Microcomputed tomography (laboratory and synchrotron) of intact archeological human second metacarpa
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Stock, Stuart R.↗
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Results for “APATITES”
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Intact archeological human bones and age at death studied with transmission x–ray diffraction and small angle x–ray scattering
In this work, high-energy, wide-angle x-ray scattering (WAXS, x-ray diffraction) and small-angle x-ray scattering (SAXS) were used to study intact human second metacarpal bones (mc2) from two UK archeological sites. A novel method correcting for irregular mass distribution was applied in these transmission geometry experiments done at beamline 1-ID of the Advanced Photon Source. The authors asked whether there were age-at-death-related changes in carbonated apatite (cAp) lattice parameters and whether SAXS could detect collagen D-period peaks in the archeological mc2. For each of the two sites, Ancaster and Wharram Percy in England, six female mc2s were studied; for each site, two were from each of three age-at-death cohorts (young, 18-29 years; middle, 30-49 years; old >= 50 years) along with a modern control mc2. The Rietveld method was applied to the WAXS patterns to provide precise lattice parameter values. The cAp lattice parameters did not correlate with age-at-death estimated from dental wear. From WAXS and the 00.2 diffraction peak widths, four archeological mc2s possessed coherently scattering domain lengths (crystallite c-axis sizes) that matched that of the modern mc2; SAXS revealed the same four archeological mc2 had D-period peak intensities equivalent to that of the modern mc2. The other eight archeological mc2s had significantly larger crystallite sizes (than the modern mc2) and weak or absent D-period peaks, differences attributed to diagenetic changes. Based on these data, the authors suggest that WAXS 00.2 peak width and SAXS D-period peak intensity can be used with intact bones to select those likely to retain largely unaltered tissue nanostructure, which might be required for other analyses. Taken as a whole, the results suggest detecting age-related deterioration in nanostructural features may be difficult in bone showing significant bioerosion.
59 BASIC BIOLOGICAL SCIENCES↗
Heat-Treated TiO{sub 2} Plasma Spray Deposition for Bioactivity Improvement in Ti-6Al-4V Alloy
In the present study, titanium di-oxide (TiO{sub 2}) coating has been developed on Ti-6Al-4V substrate by plasma spray deposition. Followed by plasma spraying, heat treatment of the sprayed sample has been carried out by isothermally holding it at 823 K (550 °C) for 2 h. Microstructural analysis shows the presence of porosity and unmelted particles on the as-sprayed surface, the area fraction of which reduces after heat treatment. X-ray diffraction analysis shows the phase transformation from anatase (in precursor powder) to rutile (in as-sprayed coating and the same after heat treatment). There is an improvement in nano-hardness, “Young’s modulus” and wear resistance in plasma-sprayed TiO{sub 2} coating (as-sprayed as well as post-heat-treated condition) as compared to as-received Ti-6Al-4V, though post-heat treatment offers a superior hardness, “young’s modulus” and wear resistance as compared to as-sprayed coating. The corrosion behavior in “hank’s solution” shows decrease in corrosion resistance after plasma spraying and post-heat treatment as compared to as-received substrate. A significant decrease in contact angle and improvement in bioactivity (in terms of apatite deposition) were observed in TiO{sub 2}-coated surface as compared to as-received Ti-6Al-4V.
36 MATERIALS SCIENCE↗
Electrochemical Corrosion and In vitro Biocompatibility Performance of AZ31Mg/Al{sub 2}O{sub 3} Nanocomposite in Simulated Body Fluid
In this present investigation, AZ31 alloy nanocomposite was prepared with the inclusion of Al{sub 2}O{sub 3} nanoparticles using innovative disintegrated melt deposition (DMD) process followed by hot extrusion to improve the corrosion resistance and in vitro biocompatibility in simulated body fluid (SBF). This investigation systematically inspected the degradation performances of AZ31 alloy with Al{sub 2}O{sub 3} nanoparticles through hydrogen evolution, weight loss and electrochemical methods in SBF. Further, the surface microstructure with the in vitro mineralization of the alloys in SBF was characterized by XRD, XPS, and SEM/EDS analysis. It was seen that the addition of Al{sub 2}O{sub 3} nanoparticles significantly decreased the weight loss of AZ31 alloy substrates after 336 h of exposure in SBF. The corrosion resistance of the monolithic and nanocomposite samples was evaluated using potentiodynamic polarization tests, electrochemical impedance spectroscopy measurements in short- and long-term periods. Accordingly, the electrochemical analysis in SBF showed that the corrosion resistance performance of the AZ31 alloy enhanced considerably due to the incorporation of Al{sub 2}O{sub 3} nanoparticles as reinforcement. Moreover, the rapid formation of bone-like apatite layer on the surface of the nanocomposite substrate demonstrated a good bioactivity of the nanocomposite samples in SBF.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Nonlinear Resonance Response of Porous Beam-Type Implants Corresponding to Various Morphology Shapes for Bone Tissue Engineering Applications
Having excellent biocompatibility and apatite mineralization as well as efficient mechanical properties makes bredigite as one of the most attractive bioceramics. A beam-type porous biological implant in a 3D-printed architecture is designed with micron pore size. The surface properties, morphology, and size of the composed powders are evaluated using Scherrer and Williamson-Hall equation. The effect of MNPs deposition into the bredigite bioceramics and correlation with temperature effect on roughness of the prepared bio-nanocomposite are also investigated for hyperthermia application potential. The composed powders are characterized by x-ray diffraction, and then scanning electron microscopy (SEM), differential scanning calorimetry, thermogravimetric analysis (weight change, TGA), and atomic force microscopy are utilized to evaluate the surface topography. The resonance response is the tendency of a bone scaffold to respond at prominent amplitude while the frequency of its oscillations is equal to the structure’s natural frequency of vibration. Therefore, based on the obtained mechanical properties via the experimental approach for the bio-nanocomposite material, an analytical solution based upon the multiple-timescale method is carried out to analyze the nonlinear primary resonance of a 3D-printed porous beam-type biological implant under uniform-distributed load. According to SEM observations, there are hard agglomerates in the bredigite-magnetite nanoparticles (Br-MNPs) bio-nanocomposite material with low weight fraction of MNPs. However, they are broken down by increasing the amount of MNPs. Also, it is displayed that for lower MNPs weight fraction, the height of jump phenomenon related to the nonlinear resonance response is maximum and minimum for, respectively, irregular and mesoporous shapes of morphology, but their associated forcing amplitudes related to the bifurcation points are minimum and maximum, respectively.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Understanding the structural drivers governing glass–water interactions in borosilicate based model bioactive glasses
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Stone-Weiss, Nicholas↗
Black Drum Fish Teeth: Built for Crushing Mollusk Shells
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Deng, Zhifei↗
Studying biomineralization pathways in a 3D culture model of breast cancer microcalcifications
Microcalcifications serve as diagnostic markers for breast cancer, yet their formation pathway(s) and role in cancer progression are debated due in part to a lack of relevant 3D culture models that allow studying the extent of cellular regulation over mineralization. Previous studies have suggested processes ranging from dystrophic mineralization associated with cell death to bone-like mineral deposition. In this paper, we evaluated microcalcification formation in 3D multicellular spheroids, generated from non-malignant, pre-cancer, and invasive cell lines from the MCF10A human breast tumor progression series. The spheroids with greater malignancy potential developed necrotic cores, thus recapitulating spatially distinct viable and non-viable areas known to regulate cellular behavior in tumors in vivo. The spatial distribution of the microcalcifications, as well as their compositions, were characterized using nanoCT, electron-microscopy, and X-ray spectroscopy. Apatite microcalcifications were primarily detected within the viable cell regions and their number and size increased with malignancy potential of the spheroids. Levels of alkaline phosphatase decreased with malignancy potential, whereas levels of osteopontin increased. Finally, these findings support a mineralization pathway in which cancer cells induce mineralization in a manner that is linked to their malignancy potential, but that is distinct from physiological osteogenic mineralization.
60 APPLIED LIFE SCIENCES↗
Cadmium retention and distribution in contaminated soil: effects and interactions of soil properties, contamination level, aging time and in situ immobilization agents
As soil cadmium (Cd) contamination becomes a serious concern and one of the significant environmental pollution issues all over the world, knowledge of the basic chemistry, origin, inputs, sources, quantity, chemical forms, reactions, as well as the fate and transport of Cd in different types of soil is crucial for better understanding Cd bioavailability, health risks and remedial options. This study aimed to increase the current knowledge on the complex interdependence between the factors affecting behavior, transport and fate of Cd in the soil and to test and compare the performance of the stabilization agents in different soil types. Soils demonstrated various sorption affinity and capacity for Cd accumulation, which proved to be positively correlated with soil pH and the cation exchange capacity (CEC). With increasing levels of contamination, sequential extraction analysis showed the highest increase of relative Cd amounts in the exchangeable fraction regardless of the soil properties, suggesting that added Cd is principally associated with the easily accessible and mobile fraction. For different initial Cd concentrations and soil types, Cd sorption reached the quasi-equilibrium within 24 h of contact. Prolonged aging (two months) influenced the natural stabilization of Cd in all types of soil, but only at low contamination level. The application of both, conventional (slaked lime Ca(OH) 2) and alternative phosphate-rich (annealed bovine bones B 400) amendments, resulted in Cd relocation and reduction of exchangeable Cd content. Although the effect was smaller when apatite amendment was utilized, observed re-distribution of Cd to more stable soil fractions is preferable for achieving long-term stabilization. Cd concentrations extracted in exchangeable and acid soluble fractions after the treatments of contaminated soil samples suggest that the practical applicability of in situ immobilization depends on the soil properties and the level of contamination, as well as that effect, should be monitored for the possible re-mobilization of Cd. © 2019 Elsevier Inc.
02 PETROLEUM↗
Evaluating the paleomagnetic potential of single zircon crystals using the Bishop Tuff
We report zircon crystals offer a unique combination of suitability for high-precision radiometric dating and high resistance to alteration. Paleomagnetic experiments on ancient zircons may potentially constrain the history of the earliest geodynamo, which would hold broad implications for the early Earth's interior and atmosphere. However, the ability of zircons to record accurately the geomagnetic field has not been demonstrated. Here we conduct thermal and alternating field (AF) paleointensity experiments on 767.1 thousand year old (ka) zircons from the Bishop Tuff, California. The rapid emplacement of these zircons in a well-characterized magnetic field provides a high-fidelity test of the zircons' intrinsic paleomagnetic recording accuracy. Successful dual heating experiments on eleven zircons measured using a superconducting quantum interference device (SQUID) microscope yield a mean paleointensity of (1σ; after excluding possible maghemite-bearing zircons), which is consistent with high-precision results from Bishop Tuff whole rock (). High-resolution quantum diamond magnetic (QDM) mapping, electron microscopy, and X-ray tomography indicate that the bulk of the remanent magnetization in Bishop Tuff zircons is carried by Fe oxides associated with apatite inclusions, which may be susceptible to destruction via metamorphism and aqueous alteration in older zircons. As such, while zircons can reliably record the geomagnetic field, robust zircon-derived paleomagnetic results require careful characterization of the ferromagnetic carrier and demonstration of their occurrence in primary inclusions. We further conclude that a combination of quantum diamond magnetometry and high-resolution imaging can provide detailed, direct characterization of the ferromagnetic mineralogy of geological samples.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
The clumped-isotope geochemistry of exhumed marbles from Naxos, Greece
Exhumation and accompanying retrograde metamorphism alter the compositions and textures of metamorphic rocks through deformation, mineral–mineral reactions, water–rock reactions, and diffusion-controlled intra- and inter-mineral atomic mobility. Here, we demonstrate that these processes are recorded in the clumped- and single-isotope (δ 13 C and δ 18 O) compositions of marbles, which can be used to constrain retrograde metamorphic histories. We collected 27 calcite and dolomite marbles along a transect from the rim to the center of the metamorphic core-complex of Naxos (Greece), and analyzed their carbonate single- and clumped-isotope compositions. The majority of Δ 47 values of whole-rock samples are consistent with exhumation- controlled cooling of the metamorphic complex. However, the data also reveal that water–rock interaction, deformation driven recrystallization and thermal shock associated with hydrothermal alteration may considerably impact the overall distribution of Δ 47 values. We analyzed specific carbonate fabrics influenced by deformation and fluid–rock reaction to study how these processes register in the carbonate clumped-isotope system. Δ 47 values of domains drilled from a calcite marble show a bimodal distribution. Low Δ 47 values correspond to an apparent temperature of 260 °C and are common in static fabrics; high Δ 47 values correspond to an apparent temperature of 200 °C and are common in dynamically recrystallized fabrics. We suggest that the low Δ 47 values reflect diffusion-controlled isotopic reordering during cooling, whereas high Δ 47 values reflect isotopic reordering driven by dynamic recrystallization. We further studied the mechanism by which dynamic recrystallization may alter Δ 47 values by controlled heating experiments. Results show no significant difference between laboratory reactions rates in the static and dynamic fabrics, consistent with a mineral-extrinsic mechanism, in which slip along crystal planes was associated with atomic-scale isotopic reordering in the calcite lattice. An intrinsic mechanism (enhanced isotopic reordering rate in deformed minerals) is contraindicated by these experiments. We suggest that Δ 47 values of dynamically recrystallized fabrics that form below the diffusion-controlled blocking-temperature for calcite constrain the temperature of deformation. We find that Δ 47 -based temperatures of static fabrics from Naxos marbles are ~60–80 °C higher than commonly observed in slowly cooled metamorphic rocks, and would suggest cooling rates of ~10 5 °CMyr -1 . A similar thermal history is inferred for dolomite marbles from the core vicinity, which preserve apparent temperatures up to 200 °C higher than a typical blocking temperature (~300 °C). This finding could be explained by a hydrothermal event driving a brief thermal pulse and locally resetting Δ 47 values. Rapid cooling of the core-complex region is consistent with a compilation of published cooling ages and a new apatite U–Th/He age, associating the thermal event with the emplacement of a granodiorite pluton at ~12 Ma.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Petrogenesis, alteration, and shock history of intermediate shergottite Northwest Africa 7042: Evidence for hydrous magmatism on Mars?
We report Northwest Africa (NWA) 7042 is an intermediate, permafic shergottite consisting of two generations of zoned olivine (early olivine Fo 41-76 , and late-stage olivine Fo 46-56 ), complexly zoned pyroxene (En 35-64 Fs 22-46 Wo 5-34 ), maskelynitized feldspar and shock melt (An 5-30 Ab 16-61 Or 1-47 ), and accessory merrillite, apatite, ilmenite, titanomagnetite, Fe-Cr-Ti spinels, pyrrhotite, and baddeleyite. The olivine grains have been pervasively altered resulting in orange-brown stained cores with dark-brown margins, surrounded by significantly less altered overgrowth rims. This textural relationship suggests that the alteration of the cores took place at magmatic temperatures prior to crystallization of the rims on Mars. While this type of olivine alteration is rare in shergottites, it is similar to deuterically altered olivine in basalts and gabbros on Earth, caused by residual water-rich magmatic fluids. Launch-generated shock veins in NWA 7042 crosscut and displace several of the altered olivine grains indicating that the alteration occurred before ejection of the meteorite from Mars. However, NWA 7042 has also been subjected to extensive terrestrial weathering, with terrestrial calcite/barite veins occurring throughout the sample. Transmission electron microscopy analysis of the olivine alteration also reveals an absence of high-temperature phases typically associated with hydrous deuteric alteration on Earth, complicating our interpretation. The potential presence of deuterically altered olivine in NWA 7042 has significant implications, as it is the third martian meteorite where deuteric alteration of olivine has been observed (the others being NWA 10416, ALH 77005). The different mantle sources for the parental melts of these three meteorites would suggest many, if not all martian mantle reservoirs have the potential to produce water-rich magmas.
58 GEOSCIENCES↗
Fractionation of REE, U, and Th in natural ore-forming hydrothermal systems: Thermodynamic modeling
This contribution presents a thermodynamic model revealing the mechanisms responsible for separation of Heavy and Light Rare Earth (HREE and LREE) phosphates in natural hydrothermal systems at temperatures of 250–350 °C. Our calculations were performed for an isothermal column of rock containing 0.5 wt% of apatite (Ca phosphate), which served as an immobilizing agent for REE dissolved in the solution. REE were transported by 10 wt% NaCl acidic solution. The model accounted for formation of REE phosphate solid solutions through a regular mixing model. It demonstrates that hydrothermal flushing can efficiently separate REE forming xenotime (HREE phosphate solid solutions) at the beginning of the column, and re-transportation of monazite (LREE rich) to the end of the column. This separation is primarily due to the fact that at elevated temperatures stability LREE chloride complexes is significantly higher than that for HREE. The model also evaluates behavior of U and Th, which accompany REE in vast majority of natural locations. It was found that U strongly fractionates to xenotime, whereas Th fractionates to monazite. Finally, this phenomenon can be explained by the differences in crystal-chemical characteristics between monazite and xenotime, and the mobility of Th in aqueous solutions at elevated temperatures.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Getters for improved technetium containment in cementitious waste forms
A cementitious waste form, Cast Stone, is a possible candidate technology for the immobilization of low activity nuclear waste (LAW) at the Hanford site. This paper focuses on the addition of getter materials to Cast Stone that can sequester Tc from the LAW, and in turn, lower Tc release from the Cast Stone. Two getters which produce different products upon sequestering Tc from LAW were tested: Sn(II) apatite (Sn-A) that removes Tc as a Tc(IV)-oxide and potassium metal sulfide (KMS-2) that removes Tc as a Tc(IV)-sulfide species, allowing for a comparison of stability of the form of Tc upon entering the waste form. The Cast Stone with KMS-2 getter had the best performance with addition equivalent to ~0.08 wt% of the total waste form mass. The observed diffusion (D obs ) of Tc decreased from 4.6 ± 0.2 × 10 -12 cm 2 /s for Cast Stone that did not contain a getter to 5.4 ± 0.4 × 10 -13 cm 2 /s for KMS-2 containing Cast Stone. Finally, it was found that Tc-sulfide species are more stable against re-oxidation within getter containing Cast Stone compared with Tc-oxide and is the origin of the decrease in Tc D obs when using the KMS-2.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Three-dimensional mapping of mineral in intact shark centra with energy dispersive x-ray diffraction
The centra of shark vertebrae consist of cartilage mineralized by a bioapatite similar to bone's carbonated hy-droxyapatite, and, without a repair mechanism analogous to remodeling in bone, these structures still survive millions of cycles of high-strain loading. The main structures of the centrum are an hourglass-shaped double cone and the intermedialia which supports the cones. Little is known about the nanostructure of shark centra, spe-cifically the relationship between bioapatite and cartilage fibers, and this study uses energy dispersive diffraction (EDD) with polychromatic synchrotron x-radiation to study the spatial organization of the mineral phase and its crystallographic texture. The unique energy-sensitive detector array at beamline 6-BM-B, the Advanced Photon Source, enables EDD to quantify the texture within each sampling volume with one exposure while constructing 3D maps via specimen translation across the sampling volume. Herein this study maps a centrum from two shark orders, a carcharhiniform and a lamniform, with different intermedialia structures. In the blue shark (Prionace glauca, Carcharhiniformes), the bioapatite's c-axes are oriented laterally within the centrum's cone walls but axially within the wide wedges of the intermedialia; the former is interpreted to resist lateral deformation, the latter to support axial loads. In the shortfin mako (Isurus oxyrinchus, Lamniformes), there is some tendency for c-axis variation with position, but the situation is unclear because one dimension of the sampling volume is consid-erably larger than the thickness and spacing of the intermedialia's radially-oriented lamellae. Because elastic modulus in collagen plus bioapatite mineralized tissues varies significantly with both volume fraction of bio-apatite and crystallographic texture, the present 3D EDD-derived maps should inform future 3D numerical models of shark centra under applied load.
59 BASIC BIOLOGICAL SCIENCES↗
Ruthenium solubility and its impact on the crystallization behavior and electrical conductivity of MoO 3 -containing borosilicate-based model high-level nuclear waste glasses
The present study focuses on investigating the solubility of RuO 2 in a borosilicate-based model high-level waste glass and understanding its impact on the crystallization behavior and electrical conductivity of the resulting vitrified waste forms. The solubility limit of RuO 2 in the investigated glass composition has been determined to be 460 ppm by weight. The higher concentration of RuO 2 results in sub-micron sized Ru-rich inclusions in the glassy matrix, which eventually agglomerate to form needle-like and polyhedral RuO 2 crystals. It is observed that RuO 2 selectively promotes the crystallization of the rare-earth apatite phase over the powellite phase. The as-synthesized RuO 2 -containing glasses exhibit semiconducting behavior with a similar level of electrical conductivity below the glass transition. Here, the percolation of non-uniformly distributed RuO 2 inclusions may result in a formation of short-range low-resistive conduction pathways in the host glass matrix leading to an apparent metallic-like behavior of selected thin samples with the highest ruthenium content.
36 MATERIALS SCIENCE↗
Impact of rare earth ion size on the phase evolution of MoO3-containing aluminoborosilicate glass-ceramics
Transition metal and rare earth cations are important fission products present in used nuclear fuel, which in high concentrations tend to precipitate crystalline phases in vitreous nuclear waste forms. Two phases of particular interest are powellite (CaMoO 4 ) and oxyapatite (Ca 2 RE 8 (SiO 4 ) 6 O 2 ). The glass compositional dependencies controlling crystallization of these phases on cooling from the melt are poorly understood. In the present study, the effect of rare earth identity and modifier cation field strength on powellite and apatite crystallization were studied in a model MoO3-containing alkali/alkaline-earth aluminoborosilicate glass with focus on (1) influence of rare earth cation size (for RE 3+ : Ce, La, Nd, Sm, Er, Yb) and (2) influence of non-framework cations (RE 3+ , Mo 6+ , Na + , Ca 2+ ). Quenched glasses and glass-ceramics (obtained by slow cooling) were characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray absorption (XAS), and electron probe microanalysis (EPMA). All samples were X-ray amorphous upon quenching, except the Ce-containing composition which crystallized ceria (CeO 2 ), and the sample devoid of any rare earth cations which crystallized powellite (CaMoO 4 ). On heat treatment, powellite and oxyapatite crystallized in the majority of the samples with the former crystallizing in the volume, while the latter on the surface. The EPMA results confirmed a small concentration of boron in the oxyapatite crystal structure. RE cations were incorporated in the glass, as well as in powellite, oxyapatite, and in the case of Yb 3+ , keiviite (Yb 2 Si 2 O 7 ). Raman spectroscopy showed that the primary vibration band for molybdate MoO 4 2- in the glasses was strongly affected by the ionic field strength of the modifying cations (alkali, alkaline earth, and RE), suggesting their proximity to the MoO 4 2- ions in the glass, though the MoO bond length and coordination according to XAS suggested little local change.
36 MATERIALS SCIENCE↗
Fabrication of radioactive and non-radioactive titanate and zirconate ceramics for immobilization of
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Reiser, Joelle T.↗