caries. However, remineralization of dentin is more difficult than remineralization of enamel due to the paucity of apatite seed crystallites along the lesion surface for heterogeneous crystal growth. Extracellular matrix proteins play critical roles in controlling apatite nucleation/growth in collagenous tissues. This study examined the remineralization efficacy of mineral trioxide aggregate (MTA) in phosphate-containing simulated body fluid (SBF) by incorporating polyacrylic acid and sodium tripolyphosphate as biomimetic analogs of matrix proteins for remineralizing caries-like dentin. Artificial caries-like dentin lesions incubated in SBF were remineralized over a 6 week period using MTA alone or MTA containing biomimetic analogs in the absence or presence of dentin adhesive application. Lesion depths and integrated mineral loss were monitored with microcomputed tomography. The ultrastructure of baseline and remineralized lesions was examined by transmission electron microscopy. Dentin remineralization was best achieved using MTA containing biomimetic analogs regardless of whether an adhesive was applied; dentinal tubules within the remineralized dentin were occluded by apatite. It is concluded that the version of MTA employed in this study may be doped with biomimetic analogs for remineralization of unbonded and bonded artificial caries-like lesions in the presence of SBF. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

PubMed

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

2014-06-01

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

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

PubMed

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

2008-09-01

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

Behavior of carbonate and magnesium ions in the initial crystallites at the early developmental stages of the rat calvaria.

PubMed

Kakei, M; Nakahara, H; Tamura, N; Itoh, H; Kumegawa, M

1997-08-01

Analysis of the contents of calcium (Ca), magnesium (Mg), phosphate, and carbonate ions in the mineral phase of rat calvaria specimens obtained at different developmental stages indicated that the mineral at the newborn stage contained a negligible amount of carbonate, but a high content of Mg. There was no significant difference in Ca and phosphate (as PO4) contents between the newborn material and that from later stages. A relatively large amount of carbonate was detected in the calvaria from 6-day-old rats, in which only immature crystals were observed, thus indicating the beginning of apatite formation. Furthermore, using laser Raman microprobe analysis we confirmed that the Raman peak at 1120 cm-1 band, indicative of a Mg-CO3 compound, appeared at the 6-day stage. We also observed that the Raman peak at 988 cm-1 found in the samples from the newborn seemed to have shifted to 963-962 cm-1 in the case of those obtained from 6-day-old rats, a shift which suggests the conversion from the non-apatitic to the apatitic form. These results indicate that carbonate ions might facilitate the initiation of crystal development by converting the inhibitory Mg ion into its inactive form (Mg-carbonate compound).

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

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

Silk fibroin/kappa-carrageenan composite scaffolds with enhanced biomimetic mineralization for bone regeneration applications.

PubMed

Nourmohammadi, Jhamak; Roshanfar, Fahimeh; Farokhi, Mehdi; Haghbin Nazarpak, Masoumeh

2017-07-01

The combination of protein-polysaccharide in scaffolding together with the ability to induce bone-like apatite formation has become a promising approach to mimic extracellular matrix composition. In the present study, we developed and characterized new bioactive composite scaffolds from kappa-carrageenan/silk fibroin for bone regeneration applications. Three dimensional (3D) scaffolds were fabricated by adding various amounts of carrageenan to a silk fibroin solution, followed by freeze-drying. Various characterization techniques were applied to analyze such items as the structure, morphology, compressive strength, and bone-like apatite mineralization of the composites, which were then compared to those of pure fibroin scaffolds. The results demonstrated the formation of a highly porous structure with interconnected pores. The mean pore size and porosity both increased by increasing carrageenan content. Moreover, the addition of carrageenan to silk fibroin led to the formation of a bone-like apatite layer throughout the scaffolds after 7days of soaking them in simulated body fluid. Osteoblast-like cell (MG 63) culture experiments indicated that all scaffolds are biocompatible. The cells attached well to the surfaces of all scaffolds and tended to join their adjacent cells. However, higher carrageenan content led to better cellular proliferation and higher Alkaline phosphatase expression. Copyright © 2017 Elsevier B.V. All rights reserved.

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

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.

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.

An NMR Study of Biomimetic Fluorapatite – Gelatine Mesocrystals

PubMed Central

Vyalikh, Anastasia; Simon, Paul; Rosseeva, Elena; Buder, Jana; Scheler, Ulrich; Kniep, Rüdiger

2015-01-01

The mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43− groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers, and with experimental observations of an amorphous cover layer in biominerals. PMID:26515127

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.

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.

Asymmetric Exhumation Patterns Revealed through Apatite-Zircon Thermochronology of the Santa Lucia Range, Central California

NASA Astrophysics Data System (ADS)

Mere, A.; Steely, A.; Hourigan, J. K.

2016-12-01

Previous thermochronological analyses of crystalline bedrock in the central Santa Lucia range have yielded surprisingly rapid rates of surface uplift and bedrock extrusion despite lack of modern seismicity along nearby faults. We use 8 new apatite and zircon (U-Th)/He dates in order to better constrain the history of bedrock extrusion in response to the transpressional North American-Pacific plate boundary. Granitic samples were collected along coastal fault blocks bounded by the Palo Colorado (PCF), Sur-Nacimiento (SNF), and San Gregorio Hosgri faults (SGHF); as well as one sample from Salinian Basement >25km NE of the SGHF. Helium was extracted and analyzed using a quadrupole equipped multi-sample laser microfurnace and U/Th content was measured using high precision isotope-dilution ICP mass spectrometry. Rapid late Cretaceous unroofing is captured in Salinian basement zircon and apatite by the respective 67Ma and 63Ma dates. Zircon along coastal silvers proximal to PCF and SNF record 28-31Ma dates while zircon in close proximity to SGHF record ages as young as 6.5Ma. Apatite ages proximal to PCF and SNF range between 6-9Ma and are as young as 1.5Ma directly NE of the SGHF. These data reflect increased exhumation beginning as recently as the Miocene and additionally indicate rates of modern (<2Ma) uplift exceeding 1.3 mm/yr. These results indicate that stresses caused by the active plate boundary are accommodated by the SGHF and associated faults as vertical deformation despite low rates of modern seismicity. We suggest that the SGHF and nearby faults are more active, or behave differently, that previously acknowledged. The pattern of focused exhumation within narrow fault blocks appears to be related to underplating of low strength schist that is thought to be synchronous with late Cretaceous unroofing of Salinian basement.

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.

Decoding Dynamic Topography: Geologic and Thermochronologic Constraints From Madagascar

NASA Astrophysics Data System (ADS)

Stephenson, S.; White, N.

2017-12-01

Madagascar's topography is characterized by flights of low relief peneplains separated by escarpments. Remarkably, nearly 50% of the landscape is higher than 500 m despite being surrounded by passive margins. Eocene marine limestones crop out at elevations of 400-800 m, staircases of Pleistocene marine terraces fringe the coastline and longitudinal river profiles are disequilibrated. Together, these observations suggest that Madagascar has experienced Neogene epeirogenic uplift. Positive oceanic residual depth anomalies surrounding the island, long wavelength free-air gravity anomalies, Neogene basaltic volcanism and slow sub-plate shear wave velocities show that Neogene uplift is generated by convective circulation within the upper mantle. However, the landscape's erosional response to long wavelength uplift is poorly known. Here, we present 18 apatite fission track and apatite He analyses of granitoid samples from sub-vertical transects in central and northern Madagascar. Apatite fission track ages are 200-250 Ma with mean track lengths of 12 μm. Apatite He ages are highly dispersed in samples from the highlands (i.e. AHe age > 150 Ma) but a narrower, younger range of 30-60 Ma is found on the coastal lowlands. Joint inverse modeling was carried out using the QTQt transdimensional reversible jump Markov Chain Monte Carlo (MCMC) algorithm to determine time-temperature histories. Results show that the coastal lowlands experienced up to 1 km of exhumation during the Neogene Period, whilst the central highlands experienced either very slow or negligible exhumation. This spatial distribution is expected when kinematic waves of incision propagate through a fluvially eroding landscape from coast to interior. Inverse modeling of suites of river profiles and forward landscape simulations support this interpretation. Our results show that the landscape response to modest (i.e. 1 km) regional uplift is diachronous and that thermochronologic observations can be used to detect spatial patterns of denudation. These combined observations help to constrain the fluid dynamical evolution of the upper mantle beneath Madagascar.

Effects of Arabia-Eurasia Collision on Strike-slip Faults in Central Anatolia?

NASA Astrophysics Data System (ADS)

Whitney, D. L.; Lefebvre, C.; Thomson, S. N.; Idleman, L.; Cosca, M. A.; Kaymakci, N.; Teyssier, C. P.; Umhoefer, P. J.

2013-12-01

The North and East Anatolian faults accommodate much of the tectonic escape of Anatolia in response to Arabia-Eurasia collision and building of the Turkish-Iranian plateau, but these structures formed <10 m.y. ago, at least 25 m.y. after the onset of collision at ~35 Ma. Some of the major strike-slip fault zones located between the North and East Anatolian faults have had long and complex histories of displacement. These faults have deformed, and in some cases exhumed, metamorphic massifs located between fault strands. One example is the Nigde Massif, which was initially exhumed in the Late Cretaceous, then reburied and reheated, along with its overlying sedimentary basin, to a depth of ~10 km at 30 × 5 Ma. Final exhumation and cooling occurred by ~15-17 Ma (massif margin) to ~12 Ma (structurally deepest levels). This depth-temperature-time-deformation history is tracked by a combination of thermobarometric methods, structural and stratigraphic analysis, and geo/thermochronometry (U-Pb zircon, monazite; 40Ar/39Ar hornblende, muscovite, biotite, K-feldspar; zircon and apatite fission-track in metamorphic rocks and basin deposits; and apatite (U-Th)/He). Recent mapping shows the presence of at least two oblique-thrust slices; the structurally higher one accounts for the resetting of detrital apatite fission track and AHe ages in the basin rocks as well as metamorphic apatite near the margin of the massif. The structurally deeper one cuts through the metamorphic basement and explains why mineral lineations and metamorphic assemblages are different along the eastern margin relative to those in the core of the massif. Although the timing of displacement has not been dated directly, low-T thermochronology age and modeling results document a perturbation at ~30 Ma, consistent with the idea that the Ecemis Fault of the Central Anatolian Fault Zone, and probably other pre-existing strike-slip faults in central Anatolia, experienced Late Eocene-Oligocene displacement in response to Arabia-Eurasia collision to the south and SE.

Thermal and exhumation history of the central Tianshan (NW China): Constraints by U-Pb geochronology and Ar-Ar and (U-Th)/He thermochronology

NASA Astrophysics Data System (ADS)

Yin, J.; Chen, W.; Hodges, K. V.; Xiao, W.; Van Soest, M. C.; Cai, K.; Zhang, B.; Mercer, C. M.; Yuan, C.

2015-12-01

Geochronology and thermochronology using multiple mineral-isotopic chronometers reveals the thermo-tectonic history of the central Tianshan (NW China) from emplacement to exhumation. Granites from the central Tianshan, which are associated with the southward subduction of the northern Tianshan Ocean, have been dated at 362-354 Ma using the LA-ICP-MS Zircon U-Pb method. A younger diorite sample (282 ± 1 Ma, Zircon U-Pb method by LA-ICP-MS) from northern Tianshan formed during the final closure of the Northern Tianshan Ocean when the Junggar Block collided with the Yili-Central Tianshan Block. 40Ar/39Ar step-wise heating plateau dates (biotite Ar/Ar: 312-293 Ma; Plagioclase Ar/Ar: 270-229 Ma) from the Central Tianshan show rapid post-magmatic cooling during the Late Carboniferous-Early Permian followed by a more modest rate of cooling from the middle Permian to the middle Jurassic. The northern Tianshan diorite (biotite Ar/Ar: 240 ± 1 Ma) also reveals a middle Jurassic cooling. Apatite (U-Th )/He dates from the central Tianshan samples range from ca. 130 Ma to ca. 116 Ma. The Apatite (U-Th )/He date for the northern Tianshan sample is ca. 27 Ma. Previous studies also reported Apatite (U-Th)/He ages of ca. 44 Ma-11 Ma in the Baluntai area of the southern Central Tianshan[1]. Two episodes of cooling are distinguished by thermal history modelling: (1) Mesozoic cooling occurred as the result of the exhumation and tectonic reactivation of the central Tianshan; and (2) The Tianshan orogenic belt has been rapidly exhumed since the Middle Cenozoic. References [1] Lü, H.H., Chang, Y., Wang, W., Zhou, Z.Y., 2013. Rapid exhumation of the Tianshan Mountains since the early Miocene: Evidence from combined apatite fission track and (U-Th)/He thermochronology. Science China: Earth Sciences, 43(12): 1964-1974 (in Chinese).

A protocol for pressurized liquid extraction and processing methods to isolate modern and ancient bone cholesterol for compound-specific stable isotope analysis.

PubMed

Laffey, Ann O; Krigbaum, John; Zimmerman, Andrew R

2017-02-15

Bone lipid compound-specific isotope analysis (CSIA) and bone collagen and apatite stable isotope ratio analysis are important sources of ecological and paleodietary information. Pressurized liquid extraction (PLE) is quicker and utilizes less solvent than traditional methods of lipid extraction such as soxhlet and ultrasonication. This study facilitates dietary analysis by optimizing and testing a standardized methodology for PLE of bone cholesterol. Modern and archaeological bones were extracted by PLE using varied temperatures, solvent solutions, and sample weights. The efficiency of PLE was assessed via quantification of cholesterol yields. Stable isotopic ratio integrity was evaluated by comparing isotopic signatures (δ 13 C and δ 18 O values) of cholesterol derived from whole bone, bone collagen and bone apatite. Gas chromatography/mass spectrometry (GC/MS) and gas chromatography isotope ratio mass spectrometry (GC/IRMS) were conducted on purified collagen and lipid extracts to assess isotopic responses to PLE. Lipid yield was optimized at two PLE extraction cycles of 75 °C using dichloromethane/methanol (2:1 v/v) as a solvent with 0.25-0.75 g bone sample. Following lipid extraction, saponification combined with the derivatization of the neutral fraction using trimethylsilylation yielded nearly twice the cholesterol of non-saponified or non-derivatized samples. It was also found that lipids extracted from purified bone collagen and apatite could be used for cholesterol CSIA. There was no difference in the bulk δ 13 C values of collagen extracted from bone with or without lipid. However, there was a significant depletion in 18 O of bone apatite due to lipid presence or processing. These results should assist sample selection and provide an effective, alternative extraction method for bone cholesterol that may be used for isotopic and paleodietary analysis. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

In situ synthesis of magnesium-substituted biphasic calcium phosphate and in vitro biodegradation

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

Kim, Tae-Wan; Lee, Hyeong-Shin; Kim, Dong-Hyun

Highlights: ► Mg–BCP were successfully prepared through in situ aqueous co-precipitation method. ► The amount of β-TCP phase was changed with the magnesium substitution level. ► The substitution of magnesium led to a decrease in the unit cell volume. ► Mg–BCP could be able to develop a new apatite phase on the surface faster than BCP. -- Abstract: In situ preparation of magnesium (Mg) substituted biphasic calcium phosphate (BCP) of hydroxyapatite (HAp)/β-tricalcium phosphate (β-TCP) were carried out through aqueous co-precipitation method. The concentrations of added magnesium were varied with the calcium in order to obtain constant (Ca + Mg)/P ratiosmore » of 1.602. X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) spectroscopy were used to characterize the structure of synthesized magnesium substituted BCP powders. The results have shown that substitution of magnesium in the calcium deficient apatites revealed the formation of biphasic mixtures of different HAp/β-TCP ratios after heating at 1000 °C. The ratios of the formation of phase mixtures were dependent on the content of magnesium. After immersing in Hanks’ balanced salt solution (HBSS) for 1 week, 1 wt% magnesium substituted BCP powders were degraded and precipitation started to be formed with small granules consisting of number of flake-like crystal onto the surface of synthesized powders. On the other hand, in the case of pure BCP powders, the formation of new precipitates was detected after immersion in HBSS for 2 weeks. On the basis of these results, magnesium substituted BCP could be able to develop a new apatite phase on the surface in contact with physiological fluids faster than BCP does. In addition, the retention time to produce the new apatite phase in implantation operation for the BCP powder could be controlled by the amount of magnesium substitution.« less

The Thermal Evolution of the Southeast Baffin Island Continental Margin: An Integrated Apatite Fission Track and Apatite (U-Th)/He Study

NASA Astrophysics Data System (ADS)

Jess, S.; Stephenson, R.; Brown, R. W.

2017-12-01

The elevated continental margins of the North Atlantic continue to be a focus of considerable geological and geomorphological debate, as the timing of major tectonic events and the age of topographic relief remain controversial. The West Greenland margin, on the eastern flank of Baffin Bay, is believed by some authors to have experienced tectonic rejuvenation and uplift during the Neogene. However, the opposing flank, Baffin Island, is considered to have experienced a protracted erosional regime with little tectonic activity since the Cretaceous. This work examines the thermal evolution of the Cumberland Peninsula, SE Baffin Island, using published apatite fission track (AFT) data with the addition of 103 apatite (U-Th)/He (AHe) ages. This expansion of available thermochronological data introduces a higher resolution of thermal modelling, whilst the application of the newly developed `Broken Crystals' technique provides a greater number of thermal constraints for an area dominated by AHe age dispersion. Results of joint thermal modelling of the AFT and AHe data exhibit two significant periods of cooling across the Cumberland Peninsula: Devonian/Carboniferous to the Triassic and Late Cretaceous to present. The earliest phase of cooling is interpreted as the result of major fluvial systems present throughout the Paleozoic that flowed across the Canadian Shield to basins in the north and south. The later stage of cooling is believed to result from rift controlled fluvial systems that flowed into Baffin Bay during the Mesozoic and Cenozoic during the early stages and culmination of rifting along the Labrador-Baffin margins. Glaciation in the Late Cenozoic has likely overprinted these later river systems creating a complex fjordal distribution that has shaped the modern elevated topography. This work demonstrates how surface processes, and not tectonism, can explain the formation of elevated continental margins and that recent methodological developments in the field of low temperature thermochronology are improving our understanding of onshore passive margin development.

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.

The effectiveness of the controlled release of simvastatin from β-TCP macrosphere in the treatment of OVX mice.

PubMed

Chou, Joshua; Ito, Tomoko; Otsuka, Makoto; Ben-Nissan, Besim; Milthorpe, Bruce

2016-03-01

Simvastatin, a cholesterol treatment drug, has been shown to stimulate bone regeneration. As such, there has been an increase interest in the development of suitable materials and systems for the delivery of simvastatin. Without the appropriate dosage of simvastatin, the therapeutic effects on bone growth will be significantly reduced. Furthermore, similar to many pharmaceutical compounds, at high concentration simvastatin can cause various adverse side-effects. Given the associated side-effects with the usage of simvastatin, the development of suitable controlled drug release system is pertinent. Calcium phosphate in particularly beta-tricalcium phosphate (β-TCP) has been extensively studied and used as a carrier material for drug delivery system. In this study, Foraminifera exoskeletons were used as calcium carbonate precursor materials, which were hydrothermally converted to β-TCP as a carrier material for simvastatin. Natural marine exoskeletons posses interconnected and uniformly porous network capable of improving drug loading and release rate. To prolong the release of simvastatin, an apatite coating was made around the β-TCP sample and in vitro release studies in simulated body fluid (SBF) showed a significant decrease in release rate. Osteoporotic mice were used to examine the compare therapeutic effectiveness of β-TCP, β-TCP with simvastatin, apatite-coated β-TCP with simvastatin and direct injection of simvastatin near the right femur of the mice. Localized and systemic effect were compared with the femur of the non-implanted side (left) and showed that β-TCP with or without simvastatin was able to induce significant bone formation over 6 weeks. Mechanical analysis showed that apatite-coated β-TCP with simvastatin produced significantly stronger bones compared with other experimental groups. This study shows that natural exoskeletons with the appropriate structure can be successfully used as a drug delivery system for simvastatin and can its release can be prolonged with an apatite coating to significantly promote relevant bone formation. Copyright © 2013 John Wiley & Sons, Ltd.

Preparation and properties of calcium-silicate filled resins for dental restoration. Part I: chemical-physical characterization and apatite-forming ability.

PubMed

Profeta, Andrea Corrado

2014-11-01

The aim of this study was to measure dimensional changes due to hygroscopic expansion and the bioactivity of two experimental methacrylate-based dental adhesives either incorporating Bioglass 45S5 (3-E&RA/BG) or MTA (3-E&RA/WMTA). 3-E&RA/BG, 3-E&RA/WMTA and a control filler-free resin blend (3-E&RA) were formulated from commercially available monomers. Water sorption (WS) and solubility (SL) behaviour were evaluated by weighing material disks at noted intervals; the relationship between degree of hydration and the glass transition temperature (Tg) was investigated by using differential scanning calorimetry (DSC). In vitro apatite-forming ability as a function of soaking time in phosphate-containing solutions was also determined. Kruskal-Wallis analysis of variance (ANOVA) was used to evaluate differences between groups for maximum WS, SL, net water uptake and the percentage change in Tg values. Post-ANOVA pair-wise comparisons were conducted using Mann-Whitney-U tests. 3-E&RA/BG and 3-E&RA/WMTA exhibited values of maximum WS and net water uptake that were significantly higher when compared to 3-E&RA. However, no statistically significant differences were observed in terms of SL between all the adhesives. The addition of the Bioglass 45S5 and MTA to the 3-E&RA showed no reduction of the Tg after 60 days of storage in deionized water. ATR Fourier Transform Infrared Spectroscopy (ATR-FTIR) of the filled resin disks soaked in DPBS for 60 days showed the presence of carbonate ions in different chemical phases. Dentine bonding agents comprising calcium-silicates are not inert materials in a simulated oral environment and apatite formation may occur in the intra-oral conditions. A bioactive dental material which forms apatite on the surface would have several benefits including closure of gaps forming at the resin-dentine interface and potentially better bond strength over time (less degradation of bond).

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.

Removal of phosphorus, fluoride and metals from a gypsum mining leachate using steel slag filters.

PubMed

Claveau-Mallet, Dominique; Wallace, Scott; Comeau, Yves

2013-03-15

The objective of this work was to evaluate the capacity of steel slag filters to treat a gypsum mining leachate containing 11-107 mg P/L ortho-phosphates, 9-37 mg/L fluoride, 0.24-0.83 mg/L manganese, 0.20-3.3 zinc and 1.7-8.2 mg/L aluminum. Column tests fed with reconstituted leachates were conducted for 145-222 days and sampled twice a week. Two types of electric arc furnace (EAF) slags and three filter sequences were tested. The voids hydraulic retention time (HRT(v)) of columns ranged between 4.3 and 19.2 h. Precipitates of contaminants present in columns were sampled and analyzed with X-ray diffraction at the end of tests. The best removal efficiencies over a period of 179 days were obtained with sequential filters that were composed of Fort Smith EAF slag operated at a total HRT(v) of 34 h which removed 99.9% of phosphorus, 85.3% of fluoride, 98.0% of manganese and 99.3% of zinc. Mean concentration at this system's effluent was 0.04 mg P/L ortho-phosphates, 4 mg/L fluoride, 0.02 mg/L manganese, 0.02 zinc and 0.5 mg/L aluminum. Thus, slag filters are promising passive and economical systems for the remediation of mining effluents. Phosphorus was removed by the formation of apatite (hydroxyapatite, Ca(5)(PO(4))(3)OH or fluoroapatite, Ca(5)(PO(4))(3)F) as confirmed by visual and X-ray diffraction analyses. The growth rate of apatite was favored by a high phosphorus concentration. Calcite crystals were present in columns and appeared to be competing for calcium and volume needed for apatite formation. The calcite crystal growth rate was higher than that of apatite crystals. Fluoride was removed by precipitation of fluoroapatite and its removal was favored by a high ratio of phosphorus to fluoride in the wastewater. Copyright © 2012 Elsevier Ltd. All rights reserved.

Thermal and unroofing history of a thick, tilted Basin-and-Range crustal section in the Tortilla Mountains, Arizona

USGS Publications Warehouse

Howard, K.A.; Foster, D.A.

1996-01-01

We estimate here a geothermal gradient of only 17 ?? 5??C km-1 for the tilted Grayback fault block in southeastern Arizona when extension began ???25 Ma. This gradient is lower than preextension gradients estimated elsewhere in the Basin and Range, is only about 50% of typical gradients in the Basin and Range today, and needs to be accounted for in models of continental extension. The Grayback block exposes a 12-km-thick crustal section of Proterozoic and Cretaceous granitoids, which was tilted 90?? during extension between 25 and 15 Ma. Zircon fission-track ages decrease structurally downward (westward) across the block and were all within a zone of partial track annealing prior to tilting and quenching. The zircon age gradient suggests that the 220??-240??C isotherm migrated downward 5-6 km during Paleogene erosion and regional cooling. Apatite fission-track ages decrease westward from ???83 Ma in the structurally highest crystalline rocks to ???24 Ma at ???6-km paleodepth and then to ???15 Ma another 6 km farther west. Track-length analysis confirms that apatites above the break in slope in age at ???5.7-km paleodepth resided in a zone of partial annealing prior to tilting, and deeper apatites record rapid cooling upon tilting and unroofing beginning ???25 Ma. At that time the 110 ?? 10??C isotherm determined by the depth at which tracks in apatite were fully erased was at a basement paleodepth of ???5.7 km, and the 220 ?? 30??C isotherm as estimated from zircon data resided at a pretilting basement depth of ???12.15 km. From consistent values of paleogeothermal gradient for two depth intervals we estimate the pretilt gradient was 17 ?? 5??C km-1. From 25 to 15 Ma the rotating Grayback block cooled rapidly as higher, westward moving blocks unroofed it tectonically at a rate of ???1 km m.y.-1.

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.

From ocean depths to mountain tops: uplift of the Troodos Massif (Cyprus) constrained by (U-Th)/He thermochronology and geomorphic analysis

NASA Astrophysics Data System (ADS)

Morag, N.; Haviv, I.; Katzir, Y.

2013-12-01

The Troodos Massif of Cyprus, rising to nearly 2000 meters above sea level, encompasses one of the world's classic ophiolites. Following its formation at a seafloor spreading center in Late Cretaceous times, this slice of the NeoTethyan oceanic lithosphere was uplifted and eventually exposed on mountain tops during the Neogene. The final uplift and exhumation of the Troodos was previously assigned to Pleistocene age by observations in the circum-Troodos sedimentary strata. However, quantitative thermochronological and geomorphological data from the Massif itself were not available. Here we use apatite (U-Th)/He low-temperature thermochronology complemented by zircon (U-Th)/He and apatite fission track data, and combined with geomorphic analysis to constrain the exhumation and uplift history of the Troodos ophiolite. Apatite (U-Th)/He ages vary with depth from ~ 22 Ma at the top of the Gabbro sequence to ~ 6 Ma at the bottom of the sequence. The deepest sample from a Gabbro pegmatitic dyke intruding the ultramafic sequence yielded an age of ~ 3 Ma. Thermal modeling of apatite (U-Th)/He and fission track data delineates Plio - Pleistocene initiation of rapid uplift and exhumation of the Troodos ophiolite. The estimated cumulative exhumation since its initiation is 2-3 km. No evidence was found for significant uplift of the central Troodos area prior to that time. The geomorphic analysis delineates a bull's-eye zone at the center of the Troodos Massif, where local relief and channel steepness index are highest. The boundaries of this zone roughly correspond with the Mt. Olympus mantle outcrop and suggest recent, differential uplift of this zone relative to its surroundings. The most likely mechanism, which could drive such a focused bull's-eye uplift pattern is hydration of ultramafic rocks (serpentinization) leading to a decrease in rock density and subsequent diapiric uplift of the serpentinized lithospheric mantle.

Sulphur bacteria mediated formation of Palaeoproterozoic phosphorites

NASA Astrophysics Data System (ADS)

Joosu, Lauri; Lepland, Aivo; Kirsimäe, Kalle

2014-05-01

Modern phosphorite formation is typically associated with high productivity in upwelling areas where apatite (Ca-phosphate) precipitation is mediated by sulphur oxidising bacteria [1]. They inhabit the oxic/anoxic interface within the upper few centimetres of sediment column, accumulating phosphate in their cells under oxic conditions and releasing it rapidly when conditions become anoxic. Sulphur bacteria are known to live in close association with a consortium of anaerobic methane oxidising archaea and syntrophic sulphate-reducing bacteria. Paleoproterozoic, c. 2.0 Ga Zaonega Formation in Karelia, Russia contains several P-rich intervals in the upper part of 1500 m thick succession of organic-rich sedimentary rocks interlayered with mafic tuffs and lavas. Apatite in these P-rich intervals forms impure laminae, lenses and round-oval nodules which diameters typically range from 300 to 1000 μm. Individual apatite particles in P-rich laminae and nodules commonly occur as cylinders that are 1-8 μm long and have diameters of 0.5-4 μm. Cross-sections of best preserved cylindrical apatite particles reveal a thin outer rim whereas the internal parts consist of small anhedral elongated crystallites, intergrown with carbonaceous material. During recrystallization the outer rim thickens towards interior and cylinders may attain hexagonal crystal habit, but their size and shape remains largely unchanged [2]. The sizes of Zaonega nodules are similar to giant sulphide-oxidising bacteria known from modern and ancient settings [3, 4]. Individual apatite cylinders and aggregates have shapes and sizes similar to the methanotrophic archaea that inhabit microbial mats in modern seep/vent areas where they operate in close associations with sulphur-oxidising microbial communities [5]. Seep/vent influence during the Zaonega phosphogenesis is indicated by variable, though positive Eu anomaly, expected in magmatically active sedimentary environment experiencing several lava flows. Moreover, P-rich intervals in the Zaonega Formation are found in organic-rich sediments exhibiting strongly negative δ13Corg values (-37 to -34 per mil) which is interpreted to reflect the methanotrophic biomass. We conclude that modern-style phosphogenesis, mediated by sulphide-oxidising bacteria living in consortium with methanotrophs, was established at least 2 Ga ago. [1] Schulz and Schulz (2005) Science 307, 416-418 [2] Lepland, Joosu, Kirsimäe, Prave, Romashkin, Črne, Martin, Fallick, Somelar, Üpraus, Mänd, Roberts, van Zuilen, Wirth, Schreiber (2014) Nature geoscience 7, 20-24 [3] Bailey, Joye, Kalanetra, Flood, and Corsetti (2007) Nature 445, 198-201 [4] Schulz, Brinkhoff, Ferdelman, Marine, Teske and Jorgensen (1999) Science 284, 493-495 [5] Knittel, Losekann, Boetius, Kort and Amann (2005) Applied and Environmental Microbiology 71, 467-479.

Crystallization conditions and controls on trace element residence in the main minerals from the Pedra Branca Syenite, Brazil: An electron microprobe and LA-ICPMS study

NASA Astrophysics Data System (ADS)

Carvalho, Bruna Borges; Janasi, Valdecir de Assis

2012-11-01

Major and trace-element microanalyses of the main minerals from the 610 Ma Pedra Branca Syenite, southeast Brazil, allow inferences on intensive parameters of magmatic crystallization and on the partition of trace-elements among these minerals, with important implications for the petrogenetic evolution of the pluton. Two main syenite types make up the pluton, a quartz-free syenite with tabular alkali feldspar (laminated silica-saturated syenite, LSS, with Na-rich augite + phlogopite + hematite + magnetite + titanite + apatite) and a quartz-bearing syenite (laminated silica-oversaturated syenite, LSO, with scarce corroded plagioclase plus diopside + biotite ± hornblende + ilmenite ± magnetite + titanite + apatite). Both types share a remarkable enrichment in incompatible elements as K, Ba, Sr, P and LREE. Apatite saturation temperatures of ~ 1060-1090 °C are the best estimates of liquidus, whereas the pressure of emplacement, based on Al-in-hornblende barometry, is estimated as 3.3 to 4.8 kbar. Although both units crystallized under oxidizing conditions, oxygen fugacity was probably higher in LSS, as shown by higher mg# of the mafic minerals and higher hematite contents in Hem-Ilmss. In contrast with the Ca-bearing alkali-feldspar from LSO, which hosts most of the whole-rock Sr and Pb, virtually Ca-free alkali-feldspar from LSS hosts ~ 50% of whole-rock Sr and ~ 80% of Pb, the remainder of these elements being shared by apatite, pyroxene and titanite. This contrast reflects a strong crystal-chemical control, whereby a higher proportion of an element with similar ratio and charge (Ca2 +) enhances the residence of Sr and Pb in the M-site of alkali feldspar. The more alkaline character of the LSS magma is inferred to have inhibited zircon saturation; Zr + Hf remained in solution until late in the crystallization, and were mostly accommodated in the structure of Ca-Na pyroxene and titanite, which are one order of magnitude richer in these elements compared to the same minerals in LSO, where most of Zr and Hf are inferred to reside in zircon. The REE, Th and U reside mostly in titanite and apatite; D(REE)Tit/Ap raises steadily from 1 to 6 from La to Tb then remains constant up to Lu in the LSO sample; these values are about half as much in the LSS sample, where lower contents of incompatible elements in titanite are attributed to its greater modal abundance and earlier crystallization.

Exhumation Across Hells Canyon and the Arc-continent Boundary of Idaho-Oregon

NASA Astrophysics Data System (ADS)

Kahn, M.; Fayon, A. K.; Tikoff, B.

2015-12-01

Hells Canyon is located along the Idaho-Oregon border. It is proximal to the Salmon River suture zone, the Cretaceous-age western margin of North America that juxtaposes accreted terranes to the west and cratonic North America to the east. We applied (U-Th)/He zircon and apatite thermochronometry to samples along an EW transect across Hells Canyon. (U-Th)/He zircon and apatite ages record the time at which rocks cool below ~ 200 and 60 °C, respectively, providing information on both the timing and rate at which rocks cooled. Samples were collected with respect to structural position relative to the basal Columbia River basalt flow (Imnaha), dated at ~ 17.4 Ma, with most samples taken <100 m below the contact. Given that all localities were at the Earth's surface - and thus cooled below 60˚C - at ~ 17.4 Ma, the variation in obtained ages are assessed relative to this common datum. The easternmost sites were taken on the western margin of the Idaho batholith at Lava Buttes, ID at ~2,700 m elevation: The (U-Th)/He zircon and apatite ages are 64.9±4.6 Ma and 53.8±4.9 Ma, respectively. The westernmost sites occur in the Wallowa Mountains, Oregon, where the base of the Imnaha flow exists at ~3,000 m: The (U-Th)/He zircon and apatite ages are 136.2±42.8 Ma and 21.7±10.0 Ma. Additionally, the basal basalt contact occurs at ~900 m and ~600 m at the bottom of the Salmon River Canyon and Hells Canyon respectively. The (U-Th)/He zircon and apatite ages are 73.1±14.6 Ma and 20.0±7.4 Ma, respectively, for the Salmon River Canyon and 88.6±2.4 Ma and 3.4±0.6 Ma, respectively, for Hells Canyon. The data indicate that: 1) The western Wallowa (accreted) terrane cooled below ~200 °C prior to the formation of the Idaho batholith; 2) The western side of the Idaho batholith shows a rapid and consistent cooling between ~200 °C and ~60 °C in the Paleogene; and 3) Samples at low elevation in Hells Canyon cooled below 60˚C in the Pliocene, which requires reburial of the rocks after deposition of the basal portions of the Miocene Columbia River basalts. The young cooling age in Hells Canyon is consistent with recent geomorphological studies constraining incision rates.

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

NASA Astrophysics Data System (ADS)

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

2004-12-01

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

Supplemental groundwater remediation technologies to protect the Columbia River at Hanford, WA

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

Thompson, K.M.; Petersen, S.W.; Fruchter, J.S.

2007-07-01

Nine projects have been recently selected by the US Department of Energy (EM-22) to address groundwater contaminant migration at the Hanford Site. This paper summarizes the background and objectives of these projects. Five of the selected projects are targeted at hexavalent chromium contamination in Hanford 100 Area groundwater. These projects represent an integrated approach towards identifying the source of hexavalent chromium contamination in the Hanford 100-D Area and treating the groundwater contamination. Currently, there is no effective method to stop strontium-90 associated with the riparian zone sediments from leaching into the river. Phyto-remediation may be a possible way to treatmore » this contamination. Its use at the 100-N Area will be investigated. Another technology currently being tested for strontium-90 contamination at the 100-N Area involves injection (through wells) of a calcium-citrate-phosphate solution, which will precipitate apatite, a natural calcium phosphate mineral. Apatite will adsorb the strontium-90, and then incorporate it as part of the apatite structure, isolating the strontium-90 contamination from entering the river. This EM-22 funded apatite project will develop a strategy for infiltrating the apatite solution from ground surface or a shallow trench to provide treatment over the upper portion of the contaminated zone, which is unsaturated during low river stage. Uranium in groundwater at the Hanford 300 Area is another environmental concern. Preliminary laboratory tests indicate that it may be possible to inject water-soluble phosphate compounds into the uranium contamination to stabilize it. One of the projects will perform laboratory tests using long-chain polyphosphate materials. Then, a field test will be conducted to determine if it is possible to treat groundwater in the unconfined aquifer at the Hanford 300 Area using polyphosphate materials. The rates of abiotic hydrolysis of are key parameters needed to predict the movement of carbon tetrachloride and one of its reductive degradation products, chloroform, from the Hanford 200 West Area towards the Columbia River. Current values for these rates have high uncertainty associated with them because they are extrapolated from determinations made at high temperatures (>70 deg. C) to ambient groundwater temperatures ({approx}19 deg. C) and have ignored possible contributions from sorptive interactions with sediments. One of the EM-22 projects will improve this situation by measuring the hydrolysis rates at temperatures down to 20 deg. C and in contact with various sediment solids. (authors)« less

Mirror denudation pattern on both sides of the Central Atlantic - a trace of the Pangea break-up?

NASA Astrophysics Data System (ADS)

Ruiz, G.; Saddiqi, O.; Sebti, S.; Negro, F.; Stuart, F.; Foeken, J.; Frizon de Lamotte, D.; Kramers, J.

2009-04-01

The target area of this project is the WSW- ENE oriented intra-continental Atlas chain in Morocco located between the West Africa Craton and the Betic-Rif system. It is a key natural laboratory because it 1) is the southernmost expression of Alpine deformation in Africa, and 2) encompasses Pre-Cambrian to recent evolution of the region. The presence of high surface elevations today in the High-Atlas (>4000m) and Anti-Atlas (>2500m) to the south is subject to discussions because there is little quantitative data available at present. Phases of uplift are thus ill constrained as places where the associated erosion products were accumulated. To better constrain the most recent orogenic growth of the Atlas chain, we selected a section located to the SW of Morocco, and investigated the time-Temperature paths from the different morpho-structural domains using low-temperature thermochronology analyses. These are Fission-Track analysis on Apatite (120-60°C), Zircon (270-210°C) and U-Th/He analysis still on Apatite (80-45°C) and Zircon (200-170°C) minerals. Results are much contrasted from one domain to the other: Pre-Cambrian bedrocks from the Anti-Atlas domain yield old thermochronological Fission-Track ages on zircon (380-300 Ma) and apatite (180-120 Ma) minerals that are associated with slightly younger (U-Th)/He ages on apatite (150-110 Ma). U-Th/He ages on apatite from the High-Atlas are much younger (~35-5 Ma) with a clear alpine signature. Apatite Fission-Track ages from the Meseta region further north are also relatively old ranging between 200 and 140 Ma. We here concentrate on the interpretation of old thermochronological ages from the Meseta and Anti-Atlas regions leaving the Alpine signal for another contribution. There are two direct, possibly inter fingering, interpretations for the preservation of such old thermal record in the Anti-Atlas and Meseta regions. First they remained "stable" being unaffected by 'Alpine' deformation that took place in the High-Atlas. Second, they are being affected "now" but no level with such record is yet exposed. Thermal modelling was performed to decipher between the 2 scenarios using our new thermochronological and available geological constraints. Models suggest that the first scenario is most likely with a clear Triassic to Late Jurassic phase of heating until ~100-90°C that was followed by a phase of cooling until the Middle Cretaceous. These results suggest that the Meseta was buried by a 2-3 kilometres thick sedimentary pile until ~180 Ma and as a result that the concept of a topographic high limiting the Tethysian from the Atlantic has to be reconsidered. Further, denudation patterns from the mirror image of the Atlas system on the other side of the Atlantic ocean are almost identical (Grist and Zentilli, 2003) suggesting that the patterns we constrained for the Triassic until Middle Cretaceous in SW Morocco have to be related to the break-up of the Pangea and oceanization in the Central Atlantic from ~180 Ma.

Contact metamorphism, partial melting and fluid flow in the granitic footwall of the South Kawishiwi Intrusion, Duluth Complex, USA

NASA Astrophysics Data System (ADS)

Benko, Z.; Mogessie, A.; Molnar, F.; Severson, M.; Hauck, S.; Lechler, P.; Arehart, G.

2012-04-01

The footwall of the South Kawishiwi Intrusion (SKI) a part of the Mesoproterozoic (1.1 Ga) Duluth Complex consists of Archean granite-gneiss, diorite, granodiorite (Giant Range Batholith), thin condensed sequences of Paleoproterozoic shale (Virginia Fm.), as well as banded iron formation (Biwabik Iron Fm). Detailed (re)logging and petrographic analysis of granitic footwall rocks in the NM-57 drillhole from the Dunka Pit area has been performed to understand metamorphic processes, partial melting, deformation and geochemical characteristics of de-volatilization or influx of fluids. In the studied drillhole the footwall consists of foliated metagranite that is intersected by mafic (dioritic) dykes of older age than the SKI. In the proximal contact zones, in the mafic dykes, the orthopyroxene+clinopyroxene+plagioclase+quartz+Fe-Ti-oxide+hornblende±biotite porphyroblasts embedded in a plagioclase+K-feldspar+orthopyroxene+apatite matrix indicate pyroxene-hornfels facies conditions. Migmatitization is revealed by the euhedral crystal faces of plagioclase and pyroxene against anhedral quartz crystals in the in-situ leucosome and by the presence of abundant in-source plagioclase±biotite leucosome veinlets. Amphibole in the melanosome of mafic dykes was formed with breakdown of biotite and implies addition of H2O to the system during partial melting. Towards the deeper zones, the partially melted metatexite-granite can be characterized by K-feldspar+plagioclase+quartz+ortho/clinopyroxene+biotite+Fe-Ti-oxide+apatite mineral assemblage. The felsic veins with either pegmatitic or aplititic textures display sharp contact both to the granite and the mafic veins. They are characterized by K-feldspar+quartz±plagioclase±muscovite mineral assemblage. Sporadic occurrence of muscovite suggest local fluid saturated conditions. Emplacement of gabbroic rocks of the SKI generated intense shear in some zones of the granitic footwall resulting in formation of biotite-rich mylonites with lepidoblastic texture. High modal content of syn-tectonic biotite in these shear zones indicate involvement of large amount of fluids during deformation. Apatite is an omnipresent accessory mineral in all rock types, with up to 1-3% modal proportion. Crystal habit is columnar or rarely needle-like. XCl/XF and XOH/XF ratios of apatite were compared with depth in the drillhole and in relation to the host rock type. Apatite in the metagranite and in the mafic dyke is fluorine-rich (XFgranite≈1,27-1,63; XFmafic dyke≈1,51-1,83) and their XCl/XFgranite≈0,083 to 0,051 and XCl/XFmafic dyke≈0,051 to 0,044 ratios decrease towards the distal parts of the contact. Apatite in biotite-rich mylonite, as well as in the porphyroblasts of mafic dykes, is extremely depleted in chlorine- and hydroxyl-anions (XCl/XFmylonite≈0,02 and XOH/XFmylonite≈0,14), whereas apatite in felsic dykes and in the in-source leucosome are enriched in hydroxyl and chlorine relative to fluorine (XCl/XFfelsic vein≈0,21 and XOH/XFfelsic vein≈0,37). These variations suggest release of chlorine enriched fluids from the partially melted contact zones and movement and enrichments of these fluids in migration channels of partial melts. It has been for a long time accepted that fluids emerging from the metamorphosed Virginia Formation played an essential role in the formation of the Cu-Ni sulphide and PGE mineralization at the bottom of the gabbroic intrusions in the northwestern marginal zones of the Duluth Complex. Our study proves that the granitic footwall was also an important source of fluids and melts. We acknowledge the Austrian Science Found (FWF P23157-N21) to A. Mogessie for the financial support.

Bacteria mediated dissolution of pyromorphite Pb5(PO4)3Cl in presence of Pseudomonas putida bacteria - an effect on Pb remobilization in the environment

NASA Astrophysics Data System (ADS)

Flis, Justyna; Manecki, Maciej; Merkel, Broder J.; Latowski, Dariusz

2010-05-01

The objective of the study was to determine the mechanisms of microbially enhanced dissolution of lead phosphate-pyromorphite Pb5(PO4)3Cl). Contrary to the current literature, the results of our experiments indicate a great potential for Pb remobilization in the environment by an aerobic microorganism acquiring phosphates. Broad knowledge exists about the role of Pb-apatites in regulating the behavior and the bioavailability of Pb in soils and wastewater. In situ Pb immobilization is one of the methods now routinely applied for the reclamation of Pb-contaminated soils, including shallow unconfined aquifers (Magalhaes & Silva, 2003; Magalhaes, 2002; Ma et al. 1993). This method is based on the principle that aqueous phosphates added to soil pore solutions form a very stable (insoluble) mineral pyromorphite (Pb-apatite) Pb5(PO4)3Cl. Bioavailability of aqueous Pb is thus minimized due to the very low solubility and the high thermodynamic stability of pyromorphite (Flis, 2007; Nriagu, 1974). Several reports have examined the ability of different bacterial species including Pseudomonas to solubilise insoluble inorganic phosphate compounds for example apatites (Welch et al., 2002; Maurice et al., 1999; Rodriguez and Fraga, 1999 ). Various species of Pseudomonas genera are encountered as common inhabitants of soils and wastes in the industrial areas under strong pollution influence. To date, there has not been any published evidence of microbial dissolution of pyromorphite. The major objective of the project was to study Pseudomonas putida growth in the presence of Pb-apatite (Pb5(PO4)3Cl) as the sole source of phosphate. It was to test the hypothesis that in the phosphate deficient environment bacteria are able to actively scavenge for P from the Pb-apatite which results in remobilization of Pb in the environment. The bacteria growth was investigated at 22oC. Commercially available Pseudomonas putida strain was used throughout. The experiment and its controls were run in standard growth medium for the period of 10 days, at starting pH=6.5. Samples were periodically analysed for pH, bacterial density, Pb and P (UV-vis, ICP). Our results indicate that Pb may be mobilized from pyromorphite by microbial activity, both in phosphorous-rich and phosphorous-deficient environment. At the experimental conditions the presence of bacteria enhances the dissolution of pyromorphite, resulting in up to 20 times increase of Pbaq. The observed effects of microorganisms on Pb remobilization need to be considered in Pb remediation strategies that rely on pyromorphite formation. References: FLIS J.M., (2007). "Thermodynamic properties of minerals from pyromorphite-mimetite series"- Master Thesis, AGH-University of Science and Technology, Faculty of Geology, Geophysics and Environmental Protection, Department of Mineralogy, Petrography and Geochemistry, Cracow, Poland. MA Q.Y., TRAINA S.J., LOGAN T.J., RYAN J.A. (1993). "In-situ lead immobilization by apatite". Environ. Sci. Technol., 27: 1803-1810. MAURICE P.A, LEE Y.J., HERSMAN L.E. (1999). "Dissolution of Al-substituted goethites by an aerobic Pseudomonas mendocina var. Bacteria." Gechim. Cosmochim. Acta. 64: 1363-1374. MAGALHÃES M.C.F. (2002). "Arsenic. An environmental problem limited by solubility". Pure Appl. Chem., 74(10): 1843-1850. MAGALHÃES M.C.F., SLIVA, M.C.M.(2003). "Stability of lead(II) arsenates". Monat. fur Chem. 134: 735-743 NRIAGU J.O., (1974). "Lead orthophosphates IV. Formation and stability in the environment." Geochim. Cosmochim. Acta, 37: 367-377. RODRIGUEZ H. & FRAGA R. (1999). "Phosphate solubilizing bacteria and their role in plant growth promotion". Biotechn. Advan. 17: 319-339. WELCH S.A., TAUNTON A.E., BANFIELD J.F. (2002). "Effect of Microorganisms and Microbial Metabolites on Apatite Dissolution". Geomicrobil. J. 19: 343-367.

In situ formation of phosphate barriers in soil

DOEpatents

Moore, Robert C.

2002-01-01

Reactive barriers and methods for making reactive barriers in situ in soil for sequestering soil ontaminants including actinides and heavy metals. The barrier includes phosphate, and techniques are disclosed for forming specifically apatite barriers. The method includes injecting dilute reagents into soil in proximity to a contamination plume or source such as a waste drum to achieve complete or partial encapsulation of the waste. Controlled temperature and pH facilitates rapid formation of apatite, for example, where dilute aqueous calcium chloride and dilute aqueous sodium phosphate are the selected reagents. Mixing of reagents to form precipitate is mediated and enhanced through movement of reagents in soil as a result of phenomena including capillary action, movement of groundwater, soil washing and reagent injection pressure.

Amelogenin and Enamel Biomimetics.

PubMed

Ruan, Qichao; Moradian-Oldak, Janet

Mature tooth enamel is acellular and does not regenerate itself. Developing technologies that rebuild tooth enamel and preserve tooth structure is therefore of great interest. Considering the importance of amelogenin protein in dental enamel formation, its ability to control apatite mineralization in vitro , and its potential to be applied in fabrication of future bio-inspired dental material this review focuses on two major subjects: amelogenin and enamel biomimetics. We review the most recent findings on amelogenin secondary and tertiary structural properties with a focus on its interactions with different targets including other enamel proteins, apatite mineral, and phospholipids. Following a brief overview of enamel hierarchical structure and its mechanical properties we will present the state-of-the-art strategies in the biomimetic reconstruction of human enamel.

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.

Amelogenin and Enamel Biomimetics

PubMed Central

Ruan, Qichao; Moradian-Oldak, Janet

2015-01-01

Mature tooth enamel is acellular and does not regenerate itself. Developing technologies that rebuild tooth enamel and preserve tooth structure is therefore of great interest. Considering the importance of amelogenin protein in dental enamel formation, its ability to control apatite mineralization in vitro, and its potential to be applied in fabrication of future bio-inspired dental material this review focuses on two major subjects: amelogenin and enamel biomimetics. We review the most recent findings on amelogenin secondary and tertiary structural properties with a focus on its interactions with different targets including other enamel proteins, apatite mineral, and phospholipids. Following a brief overview of enamel hierarchical structure and its mechanical properties we will present the state-of-the-art strategies in the biomimetic reconstruction of human enamel. PMID:26251723

Magnetic apatite for structural insights on the plasma membrane

NASA Astrophysics Data System (ADS)

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

2015-01-01

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

Trace element abundances in megacrysts and their host basalts - Constraints on partition coefficients and megacryst genesis

NASA Technical Reports Server (NTRS)

Irving, A. J.; Frey, F. A.

1984-01-01

Rare earth and other trace element abundances are determined in megacrysts of clinopyroxene, orthopyroxene, amphibole, mica, anorthoclase, apatite and zircon, as well as their host basalts, in an effort to gather data on mineral/melt trace element partitioning during the high pressure petrogenesis of basic rocks. Phase equilibria, major element partitioning and isotopic ratio considerations indicate that while most of the pyroxene and amphibole megacrysts may have been in equilibrium with their host magmas at high pressures, mica, anorthoclase, apatite, and zircon megacrysts are unlikely to have formed in equilibrium with their host basalts. It is instead concluded that they were precipitated from more evolved magmas, and have been mixed into their present hosts.

Calcium Solubility In Zeolite Synthetic-Apatite Mixtures

NASA Technical Reports Server (NTRS)

Beiersdorfer, R.; Ming, D. W.

1999-01-01

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

Magnetic apatite for structural insights on the plasma membrane.

PubMed

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

2015-01-21

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

Inhibition of crystallization caused by Proteus mirabilis during the development of infectious urolithiasis by various phenolic substances.

PubMed

Torzewska, Agnieszka; Rozalski, Antoni

2014-01-01

Infectious urolithiasis is a consequence of persistent urinary tract infections caused by urease producing bacteria e.g. Proteus mirabilis. These stones are composed of struvite and carbonate apatite. Their rapid growth and high recurrence indicate that so far appropriate methods of treatment have not been found. In the present study, the inhibitory effect of phenolic compounds was investigated in vitro against formation of struvite/apatite crystals. The impact of these substances with different chemical structures on crystallization caused by clinical isolates of P. mirabilis was tested spectrophotometrically using a microdilution method. Among the 11 tested compounds resveratrol, epigallocatechin gallate, peralgonidin, vanillic and coffee acids at the concentrations 250-1000 μg/ml inhibited P. mirabilis urease activity and crystallization. However, only vanillic acid had such an effect on all tested strains of P. mirabilis. Therefore, using an in vitro model, bacterial growth, crystallization, urease activity and pH were examined for 24h in synthetic urine with vanillic acid. Effect of vanillic acid was compared with that of other known struvite/apatite crystallization inhibitors (acetohydroxamic acid, pyrophosphate) and it was shown that vanillic acid strongly inhibited bacterial growth and the formation of crystals. It can be assumed that this compound, after further studies, can be used in the treatment or prophylaxis of infectious urolithiasis. Copyright © 2013 Elsevier GmbH. All rights reserved.

Research on the preparation, biocompatibility and bioactivity of magnesium matrix hydroxyapatite composite material.

PubMed

Linsheng, Li; Guoxiang, Lin; Lihui, Li

2016-08-12

In this paper, magnesium matrix hydroxyapatite composite material was prepared by electrophoretic deposition method. The optimal process parameters of electrophoretic deposition were HA suspension concentration of 0.02 kg/L, aging time of 10 days and voltage of 60 V. Animal experiment and SBF immersion experiment were used to test the biocompatibility and bioactivity of this material respectively. The SD rats were divided into control group and implant group. The implant surrounding tissue was taken to do tissue biopsy, HE dyed and organizational analysis after a certain amount of time in the SD rat body. The biological composite material was soaked in SBF solution under homeothermic condition. After 40 days, the bioactivity of the biological composite material was evaluated by testing the growth ability of apatite on composite material. The experiment results showed that magnesium matrix hydroxyapatite biological composite material was successfully prepared by electrophoretic deposition method. Tissue hyperplasia, connective tissue and new blood vessels appeared in the implant surrounding soft tissue. No infiltration of inflammatory cells of lymphocytes and megakaryocytes around the implant was found. After soaked in SBF solution, a layer bone-like apatite was found on the surface of magnesium matrix hydroxyapatite biological composite material. The magnesium matrix hydroxyapatite biological composite material could promot calcium deposition and induce bone-like apatite formation with no cytotoxicity and good biocompatibility and bioactivity.

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.

Phosphorous availability influences the dissolution of apatite by soil fungi

NASA Astrophysics Data System (ADS)

Rosling, A.; Suttle, K. B.; Johansson, E.; van Hees, P. W.; Banfield, J. F.

2007-12-01

We conducted mineral dissolution experiments using fungi isolated from a grassland soil in northern California to determine the response of fungi to different levels of phosphorus availability and to identify pathways of apatite dissolution by fungal exudates. Fluorapatite dissolution experiments were performed either with fungi present or under abiotic conditions using cell-free liquid media conditioned by fungal growth at different phosphorus and calcium availabilities. Among biogeochemically active soil fungal isolates apatite dissolution was either active in response to phosphorus limiting growth conditions or passive as a result of mycelial growth. Zygomycete isolates in the order of Mucorales acidify their growth media substrate in the presence of phosphorus, mainly through production of oxalic acid. Cell-free exudates induced fluorapatite dissolution at a rate of 10 -0.9 ± 0.14 and 10 -1.2 ± 0.22 mmol P/m2/s. The Ascomycete isolate, in the family Trichocomaceae, induced fluorapatite dissolution at a rate of 10 - 1.1 ± 0.05 mmol P/m2/s by lowering the pH of the media under phosphorus-limited conditions, without producing significant amounts of low molecular weight organic acids (LMWOAs). Oxalate strongly etches fluorapatite along channels parallel to [001], forming needle like features, while exudates from Trichocomaceae induced surface rounding. We conclude that while LMWOAs are well-studied weathering agents these does not appear to be produced by fungi in response to phosphorus limiting growth conditions.

Biomechanical Evaluation of a Novel Apatite-Wollastonite Ceramic Cage Design for Lumbar Interbody Fusion: A Finite Element Model Study

PubMed Central

Şenköylü, Alpaslan; Aktaş, Erdem; Sarıkaya, Baran; Sipahioğlu, Serkan; Gürbüz, Rıza; Timuçin, Muharrem

2018-01-01

Objectives Cage design and material properties play a crucial role in the long-term results, since interbody fusions using intervertebral cages have become one of the basic procedures in spinal surgery. Our aim is to design a novel Apatite-Wollastonite interbody fusion cage and evaluate its biomechanical behavior in silico in a segmental spinal model. Materials and Methods Mechanical properties for the Apatite-Wollastonite bioceramic cages were obtained by fitting finite element results to the experimental compression behavior of a cage prototype. The prototype was made from hydroxyapatite, pseudowollastonite, and frit by sintering. The elastic modulus of the material was found to be 32 GPa. Three intact lumbar vertebral segments were modelled with the ANSYS 12.0.1 software and this model was modified to simulate a Posterior Lumbar Interbody Fusion. Four cage designs in different geometries were analyzed in silico under axial loading, flexion, extension, and lateral bending. Results The K2 design had the best overall biomechanical performance for the loads considered. Maximum cage stress recorded was 36.7 MPa in compression after a flexion load, which was within the biomechanical limits of the cage. Conclusion Biomechanical analyses suggest that K2 bioceramic cage is an optimal design and reveals essential material properties for a stable interbody fusion. PMID:29581974

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

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

PubMed Central

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

2015-01-01

Carbonate apatite (CO3Ap), the form of apatite found in bone, has recently attracted attention. The purpose of the present study was to histologically evaluate the tissue/cellular response toward the low-crystalline CO3Ap fabricated using a dissolution-precipitation reaction with set gypsum as a precursor. When set gypsum was immersed in a 100°C 1 mol/L Na3PO4 aqueous solution for 24 h, the set gypsum transformed into CO3Ap. Both CO3Ap and sintered hydroxyapatite (s-HAp), which was used as a control, were implanted into surgically created tibial bone defects of rats for histological evaluation. Two and 4 weeks after the implantation, histological sections were created and observed using light microscopy. The CO3Ap granules revealed both direct apposition of the bone matrix by osteoblasts and osteoclastic resorption. In contrast, the s-HAp granules maintained their contour even after 4 weeks following implantation which implied that there was a lack of replacement into the bone. The s-HAp granules were sometimes encapsulated with fibrous tissue, and macrophage polykaryon was occasionally observed directly apposed to the implanted granules. From the viewpoint of bone remodeling, the CO3Ap granules mimicked the bone matrix, suggesting that CO3Ap may be an appropriate bone substitute. PMID:26504813

Adipose-derived stem cells and BMP-2 delivery in chitosan-based 3D constructs to enhance bone regeneration in a rat mandibular defect model.

PubMed

Fan, Jiabing; Park, Hyejin; Lee, Matthew K; Bezouglaia, Olga; Fartash, Armita; Kim, Jinku; Aghaloo, Tara; Lee, Min

2014-08-01

Reconstructing segmental mandiblular defects remains a challenge in the clinic. Tissue engineering strategies provide an alternative option to resolve this problem. The objective of the present study was to determine the effects of adipose-derived stem cells (ASCs) and bone morphogenetic proteins-2 (BMP-2) in three-dimensional (3D) scaffolds on mandibular repair in a small animal model. Noggin expression levels in ASCs were downregulated by a lentiviral short hairpin RNA strategy to enhance ASC osteogenesis (ASCs(Nog-)). Chitosan (CH) and chondroitin sulfate (CS), natural polysaccharides, were fabricated into 3D porous scaffolds, which were further modified with apatite coatings for enhanced cellular responses and efficient delivery of BMP-2. The efficacy of 3D apatite-coated CH/CS scaffolds supplemented with ASCs(Nog-) and BMP-2 were evaluated in a rat critical-sized mandibular defect model. After 8 weeks postimplantation, the scaffolds treated with ASCs(Nog-) and BMP-2 significantly promoted rat mandibular regeneration as demonstrated by micro-computerized tomography, histology, and immunohistochemistry, compared with the groups treated with ASCs(Nog-) or BMP-2 alone. These results suggest that our combinatorial strategy of ASCs(Nog-)+BMP-2 in 3D apatite microenvironments can significantly promote mandibular regeneration, and these may provide a potential tissue engineering approach to repair large bony defects.

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.

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.

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.

Sedimentary rocks in our mouth: dental pulp stones made by nanobacteria

NASA Astrophysics Data System (ADS)

Ciftcioglu, Neva; Ciftcioglu, Vefa; Vali, Hojatollah; Turcott, Eduardo; Kajander, E. Olavi

1998-07-01

The mechanisms of dental pulp stone formation are still largely unknown. Pulp stones are mainly composed of carbonate apatite. Only few experimental reports have elucidated the potential of some selected bacteria to produce apatite under in vitro conditions using special calcification media. The tested stone forming bacteria were, in fact, often better known for their cariogenic potential. Our preliminary work with 18 dental pulp stones from Turkey, selected only by severity of the stone formation, indicated the presence of nanobacterial antigens in the demineralized stones. Furthermore, high incidence of kidney stones and gall stones in the patient group and in their parents was found. This raises the implication that nanobacteria may enter the body also via oral route, in addition to the parenteral and transplacental routes. The role of nanobacteria in dental pulp stone formation was further studied by following nanobacterial colonization and mineral formation on human tooth in vitro. Two molar teeth, one having pulp stone and one without, were vertically cut into two pieces, sterilized by autoclaving and incubated with or without nanobacteria in DMEM. Electron microscopic observations indicate that nanobacteria can cause apatite stone formation on tooth surface. The sever from of dental pulp stone formation might be associated with nanobacteria. This form of dental disease results in loss of teeth due to osteolytic processes. This addresses the necessity for a study on unconventional mineral-forming bacteria as a cause for human diseases.

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.

Radionuclide Incorporation and Long Term Performance of Apatite Waste Forms

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

Wang, Jianwei; Lian, Jie; Gao, Fei

2016-01-04

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

Graphite as a Biomarker in Rocks of the 3.8 Ga Isua Supracrustal Belt

NASA Astrophysics Data System (ADS)

Lepland, A.; van Zuilen, M.; Layne, G. D.; Arrhenius, G.

2002-12-01

Recent petrographic and isotopic studies of graphite and apatite in supracrustal rocks from the 3.8 Ga Isua belt (ISB) in southern West Greenland [1, 2] have shown inconsistencies in interpreting traces of life in the earliest terrestrial sediment record. Isotopically light graphitic carbon, suggestive of a bioorganic origin, has been previously reported from the carbonate-rich Isua rocks [3, 4] that at the time were recognized as sedimentary deposits. However, these carbonate-rich rocks, that provided the basis for original biologic interpretations, have been shown to have a metasomatic origin [5] not sedimentary as previously believed. This protolith reinterpretation has highlighted the need for assessment of graphite genesis and related isotopic systematics when using graphite as an ancient biomarker. We have, for this purpose, studied graphite in a suite of samples from the ISB including metacarbonates, turbidites, cherts and banded iron formations (BIFs). Graphite is relatively abundant (0.1-2 wt. %) in metacarbonate samples, while the abundances of reduced carbon in metasedimentary BIFs and metacherts are below 100 ppm. Petrographic analyses show that graphite in metacarbonates typically associates with Fe-bearing carbonate and magnetite. This mineral association indicates graphite formation in Isua metacarbonates by thermal-metamorphic reduction of carbonate ion, in which the carbonate ion is reduced to form graphite and ferrous iron is oxidized to form magnetite. Carbon isotopic compositions of graphite (δ13C ca. -2 per mil) and associated Fe-carbonate (δ13C ca. -6 per mil) indicate isotopic equilibrium between these two phases at ca. 500 C, consistent with the metamorphic history of the ISB. Stepped-combustion experiments undertaken on Isua BIFs and metacherts reveal that these sediments contain virtually no graphite, and the small amount of reduced carbon found there represents recent organic contamination. Our stepped-combustion-mass-spectrometry data demonstrate that previous isotopic results on graphite deficient Isua rocks obtained by single step combustion are unreliable. The proposed biologic significance of graphite occurring as inclusions in apatite [4] in Isua rocks is not supported by our findings because such graphite-apatite association can only be found in biologically irrelevant metacarbonate rocks. The isotopic systematics of the epigenetic processes responsible for formation of isotopically light graphite enclosed in apatite crystals [4] will be discussed, integrating new ion microprobe isotope data on graphite in apatite and other mineral phases occurring in Isua metacarbonates. References: [1] van Zuilen, M., Lepland, A. and Arrhenius, G., 2002. Reassessing the evidence for the earliest traces of life. Nature 418: 627-630. [2] Lepland, A., Arrhenius, G. and Cornell, D. in press. Apatite in early Archean Isua supracrustal rocks, southern West Greenland: its origin, association with graphite and potential as a biomarker. Precam. Res. [3] Schidlowski, M., 1988. A 3,800-million-year isotopic record of life from carbon in sedimentary rocks. Nature 333: 313-318. [4] Mojzsis, S.J., Arrhenius, G., McKeegan, K.D., Harrison, T.M., Nutman, A.P. and Friend, C.R.L., 1996. Evidence for life on Earth before 3800 million years ago. Nature 384: 55-59. [5] Rosing, M.T., Rose, N.M., Bridgwater, D. and Thomsen, H.S., 1996. Earliest part of Earth's stratigraphic record: a reappraisal of the >3.7 Ga Isua (Greenland) supracrustal sequence. Geol. 24: 43-46.

Adsorption of benzoxaboroles on hydroxyapatite phases.

PubMed

Pizzoccaro, Marie-Alix; Nikel, Ondrej; Sene, Saad; Philippe, Coralie; Mutin, P Hubert; Bégu, Sylvie; Vashishth, Deepak; Laurencin, Danielle

2016-09-01

Benzoxaboroles are a family of molecules that are finding an increasing number of applications in the biomedical field, particularly as a "privileged scaffold" for the design of new drugs. Here, for the first time, we determine the interaction of these molecules with hydroxyapatites, in view of establishing (i) how benzoxaborole drugs may adsorb onto biological apatites, as this could impact on their bioavailability, and (ii) how apatite-based materials can be used for their formulation. Studies on the adsorption of the benzoxaborole motif (C7H7BO2, referred to as BBzx) on two different apatite phases were thus performed, using a ceramic hydroxyapatite (HAceram) and a nanocrystalline hydroxyapatite (HAnano), the latter having a structure and composition more similar to the one found in bone mineral. In both cases, the grafting kinetics and mechanism were studied, and demonstration of the surface attachment of the benzoxaborole under the form of a tetrahedral benzoxaborolate anion was established using (11)B solid state NMR (including (11)B-(31)P correlation experiments). Irrespective of the apatite used, the grafting density of the benzoxaborolates was found to be low, and more generally, these anions demonstrated a poor affinity for apatite surfaces, notably in comparison with other anions commonly found in biological media, such as carboxylates and (organo)phosphates. The study was then extended to the adsorption of a molecule with antimicrobial and antifungal properties (3-piperazine-bis(benzoxaborole)), showing, on a more general perspective, how hydroxyapatites can be used for the development of novel formulations of benzoxaborole drugs. Benzoxaboroles are an emerging family of molecules which have attracted much attention in the biomedical field, notably for the design of new drugs. However, the way in which these molecules, once introduced in the body, may interact with bone mineral is still unknown, and the possibility of associating benzoxaboroles to calcium phosphates for drug-formulation purposes has not been looked into. Here, we describe the first study of the adsorption of benzoxaboroles on hydroxyapatite, which is the main mineral phase present in bone. We describe the mode of grafting of benzoxaboroles on this material, and show that they only weakly bind to its surface, especially in comparison to other ionic species commonly found in physiological media, such as phosphates and carboxylates. This demonstrates that administered benzoxaborole drugs are unlikely to remain adsorbed on hydroxyapatite surfaces for long periods of time, which means that their biodistribution will not be affected by such phenomena. Moreover, this work shows that the formulation of benzoxaborole drugs by association to calcium phosphates like hydroxyapatite will lead to a rapid release of the molecules. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

Water Content of Lunar Alkali Fedlspar

NASA Technical Reports Server (NTRS)

Mills, R. D.; Simon, J. I.; Wang, J.; Alexander, C. M. O'D.; Hauri, E. H.

2016-01-01

Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of < 1 ppm in urKREEP. Using these data, predict that the bulk water content of the magma ocean would have <10 ppm. In contrast, estimate water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was likely very significant in the evolution of the lunar mantle. Conclusions: Lunar granites crystallized between 4.3-3.8 Ga from relatively wet melts that degassed upon crystallization. The formation of these granites likely removed significant amounts of water from some mantle source regions, e.g. later mare basalts predicting derivation from a mantle with <10 ppm water. However, this would have been a heterogeneous pro-cess based on K distribution. Thus some, if not most of the mantle may not have been devolatilized by this process; as seen by water in volcanic glasses and melt inclusions.

Apatite-coated Silk Fibroin Scaffolds to Healing Mandibular Border Defects in Canines

PubMed Central

Zhao, Jun; Zhang, Zhiyuan; Wang, Shaoyi; Sun, Xiaojuan; Zhang, Xiuli; Chen, Jake; Kaplan, David L.; Jiang, Xinquan

2010-01-01

Tissue engineering has become a new approach for repairing bony defects. Highly porous osteoconductive scaffolds perform the important role for the success of bone regeneration. By biomimetic strategy, apatite-coated porous biomaterial based on silk fibroin scaffolds (SS) might provide an enhanced osteogenic environment for bone-related outcomes. To assess the effects of apatite-coated silk fibroin (mSS) biomaterials for bone healing as a tissue engineered bony scaffold, we explored a tissue engineered bony graft using mSS seeded with osteogenically induced autologous bone marrow stromal cells (bMSCs) to repair inferior mandibular border defects in a canine model. The results were compared with those treated with bMSCs/SS constructs, mSS alone, SS alone, autologous mandibular grafts and untreated blank defects. According to radiographic and histological examination, new bone formation was observed from 4 weeks post-operation, and the defect site was completely repaired after 12 months for the bMSCs/mSS group. In the bMSCs/SS group, new bone formation was observed with more residual silk scaffold remaining at the center of the defect compared with the bMSCs/mSS group. The engineered bone with bMSCs/mSS achieved satisfactory bone mineral densities (BMD) at 12 months post-operation close to those of normal mandible (p>0.05). The quantities of newly formed bone area for the bMSCs/mSS group was higher than the bMSCs/SS group (p<0.01), but no significant differences were found when compared with the autograft group (p>0.05). In contrast, bony defects remained in the center with undegraded silk fibroin scaffold and fibrous connective tissue, and new bone only formed at the periphery in the groups treated with mSS or SS alone. The results suggested apatite-coated silk fibroin scaffolds combined with bMSCs could be successfully used to repair mandibular critical size border defects and the premineralization of these porous silk fibroin protein scaffolds provided an increased osteoconductive environment for bMSCs to regenerate sufficient new bone tissue. PMID:19505603

Tectonic and thermal history of the western Serrania del Interior foreland fold and thrust belt and Guarico Basin, north central Venezuela: Implications of new apatite fission track analysis and seismic interpretation

NASA Astrophysics Data System (ADS)

Perez de Armas, Jaime Gonzalo

Structural analysis, interpretation of seismic reflection lines, and apatite fission-track analysis in the Western Serrania del Interior fold and thrust belt and in the Guarico basin of north-central Venezuela indicate that the area underwent Mesozoic and Tertiary-to-Recent deformation. Mesozoic deformation, related to the breakup of Pangea, resulted in the formation of the Espino graben in the southernmost portion of the Guarico basin and in the formation of the Proto-Caribbean lithosphere between the diverging North and South American plates. The northern margin of Venezuela became a northward facing passive margin. Minor normal faults formed in the Guarico basin. The most intense deformation took place in the Neogene when the Leeward Antilles volcanic island arc collided obliquely with South America. The inception of the basal foredeep unconformity in the Late Eocene-Early Oligocene marks the formation of a perisutural basin on top of a buried graben system. It is coeval with minor extension and possible reactivation of Cretaceous normal faults in the Guarico basin. It marks the deepening of the foredeep. Cooling ages derived from apatite fission-tracks suggest that the obduction of the fold and thrust belt in the study area occurred in the Late Oligocene through the Middle Miocene. Field data and seismic interpretations suggest also that contractional deformation began during the Neogene, and specifically during the Miocene. The most surprising results of the detrital apatite fission-track study are the ages acquired in the sedimentary rocks of the easternmost part of the study area in the foreland fold and thrust belt. They indicate an Eocene thermal event. This event may be related to the Eocene NW-SE convergence of the North and South American plates that must have caused the Proto-Caribbean lithosphere to be shortened. This event is not related to the collision of the arc with South America, as the arc was far to the west during the Eocene.

Unroofing history of a suture zone in the Himalaya of Pakistan by means of fission-track annealing ages

USGS Publications Warehouse

Zeitler, P.K.; Tahirkheli, R.A.K.; Naeser, C.W.; Johnson, N.M.

1982-01-01

The uplift history of the Swat Valley and Hazara region of northwestern Pakistan has been established using 22 fission-track dates on apatite, zircon and sphene. A major fault, the Main Mantle Thrust (MMT) strikes east-west across the Swat Valley, separates regions of markedly differing fission-track age regimesm, and may be a suture zone separating an extinct island arc terrane on the north from the Indian plate to the south. Fission-track ages ranging from about 55 to 58 m.y. for sphene, 18 to 53 m.y. for zircon, and 9 to 17 m.y. for apatite were obtained from the region north of the MMT. To the south the fission-track age ranges are 20 to 25 m.y. for sphene, 17 to 26 m.y. for zircon, and 16 to 23 m.y. for apatite. Disparate zircon and sphene ages on each side of the MMT imply different cooling histories for each side of the fault prior to 15 m.y. Similar apatite ages on both sides of the fault imply similar cooling histories during the past 15 m.y. This may indicate that faulting ceased by 15 m.y. Mean uplift rates have been derived from the fission-track data using mainly the mineral-pair method. Uplift rates in the region north of the MMT increased from 0.07 to 0.20 mm/yr during the period 55 to 15 m.y. South of the fault, uplift rates averaged in excess of 0.70 mm/yr for the period 25 to 15 m.y. During the past 15 m.y. uplift across the MMT in the Swat Valley showsno discontinuities, ranging from 0.16 mm/yr in the south to 0.39 mm/yr in the north. A plausible interpretation for the fission-track uplift data has the MMT verging to the south with overthrusting taking place at a depth between 3.5 and 6.0 km, juxtaposing two terranes that were originally separated by a substantial, but unknown distance. In this model, regional uplift followed cessation of faulting just prior to 15 m.y. ?? 1982.

Accessory Mineral Depth-Profiling Applied to the Corsican Lower Crust: A Continuous Thermal History of Mesozoic Continental Rifting

NASA Astrophysics Data System (ADS)

Seymour, N. M.; Stockli, D. F.; Beltrando, M.; Smye, A.

2015-12-01

Despite advances in understanding the structural development of hyperextended magma-poor rift margins, the temporal and thermal evolution of lithospheric hyperextension during rifting remains only poorly understood. In contrast to classic pure-shear models, multi-stage rift models that include depth-dependent thinning predict significant lower-crustal reheating during the necking phase due to buoyant rise of the asthenosphere. The Santa Lucia nappe of NE Corsica is an ideal laboratory to test for lower-crustal reheating as it preserves Permian lower crust exhumed from granulitic conditions during Mesozoic Tethyan rifting. This study presents the first use of apatite U-Pb depth-profile thermochronology in conjunction with novel rutile U-Pb and zircon U-Pb thermo- and geochronology to reconstruct a continuous t-T path to constrain the syn-rift thermal evolution of this exposed lower-crustal section. LASS-ICP-MS depth-profile analyses of zircon reveal thin (<10 μm) ~210-180 Ma overgrowths on 300-270 Ma cores in lower-crustal lithologies, indicative of renewed thermal activity during Mesozoic rifting. Cooling due to rapid rift margin exhumation is recorded by the topology of rutile and apatite depth profiles caused by thermally-activated volume diffusion at T >400°C. Lower-crustal rutile reveal a rounded progression from core plateaus at ~170 Ma to 150-145 Ma at the outer 8-10 μm of grains while middle-crustal apatite records 170 Ma cores grading to 140-135 Ma rims. Inverse modeling of rutile profiles suggests the lower crust cooled from 700°C at 200 Ma to 425°C at 140 Ma. Middle-crustal apatite yield a two-stage history, with rapid cooling from 500°C at 200 Ma to 420°C at ~180 Ma followed by slow cooling to 400°C by 160 Ma. Combined with zircon overgrowth ages, these data indicate the Santa Lucia nappe underwent a thermal pulse in the late Triassic-early Jurassic associated with depth-dependent thinning and hyperextension of the Corsican margin.

Magmatic origin and fluid alteration versus inheritance: Complex history of accessory minerals from I-type granites from northern Victoria Land (Antarctica)

NASA Astrophysics Data System (ADS)

Menneken, M.; John, T.; Läufer, A.; Berndt, J.; Henjes-Kunst, F.; Giese, J.

2016-12-01

When reconstructing the formation and evolution of Earths earliest crust, one is still heavily reliant on information that can be gathered from detrital zircon grains, which have been proven to be a useful tool concerning the various isotopic, chemical, and mineralogical features that can be utilized within. However, detailed investigations have shown that some of these tracers might be prone to alteration and will not necessarily reflect conditions during formation [1, 2]. In this study, zircons and their host rocks from the Granite Harbour Intrusives (GHI) of northern Victoria Land, Antarctica, have been investigated with respect to regional evolution of continental crust as well as the reliability of zircon as a recorder of crustal formation. Here we present U-Pb, δ18O, trace element and inclusion data of zircons from Cambro-Ordovician granitoids, as well as geochemical analyses of accessory apatites. Our initial results show that even in I-type granitoids with a presumably simple formation history, U-Pb-age data and related isotopic, chemical, or mineralogical features have to be evaluated carefully in order to constrain the timing of magmatic events, inheritance or fluid alteration events. They do, for example, incorporate a large portion of recycled material, which is clearly reflected by a strong component of inherited U-Pb-zircon ages, but can also be inferred by comparing main- and trace-element compositions of apatite inclusions in zircon with accessory apatites. Apatite inclusions from all investigated samples for example, are clearly higher in F concentration, than their accessory counterparts. However, not all zircon grains record the youngest event, emphasizing that not only alteration might be a key factor to consider when evaluating zircon characteristics with respect to their host rock, but also, the timing and preservation of predating features. [1] Rasmussen et al. (2011) Metamorphic replacement of mineral inclusions in detrital zircon from Jack Hills, Australia: Implications for the Hadean Earth: Geology 39, 1143-1146. [2] Nemchin et al. (2006) Re-evaluation of the origin and evolution of > 4.2 Ga zircons from the Jack Hills metasedimentary rocks: Earth and Planetary Science Letters, v. 244, p. 218-233.

Phosphorus burial in sediments of the sulfidic deep Black Sea: Key roles for adsorption by calcium carbonate and apatite authigenesis

NASA Astrophysics Data System (ADS)

Kraal, Peter; Dijkstra, Nikki; Behrends, Thilo; Slomp, Caroline P.

2017-05-01

Sedimentary burial of the essential nutrient phosphorus (P) under anoxic and sulfidic conditions is incompletely understood. Here, we use chemical and micro-scale spectroscopic methods to characterize sedimentary P burial along a water column redox transect (six stations, 78-2107 m water depth) in the Black Sea from the shelf with its oxygenated waters to the anoxic and sulfidic deep basin. Organic P is an important P pool under all redox regimes, accounting for up to 60% of P burial. We find a general down-core increase in the relative importance of organic P, especially on the shelf where P bound to iron (Fe) and manganese (Mn) (oxyhydr)oxides is abundant in the uppermost sediment but rapidly declines in concentration with sediment depth. Our chemical and spectroscopic data indicate that the carbonate-rich sediments (Unit I, ∼3000 years, ∼0-30 cm depth) of the sulfidic deep Black Sea contain three major P pools: calcium phosphate (apatite), organic P and P that is strongly associated with CaCO3 and possibly clay surfaces. Apatite concentrations increase from 5% to 25% of total P in the uppermost centimeters of the deep basin sediments, highlighting the importance of apatite formation for long-term P burial. Iron(II)-associated P (ludlamite) was detected with X-ray absorption spectroscopy but was shown to be a minor P pool (∼5%), indicating that lateral Fe-P transport from the shelf ("shuttling") likely occurs but does not impact the P burial budget of the deep Black Sea. The CaCO3-P pool was relatively constant throughout the Unit I sediment interval and accounted for up to 55% of total P. Our results highlight that carbonate-bound P can be an important sink for P in CaCO3-rich sediments of anoxic, sulfidic basins and should also be considered as a potential P sink (and P source in case of CaCO3 dissolution) when reconstructing past ocean P dynamics from geological records.

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.

Mechanisms of iodine release from iodoapatite in aqueous solution

NASA Astrophysics Data System (ADS)

Zhang, Z.; Wang, J.

2017-12-01

Immobilization of iodine-129 with waste forms in geological setting is challenging due to its extremely long half-life and high volatility in the environment. To evaluate the long-term performance of waste form, it is imperative to determine the release mechanism of iodine hosted in the waste form materials. This study investigated the iodine released from apatite structured waste form Pb9.85 (VO4)6 I1.7 to understand how diffusion and dissolution control the durability of apatite waste form. A standard semi-dynamic leach test was adopted in this study. Samples were exposed in fresh leachant periodically and the leachant was replaced after each interval. Each experiment was carried out in cap-sealed Teflon vessels under constant temperature (e.g. 90 °C). ICP-MS analysis on the reacted leachates shows that Pb and V were released constantly and congruently with the stoichiometric ratio of Pb/V. However, iodine release is incongruent and time dependent. The iodine release rate starts significantly higher than the corresponding stoichiometric value and gradually decreases, approaching the stoichiometric value. Therefore, a dual-mode mechanism is proposed to account for the iodine release from apatite, which is dominated by short-term diffusion and long-term dissolution processes. Additional tests show that the element release rates depend on a number of test parameters, including sample surface to solution volume ratio (m-1), interval (day), temperature (°C), and solution pH. This study provides a quantitative characterization of iodine release mechanism. The activation energy of iodine leaching 21±1.6 kJ/mol was obtained by varying the test temperature. At the test conditions of to neutral pH and 90 °C, the long-term iodine release rate 3.3 mg/(m2 • day) is projected by normalizing sample surface area to solution volume ratio (S/V) to 1.0 m-1 and interval to 1 day. These findings demonstrate i) the feasibility of our approach to quantify the release mechanism and ii) the performance of iodine apatite as a favorable waste form candidate for I-129 disposal.

Impact of mineral fertility and bedrock erosion on single-mineral detrital studies: insights from trace-element and Nd-isotope systematics of detrital apatite from the Po River catchment

NASA Astrophysics Data System (ADS)

Malusa', Marco Giovanni; Wang, Jiangang; Garzanti, Eduardo; Villa, Igor M.; Wittman, Hella

2017-04-01

The detrital record provides an archive of mountain erosion that preserves key information for paleotectonic and paleoclimatic reconstructions. Detrital studies are often based on single-mineral analyses (e.g., geo/thermochronologic analyses on apatite and zircon). Their geologic interpretation can be challenging, because the impact of each eroding source on the detrital record is controlled by a range of factors including the rate of erosion and the fertility of chosen minerals in eroded bedrock. Here, we combine (i) a state-of-the art dataset of trace element and Nd isotope fingerprints of detrital apatite, (ii) a comprehensive dataset of apatite-fertility measurements (Malusà et al. 2016), (iii) fission-track data, and (iv) cosmogenic-derived erosion rates from the Po River catchment (Wittmann et al. 2016), to test the impact of mineral fertility and bedrock erosion on the single-mineral detrital signal preserved in the final sediment sink. Our results show that the information provided by accessory minerals, when complemented with accurate mineral fertility measurements, are fully consistent with information provided by the analysis of more abundant framework minerals. We found that trace element and Nd isotope analyses provide a reliable tool to disentangle the complex single-mineral record of orogenic erosion, and demonstrate that such a record is largely determined by high-fertility source rocks exposed within the drainage. Detrital thermochronology studies based on the lag-time approach should thus preferably include independent provenance discriminations and a full mineral fertility characterization of the potential source areas, in order to ensure a correct identification of the sediment sources and of the exogenic and endogenic processes monitored in the stratigraphic archive. Malusà M.G., Resentini A., Garzanti E., 2016. Hydraulic sorting and mineral fertility bias in detrital geochronology. Gondwana Res., 31, 1-19 Wittmann H., Malusà M.G., Resentini A., Garzanti E., Niedermann S., 2016. The cosmogenic record of mountain erosion transmitted across a foreland basin: Source-to-sink analysis of in situ 10Be, 26Al and 21Ne in sediment of the Po river catchment. Earth Planet. Sci. Lett. 452, 258-271

Results of interlaboratory comparison of fission track ages for 1992 fission track workshop

USGS Publications Warehouse

Miller, D.S.; Crowley, K.D.; Dokka, R.K.; Galbraith, R.F.; Kowallis, B.J.; Naeser, C.W.

1993-01-01

Two apatites and one sphene were made available to the fission track research community for analysis prior to the 1992 Fission Track Workshop held in Philadelphia, U.S.A., 13-17 July. Eighteen laboratories throughout the world received aliquots of apatite and sphene. To date, analyses by 33 different scientists have been representing 15 different laboratories. With respect to the previous two interlaboratory comparisons, there is a noticeable improvement in the accuracy of the age results (Naeser and Cebula, 1978; Naeser et al., 1981; Miller et al., 1985;Miller et al.1990). Ninety-four percent of the analysis used the external detector method (EDM) combined with the zeta technique while the remaining individuals used the population method (POP). Track length measurements (requested for the first time in the interlaboratory comparison studies) were in relatively good agreement. ?? 1993.

Rare earth element carriers in the Shergotty meteorite and implications for its chronology

NASA Technical Reports Server (NTRS)

Lundberg, Laura L.; Crozaz, Ghislaine; Zinner, Ernst; Mckay, Gordon

1988-01-01

This paper reports on the results of ion-probe measurements of REE concentrations in individual grains of the Shergotty meteorite. The phases analyzed included whitlockite, apatite, baddeleyite, augite, pigeonite, maskelynite, and K-rich glass; the whitlockite and apatite phases were also analyzed for U. Results indicate that whitlockite contains the bulk of the REE in Shergotty, with no evidence for distinct light-REE patterns in texturally different whitlockites. The results on the evolution of the REE abundances in the Shergotty late-stage interstitial melt, inferred from the analysis of whitlockite, are consistent with closed system crystallization. No metasomatic alteration is required to explain the REE data. It is concluded that there is no compelling reason to attribute chronological significance to the Sm-Nd array, as was done by Jagoutz and Waenke (1986).

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.

In vitro bioactivity of novel tricalcium silicate ceramics.

PubMed

Zhao, Wenyuan; Chang, Jiang; Wang, Junying; Zhai, Wanyin; Wang, Zheng

2007-05-01

In this study, bone-like apatite-formation ability of tricalcium silicate (Ca(3)SiO(5)) ceramics in simulated body fluid (SBF) was evaluated and the in vitro degradability was investigated by soaking in Ringer's solution. The effect of ionic products from Ca(3)SiO(5) dissolution on osteobalsts proliferation was investigated. The result indicated that hydroxyapatite (HA) was formed on the surface of the Ca(3)SiO(5) ceramics after soaking in SBF for 1 day, and Ca(3)SiO(5) ceramics could degraded in Ringer's solution. The Si ions from Ca(3)SiO(5) dissolution at certain concentration range significantly stimulated osteoblasts proliferation. Our results show that Ca(3)SiO(5) ceramics possess bone-like apatite-formation ability and degradability, and can release soluble ionic products to stimulate cell proliferation.