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Pyridoxine deficiency affects biomechanical properties of chick tibial bone

The mechanical integrity of bone is dependent on the bone matrix, which is believed to account for the plastic deformation of the tissue, and the mineral, which is believed to account for the elastic deformation. The validity of this model is shown in this study based on analysis of the bones of vitamin B6-deficient and vitamin B6-replete chick bones. In this model, when B6-deficient and control animals are compared, vitamin B6 deficiency has no effect on the mineral content or composition of cortical bone as measured by ash weight (63 +/- 6 vs. 58 +/- 3); mineral to matrix ratio of the FTIR spectra (4.2 +/- 0.6 vs. 4.5 +/- 0.2), line-broadening analyses of the X-ray diffraction 002 peak (beta 002 = 0.50 +/- 0.1 vs. 0.49 +/- 0.01), or other features of the infrared spectra. In contrast, collagen was significantly more extractable from vitamin B6-deficient chick bones (20 +/- 2% of total hydroxyproline extracted vs. 10 +/- 3% p < or = 0.001). The B6-deficient bones also contained an increased amount of the reducible cross-links DHLNL, dehydro-dihydroxylysinonorleucine, (1.03 +/- 0.07 vs. 0.84 +/- 0.13 p < or = 0.001); and a nonsignificant increase in HLNL, dehydro-hydroxylysinonorleucine, (0.51 +/- 0.03 vs. 0.43 +/- 0.03, p < or = 0.10). There were no significant changes in bone length, bone diameter, or area moment of inertia. In four-point bending, no significant changes in elastic modulus, stiffness, offset yield deflection, or fracture deflection were detected. However, fracture load in the B6-deficient animals was decreased from 203 +/- 35 MPa to 151 +/- 23 MPa, p < or = 0.01, and offset yield load was decreased from 165 +/- 9 MPa to 125 +/- 14 MPa, p < or = 0.05. Since earlier histomorphometric studies had demonstrated that the B6-deficient bones were osteopenic, these data suggest that although proper cortical bone mineralization occurred, the alterations of the collagen resulted in changes to bone mechanical performance.

Non-NASA Center↗

X-ray diffraction identification of minerals in lunar regolith returned by Luna 16 automatic station

The methods of powder and monocrystal X-ray diffraction served in identifying the mineral composition of gross samples of regolith from different levels of the drill core and about 80 individual regolith particles returned by the Luna 16 station. It was established that the Sea of Fertility regolith includes pyroxenes of the augite-pigeonite series, anorthites, ilmenite, olivines, spinels, alpha cristobalite, iron particles, glass, and several as yet unidentified particles. Crystallographic and roentgenometric data are given for all the lunar minerals found.

Makarov, Y. S.↗

Observation of radiation induced changes in stress and electrical properties in MOS devices

Strain measurements using X-ray diffraction were performed on irradiated commercial and radiation-hardened metal gate CMOS devices in addition to polysilicon gate NMOS devices. I-V curves were taken and V(ot) and V(it) were separated using the subthreshold slope method for all devices. A correlation has been shown to exist between physical strain relaxation and the electrical properties as a function of radiation dose and recovery. Data shown suggest that the physical response (strain relaxation) in the silicon at the oxide interface is a measure of the type of damage induced and the recovery mechanism. Postradiation measurements of Delta V(it) and Delta V(ot) taken immediately after irradiation support the conclusions of V. Zekeriya and T.-P. Ma (1983) and K. Kasama et al. (1986, 1987); compressive stress at the silicon/SiO2 interface does reduce radiation damage in the device.

Shaw, D. C.↗

X-ray diffractometer studies of shocked materials

This study explores the utility of X-ray diffractometer scans for determination of shock pressure histories of geological materials from meteorite impact sites. The technique is based on quantification of increased crystal lattice disorder with increasing shock pressure as expressed by decreasing diffraction peak amplitude and pronounced line-broadening caused by decreasing mosaic domain size and increasing strain. The ratio of peak height (PH) to half width (HW) decreases systematically with increasing shock pressure. Data are given for experimentally shocked quartz, feldspars, pyroxene and olivine along with data for granitic materials from the Piledriver nuclear event and from the Ries Crater, Germany. Although the technique in principle may be capable of yielding relatively accurate pressure determinations, its application to naturally shocked materials may be severely limited.

Hanss, R. E.↗

Static compression of Ca(OH)2 at room temperature - Observations of amorphization and equation of state measurements to 10.7 GPa

X-ray diffraction measurements are reported for Ca(OH)2 portlandite as it is compressed to 37.6 GPa in the diamond cell at room temperature. Between 10.7 and 15.4 GPa crystalline Ca(OH)2 transforms to a glass, and on decompression the glass recrystallizes between 3.6 and 5.1 GPa. Below pressures of 10.7 GPa the elastic compression of crystalline Ca(OH)2 was measured. A finite strain analysis of these data shows that the isothermal bulk modulus and its pressure derivative are 37.8 + or - 1.8 GPa and 5.2 + or - 0.7 at zero pressure. The change in the unit cell dimensions indicates that the linear incompressibilities of Ca(OH)2 differ by a factor of three.

Meade, Charles↗

Magnetite: What it reveals about the origin of the banded iron formations

Magnetite, Fe3O4 is produced abiotically and biotically. Abiotically, magnetite is a late magmatic mineral and forms as a consequence of the cooling of iron rich magma. Biotically, magnetite is produced by several organisms, including magnetotactic bacteria. Hematite, Fe2O3, is also produced abiotically and biotically. Abiotically, hematite rarely occurs as a primary mineral in igneous rocks, but is common as an alteration product, fumarole deposit, and in some metamorphosed Fe-rich rocks. Biotically, hematite is produced by several types of microorganisms. Biologically-produced magnetite and hematite are formed under the control of the host organism, and consequently, have characteristics not found in abiotically produced magnetite and hematite crystals. To determine if the magnetite and hematite in the Banded Iron Formation was biologically or abiotically produced, the characteristics of biologically-produced magnetite and hematite (concentrated from Aquaspirillum magnetotacticum) and abiotically-produced magnetite and hematite obtained from Wards Scientific Supply Company, were compared with characteristics of magnetite and hematite concentrated from the Gunflint Banded Iron Formation (Ontario, Canada) using thermal and crystallographic analytical techniques. Whole rock analysis of the Gunflint Banded Iron Formation by x-ray diffraction (XRD) and differential thermal analysis (DTA) revealed the presence of quartz, hematite, siderite and dolomite as the major minerals, and magnetite, greenalite, pyrite, pyrrhotite and apatite as the minor minerals. Analysis of a crude magnetic fraction of the Gunflint showed the minerals quartz, hematite, siderite, dolomite, and magnetite. Analysis of the crude magnetic fraction from Aquaspirillum magnetotacticum revealed organic compounds plus hematite and magnetite. The mineral identification and particle size distribution data obtained from the DTA along with XRD data indicate that the magnetite and hematite from the Gunflint BIF share some similarities with biologically formed magnetite and hematite.

Schwartz, D. E.↗

Structure and stability of hydrous minerals at high pressure

The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

Duffy, T. S.↗

The effect of zirconium on the isothermal oxidation of nominal Ni-14Cr-24Al alloys

The isothermal oxidation of Ni-14Cr-24Al-xZr-type alloys was performed in still air at 1100, 1150, and 1200 C for times up to 200 hr. The zirconium content of the alloys varied from 0-0.63 atom percent (a/o). The oxidized surfaces were studied by optical microscopy, X-ray diffraction, and scanning electron microscopy. The base alloy was an alumina former with the zirconium-containing alloys also developing some ZrO2. The addition of zirconium above 0.066 a/o increased the rate of weight gain relative to the base alloy. Due to oxide penetratio, the weight gain increased with Zr content; however, the scale thickness did not increase. The Zr did increase the adherence of the oxide, particularly at 1200 C. The delta W/A vs. time data fit the parabolic model of oxidation. The specific diffusion mechanism operative could not be identified by analysis of the calculated activation energies. Measurements of the Al2O3 scale lattice constants yielded the same values for all alloys.

Kahn, A. S.↗

Simultaneous high-P, high-T X ray diffraction study of beta-(Mg,Fe)2SiO4 to 26 GPa and 900 K

Attention is given to the lattice parameters of beta phase (Mg(0.84)Fe(0.16))2SiO4 determined by X-ray diffraction using synchrotron radiation under simultaneous high-pressure and high-temperature conditions. The experiments were conducted up to a pressure of 26 GPa and a temperature of 900 K. High pressures were generated in a Mao-Bell type diamond anvil cell using neon gas as a pressure medium. The sample was heated with an external Ni80Cr20 wire heater. Gold was used as an internal high-pressure calibrant at high temperature. The experimental data indicated the anisotropic behavior of the beta phase at high pressure and temperature, i.e., the c axis is about 35-percent more expansible and about 25-percent more compressible than the a and b axes. A value of 5.1 +/-0.8 was found for the Anderson-Grueneisen parameter. The derived thermodynamic parameters for the beta phase are summarized.

Fei, Yingwei↗

Kinetics of the phase transformation in a Ti-15Mo-5Zr-3Al alloy as studied by X-ray diffraction

The purpose of the study is to make the T-T-T diagram available and to describe the X-ray diffraction techniques used to determine the fraction of transformed phase in the Ti-15Mo-5Zr-3Al metastable beta-alloy which decomposes into the hexagonal alpha-phase and the bcc beta-phase of a higher Mo concentration. The sheet material studied for this study is not ideal for an X-ray examination because of both a rolling and annealing texture as well as grain size problems. These difficulties are overcome using special X-ray techniques. Equations are given that indicate the approximations to be accepted if pole figure data are disregarded. Lattice parameter data from the beta phase enables one to obtain an approximate phase diagram.

Rao, V. B.↗

Evaluation of zirconia, thoria and zirconium diboride for advanced resistojet use

A literature survey was conducted to collect material properties data on all advanced high temperature materials. Three of these, Y2O3-stabilized ZrO2, ThO2, and ZrB2 with additives of C and SiC were selected for further study. Stabilized ZrO2 and ThO2 were found to have higher temperature oxidation resistance than any metal and great potential for use in advanced biowaste resistojets. ZrO2 has a lower electrical resistivity and sublimation and a higher creep endurance strength. ZrO2 and ThO2 tubular heat exchangers, electrically heated indirectly, were evaluated in short tests to about 1900 K in flowing CO2. ZrO2 was subjected to N2, H2, H2O and vacuum as well. X-ray diffraction and fluorescence analyses were made. The metal-to-ceramic seal technology for ZrO2 and ThO2 was developed using chemical vapor deposition of tantalum for metallizing and 82 Au - 18 Ni filler braze.

Page, R. J.↗

Effect of Stacking Faults on the X-Ray Diffraction Profiles of Beta-SiC Powders

X-ray diffraction patterns or beta-SiC (3C or the cubic polytype or sic) powders often exhibit an additional peak at d = 0.266 nm, high background intensity around the (111) peak, and relative intensities for peaks which differ from those predicted from the crystal structure. Computer simulations were used to show that all these features are due to stacking faults in the powders and not due to the presence of other polytypes in the powders. Such simulations allow diffraction patterns to be generated for different types, frequencies, and spatial distribution or faults. Comparison of the simulation results to the XRD data indicates that the B-SiC particles consist either of heavily faulted clusters distributed irregularly between regions that have only occasional faults or twins, or the powders consist of two types of particles with different populations of faults: those with a high density of faults and those with only twins or occasional faults. Additional information is necessary to determine which description is correct. However, the simulation results can be used to rule out certain fault configurations.

Pujar, Vijay V.↗

Preliminary Work in Obtaining Site-Directed Mutants of Hen Egg White Lysozyme

Protein crystal growth studies are recognized as a critical endeavor in the field of molecular biotechnology. The scientific applications of this field include the understanding of how enzymes function and the accumulation of accurate information of atomic structures, a key factor in the process of rational drug design. NASA has committed substantial investment and resources to the field of protein crystal growth and has conducted many microgravity protein crystal growth experiments aboard shuttle flights. Crystals grown in space tend to be larger, denser and have a more perfect habit and geometry. These improved properties gained in the microgravity environment of space result largely from the reduction of solutal convection, and the elimination of sedimentation at the growing crystal surface. Shuttle experiments have yielded many large, high quality crystals that are suitable for high resolution X-ray diffraction analysis. Examples of biologically important macromolecules which have been successfully crystallized during shuttle missions include: lysozyme, isocitrate lyase, gamma-interferon, insulin, human serum albumin and canavalin. Numerous other examples are also available. In addition to obtaining high quality crystals, investigators are also interested in learning the mechanisms by which the growth events take place. Crystallization experiments indicate that for the enzyme HEWL, measured growth rates do not follow mathematical models for 2D nucleation and dislocation-led growth of tetragonal protein crystals. As has been suggested by the laboratory of Marc L. Pusey, a possible explanation for the disagreement between observation and data is that HEWL tetraconal crystals form by aggregated units of lysozyme in supersaturated solutions. Surface measurement data was shown to fit very well with a model using an octamer unit cell as the growth unit. According to this model, the aggregation pathway and subsequent crystal growth is described by: monomer < ------ > dimer < ------- > tetramer < ------ > octamer < ------ > higher order. It is believed that multimer aggregation of lysozyme occurs by interaction at specific binding sites on the surface of the protein crystals. If the presence of discrete binding sites and the aggregation hypothesis is true, then it follows that the alteration of the binding site(s) should have significant effect on the measurements obtained during growth experiments. Site-directed mutagenesis allows the specific alteration of proteins by replacement, deletion or addition of specific amino acid residues. This report outlines the approach for this strategy and the progress made thus far toward that end.

Holmes, Leonard D.↗

Phosphate Textural Diversity in CI Chondrites and C-Type Asteroids

Introduction: Apatite, Ca 5 (PO 4 ) 3 (CL/F/OH-), is a ubiquitous phosphate found throughout the solar system, including the most primitive solids, CI-chondrites [1,2] and related samples of carbonaceous asteroids Ryugu [3] and Bennu [4], returned by JAXA’s Hayabusa2 and NASA’s OSIRIS-REx missions, respectively. Apatite in these primitive solids is found as individual grains or mineral clusters and has been inferred to form from the hydrothermal sequence during cooling of their respective parent body or bodies. To better understand the formation history and reworking of these early phosphates we have undertaken a highly coordinated study of phosphate microstructures, geochemistry and U/Pb geochronology from a suite of CI meteorites and carbonaceous asteroid samples. These data have identified novel phosphate microstructures and complex relationships across a suite of apatite grains from the early solar system, indicating multiple episodes of growth and modification on the CI parent body(ies). Methods: Samples of CI chondrites, Alais, Ivuna, Orgueil, Oued Chebeika 002, Yamato (Y) 82162, Y980115, Y980134, and two chips of Hayabusa2 Ryugu particles (A0262 and C0263) have been acquired for analysis. The bulk texture of the samples were first scanned by X-ray Computed Tomography (XCT) using the Nikon XT H 320 within the XFACT facility at NASA JSC or the Xradia 620 Versa at the UTCT facility. Based on the identification of petrofabrics or features of interest from the XCT data, samples were chipped, oriented, potted in epoxy and thick sections were prepared. After anhydrously polishing the samples with silicon carbide and dry diamond powder down to 1 µm, the samples were ion polished using a Hitachi ArBlade. Energy dispersive Xray spectrometry (EDS) maps were collected to ID phosphates of interest using a JEOL 7900F SEM. The internal microstructures of identified phosphates were then mapped by electron backscatter diffraction (EBSD) using the JEOL 7900F. Based on the EDS and EBSD data, domains of interest were targeted for quantitative chemical analyses using a JEOL 8530 EPMA. Subsequently, in situ U-Pb and 207 Pb/ 206 Pb ages will be collected using a Cameca ims1290 secondary ion mass spectrometer at UCLA across a range of microstructures. Results: Apatite grains are ubiquitous throughout the CI chondrites and carbonaceous asteroid materials, found as individual grains, disseminated clusters or grain aggregates. Apatite grains are associated with serpentine, magnet-ite, and/or carbonate. Of particular interest, we have identified individual and aggregate polycrystalline grains ex-hibiting an internal ‘honeycomb’ texture (Fig. 1). Some of these grains appear overprinted by subsequent alteration while others remain unaltered. Apatite halogen sites are dominated by the missing component, assumed to be OH, and F, comparable to published values from Bennu, Ryugu and CM-chondrites [3-5]. However, the Yamato CI-like meteorites show a broader range of Cl values, and one grain from Alais is dominated by CL. Summary: Apatite growth features indicate a protracted and complex growth history, consistent with precipitation from an evolving fluid system. The ‘honeycomb’ texture identified in some CI meteorites is, to the best of our knowledge, the first report of such a microstructure in meteoritic phosphate. The microtextures and zoning will guide subsequent age analyses, to better constrain the formation and reworking of phosphate in CI(-like) materials. Acknowledgments: We thank the National Institute of Polar Research, Japan for samples of Y82162, 980115 and 980134 meteorites, ASU’s Buseck Center for Meteorite Studies for samples of Ivuna and Alais meteorites, and JAXA curation for chips of Ryugu material. This work was funded by NASA ROSES LARS grant 24-LARS24-0014. References: [1] Morlok et al., 2016, GCA 70:5371-5394. [2] Alfin g et al., 2019, Geochemistry 79:125532. [3] Nakamura et al. (2022) Science 379:1-15. [4] Seifert et al. (2026) MAPS 61:504-521. [5] Piralla et al. (2021) MAPS 56:809-828.

CI chondrites↗

Nature and origin of interstellar diamond from the Allende CV3 meteorite

Data and experimental evidence which support the contention that the C delta diamonds may result from grain-grain collisions in supernova shocks in the interstellar medium are presented. Fragments of the Allende CV3 chondrite were acid-treated. A whitish powder was obtained. For the Analytical Electron Microscopy (AEM) a small drop of ethanol suspension was transferred onto holey carbon support films on 3 mm EM grids. The AEM was performed on transmission-thin fragments of the material which overlay holes in the film, to eliminate interference from the substrate. Electron Spectroscopy for Chemical Analysis (ESCA) was performed on a large aliquot of C. Diamond was identified by selected area electron diffraction. Scanning Transmission Electron Microscope / Energy Dispersive X-ray (STEM-EDS) microanalyses of the C delta diamond, using a light-element detector, show that oxygen and possibly nitrogen are the only impurities consistently present. ESCA spectra from bulk C delta material confirm the presence of N at a level of 0.35 percent or less. Under UV irradiation a yellow-red fluorescence is observed, consistent with that of natural diamonds containing substitutional N. Electron Energy Loss Spectra (EELS) were recorded at 2 eV resolution from the C delta diamond, high pressure synthetic diamond, a diamond film produced in a low pressure plasma by chemical vapor deposition (CVD) on a heated silicon substrate (Roy, 1987), graphite, and amorphous arc sputtered carbon. Comparison of the carbon K edge shape and fine structure shows the Allende C delta phase to be largely diamond, but with a significant pre-edge absorption feature indicative of transitions of C 1s electrons into pi asterisk orbitals which are absent in the purely sp(3)-bonded diamond but present in graphite and amorphous carbon.

Blake, David↗

The in situ exobiological investigation of the Martian surface mineralogy during unmanned missions

An important goal of exobiological research is to determine if life arose on planets other than Earth. The only other planet known, to date, on which life may have arisen is Mars. The data suggest that the physical environment of early Mars (i.e., temperature, pressure, and radiation regimes) was suitable for life to arise. Thus far, the data also suggest that early Mars possessed sufficient quantities of the required building blocks and a number of the chemical compounds necessary for life to arise. It is not known, however, if water existed in the appropriate state (i.e., liquid) in sufficient quantities long enough for life to arise. Determining the mineralogy and components of the Martian soil through in situ analyses during missions to Mars will provide information from which an assessment can be made for the probability of the origin of life on Mars. Missions to Mars in the near future will be unmanned and capable of in situ analyses. Our studies have shown that differential thermal analysis coupled with gas chromatography (DTA/GC) is a more appropriate analytical technique than, x-ray fluorescence, x-ray diffraction, alpha-proton backscatter, gamma-ray spectrometry, differential scanning calorimetry coupled with mass spectrometry (DSC/MS), or DSC/GC to identify the mineralogy of the Martian surface material in situ. DTA/GC is an advancement over the pyrolytic techniques flown on previous missions that have supplied only limited mineralogical information (Biemann et al. 1977).

Mancinelli, Rocco L.↗

Quantitative remote sensing of ammonium minerals, Cedar Mountains, Esmeralda County, Nevada

Mineral-bound ammonium (NH4+) was discovered by the U.S. Geological Survey in the southern Cedar Mountains of Esmeralda County, Nevada in 1989. At 10 km in length, this site is 100 times larger than any previously known occurrence in volcanic rocks. The ammonium occurs in two hydrothermally altered, crystal-rich rhyolitic tuff units of Oligocene age, and is both structurally and stratigraphically controlled. This research uses Advanced Visible/Infrared Imaging Spectrometer (AVIRIS) data to quantitatively map the mineral-bound ammonium (buddingtonite) concentration in the altered volcanic rocks. Naturally occurring mineral-bound ammonium is fairly rare; however, it has been found to occur in gold-bearing hydrothermal deposits. Because of this association, it is thought that ammonium may be a useful too in exploration for gold and other metal deposits. Mineral-bound ammonium is produced when an ammonium ion (NH4+) replaces the alkali cation site (usually K+) in the crystal structure of silicate minerals such as feldspars, micas and clays. Buddingtonite is an ammonium feldspar. The ammonium originates in buried organic plant matter and is transported to the host rock by hydrothermal fluids. Ammonium alteration does not produce visible changes in the rock, and it is barely detectable with standard x-ray diffraction methods. It is clearly identified, however, by absorption features in short wave-infrared (SWIR) wavelengths (2.0 - 2.5 micrometers). The ammonium absorption features are believed to be caused by N-H vibrational modes and are analogous to hydroxyl (O-H) vibrational modes, only shifted slightly in wavelength. Buddingtonite absorption features in the near- and SWIR lie at 1.56, 2.02 and 2.12 micrometers. The feature at 2.12 micrometer is the strongest of the three and is the only one used in this study. The southern Cedar Mountains are sparsely vegetated and are an ideal site for a remote sensing study.

Baugh, William M.↗

X-Ray-Diffraction Tests Of Irradiated Electronic Devices: II

Report describes research on use of x-ray diffraction to measure stresses in metal conductors of complementary metal oxide/semiconductor (CMOS) integrated circuits exposed to ionizing radiation. Expanding upon report summarized in "X-Ray-Diffraction Tests Of Irradiated Electronic Devices: I" (NPO-18803), presenting data further suggesting relationship between electrical performances of circuits and stresses and strains in metal conductors.

Shaw, David C.↗